Book Insights

5.12 Write all the geometrical isomers of [Pt(NH3)(Br)(Cl)(py)] and how many of these will exhibit optical isomers?

5.15 Discuss the nature of bonding in the following coordination entities on the basis of valence bond theory: (i) [Fe(CN)6] 4– (ii) [FeF6] 3– (iii) [Co(C2O4)3]3– (iv) [CoF6] 3–

5.11 Draw all the isomers (geometrical and optical) of: (i) [CoCl2(en)2] + (ii) [Co(NH3)Cl(en)2] 2+ (iii) [Co(NH3)2Cl2(en)]+

5.29 Amongst the following ions which one has the highest magnetic moment value? (i) [Cr(H2O)6]3+ (ii) [Fe(H2O)6] 2+ (iii) [Zn(H2O)6]2+ 5.30 Amongst the following, the most stable complex is (i) [Fe(H2O)6]3+ (ii) [Fe(NH3)6] 3+ (iii) [Fe(C2O4)3]3– (iv) [FeCl6] 3– 5.31 What will be the correct order for the wavelengths of absorption in the visible region for the following: [Ni(NO2)6] 4–, [Ni(NH3)6] 2+, [Ni(H2O)6] 2+ ? Answers to Some Intext Questions 5.1 (i) [Co(NH3)4(H2O)2]Cl3 (iv) [Pt(NH3)BrCl(NO2)]– (ii) K2[Ni(CN)4] (v) [PtCl2(en)2](NO3)2 (iii) [Cr(en)3]Cl3 (vi) Fe4[Fe(CN)6]3 5.2 (i) Hexaamminecobalt(III) chloride (ii) Pentaamminechloridocobalt(III) chloride (iii) Potassium hexacyanidoferrate(III) (iv) Potassium trioxalatoferrate(III) (v) Potassium tetrachloridopalladate(II) (vi) Diamminechlorido(methanamine)platinum(II) chloride 5.3 (i) Both geometrical (cis-, trans-) and optical isomers for cis can exist. (ii) Two optical isomers can exist. (iii) There are 10 possible isomers. (Hint: There are geometrical, ionisation and linkage isomers possible). (iv) Geometrical (cis-, trans-) isomers can exist. 5.4 The ionisation isomers dissolve in water to yield different ions and thus react differently to various reagents: [Co(NH3)5Br]SO4 + Ba2+ ® BaSO4 (s) [Co(NH3)5SO4]Br + Ba2+ ® No reaction [Co(NH3)5Br]SO4 + Ag+ ® No reaction [Co(NH3)5SO4]Br + Ag+ ® AgBr (s) 5.6 In Ni(CO)4, Ni is in zero oxidation state whereas in NiCl42–, it is in +2 oxidation state. In the presence of CO ligand, the unpaired d electrons of Ni pair up but Cl– being a weak ligand is unable to pair up the unpaired electrons. 5.7 In presence of CN–, (a strong ligand) the 3d electrons pair up leaving only one unpaired electron. The hybridisation is d 2sp 3 forming inner orbital complex. In the presence of H2O, (a weak ligand), 3d electrons do not pair up. The hybridisation is sp 3d 2 forming an outer orbital complex containing five unpaired electrons, it is strongly paramagnetic. 5.8 In the presence of NH3, the 3d electrons pair up leaving two d orbitals empty to be involved in d2sp3 hybridisation forming inner orbital complex in case of [Co(NH3)6]3+. In Ni(NH3)6 2+, Ni is in +2 oxidation state and has d 8 configuration, the hybridisation involved is sp 3d 2 forming outer orbital complex. 5.9 For square planar shape, the hybridisation is dsp 2. Hence the unpaired electrons in 5d orbital pair up to make one d orbital empty for dsp2 hybridisation. Thus there is no unpaired electron. Chemistry 140 Reprint 2025-26

5.23 Give the oxidation state, d orbital occupation and coordination number of the central metal ion in the following complexes: (i) K3[Co(C2O4)3] (iii) (NH4)2[CoF4] (ii) cis-[CrCl2(en)2]Cl (iv) [Mn(H2O)6]SO4

5.16 Draw figure to show the splitting of d orbitals in an octahedral crystal field.

5.28 How many ions are produced from the complex Co(NH3)6Cl2 in solution? (i) 6 (ii) 4 (iii) 3 (iv) 2 139 Coordination Compounds Reprint 2025-26

5.19 [Cr(NH3)6] 3+ is paramagnetic while [Ni(CN)4] 2– is diamagnetic. Explain why? 5.20 A solution of [Ni(H2O)6] 2+ is green but a solution of [Ni(CN)4] 2– is colourless. Explain. 5.21 [Fe(CN)6] 4– and [Fe(H2O)6] 2+ are of different colours in dilute solutions. Why?

2.1 Two charges 5 × 10–8 C and –3 × 10–8 C are located 16 cm apart. At what point(s) on the line joining the two charges is the electric potential zero? Take the potential at infinity to be zero.

2.2 A regular hexagon of side 10 cm has a charge 5 mC at each of its vertices. Calculate the potential at the centre of the hexagon.

2.2 INSTANTANEOUS VELOCITY AND SPEED The average velocity tells us how fast an object has been moving over a given time interval but does not tell us how fast it moves at different instants of time during that interval. For this, we define instantaneous velocity or simply velocity v at an instant t. The velocity at an instant is defined as the limit of the average velocity as the time interval ∆t becomes infinitesimally small. In other words, ∆ x v = lim (2.1a) ∆ t → 0 ∆ t Fig. 2.1 Determining velocity from position-time d x = (2.1b) graph. Velocity at t = 4 s is the slope of the dt tangent to the graph at that instant. lim where the symbol stands for the operation ∆→t 0 Now, we decrease the value of ∆t from 2 s to 1 of taking limit as ∆tg0 of the quantity on its s. Then line P1P2 becomes Q1Q2 and its slope right. In the language of calculus, the quantity gives the value of the average velocity over on the right hand side of Eq. (2.1a) is the the interval 3.5 s to 4.5 s. In the limit ∆t → 0, differential coefficient of x with respect to t and the line P1P2 becomes tangent to the position- d x time curve at the point P and the velocity at t is denoted by (see Appendix 2.1). It is the d t = 4 s is given by the slope of the tangent at rate of change of position with respect to time, that point. It is difficult to show this process graphically. But if we useat that instant. numerical method to obtain the value of We can use Eq. (2.1a) for obtaining the the velocity, the meaning of the limiting value of velocity at an instant either process becomes clear. For the graph shown graphically or numerically. Suppose that we in Fig. 2.1, x = 0.08 t3. Table 2.1 gives the want to obtain graphically the value of value of ∆x/∆t calculated for ∆t equal to 2.0 s, velocity at time t = 4 s (point P) for the motion 1.0 s, 0.5 s, 0.1 s and 0.01 s centred at t = of the car represented in Fig.2.1 calculation. 4.0 s. The second and third columns give theLet us take ∆t = 2 s centred at t = 4 s. Then, t  t    ∆ ∆by the definition of the average velocity, the t + t −     and t 2 = and the value of t1= 2 2slope of ( Fig. 2.1) gives the value of     line P1P2 average velocity over the interval 3 s to 5 s. fourth and the fifth columns give the ∆x Table 2.1 Limiting value of at t = 4 s ∆ t Reprint 2025-26 MOTION IN A STRAIGHT LINE 15 3 a + 16b – a – 4b corresponding values of x, i.e. x (t1) = 0.08 t1 = = 6.0 × b 2.0 -1 ⊳and x (t2) = 0.08 t23. The sixth column lists the = 6.0 × 2.5 =15 m s difference ∆x = x (t2) – x (t1) and the last column gives the ratio of ∆x and ∆t, i.e. the Note that for uniform motion, velocity is average velocity corresponding to the value the same as the average velocity at all of ∆t listed in the first column. instants. We see from Table 2.1 that as we decrease Instantaneous speed or simply speed is the the value of ∆t from 2.0 s to 0.010 s, the value of magnitude of velocity. For example, a velocity of the average velocity approaches the limiting + 24.0 m s–1 and a velocity of – 24.0 m s–1 — value 3.84 m s–1 which is the value of velocity at both have an associated speed of 24.0 m s-1. It should be noted that though average speed over dx t = 4.0 s, i.e. the value of at t = 4.0 s. In this a finite interval of time is greater or equal to the dt magnitude of the average velocity, manner, we can calculate velocity at each instantaneous speed at an instant is equal to instant for motion of the car. the magnitude of the instantaneous velocity at The graphical method for the determination that instant. Why so ? of the instantaneous velocity is always not a 2.3 ACCELERATIONconvenient method. For this, we must carefully plot the position–time graph and calculate the The velocity of an object, in general, changes value of average velocity as ∆t becomes smaller during its course of motion. How to describe and smaller. It is easier to calculate the value this change? Should it be described as the rate of velocity at different instants if we have data of change in velocity with distance or with of positions at different instants or exact time ? This was a problem even in Galileo’s expression for the position as a function of time. time. It was first thought that this change could Then, we calculate ∆x/∆t from the data for be described by the rate of change of velocity decreasing the value of ∆t and find the limiting with distance. But, through his studies of value as we have done in Table 2.1 or use motion of freely falling objects and motion of differential calculus for the given expression and objects on an inclined plane, Galileo concluded that the rate of change of velocity with time is dx calculate at different instants as done in a constant of motion for all objects in free fall. dt On the other hand, the change in velocity with the following example. distance is not constant – it decreases with the ⊳ increasing distance of fall. This led to the Example 2.1 The position of an object concept of acceleration as the rate of change moving along x-axis is given by x = a + bt2 of velocity with time. where a = 8.5 m, b = 2.5 m s–2 and t is The average acceleration a over a time interval measured in seconds. What is its velocity at is defined as the change of velocity divided by t = 0 s and t = 2.0 s. What is the average the time interval : velocity between t = 2.0 s and t = 4.0 s ? v 2 – v1 ∆v (2.2)Answer In notation of differential calculus, the a = = t 2 – t1 ∆tvelocity is where v2 and v1 are the instantaneous velocities dx d 2 -1 2b t = 5.0 t m s or simply velocities at time t2 and t1 . It is thev = = ( a + bt ) = dt dt average change of velocity per unit time. The SI At t = 0 s, v = 0 m s–1 and at t = 2.0 s, unit of acceleration is m s–2 . v = 10 m s-1 . On a plot of velocity versus time, the average acceleration is the slope of the straight line x ( 4.0 ) − x ( 2.0 )Average velocity = connecting the points corresponding to (v2, t2) 4.0 − 2.0 and (v1, t1). Reprint 2025-26 16 PHYSICS Instantaneous acceleration is defined in the (c) An object is moving in negative direction same way as the instantaneous velocity : with a negative acceleration. ∆v d v (d) An object is moving in positive direction lim a = = (2.3) till time t1, and then turns back with the d t ∆→ t 0 ∆ t same negative acceleration. The acceleration at an instant is the slope of the tangent to the v–t curve at that An interesting feature of a velocity-time instant. graph for any moving object is that the area Since velocity is a quantity having both under the curve represents the magnitude and direction, a change in displacement over a given time interval. A velocity may involve either or both of these general proof of this statement requires use of factors. Acceleration, therefore, may result calculus. We can, however, see that it is true from a change in speed (magnitude), a for the simple case of an object moving with change in direction or changes in both. Like constant velocity u. Its velocity-time graph is velocity, acceleration can also be positive, as shown in Fig. 2.4. negative or zero. Position-time graphs for motion with positive, negative and zero acceleration are shown in Figs. 2.4 (a), (b) and (c), respectively. Note that the graph curves upward for positive acceleration; downward for negative acceleration and it is a straight line for zero acceleration. Although acceleration can vary with time, our study in this chapter will be restricted to motion with constant acceleration. In this case, the average acceleration equals the constant value of acceleration during the interval. If the velocity of an object is vo at t = 0 and v at time t, we have v − v 0 a = or, v = v 0 + a t (2.4) t − 0 Fig. 2.3 Velocity–time graph for motions with Fig. 2.2 Position-time graph for motion with constant acceleration. (a) Motion in positive (a) positive acceleration; (b) negative direction with positive acceleration, acceleration, and (c) zero acceleration. (b) Motion in positive direction with Let us see how velocity-time graph looks like negative acceleration, (c) Motion in for some simple cases. Fig. 2.3 shows velocity- negative direction with negative acceleration, (d) Motion of an object withtime graph for motion with constant acceleration negative acceleration that changesfor the following cases : direction at time t1. Between times 0 to (a) An object is moving in a positive direction t1, it moves in positive x - direction with a positive acceleration. and between t1 and t2 it moves in the (b) An object is moving in positive direction opposite direction. with a negative acceleration. Reprint 2025-26 MOTION IN A STRAIGHT LINE 17 Fig. 2.4 Area under v–t curve equals displacement of the object over a given time interval. The v-t curve is a straight line parallel to the time axis and the area under it between t = 0 and t = T is the area of the rectangle of height u and base T. Therefore, area = u × T = uT which Fig. 2.5 Area under v-t curve for an object with is the displacement in this time interval. How uniform acceleration. come in this case an area is equal to a distance? Think! Note the dimensions of quantities on the two coordinate axes, and you will arrive at As explained in the previous section, the area the answer. under v-t curve represents the displacement. Therefore, the displacement x of the object is : Note that the x-t, v-t, and a-t graphs shown in several figures in this chapter have sharp 1 x = ( v – v 0 ) t + v 0 t (2.5)kinks at some points implying that the 2 functions are not differentiable at these But v − v 0 = a tpoints. In any realistic situation, the functions will be differentiable at all points 1 2 Therefore, x = a t + v 0 tand the graphs will be smooth. 2 What this means physically is that 1 2 or, x = v 0 t + at (2.6)acceleration and velocity cannot change 2 values abruptly at an instant. Changes are Equation (2.5) can also be written as always continuous. v + v 0 x = t = v t (2.7a)2.4 KINEMATIC EQUATIONS FOR 2 UNIFORMLY ACCELERATED MOTION where, For uniformly accelerated motion, we can derive some simple equations that relate displacement v + v 0 v = (constant acceleration only)(x), time taken (t), initial velocity (v0), final 2 velocity (v) and acceleration (a). Equation (2.4) (2.7b) already obtained gives a relation between final and initial velocities v and v0 of an object moving Equations (2.7a) and (2.7b) mean that the object with uniform acceleration a : has undergone displacement x with an average velocity equal to the arithmetic average of the v = v0 + at (2.4) initial and final velocities. From Eq. (2.4), t = (v – v0)/a. Substituting this in This relation is graphically represented in Fig. 2.5. Eq. (2.7a), we get The area under this curve is : Area between instants 0 and t = Area of triangle  v + v 0   v − v 0  v 2 − v 02 x = v t =ABC + Area of rectangle OACD  2   a = 2a 1 2 2 = (v – v 0 ) t + v 0 t v = v 0 + 2ax (2.8) 2 Reprint 2025-26 18 PHYSICS This equation can also be obtained by t v 0 + at ) d tsubstituting the value of t from Eq. (2.4) into Eq. = ∫ 0 ( (2.6). Thus, we have obtained three important equations : 1 2 x – x 0 = v 0 t + a t 2 v = v 0 + at 1 2 1 2 x = x 0 + v 0 t + a t x = v 0t + at 2 2 We can write v 2 = v 02 + 2ax (2.9a) d v d v d x d v a = = = v d t d x d t d x connecting five quantities v0, v, a, t and x. These or, v dv = a dxare kinematic equations of rectilinear motion for Integrating both sides,constant acceleration. The set of Eq. (2.9a) were obtained by v x v d v = a d xassuming that at t = 0, the position of the particle, ∫ v 0 ∫ x 0 x is 0. We can obtain a more general equation if we take the position coordinate at t = 0 as non- v 2 – v 02 = a ( x – x 0 ) zero, say x0. Then Eqs. (2.9a) are modified 2 (replacing x by x – x0 ) to : 2 2 v = v 0 + 2a ( x – x 0 ) v = v 0 + at The advantage of this method is that it can be used 1 2 for motion with non-uniform acceleration x = x 0 + v 0t + at (2.9b) also. 2 Now, we shall use these equations to some v 2 = v 02 + 2a ( x − x 0 ) (2.9c) important cases. ⊳ ⊳ ⊳ Example 2.3 A ball is thrown vertically Example 2.2 Obtain equations of motion upwards with a velocity of 20 m s–1 from for constant acceleration using method of the top of a multistorey building. The calculus. height of the point from where the ball is thrown is 25.0 m from the ground. (a) How high will the ball rise ? and (b) how longAnswer By definition will it be before the ball hits the ground? d v Take g = 10 m s–2. a = d t dv = a dt Answer (a) Let us take the y-axis in the Integrating both sides vertically upward direction with zero at the v t ∫ v 0 d v = ∫ 0 a d t ground, as shown in Fig. 2.6. Now vo = + 20 m s–1, t d t (a is a = – g = –10 m s–2, = a ∫ 0 v = 0 m s–1 constant) If the ball rises to height y from the point of v – v 0 = at launch, then using the equation 2 + 2 a 0 ( y – y 0 ) v = v 0 + at v 2 = v we get d x Further, v = 0 = (20)2 + 2(–10)(y – y0) d t Solving, we get, (y – y0) = 20 m. dx = v dt Integrating both sides (b) We can solve this part of the problem in two x t ways. Note carefully the methods used. ∫ x 0 dx = ∫v0 d t Reprint 2025-26 MOTION IN A STRAIGHT LINE 19 0 = 25 +20 t + (½) (-10) t2 Or, 5t2 – 20t – 25 = 0 Solving this quadratic equation for t, we get t = 5s Note that the second method is better since we do not have to worry about the path of the motion as the motion is under constant acceleration. ⊳ ⊳ Example 2.4 Free-fall : Discuss the motion of an object under free fall. Neglect air resistance. Answer An object released near the surface of the Earth is accelerated downward under the influence of the force of gravity. The magnitude of acceleration due to gravity is represented by g. If air resistance is neglected, the object is Fig. 2.6 said to be in free fall. If the height through which the object falls is small compared to the FIRST METHOD : In the first method, we split earth’s radius, g can be taken to be constant, the path in two parts : the upward motion (A to equal to 9.8 m s–2. Free fall is thus a case of B) and the downward motion (B to C) and motion with uniform acceleration. calculate the corresponding time taken t1 and We assume that the motion is in y-direction, t2. Since the velocity at B is zero, we have : more correctly in –y-direction because we v = vo + at choose upward direction as positive. Since the 0 = 20 – 10t1 acceleration due to gravity is always downward, Or, t1 = 2 s it is in the negative direction and we have This is the time in going from A to B. From B, or a = – g = – 9.8 m s–2 the point of the maximum height, the ball falls The object is released from rest at y = 0. Therefore, freely under the acceleration due to gravity. The v0 = 0 and the equations of motion become: ball is moving in negative y direction. We use v = 0 – g t = –9.8 t m s–1equation y = 0 – ½ g t2 = –4.9 t 2 m 1 2 y = y 0 + v 0t + at v2 = 0 – 2 g y = –19.6 y m2 s–2 2 These equations give the velocity and the We have, y0 = 45 m, y = 0, v0 = 0, a = – g = –10 m s–2 distance travelled as a function of time and also 0 = 45 + (½) (–10) t2 2 the variation of velocity with distance. The Solving, we get t2 = 3 s variation of acceleration, velocity, and distance, with time have been plotted in Fig. 2.7(a), (b)Therefore, the total time taken by the ball before and (c). it hits the ground = t1 + t2 = 2 s + 3 s = 5 s. SECOND METHOD : The total time taken can also be calculated by noting the coordinates of initial and final positions of the ball with respect to the origin chosen and using equation 1 2 y = y0 + v 0t + at 2 Now y0 = 25 m y = 0 m vo = 20 m s-1, a = –10m s–2, t = ? (a) Reprint 2025-26 20 PHYSICS traversed during successive intervals of time. Since initial velocity is zero, we have 2 y = −1 gt 2 Using this equation, we can calculate the position of the object after different time intervals, 0, τ, 2τ, 3τ… which are given in second column of Table 2.2. If we take (–1/ 2) gτ2 as y0 — the position coordinate after first time interval τ, then third column gives (b) the positions in the unit of yo. The fourth column gives the distances traversed in successive τs. We find that the distances are in the simple ratio 1: 3: 5: 7: 9: 11… as shown in the last column. This law was established by Galileo Galilei (1564-1642) who was the first to make quantitative studies of free fall. ⊳ ⊳ Example 2.6 Stopping distance of vehicles : When brakes are applied to a moving vehicle, the distance it travels before stopping is called stopping distance. It is (c) an important factor for road safety and depends on the initial velocity (v0) and theFig. 2.7 Motion of an object under free fall. braking capacity, or deceleration, –a that (a) Variation of acceleration with time. (b) Variation of velocity with time. is caused by the braking. Derive an (c) Variation of distance with time ⊳ expression for stopping distance of a vehicle in terms of vo and a. ⊳ Example 2.5 Galileo’s law of odd Answer Let the distance travelled by the vehicle numbers : “The distances traversed, during before it stops be ds. Then, using equation of equal intervals of time, by a body falling 2 motion v2 = vo + 2 ax, and noting that v = 0, we from rest, stand to one another in the same have the stopping distance ratio as the odd numbers beginning with unity [namely, 1: 3: 5: 7…...].” Prove it. – v 02 d s = 2aAnswer Let us divide the time interval of motion of an object under free fall into many Thus, the stopping distance is proportional to equal intervals τ and find out the distances the square of the initial velocity. Doubling the Table 2.2 Reprint 2025-26 MOTION IN A STRAIGHT LINE 21 initial velocity increases the stopping distance by a factor of 4 (for the same deceleration). For the car of a particular make, the braking distance was found to be 10 m, 20 m, 34 m and 50 m corresponding to velocities of 11, 15, 20 and 25 m/s which are nearly consistent with the above formula. Stopping distance is an important factor considered in setting speed limits, for example, in school zones. ⊳ ⊳ Example 2.7 Reaction time : When a situation demands our immediate action, it takes some time before we really respond. Reaction time is the time a person takes to observe, think Fig. 2.8 Measuring the reaction time. and act. For example, if a person is driving and suddenly a boy appears on the road, then the time elapsed before Answer The ruler drops under free fall. he slams the brakes of the car is the Therefore, vo = 0, and a = – g = –9.8 m s–2. The reaction time. Reaction time depends distance travelled d and the reaction time tr are on complexity of the situation and on related by an individual. You can measure your reaction time by a simple experiment. Take a ruler and ask your friend to drop it vertically through the gap between Or, your thumb and forefinger (Fig. 2.8). Given d = 21.0 cm and g = 9.8 m s–2 the reaction After you catch it, find the distance d time is travelled by the ruler. In a particular case, d was found to be 21.0 cm. ⊳ Estimate reaction time. SUMMARY 1. An object is said to be in motion if its position changes with time. The position of the object can be specified with reference to a conveniently chosen origin. For motion in a straight line, position to the right of the origin is taken as positive and to the left as negative. The average speed of an object is greater or equal to the magnitude of the average velocity over a given time interval. 2. Instantaneous velocity or simply velocity is defined as the limit of the average velocity as the time interval ∆t becomes infinitesimally small : ∆ x d x v = lim v = lim = ∆→t 0 ∆→t 0 ∆t d t The velocity at a particular instant is equal to the slope of the tangent drawn on position-time graph at that instant. Reprint 2025-26 22 PHYSICS 3. Average acceleration is the change in velocity divided by the time interval during which the change occurs : ∆ v a = ∆t 4. Instantaneous acceleration is defined as the limit of the average acceleration as the time interval ∆t goes to zero : ∆v d v a = lim a = lim = ∆→t 0 ∆→t 0 ∆ t d t The acceleration of an object at a particular time is the slope of the velocity-time graph at that instant of time. For uniform motion, acceleration is zero and the x-t graph is a straight line inclined to the time axis and the v-t graph is a straight line parallel to the time axis. For motion with uniform acceleration, x-t graph is a parabola while the v-t graph is a straight line inclined to the time axis. 5. The area under the velocity-time curve between times t1 and t2 is equal to the displacement of the object during that interval of time. 6. For objects in uniformly accelerated rectilinear motion, the five quantities, displacement x, time taken t, initial velocity v0, final velocity v and acceleration a are related by a set of simple equations called kinematic equations of motion : v = v0 + at 1 2 x = v0 t + at 2 v 2 = v 02 + 2ax if the position of the object at time t = 0 is 0. If the particle starts at x = x0 , x in above equations is replaced by (x – x0). Reprint 2025-26 MOTION IN A STRAIGHT LINE 23 POINTS TO PONDER 1. The origin and the positive direction of an axis are a matter of choice. You should first specify this choice before you assign signs to quantities like displacement, velocity and acceleration. 2. If a particle is speeding up, acceleration is in the direction of velocity; if its speed is decreasing, acceleration is in the direction opposite to that of the velocity. This statement is independent of the choice of the origin and the axis. 3. The sign of acceleration does not tell us whether the particle’s speed is increasing or decreasing. The sign of acceleration (as mentioned in point 3) depends on the choice of the positive direction of the axis. For example, if the vertically upward direction is chosen to be the positive direction of the axis, the acceleration due to gravity is negative. If a particle is falling under gravity, this acceleration, though negative, results in increase in speed. For a particle thrown upward, the same negative acceleration (of gravity) results in decrease in speed. 4. The zero velocity of a particle at any instant does not necessarily imply zero acceleration at that instant. A particle may be momentarily at rest and yet have non-zero acceleration. For example, a particle thrown up has zero velocity at its uppermost point but the acceleration at that instant continues to be the acceleration due to gravity. 5. In the kinematic equations of motion [Eq. (2.9)], the various quantities are algebraic, i.e. they may be positive or negative. The equations are applicable in all situations (for one dimensional motion with constant acceleration) provided the values of different quantities are substituted in the equations with proper signs. 6. The definitions of instantaneous velocity and acceleration (Eqs. (2.1) and (2.3)) are exact and are always correct while the kinematic equations (Eq. (2.9)) are true only for motion in which the magnitude and the direction of acceleration are constant during the course of motion. Reprint 2025-26 24 PHYSICS EXERCISES 2.1 In which of the following examples of motion, can the body be considered approximately a point object: (a) a railway carriage moving without jerks between two stations. (b) a monkey sitting on top of a man cycling smoothly on a circular track. (c) a spinning cricket ball that turns sharply on hitting the ground. (d) a tumbling beaker that has slipped off the edge of a table. 2.2 The position-time (x-t) graphs for two children A and B returning from their school O to their homes P and Q respectively are shown in Fig. 2.9. Choose the correct entries in the brackets below ; (a) (A/B) lives closer to the school than (B/A) (b) (A/B) starts from the school earlier than (B/A) (c) (A/B) walks faster than (B/A) (d) A and B reach home at the (same/different) time (e) (A/B) overtakes (B/A) on the road (once/twice). Fig. 2.9 2.3 A woman starts from her home at 9.00 am, walks with a speed of 5 km h–1 on a straight road up to her office 2.5 km away, stays at the office up to 5.00 pm, and returns home by an auto with a speed of 25 km h–1. Choose suitable scales and plot the x-t graph of her motion. 2.4 A drunkard walking in a narrow lane takes 5 steps forward and 3 steps backward, followed again by 5 steps forward and 3 steps backward, and so on. Each step is 1 m long and requires 1 s. Plot the x-t graph of his motion. Determine graphically and otherwise how long the drunkard takes to fall in a pit 13 m away from the start. 2.5 A car moving along a straight highway with speed of 126 km h–1 is brought to a stop within a distance of 200 m. What is the retardation of the car (assumed uniform), and how long does it take for the car to stop ? 2.6 A player throws a ball upwards with an initial speed of 29.4 m s–1. (a) What is the direction of acceleration during the upward motion of the ball ? (b) What are the velocity and acceleration of the ball at the highest point of its motion ? (c) Choose the x = 0 m and t = 0 s to be the location and time of the ball at its highest point, vertically downward direction to be the positive direction of x-axis, and give the signs of position, velocity and acceleration of the ball during its upward, and downward motion. (d) To what height does the ball rise and after how long does the ball return to the player’s hands ? (Take g = 9.8 m s–2 and neglect air resistance). 2.7 Read each statement below carefully and state with reasons and examples, if it is true or false ; A particle in one-dimensional motion (a) with zero speed at an instant may have non-zero acceleration at that instant (b) with zero speed may have non-zero velocity, (c) with constant speed must have zero acceleration, (d) with positive value of acceleration must be speeding up. Reprint 2025-26 MOTION IN A STRAIGHT LINE 25 2.8 A ball is dropped from a height of 90 m on a floor. At each collision with the floor, the ball loses one tenth of its speed. Plot the speed-time graph of its motion between t = 0 to 12 s. 2.9 Explain clearly, with examples, the distinction between : (a) magnitude of displacement (sometimes called distance) over an interval of time, and the total length of path covered by a particle over the same interval; (b) magnitude of average velocity over an interval of time, and the average speed over the same interval. [Average speed of a particle over an interval of time is defined as the total path length divided by the time interval]. Show in both (a) and (b) that the second quantity is either greater than or equal to the first. When is the equality sign true ? [For simplicity, consider one-dimensional motion only]. 2.10 A man walks on a straight road from his home to a market 2.5 km away with a speed of 5 km h–1. Finding the market closed, he instantly turns and walks back home with a speed of 7.5 km h–1. What is the (a) magnitude of average velocity, and (b) average speed of the man over the interval of time (i) 0 to 30 min, (ii) 0 to 50 min, (iii) 0 to 40 min ? [Note: You will appreciate from this exercise why it is better to define average speed as total path length divided by time, and not as magnitude of average velocity. You would not like to tell the tired man on his return home that his average speed was zero !] Fig. 2.10 2.11 In Exercises 2.9 and 2.10, we have carefully distinguished between average speed and magnitude of average velocity. No such distinction is necessary when we consider instantaneous speed and magnitude of velocity. The instantaneous speed is always equal to the magnitude of instantaneous velocity. Why? 2.12 Look at the graphs (a) to (d) (Fig. 2.10) carefully and state, with reasons, which of these cannot possibly represent one-dimensional motion of a particle. 2.13 Figure 2.11shows the x-t plot of one- dimensional motion of a particle. Is it correct to say from the graph that the particle moves Fig. 2.11 in a straight line for t < 0 and on a parabolic path for t >0 ? If not, suggest a suitable physical context for this graph. 2.14 A police van moving on a highway with a speed of 30 km h–1 fires a bullet at a thief’s car speeding away in the same direction with a speed of 192 km h–1. If the muzzle speed of the bullet is 150 m s–1, with what speed does the bullet hit the thief’s car ? (Note: Obtain that speed which is relevant for damaging the thief’s car). Reprint 2025-26 26 PHYSICS 2.15 Suggest a suitable physical situation for each of the following graphs (Fig 2.12): Fig. 2.12 2.16 Figure 2.13 gives the x-t plot of a particle executing one-dimensional simple harmonic motion. (You will learn about this motion in more detail in Chapter13). Give the signs of position, velocity and acceleration variables of the particle at t = 0.3 s, 1.2 s, – 1.2 s. Fig. 2.13 2.17 Figure 2.14 gives the x-t plot of a particle in one-dimensional motion. Three different equal intervals of time are shown. In which interval is the average speed greatest, and in which is it the least ? Give the sign of average velocity for each interval. Fig. 2.14 2.18 Figure 2.15 gives a speed-time graph of a particle in motion along a constant direction. Three equal intervals of time are shown. In which interval is the average acceleration greatest in magnitude? In which interval is the average speed greatest ? Choosing the positive direction as the constant direction of motion, give the signs of v and a in the three intervals. What are the accelerations at the points A, B, C and D ? Fig. 2.15 Reprint 2025-26 CHAPTER THREE MOTION IN A PLANE 3.1 INTRODUCTION In the last chapter we developed the concepts of position, displacement, velocity and acceleration that are needed to 3.1 Introduction describe the motion of an object along a straight line. We 3.2 Scalars and vectors found that the directional aspect of these quantities can be taken care of by + and – signs, as in one dimension only two3.3 Multiplication of vectors by real numbers directions are possible. But in order to describe motion of an 3.4 Addition and subtraction of object in two dimensions (a plane) or three dimensions vectors — graphical method (space), we need to use vectors to describe the above- 3.5 Resolution of vectors mentioned physical quantities. Therefore, it is first necessary to learn the language of vectors. What is a vector? How to3.6 Vector addition — analytical method add, subtract and multiply vectors ? What is the result of 3.7 Motion in a plane multiplying a vector by a real number ? We shall learn this to enable us to use vectors for defining velocity and3.8 Motion in a plane with constant acceleration acceleration in a plane. We then discuss motion of an object 3.9 Projectile motion in a plane. As a simple case of motion in a plane, we shall discuss motion with constant acceleration and treat in detail3.10 Uniform circular motion the projectile motion. Circular motion is a familiar class of Summary motion that has a special significance in daily-life situations. Points to ponder We shall discuss uniform circular motion in some detail. Exercises The equations developed in this chapter for motion in a plane can be easily extended to the case of three dimensions. 3.2 SCALARS AND VECTORS In physics, we can classify quantities as scalars or vectors. Basically, the difference is that a direction is associated with a vector but not with a scalar. A scalar quantity is a quantity with magnitude only. It is specified completely by a single number, along with the proper unit. Examples are : the distance between two points, mass of an object, the temperature of a body and the time at which a certain event happened. The rules for combining scalars are the rules of ordinary algebra. Scalars can be added, subtracted, multiplied and divided Reprint 2025-26 28 PHYSICS just as the ordinary numbers*. For example, represented by another position vector, OP′ if the length and breadth of a rectangle are denoted by r′. The length of the vector r 1.0 m and 0.5 m respectively, then its represents the magnitude of the vector and its perimeter is the sum of the lengths of the direction is the direction in which P lies as seen four sides, 1.0 m + 0.5 m +1.0 m + 0.5 m = from O. If the object moves from P to P′, the 3.0 m. The length of each side is a scalar vector PP′ (with tail at P and tip at P′) is called and the perimeter is also a scalar. Take the displacement vector corresponding to another example: the maximum and motion from point P (at time t) to point P′ (at time t′). minimum temperatures on a particular day are 35.6 °C and 24.2 °C respectively. Then, the difference between the two temperatures is 11.4 °C. Similarly, if a uniform solid cube of aluminium of side 10 cm has a mass of

2.5 A parallel plate capacitor with air between the plates has a capacitance of 8 pF (1pF = 10–12 F). What will be the capacitance if the distance between the plates is reduced by half, and the space between them is filled with a substance of dielectric constant 6?

2.7 kg, then its volume is 10–3 m3 (a scalar) and its density is 2.7×103 kg m–3 (a scalar). A vector quantity is a quantity that has both a magnitude and a direction and obeys the triangle law of addition or equivalently the Fig. 3.1 (a) Position and displacement vectors. parallelogram law of addition. So, a vector is (b) Displacement vector PQ and different specified by giving its magnitude by a number courses of motion. and its direction. Some physical quantities that It is important to note that displacement are represented by vectors are displacement, vector is the straight line joining the initial and velocity, acceleration and force. final positions and does not depend on the actual To represent a vector, we use a bold face type path undertaken by the object between the two in this book. Thus, a velocity vector can be positions. For example, in Fig. 3.1(b), given the represented by a symbol v. Since bold face is initial and final positions as P and Q, the difficult to produce, when written by hand, a displacement vector is the same PQ for different vector is often representedrv by an arrow placedrv paths of journey, say PABCQ, PDQ, and PBEFQ.over a letter, say . Thus, both v and Therefore, the magnitude of displacement is represent the velocity vector. The magnitude of either less or equal to the path length of an a vector is often called its absolute value, object between two points. This fact was indicated by |v| = v. Thus, a vector is emphasised in the previous chapter also whilerepresented by a bold face, e.g. by A, a, p, q, r, ... discussing motion along a straight line.x, y, with respective magnitudes denoted by light face A, a, p, q, r, ... x, y. 3.2.2 Equality of Vectors 3.2.1 Position and Displacement Vectors Two vectors A and B are said to be equal if, and only if, they have the same magnitude and theTo describe the position of an object moving in same direction.**a plane, we need to choose a convenient point, say O as origin. Let P and P′ be the positions of Figure 3.2(a) shows two equal vectors A and the object at time t and t′, respectively [Fig. 3.1(a)]. B. We can easily check their equality. Shift B We join O and P by a straight line. Then, OP is parallel to itself until its tail Q coincides with that the position vector of the object at time t. An of A, i.e. Q coincides with O. Then, since their arrow is marked at the head of this line. It is tips S and P also coincide, the two vectors are represented by a symbol r, i.e. OP = r. Point P′ is said to be equal. In general, equality is indicated * Addition and subtraction of scalars make sense only for quantities with same units. However, you can multiply and divide scalars of different units. ** In our study, vectors do not have fixed locations. So displacing a vector parallel to itself leaves the vector unchanged. Such vectors are called free vectors. However, in some physical applications, location or line of application of a vector is important. Such vectors are called localised vectors. Reprint 2025-26 MOTION IN A PLANE 29 The factor λ by which a vector A is multiplied could be a scalar having its own physical dimension. Then, the dimension of λ A is the product of the dimensions of λ and A. For example, if we multiply a constant velocity vector by duration (of time), we get a displacement vector. 3.4 ADDITION AND SUBTRACTION OF VECTORS — GRAPHICAL METHOD Fig. 3.2 (a) Two equal vectors A and B. (b) Two As mentioned in section 4.2, vectors, by vectors A′ and B′ are unequal though they definition, obey the triangle law or equivalently, are of the same length. the parallelogram law of addition. We shall now describe this law of addition using the graphical as A = B. Note that in Fig. 3.2(b), vectors A′ and method. Let us consider two vectors A and B that B′ have the same magnitude but they are not lie in a plane as shown in Fig. 3.4(a). The lengths equal because they have different directions. of the line segments representing these vectors Even if we shift B′ parallel to itself so that its tail are proportional to the magnitude of the vectors. Q′ coincides with the tail O′ of A′, the tip S′ of B′ To find the sum A + B, we place vector B so that does not coincide with the tip P′ of A′. its tail is at the head of the vector A, as in 3.3 MULTIPLICATION OF VECTORS BY REAL Fig. 3.4(b). Then, we join the tail of A to the head NUMBERS of B. This line OQ represents a vector R, that is, the sum of the vectors A and B. Since, in thisMultiplying a vector A with a positive number λ procedure of vector addition, vectors aregives a vector whose magnitude is changed by the factor λ but the direction is the same as that of A : λ A = λ A if λ > 0. For example, if A is multiplied by 2, the resultant vector 2A is in the same direction as A and has a magnitude twice of |A| as shown in Fig. 3.3(a). Multiplying a vector A by a negative number −λ gives another vector whose direction is opposite to the direction of A and whose magnitude is λ times |A|. Multiplying a given vector A by negative numbers, say –1 and –1.5, gives vectors as shown in Fig 3.3(b). (c) (d) Fig. 3.3 (a) Vector A and the resultant vector after multiplying A by a positive number 2. Fig. 3.4 (a) Vectors A and B. (b) Vectors A and B (b) Vector A and resultant vectors after added graphically. (c) Vectors B and A multiplying it by a negative number –1 added graphically. (d) Illustrating the and –1.5. associative law of vector addition. Reprint 2025-26 30 PHYSICS arranged head to tail, this graphical method is What is the physical meaning of a zero vector? called the head-to-tail method. The two vectors Consider the position and displacement vectors and their resultant form three sides of a triangle, in a plane as shown in Fig. 3.1(a). Now suppose so this method is also known as triangle method that an object which is at P at time t, moves to of vector addition. If we find the resultant of P′ and then comes back to P. Then, what is its B + A as in Fig. 3.4(c), the same vector R is displacement? Since the initial and final obtained. Thus, vector addition is commutative: positions coincide, the displacement is a “null vector”. A + B = B + A (3.1) Subtraction of vectors can be defined in termsThe addition of vectors also obeys the associative of addition of vectors. We define the differencelaw as illustrated in Fig. 3.4(d). The result of of two vectors A and B as the sum of two vectorsadding vectors A and B first and then adding A and –B :vector C is the same as the result of adding B and C first and then adding vector A : A – B = A + (–B) (3.5) (A + B) + C = A + (B + C) (3.2) It is shown in Fig 3.5. The vector –B is added to vector A to get R2 = (A – B). The vector R1 = A + BWhat is the result of adding two equal and is also shown in the same figure for comparison.opposite vectors ? Consider two vectors A and We can also use the parallelogram method to–A shown in Fig. 3.3(b). Their sum is A + (–A). find the sum of two vectors. Suppose we haveSince the magnitudes of the two vectors are the same, but the directions are opposite, the two vectors A and B. To add these vectors, we resultant vector has zero magnitude and is bring their tails to a common origin O as represented by 0 called a null vector or a zero shown in Fig. 3.6(a). Then we draw a line from vector : the head of A parallel to B and another line from the head of B parallel to A to complete a A – A = 0 |0|= 0 (3.3) parallelogram OQSP. Now we join the point of Since the magnitude of a null vector is zero, its the intersection of these two lines to the origin direction cannot be specified. O. The resultant vector R is directed from the The null vector also results when we multiply common origin O along the diagonal (OS) of the a vector A by the number zero. The main parallelogram [Fig. 3.6(b)]. In Fig.3.6(c), the properties of 0 are : triangle law is used to obtain the resultant of A A + 0 = A and B and we see that the two methods yield the λ 0 = 0 same result. Thus, the two methods are 0 A = 0 (3.4) equivalent. Fig. 3.5 (a) Two vectors A and B, – B is also shown. (b) Subtracting vector B from vector A – the result is R2. For comparison, addition of vectors A and B, i.e. R1 is also shown. Reprint 2025-26 MOTION IN A PLANE 31 Fig. 3.6 (a) Two vectors A and B with their tails brought to a common origin. (b) The sum A + B obtained using the parallelogram method. (c) The parallelogram method of vector addition is equivalent to the triangle method. ⊳ Example 3.1 Rain is falling vertically with 3.5 RESOLUTION OF VECTORS a speed of 35 m s–1. Winds starts blowing Let a and b be any two non-zero vectors in a after sometime with a speed of 12 m s–1 in plane with different directions and let A be east to west direction. In which direction another vector in the same plane (Fig. 3.8). A should a boy waiting at a bus stop hold can be expressed as a sum of two vectors — one his umbrella ? obtained by multiplying a by a real number and the other obtained by multiplying b by another real number. To see this, let O and P be the tail and head of the vector A. Then, through O, draw a straight line parallel to a, and through P, a straight line parallel to b. Let them intersect at Q. Then, we have A = OP = OQ + QP (3.6) But since OQ is parallel to a, and QP is parallel to b, we can write : OQ = λ a, and QP = µ b (3.7) Fig. 3.7 where λ and µ are real numbers. Answer The velocity of the rain and the wind Therefore, A = λ a + µ b (3.8)are represented by the vectors vr and vw in Fig.

2.4 A spherical conductor of radius 12 cm has a charge of 1.6 × 10–7C distributed uniformly on its surface. What is the electric field (a) inside the sphere (b) just outside the sphere (c) at a point 18 cm from the centre of the sphere?

3.10 In a reaction between A and B, the initial rate of reaction (r0) was measured for different initial concentrations of A and B as given below: A/ mol L–1 0.20 0.20 0.40 B/ mol L–1 0.30 0.10 0.05 r0/mol L–1s–1 5.07 × 10–5 5.07 × 10–5 1.43 × 10–4 What is the order of the reaction with respect to A and B? 3.11 The following results have been obtained during the kinetic studies of the reaction: 2A + B ® C + D Experiment [A]/mol L–1 [B]/mol L–1 Initial rate of formation of D/mol L–1 min–1 I 0.1 0.1 6.0 × 10–3 II 0.3 0.2 7.2 × 10–2 III 0.3 0.4 2.88 × 10–1 IV 0.4 0.1 2.40 × 10–2 Determine the rate law and the rate constant for the reaction. 3.12 The reaction between A and B is first order with respect to A and zero order with respect to B. Fill in the blanks in the following table: Experiment [A]/ mol L–1 [B]/ mol L–1 Initial rate/ mol L–1 min–1 I 0.1 0.1 2.0 × 10–2 II – 0.2 4.0 × 10–2 III 0.4 0.4 – IV – 0.2 2.0 × 10–2 3.13 Calculate the half-life of a first order reaction from their rate constants given below: (i) 200 s–1 (ii) 2 min–1 (iii) 4 years–1 3.14 The half-life for radioactive decay of 14C is 5730 years. An archaeological artifact containing wood had only 80% of the 14C found in a living tree. Estimate the age of the sample. 3.15 The experimental data for decomposition of N2O5 [2N2O5 ® 4NO2 + O2] in gas phase at 318K are given below: t/s 0 400 800 1200 1600 2000 2400 2800 3200 102 × [N2O5]/ 1.63 1.36 1.14 0.93 0.78 0.64 0.53 0.43 0.35 mol L–1 (i) Plot [N2O5] against t. (ii) Find the half-life period for the reaction. (iii) Draw a graph between log[N2O5] and t. (iv) What is the rate law ? Chemistry 86 Reprint 2025-26 (v) Calculate the rate constant. (vi) Calculate the half-life period from k and compare it with (ii).

3.27 The rate constant for the first order decomposition of H2O2 is given by the following equation: log k = 14.34 – 1.25 × 104K/T Calculate Ea for this reaction and at what temperature will its half-period be 256 minutes? 3.28 The decomposition of A into product has value of k as 4.5 × 103 s–1 at 10°C and energy of activation 60 kJ mol–1. At what temperature would k be 1.5 × 104s–1? 3.29 The time required for 10% completion of a first order reaction at 298K is equal to that required for its 25% completion at 308K. If the value of A is 4 × 1010s–1. Calculate k at 318K and Ea. 3.30 The rate of a reaction quadruples when the temperature changes from 293 K to 313 K. Calculate the energy of activation of the reaction assuming that it does not change with temperature. Answers to Some Intext Questions 3.1 rav = 6.66 × 10–6 Ms–1 3.2 Rate of reaction = rate of diappearance of A = 0.005 mol litre–1min–1 3.3 Order of the reaction is 2.5 3.4 X ® Y Rate = k[X]2 The rate will increase 9 times 3.5 t = 444 s 3.6 1.925 × 10–4 s–1 3.8 Ea = 52.897 kJ mol–1 3.9 1.471 × 10–19 Chemistry 88 Reprint 2025-26 UnitUnitUnitUnit Unit44 TheThe dd-- andand f-f-Objectives After studying this Unit, you will beable to BlockBlock ElementsElements • learn the positions of the d– and f-block elements in the periodic table; Iron, copper, silver and gold are among the transition elements that • know the electronic configurations have played important roles in the development of human civilisation. of the transition (d-block) and the The inner transition elements such as Th, Pa and U are proving inner transition (f-block) elements; excellent sources of nuclear energy in modern times. • appreciate the relative stability of various oxidation states in terms of electrode potential values; The d-block of the periodic table contains the elements of the groups 3-12 in which the d orbitals are• describe the preparation, progressively filled in each of the four long periods. properties, structures and uses of some important compounds The f-block consists of elements in which 4 f and 5 f such as K2Cr2O7 and KMnO4; orbitals are progressively filled. They are placed in a • understand the general separate panel at the bottom of the periodic table. The characteristics of the d– and names transition metals and inner transition metals f–block elements and the general are often used to refer to the elements of d-and horizontal and group trends in f-blocks respectively. them; There are mainly four series of the transition metals, • describe the properties of the 3d series (Sc to Zn), 4d series (Y to Cd), 5d series (La f-block elements and give a and Hf to Hg) and 6d series which has Ac and elements comparative account of the from Rf to Cn. The two series of the inner transition lanthanoids and actinoids with metals; 4f (Ce to Lu) and 5f (Th to Lr) are known as respect to their electronic lanthanoids and actinoids respectively. configurations, oxidation states Originally the name transition metals was derived and chemical behaviour. from the fact that their chemical properties were transitional between those of s and p-block elements. Now according to IUPAC, transition metals are defined as metals which have incomplete d subshell either in neutral atom or in their ions. Zinc, cadmium and mercury of group 12 have full d10 configuration in their ground state as well as in their common oxidation states and hence, are not regarded as transition metals. However, being the end members of the 3d, 4d and 5d transition series, respectively, their chemistry is studied along with the chemistry of the transition metals. The presence of partly filled d or f orbitals in their atoms makes transition elements different from that of Reprint 2025-26 the non-transition elements. Hence, transition elements and their compounds are studied separately. However, the usual theory of valence as applicable to the non- transition elements can be applied successfully to the transition elements also. Various precious metals such as silver, gold and platinum and industrially important metals like iron, copper and titanium belong to the transition metals series. In this Unit, we shall first deal with the electronic configuration, occurrence and general characteristics of transition elements with special emphasis on the trends in the properties of the first row (3d) transition metals along with the preparation and properties of some important compounds. This will be followed by consideration of certain general aspects such as electronic configurations, oxidation states and chemical reactivity of the inner transition metals. THE TRANSITION ELEMENTS (d-BLOCK) 4.14.14.14.14.1 PositionPositionPositionPositionPosition ininininin thethethethethe The d–block occupies the large middle section of the periodic table PeriodicPeriodicPeriodicPeriodicPeriodic TableTableTableTableTable flanked between s– and p– blocks in the periodic table. The d–orbitals of the penultimate energy level of atoms receive electrons giving rise to four rows of the transition metals, i.e., 3d, 4d, 5d and 6d. All these series of transition elements are shown in Table 4.1. 4.24.24.24.24.2 ElectronicElectronicElectronicElectronicElectronic In general1– the electronic configuration of outer orbitals of these elements is (n-1)d 10ns1–2except for Pd where its electronic configuration is 4d105s0. ConfigurationsConfigurationsConfigurationsConfigurationsConfigurations The (n–1) stands for the inner d orbitals which may have one to ten ofofofofof thethethethethe d-Blockd-Blockd-Blockd-Blockd-Block electrons and the outermost ns orbital may have one or two electrons. ElementsElementsElementsElementsElements However, this generalisation has several exceptions because of very little energy difference between (n-1)d and ns orbitals. Furthermore, half and completely filled sets of orbitals are relatively more stable. A consequence of this factor is reflected in the electronic configurations of Cr and Cu in the 3d series. For example, consider the case of Cr, which has 3d 5 4s 1 configuration instead of 3d44s 2; the energy gap between the two sets (3d and 4s) of orbitals is small enough to prevent electron entering the 3d orbitals. Similarly in case of Cu, the configuration is 3d104s 1 and not 3d 94s2. The ground state electronic configurations of the outer orbitals of transition elements are given in Table 4.1. Table 4.1: Electronic Configurations of outer orbitals of the Transition Elements (ground state) 1st Series Sc Ti V Cr Mn Fe Co Ni Cu Zn Z 21 22 23 24 25 26 27 28 29 30 4s 2 2 2 1 2 2 2 2 1 2 3d 1 2 3 5 5 6 7 8 10 10 Chemistry 90 Reprint 2025-26 2nd Series Y Zr Nb Mo Tc Ru Rh Pd Ag Cd Z 39 40 41 42 43 44 45 46 47 48 5s 2 2 1 1 1 1 1 0 1 2 4d 1 2 4 5 6 7 8 10 10 10 3rd Series La Hf Ta W Re Os Ir Pt Au Hg Z 57 72 73 74 75 76 77 78 79 80 6s 2 2 2 2 2 2 2 1 1 2 5d 1 2 3 4 5 6 7 9 10 10 4th Series Ac Rf Db Sg Bh Hs Mt Ds Rg Cn Z 89 104 105 106 107 108 109 110 111 112 7s 2 2 2 2 2 2 2 2 1 2 6d 1 2 3 4 5 6 7 8 10 10 The electronic configurations of outer orbitals of Zn, Cd, Hg and Cn are represented by the general formula (n-1)d 10ns2. The orbitals in these elements are completely filled in the ground state as well as in their common oxidation states. Therefore, they are not regarded as transition elements. The d orbitals of the transition elements protrude to the periphery of an atom more than the other orbitals (i.e., s and p), hence, they are more influenced by the surroundings as well as affect the atoms or molecules surrounding them. In some respects, ions of a given dn configuration (n = 1 – 9) have similar magnetic and electronic properties. With partly filled d orbitals these elements exhibit certain characteristic properties such as display of a variety of oxidation states, formation of coloured ions and entering into complex formation with a variety of ligands. The transition metals and their compounds also exhibit catalytic property and paramagnetic behaviour. All these characteristics have been discussed in detail later in this Unit. There are greater similarities in the properties of the transition elements of a horizontal row in contrast to the non-transition elements. However, some group similarities also exist. We shall first study the general characteristics and their trends in the horizontal rows (particularly 3d row) and then consider some group similarities. On what ground can you say that scandium (Z = 21) is a transition ExampleExampleExampleExampleExample 4.14.14.14.14.1 element but zinc (Z = 30) is not? On the basis of incompletely filled 3d orbitals in case of scandium atom SolutionSolutionSolutionSolutionSolution in its ground state (3d1), it is regarded as a transition element. On the other hand, zinc atom has completely filled d orbitals (3d10) in its ground state as well as in its oxidised state, hence it is not regarded as a transition element. 91 The d- and f- Block Elements Reprint 2025-26 IntextIntextIntextIntextIntext QuestionQuestionQuestionQuestionQuestion 4.1 Silver atom has completely filled d orbitals (4d10) in its ground state. How can you say that it is a transition element? We will discuss the properties of elements of first transition series only in the following sections. 4.34.34.34.34.3 GeneralGeneralGeneralGeneralGeneral 4.3.1 Physical Properties PropertiesPropertiesPropertiesPropertiesProperties ofofofofof Nearly all the transition elements display typical metallic properties thethethethethe TransitionTransitionTransitionTransitionTransition such as high tensile strength, ductility, malleability, high thermal and electrical conductivity and metallic lustre. With the exceptions of Zn, ElementsElementsElementsElementsElements Cd, Hg and Mn, they have one or more typical metallic structures at (d-Block)(d-Block)(d-Block)(d-Block)(d-Block) normal temperatures. Lattice Structures of Transition Metals Sc Ti V Cr Mn Fe Co Ni Cu Zn hcp hcp bcc bcc X bcc ccp ccp ccp X (bcc) (bcc) (bcc, ccp) (hcp) (hcp) (hcp) Y Zr Nb Mo Tc Ru Rh Pd Ag Cd hcp hcp bcc bcc hcp hcp ccp ccp ccp X (bcc) (bcc) (hcp) La Hf Ta W Re Os Ir Pt Au Hg hcp hcp bcc bcc hcp hcp ccp ccp ccp X (ccp,bcc) (bcc) 4 (bcc = body centred cubic; hcp = hexagonal close packed; ccp = cubic close packed; X = a typical metal structure). W The transition metals (with the exception Re Ta of Zn, Cd and Hg) are very hard and have low volatility. Their melting and boiling points are 3 Mo Os high. Fig. 4.1 depicts the melting points of Nb Ru transition metals belonging to 3d, 4d and 5d Ir series. The high melting points of these metals Hf Tc K are attributed to the involvement of greater 3 Cr Rh number of electrons from (n-1)d in addition to Zr V Pt 2 the ns electrons in the interatomic metallic bonding. In any row the melting points of these M.p./10 Ti Fe Co Pd 5 metals rise to a maximum at d except for Ni anomalous values of Mn and Tc and fall Mn Cu regularly as the atomic number increases. Au Ag They have high enthalpies of atomisation which 1 are shown in Fig. 4.2. The maxima at about Atomic number the middle of each series indicate that one Fig. 4.1: Trends in melting points of unpaired electron per d orbital is particularly transition elements Chemistry 92 Reprint 2025-26 favourable for strong interatomic interaction. In general, greater the number of valence electrons, stronger is the resultant bonding. Since the enthalpy of atomisation is an important factor in determining the standard electrode potential of a metal, metals with very high enthalpy of atomisation (i.e., very high boiling point) tend to be noble in their reactions (see later for electrode potentials). Another generalisation that may be drawn from Fig. 4.2 is that the metals of the second and third series have greater enthalpies of atomisation than the corresponding elements of the first series; this is an important factor in accounting for the occurrence of much more frequent metal – metal bonding in compounds of the heavy transition metals. –1 mol V/kJ DaH Fig. 4.2 Trends in enthalpies of atomisation of transition elements 4.3.2 Variation in In general, ions of the same charge in a given series show progressive Atomic and decrease in radius with increasing atomic number. This is because the Ionic Sizes new electron enters a d orbital each time the nuclear charge increases of by unity. It may be recalled that the shielding effect of a d electron is Transition not that effective, hence the net electrostatic attraction between the Metals nuclear charge and the outermost electron increases and the ionic radius decreases. The same trend is observed in the atomic radii of a given series. However, the variation within a series is quite small. An interesting point emerges when atomic sizes of one series are compared with those of the corresponding elements in the other series. The curves in Fig. 4.3 show an increase from the first (3d) to the second (4d) series of the elements but the radii of the third (5d) series are virtually the same as those of the corresponding members of the second series. This phenomenon is associated with the intervention of the 4f orbitals which must be filled before the 5d series of elements begin. The filling of 4f before 5d orbital results in a regular decrease in atomic radii called Lanthanoid contraction which essentially compensates for the expected 93 The d- and f- Block Elements Reprint 2025-26 increase in atomic size with increasing atomic number. The net result of the lanthanoid contraction is that the second and the third d series exhibit similar radii (e.g., Zr 160 pm, Hf 159 pm) and have very similar physical and chemical properties much more than that expected on the basis of usual family relationship. 19 The factor responsible for the lanthanoid 18 contraction is somewhat similar to that observed in an ordinary transition series and is attributed 17 to similar cause, i.e., the imperfect shielding of 16 one electron by another in the same set of orbitals. However, the shielding of one 4f electron by 15 Radius/nm another is less than that of one d electron by 14 another, and as the nuclear charge increases 13 along the series, there is fairly regular decrease in the size of the entire 4f n orbitals. 12 Sc Ti V Cr Mn Fe Co Ni Cu Zn The decrease in metallic radius coupled with Y Zr Nb Mo Tc Ru Rh Pd Ag Cd increase in atomic mass results in a general increase in the density of these elements. Thus, La Hf Ta W Re Os Ir Pt Au Hg from titanium (Z = 22) to copper (Z = 29) the Fig. 4.3: Trends in atomic radii of significant increase in the density may be noted transition elements (Table 4.2). Table 4.2: Electronic Configurations and some other Properties of the First Series of Transition Elements Element Sc Ti V Cr Mn Fe Co Ni Cu Zn Atomic number 21 22 23 24 25 26 27 28 29 30 Electronic configuration M 3d 14s 2 3d 24s 2 3d 34s 2 3d 54s 1 3d 54s 2 3d 64s 2 3d 74s 2 3d 84s 2 3d 104s 1 3d 104s 2 M + 3d 14s 1 3d 24s 1 3d 34s 1 3d 5 3d 54s 1 3d 64s 1 3d 74s 1 3d 84s 1 3d 10 3d 104s 1 M 2+ 3d 1 3d 2 3d 3 3d 4 3d 5 3d 6 3d 7 3d 8 3d 9 3d 10 M 3+ [Ar] 3d 1 3d 2 3d 3 3d 4 3d 5 3d 6 3d 7 – – Enthalpy of atomisation, DaH o/kJ mol–1 326 473 515 397 281 416 425 430 339 126 Ionisation enthalpy/DiH o/kJ mol –1 DiHo I 631 656 650 653 717 762 758 736 745 906 DiHo II 1235 1309 1414 1592 1509 1561 1644 1752 1958 1734 DiHo III 2393 2657 2833 2990 3260 2962 3243 3402 3556 3837 Metallic/ionic M 164 147 135 129 137 126 125 125 128 137 radii/pm M 2+ – – 79 82 82 77 74 70 73 75 M 3+ 73 67 64 62 65 65 61 60 – – Standard electrode M 2+/M – –1.63 –1.18 –0.90 –1.18 –0.44 –0.28 –0.25 +0.34 -0.76 potential Eo/V M 3+/M 2+ – –0.37 –0.26 –0.41 +1.57 +0.77 +1.97 – – – Density/g cm –3 3.43 4.1 6.07 7.19 7.21 7.8 8.7 8.9 8.9 7.1 Chemistry 94 Reprint 2025-26 Why do the transition elements exhibit higher enthalpies of ExampleExampleExampleExampleExample 4.24.24.24.24.2 atomisation? Because of large number of unpaired electrons in their atoms they SolutionSolutionSolutionSolutionSolution have stronger interatomic interaction and hence stronger bonding between atoms resulting in higher enthalpies of atomisation. IntextIntextIntextIntextIntext QuestionQuestionQuestionQuestionQuestion 4.2 In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomisation of zinc is the lowest, i.e., 126 kJ mol–1. Why? 4.3.3 Ionisation There is an increase in ionisation enthalpy along each series of the Enthalpies transition elements from left to right due to an increase in nuclear charge which accompanies the filling of the inner d orbitals. Table 4.2 gives the values of the first three ionisation enthalpies of the first series of transition elements. These values show that the successive enthalpies of these elements do not increase as steeply as in the case of non-transition elements. The variation in ionisation enthalpy along a series of transition elements is much less in comparison to the variation along a period of non-transition elements. The first ionisation enthalpy, in general, increases, but the magnitude of the increase in the second and third ionisation enthalpies for the successive elements, is much higher along a series. The irregular trend in the first ionisation enthalpy of the metals of 3d series, though of little chemical significance, can be accounted for by considering that the removal of one electron alters the relative energies of 4s and 3d orbitals. You have learnt that when d-block elements form ions, ns electrons are lost before (n – 1) d electrons. As we move along the period in 3d series, we see that nuclear charge increases from scandium to zinc but electrons are added to the orbital of inner subshell, i.e., 3d orbitals. These 3d electrons shield the 4s electrons from the increasing nuclear charge somewhat more effectively than the outer shell electrons can shield one another. Therefore, the atomic radii decrease less rapidly. Thus, ionization energies increase only slightly along the 3d series. The doubly or more highly charged ions have dn configurations with no 4s electrons. A general trend of increasing values of second ionisation enthalpy is expected as the effective nuclear charge increases because one d electron does not shield another electron from the influence of nuclear charge because d-orbitals differ in direction. However, the trend of steady increase in second and third ionisation enthalpy breaks for the formation of Mn2+ and Fe3+ respectively. In both the cases, ions have d5 configuration. Similar breaks occur at corresponding elements in the later transition series. The interpretation of variation in ionisation enthalpy for an electronic configuration dn is as follows: The three terms responsible for the value of ionisation enthalpy are attraction of each electron towards nucleus, repulsion between the 95 The d- and f- Block Elements Reprint 2025-26 electrons and the exchange energy. Exchange energy is responsible for the stabilisation of energy state. Exchange energy is approximately proportional to the total number of possible pairs of parallel spins in the degenerate orbitals. When several electrons occupy a set of degenerate orbitals, the lowest energy state corresponds to the maximum possible extent of single occupation of orbital and parallel spins (Hunds rule). The loss of exchange energy increases the stability. As the stability increases, the ionisation becomes more difficult. There is no loss of exchange energy at d6 configuration. Mn+ has 3d54s1 configuration and configuration of Cr+ is d5, therefore, ionisation enthalpy of Mn+ is lower than Cr+. In the same way, Fe2+ has d6 configuration and Mn2+ has 3d5 configuration. Hence, ionisation enthalpy of Fe2+ is lower than the Mn2+. In other words, we can say that the third ionisation enthalpy of Fe is lower than that of Mn. The lowest common oxidation state of these metals is +2. To form the M 2+ ions from the gaseous atoms, the sum of the first and second ionisation enthalpy is required in addition to the enthalpy of atomisation. The dominant term is the second ionisation enthalpy which shows unusually high values for Cr and Cu where M + ions have the d 5 and d 10 configurations respectively. The value for Zn is correspondingly low as the ionisation causes the removal of one 4s electron which results in the formation of stable d 10 configuration. The trend in the third ionisation enthalpies is not complicated by the 4s orbital factor and shows the greater difficulty of removing an electron from the d 5 (Mn 2+) and d 10 (Zn 2+) ions. In general, the third ionisation enthalpies are quite high. Also the high values for third ionisation enthalpies of copper, nickel and zinc indicate why it is difficult to obtain oxidation state greater than two for these elements. Although ionisation enthalpies give some guidance concerning the relative stabilities of oxidation states, this problem is very complex and not amenable to ready generalisation. 4.3.4 Oxidation One of the notable features of a transition elements is the great variety States of oxidation states these may show in their compounds. Table 4.3 lists the common oxidation states of the first row transition elements. Table 4.3: Oxidation States of the first row Transition Metal (the most common ones are in bold types) Sc Ti V Cr Mn Fe Co Ni Cu Zn +2 +2 +2 +2 +2 +2 +2 +1 +2 +3 +3 +3 +3 +3 +3 +3 +3 +2 +4 +4 +4 +4 +4 +4 +4 +5 +5 +5 +6 +6 +6 +7 Chemistry 96 Reprint 2025-26 The elements which give the greatest number of oxidation states occur in or near the middle of the series. Manganese, for example, exhibits all the oxidation states from +2 to +7. The lesser number of oxidation states at the extreme ends stems from either too few electrons to lose or share (Sc, Ti) or too many d electrons (hence fewer orbitals available in which to share electrons with others) for higher valence (Cu, Zn). Thus, early in the series scandium(II) is virtually unknown and titanium (IV) is more stable than Ti(III) or Ti(II). At the other end, the only oxidation state of zinc is +2 (no d electrons are involved). The maximum oxidation states of reasonable stability correspond in value to the sum of the s and d electrons upto manganese (Ti IVO2, VVO2 +, Cr V1O42–, MnVIIO4–) followed by a rather abrupt decrease in stability of higher oxidation states, so that the typical species to follow are FeII,III, Co II,III, NiII, CuI,II, Zn II. The variability of oxidation states, a characteristic of transition elements, arises out of incomplete filling of d orbitals in such a way that their oxidation states differ from each other by unity, e.g., V II, V III, VIV, VV. This is in contrast with the variability of oxidation states of non transition elements where oxidation states normally differ by a unit of two. An interesting feature in the variability of oxidation states of the d– block elements is noticed among the groups (groups 4 through 10). Although in the p–block the lower oxidation states are favoured by the heavier members (due to inert pair effect), the opposite is true in the groups of d-block. For example, in group 6, Mo(VI) and W(VI) are found to be more stable than Cr(VI). Thus Cr(VI) in the form of dichromate in acidic medium is a strong oxidising agent, whereas MoO3 and WO3 are not. Low oxidation states are found when a complex compound has ligands capable of p-acceptor character in addition to the s-bonding. For example, in Ni(CO)4 and Fe(CO)5, the oxidation state of nickel and iron is zero. Name a transition element which does not exhibit variable ExampleExampleExampleExampleExample 4.34.34.34.34.3 oxidation states. Scandium (Z = 21) does not exhibit variable oxidation states. SolutionSolutionSolutionSolutionSolution IntextIntextIntextIntextIntext QuestionQuestionQuestionQuestionQuestion 4.3 Which of the 3d series of the transition metals exhibits the largest number of oxidation states and why? 97 The d- and f- Block Elements Reprint 2025-26 4.3.5 Trends in the Table 4.4 contains the thermochemical parameters related to the M2+/M transformation of the solid metal atoms to M2+ ions in solution and their V Standard standard electrode potentials. The observed values of E and those Electrode calculated using the data of Table 4.4 are compared in Fig. 4.4. Potentials The unique behaviour of Cu, having a positive EV, accounts for its inability to liberate H2 from acids. Only oxidising acids (nitric and hot concentrated sulphuric) react with Cu, the acids being reduced. The high energy to transform Cu(s) to Cu2+(aq) is not balanced by its hydration V enthalpy. The general trend towards less negative E values across the Fig. 4.4: Observed and calculated values for the standard electrode potentials (M2+ ® M°) of the elements Ti to Zn series is related to the general increase in the sum of the first and second V ionisation enthalpies. It is interesting to note that the value of E for Mn, Ni and Zn are more negative than expected from the trend. Why is Cr2+ reducing and Mn3+ oxidising when both have d4 configuration? ExampleExampleExampleExampleExample 4.44.44.44.44.4 Cr 2+ is reducing as its configuration changes from d 4 to d 3, the latter SolutionSolutionSolutionSolutionSolution having a half-filled t2g level (see Unit 5). On the other hand, the change from Mn3+ to Mn2+ results in the half-filled (d5) configuration which has extra stability. IntextIntextIntextIntextIntext QuestionQuestionQuestionQuestionQuestion 4.4 The E o(M2+/M) value for copper is positive (+0.34V). What is possible reason for this? (Hint: consider its high DaH o and low DhydH o) Chemistry 98 Reprint 2025-26 Table 4.4: Thermochemical data (kJ mol-1) for the first row Transition Elements and the Standard Electrode Potentials for the Reduction of MII to M. Element (M) DaH o (M) DiH1o D1H2o DhydH o(M2+) Eo/V Ti 469 656 1309 -1866 -1.63 V 515 650 1414 -1895 -1.18 Cr 398 653 1592 -1925 -0.90 Mn 279 717 1509 -1862 -1.18 Fe 418 762 1561 -1998 -0.44 Co 427 758 1644 -2079 -0.28 Ni 431 736 1752 -2121 -0.25 Cu 339 745 1958 -2121 0.34 Zn 130 906 1734 -2059 -0.76 The stability of the half-filled d sub-shell in Mn2+ and the completely filled d10 configuration in Zn2+ are related to their E o values, whereas E o for Ni is related to the highest negative DhydH o. 4.3.6 Trends in An examination of the E o(M3+/M2+) values (Table 4.2) shows the varying the M3+/M2+ trends. The low value for Sc reflects the stability of Sc3+ which has a Standard noble gas configuration. The highest value for Zn is due to the removal Electrode of an electron from the stable d 10 configuration of Zn 2+. The Potentials comparatively high value for Mn shows that Mn 2+(d5) is particularly stable, whereas comparatively low value for Fe shows the extra stability of Fe 3+ (d5). The comparatively low value for V is related to the stability of V 2+ (half-filled t2g level, Unit 5). 4.3.7 Trends in Table 4.5 shows the stable halides of the 3d series of transition metals. Stability of The highest oxidation numbers are achieved in TiX4 (tetrahalides), VF5 Higher and CrF6. The +7 state for Mn is not represented in simple halides but Oxidation MnO3F is known, and beyond Mn no metal has a trihalide except FeX3 States and CoF3. The ability of fluorine to stabilise the highest oxidation state is due to either higher lattice energy as in the case of CoF3, or higher bond enthalpy terms for the higher covalent compounds, e.g., VF5 and CrF6. Although V +5 is represented only by VF5, the other halides, however, undergo hydrolysis to give oxohalides, VOX3. Another feature of fluorides is their instability in the low oxidation states e.g., VX2 (X = CI, Br or I) Table 4.5: Formulas of Halides of 3d Metals Oxidation Number + 6 CrF6 + 5 VF5 CrF5 + 4 TiX4 VXI4 CrX4 MnF4 + 3 TiX3 VX3 CrX3 MnF3 FeXI3 CoF3 + 2 TiX2III VX2 CrX2 MnX2 FeX2 CoX2 NiX2 CuX2II ZnX2 + 1 CuXIII Key: X = F ® I; XI = F ® Br; XII = F, CI; XIII = CI ® I 99 The d- and f- Block Elements Reprint 2025-26 and the same applies to CuX. On the other hand, all Cu II halides are known except the iodide. In this case, Cu 2+ oxidises I – to I2: 2Cu 2   4I   Cu2 I2 s  I2 However, many copper (I) compounds are unstable in aqueous solution and undergo disproportionation. 2Cu + ® Cu 2+ + Cu The stability of Cu 2+ (aq) rather than Cu+(aq) is due to the much more negative DhydH o of Cu 2+ (aq) than Cu +, which more than compensates for the second ionisation enthalpy of Cu. The ability of oxygen to stabilise the highest oxidation state is demonstrated in the oxides. The highest oxidation number in the oxides (Table 4.6) coincides with the group number and is attained in Sc2O3 to Mn2O7. Beyond Group 7, no higher oxides of Fe above Fe2O3, are known, although ferrates (VI)(FeO4)2–, are formed in alkaline media but they readily decompose to Fe2O3 and O2. Besides the oxides, oxocations stabilise V v as VO2 +, V IV as VO2+ and Ti IV as TiO 2+. The ability of oxygen to stabilise these high oxidation states exceeds that of fluorine. Thus the highest Mn fluoride is MnF4 whereas the highest oxide is Mn2O7. The ability of oxygen to form multiple bonds to metals explains its superiority. In the covalent oxide Mn2O7, each Mn is tetrahedrally surrounded by O’s including a Mn–O–Mn bridge. The tetrahedral [MO4]n- ions are known for V V, Cr Vl, Mn V, Mn Vl and Mn VII. Table 4.6: Oxides of 3d Metals Oxidation Groups Number 3 4 5 6 7 8 9 10 11 12 + 7 Mn2O7 + 6 CrO3 + 5 V2O5 + 4 TiO2 V2O4 CrO2 MnO2 + 3 Sc2O3 Ti2O3 V2O3 Cr2O3 Mn2O3 Fe2O3 Mn3O4* Fe3O4 * Co3O4* + 2 TiO VO (CrO) MnO FeO CoO NiO CuO ZnO + 1 Cu2O * mixed oxides How would you account for the increasing oxidising power in the ExampleExampleExampleExampleExample 4.54.54.54.54.5 series VO2+ < Cr2O7 2– < MnO4 – ? This is due to the increasing stability of the lower species to which they SolutionSolutionSolutionSolutionSolution are reduced. IntextIntextIntextIntextIntext QuestionQuestionQuestionQuestionQuestion 4.5 How would you account for the irregular variation of ionisation enthalpies (first and second) in the first series of the transition elements? Chemistry 100 Reprint 2025-26 4.3.8 Chemical Transition metals vary widely in their chemical reactivity. Many of Reactivity them are sufficiently electropositive to dissolve in mineral acids, although and Eo a few are ‘noble’—that is, they are unaffected by single acids. Values The metals of the first series with the exception of copper are relatively more reactive and are oxidised by 1M H +, though the actual rate at which these metals react with oxidising agents like hydrogen ion (H +) is sometimes slow. For example, titanium and vanadium, in practice, are passive to dilute non oxidising acids at room temperature. The E o values for M2+/M (Table 4.2) indicate a decreasing tendency to form divalent cations across the series. This general trend towards less negative E o values is related to the increase in the sum of the first and second ionisation enthalpies. It is interesting to note that the E o values for Mn, Ni and Zn are more negative than expected from the general trend. Whereas the stabilities of half-filled d subshell (d5) in Mn2+ and completely filled d subshell (d10) in zinc are related to their E e values; for nickel, Eo value is related to the highest negative enthalpy of hydration. An examination of the E o values for the redox couple M 3+/M2+ (Table 4.2) shows that Mn 3+ and Co 3+ ions are the strongest oxidising agents in aqueous solutions. The ions Ti 2+, V 2+ and Cr2+ are strong reducing agents and will liberate hydrogen from a dilute acid, e.g., 2 Cr 2+(aq) + 2 H+(aq) ® 2 Cr 3+(aq) + H2(g) ExampleExampleExampleExampleExample 4.64.64.64.64.6 For the first row transition metals the Eo values are: E o V Cr Mn Fe Co Ni Cu (M2+/M) –1.18 – 0.91 –1.18 – 0.44 – 0.28 – 0.25 +0.34 Explain the irregularity in the above values. SolutionSolutionSolutionSolutionSolution The E o (M2+/M) values are not regular which can be explained from the irregular variation of ionisation enthalpies (  i H1  i H 2 ) and also the sublimation enthalpies which are relatively much less for manganese and vanadium. ExampleExampleExampleExampleExample 4.74.74.74.74.7 Why is the E o value for the Mn3+/Mn 2+ couple much more positive than that for Cr 3+/Cr2+ or Fe 3+/Fe 2+? Explain. SolutionSolutionSolutionSolutionSolution Much larger third ionisation energy of Mn (where the required change is d5 to d4) is mainly responsible for this. This also explains why the +3 state of Mn is of little importance. IntextIntextIntextIntextIntext QuestionsQuestionsQuestionsQuestionsQuestions 4.6 Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only? 4.7 Which is a stronger reducing agent Cr2+ or Fe2+ and why ? 4.3.9 Magnetic When a magnetic field is applied to substances, mainly two types of Properties magnetic behaviour are observed: diamagnetism and paramagnetism. Diamagnetic substances are repelled by the applied field while the paramagnetic substances are attracted. Substances which are 101 The d- and f- Block Elements Reprint 2025-26 attracted very strongly are said to be ferromagnetic. In fact, ferromagnetism is an extreme form of paramagnetism. Many of the transition metal ions are paramagnetic. Paramagnetism arises from the presence of unpaired electrons, each such electron having a magnetic moment associated with its spin angular momentum and orbital angular momentum. For the compounds of the first series of transition metals, the contribution of the orbital angular momentum is effectively quenched and hence is of no significance. For these, the magnetic moment is determined by the number of unpaired electrons and is calculated by using the ‘spin-only’ formula, i.e.,  n  n  2  where n is the number of unpaired electrons and µ is the magnetic moment in units of Bohr magneton (BM). A single unpaired electron has a magnetic moment of 1.73 Bohr magnetons (BM). The magnetic moment increases with the increasing number of unpaired electrons. Thus, the observed magnetic moment gives a useful indication about the number of unpaired electrons present in the atom, molecule or ion. The magnetic moments calculated from the ‘spin-only’ formula and those derived experimentally for some ions of the first row transition elements are given in Table 4.7. The experimental data are mainly for hydrated ions in solution or in the solid state. Table 4.7: Calculated and Observed Magnetic Moments (BM) Ion Configuration Unpaired Magnetic moment electron(s) Calculated Observed Sc3+ 3d0 0 0 0 Ti 3+ 3d1 1 1.73 1.75 Tl2+ 3d2 2 2.84 2.76 V2+ 3d3 3 3.87 3.86 Cr2+ 3d4 4 4.90 4.80 Mn2+ 3d5 5 5.92 5.96 Fe2+ 3d6 4 4.90 5.3 – 5.5 Co2+ 3d7 3 3.87 4.4 – 5.2 Ni2+ 3d8 2 2.84 2.9 – 3, 4 Cu 2+ 3d9 1 1.73 1.8 – 2.2 Zn2+ 3d10 0 0 Calculate the magnetic moment of a divalent ion in aqueous solution ExampleExampleExampleExampleExample 4.84.84.84.84.8 if its atomic number is 25. With atomic number 25, the divalent ion in aqueous solution will have SolutionSolutionSolutionSolutionSolution d5 configuration (five unpaired electrons). The magnetic moment, µ is  5  5  2   5.92BM Chemistry 102 Reprint 2025-26 IntextIntextIntextIntextIntext QuestionQuestionQuestionQuestionQuestion 4.8 Calculate the ‘spin only’ magnetic moment of M 2+ (aq) ion (Z = 27). 4.3.10 Formation When an electron from a lower energy d orbital is excited to a higher of Coloured energy d orbital, the energy of excitation corresponds to the frequency Ions of light absorbed (Unit 5). This frequency generally lies in the visible region. The colour observed corresponds to the complementary colour of the light absorbed. The frequency of the light absorbed is determined by the nature of the ligand. In aqueous solutions where water molecules are the ligands, the colours of the ions observed are listed in Table 4.8. A few coloured solutions of Fig. 4.5: Colours of some of the first row d–block elements are transition metal ions in aqueous solutions. From illustrated in Fig. 4.5. left to right: V4+,V3+,Mn2+,Fe3+,Co2+,Ni2+and Cu2+ . Table 4.8: Colours of Some of the First Row (aquated) Transition Metal Ions Configuration Example Colour 3d0 Sc3+ colourless 3d0 Ti 4+ colourless 3d1 Ti 3+ purple 3d1 V4+ blue 3d2 V3+ green 3d3 V2+ violet 3d3 Cr3+ violet 3d4 Mn 3+ violet 3d4 Cr2+ blue 3d5 Mn 2+ pink 3d5 Fe3+ yellow 3d6 Fe2+ green 3d63d7 Co3+Co2+ bluepink 3d8 Ni2+ green 3d9 Cu 2+ blue 3d10 Zn2+ colourless 4.3.11 Formation Complex compounds are those in which the metal ions bind a number of Complex of anions or neutral molecules giving complex species with Compounds characteristic properties. A few examples are: [Fe(CN)6] 3–, [Fe(CN)6]4–, [Cu(NH3)4] 2+ and [PtCl4] 2–. (The chemistry of complex compounds is 103 The d- and f- Block Elements Reprint 2025-26 dealt with in detail in Unit 5). The transition metals form a large number of complex compounds. This is due to the comparatively smaller sizes of the metal ions, their high ionic charges and the availability of d orbitals for bond formation. 4.3.12 Catalytic The transition metals and their compounds are known for their catalytic Properties activity. This activity is ascribed to their ability to adopt multiple oxidation states and to form complexes. Vanadium(V) oxide (in Contact Process), finely divided iron (in Haber’s Process), and nickel (in Catalytic Hydrogenation) are some of the examples. Catalysts at a solid surface involve the formation of bonds between reactant molecules and atoms of the surface of the catalyst (first row transition metals utilise 3d and 4s electrons for bonding). This has the effect of increasing the concentration of the reactants at the catalyst surface and also weakening of the bonds in the reacting molecules (the activation energy is lowering). Also because the transition metal ions can change their oxidation states, they become more effective as catalysts. For example, iron(III) catalyses the reaction between iodide and persulphate ions. 2 I– + S2O8 2– ® I2 + 2 SO4 2– An explanation of this catalytic action can be given as: 2 Fe 3+ + 2 I – ® 2 Fe 2+ + I2 2 Fe 2+ + S2O82– ® 2 Fe3+ + 2SO42– 4.3.13 Formation Interstitial compounds are those which are formed when small atoms of like H, C or N are trapped inside the crystal lattices of metals. They are Interstitial usually non stoichiometric and are neither typically ionic nor covalent, Compounds for example, TiC, Mn4N, Fe3H, VH0.56 and TiH1.7, etc. The formulas quoted do not, of course, correspond to any normal oxidation state of the metal. Because of the nature of their composition, these compounds are referred to as interstitial compounds. The principal physical and chemical characteristics of these compounds are as follows: (i) They have high melting points, higher than those of pure metals. (ii) They are very hard, some borides approach diamond in hardness. (iii) They retain metallic conductivity. (iv) They are chemically inert. 4.3.14 Alloy An alloy is a blend of metals prepared by mixing the components. Formation Alloys may be homogeneous solid solutions in which the atoms of one metal are distributed randomly among the atoms of the other. Such alloys are formed by atoms with metallic radii that are within about 15 percent of each other. Because of similar radii and other characteristics of transition metals, alloys are readily formed by these metals. The alloys so formed are hard and have often high melting points. The best known are ferrous alloys: chromium, vanadium, tungsten, molybdenum and manganese are used for the production of a variety of steels and stainless steel. Alloys of transition metals with non transition metals such as brass (copper-zinc) and bronze (copper-tin), are also of considerable industrial importance. Chemistry 104 Reprint 2025-26 ExampleExampleExampleExampleExample 4.94.94.94.94.9 What is meant by ‘disproportionation’ of an oxidation state? Give an example. SolutionSolutionSolutionSolutionSolution When a particular oxidation state becomes less stable relative to other oxidation states, one lower, one higher, it is said to undergo disproportionation. For example, manganese (VI) becomes unstable relative to manganese(VII) and manganese (IV) in acidic solution. 3 Mn VIO4 2– + 4 H + ® 2 Mn VIIO –4 + Mn IVO2 + 2H2O IntextIntextIntextIntextIntext QuestionQuestionQuestionQuestionQuestion 4.9 Explain why Cu+ ion is not stable in aqueous solutions? 4.44.44.44.44.4 SomeSomeSomeSomeSome 4.4.1 Oxides and Oxoanions of Metals ImportantImportantImportantImportantImportant These oxides are generally formed by the reaction of metals with CompoundsCompoundsCompoundsCompoundsCompounds ofofofofof oxygen at high temperatures. All the metals except scandium form TransitionTransitionTransitionTransitionTransition MO oxides which are ionic. The highest oxidation number in the oxides, coincides with the group number and is attained in Sc2O3 to ElementsElementsElementsElementsElements Mn2O7. Beyond group 7, no higher oxides of iron above Fe2O3 are known. Besides the oxides, the oxocations stabilise V V as VO2 +, V IV as VO 2+ and Ti IV as TiO 2+. As the oxidation number of a metal increases, ionic character decreases. In the case of Mn, Mn2O7 is a covalent green oil. Even CrO3 and V2O5 have low melting points. In these higher oxides, the acidic character is predominant. Thus, Mn2O7 gives HMnO4 and CrO3 gives H2CrO4 and H2Cr2O7. V2O5 is, however, amphoteric though mainly acidic and it gives VO4 3– as well as VO2+ salts. In vanadium there is gradual change from the basic V2O3 to less basic V2O4 and to amphoteric V2O5. V2O4 dissolves in acids to give VO 2+ salts. Similarly, V2O5 reacts with alkalies as well as acids to give VO 34  and VO4 respectively. The well characterised CrO is basic but Cr2O3 is amphoteric. Potassium dichromate K2Cr2O7 Potassium dichromate is a very important chemical used in leather industry and as an oxidant for preparation of many azo compounds. Dichromates are generally prepared from chromate, which in turn are obtained by the fusion of chromite ore (FeCr2O4) with sodium or potassium carbonate in free access of air. The reaction with sodium carbonate occurs as follows: 4 FeCr2O4 + 8 Na2CO3 + 7 O2 ® 8 Na2CrO4 + 2 Fe2O3 + 8 CO2 The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to give a solution from which orange sodium dichromate, Na2Cr2O7. 2H2O can be crystallised. 2Na2CrO4 + 2 H+ ® Na2Cr2O7 + 2 Na + + H2O 105 The d- and f- Block Elements Reprint 2025-26 Sodium dichromate is more soluble than potassium dichromate. The latter is therefore, prepared by treating the solution of sodium dichromate with potassium chloride. Na2Cr2O7 + 2 KCl ® K2Cr2O7 + 2 NaCl Orange crystals of potassium dichromate crystallise out. The chromates and dichromates are interconvertible in aqueous solution depending upon pH of the solution. The oxidation state of chromium in chromate and dichromate is the same. 2 CrO4 2– + 2H + ® Cr2O7 2– + H2O Cr2O7 2– + 2 OH- ® 2 CrO4 2– + H2O The structures of chromate ion, CrO4 2– and the dichromate ion, Cr2O7 2– are shown below. The chromate ion is tetrahedral whereas the dichromate ion consists of two tetrahedra sharing one corner with Cr–O–Cr bond angle of 126°. Sodium and potassium dichromates are strong oxidising agents; the sodium salt has a greater solubility in water and is extensively used as an oxidising agent in organic chemistry. Potassium dichromate is used as a primary standard in volumetric analysis. In acidic solution, its oxidising action can be represented as follows: Cr2O7 2– + 14H + + 6e – ® 2Cr 3+ + 7H2O (E o = 1.33V) Thus, acidified potassium dichromate will oxidise iodides to iodine, sulphides to sulphur, tin(II) to tin(IV) and iron(II) salts to iron(III). The half-reactions are noted below: 6 I– ® 3I2 + 6 e – ; 3 Sn 2+ ® 3Sn 4+ + 6 e – 3 H2S ® 6H+ + 3S + 6e – ; 6 Fe 2+ ® 6Fe3+ + 6 e– The full ionic equation may be obtained by adding the half-reaction for potassium dichromate to the half-reaction for the reducing agent, for e.g., Cr2O7 2– + 14 H+ + 6 Fe2+ ® 2 Cr3+ + 6 Fe3+ + 7 H2O Potassium permanganate KMnO4 Potassium permanganate is prepared by fusion of MnO2 with an alkali metal hydroxide and an oxidising agent like KNO3. This produces the dark green K2MnO4 which disproportionates in a neutral or acidic solution to give permanganate. 2MnO2 + 4KOH + O2 ® 2K2MnO4 + 2H2O 3MnO4 2– + 4H+ ® 2MnO4 – + MnO2 + 2H2O Commercially it is prepared by the alkaline oxidative fusion of MnO2 followed by the electrolytic oxidation of manganate (Vl). F used with KOH, oxidised Electrolytic oxidation in MnO 2 →with air or KNO 3 MnO 24 − ; MnO 24  alkaline solution MnO 4 manganate ion manganate permanganate ion Chemistry 106 Reprint 2025-26 In the laboratory, a manganese (II) ion salt is oxidised by peroxodisulphate to permanganate. 2Mn2+ + 5S2O8 2– + 8H2O ® 2MnO4 – + 10SO42– + 16H + Potassium permanganate forms dark purple (almost black) crystals which are isostructural with those of KClO4. The salt is not very soluble in water (6.4 g/100 g of water at 293 K), but when heated it decomposes at 513 K. 2KMnO4 ® K2MnO4 + MnO2 + O2 It has two physical properties of considerable interest: its intense colour and its diamagnetism along with temperature-dependent weak paramagnetism. These can be explained by the use of molecular orbital theory which is beyond the present scope. The manganate and permanganate ions are tetrahedral; the p- bonding takes place by overlap of p orbitals of oxygen with d orbitals of manganese. The green manganate is paramagnetic because of one unpaired electron but the permanganate is diamagnetic due to the absence of unpaired electron. Acidified permanganate solution oxidises oxalates to carbon dioxide, iron(II) to iron(III), nitrites to nitrates and iodides to free iodine. The half-reactions of reductants are: COO – 5 10CO2 + 10e – COO – 5 Fe2+ ® 5 Fe3+ + 5e– 5NO2 – + 5H2O ® 5NO3 – + 10H+ + l0e– 10I– ® 5I2 + 10e– The full reaction can be written by adding the half-reaction for KMnO4 to the half-reaction of the reducing agent, balancing wherever necessary. If we represent the reduction of permanganate to manganate, manganese dioxide and manganese(II) salt by half-reactions, MnO4 – + e– ® MnO4 2– (E o = + 0.56 V) MnO4 – + 4H+ + 3e– ® MnO2 + 2H2O (E o = + 1.69 V) MnO4 – + 8H+ + 5e– ® Mn2+ + 4H2O (E o = + 1.52 V) We can very well see that the hydrogen ion concentration of the solution plays an important part in influencing the reaction. Although many reactions can be understood by consideration of redox potential, kinetics of the reaction is also an important factor. Permanganate at [H+] = 1 should oxidise water but in practice the reaction is extremely slow unless either manganese(ll) ions are present or the temperature is raised. A few important oxidising reactions of KMnO4 are given below: 1. In acid solutions: (a) Iodine is liberated from potassium iodide : 10I – + 2MnO4 – + 16H + ® 2Mn2+ + 8H2O + 5I2 (b) Fe2+ ion (green) is converted to Fe3+ (yellow): 5Fe 2+ + MnO4 – + 8H+ ® Mn2+ + 4H2O + 5Fe 3+ 107 The d- and f- Block Elements Reprint 2025-26 (c) Oxalate ion or oxalic acid is oxidised at 333 K: 5C2O4 2– + 2MnO4 – + 16H + ——> 2Mn 2+ + 8H2O + 10CO2 (d) Hydrogen sulphide is oxidised, sulphur being precipitated: H2S —> 2H + + S2– 5S 2– + 2MnO – 4 + 16H + ——> 2Mn2+ + 8H2O + 5S (e) Sulphurous acid or sulphite is oxidised to a sulphate or sulphuric acid: 5SO3 2– + 2MnO4 – + 6H + ——> 2Mn 2+ + 3H2O + 5SO42– (f) Nitrite is oxidised to nitrate: 5NO2– + 2MnO4– + 6H + ——> 2Mn 2+ + 5NO3 – + 3H2O 2. In neutral or faintly alkaline solutions: (a) A notable reaction is the oxidation of iodide to iodate: 2MnO4 – + H2O + I– ——> 2MnO2 + 2OH – + IO3 – (b) Thiosulphate is oxidised almost quantitatively to sulphate: 8MnO4 – + 3S2O3 2– + H2O ——> 8MnO2 + 6SO4 2– + 2OH – (c) Manganous salt is oxidised to MnO2; the presence of zinc sulphate or zinc oxide catalyses the oxidation: 2MnO4 – + 3Mn 2+ + 2H2O ——> 5MnO2 + 4H+ Note: Permanganate titrations in presence of hydrochloric acid are unsatisfactory since hydrochloric acid is oxidised to chlorine. UsesUsesUses:UsesUses Besides its use in analytical chemistry, potassium permanganate is used as a favourite oxidant in preparative organic chemistry. Its uses for the bleaching of wool, cotton, silk and other textile fibres and for the decolourisation of oils are also dependent on its strong oxidising power. THE INNER TRANSITION ELEMENTS ( f-BLOCK) The f-block consists of the two series, lanthanoids (the fourteen elements following lanthanum) and actinoids (the fourteen elements following actinium). Because lanthanum closely resembles the lanthanoids, it is usually included in any discussion of the lanthanoids for which the general symbol Ln is often used. Similarly, a discussion of the actinoids includes actinium besides the fourteen elements constituting the series. The lanthanoids resemble one another more closely than do the members of ordinary transition elements in any series. They have only one stable oxidation state and their chemistry provides an excellent opportunity to examine the effect of small changes in size and nuclear charge along a series of otherwise similar elements. The chemistry of the actinoids is, on the other hand, much more complicated. The complication arises partly owing to the occurrence of a wide range of oxidation states in these elements and partly because their radioactivity creates special problems in their study; the two series will be considered separately here. 4.54.54.54.54.5 TheTheTheTheThe The names, symbols, electronic configurations of atomic and some LanthanoidsLanthanoidsLanthanoidsLanthanoidsLanthanoids ionic states and atomic and ionic radii of lanthanum and lanthanoids (for which the general symbol Ln is used) are given in Table 4.9. Chemistry 108 Reprint 2025-26 4.5.1 Electronic It may be noted that atoms of these elements have electronic Configurations configuration with 6s 2 common but with variable occupancy of 4f level (Table 4.9). However, the electronic configurations of all the tripositive ions (the most stable oxidation state of all the lanthanoids) are of the form 4f n (n = 1 to 14 with increasing atomic number). 4.5.2 Atomic and The overall decrease in atomic and ionic radii from lanthanum to Ionic Sizes lutetium (the lanthanoid contraction) is a unique feature in the chemistry of the lanthanoids. It has far reaching Sm 2+ consequences in the chemistry of the third 110 2+ transition series of the elements. The decrease Eu in atomic radii (derived from the structures of La3+ metals) is not quite regular as it is regular in 3+ M3+ ions (Fig. 4.6). This contraction is, of Ce course, similar to that observed in an ordinary Pr3+ transition series and is attributed to the same 100 Nd3+ cause, the imperfect shielding of one electron Pm 3+ by another in the same sub-shell. However, the Sm3+ shielding of one 4 f electron by another is less Eu3+ than one d electron by another with the increase Gd3+ Tm 2+radii/pm 2+ in nuclear charge along the series. There is Yb Ce 4+ Tb 3+ fairly regular decrease in the sizes with 3+ DyIonic Pr4+ 3+ increasing atomic number. 90 Ho Er 3+ The cumulative effect of the contraction of Tm3+ the lanthanoid series, known as lanthanoid Yb3+ 3+ contraction, causes the radii of the members 4+ Lu Tb of the third transition series to be very similar to those of the corresponding members of the second series. The almost identical radii of Zr 57 59 61 63 65 67 69 71 (160 pm) and Hf (159 pm), a consequence of the lanthanoid contraction, account for their Atomic number occurrence together in nature and for the Fig. 4.6: Trends in ionic radii of lanthanoids difficulty faced in their separation. 4.5.3 Oxidation In the lanthanoids, La(II) and Ln(III) compounds are predominant States species. However, occasionally +2 and +4 ions in solution or in solid compounds are also obtained. This irregularity (as in ionisation enthalpies) arises mainly from the extra stability of empty, half-filled or filled f subshell. Thus, the formation of Ce IV is favoured by its noble gas configuration, but it is a strong oxidant reverting to the common +3 state. The E o value for Ce 4+/ Ce 3+ is + 1.74 V which suggests that it can oxidise water. However, the reaction rate is very slow and hence Ce(IV) is a good analytical reagent. Pr, Nd, Tb and Dy also exhibit +4 state but only in oxides, MO2. Eu2+ is formed by losing the two s electrons and its f 7 configuration accounts for the formation of this ion. However, Eu 2+ is a strong reducing agent changing to the common +3 state. Similarly Yb 2+ which has f 14 configuration is a reductant. Tb IV has half-filled f-orbitals and is an oxidant. The behaviour of samarium is very much like europium, exhibiting both +2 and +3 oxidation states. 109 The d- and f- Block Elements Reprint 2025-26 Table 4.9: Electronic Configurations and Radii of Lanthanum and Lanthanoids Electronic configurations* Radii/pm Atomic Name Symbol Ln Ln2+ Ln3+ Ln4+ Ln Ln3+ Number 57 Lanthanum La 5d16s2 5d1 4f 0 187 106 58 Cerium Ce 4f15d16s2 4f 2 4f 1 4f 0 183 103 59 Praseodymium Pr 4f 36s2 4f 3 4f 2 4f 1 182 101 60 Neodymium Nd 4f 46s2 4f 4 4f 3 4f 2 181 99 61 Promethium Pm 4f 56s2 4f 5 4f 4 181 98 62 Samarium Sm 4f 66s2 4f 6 4f 5 180 96 63 Europium Eu 4f 76s2 4f 7 4f 6 199 95 64 Gadolinium Gd 4f 75d16s2 4f 75d 1 4f 7 180 94 65 Terbium Tb 4f 96s2 4f 9 4f 8 4f 7 178 92 66 Dysprosium Dy 4f 106s2 4f 10 4f 9 4f 8 177 91 67 Holmium Ho 4f 116s2 4f 11 4f 10 176 89 68 Erbium Er 4f 126s2 4f 12 4f 11 175 88 69 Thulium Tm 4f 136s2 4f 13 4f 12 174 87 70 Ytterbium Yb 4f 146s2 4f 14 4f 13 173 86 71 Lutetium Lu 4f 145d16s2 4f 145d1 4f 14 – – – * Only electrons outside [Xe] core are indicated 4.5.4 General All the lanthanoids are silvery white soft metals and tarnish rapidly in air. Characteristics The hardness increases with increasing atomic number, samarium being steel hard. Their melting points range between 1000 to 1200 K but samarium melts at 1623 K. They have typical metallic structure and are good conductors of heat and electricity. Density and other properties change smoothly except for Eu and Yb and occasionally for Sm and Tm. Many trivalent lanthanoid ions are coloured both in the solid state and in aqueous solutions. Colour of these ions may be attributed to the presence of f electrons. Neither La 3+ nor Lu3+ ion shows any colour but the rest do so. However, absorption bands are narrow, probably because of the excitation within f level. The lanthanoid ions other than the f 0 type (La 3+ and Ce4+) and the f 14 type (Yb2+ and Lu3+) are all paramagnetic. The first ionisation enthalpies of the lanthanoids are around 600 kJ mol –1, the second about 1200 kJ mol–1 comparable with those of calcium. A detailed discussion of the variation of the third ionisation enthalpies indicates that the exchange enthalpy considerations (as in 3d orbitals of the first transition series), appear to impart a certain degree of stability to empty, half-filled and completely filled orbitals f level. This is indicated from the abnormally low value of the third ionisation enthalpy of lanthanum, gadolinium and lutetium. In their chemical behaviour, in general, the earlier members of the series are quite reactive similar to calcium but, with increasing atomic number, they behave more like aluminium. Values for E o for the half-reaction: Ln 3+(aq) + 3e – ® Ln(s) Chemistry 110 Reprint 2025-26 Ln2 O 3 H2 are in the range of –2.2 to –2.4 V except for Eu for which the value is – 2.0 V. This is, of course, a small acids variation. The metals combine with burns in with hydrogen when gently heated in the O2 gas. The carbides, Ln3C, Ln2C3 and LnC2 are formed when the metals are heated heated with S Ln with halogens with carbon. They liberate hydrogen Ln 2 S3 LnX 3 from dilute acids and burn in halogens N with with toandform hydroxideshalides. They formM(OH)3.oxides M2O3The C K H2 O hydroxides are definite compounds, not heated just hydrated oxides. They are basic with 2773 like alkaline earth metal oxides and Ln N LnC2 Ln(OH)3 + H2 hydroxides. Their general reactions are depicted in Fig. 4.7. Fig 4.7: Chemical reactions of the lanthanoids. The best single use of the lanthanoids is for the production of alloy steels for plates and pipes. A well known alloy is mischmetall which consists of a lanthanoid metal (~ 95%) and iron (~ 5%) and traces of S, C, Ca and Al. A good deal of mischmetall is used in Mg-based alloy to produce bullets, shell and lighter flint. Mixed oxides of lanthanoids are employed as catalysts in petroleum cracking. Some individual Ln oxides are used as phosphors in television screens and similar fluorescing surfaces. 4.64.64.64.64.6 TheTheTheTheThe ActinoidsActinoidsActinoidsActinoidsActinoids The actinoids include the fourteen elements from Th to Lr. The names, symbols and some properties of these elements are given in Table 4.10. Table 4.10: Some Properties of Actinium and Actinoids Electronic conifigurations* Radii/pm Atomic Name Symbol M M3+ M4+ M3+ M4+ Number 89 Actinium Ac 6d 17s 2 5f 0 111 90 Thorium Th 6d 27s 2 5f 1 5f 0 99 91 Protactinium Pa 5f 26d 17s 2 5f 2 5f 1 96 92 Uranium U 5f 36d 17s 2 5f 3 5f 2 103 93 93 Neptunium Np 5f 46d 17s 2 5f 4 5f 3 101 92 94 Plutonium Pu 5f 67s 2 5f 5 5f 4 100 90 95 Americium Am 5f 77s 2 5f 6 5f 5 99 89 96 Curium Cm 5f 76d 17s 2 5f 7 5f 6 99 88 97 Berkelium Bk 5f 97s 2 5f 8 5f 7 98 87 98 Californium Cf 5f 107s 2 5f 9 5f 8 98 86 99 Einstenium Es 5f 117s 2 5f 10 5f 9 – – 100 Fermium Fm 5f 127s 2 5f 11 5f 10 – – 101 Mendelevium Md 5f 137s 2 5f 12 5f 11 – – 102 Nobelium No 5f 147s 2 5f 13 5f 12 – – 103 Lawrencium Lr 5f 146d 17s 2 5f 14 5f 13 – – 111 The d- and f- Block Elements Reprint 2025-26 The actinoids are radioactive elements and the earlier members have relatively long half-lives, the latter ones have half-life values ranging from a day to 3 minutes for lawrencium (Z =103). The latter members could be prepared only in nanogram quantities. These facts render their study more difficult. 4.6.1 Electronic All the actinoids are believed to have the electronic configuration of 7s2 Configurations and variable occupancy of the 5f and 6d subshells. The fourteen electrons are formally added to 5f, though not in thorium (Z = 90) but from Pa onwards the 5f orbitals are complete at element 103. The irregularities in the electronic configurations of the actinoids, like those in the lanthanoids are related to the stabilities of the f 0, f 7 and f 14 occupancies of the 5f orbitals. Thus, the configurations of Am and Cm are [Rn] 5f 77s2 and [Rn] 5f 76d17s2. Although the 5f orbitals resemble the 4f orbitals in their angular part of the wave-function, they are not as buried as 4f orbitals and hence 5f electrons can participate in bonding to a far greater extent. 4.6.2 Ionic Sizes The general trend in lanthanoids is observable in the actinoids as well. There is a gradual decrease in the size of atoms or M3+ ions across the series. This may be referred to as the actinoid contraction (like lanthanoid contraction). The contraction is, however, greater from element to element in this series resulting from poor shielding by 5f electrons. 4.6.3 Oxidation There is a greater range of oxidation states, which is in part attributed to States the fact that the 5f, 6d and 7s levels are of comparable energies. The known oxidation states of actinoids are listed in Table 4.11. The actinoids show in general +3 oxidation state. The elements, in the first half of the series frequently exhibit higher oxidation states. For example, the maximum oxidation state increases from +4 in Th to +5, +6 and +7 respectively in Pa, U and Np but decreases in succeeding elements (Table 4.11). The actinoids resemble the lanthanoids in having more compounds in +3 state than in the +4 state. However, +3 and +4 ions tend to hydrolyse. Because the distribution of oxidation states among the actinoids is so uneven and so different for the former and later elements, it is unsatisfactory to review their chemistry in terms of oxidation states. Table 4.11: Oxidation States of Actinium and Actinoids Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr 3 3 3 3 3 3 3 3 3 3 3 3 3 3 4 4 4 4 4 4 4 4 5 5 5 5 5 6 6 6 6 7 7 4.6.4 General The actinoid metals are all silvery in appearance but display Characteristics a variety of structures. The structural variability is obtained and Comparison due to irregularities in metallic radii which are far greater with Lanthanoids than in lanthanoids. Chemistry 112 Reprint 2025-26 The actinoids are highly reactive metals, especially when finely divided. The action of boiling water on them, for example, gives a mixture of oxide and hydride and combination with most non metals takes place at moderate temperatures. Hydrochloric acid attacks all metals but most are slightly affected by nitric acid owing to the formation of protective oxide layers; alkalies have no action. The magnetic properties of the actinoids are more complex than those of the lanthanoids. Although the variation in the magnetic susceptibility of the actinoids with the number of unpaired 5 f electrons is roughly parallel to the corresponding results for the lanthanoids, the latter have higher values. It is evident from the behaviour of the actinoids that the ionisation enthalpies of the early actinoids, though not accurately known, but are lower than for the early lanthanoids. This is quite reasonable since it is to be expected that when 5f orbitals are beginning to be occupied, they will penetrate less into the inner core of electrons. The 5f electrons, will therefore, be more effectively shielded from the nuclear charge than the 4f electrons of the corresponding lanthanoids. Because the outer electrons are less firmly held, they are available for bonding in the actinoids. A comparison of the actinoids with the lanthanoids, with respect to different characteristics as discussed above, reveals that behaviour similar to that of the lanthanoids is not evident until the second half of the actinoid series. However, even the early actinoids resemble the lanthanoids in showing close similarities with each other and in gradual variation in properties which do not entail change in oxidation state. The lanthanoid and actinoid contractions, have extended effects on the sizes, and therefore, the properties of the elements succeeding them in their respective periods. The lanthanoid contraction is more important because the chemistry of elements succeeding the actinoids are much less known at the present time. ExampleExampleExampleExampleExample 4.104.104.104.104.10 Name a member of the lanthanoid series which is well known to exhibit +4 oxidation state. SolutionSolutionSolutionSolutionSolution Cerium (Z = 58) IntextIntextIntextIntextIntext QuestionQuestionQuestionQuestionQuestion 4.10 Actinoid contraction is greater from element to element than lanthanoid contraction. Why? 4.74.74.74.74.7 SomeSomeSomeSomeSome Iron and steels are the most important construction materials. Their ApplicationsApplicationsApplicationsApplicationsApplications production is based on the reduction of iron oxides, the removal of impurities and the addition of carbon and alloying metals such as Cr, Mn ofofofofof d-d-d-d-d- andandandandand and Ni. Some compounds are manufactured for special purposes such as f-Blockf-Blockf-Blockf-Blockf-Block TiO for the pigment industry and MnO2 for use in dry battery cells. The ElementsElementsElementsElementsElements battery industry also requires Zn and Ni/Cd. The elements of Group 11 are still worthy of being called the coinage metals, although Ag and Au 113 The d- and f- Block Elements Reprint 2025-26 are restricted to collection items and the contemporary UK ‘copper’ coins are copper-coated steel. The ‘silver’ UK coins are a Cu/Ni alloy. Many of the metals and/or their compounds are essential catalysts in the chemical industry. V2O5 catalyses the oxidation of SO2 in the manufacture of sulphuric acid. TiCl4 with A1(CH3)3 forms the basis of the Ziegler catalysts used to manufacture polyethylene (polythene). Iron catalysts are used in the Haber process for the production of ammonia from N2/H2 mixtures. Nickel catalysts enable the hydrogenation of fats to proceed. In the Wacker process the oxidation of ethyne to ethanal is catalysed by PdCl2. Nickel complexes are useful in the polymerisation of alkynes and other organic compounds such as benzene. The photographic industry relies on the special light-sensitive properties of AgBr. SummarySummarySummarySummarySummary The d-block consisting of Groups 3-12 occupies the large middle section of the periodic table. In these elements the inner d orbitals are progressively filled. The f-block is placed outside at the bottom of the periodic table and in the elements of this block, 4f and 5f orbitals are progressively filled. Corresponding to the filling of 3d, 4d and 5d orbitals, three series of transition elements are well recognised. All the transition elements exhibit typical metallic properties such as –high tensile strength, ductility, malleability, thermal and electrical conductivity and metallic character. Their melting and boiling points are high which are attributed to the involvement of (n –1) d electrons resulting into strong interatomic bonding. In many of these properties, the maxima occur at about the middle of each series which indicates that one unpaired electron per d orbital is particularly a favourable configuration for strong interatomic interaction. Successive ionisation enthalpies do not increase as steeply as in the main group elements with increasing atomic number. Hence, the loss of variable number of electrons from (n –1) d orbitals is not energetically unfavourable. The involvement of (n–1) d electrons in the behaviour of transition elements impart certain distinct characteristics to these elements. Thus, in addition to variable oxidation states, they exhibit paramagnetic behaviour, catalytic properties and tendency for the formation of coloured ions, interstitial compounds and complexes. The transition elements vary widely in their chemical behaviour. Many of them are sufficiently electropositive to dissolve in mineral acids, although a few are ‘noble’. Of the first series, with the exception of copper, all the metals are relatively reactive. The transition metals react with a number of non-metals like oxygen, nitrogen, sulphur and halogens to form binary compounds. The first series transition metal oxides are generally formed from the reaction of metals with oxygen at high temperatures. These oxides dissolve in acids and bases to form oxometallic salts. Potassium dichromate and potassium permanganate are common examples. Potassium dichromate is prepared from the chromite ore by fusion with alkali in presence of air and acidifying the extract. Pyrolusite ore (MnO2) is used for the preparation of potassium permanganate. Both the dichromate and the permanganate ions are strong oxidising agents. The two series of inner transition elements, lanthanoids and actinoids constitute the f-block of the periodic table. With the successive filling of the inner orbitals, 4f, there is a gradual decrease in the atomic and ionic sizes of these metals along the series (lanthanoid contraction). This has far reaching consequences in the chemistry of the elements succeeding them. Lanthanum and all the lanthanoids are rather soft white metals. They react easily with water to give solutions giving +3 ions. The principal oxidation state is +3, although +4 and +2 oxidation states are also exhibited by some Chemistry 114 Reprint 2025-26 occasionally. The chemistry of the actinoids is more complex in view of their ability to exist in different oxidation states. Furthermore, many of the actinoid elements are radioactive which make the study of these elements rather difficult. There are many useful applications of the d- and f-block elements and their compounds, notable among them being in varieties of steels, catalysts, complexes, organic syntheses, etc. Exercises 4.1 Write down the electronic configuration of: (i) Cr3+ (iii) Cu+ (v) Co2+ (vii) Mn2+ (ii) Pm3+ (iv) Ce4+ (vi) Lu2+ (viii) Th4+ 4.2 Why are Mn2+ compounds more stable than Fe2+ towards oxidation to their +3 state? 4.3 Explain briefly how +2 state becomes more and more stable in the first half of the first row transition elements with increasing atomic number? 4.4 To what extent do the electronic configurations decide the stability of oxidation states in the first series of the transition elements? Illustrate your answer with examples. 4.5 What may be the stable oxidation state of the transition element with the following d electron configurations in the ground state of their atoms : 3d 3, 3d 5, 3d 8 and 3d 4? 4.6 Name the oxometal anions of the first series of the transition metals in which the metal exhibits the oxidation state equal to its group number. 4.7 What is lanthanoid contraction? What are the consequences of lanthanoid contraction? 4.8 What are the characteristics of the transition elements and why are they called transition elements? Which of the d-block elements may not be regarded as the transition elements? 4.9 In what way is the electronic configuration of the transition elements different from that of the non transition elements?

3.23 The rate constant for the decomposition of hydrocarbons is 2.418 × 10–5s–1 at 546 K. If the energy of activation is 179.9 kJ/mol, what will be the value of pre-exponential factor.

3.9 A reaction is first order in A and second order in B. (i) Write the differential rate equation. (ii) How is the rate affected on increasing the concentration of B three times? (iii) How is the rate affected when the concentrations of both A and B are doubled? 85 Chemical Kinetics Reprint 2025-26

3.5 ELECTRONIC CONFIGURATIONS transition series of elements. This starts from OF ELEMENTS AND THE PERIODIC scandium (Z = 21) which has the electronic TABLE configuration 3d14s2. The 3d orbitals are filled In the preceding unit we have learnt that an at zinc (Z=30) with electronic configuration electron in an atom is characterised by a set 3d104s2. The fourth period ends at krypton of four quantum numbers, and the principal with the filling up of the 4p orbitals. Altogether quantum number (n ) defines the main energy we have 18 elements in this fourth period. The level known as shell. We have also studied fifth period (n = 5) beginning with rubidium about the filling of electrons into different is similar to the fourth period and contains subshells, also referred to as orbitals (s, p, the 4d transition series starting at yttrium (Z = 39). This period ends at xenon with thed, f ) in an atom. The distribution of electrons filling up of the 5p orbitals. The sixth periodinto orbitals of an atom is called its electronic configuration. An element’s location in the (n = 6) contains 32 elements and successive electrons enter 6s, 4f, 5d and 6p orbitals, inPeriodic Table reflects the quantum numbers the order — filling up of the 4f orbitals beginsof the last orbital filled. In this section we with cerium (Z = 58) and ends at lutetiumwill observe a direct connection between the (Z = 71) to give the 4f-inner transition serieselectronic configurations of the elements and which is called the lanthanoid series. Thethe long form of the Periodic Table. seventh period (n = 7) is similar to the sixth (a) Electronic Configurations in Periods period with the successive filling up of the 7s, 5f, 6d and 7p orbitals and includes mostThe period indicates the value of n for the of the man-made radioactive elements. Thisoutermost or valence shell. In other words, period will end at the element with atomicsuccessive period in the Periodic Table is number 118 which would belong to the nobleassociated with the filling of the next higher gas family. Filling up of the 5f orbitals afterprincipal energy level (n = 1, n = 2, etc.). It can 82 chemistry actinium (Z = 89) gives the 5f-inner transition a theoretical foundation for the periodic series known as the actinoid series. The 4f- classification. The elements in a vertical column and 5f-inner transition series of elements of the Periodic Table constitute a group or are placed separately in the Periodic Table family and exhibit similar chemical behaviour. to maintain its structure and to preserve the This similarity arises because these elements principle of classification by keeping elements have the same number and same distribution with similar properties in a single column. of electrons in their outermost orbitals. We can classify the elements into four blocks viz., Problem 3.2 s-block, p-block, d-block and f-block How would you justify the presence depending on the type of atomic orbitals that of 18 elements in the 5th period of the are being filled with electrons. This is illustrated Periodic Table? in Fig. 3.3. We notice two exceptions to this Solution categorisation. Strictly, helium belongs to the s-block but its positioning in the p-block When n = 5, l = 0, 1, 2, 3. The order along with other group 18 elements is in which the energy of the available justified because it has a completely filled orbitals 4d, 5s and 5p increases is 5s < 4d < 5p. The total number of orbitals valence shell (1s2) and as a result, exhibits available are 9. The maximum number properties characteristic of other noble gases. of electrons that can be accommodated The other exception is hydrogen. It has only is 18; and therefore 18 elements are one s-electron and hence can be placed in there in the 5th period. group 1 (alkali metals). It can also gain an electron to achieve a noble gas (b) Groupwise Electronic Configurations arrangement and hence it can behave similar to a group 17 (halogen family)Elements in the same vertical column or elements. Because it is a special case, wegroup have similar valence shell electronic shall place hydrogen separately at the top ofconfigurations, the same number of electrons the Periodic Table as shown in Fig. 3.2 andin the outer orbitals, and similar properties. Fig. 3.3. We will briefly discuss the salientFor example, the Group 1 elements (alkali metals) all have ns1 valence shell electronic features of the four types of elements marked in configuration as shown below. the Periodic Table. More about these elements Atomic number Symbol Electronic configuration 3 Li 1s22s1 (or) [He]2s1 11 Na 1s22s22p63s1 (or) [Ne]3s1 19 K 1s22s22p63s23p64s1 (or) [Ar]4s1 37 Rb 1s22s22p63s23p63d104s24p65s1 (or) [Kr]5s1 55 Cs 1s22s22p63s23p63d104s24p64d105s25p66s1 (or) [Xe]6s1 87 Fr [Rn]7s1 Thus it can be seen that the properties of will be discussed later. During the description an element have periodic dependence upon of their features certain terminology has been its atomic number and not on relative atomic used which has been classified in section 3.7. mass. 3.6.1 The s-Block Elements3.6 ELECTRONIC CONFIGURATIONS A N D T Y P E S O F E L E M E N T S : The elements of Group 1 (alkali metals) and s-, p-, d-, f- BLOCKS Group 2 (alkaline earth metals) which have The aufbau (build up) principle and the ns1 and ns2 outermost electronic configuration electronic configuration of atoms provide belong to the s-Block Elements. They are all Classification of Elements and Periodicity in Properties 83 Og Ts Mc that Nh ). METALS ( orbitalsinto the on elements of METALLOIDS based and ) Tabledivision broad ( Periodicthe theis in shown NON-METALS Also), elements of filled. types being Theare( 3.3 Fig. 84 chemistry reactive metals with low ionization enthalpies. valence (oxidation states), paramagnetism and They lose the outermost electron(s) readily to oftenly used as catalysts. However, Zn, Cd and form 1+ ion (in the case of alkali metals) or 2+ Hg which have the electronic configuration, ion (in the case of alkaline earth metals). The (n-1) d10ns2 do not show most of the properties metallic character and the reactivity increase of transition elements. In a way, transition as we go down the group. Because of high metals form a bridge between the chemically reactivity they are never found pure in nature. active metals of s-block elements and the The compounds of the s-block elements, with less active elements of Groups 13 and 14 and thus take their familiar name “Transitionthe exception of those of lithium and beryllium Elements”.are predominantly ionic. 3.6.4 The f-Block Elements3.6.2 The p-Block Elements (Inner-Transition Elements) The p-Block Elements comprise those The two rows of elements at the bottom ofbelonging to Group 13 to 18 and these the Periodic Table, called the Lanthanoids,together with the s-Block Elements are Ce(Z = 58) – Lu(Z = 71) and Actinoids,called the Representative Elements or Main Th(Z = 90) – Lr (Z = 103) are characterised by Group Elements. The outermost electronic the outer electronic configuration (n-2)f1-14 configuration varies from ns2np1 to ns2np6 (n-1)d0–1ns2. The last electron added to each in each period. At the end of each period is element is filled in f- orbital. These two series a noble gas element with a closed valence of elements are hence called the Inner- shell ns2np6 configuration. All the orbitals Transition Elements (f-Block Elements). in the valence shell of the noble gases are They are all metals. Within each series, the completely filled by electrons and it is very properties of the elements are quite similar. difficult to alter this stable arrangement by The chemistry of the early actinoids is the addition or removal of electrons. The more complicated than the corresponding lanthanoids, due to the large number ofnoble gases thus exhibit very low chemical oxidation states possible for these actinoidreactivity. Preceding the noble gas family elements. Actinoid elements are radioactive.are two chemically important groups of non- Many of the actinoid elements have been mademetals. They are the halogens (Group 17) and only in nanogram quantities or even less bythe chalcogens (Group 16). These two groups nuclear reactions and their chemistry is not of elements have highly negative electron fully studied. The elements after uranium are gain enthalpies and readily add one or two called Transuranium Elements. electrons respectively to attain the stable noble gas configuration. The non-metallic Problem 3.3 character increases as we move from left to The elements Z = 117 and 120 have not yetright across a period and metallic character been discovered. In which family/group increases as we go down the group. would you place these elements and also give the electronic configuration in3.6.3 The d-Block Elements (Transition each case. Elements) SolutionThese are the elements of Group 3 to 12 in the centre of the Periodic Table. These are We see from Fig. 3.2, that element characterised by the filling of inner d orbitals with Z = 117, would belong to the halogen family (Group 17) and theby electrons and are therefore referred to as electronic configuration would be [Rn]d-Block Elements. These elements have 5f146d107s27p5. The element with Z = 120,the general outer electronic configuration will be placed in Group 2 (alkaline earth (n-1)d1-10ns0-2 except for Pd where its electronic metals), and will have the electronic configuration is 4d105s0.. They are all metals. configuration [Uuo]8s2. They mostly form coloured ions, exhibit variable Classification of Elements and Periodicity in Properties 85 3.6.5 Metals, Non-metals and Metalloids SolutionIn addition to displaying the classification Metallic character increases down aof elements into s-, p-, d-, and f-blocks, group and decreases along a period asFig. 3.3 shows another broad classification we move from left to right. Hence the of elements based on their properties. The order of increasing metallic character elements can be divided into Metals and is: P < Si < Be < Mg < Na. Non-Metals. Metals comprise more than 78% of all known elements and appear on 3.7 PERIODIC TRENDS IN PROPERTIES the left side of the Periodic Table. Metals are OF ELEMENTS usually solids at room temperature [mercury There are many observable patterns in theis an exception; gallium and caesium also physical and chemical properties of elements have very low melting points (303K and as we descend in a group or move across a 302K, respectively)]. Metals usually have high period in the Periodic Table. For example, melting and boiling points. They are good within a period, chemical reactivity tends to conductors of heat and electricity. They are be high in Group 1 metals, lower in elements malleable (can be flattened into thin sheets by towards the middle of the table, and increases hammering) and ductile (can be drawn into to a maximum in the Group 17 non-metals. wires). In contrast, non-metals are located at Likewise within a group of representative the top right hand side of the Periodic Table. metals (say alkali metals) reactivity increases In fact, in a horizontal row, the property of on moving down the group, whereas within a elements change from metallic on the left to group of non-metals (say halogens), reactivity non-metallic on the right. Non-metals are decreases down the group. But why do the usually solids or gases at room temperature properties of elements follow these trends? with low melting and boiling points (boron And how can we explain periodicity? To and carbon are exceptions). They are poor answer these questions, we must look into the conductors of heat and electricity. Most non- theories of atomic structure and properties metallic solids are brittle and are neither of the atom. In this section we shall discuss malleable nor ductile. The elements become the periodic trends in certain physical and more metallic as we go down a group; the chemical properties and try to explain them non-metallic character increases as one goes in terms of number of electrons and energy from left to right across the Periodic Table. levels. The change from metallic to non-metallic 3.7.1 Trends in Physical Propertiescharacter is not abrupt as shown by the thick There are numerous physical properties ofzig-zag line in Fig. 3.3. The elements (e.g., elements such as melting and boiling points,silicon, germanium, arsenic, antimony and heats of fusion and vaporization, energytellurium) bordering this line and running of atomization, etc. which show periodicdiagonally across the Periodic Table show variations. However, we shall discuss theproperties that are characteristic of both periodic trends with respect to atomic andmetals and non-metals. These elements are ionic radii, ionization enthalpy, electron gaincalled Semi-metals or Metalloids. enthalpy and electronegativity. Problem 3.4 (a) Atomic Radius Considering the atomic number and You can very well imagine that finding the position in the periodic table, arrange size of an atom is a lot more complicated than the following elements in the increasing measuring the radius of a ball. Do you know order of metallic character : Si, Be, Mg, why? Firstly, because the size of an atom Na, P. (~ 1.2 Å i.e., 1.2 × 10–10 m in radius) is very 86 chemistry small. Secondly, since the electron cloud The atomic radii of a few elements are listed surrounding the atom does not have a sharp in Table 3.6. Two trends are obvious. We can boundary, the determination of the atomic explain these trends in terms of nuclear charge size cannot be precise. In other words, there and energy level. The atomic size generally is no practical way by which the size of an decreases across a period as illustrated in individual atom can be measured. However, Fig. 3.4(a) for the elements of the second an estimate of the atomic size can be made by period. It is because within the period the knowing the distance between the atoms in outer electrons are in the same valence shell the combined state. One practical approach to and the effective nuclear charge increases estimate the size of an atom of a non-metallic as the atomic number increases resulting in element is to measure the distance between the increased attraction of electrons to the two atoms when they are bound together nucleus. Within a family or vertical column by a single bond in a covalent molecule and of the periodic table, the atomic radius from this value, the “Covalent Radius” of the increases regularly with atomic number as element can be calculated. For example, the illustrated in Fig. 3.4(b). For alkali metals bond distance in the chlorine molecule (Cl2) and halogens, as we descend the groups, is 198 pm and half this distance (99 pm), is the principal quantum number (n) increases taken as the atomic radius of chlorine. For and the valence electrons are farther frommetals, we define the term “Metallic Radius” the nucleus. This happens because the innerwhich is taken as half the internuclear energy levels are filled with electrons, whichdistance separating the metal cores in the serve to shield the outer electrons from themetallic crystal. For example, the distance pull of the nucleus. Consequently the size ofbetween two adjacent copper atoms in solid the atom increases as reflected in the atomiccopper is 256 pm; hence the metallic radius radii.of copper is assigned a value of 128 pm. For simplicity, in this book, we use the term Note that the atomic radii of noble gases Atomic Radius to refer to both covalent or are not considered here. Being monoatomic, metallic radius depending on whether the their (non-bonded radii) values are very element is a non-metal or a metal. Atomic large. In fact radii of noble gases should be radii can be measured by X-ray or other compared not with the covalent radii but with spectroscopic methods. the van der Waals radii of other elements. Table 3.6(a) Atomic Radii/pm Across the Periods Atom (Period II) Li Be B C N O F Atomic radius 152 111 88 77 74 66 64 Atom (Period III) Na Mg Al Si P S Cl Atomic radius 186 160 143 117 110 104 99 Table 3.6(b) Atomic Radii/pm Down a Family Atom Atomic Atom Atomic (Group I) Radius (Group 17) Radius Li 152 F 64 Na 186 Cl 99 K 231 Br 114 Rb 244 I 133 Cs 262 At 140 Classification of Elements and Periodicity in Properties 87 Fig. 3.4 (a) Variation of atomic radius with atomic Fig. 3.4 (b) Variation of atomic radius with number across the second period atomic number for alkali metals and halogens (b) Ionic Radius cation with the greater positive charge will have a smaller radius because of the greaterThe removal of an electron from an atom attraction of the electrons to the nucleus.results in the formation of a cation, whereas Anion with the greater negative charge willgain of an electron leads to an anion. The have the larger radius. In this case, the netionic radii can be estimated by measuring repulsion of the electrons will outweigh thethe distances between cations and anions nuclear charge and the ion will expand in size.in ionic crystals. In general, the ionic radii of elements exhibit the same trend as the Problem 3.5atomic radii. A cation is smaller than its parent atom because it has fewer electrons Which of the following species will have while its nuclear charge remains the same. the largest and the smallest size? Mg, Mg2+, Al, Al3+.The size of an anion will be larger than that of the parent atom because the addition of one Solution or more electrons would result in increased Atomic radii decrease across a period. repulsion among the electrons and a decrease Cations are smaller than their parent in effective nuclear charge. For example, the atoms. Among isoelectronic species, ionic radius of fluoride ion (F–) is 136 pm the one with the larger positive nuclear whereas the atomic radius of fluorine is only charge will have a smaller radius. 64 pm. On the other hand, the atomic radius Hence the largest species is Mg; the of sodium is 186 pm compared to the ionic smallest one is Al3+. radius of 95 pm for Na+. When we find some atoms and ions which (c) Ionization Enthalpy contain the same number of electrons, we call A quantitative measure of the tendency of them isoelectronic species*. For example, an element to lose electron is given by its O2–, F–, Na+ and Mg2+ have the same number Ionization Enthalpy. It represents the of electrons (10). Their radii would be different energy required to remove an electron from an because of their different nuclear charges. The isolated gaseous atom (X) in its ground state. * Two or more species with same number of atoms, same number of valence electrons and same structure, regardless of the nature of elements involved. 88 chemistry In other words, the first ionization enthalpy for an element X is the enthalpy change (∆i H) for the reaction depicted in equation 3.1. X(g) → X+(g) + e– (3.1) The ionization enthalpy is expressed in units of kJ mol–1. We can define the second ionization enthalpy as the energy required to remove the second most loosely bound electron; it is the energy required to carry out the reaction shown in equation 3.2. X+(g) → X2+(g) + e– (3.2) Energy is always required to remove Fig. 3.5 Variation of first ionization enthalpieselectrons from an atom and hence ionization (∆iH) with atomic number for elementsenthalpies are always positive. The second with Z = 1 to 60ionization enthalpy will be higher than the first ionization enthalpy because it is more can be correlated with their high reactivity. difficult to remove an electron from a positively In addition, you will notice two trends the charged ion than from a neutral atom. In the first ionization enthalpy generally increases same way the third ionization enthalpy will be as we go across a period and decreases higher than the second and so on. The term as we descend in a group. These trends “ionization enthalpy”, if not qualified, is taken are illustrated in Figs. 3.6(a) and 3.6(b) as the first ionization enthalpy. respectively for the elements of the second The first ionization enthalpies of elements period and the first group of the periodic having atomic numbers up to 60 are plotted table. You will appreciate that the ionization in Fig. 3.5. The periodicity of the graph is enthalpy and atomic radius are closely related quite striking. You will find maxima at the properties. To understand these trends, we noble gases which have closed electron shells have to consider two factors : (i) the attraction and very stable electron configurations. On of electrons towards the nucleus, and (ii) the the other hand, minima occur at the alkali repulsion of electrons from each other. The metals and their low ionization enthalpies effective nuclear charge experienced by a 3.6 (a) 3.6 (b) Fig. 3.6(a) First ionization enthalpies (∆iH) of elements of the second period as a function of atomic number (Z) and Fig. 3.6(b) ∆iH of alkali metals as a function of Z. Classification of Elements and Periodicity in Properties 89 valence electron in an atom will be less than the 2s electrons of beryllium. Therefore, it is the actual charge on the nucleus because of easier to remove the 2p-electron from boron “shielding” or “screening” of the valence compared to the removal of a 2s- electron from electron from the nucleus by the intervening beryllium. Thus, boron has a smaller first core electrons. For example, the 2s electron ionization enthalpy than beryllium. Another in lithium is shielded from the nucleus by “anomaly” is the smaller first ionization the inner core of 1s electrons. As a result, the enthalpy of oxygen compared to nitrogen. This valence electron experiences a net positive arises because in the nitrogen atom, three charge which is less than the actual charge 2p-electrons reside in different atomic orbitals of +3. In general, shielding is effective when (Hund’s rule) whereas in the oxygen atom, the orbitals in the inner shells are completely two of the four 2p-electrons must occupy the filled. This situation occurs in the case of same 2p-orbital resulting in an increased alkali metals which have single outermost electron-electron repulsion. Consequently, ns-electron preceded by a noble gas electronic it is easier to remove the fourth 2p-electron configuration. from oxygen than it is, to remove one of the When we move from lithium to fluorine three 2p-electrons from nitrogen. across the second period, successive electrons are added to orbitals in the same principal Problem 3.6 quantum level and the shielding of the nuclear The first ionization enthalpy (∆i H ) values charge by the inner core of electrons does of the third period elements, Na, Mg and not increase very much to compensate for Si are respectively 496, 737 and 786 kJ the increased attraction of the electron to the mol–1. Predict whether the first ∆i H value nucleus. Thus, across a period, increasing for Al will be more close to 575 or 760 kJ nuclear charge outweighs the shielding. mol–1 ? Justify your answer. Consequently, the outermost electrons are Solution held more and more tightly and the ionization It will be more close to 575 kJ mol–1.enthalpy increases across a period. As we go The value for Al should be lower thandown a group, the outermost electron being that of Mg because of effective shielding increasingly farther from the nucleus, there is of 3p electrons from the nucleus by an increased shielding of the nuclear charge 3s-electrons. by the electrons in the inner levels. In this case, increase in shielding outweighs the (d) Electron Gain Enthalpy increasing nuclear charge and the removal of When an electron is added to a neutralthe outermost electron requires less energy gaseous atom (X) to convert it into a negativedown a group. ion, the enthalpy change accompanying the From Fig. 3.6(a), you will also notice that process is defined as the Electron Gain the first ionization enthalpy of boron (Z = 5) Enthalpy (∆egH). Electron gain enthalpyis slightly less than that of beryllium (Z = 4) provides a measure of the ease with which even though the former has a greater nuclear an atom adds an electron to form anion as charge. When we consider the same principal represented by equation 3.3. quantum level, an s-electron is attracted to the X(g) + e– → X –(g) (3.3)nucleus more than a p-electron. In beryllium, the electron removed during the ionization is Depending on the element, the process an s-electron whereas the electron removed of adding an electron to the atom can be during ionization of boron is a p-electron. The either endothermic or exothermic. For many penetration of a 2s-electron to the nucleus is elements energy is released when an electron more than that of a 2p-electron; hence the 2p is added to the atom and the electron gain electron of boron is more shielded from the enthalpy is negative. For example, group nucleus by the inner core of electrons than 17 elements (the halogens) have very high 90 chemistry Table 3.7 Electron Gain Enthalpies* / (kJ mol–1) of Some Main Group Elements Group 1 ∆egH Group 16 ∆egH Group 17 ∆egH Group 0 ∆egH H – 73 He + 48 Li – 60 O – 141 F – 328 Ne + 116 Na – 53 S – 200 Cl – 349 Ar + 96 K – 48 Se – 195 Br – 325 Kr + 96 Rb – 47 Te – 190 I – 295 Xe + 77 Cs – 46 Po – 174 At – 270 Rn + 68 negative electron gain enthalpies because they can attain stable noble gas electronic Problem 3.7 configurations by picking up an electron. Which of the following will have the most On the other hand, noble gases have large negative electron gain enthalpy and positive electron gain enthalpies because the which the least negative? electron has to enter the next higher principal P, S, Cl, F. quantum level leading to a very unstable Explain your answer. electronic configuration. It may be noted that Solution electron gain enthalpies have large negative Electron gain enthalpy generallyvalues toward the upper right of the periodic becomes more negative across atable preceding the noble gases. period as we move from left to right. The variation in electron gain enthalpies of Within a group, electron gain enthalpy elements is less systematic than for ionization becomes less negative down a group. enthalpies. As a general rule, electron gain However, adding an electron to the enthalpy becomes more negative with increase 2p-orbital leads to greater repulsion in the atomic number across a period. The than adding an electron to the larger effective nuclear charge increases from left to 3p-orbital. Hence the element with right across a period and consequently it will most negative electron gain enthalpy is be easier to add an electron to a smaller atom chlorine; the one with the least negative since the added electron on an average would electron gain enthalpy is phosphorus. be closer to the positively charged nucleus. We should also expect electron gain enthalpy to (e) Electronegativity become less negative as we go down a group A qualitative measure of the ability of an atombecause the size of the atom increases and in a chemical compound to attract sharedthe added electron would be farther from the electrons to itself is called electronegativity.nucleus. This is generally the case (Table Unlike ionization enthalpy and electron gain3.7). However, electron gain enthalpy of O or enthalpy, it is not a measureable quantity.F is less negative than that of the succeeding However, a number of numerical scales ofelement. This is because when an electron is added to O or F, the added electron goes to electronegativity of elements viz., Pauling the smaller n = 2 quantum level and suffers scale, Mulliken-Jaffe scale, Allred-Rochow significant repulsion from the other electrons scale have been developed. The one which present in this level. For the n = 3 quantum is the most widely used is the Pauling scale. level (S or Cl), the added electron occupies Linus Pauling, an American scientist, in 1922 a larger region of space and the electron- assigned arbitrarily a value of 4.0 to fluorine, electron repulsion is much less. the element considered to have the greatest * In many books, the negative of the enthalpy change for the process depicted in equation 3.3 is defined as the ELECTRON AFFINITY (Ae ) of the atom under consideration. If energy is released when an electron is added to an atom, the electron affinity is taken as positive, contrary to thermodynamic convention. If energy has to be supplied to add an electron to an atom, then the electron affinity of the atom is assigned a negative sign. However, electron affinity is defined as absolute zero and, therefore at any other temperature (T) heat capacities of the reactants and the products have to be taken into account in ∆egH = –Ae – 5/2 RT. Classification of Elements and Periodicity in Properties 91 ability to attract electrons. Approximate On the same account electronegativity values values for the electronegativity of a few decrease with the increase in atomic radii elements are given in Table 3.8(a) down a group. The trend is similar to that of ionization enthalpy. The electronegativity of any given element Knowing the relationship betweenis not constant; it varies depending on the electronegativity and atomic radius, canelement to which it is bound. Though it is you now visualise the relationship betweennot a measurable quantity, it does provide a electronegativity and non-metallic properties?means of predicting the nature of force that Non-metallic elements have strong tendencyholds a pair of atoms together – a relationship that you will explore later. Electronegativity generally increases across a period from left to right (say from lithium to fluorine) and decrease down a group (say from fluorine to astatine) in the periodic table. How can these trends be explained? Can the electronegativity be related to atomic radii, which tend to decrease across each period from left to right, but increase down each group ? The attraction between the outer (or valence) electrons and the nucleus increases as the atomic radius decreases in a period. The electronegativity also increases. Fig. 3.7 The periodic trends of elements in the periodic table Table 3.8(a) Electronegativity Values (on Pauling scale) Across the Periods Atom (Period II) Li Be B C N O F Electronegativity 1.0 1.5 2.0 2.5 3.0 3.5 4.0 Atom (Period III) Na Mg Al Si P S Cl Electronegativity 0.9 1.2 1.5 1.8 2.1 2.5 3.0 Table 3.8(b) Electronegativity Values (on Pauling scale) Down a Family Atom Electronegativity Atom Electronegativity (Group I) Value (Group 17) Value Li 1.0 F 4.0 Na 0.9 Cl 3.0 K 0.8 Br 2.8 Rb 0.8 I 2.5 Cs 0.7 At 2.2 92 chemistry to gain electrons. Therefore, electronegativity is with outer electronic configuration 2s22p5, directly related to that non-metallic properties shares one electron with oxygen in the OF2 of elements. It can be further extended to say molecule. Being highest electronegative that the electronegativity is inversely related element, fluorine is given oxidation state to the metallic properties of elements. Thus, –1. Since there are two fluorine atoms in the increase in electronegativities across this molecule, oxygen with outer electronic a period is accompanied by an increase configuration 2s22p4 shares two electrons in non-metallic properties (or decrease in with fluorine atoms and thereby exhibits metallic properties) of elements. Similarly, the oxidation state +2. In Na2O, oxygen being decrease in electronegativity down a group is more electronegative accepts two electrons, accompanied by a decrease in non-metallic one from each of the two sodium atoms and, properties (or increase in metallic properties) thus, shows oxidation state –2. On the other of elements. hand sodium with electronic configuration All these periodic trends are summarised 3s1 loses one electron to oxygen and is given in Figure 3.7. oxidation state +1. Thus, the oxidation state of an element in a particular compound can 3.7.2 Periodic Trends in Chemical be defined as the charge acquired by its atom Properties on the basis of electronegative consideration Most of the trends in chemical properties of from other atoms in the molecule. elements, such as diagonal relationships, inert pair effect, effects of lanthanoid contraction Problem 3.8 etc. will be dealt with along the discussion Using the Periodic Table, predict the of each group in later units. In this section formulas of compounds which might we shall study the periodicity of the valence be formed by the following pairs of state shown by elements and the anomalous elements; (a) silicon and bromine properties of the second period elements (from (b) aluminium and sulphur. lithium to fluorine). Solution (a) Periodicity of Valence or Oxidation (a) Silicon is group 14 element with States a valence of 4; bromine belongs to the halogen family with a valenceThe valence is the most characteristic property of 1. Hence the formula of theof the elements and can be understood in compound formed would be SiBr4.terms of their electronic configurations. The (b) Aluminium belongs to groupvalence of representative elements is usually 13 with a valence of 3; sulphur(though not necessarily) equal to the number belongs to group 16 elements withof electrons in the outermost orbitals and/or a valence of 2. Hence, the formulaequal to eight minus the number of outermost of the compound formed would be electrons as shown below. Al2S3. Nowadays the term oxidation state is Some periodic trends observed in thefrequently used for valence. Consider the valence of elements (hydrides and oxides)two oxygen containing compounds: OF2 and are shown in Table 3.9. Other such periodicNa2O. The order of electronegativity of the trends which occur in the chemical behaviourthree elements involved in these compounds of the elements are discussed elsewhere inis F > O > Na. Each of the atoms of fluorine, Group 1 2 13 14 15 16 17 18 Number of valence 1 2 3 4 5 6 7 8 electron alence 1 2 3 4 3,5 2,6 1,7 0,8 Classification of Elements and Periodicity in Properties 93 Table 3.9 Periodic Trends in Valence of Elements as shown by the Formulas of Their Compounds Group 1 2 13 14 15 16 17 Formula of LiH CaH2 B2H6 CH4 NH3 H2O HF hydride NaH AlH3 SiH4 PH3 H2S HCl KH GeH4 AsH3 H2Se HBr SnH4 H2Te HI Formula Li2O MgO B2O3 CO2 N2O3, N2O5 – of oxide Na2O CaO Al2O3 SiO2 P4O6, P4O10 SO3 Cl2 O7 SrO K2O Ga2O3 GeO2 As2O3, As2O5 SeO3 – BaO In2O3 SnO2 Sb2O3, Sb2O5 TeO3 – PbO2 Bi2O3 – – this book. There are many elements which the second element of the following group exhibit variable valence. This is particularly i.e., magnesium and aluminium, respectively. characteristic of transition elements and This sort of similarity is commonly referred actinoids, which we shall study later. to as diagonal relationship in the periodic properties. (b) Anomalous Properties of Second Period Elements What are the reasons for the different chemical behaviour of the first member ofThe first element of each of the groups 1 a group of elements in the s- and p-blocks(lithium) and 2 (beryllium) and groups 13-17 compared to that of the subsequent members(boron to fluorine) differs in many respects in the same group? The anomalous behaviourfrom the other members of their respective is attributed to their small size, large charge/group. For example, lithium unlike other radius ratio and high electronegativity of the alkali metals, and beryllium unlike other elements. In addition, the first member of alkaline earth metals, form compounds with group has only four valence orbitals (2s and pronounced covalent character; the other 2p) available for bonding, whereas the second members of these groups predominantly member of the groups have nine valence form ionic compounds. In fact the behaviour orbitals (3s, 3p, 3d). As a consequence of of lithium and beryllium is more similar with this, the maximum covalency of the first member of each group is 4 (e.g., boron Property Element can only form  BF4 , whereas the other members of the groups can expand their Metallic radius M/pm Li Be B valence shell to accommodate more than 152 111 88 four pairs of electrons e.g., aluminium forms). Furthermore, the first Na Mg Al  AlF6 3  186 160 143 member of p-block elements displays greater ability to form pπ – pπ multiple Ionic radius M+/pm Li Be bonds to itself (e.g., C = C, C ≡ C, 76 31 N = N, N ≡ Ν) and to other second period Na Mg elements (e.g., C = O, C = N, C ≡ N, 102 72 N = O) compared to subsequent members of the same group. 94 chemistry here it can be directly related to the metallic Problem 3.9 and non-metallic character of elements. Thus, Are the oxidation state and covalency of the metallic character of an element, which Al in [AlCl(H2O)5]2+ same ? is highest at the extremely left decreases and Solution the non-metallic character increases while moving from left to right across the period. No. The oxidation state of Al is +3 and the covalency is 6. The chemical reactivity of an element can be best shown by its reactions with oxygen and 3.7.3 Periodic Trends and Chemical halogens. Here, we shall consider the reaction Reactivity of the elements with oxygen only. Elements on two extremes of a period easily combineWe have observed the periodic trends in with oxygen to form oxides. The normal oxidecertain fundamental properties such as formed by the element on extreme left is theatomic and ionic radii, ionization enthalpy, most basic (e.g., Na2O), whereas that formedelectron gain enthalpy and valence. We know by now that the periodicity is related to by the element on extreme right is the most electronic configuration. That is, all chemical acidic (e.g., Cl2O7). Oxides of elements in the and physical properties are a manifestation of centre are amphoteric (e.g., Al2O3, As2O3) or the electronic configuration of elements. We neutral (e.g., CO, NO, N2O). Amphoteric oxides shall now try to explore relationships between behave as acidic with bases and as basic with these fundamental properties of elements with acids, whereas neutral oxides have no acidic their chemical reactivity. or basic properties. The atomic and ionic radii, as we know, Problem 3.10generally decrease in a period from left to right. As a consequence, the ionization enthalpies Show by a chemical reaction with water that Na2O is a basic oxide and Cl2O7 isgenerally increase (with some exceptions as an acidic oxide.outlined in section 3.7.1(a)) and electron gain enthalpies become more negative across a Solution period. In other words, the ionization enthalpy Na2O with water forms a strong base of the extreme left element in a period is the whereas Cl2O7 forms strong acid. least and the electron gain enthalpy of the Na2O + H2O → 2NaOH element on the extreme right is the highest Cl2O7 + H2O → 2HClO4 negative (note : noble gases having completely Their basic or acidic nature can befilled shells have rather positive electron qualitatively tested with litmus paper.gain enthalpy values). This results into high chemical reactivity at the two extremes and the lowest in the centre. Thus, the maximum Among transition metals (3d series), the chemical reactivity at the extreme left (among change in atomic radii is much smaller as alkali metals) is exhibited by the loss of an compared to those of representative elements electron leading to the formation of a cation across the period. The change in atomic radii and at the extreme right (among halogens) is still smaller among inner-transition metals shown by the gain of an electron forming (4f series). The ionization enthalpies are an anion. This property can be related with intermediate between those of s- and p-blocks. the reducing and oxidizing behaviour of the As a consequence, they are less electropositive elements which you will learn later. However, than group 1 and 2 metals. Classification of Elements and Periodicity in Properties 95 In a group, the increase in atomic and increases down the group and non-metallic ionic radii with increase in atomic number character decreases. This trend can be related generally results in a gradual decrease in with their reducing and oxidizing property ionization enthalpies and a regular decrease which you will learn later. In the case of (with exception in some third period elements transition elements, however, a reverse trend as shown in section 3.7.1(d)) in electron is observed. This can be explained in terms of gain enthalpies in the case of main group atomic size and ionization enthalpy. elements. Thus, the metallic character SUMMARY In this Unit, you have studied the development of the Periodic Law and the Periodic Table. Mendeleev’s Periodic Table was based on atomic masses. Modern Periodic Table arranges the elements in the order of their atomic numbers in seven horizontal rows (periods) and eighteen vertical columns (groups or families). Atomic numbers in a period are consecutive, whereas in a group they increase in a pattern. Elements of the same group have similar valence shell electronic configuration and, therefore, exhibit similar chemical properties. However, the elements of the same period have incrementally increasing number of electrons from left to right, and, therefore, have different valencies. Four types of elements can be recognized in the periodic table on the basis of their electronic configurations. These are s-block, p-block, d-block and f-block elements. Hydrogen with one electron in the 1s orbital occupies a unique position in the periodic table. Metals comprise more than seventy eight per cent of the known elements. Non-metals, which are located at the top of the periodic table, are less than twenty in number. Elements which lie at the border line between metals and non-metals (e.g., Si, Ge, As) are called metalloids or semi-metals. Metallic character increases with increasing atomic number in a group whereas decreases from left to right in a period. The physical and chemical properties of elements vary periodically with their atomic numbers. Periodic trends are observed in atomic sizes, ionization enthalpies, electron gain enthalpies, electronegativity and valence. The atomic radii decrease while going from left to right in a period and increase with atomic number in a group. Ionization enthalpies generally increase across a period and decrease down a group. Electronegativity also shows a similar trend. Electron gain enthalpies, in general, become more negative across a period and less negative down a group. There is some periodicity in valence, for example, among representative elements, the valence is either equal to the number of electrons in the outermost orbitals or eight minus this number. Chemical reactivity is highest at the two extremes of a period and is lowest in the centre. The reactivity on the left extreme of a period is because of the ease of electron loss (or low ionization enthalpy). Highly reactive elements do not occur in nature in free state; they usually occur in the combined form. Oxides formed of the elements on the left are basic and of the elements on the right are acidic in nature. Oxides of elements in the centre are amphoteric or neutral. 96 chemistry Exercises 3.1 What is the basic theme of organisation in the periodic table? 3.2 Which important property did Mendeleev use to classify the elements in his periodic table and did he stick to that? 3.3 What is the basic difference in approach between the Mendeleev’s Periodic Law and the Modern Periodic Law? 3.4 On the basis of quantum numbers, justify that the sixth period of the periodic table should have 32 elements. 3.5 In terms of period and group where would you locate the element with Z =114? 3.6 Write the atomic number of the element present in the third period and seventeenth group of the periodic table. 3.7 Which element do you think would have been named by (i) Lawrence Berkeley Laboratory (ii) Seaborg’s group? 3.8 Why do elements in the same group have similar physical and chemical properties? 3.9 What does atomic radius and ionic radius really mean to you? 3.10 How do atomic radius vary in a period and in a group? How do you explain the variation? 3.11 What do you understand by isoelectronic species? Name a species that will be isoelectronic with each of the following atoms or ions. (i) F– (ii) Ar (iii) Mg2+ (iv) Rb+ 3.12 Consider the following species : N3–, O2–, F–, Na+, Mg2+ and Al3+ (a) What is common in them? (b) Arrange them in the order of increasing ionic radii. 3.13 Explain why cation are smaller and anions larger in radii than their parent atoms? 3.14 What is the significance of the terms — ‘isolated gaseous atom’ and ‘ground state’ while defining the ionization enthalpy and electron gain enthalpy? Hint : Requirements for comparison purposes. 3.15 Energy of an electron in the ground state of the hydrogen atom is –2.18×10–18J. Calculate the ionization enthalpy of atomic hydrogen in terms of J mol–1. Hint: Apply the idea of mole concept to derive the answer. 3.16 Among the second period elements the actual ionization enthalpies are in the order Li < B < Be < C < O < N < F < Ne. Explain why (i) Be has higher ∆i H than B (ii) O has lower ∆i H than N and F? Classification of Elements and Periodicity in Properties 97 3.17 How would you explain the fact that the first ionization enthalpy of sodium is lower than that of magnesium but its second ionization enthalpy is higher than that of magnesium? 3.18 What are the various factors due to which the ionization enthalpy of the main group elements tends to decrease down a group? 3.19 The first ionization enthalpy values (in kJ mol–1) of group 13 elements are : B Al Ga In Tl 801 577 579 558 589 How would you explain this deviation from the general trend ? 3.20 Which of the following pairs of elements would have a more negative electron gain enthalpy? (i) O or F (ii) F or Cl 3.21 Would you expect the second electron gain enthalpy of O as positive, more negative or less negative than the first? Justify your answer. 3.22 What is the basic difference between the terms electron gain enthalpy and electronegativity? 3.23 How would you react to the statement that the electronegativity of N on Pauling scale is 3.0 in all the nitrogen compounds? 3.24 Describe the theory associated with the radius of an atom as it (a) gains an electron (b) loses an electron 3.25 Would you expect the first ionization enthalpies for two isotopes of the same element to be the same or different? Justify your answer. 3.26 What are the major differences between metals and non-metals? 3.27 Use the periodic table to answer the following questions. (a) Identify an element with five electrons in the outer subshell. (b) Identify an element that would tend to lose two electrons. (c) Identify an element that would tend to gain two electrons. (d) Identify the group having metal, non-metal, liquid as well as gas at the room temperature. 3.28 The increasing order of reactivity among group 1 elements is Li < Na < K < Rb <Cs whereas that among group 17 elements is F > CI > Br > I. Explain. 3.29 Write the general outer electronic configuration of s-, p-, d- and f- block elements. 3.30 Assign the position of the element having outer electronic configuration (i) ns2np4 for n=3 (ii) (n-1)d2ns2 for n=4, and (iii) (n-2) f 7 (n-1)d1ns2 for n=6, in the periodic table. 98 chemistry 3.31 The first (∆iH1) and the second (∆iH2) ionization enthalpies (in kJ mol–1) and the (∆egH) electron gain enthalpy (in kJ mol–1) of a few elements are given below: Elements ∆H1 ∆H2 ∆egH I 520 7300 –60 II 419 3051 –48 III 1681 3374 –328 IV 1008 1846 –295 V 2372 5251 +48 VI 738 1451 –40 Which of the above elements is likely to be : (a) the least reactive element. (b) the most reactive metal. (c) the most reactive non-metal. (d) the least reactive non-metal. (e) the metal which can form a stable binary halide of the formula MX2(X=halogen). (f) the metal which can form a predominantly stable covalent halide of the formula MX (X=halogen)? 3.32 Predict the formulas of the stable binary compounds that would be formed by the combination of the following pairs of elements. (a) Lithium and oxygen (b) Magnesium and nitrogen (c) Aluminium and iodine (d) Silicon and oxygen (e) Phosphorus and fluorine (f) Element 71 and fluorine 3.33 In the modern periodic table, the period indicates the value of : (a) atomic number (b) atomic mass (c) principal quantum number (d) azimuthal quantum number. 3.34 Which of the following statements related to the modern periodic table is incorrect? (a) The p-block has 6 columns, because a maximum of 6 electrons can occupy all the orbitals in a p-shell. (b) The d-block has 8 columns, because a maximum of 8 electrons can occupy all the orbitals in a d-subshell. (c) Each block contains a number of columns equal to the number of electrons that can occupy that subshell. (d) The block indicates value of azimuthal quantum number (l) for the last subshell that received electrons in building up the electronic configuration. Classification of Elements and Periodicity in Properties 99 3.35 Anything that influences the valence electrons will affect the chemistry of the element. Which one of the following factors does not affect the valence shell? (a) Valence principal quantum number (n) (b) Nuclear charge (Z ) (c) Nuclear mass (d) Number of core electrons. 3.36 The size of isoelectronic species — F–, Ne and Na+ is affected by (a) nuclear charge (Z ) (b) valence principal quantum number (n) (c) electron-electron interaction in the outer orbitals (d) none of the factors because their size is the same. 3.37 Which one of the following statements is incorrect in relation to ionization enthalpy? (a) Ionization enthalpy increases for each successive electron. (b) The greatest increase in ionization enthalpy is experienced on removal of electron from core noble gas configuration. (c) End of valence electrons is marked by a big jump in ionization enthalpy. (d) Removal of electron from orbitals bearing lower n value is easier than from orbital having higher n value. 3.38 Considering the elements B, Al, Mg, and K, the correct order of their metallic character is : (a) B > Al > Mg > K (b) Al > Mg > B > K (c) Mg > Al > K > B (d) K > Mg > Al > B 3.39 Considering the elements B, C, N, F, and Si, the correct order of their non-metallic character is : (a) B > C > Si > N > F (b) Si > C > B > N > F (c) F > N > C > B > Si (d) F > N > C > Si > B 3.40 Considering the elements F, Cl, O and N, the correct order of their chemical reactivity in terms of oxidizing property is : (a) F > Cl > O > N (b) F > O > Cl > N (c) Cl > F > O > N (d) O > F > N > Cl Unit 4 CHEMICAL BONDING AND MOLECULAR STRUCTURE Scientists are constantly discovering new compounds, orderly arranging the facts about them, trying to explain with the existing knowledge, organising to modify the earlier views or evolve theories for explaining the newly After studying this Unit, you will be observed facts. able to • understand Kössel-Lewis approach to chemical bonding; • explain the octet rule and its Matter is made up of one or different type of elements. limitations, draw Lewis structures Under normal conditions no other element exists as an of simple molecules; independent atom in nature, except noble gases. However, • explain the formation of different a group of atoms is found to exist together as one species types of bonds; having characteristic properties. Such a group of atoms is called a molecule. Obviously there must be some force • describe the VSEPR theory and which holds these constituent atoms together in the predict the geometry of simple molecules. The attractive force which holds various molecules; constituents (atoms, ions, etc.) together in different • explain the valence bond chemical species is called a chemical bond. Since the approach for the formation of formation of chemical compounds takes place as a result of covalent bonds; combination of atoms of various elements in different ways, • predict the directional properties it raises many questions. Why do atoms combine? Why are of covalent bonds; only certain combinations possible? Why do some atoms combine while certain others do not? Why do molecules• explain the different types of hybridisation involving s, p and possess definite shapes? To answer such questions different d orbitals and draw shapes of theories and concepts have been put forward from time simple covalent molecules; to time. These are Kössel-Lewis approach, Valence Shell Electron Pair Repulsion (VSEPR) Theory, Valence Bond (VB)• describe the molecular orbital theory of homonuclear diatomic Theory and Molecular Orbital (MO) Theory. The evolution molecules; of various theories of valence and the interpretation of the nature of chemical bonds have closely been related to • explain the concept of hydrogen the developments in the understanding of the structure bond. of atom, the electronic configuration of elements and the periodic table. Every system tends to be more stable and bonding is nature’s way of lowering the energy of the system to attain stability. Reprint 2025-26 Chemical Bonding And Molecular Structure 101

1.3 Define the following terms: (i) Mole fraction (ii) Molality (iii) Molarity (iv) Mass percentage.

1.37 Vapour pressures of pure acetone and chloroform at 328 K are 741.8 mm Hg and 632.8 mm Hg respectively. Assuming that they form ideal solution over the entire range of composition, plot ptotal, pchloroform, and pacetone as a function of xacetone. The experimental data observed for different compositions of mixture is: 100 x xacetone 0 11.8 23.4 36.0 50.8 58.2 64.5 72.1 pacetone /mm Hg 0 54.9 110.1 202.4 322.7 405.9 454.1 521.1 pchloroform /mm Hg 632.8 548.1 469.4 359.7 257.7 193.6 161.2 120.7 Plot this data also on the same graph paper. Indicate whether it has positive deviation or negative deviation from the ideal solution. 1.38 Benzene and toluene form ideal solution over the entire range of composition. The vapour pressure of pure benzene and toluene at 300 K are 50.71 mm Hg and 32.06 mm Hg respectively. Calculate the mole fraction of benzene in vapour phase if 80 g of benzene is mixed with 100 g of toluene. 1.39 The air is a mixture of a number of gases. The major components are oxygen and nitrogen with approximate proportion of 20% is to 79% by volume at 298 K. The water is in equilibrium with air at a pressure of 10 atm. At 298 K if the Henry’s law constants for oxygen and nitrogen at 298 K are 3.30 × 107 mm and 6.51 × 107 mm respectively, calculate the composition of these gases in water. 1.40 Determine the amount of CaCl2 (i = 2.47) dissolved in 2.5 litre of water such that its osmotic pressure is 0.75 atm at 27° C. 1.41 Determine the osmotic pressure of a solution prepared by dissolving 25 mg of K2SO4 in 2 litre of water at 25° C, assuming that it is completely dissociated. Answers to Some Intext Questions 1.1 C6H6 = 15.28%, CCl4 = 84.72% 1.2 0.459, 0.541 1.3 0.024 M, 0.03 M 1.4 36.946 g 1.5 1.5 mol kg–1 , 1.45 mol L–1 0.0263 1.9 23.4 mm Hg 1.10 121.67 g 1.11 5.077 g 1.12 30.96 Pa Chemistry 30 Reprint 2025-26 UnitUnitUnitUnit Unit22 Objectives ElectrochemistryElectrochemistry After studying this Unit, you will be able to · describe an electrochemical cell Chemical reactions can be used to produce electrical energy, and differentiate between galvanic conversely, electrical energy can be used to carry out chemical and electrolytic cells; reactions that do not proceed spontaneously.· apply Nernst equation for calculating the emf of galvanic cell and define standard potential of Electrochemistry is the study of production of the cell; · derive relation between standard electricity from energy released during spontaneous potential of the cell, Gibbs energy chemical reactions and the use of electrical energy of cell reaction and its equilibrium to bring about non-spontaneous chemical constant; transformations. The subject is of importance both · define resistivity (r), conductivity for theoretical and practical considerations. A large (k) and molar conductivity (✆m) of number of metals, sodium hydroxide, chlorine, ionic solutions; fluorine and many other chemicals are produced by · differentiate between ionic electrochemical methods. Batteries and fuel cells (electrolytic) and electronic convert chemical energy into electrical energy and are conductivity; · describe the method for used on a large scale in various instruments and measurement of conductivity of devices. The reactions carried out electrochemically electrolytic solutions and can be energy efficient and less polluting. Therefore, calculation of their molar study of electrochemistry is important for creating new conductivity; technologies that are ecofriendly. The transmission of · justify the variation of sensory signals through cells to brain and vice versa conductivity and molar and communication between the cells are known to conductivity of solutions with have electrochemical origin. Electrochemistry, is change in their concentration and therefore, a very vast and interdisciplinary subject. In define m (molar conductivity at this Unit, we will cover only some of its important zero concentration or infinite elementary aspects. dilution); · enunciate Kohlrausch law and learn its applications; · understand quantitative aspects of electrolysis; · describe the construction of some primary and secondary batteries and fuel cells; · explain corrosion as an electrochemical process. Reprint 2025-26 2.12.12.12.12.1 ElectrochemicalElectrochemicalElectrochemicalElectrochemicalElectrochemical We had studied the construction and functioning of Daniell cell CellsCellsCellsCellsCells (Fig. 2.1). This cell converts the chemical energy liberated during the redox reaction Zn(s) + Cu2+(aq) ® Zn2+(aq) + Cu(s) (2.1) to electrical energy and has an electrical potential equal to 1.1 V when concentration of Zn2+ and Cu2+ ions is unity (1 mol dm–3)*. Such a device is called a galvanic or a voltaic cell. If an external opposite potential is applied in the galvanic cell [Fig. 2.2(a)] and increased slowly, we find that the reaction continues to take place till the opposing voltage reaches the value 1.1 V [Fig. 2.2(b)] when, the reaction stops altogether and no current flows through the cell. Any further increase in the external potential again starts the reaction but in the opposite direction [Fig. 2.2(c)]. It now functions as an electrolytic cell, a device for using electrical energy to carry non-spontaneous chemical reactions. Both types of cells are Fig. 2.1: Daniell cell having electrodes of zinc and quite important and we shall study some of copper dipping in the solutions of their their salient features in the following pages. respective salts. Eext < 1.1V Eext = 1.1V (a) (b) e current cathodeanode I=0 Zn salt Cu Zn Cu -ve bridge +ve When Eext = 1.1 V (i) No flow of electrons or current. (ii) No chemical ZnSO4 CuSO4 ZnSO4 CuSO4 reaction. When Eext < 1.1 V Eext >1.1 (i) Electrons flow from Zn rod to (c) Cu rod hence current flows from Cu to Zn. – When Eext > 1.1 V (ii) Zn dissolves at anode and e (i) Electrons flow copper deposits at cathode. Cathode Current Anode from Cu to Zn +ve –ve and current flows Zn Cu from Zn to Cu. Fig. 2.2 (ii) Zinc is deposited Functioning of Daniell at the zinc cell when external electrode and voltage Eext opposing the copper dissolves at cell potential is applied. copper electrode. *Strictly speaking activity should be used instead of concentration. It is directly proportional to concentration. In dilute solutions, it is equal to concentration. You will study more about it in higher classes. Chemistry 32 Reprint 2025-26 2.22.22.22.22.2 GalvanicGalvanicGalvanicGalvanicGalvanic CellsCellsCellsCellsCells As mentioned earlier a galvanic cell is an electrochemical cell that converts the chemical energy of a spontaneous redox reaction into electrical energy. In this device the Gibbs energy of the spontaneous redox reaction is converted into electrical work which may be used for running a motor or other electrical gadgets like heater, fan, geyser, etc. Daniell cell discussed earlier is one such cell in which the following redox reaction occurs. Zn(s) + Cu2+(aq) ® Zn2+ (aq) + Cu(s) This reaction is a combination of two half reactions whose addition gives the overall cell reaction: (i) Cu2+ + 2e– ® Cu(s) (reduction half reaction) (2.2) (ii) Zn(s) ® Zn2+ + 2e– (oxidation half reaction) (2.3) These reactions occur in two different portions of the Daniell cell. The reduction half reaction occurs on the copper electrode while the oxidation half reaction occurs on the zinc electrode. These two portions of the cell are also called half-cells or redox couples. The copper electrode may be called the reduction half cell and the zinc electrode, the oxidation half-cell. We can construct innumerable number of galvanic cells on the pattern of Daniell cell by taking combinations of different half-cells. Each half- cell consists of a metallic electrode dipped into an electrolyte. The two half-cells are connected by a metallic wire through a voltmeter and a switch externally. The electrolytes of the two half-cells are connected internally through a salt bridge as shown in Fig. 2.1. Sometimes, both the electrodes dip in the same electrolyte solution and in such cases we do not require a salt bridge. At each electrode-electrolyte interface there is a tendency of metal ions from the solution to deposit on the metal electrode trying to make it positively charged. At the same time, metal atoms of the electrode have a tendency to go into the solution as ions and leave behind the electrons at the electrode trying to make it negatively charged. At equilibrium, there is a separation of charges and depending on the tendencies of the two opposing reactions, the electrode may be positively or negatively charged with respect to the solution. A potential difference develops between the electrode and the electrolyte which is called electrode potential. When the concentrations of all the species involved in a half-cell is unity then the electrode potential is known as standard electrode potential. According to IUPAC convention, standard reduction potentials are now called standard electrode potentials. In a galvanic cell, the half-cell in which oxidation takes place is called anode and it has a negative potential with respect to the solution. The other half-cell in which reduction takes place is called cathode and it has a positive potential with respect to the solution. Thus, there exists a potential difference between the two electrodes and as soon as the switch is in the on position the electrons flow from negative electrode to positive electrode. The direction of current flow is opposite to that of electron flow. 33 Electrochemistry Reprint 2025-26 The potential difference between the two electrodes of a galvanic cell is called the cell potential and is measured in volts. The cell potential is the difference between the electrode potentials (reduction potentials) of the cathode and anode. It is called the cell electromotive force (emf) of the cell when no current is drawn through the cell. It is now an accepted convention that we keep the anode on the left and the cathode on the right while representing the galvanic cell. A galvanic cell is generally represented by putting a vertical line between metal and electrolyte solution and putting a double vertical line between the two electrolytes connected by a salt bridge. Under this convention the emf of the cell is positive and is given by the potential of the half- cell on the right hand side minus the potential of the half-cell on the left hand side i.e., Ecell = Eright – Eleft This is illustrated by the following example: Cell reaction: Cu(s) + 2Ag+(aq) ¾® Cu2+(aq) + 2 Ag(s) (2.4) Half-cell reactions: Cathode (reduction): 2Ag+(aq) + 2e– ® 2Ag(s) (2.5) Anode (oxidation): Cu(s) ® Cu2+(aq) + 2e– (2.6) It can be seen that the sum of (3.5) and (3.6) leads to overall reaction (2.4) in the cell and that silver electrode acts as a cathode and copper electrode acts as an anode. The cell can be represented as: Cu(s)|Cu2+(aq)||Ag+(aq)|Ag(s) and we have Ecell = Eright – Eleft = EAg+úAg – ECu2+úCu (2.7) 2.2.1 The potential of individual half-cell cannot be measured. We can Measurement measure only the difference between the two half-cell potentials that of Electrode gives the emf of the cell. If we arbitrarily choose the potential of one Potential electrode (half-cell) then that of the other can be determined with respect to this. According to convention, a half-cell called standard hydrogen electrode (Fig.3.3) represented by Pt(s)ú H2(g)ú H+(aq), is assigned a zero potential at all temperatures corresponding to the reaction 1 H+ (aq) + e– ® H2(g) 2 The standard hydrogen electrode consists of a platinum electrode coated with platinum black. The electrode is dipped in an acidic solution and pure hydrogen gas is bubbled through it. The concentration of both the reduced and oxidised forms of hydrogen is maintained at unity (Fig. 2.3). This implies that the pressure of hydrogen gas is one bar and the concentration of hydrogen ion in the Fig. 2.3: Standard Hydrogen Electrode (SHE). solution is one molar. Chemistry 34 Reprint 2025-26 At 298 K the emf of the cell, standard hydrogen electrode ççsecond half-cell constructed by taking standard hydrogen electrode as anode (reference half-cell) and the other half-cell as cathode, gives the reduction potential of the other half-cell. If the concentrations of the oxidised and the reduced forms of the species in the right hand half-cell are unity, then the cell potential is equal to standard electrode potential, Eo R of the given half-cell. Eo = EoR – Eo L As Eo L for standard hydrogen electrode is zero. Eo = Eo R – 0 = EoR The measured emf of the cell: Pt(s) ç H2(g, 1 bar) ç H + (aq, 1 M) çç Cu 2+ (aq, 1 M) ú Cu is 0.34 V and it is also the value for the standard electrode potential of the half-cell corresponding to the reaction: Cu2+ (aq, 1M) + 2 e – ® Cu(s) Similarly, the measured emf of the cell: Pt(s) ç H2(g, 1 bar) ç H+ (aq, 1 M) çç Zn2+ (aq, 1M) ç Zn is -0.76 V corresponding to the standard electrode potential of the half-cell reaction: Zn2+ (aq, 1 M) + 2e– ® Zn(s) The positive value of the standard electrode potential in the first case indicates that Cu2+ ions get reduced more easily than H+ ions. The reverse process cannot occur, that is, hydrogen ions cannot oxidise Cu (or alternatively we can say that hydrogen gas can reduce copper ion) under the standard conditions described above. Thus, Cu does not dissolve in HCl. In nitric acid it is oxidised by nitrate ion and not by hydrogen ion. The negative value of the standard electrode potential in the second case indicates that hydrogen ions can oxidise zinc (or zinc can reduce hydrogen ions). In view of this convention, the half reaction for the Daniell cell in Fig. 2.1 can be written as: Left electrode: Zn(s) ® Zn 2+ (aq, 1 M) + 2 e – Right electrode: Cu 2+ (aq, 1 M) + 2 e – ® Cu(s) The overall reaction of the cell is the sum of above two reactions and we obtain the equation: Zn(s) + Cu 2+ (aq) ® Zn2+ (aq) + Cu(s) emf of the cell = Eocell = Eo R – Eo L = 0.34V – (– 0.76)V = 1.10 V Sometimes metals like platinum or gold are used as inert electrodes. They do not participate in the reaction but provide their surface for oxidation or reduction reactions and for the conduction of electrons. For example, Pt is used in the following half-cells: Hydrogen electrode: Pt(s)|H2(g)| H+(aq) With half-cell reaction: H+ (aq)+ e– ® ½ H2(g) Bromine electrode: Pt(s)|Br2(aq)| Br–(aq) 35 Electrochemistry Reprint 2025-26 With half-cell reaction: ½ Br2(aq) + e– ® Br–(aq) The standard electrode potentials are very important and we can extract a lot of useful information from them. The values of standard electrode potentials for some selected half-cell reduction reactions are given in Table 2.1. If the standard electrode potential of an electrode is greater than zero then its reduced form is more stable compared to hydrogen gas. Similarly, if the standard electrode potential is negative then hydrogen gas is more stable than the reduced form of the species. It can be seen that the standard electrode potential for fluorine is the highest in the Table indicating that fluorine gas (F2) has the maximum tendency to get reduced to fluoride ions (F–) and therefore fluorine gas is the strongest oxidising agent and fluoride ion is the weakest reducing agent. Lithium has the lowest electrode potential indicating that lithium ion is the weakest oxidising agent while lithium metal is the most powerful reducing agent in an aqueous solution. It may be seen that as we go from top to bottom in Table 2.1 the standard electrode potential decreases and with this, decreases the oxidising power of the species on the left and increases the reducing power of the species on the right hand side of the reaction. Electrochemical cells are extensively used for determining the pH of solutions, solubility product, equilibrium constant and other thermodynamic properties and for potentiometric titrations. IntextIntextIntextIntextIntext QuestionsQuestionsQuestionsQuestionsQuestions 2.1 How would you determine the standard electrode potential of the system Mg2+|Mg? 2.2 Can you store copper sulphate solutions in a zinc pot? 2.3 Consult the table of standard electrode potentials and suggest three substances that can oxidise ferrous ions under suitable conditions. 2.32.32.32.32.3 NernstNernstNernstNernstNernst We have assumed in the previous section that the concentration of all EquationEquationEquationEquationEquation the species involved in the electrode reaction is unity. This need not be always true. Nernst showed that for the electrode reaction: Mn+(aq) + ne–® M(s) the electrode potential at any concentration measured with respect to standard hydrogen electrode can be represented by: RT o [M] E = E ln ( M n + / M ) ( M n + / M ) – nF [M n+ ] but concentration of solid M is taken as unity and we have o RT 1 E = E (2.8) ( M n + / M ) ( M n + /M ) – nF ln [M n+ ] o E ( M n + / M ) has already been defined, R is gas constant (8.314 JK–1 mol–1), F is Faraday constant (96487 C mol–1), T is temperature in kelvin and [Mn+] is the concentration of the species, Mn+. Chemistry 36 Reprint 2025-26 Table 2.1: Standard Electrode Potentials at 298 K Ions are present as aqueous species and H2O as liquid; gases and solids are shown by g and s. Reaction (Oxidised form + ne– ® Reduced form) E o/V ® 2F– 2.87 F2(g) + 2e– Co3+ + e– ® Co2+ 1.81 H2O2 + 2H+ + 2e– ® 2H2O 1.78 MnO4– + 8H+ + 5e– ® Mn2+ + 4H2O 1.51 Au3+ + 3e– ® Au(s) 1.40 Cl2(g) + 2e– ® 2Cl– 1.36 Cr2O72– + 14H+ + 6e– ® 2Cr3+ + 7H2O 1.33 O2(g) + 4H+ + 4e– ® 2H2O 1.23 MnO2(s) + 4H+ + 2e– ® Mn2+ + 2H2O 1.23 Br2 + 2e– ® 2Br– 1.09 NO3– + 4H+ + 3e– ® NO(g) + 2H2O 0.97 2Hg2+ + 2e– ® Hg22+ 0.92 Ag+ + e– ® Ag(s) 0.80 agent agent Fe3+ + e– ® Fe2+ 0.77 O2(g) + 2H+ + 2e– ® H2O2 0.68 I2 + 2e– ® 2I– 0.54 oxidising reducing 0.52 of Cu+ + e– ® Cu(s) of Cu2+ + 2e– ® Cu(s) 0.34 AgCl(s) + e– ® Ag(s) + Cl– 0.22 strength AgBr(s) + e– ® Ag(s) + Br– strength 0.10 2H+ + 2e– ® H2(g) 0.00 Pb2+ + 2e– ® Pb(s) –0.13 Sn2+ + 2e– ® Sn(s) –0.14 Increasing Increasing Ni2+ + 2e– ® Ni(s) –0.25 Fe2+ + 2e– ® Fe(s) –0.44 Cr3+ + 3e– ® Cr(s) –0.74 Zn2+ + 2e– ® Zn(s) –0.76 2H2O + 2e– ® H2(g) + 2OH–(aq) –0.83 Al3+ + 3e– ® Al(s) –1.66 Mg2+ + 2e– ® Mg(s) –2.36 Na+ + e– ® Na(s) –2.71 Ca2+ + 2e– ® Ca(s) –2.87 K+ + e– ® K(s) –2.93 Li+ + e– ® Li(s) –3.05 1. A negative Eo means that the redox couple is a stronger reducing agent than the H+/H2 couple. 2. A positive Eo means that the redox couple is a weaker reducing agent than the H+/H2 couple. 37 Electrochemistry Reprint 2025-26 In Daniell cell, the electrode potential for any given concentration of Cu2+ and Zn2+ ions, we write For Cathode: E E o RT 1 (2.9)  Cu 2  /Cu  = (Cu 2 + /Cu ) – 2F ln   Cu 2   aq   For Anode: E E o RT 1 (2.10)  Zn 2  /Zn  = ( Zn 2 + / Zn ) – 2F ln   Zn 2   aq   E E 2  2  /Zn  The cell potential, E(cell) =  Cu /Cu  –  Zn o RT 1 E o RT 1 E = (Cu – ( Zn 2 + / Cu ) – 2 F ln 2 + / Zn ) + 2 F ln    Zn 2+ (aq)   Cu 2+ (aq) E o E o RT 1 1 – ln = (Cu 2 + / Cu ) – ( Zn 2 + / Zn ) – 2F ln    Cu 2+  aq    Zn 2+  aq   2  ] RT [ Zn o E(cell) = E ( cell ) – 2 F ln 2 + (2.11) [Cu ] It can be seen that E(cell) depends on the concentration of both Cu2+ and Zn2+ ions. It increases with increase in the concentration of Cu2+ ions and decrease in the concentration of Zn2+ ions. By converting the natural logarithm in Eq. (2.11) to the base 10 and substituting the values of R, F and T = 298 K, it reduces to 2 + ] 0 .059 [ Zn (2.12) 2 + ] E(cell) = E (ocell ) – 2 log [Cu We should use the same number of electrons (n) for both the electrodes and thus for the following cell Ni(s)ú Ni2+(aq) úú Ag+(aq)ú Ag The cell reaction is Ni(s) + 2Ag+(aq) ® Ni2+(aq) + 2Ag(s) The Nernst equation can be written as RT [Ni 2+ ] o + E(cell) = E ( cell ) – 2F ln [Ag ]2 and for a general electrochemical reaction of the type: a A + bB ne– cC + dD Nernst equation can be written as: RT E(cell) = E (ocell ) – nF 1nQ RT [C]c [D]d o (2.13) = E ( cell ) – nF ln [A] a [B]b Chemistry 38 Reprint 2025-26 Represent the cell in which the following reaction takes place ExampleExampleExampleExampleExample 2.12.12.12.12.1 Mg(s) + 2Ag+(0.0001M) ® Mg2+(0.130M) + 2Ag(s) Calculate its E(cell) if E (ocell ) = 3.17 V. The cell can be written as Mgú Mg2+(0.130M)úú Ag+(0.0001M)ú Ag SolutionSolutionSolutionSolutionSolution 2 + Mg RT o E = E ln (  cell  cell ) – 2F + 2 Ag 0 .059V 0.130 = 3.17 V – log 2 = 3.17 V – 0.21V = 2.96 V. 2 ( 0 . 0001) 2.3.1 Equilibrium If the circuit in Daniell cell (Fig. 2.1) is closed then we note that the reaction Constant Zn(s) + Cu2+(aq) ® Zn2+(aq) + Cu(s) (2.1) from Nernst takes place and as time passes, the concentration of Zn2+ keeps Equation on increasing while the concentration of Cu2+ keeps on decreasing. At the same time voltage of the cell as read on the voltmeter keeps on decreasing. After some time, we shall note that there is no change in the concentration of Cu2+ and Zn2+ ions and at the same time, voltmeter gives zero reading. This indicates that equilibrium has been attained. In this situation the Nernst equation may be written as: o 2.303 RT [Zn 2 + ] 2 + E(cell) = 0 = E ( cell ) – 2 F log [Cu ] o 2.303 RT [Zn 2  ] or E ( cell ) = log 2  2 F [Cu ] But at equilibrium, [ Zn 2 + ] = Kc for the reaction 2.1 [Cu2 + ] and at T = 298K the above equation can be written as o 0. 059 V o E ( cell ) = log KC = 1.1 V ( E ( cell ) = 1.1V) 2 (1.1V × 2) log KC =  37.288 0.059 V KC = 2 × 1037 at 298K. In general, o 2.303RT E ( cell ) = log KC (2.14) nF Thus, Eq. (2.14) gives a relationship between equilibrium constant of the reaction and standard potential of the cell in which that reaction takes place. Thus, equilibrium constants of the reaction, difficult to measure otherwise, can be calculated from the corresponding Eo value of the cell. 39 Electrochemistry Reprint 2025-26 ExampleExampleExampleExampleExample 2.22.22.22.22.2 Calculate the equilibrium constant of the reaction: Cu(s) + 2Ag+(aq) ® Cu2+(aq) + 2Ag(s) Eo( cell ) = 0.46 V o 0. 059 V SolutionSolutionSolutionSolutionSolution E ( cell ) = log KC = 0.46 V or 2 0 .46 V × 2 = 15.6 log KC = 0 .059 V KC = 3.92 × 1015 2.3.2 Electro- Electrical work done in one second is equal to electrical potential chemical multiplied by total charge passed. If we want to obtain maximum work Cell and from a galvanic cell then charge has to be passed reversibly. The Gibbs reversible work done by a galvanic cell is equal to decrease in its Gibbs Energy of energy and therefore, if the emf of the cell is E and nF is the amount the Reaction of charge passed and DrG is the Gibbs energy of the reaction, then DrG = – nFE(cell) (2.15) It may be remembered that E(cell) is an intensive parameter but DrG is an extensive thermodynamic property and the value depends on n. Thus, if we write the reaction Zn(s) + Cu2+(aq) ¾® Zn2+(aq) + Cu(s) (2.1) DrG = – 2FE(cell) but when we write the reaction 2 Zn (s) + 2 Cu2+(aq) ¾®2 Zn2+(aq) + 2Cu(s) DrG = – 4FE(cell) If the concentration of all the reacting species is unity, then E(cell) = E (ocell ) and we have DrGo = – nF E(cell)o (2.16) Thus, from the measurement of E (ocell ) we can obtain an important thermodynamic quantity, DrGo, standard Gibbs energy of the reaction. From the latter we can calculate equilibrium constant by the equation: DrGo = –RT ln K. ExampleExampleExampleExampleExample 2.32.32.32.32.3 The standard electrode potential for Daniell cell is 1.1V. Calculate the standard Gibbs energy for the reaction: Zn(s) + Cu2+(aq) ¾® Zn2+(aq) + Cu(s) SolutionSolutionSolutionSolutionSolution DrGo = – nF E(cell)o n in the above equation is 2, F = 96487 C mol–1 and E o( cell ) = 1.1 V Therefore, DrGo = – 2 × 1.1V × 96487 C mol–1 = – 21227 J mol–1 = – 212.27 kJ mol–1 Chemistry 40 Reprint 2025-26 IntextIntextIntextIntextIntext QuestionsQuestionsQuestionsQuestionsQuestions 2.4 Calculate the potential of hydrogen electrode in contact with a solution whose pH is 10. 2.5 Calculate the emf of the cell in which the following reaction takes place: Ni(s) + 2Ag+ (0.002 M) ® Ni2+ (0.160 M) + 2Ag(s) Given that Ecello = 1.05 V 2.6 The cell in which the following reaction occurs: E o = 0.236 V at 298 K. 2Fe 3 + ( aq ) + 2I − ( aq ) → 2Fe 2 + ( aq ) + I 2 ( s ) has cell Calculate the standard Gibbs energy and the equilibrium constant of the cell reaction. 2.42.42.42.42.4 ConductanceConductanceConductanceConductanceConductance It is necessary to define a few terms before we consider the subject of ofofofofof ElectrolyticElectrolyticElectrolyticElectrolyticElectrolytic conductance of electricity through electrolytic solutions. The electrical resistance is represented by the symbol ‘R’ and it is measured in ohm (W) SolutionsSolutionsSolutionsSolutionsSolutions which in terms of SI base units is equal to (kg m2)/(S3 A2). It can be measured with the help of a Wheatstone bridge with which you are familiar from your study of physics. The electrical resistance of any object is directly proportional to its length, l, and inversely proportional to its area of cross section, A. That is, l l R µ or R = r (2.17) A A The constant of proportionality, r (Greek, rho), is called resistivity (specific resistance). Its SI units are ohm metre (W m) and quite often its submultiple, ohm centimetre (W cm) is also used. IUPAC recommends the use of the term resistivity over specific resistance and hence in the rest of the book we shall use the term resistivity. Physically, the resistivity for a substance is its resistance when it is one metre long and its area of cross section is one m2. It can be seen that: 1 W m = 100 W cm or 1 W cm = 0.01 W m The inverse of resistance, R, is called conductance, G, and we have the relation: 1 A A G = = = κ (2.18) R ρ l l The SI unit of conductance is siemens, represented by the symbol ‘S’ and is equal to ohm–1 (also known as mho) or W–1. The inverse of resistivity, called conductivity (specific conductance) is represented by the symbol, k (Greek, kappa). IUPAC has recommended the use of term conductivity over specific conductance and hence we shall use the term conductivity in the rest of the book. The SI units of conductivity are S m–1 but quite often, k is expressed in S cm–1. Conductivity of a material in S m–1 is its conductance when it is 1 m long and its area of cross section is 1 m2. It may be noted that 1 S cm–1 = 100 S m–1. 41 Electrochemistry Reprint 2025-26 Table 2.2: The values of Conductivity of some Selected Materials at 298.15 K Material Conductivity/ Material Conductivity/ S m–1 S m–1 Conductors Aqueous Solutions Sodium 2.1×103 Pure water 3.5×10–5 Copper 5.9×103 0.1 M HCl 3.91 Silver 6.2×103 0.01M KCl 0.14 Gold 4.5×103 0.01M NaCl 0.12 Iron 1.0×103 0.1 M HAc 0.047 Graphite 1.2×10 0.01M HAc 0.016 Insulators Semiconductors Glass 1.0×10–16 CuO 1×10–7 Teflon 1.0×10–18 Si 1.5×10–2 Ge 2.0 It can be seen from Table 2.2 that the magnitude of conductivity varies a great deal and depends on the nature of the material. It also depends on the temperature and pressure at which the measurements are made. Materials are classified into conductors, insulators and semiconductors depending on the magnitude of their conductivity. Metals and their alloys have very large conductivity and are known as conductors. Certain non-metals like carbon-black, graphite and some organic polymers* are also electronically conducting. Substances like glass, ceramics, etc., having very low conductivity are known as insulators. Substances like silicon, doped silicon and gallium arsenide having conductivity between conductors and insulators are called semiconductors and are important electronic materials. Certain materials called superconductors by definition have zero resistivity or infinite conductivity. Earlier, only metals and their alloys at very low temperatures (0 to 15 K) were known to behave as superconductors, but nowadays a number of ceramic materials and mixed oxides are also known to show superconductivity at temperatures as high as 150 K. Electrical conductance through metals is called metallic or electronic conductance and is due to the movement of electrons. The electronic conductance depends on (i) the nature and structure of the metal (ii) the number of valence electrons per atom (iii) temperature (it decreases with increase of temperature). * Electronically conducting polymers – In 1977 MacDiarmid, Heeger and Shirakawa discovered that acetylene gas can be polymerised to produce a polymer, polyacetylene when exposed to vapours of iodine acquires metallic lustre and conductivity. Since then several organic conducting polymers have been made such as polyaniline, polypyrrole and polythiophene. These organic polymers which have properties like metals, being composed wholly of elements like carbon, hydrogen and occasionally nitrogen, oxygen or sulphur, are much lighter than normal metals and can be used for making light-weight batteries. Besides, they have the mechanical properties of polymers such as flexibility so that one can make electronic devices such as transistors that can bend like a sheet of plastic. For the discovery of conducting polymers, MacDiarmid, Heeger and Shirakawa were awarded the Nobel Prize in Chemistry for the year 2000. Chemistry 42 Reprint 2025-26 As the electrons enter at one end and go out through the other end, the composition of the metallic conductor remains unchanged. The mechanism of conductance through semiconductors is more complex. We already know that even very pure water has small amounts of hydrogen and hydroxyl ions (~10–7M) which lend it very low conductivity (3.5 × 10–5 S m–1). When electrolytes are dissolved in water, they furnish their own ions in the solution hence its conductivity also increases. The conductance of electricity by ions present in the solutions is called electrolytic or ionic conductance. The conductivity of electrolytic (ionic) solutions depends on: (i) the nature of the electrolyte added (ii) size of the ions produced and their solvation (iii) the nature of the solvent and its viscosity (iv) concentration of the electrolyte (v) temperature (it increases with the increase of temperature). Passage of direct current through ionic solution over a prolonged period can lead to change in its composition due to electrochemical reactions (Section 2.4.1). 2.4.1 Measurement We know that accurate measurement of an unknown resistance can be of the performed on a Wheatstone bridge. However, for measuring the resistance Conductivity of an ionic solution we face two problems. Firstly, passing direct current of Ionic (DC) changes the composition of the solution. Secondly, a solution cannot Solutions be connected to the bridge like a metallic wire or other solid conductor. The first difficulty is resolved by using an alternating current (AC) source of power. The second problem is solved by using a specially designed vessel called conductivity cell. It is available in several designs and two simple ones are shown in Fig. 2.4. Connecting Connecting wires wires Platinized Pt Fig. 2.4 electrodes Two different types of conductivity cells. Platinized Pt electrode Platinized Pt electrode Basically it consists of two platinum electrodes coated with platinum black (finely divided metallic Pt is deposited on the electrodes electrochemically). These have area of cross section equal to ‘A’ and are separated by distance ‘l’. Therefore, solution confined between these electrodes is a column of length l and area of cross section A. The resistance of such a column of solution is then given by the equation: l l R = r = (2.17) A A 43 Electrochemistry Reprint 2025-26 The quantity l/A is called cell constant denoted by the symbol, G*. It depends on the distance between the electrodes and their area of cross-section and has the dimension of length–1 and can be calculated if we know l and A. Measurement of l and A is not only inconvenient but also unreliable. The cell constant is usually determined by measuring the resistance of the cell containing a solution whose conductivity is already known. For this purpose, we generally use KCl solutions whose conductivity is known accurately at various concentrations (Table 2.3) and at different temperatures. The cell constant, G*, is then given by the equation: l G* = = R k (2.18) A Table 2.3: Conductivity and Molar conductivity of KCl solutions at 298.15K Concentration/Molarity Conductivity Molar Conductivity mol L–1 mol m–3 S cm–1 S m–1 S cm2mol–1 S m2 mol–1 1.000 1000 0.1113 11.13 111.3 111.3×10–4 0.100 100.0 0.0129 1.29 129.0 129.0×10–4 0.010 10.00 0.00141 0.141 141.0 141.0×10–4 Once the cell constant is determined, we can use it for measuring the resistance or conductivity of any solution. The set up for the measurement of the resistance is shown in Fig. 2.5. It consists of two resistances R3 and R4, a variable resistance R1 and the conductivity cell having the unknown resistance R2. The Wheatstone bridge is fed by an oscillator O (a source of a.c. power in the audio frequency range 550 to 5000 cycles per second). P is a suitable detector (a headphone or other electronic device) and the bridge is balanced when no current passes through the detector. Under these conditions: Fig. 2.5: Arrangement for measurement of R 1 R 4 resistance of a solution of an Unknown resistance R2 = (2.19) R 3 electrolyte. These days, inexpensive conductivity meters are available which can directly read the conductance or resistance of the solution in the conductivity cell. Once the cell constant and the resistance of the solution in the cell is determined, the conductivity of the solution is given by the equation: cell constant G*   (2.20) R R The conductivity of solutions of different electrolytes in the same solvent and at a given temperature differs due to charge and size of the Chemistry 44 Reprint 2025-26 ions in which they dissociate, the concentration of ions or ease with which the ions move under a potential gradient. It, therefore, becomes necessary to define a physically more meaningful quantity called molar conductivity denoted by the symbol Lm (Greek, lambda). It is related to the conductivity of the solution by the equation:  Molar conductivity = Lm = (2.21) c In the above equation, if k is expressed in S m–1 and the concentration, c in mol m–3 then the units of Lm are in S m2 mol–1. It may be noted that: 1 mol m–3 = 1000(L/m3) × molarity (mol/L), and hence  (S cm  1 ) Lm(S cm2 mol–1) =  3 1 1000 L m × molarity (mol L ) If we use S cm–1 as the units for k and mol cm–3, the units of concentration, then the units for Lm are S cm2 mol–1. It can be calculated by using the equation:  (S cm 1 ) × 1000 (cm 3 /L) Lm (S cm2 mol–1) = molarity (mol/L) Both type of units are used in literature and are related to each other by the equations: 1 S m2mol–1 = 104 S cm2mol–1 or 1 S cm2mol–1 = 10–4 S m2mol–1. Resistance of a conductivity cell filled with 0.1 mol L–1 KCl solution is ExampleExampleExampleExampleExample 2.42.42.42.42.4 100 W . If the resistance of the same cell when filled with 0.02 mol L–1 KCl solution is 520 W , calculate the conductivity and molar conductivity of 0.02 mol L–1 KCl solution. The conductivity of 0.1 mol L–1 KCl solution is 1.29 S/m. SolutionSolutionSolutionSolutionSolution The cell constant is given by the equation: Cell constant = G* = conductivity × resistance = 1.29 S/m × 100 W = 129 m–1 = 1.29 cm–1 Conductivity of 0.02 mol L–1 KCl solution = cell constant / resistance G * 129 m –1 = = = 0.248 S m–1 R 520  Concentration = 0.02 mol L–1 = 1000 × 0.02 mol m–3 = 20 mol m–3  Molar conductivity = m  c 248 × 10 –3 S m –1 = –3 = 124 × 10–4 S m2mol–1 20 mol m 1.29 cm –1 Alternatively, k = = 0.248 × 10–2 S cm–1 520  45 Electrochemistry Reprint 2025-26 and Lm = k × 1000 cm3 L–1 molarity–1 0.248×10 –2 S cm –1 ×1000 cm 3 L–1 = –1 0.02 mol L = 124 S cm2 mol–1 ExampleExampleExampleExampleExample 2.52.52.52.52.5 The electrical resistance of a column of 0.05 mol L–1 NaOH solution of diameter 1 cm and length 50 cm is 5.55 × 103 ohm. Calculate its resistivity, conductivity and molar conductivity. SolutionSolutionSolutionSolutionSolution A = p r2 = 3.14 × 0.52 cm2 = 0.785 cm2 = 0.785 × 10–4 m2 l = 50 cm = 0.5 m  l RA 5.55  10 3  0.785cm 2 R = or    = 87.135 W cm A l 50cm 1  1  Conductivity =  = =   S cm–1   87.135  = 0.01148 S cm–1  × 1000 Molar conductivity, m = cm3 L–1 c 0.01148 S cm –1 ×1000 cm 3 L–1 = –1 0.05 mol L = 229.6 S cm2 mol–1 If we want to calculate the values of different quantities in terms of ‘m’ instead of ‘cm’, RA = l 5.55 × 10 3  × 0.785×10 –4 m 2 = = 87.135 ×10–2 W m 0.5 m 1 100  =  m = 1.148 S m–1 = 87.135  1.148 S m –1 and m = = –3 = 229.6 × 10–4 S m2 mol–1. c 50 mol m 2.4.2 Variation of Both conductivity and molar conductivity change with the Conductivity concentration of the electrolyte. Conductivity always decreases with and Molar decrease in concentration both, for weak and strong electrolytes. Conductivity This can be explained by the fact that the number of ions per unit with volume that carry the current in a solution decreases on dilution. Concentration The conductivity of a solution at any given concentration is the conductance of one unit volume of solution kept between two Chemistry 46 Reprint 2025-26 platinum electrodes with unit area of cross section and at a distance of unit length. This is clear from the equation: A G = =  (both A and l are unity in their appropriate units in l m or cm) Molar conductivity of a solution at a given concentration is the conductance of the volume V of solution containing one mole of electrolyte kept between two electrodes with area of cross section A and distance of unit length. Therefore, κA Λm = =κ l Since l = 1 and A = V ( volume containing 1 mole of electrolyte) Lm = k V (2.22) Molar conductivity increases with decrease in concentration. This is because the total volume, V, of solution containing one mole of electrolyte also increases. It has been found that decrease in k on dilution of a solution is more than compensated by increase in its volume. Physically, it means that at a given concentration, Lm can be defined as the conductance of the electrolytic solution kept between the electrodes of a conductivity cell at unit distance but having area of cross section large enough to accommodate sufficient volume of solution that contains one mole of the electrolyte. When concentration approaches zero, the molar conductivity is known as limiting molar conductivity and is represented by theFig. 2.6: Molar conductivity versus c½ for acetic acid (weak electrolyte) and potassium symbol L°m . The variation in Lm with chloride (strong electrolyte) in aqueous concentration is different (Fig. 2.6) for solutions. strong and weak electrolytes. Strong Electrolytes For strong electrolytes, Lm increases slowly with dilution and can be represented by the equation: Lm = L°m – A c ½ (2.23) It can be seen that if we plot (Fig. 2.6) Lm against c1/2, we obtain a straight line with intercept equal to L°m and slope equal to ‘–A’. The value of the constant ‘A’ for a given solvent and temperature depends on the type of electrolyte i.e., the charges on the cation and anion produced on the dissociation of the electrolyte in the solution. Thus, NaCl, CaCl2, MgSO4 are known as 1-1, 2-1 and 2-2 electrolytes respectively. All electrolytes of a particular type have the same value for ‘A’. 47 Electrochemistry Reprint 2025-26 ExampleExampleExampleExampleExample 2.62.62.62.62.6 The molar conductivity of KCl solutions at different concentrations at 298 K are given below: c/mol L–1 Lm/S cm2 mol–1 0.000198 148.61 0.000309 148.29 0.000521 147.81 0.000989 147.09 Show that a plot between Lm and c1/2 is a straight line. Determine the values of L°m and A for KCl. SolutionSolutionSolutionSolutionSolution Taking the square root of concentration we obtain: c1/2/(mol L–1 )1/2 Lm/S cm2mol–1 0.01407 148.61 0.01758 148.29 0.02283 147.81 0.03145 147.09 A plot of Lm ( y-axis) and c1/2 (x-axis) is shown in (Fig. 3.7). It can be seen that it is nearly a straight line. From the intercept (c1/2 = 0), we find that L°m = 150.0 S cm2 mol–1 and A = – slope = 87.46 S cm2 mol–1/(mol/L–1)1/2. Fig. 2.7: Variation of Lm against c½. Chemistry 48 Reprint 2025-26 Kohlrausch examined L°m values for a number of strong electrolytes and observed certain regularities. He noted that the difference in L°m of the electrolytes NaX and KX for any X is nearly constant. For example at 298 K: m L°m (KCl) – L°m (NaCl) = L°m (KBr) – L° (NaBr) = L°m (KI) – L°m (NaI) ≃ 23.4 S cm2 mol–1 and similarly it was found that L°m (NaBr)– L°m (NaCl) = L°m (KBr) – L°m (KCl) ≃ 1.8 S cm2 mol–1 On the basis of the above observations he enunciated Kohlrausch law of independent migration of ions. The law states that limiting molar conductivity of an electrolyte can be represented as the sum of the individual contributions of the anion and cation of the electrolyte. Thus, – are limiting molar conductivity of the sodium and chlorideif l°Na+ and l°Cl ions respectively, then the limiting molar conductivity for sodium chloride is given by the equation: l° l° L°m – (2.24) (NaCl) = Na+ + Cl In general, if an electrolyte on dissociation gives n+ cations and n– anions then its limiting molar conductivity is given by: L°m = n+ l°+ + n– l°– (2.25) Here, l°+ and l°– are the limiting molar conductivities of the cation and anion respectively. The values of l° for some cations and anions at 298 K are given in Table 2.4. Table 2.4: Limiting Molar Conductivity for some Ions in Water at 298 K Ion l0/(S cm2mol–1) Ion l 0/(S cm2 mol–1) H+ 349.6 OH– 199.1 Na+ 50.1 Cl– 76.3 K+ 73.5 Br– 78.1 Ca2+ 119.0 CH3COO– 40.9 2 Mg2+ 106.0 SO4 160.0 Weak Electrolytes Weak electrolytes like acetic acid have lower degree of dissociation at higher concentrations and hence for such electrolytes, the change in Lm with dilution is due to increase in the degree of dissociation and consequently the number of ions in total volume of solution that contains 1 mol of electrolyte. In such cases Lm increases steeply (Fig. 2.6) on dilution, especially near lower concentrations. Therefore, L°m cannot be obtained by extrapolation of Lm to zero concentration. At infinite dilution (i.e., concentration c ® zero) electrolyte dissociates completely (a =1), but at such low concentration the conductivity of the solution is so low that it cannot be measured accurately. Therefore, L°m for weak electrolytes is obtained by using Kohlrausch law of independent migration of ions (Example 2.8). At any concentration c, if a is the degree of dissociation 49 Electrochemistry Reprint 2025-26 then it can be approximated to the ratio of molar conductivity Lm at the concentration c to limiting molar conductivity, L0m . Thus we have: m  = ° (2.26) m But we know that for a weak electrolyte like acetic acid (Class XI, Unit 7), c  2 cm2 c m2 K = = =   a 1   m m  m   m  (2.27) m 2 1     m  Applications of Kohlrausch law Using Kohlrausch law of independent migration of ions, it is possible to calculate L0m for any electrolyte from the lo of individual ions. Moreover, for weak electrolytes like acetic acid it is possible to determine the value of its dissociation constant once we know the L0m and Lm at a given concentration c. ExampleExampleExampleExampleExample 2.72.72.72.72.7 Calculate L0m for CaCl2 and MgSO4 from the data given in Table 3.4. SolutionSolutionSolutionSolutionSolution We know from Kohlrausch law that – = 119.0 S cm2 mol–1 + 2(76.3) S cm2 mol–1 m  CaCl 2  = Ca 2+  2 Cl = (119.0 + 152.6) S cm2 mol–1 = 271.6 S cm2 mol–1 2+  m  MgSO 4  = Mg  SO 2–4 = 106.0 S cm2 mol–1 + 160.0 S cm2 mol–1 = 266 S cm2 mol–1 . ExampleExampleExampleExampleExample 2.82.82.82.82.8 L0m for NaCl, HCl and NaAc are 126.4, 425.9 and 91.0 S cm2 mol–1 respectively. Calculate L0 for HAc.       +  Ac – H + Cl – Ac – Na + Cl – Na + SolutionSolutionSolutionSolutionSolution m  HAc  = H = m  HCl   m  NaAc   m  NaCl  = (425.9 + 91.0 – 126.4 ) S cm2 mol –1 = 390.5 S cm2 mol–1 . ExampleExampleExampleExampleExample 2.92.92.92.92.9 The conductivity of 0.001028 mol L–1 acetic acid is 4.95 × 10–5 S cm–1. Calculate its dissociation constant if L0m for acetic acid is 390.5 S cm2 mol–1.  4 . 95 10  5 Scm  1 1000cm 3 SolutionSolutionSolutionSolutionSolution m =  1  = 48.15 S cm3 mol–1 c 0 . 001028 mol L L m 48.15 Scm 2 mol 1 a =   2  1 = 0.1233 m 390.5 Scm mol c2 0 .001028molL–1  (0 .1233) 2 k = = 1.78 × 10–5 mol L–1  1   1  0 .1233 Chemistry 50 Reprint 2025-26 IntextIntextIntextIntextIntext QuestionsQuestionsQuestionsQuestionsQuestions 2.7 Why does the conductivity of a solution decrease with dilution? 2.8 Suggest a way to determine the L°m value of water. 2.9 The molar conductivity of 0.025 mol L–1 methanoic acid is 46.1 S cm2 mol–1. Calculate its degree of dissociation and dissociation constant. Given l0(H+) = 349.6 S cm2 mol–1 and l0 (HCOO–) = 54.6 S cm2 mol–1. 2.52.52.52.52.5 ElectrolyticElectrolyticElectrolyticElectrolyticElectrolytic In an electrolytic cell external source of voltage is used to bring about a chemical reaction. The electrochemical processes are of great importance CellsCellsCellsCellsCells andandandandand in the laboratory and the chemical industry. One of the simplest electrolytic ElectrolysisElectrolysisElectrolysisElectrolysisElectrolysis cell consists of two copper strips dipping in an aqueous solution of copper sulphate. If a DC voltage is applied to the two electrodes, then Cu 2+ ions discharge at the cathode (negatively charged) and the following reaction takes place: Cu2+(aq) + 2e– ® Cu (s) (2.28) Copper metal is deposited on the cathode. At the anode, copper is converted into Cu2+ ions by the reaction: Cu(s) ® Cu2+(s) + 2e– (2.29) Thus copper is dissolved (oxidised) at anode and deposited (reduced) at cathode. This is the basis for an industrial process in which impure copper is converted into copper of high purity. The impure copper is made an anode that dissolves on passing current and pure copper is deposited at the cathode. Many metals like Na, Mg, Al, etc. are produced on large scale by electrochemical reduction of their respective cations where no suitable chemical reducing agents are available for this purpose. Sodium and magnesium metals are produced by the electrolysis of their fused chlorides and aluminium is produced by electrolysis of aluminium oxide in presence of cryolite. Quantitative Aspects of Electrolysis Michael Faraday was the first scientist who described the quantitative aspects of electrolysis. Now Faraday’s laws also flow from what has been discussed earlier. Faraday’s Laws of Electrolysis After his extensive investigations on electrolysis of solutions and melts of electrolytes, Faraday published his results during 1833-34 in the form of the following well known Faraday’s two laws of electrolysis: (i) First Law: The amount of chemical reaction which occurs at any electrode during electrolysis by a current is proportional to the quantity of electricity passed through the electrolyte (solution or melt). (ii) Second Law: The amounts of different substances liberated by the same quantity of electricity passing through the electrolytic solution are proportional to their chemical equivalent weights (Atomic Mass of Metal ÷ Number of electrons required to reduce the cation). 51 Electrochemistry Reprint 2025-26 There were no constant current sources available during Faraday’s times. The general practice was to put a coulometer (a standard electrolytic cell) for determining the quantity of electricity passed from the amount of metal (generally silver or copper) deposited or consumed. However, coulometers are now obsolete and we now have constant current (I) sources available and the quantity of electricity Q, passed is given by Q = It Q is in coloumbs when I is in ampere and t is in second. The amount of electricity (or charge) required for oxidation or reduction depends on the stoichiometry of the electrode reaction. For example, in the reaction: Ag +(aq) + e– ® Ag(s) (2.30) One mole of the electron is required for the reduction of one mole of silver ions. We know that charge on one electron is equal to 1.6021 × 10–19C. Therefore, the charge on one mole of electrons is equal to: NA × 1.6021 × 10–19 C = 6.02 × 1023 mol–1 × 1.6021 × 10–19 C = 96487 C mol–1 This quantity of electricity is called Faraday and is represented by the symbol F. For approximate calculations we use 1F ≃ 96500 C mol–1. For the electrode reactions: Mg2+(l) + 2e– ¾® Mg(s) (2.31) Al3+(l) + 3e– ¾® Al(s) (2.32) It is obvious that one mole of Mg2+ and Al3+ require 2 mol of electrons (2F) and 3 mol of electrons (3F) respectively. The charge passed through the electrolytic cell during electrolysis is equal to the product of current in amperes and time in seconds. In commercial production of metals, current as high as 50,000 amperes are used that amounts to about 0.518 F per second. ExampleExampleExampleExampleExample 2.102.102.102.102.10 A solution of CuSO4 is electrolysed for 10 minutes with a current of 1.5 amperes. What is the mass of copper deposited at the cathode? SolutionSolutionSolutionSolutionSolution t = 600 s charge = current × time = 1.5 A × 600 s = 900 C According to the reaction: Cu2+(aq) + 2e– = Cu(s) We require 2F or 2 × 96487 C to deposit 1 mol or 63 g of Cu. For 900 C, the mass of Cu deposited = (63 g mol–1 × 900 C)/(2 × 96487 C mol–1) = 0.2938 g. 2.5.1 Products of Products of electrolysis depend on the nature of material being Electrolysis electrolysed and the type of electrodes being used. If the electrode is inert (e.g., platinum or gold), it does not participate in the chemical reaction and acts only as source or sink for electrons. On the other hand, if the electrode is reactive, it participates in the electrode reaction. Thus, the products of electrolysis may be different for reactive and inert Chemistry 52 Reprint 2025-26 electrodes.The products of electrolysis depend on the different oxidising and reducing species present in the electrolytic cell and their standard electrode potentials. Moreover, some of the electrochemical processes although feasible, are so slow kinetically that at lower voltages these do not seem to take place and extra potential (called overpotential) has to be applied, which makes such process more difficult to occur. For example, if we use molten NaCl, the products of electrolysis are sodium metal and Cl2 gas. Here we have only one cation (Na+) which is reduced at the cathode (Na+ + e– ® Na) and one anion (Cl–) which is oxidised at the anode (Cl– ® ½Cl2 + e– ). During the electrolysis of aqueous sodium chloride solution, the products are NaOH, Cl2 and H2. In this case besides Na+ and Cl– ions we also have H+ and OH– ions along with the solvent molecules, H2O. At the cathode there is competition between the following reduction reactions: Na+ (aq) + e– ® Na (s) E (ocell ) = – 2.71 V H+ (aq) + e– ® ½ H2 (g) E (ocell ) = 0.00 V The reaction with higher value of Eo is preferred and therefore, the reaction at the cathode during electrolysis is: H+ (aq) + e– ® ½ H2 (g) (2.33) but H+ (aq) is produced by the dissociation of H2O, i.e., H2O (l ) ® H+ (aq) + OH– (aq) (2.34) Therefore, the net reaction at the cathode may be written as the sum of (2.33) and (2.34) and we have H2O (l ) + e– ® ½H2(g) + OH– (2.35) At the anode the following oxidation reactions are possible: Cl– (aq) ® ½ Cl2 (g) + e– E (ocell ) = 1.36 V (2.36) 2H2O (l ) ® O2 (g) + 4H+(aq) + 4e– E (ocell ) = 1.23 V (2.37) The reaction at anode with lower value of E o is preferred and therefore, water should get oxidised in preference to Cl– (aq). However, on account of overpotential of oxygen, reaction (2.36) is preferred. Thus, the net reactions may be summarised as: NaCl (aq) H 2 O → Na+ (aq) + Cl– (aq) Cathode: H2O(l ) + e– ® ½ H2(g) + OH– (aq) Anode: Cl– (aq) ® ½ Cl2(g) + e– Net reaction: NaCl(aq) + H2O(l) ® Na+(aq) + OH–(aq) + ½H2(g) + ½Cl2(g) The standard electrode potentials are replaced by electrode potentials given by Nernst equation (Eq. 2.8) to take into account the concentration effects. During the electrolysis of sulphuric acid, the following processes are possible at the anode: 2H2O(l) ® O2(g) + 4H+(aq) + 4e– E (ocell ) = +1.23 V (2.38) 53 Electrochemistry Reprint 2025-26 2SO42– (aq) ® S2O8 2– (aq) + 2e– E (ocell ) = 1.96 V (2.39) For dilute sulphuric acid, reaction (2.38) is preferred but at higher concentrations of H2SO4, reaction (2.39) is preferred. IntextIntextIntextIntextIntext QuestionsQuestionsQuestionsQuestionsQuestions 2.10 If a current of 0.5 ampere flows through a metallic wire for 2 hours, then how many electrons would flow through the wire? 2.11 Suggest a list of metals that are extracted electrolytically. 2.12 Consider the reaction: Cr2O7 2– + 14H+ + 6e– ® 2Cr3+ + 7H2O What is the quantity of electricity in coulombs needed to reduce 1 mol of Cr2O7 2–? 2.62.62.62.62.6 BatteriesBatteriesBatteriesBatteriesBatteries Any battery (actually it may have one or more than one cell connected in series) or cell that we use as a source of electrical energy is basically a galvanic cell where the chemical energy of the redox reaction is converted into electrical energy. However, for a battery to be of practical use it should be reasonably light, compact and its voltage should not vary appreciably during its use. There are mainly two types of batteries. 2.6.1 Primary In the primary batteries, the reaction occurs only once and after use Batteries over a period of time battery becomes dead and cannot be reused again. The most familiar example of this type is the dry cell (known as Leclanche cell after its discoverer) which is used commonly in our transistors and clocks. The cell consists of a zinc container that also acts as anode and the cathode is a carbon (graphite) rod surrounded by powdered manganese dioxide and carbon (Fig.2.8). The space between the electrodes is filled by a moist paste of ammonium chloride (NH4Cl) and zinc chloride (ZnCl2). The electrode reactions are complex, but they can be written approximately as follows : Anode: Zn(s) ¾® Zn2+ + 2e– Cathode: MnO2+ NH4 ++ e–¾® MnO(OH) + NH3 In the reaction at cathode, manganese is reduced from the + 4 oxidation state to the +3 state. Ammonia produced in the reaction forms a complex with Zn2+ to give [Zn (NH3)4]2+. The cell has a potential of nearly 1.5 V. Mercury cell, (Fig. 2.9) suitable for low current devices like hearing aids, watches, etc. consists of zinc – mercury amalgam as anode and a paste of HgO and carbon as the Fig. 2.8: A commercial dry cell cathode. The electrolyte is a paste of KOH and ZnO. The consists of a graphite electrode reactions for the cell are given below: (carbon) cathode in a Anode: Zn(Hg) + 2OH– ¾® ZnO(s) + H2O + 2e– zinc container; the latter Cathode: HgO + H2O + 2e– ¾® Hg(l) + 2OH– acts as the anode. Chemistry 54 Reprint 2025-26 The overall reaction is represented by Zn(Hg) + HgO(s) ¾® ZnO(s) + Hg(l) The cell potential is approximately 1.35 V and remains constant during its Fig. 2.9 life as the overall reaction does not Commonly used involve any ion in solution whose mercury cell. The concentration can change during its life reducing agent is time. zinc and the oxidising agent is mercury (II) oxide. 2.6.2 Secondary A secondary cell after use can be recharged by passing current Batteries through it in the opposite direction so that it can be used again. A good secondary cell can undergo a large number of discharging and charging cycles. The most important secondary cell is the lead storage battery (Fig. 2.10) commonly used in automobiles and invertors. It consists of a lead anode and a grid of lead packed with lead dioxide (PbO2 ) as cathode. A 38% solution of sulphuric acid is used as an electrolyte. The cell reactions when the battery is in use are given below: Anode: Pb(s) + SO42–(aq) ® PbSO4(s) + 2e– Cathode: PbO2(s) + SO42–(aq) + 4H+(aq) + 2e– ® PbSO4 (s) + 2H2O (l) i.e., overall cell reaction consisting of cathode and anode reactions is: Pb(s) + PbO2(s) + 2H2SO4(aq) ® 2PbSO4(s) + 2H2O(l) On charging the battery the reaction is reversed and PbSO4(s) on anode and cathode is converted into Pb and PbO2, respectively. Fig. 2.10: The Lead storage battery. 55 Electrochemistry Reprint 2025-26 Another important secondary cell is the nickel-cadmium cell (Fig. 2.11) which has longer life than the lead storage cell but Fig. 2.11 more expensive to manufacture. A rechargeable We shall not go into details of nickel-cadmium cell working of the cell and the Positive plate in a jelly roll electrode reactions during arrangement and Separator charging and discharging. separated by a layer Negative plate The overall reaction during soaked in moist discharge is: sodium or potassium hydroxide. Cd (s) + 2Ni(OH)3 (s) ® CdO (s) + 2Ni(OH)2 (s) + H2O (l ) 2.72.72.72.72.7 FuelFuelFuelFuelFuel CellsCellsCellsCellsCells Production of electricity by thermal plants is not a very efficient method and is a major source of pollution. In such plants, the chemical energy (heat of combustion) of fossil fuels (coal, gas or oil) is first used for converting water into high pressure steam. This is then used to run a turbine to produce electricity. We know that a galvanic cell directly converts chemical energy into electricity and is highly efficient. It is now possible to make such cells in which reactants are fed continuously to the electrodes and products are removed continuously from the electrolyte compartment. Galvanic cells that are designed to convert the energy of combustion of fuels like hydrogen, methane, methanol, etc. directly into electrical energy are called fuel cells. One of the most successful fuel cells uses the reaction of hydrogen with oxygen to form water (Fig. 2.12). The cell was used for providing electrical power in the Apollo space programme. The water vapours produced during the reaction were condensed and added to the drinking water supply for the astronauts. In the cell, hydrogen and oxygen are bubbled through porous carbon electrodes into concentrated aqueous sodium hydroxide solution. Catalysts like finely divided platinum or palladium metal are incorporated into the electrodes for increasing the rate of electrode Fig. 2.12: Fuel cell using H2 and O2 produces electricity. reactions. The electrode reactions are given below: Cathode: O2(g) + 2H2O(l) + 4e–¾® 4OH–(aq) Anode: 2H2 (g) + 4OH–(aq) ¾® 4H2O(l) + 4e– Overall reaction being: 2H2(g) + O2(g) ¾® 2H2O(l ) The cell runs continuously as long as the reactants are supplied. Fuel cells produce electricity with an efficiency of about 70 % compared Chemistry 56 Reprint 2025-26 to thermal plants whose efficiency is about 40%. There has been tremendous progress in the development of new electrode materials, better catalysts and electrolytes for increasing the efficiency of fuel cells. These have been used in automobiles on an experimental basis. Fuel cells are pollution free and in view of their future importance, a variety of fuel cells have been fabricated and tried. 2.82.82.82.82.8 CorrosionCorrosionCorrosionCorrosionCorrosion Corrosion slowly coats the surfaces of metallic objects with oxides or other salts of the metal. The rusting of iron, tarnishing of silver, development of green coating on copper and bronze are some of the examples of corrosion. It causes enormous damage to buildings, bridges, ships and to all objects made of metals especially that of iron. We lose crores of rupees every year on account of corrosion. In corrosion, a metal is oxidised by loss of electrons to oxygen and formation of oxides. Corrosion of iron (commonly known as rusting) occurs in presence of water and air. The chemistry of corrosion is quite complex but it may be considered Oxidation: Fe (s)® Fe2+ (aq) +2e– essentially as an electrochemical Reduction: O2 (g) + 4H+(aq) +4e– ® 2H2O(l) phenomenon. At a particular spot Atomospheric (Fig. 2.13) of an object made of iron,oxidation: 2Fe2+(aq) + 2H2O(l) + ½O2(g) ® Fe2O3(s) + 4H+(aq) oxidation takes place and that spot Fig. 2.13: Corrosion of iron in atmosphere behaves as anode and we can write the reaction E o Anode: 2 Fe (s) ¾® 2 Fe2+ + 4 e– (Fe 2+ /Fe) = – 0.44 V Electrons released at anodic spot move through the metal and go to another spot on the metal and reduce oxygen in the presence of H+ (which is believed to be available from H2CO3 formed due to dissolution of carbon dioxide from air into water. Hydrogen ion in water may also be available due to dissolution of other acidic oxides from the atmosphere). This spot behaves as cathode with the reaction E o =1.23 V Cathode: O2(g) + 4 H+(aq) + 4 e– ¾® 2 H2O (l) H + | O 2 | H 2 O The overall reaction being: 2Fe(s) + O2(g) + 4H+(aq) ¾® 2Fe2 +(aq) + 2 H2O (l) E o(cell) =1.67 V The ferrous ions are further oxidised by atmospheric oxygen to ferric ions which come out as rust in the form of hydrated ferric oxide (Fe2O3. x H2O) and with further production of hydrogen ions. Prevention of corrosion is of prime importance. It not only saves money but also helps in preventing accidents such as a bridge collapse or failure of a key component due to corrosion. One of the simplest methods of preventing corrosion is to prevent the surface of the metallic object to come in contact with atmosphere. This can be done by covering the surface with paint or by some chemicals (e.g. bisphenol). Another simple method is to cover the surface by other metals (Sn, Zn, etc.) that are inert or react to save the object. An electrochemical method is to provide a sacrificial electrode of another metal (like Mg, Zn, etc.) which corrodes itself but saves the object. 57 Electrochemistry Reprint 2025-26 IntextIntextIntextIntextIntext QuestionsQuestionsQuestionsQuestionsQuestions 2.13 Write the chemistry of recharging the lead storage battery, highlighting all the materials that are involved during recharging. 2.14 Suggest two materials other than hydrogen that can be used as fuels in fuel cells. 2.15 Explain how rusting of iron is envisaged as setting up of an electrochemical cell. TheTheTheTheThe HydrogenHydrogenHydrogenHydrogenHydrogen EconomyEconomyEconomyEconomyEconomy At present the main source of energy that is driving our economy is fossil fuels such as coal, oil and gas. As more people on the planet aspire to improve their standard of living, their energy requirement will increase. In fact, the per capita consumption of energy used is a measure of development. Of course, it is assumed that energy is used for productive purpose and not merely wasted. We are already aware that carbon dioxide produced by the combustion of fossil fuels is resulting in the ‘Greenhouse Effect’. This is leading to a rise in the temperature of the Earth’s surface, causing polar ice to melt and ocean levels to rise. This will flood low-lying areas along the coast and some island nations such as Maldives face total submergence. In order to avoid such a catastrope, we need to limit our use of carbonaceous fuels. Hydrogen provides an ideal alternative as its combustion results in water only. Hydrogen production must come from splitting water using solar energy. Therefore, hydrogen can be used as a renewable and non polluting source of energy. This is the vision of the Hydrogen Economy. Both the production of hydrogen by electrolysis of water and hydrogen combustion in a fuel cell will be important in the future. And both these technologies are based on electrochemical principles. SummarySummarySummarySummarySummary An electrochemical cell consists of two metallic electrodes dipping in electrolytic solution(s). Thus an important component of the electrochemical cell is the ionic conductor or electrolyte. Electrochemical cells are of two types. In galvanic cell, the chemical energy of a spontaneous redox reaction is converted into electrical work, whereas in an electrolytic cell, electrical energy is used to carry out a non- spontaneous redox reaction. The standard electrode potential for any electrode dipping in an appropriate solution is defined with respect to standard electrode potential of hydrogen electrode taken as zero. The standard potential of the cell can be obtained by taking the difference of the standard potentials of cathode and anode ( E (ocell ) = Eocathode – Eoanode). The standard potential of the cells are related to standard Gibbs energy (DrGo = –nF E (ocell ) ) and equilibrium constant (DrGo = – RT ln K) of the reaction taking place in the cell. Concentration dependence of the potentials of the electrodes and the cells are given by Nernst equation. The conductivity, k, of an electrolytic solution depends on the concentration of the electrolyte, nature of solvent and temperature. Molar conductivity, Lm, is defined by = k/c where c is the concentration. Conductivity decreases but molar conductivity increases with decrease in concentration. It increases slowly with decrease in concentration for strong electrolytes while the increase is very steep for weak electrolytes in very dilute solutions. Kohlrausch found that molar conductivity at infinite dilution, for an electrolyte is sum of the contribution of the Chemistry 58 Reprint 2025-26 molar conductivity of the ions in which it dissociates. It is known as law of independent migration of ions and has many applications. Ions conduct electricity through the solution but oxidation and reduction of the ions take place at the electrodes in an electrochemical cell. Batteries and fuel cells are very useful forms of galvanic cell. Corrosion of metals is essentially an electrochemical phenomenon. Electrochemical principles are relevant to the Hydrogen Economy. ExercisesExercisesExercisesExercisesExercises

1.27 If the solubility product of CuS is 6 × 10–16, calculate the maximum molarity of CuS in aqueous solution.

1.1 Define the term solution. How many types of solutions are formed? Write briefly about each type with an example.

1.8 Mole concept and Molar Masses molecules Atoms and molecules are extremely small 1 mol of sodium chloride = 6.022 ×1023 formula in size and their numbers in even a small units of sodium chloride amount of any substance is really very large. Having defined the mole, it is easier toTo handle such large numbers, a unit of convenient magnitude is required. know the mass of one mole of a substance Just as we denote one dozen for 12 items, or the constituent entities. The mass of one score for 20 items, gross for 144 items, we mole of a substance in grams is called its use the idea of mole to count entities at the molar mass. The molar mass in grams is microscopic level (i.e., atoms, molecules, numerically equal to atomic/molecular/ particles, electrons, ions, etc). formula mass in u. In SI system, mole (symbol, mol) was Molar mass of water = 18.02 g mol–1introduced as seventh base quantity for the amount of a substance. Molar mass of sodium chloride = 58.5 g mol–1 The mole, symbol mol, is the SI unit of 1.9 Percentage Compositionamount of substance. One mole contains exactly 6.02214076 × 1023 elementary entities. So far, we were dealing with the number of This number is the fixed numerical value of entities present in a given sample. But many the Avogadro constant, NA, when expressed a time, information regarding the percentage in the unit mol–1 and is called the Avogadro of a particular element present in a compound number. The amount of substance, symbol is required. Suppose, an unknown or new n, of a system is a measure of the number of compound is given to you, the first questionspecified elementary entities. An elementary entity may be an atom, a molecule, an ion, an electron, any other particle or specified group of particles. It may be emphasised that the mole of a substance always contains the same number of entities, no matter what the substance may be. In order to determine this number precisely, the mass of a carbon–12 atom was determined by a mass spectrometer and found to be equal to 1.992648 × 10–23 g. Knowing that one mole of carbon weighs 12 g, the number of atoms in it is equal to: 12 g / mol 12 C 1 .992648  10 23 g /12 Catom  6 .0221367  1023 atoms/mol Fig. 1.11 One mole of various substances Reprint 2025-26 Some Basic Concepts of Chemistry 19 you would ask is: what is its formula or what 1.9.1 Empirical Formula for Molecular are its constituents and in what ratio are they Formula present in the given compound? For known An empirical formula represents the simplest compounds also, such information provides a whole number ratio of various atoms present check whether the given sample contains the in a compound, whereas, the molecular same percentage of elements as present in a formula shows the exact number of different pure sample. In other words, one can check types of atoms present in a molecule of a the purity of a given sample by analysing this compound. data. If the mass per cent of various elements Let us understand it by taking the example present in a compound is known, its empirical of water (H2O). Since water contains hydrogen formula can be determined. Molecular formula and oxygen, the percentage composition of can further be obtained if the molar mass is both these elements can be calculated as known. The following example illustrates follows: this sequence. Mass % of an element = mass of that element in the compound × 100 molar mass of the compound Problem 1.2 A compound contains 4.07% hydrogen,Molar mass of water = 18.02 g 24.27% carbon and 71.65% chlorine. Its molar mass is 98.96 g. What are itsMass % of hydrogen = empirical and molecular formulas? = 11.18 Solution 16.00Mass % of oxygen = × 100 Step 1. Conversion of mass per cent 18.02 to grams = 88.79 Since we are having mass per cent, it is Let us take one more example. What is the convenient to use 100 g of the compound percentage of carbon, hydrogen and oxygen as the starting material. Thus, in the in ethanol? 100 g sample of the above compound, 4.07g hydrogen, 24.27g carbon andMolecular formula of ethanol is: C2H5OH 71.65g chlorine are present.Molar mass of ethanol is: Step 2. Convert into number moles of(2×12.01 + 6×1.008 + 16.00) g = 46.068 g each element Mass per cent of carbon Divide the masses obtained above by 24.02g = × 100 = 52.14% respective atomic masses of various 46.068g elements. This gives the number of Mass per cent of hydrogen moles of constituent elements in the compound 6.048g = × 100 = 13.13% 46.068g 4.07 g Moles of hydrogen = = 4.04 1.008gMass per cent of oxygen 16.00g = × 100 = 34.73% 24.27 g Moles of carbon = = 2 .021 46.068g 12 .01 g After understanding the calculation of 71.65g per cent of mass, let us now see what Moles of chlorine = = 2 .021 35 .453 ginformation can be obtained from the per cent composition data. Reprint 2025-26 20 chemistry equation of a given reaction. Let us consider Step 3. Divide each of the mole values the combustion of methane. A balanced obtained above by the smallest number equation for this reaction is as given below: amongst them CH4 (g) + 2O2 (g) → CO2 (g) + 2 H2O (g) Since 2.021 is smallest value, division Here, methane and dioxygen are called by it gives a ratio of 2:1:1 for H:C:Cl. reactants and carbon dioxide and water are In case the ratios are not whole numbers, called products. Note that all the reactants then they may be converted into whole and the products are gases in the above number by multiplying by the suitable reaction and this has been indicated by coefficient. letter (g) in the brackets next to its formula. Step 4. Write down the empirical Similarly, in case of solids and liquids, (s) and formula by mentioning the numbers (l) are written respectively. after writing the symbols of respective The coefficients 2 for O2 and H2O are elements called stoichiometric coefficients. Similarly CH2Cl is, thus, the empirical formula the coefficient for CH4 and CO2 is one in each of the above compound. case. They represent the number of molecules (and moles as well) taking part in the reaction Step 5. Writing molecular formula or formed in the reaction. (a) Determine empirical formula mass by Thus, according to the above chemical adding the atomic masses of various reaction, atoms present in the empirical formula. For CH2Cl, empirical formula mass is • One mole of CH4(g) reacts with two moles 12.01 + (2 ×1.008) + 35.453 of O2(g) to give one mole of CO2(g) and = 49.48 g two moles of H2O(g) (b) Divide Molar mass by empirical • One molecule of CH4(g) reacts with formula mass 2 molecules of O2(g) to give one molecule of CO2(g) and 2 molecules of H2O(g) • 22.7 L of CH4(g) reacts with 45.4 L of O2 = 2 = (n) (g) to give 22.7 L of CO2 (g) and 45.4 L of (c) Multiply empirical formula by n H2O(g) obtained above to get the molecular • 16 g of CH4 (g) reacts with 2×32 g of O2 formula (g) to give 44 g of CO2 (g) and 2×18 g of Empirical formula = CH2Cl, n = 2. Hence H2O (g). molecular formula is C2H4Cl2. From these relationships, the given data can be interconverted as follows: 1.10 Stoichiometry and mass Stoichiometric Calculations The word ‘stoichiometry’ is derived from two Greek words — stoicheion (meaning, Mass = Density element) and metron (meaning, measure). Volume Stoichiometry, thus, deals with the calculation of masses (sometimes volumes also) of the 1.10.1 Limiting Reagent reactants and the products involved in a Many a time, reactions are carried out with chemical reaction. Before understanding how the amounts of reactants that are different to calculate the amounts of reactants required than the amounts as required by a balanced or the products produced in a chemical chemical reaction. In such situations, one reaction, let us study what information reactant is in more amount than the amount is available from the balanced chemical required by balanced chemical reaction. The Reprint 2025-26 Some Basic Concepts of Chemistry 21 reactant which is present in the least amount important to understand as how the amount gets consumed after sometime and after that of substance is expressed when it is present in further reaction does not take place whatever the solution. The concentration of a solution be the amount of the other reactant. Hence, or the amount of substance present in its the reactant, which gets consumed first, given volume can be expressed in any of the limits the amount of product formed and is, following ways. therefore, called the limiting reagent. 1. Mass per cent or weight per cent (w/w %) In performing stoichiometric calculations, 2. Mole fraction this aspect is also to be kept in mind. 3. Molarity 1.10.2 Reactions in Solutions 4. Molality A majority of reactions in the laboratories Let us now study each one of them in are carried out in solutions. Therefore, it is detail. Balancing a chemical equation According to the law of conservation of mass, a balanced chemical equation has the same number of atoms of each element on both sides of the equation. Many chemical equations can be balanced by trial and error. Let us take the reactions of a few metals and non-metals with oxygen to give oxides 4 Fe(s) + 3O2(g) → 2Fe2O3(s) (a) balanced equation 2 Mg(s) + O2(g) → 2MgO(s) (b) balanced equation P4(s) + O2 (g) → P4O10(s) (c) unbalanced equation Equations (a) and (b) are balanced, since there are same number of metal and oxygen atoms on each side of the equations. However equation (c) is not balanced. In this equation, phosphorus atoms are balanced but not the oxygen atoms. To balance it, we must place the coefficient 5 on the left of oxygen on the left side of the equation to balance the oxygen atoms appearing on the right side of the equation. P4(s) + 5O2(g) → P4O10(s) balanced equation Now, let us take combustion of propane, C3H8. This equation can be balanced in steps. Step 1 Write down the correct formulas of reactants and products. Here, propane and oxygen are reactants, and carbon dioxide and water are products. C3H8(g) + O2(g) → CO2 (g) + H2O(l) unbalanced equation Step 2 Balance the number of C atoms: Since 3 carbon atoms are in the reactant, therefore, three CO2 molecules are required on the right side. C3H8 (g) + O2 (g) → 3CO2 (g) + H2O (l) Step 3 Balance the number of H atoms: on the left there are 8 hydrogen atoms in the reactants however, each molecule of water has two hydrogen atoms, so four molecules of water will be required for eight hydrogen atoms on the right side. C3H8 (g) +O2 (g) → 3CO2 (g)+4H2O (l) Step 4 Balance the number of O atoms: There are 10 oxygen atoms on the right side (3 × 2 = 6 in CO2 and 4×1= 4 in water). Therefore, five O2 molecules are needed to supply the required 10 CO2 and 4×1= 4 in water). Therefore, five O2 molecules are needed to supply the required 10 oxygen atoms. C3H8 (g) +5O2 (g) → 3CO2 (g) + 4H2O (l) Step 5 Verify that the number of atoms of each element is balanced in the final equation. The equation shows three carbon atoms, eight hydrogen atoms, and 10 oxygen atoms on each side. All equations that have correct formulas for all reactants and products can be balanced. Always remember that subscripts in formulas of reactants and products cannot be changed to balance an equation. Reprint 2025-26 22 chemistry Problem 1.3 the limiting reagent in the production of NH3 in this situation. Calculate the amount of water (g) produced by the combustion of 16 g Solution of methane. A balanced equation for the above Solution reaction is written as follows : The balanced equation for the combustion of methane is : CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (g) Calculation of moles : (i) 16 g of CH4 corresponds to one mole. Number of moles of N2 (ii) From the above equation, 1 mol of 1000 g N 2 1 mol N 2 × 2 × CH4 (g) gives 2 mol of H2O (g). = 50 .0 kg N 1 kg N 2 28 .0 g N 2 2 mol of water (H2O) = 2×(2+16) = 17.86×102 mol = 2×18 = 36 g Number of moles of H2 H 2 O ⇒18g 1000 g H 2 1 mol H 2 = 1 1 mol H2O = 18 g H2O × = 10 .00 kg H 2 × 1mol H 2 O 1 kg H 2 2 .016 g H 2 18g H 2 O = 4.96 × 103 mol Hence, 2 mol H2O× 1mol H 2 O According to the above equation, 1 mol N2 (g) requires 3 mol H2 (g), for the = 2×18 g H2O = 36 g H2O reaction. Hence, for 17.86×102 mol of Problem 1.4 N2, the moles of H2 (g) required would be How many moles of methane are 2 3 mol H 2 g 2  required to produce 22g CO2 (g) after 17 .86  10 mol N 1 mol N 2 g combustion? = 5.36 × 103 mol H2 Solution But we have only 4.96×103 mol H2. According to the chemical equation, Hence, dihydrogen is the limiting CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (g) reagent in this case. So, NH3(g) would be formed only from that amount of 44g CO2 (g) is obtained from 16 g CH4 (g). available dihydrogen i.e., 4.96 × 103 mol [∴1 mol CO2(g) is obtained from 1 mol Since 3 mol H2(g) gives 2 mol NH3(g) of CH4(g)] Number of moles of CO2 (g) 2 mol NH 3 g 2 g 4.96 ×103 mol H2 (g) × 3 mol H 2 g = 22 g CO2 (g) ×1 molCO 44 gCO 2 g = 3.30 × 103 mol NH3 (g) = 0.5 mol CO2 (g) 3.30 × 103 mol NH3 (g) is obtained. Hence, 0.5 mol CO2 (g) would be obtained from 0.5 mol CH4 (g) or 0.5 mol If they are to be converted to grams, it of CH4 (g) would be required to produce is done as follows : 22 g CO2 (g). 1 mol NH3 (g) = 17.0 g NH3 (g) Problem 1.5 .0 g NH 3 g 50.0 kg of N2 (g) and 10.0 kg of H2 (g) 3.30 ×103 mol NH3 (g) ×17 3 g are mixed to produce NH3 (g). Calculate 1 mol NH the amount of NH3 (g) formed. Identify Reprint 2025-26 Some Basic Concepts of Chemistry 23 3. Molarity = 3.30×103×17 g NH3 (g) It is the most widely used unit and is denoted = 56.1×103 g NH3 by M. It is defined as the number of moles of = 56.1 kg NH3 the solute in 1 litre of the solution. Thus, No. of moles of solute 1. Mass per cent Molarity (M) = Volume of solution in litres It is obtained by using the following relation: Suppose, we have 1 M solution of a substance, say NaOH, and we want to prepare a 0.2 M solution from it. 1 M NaOH means 1 mol of NaOH present in 1 litre of the solution. For 0.2 M solution, Problem 1.6 we require 0.2 moles of NaOH dissolved in 1 litre solution. A solution is prepared by adding 2 g of a substance A to 18 g of water. Calculate Hence, for making 0.2M solution from 1M the mass per cent of the solute. solution, we have to take that volume of 1M NaOH solution, which contains 0.2 mol of NaOH Solution and dilute the solution with water to 1 litre. Now, how much volume of concentrated (1M) NaOH solution be taken, which contains 0.2 moles of NaOH can be calculated as follows: If 1 mol is present in 1L or 1000 mL solution then, 0.2 mol is present in 1000 mL × 0 .2 mol solution 1 mol 2. Mole Fraction = 200 mL solutionIt is the ratio of number of moles of a particular component to the total number Thus, 200 mL of 1M NaOH are taken and enough water is added to dilute it to make it 1 litre.of moles of the solution. If a substance ‘A’ dissolves in substance ‘B’ and their number In fact for such calculations, a general of moles are nA and nB, respectively, then the formula, M1×V1 = M2 × V2 where M and V are molarity and volume, respectively, can be used.mole fractions of A and B are given as: In this case, M1 is equal to 0.2M; V1 = 1000 mL and, M2 = 1.0M; V2 is to be calculated. Substituting the values in the formula: 0.2 M × 1000 mL = 1.0 M × V2 Note that the number of moles of solute (NaOH) was 0.2 in 200 mL and it has remained the same, i.e., 0.2 even after dilution ( in 1000 mL) as we have changed just the amount of solvent (i.e., water) and have not done anything with respect to NaOH. But keep in mind the concentration. Reprint 2025-26 24 chemistry Problem 1.7 Problem 1.8 Calculate the molarity of NaOH in the The density of 3 M solution of NaCl is solution prepared by dissolving its 4 g 1.25 g mL–1. Calculate the molality of in enough water to form 250 mL of the the solution. solution. Solution Solution M = 3 mol L–1 Since molarity (M) Mass of NaCl in 1 L solution = 3 × 58.5 = 175.5 g Mass of 1L solution = 1000 × 1.25 = 1250 g (since density = 1.25 g mL–1) Mass of water in solution = 1250 –75.5 = 1074.5 g No. of moles of solute Molality = Mass of solvent in kg 3 mol = = 2.79 m Note that molarity of a solution depends 1 .0745 kg upon temperature because volume of a Often in a chemistry laboratory, a solution is temperature dependent. solution of a desired concentration is prepared by diluting a solution of known 4. Molality higher concentration. The solution of higher concentration is also known as It is defined as the number of moles of solute stock solution. Note that the molality present in 1 kg of solvent. It is denoted by m. of a solution does not change with temperature since mass remains No. of moles of solute Thus, Molality (m) = unaffected with temperature. Mass of solvent in kg Summary Chemistry, as we understand it today is not a very old discipline. People in ancient India, already had the knowledge of many scientific phenomenon much before the advent of modern science. They applied the knowledge in various walks of life. The study of chemistry is very important as its domain encompasses every sphere of life. Chemists study the properties and structure of substances and the changes undergone by them. All substances contain matter, which can exist in three states – solid, liquid or gas. The constituent particles are held in different ways in these states of matter and they exhibit their characteristic properties. Matter can also be classified into elements, compounds or mixtures. An element contains particles of only one type, which may be atoms or molecules. The compounds are formed where atoms of two or more elements combine in a fixed ratio to each other. Mixtures occur widely and many of the substances present around us are mixtures. When the properties of a substance are studied, measurement is inherent. The quantification of properties requires a system of measurement and units in which the quantities are to be expressed. Many systems of measurement exist, of which the English Reprint 2025-26 Some Basic Concepts of Chemistry 25 and the Metric Systems are widely used. The scientific community, however, has agreed to have a uniform and common system throughout the world, which is abbreviated as SI units (International System of Units). Since measurements involve recording of data, which are always associated with a certain amount of u is very important. The measurements of quantities in chemistry are spread over a wide range of 10–31 to 10+23. Hence, a convenient system of expressing the numbers in scientific notation is used. The u figures, in which the observations are reported. The dimensional analysis helps to express the measured quantities in different systems of units. Hence, it is possible to interconvert the results from one system of units to another. The combination of different atoms is governed by basic laws of chemical combination — these being the Law of Conservation of Mass, Law of Definite Proportions, Law of Multiple Proportions, Gay Lussac’s Law of Gaseous Volumes and Avogadro Law. All these laws led to the Dalton’s atomic theory, which states that atoms are building blocks of matter. The atomic mass of an element is expressed relative to 12C isotope of carbon, which has an exact value of 12u. Usually, the atomic mass used for an element is the average atomic mass obtained by taking into account the natural abundance of different isotopes of that element. The molecular mass of a molecule is obtained by taking sum of the atomic masses of different atoms present in a molecule. The molecular formula can be calculated by determining the mass per cent of different elements present in a compound and its molecular mass. The number of atoms, molecules or any other particles present in a given system are expressed in the terms of Avogadro constant (6.022 × 1023). This is known as 1 mol of the respective particles or entities. Chemical reactions represent the chemical changes undergone by different elements and compounds. A balanced chemical equation provides a lot of information. The coefficients indicate the molar ratios and the respective number of particles taking part in a particular reaction. The quantitative study of the reactants required or the products formed is called stoichiometry. Using stoichiometric calculations, the amount of one or more reactant(s) required to produce a particular amount of product can be determined and vice-versa. The amount of substance present in a given volume of a solution is expressed in number of ways, e.g., mass per cent, mole fraction, molarity and molality. exerciseS 1.1 Calculate the molar mass of the following: (i) H2O (ii) CO2 (iii) CH4 1.2 Calculate the mass per cent of different elements present in sodium sulphate (Na2SO4). 1.3 Determine the empirical formula of an oxide of iron, which has 69.9% iron and 30.1% dioxygen by mass. 1.4 Calculate the amount of carbon dioxide that could be produced when (i) 1 mole of carbon is burnt in air. (ii) 1 mole of carbon is burnt in 16 g of dioxygen. (iii) 2 moles of carbon are burnt in 16 g of dioxygen. 1.5 Calculate the mass of sodium acetate (CH3COONa) required to make 500 mL of 0.375 molar aqueous solution. Molar mass of sodium acetate is 82.0245 g mol–1. Reprint 2025-26 26 chemistry 1.6 Calculate the concentration of nitric acid in moles per litre in a sample which has a density, 1.41 g mL–1 and the mass per cent of nitric acid in it being 69%. 1.7 How much copper can be obtained from 100 g of copper sulphate (CuSO4)? 1.8 Determine the molecular formula of an oxide of iron, in which the mass per cent of iron and oxygen are 69.9 and 30.1, respectively. 1.9 Calculate the atomic mass (average) of chlorine using the following data: % Natural Abundance Molar Mass 35Cl 75.77 34.9689 37Cl 24.23 36.9659 1.10 In three moles of ethane (C2H6), calculate the following: (i) Number of moles of carbon atoms. (ii) Number of moles of hydrogen atoms. (iii) Number of molecules of ethane. 1.11 What is the concentration of sugar (C12H22O11) in mol L–1 if its 20 g are dissolved in enough water to make a final volume up to 2L? 1.12 If the density of methanol is 0.793 kg L–1, what is its volume needed for making 2.5 L of its 0.25 M solution? 1.13 Pressure is determined as force per unit area of the surface. The SI unit of pressure, pascal is as shown below: 1Pa = 1N m–2 If mass of air at sea level is 1034 g cm–2, calculate the pressure in pascal. 1.14 What is the SI unit of mass? How is it defined? 1.15 Match the following prefixes with their multiples: Prefixes Multiples (i) micro 106 (ii) deca 109 (iii) mega 10–6 (iv) giga 10–15 (v) femto 10 1.16 What do you mean by significant figures? 1.17 A sample of drinking water was found to be severely contaminated with chloroform, CHCl3, supposed to be carcinogenic in nature. The level of contamination was 15 ppm (by mass). (i) Express this in per cent by mass. (ii) Determine the molality of chloroform in the water sample. 1.18 Express the following in the scientific notation: (i) 0.0048 (ii) 234,000 (iii) 8008 (iv) 500.0 (v) 6.0012 1.19 How many significant figures are present in the following? (i) 0.0025 (ii) 208 (iii) 5005 Reprint 2025-26 Some Basic Concepts of Chemistry 27 (iv) 126,000 (v) 500.0 (vi) 2.0034 1.20 Round up the following upto three significant figures: (i) 34.216 (ii) 10.4107 (iii) 0.04597 (iv) 2808 1.21 The following data are obtained when dinitrogen and dioxygen react together to form different compounds: Mass of dinitrogen Mass of dioxygen (i) 14 g 16 g (ii) 14 g 32 g (iii) 28 g 32 g (iv) 28 g 80 g (a) Which law of chemical combination is obeyed by the above experimental data? Give its statement. (b) Fill in the blanks in the following conversions: (i) 1 km = ...................... mm = ...................... pm (ii) 1 mg = ...................... kg = ...................... ng (iii) 1 mL = ...................... L = ...................... dm3 1.22 If the speed of light is 3.0 × 108 m s–1, calculate the distance covered by light in 2.00 ns. 1.23 In a reaction A + B2  AB2 Identify the limiting reagent, if any, in the following reaction mixtures. (i) 300 atoms of A + 200 molecules of B (ii) 2 mol A + 3 mol B (iii) 100 atoms of A + 100 molecules of B (iv) 5 mol A + 2.5 mol B (v) 2.5 mol A + 5 mol B 1.24 Dinitrogen and dihydrogen react with each other to produce ammonia according to the following chemical equation: N2 (g) + H2 (g)  2NH3 (g) (i) Calculate the mass of ammonia produced if 2.00 × 103 g dinitrogen reacts with 1.00 × 103 g of dihydrogen. (ii) Will any of the two reactants remain unreacted? (iii) If yes, which one and what would be its mass? 1.25 How are 0.50 mol Na2CO3 and 0.50 M Na2CO3 different? 1.26 If 10 volumes of dihydrogen gas reacts with five volumes of dioxygen gas, how many volumes of water vapour would be produced? 1.27 Convert the following into basic units: (i) 28.7 pm (ii) 15.15 pm (iii) 25365 mg Reprint 2025-26 28 chemistry 1.28 Which one of the following will have the largest number of atoms? (i) 1 g Au (s) (ii) 1 g Na (s) (iii) 1 g Li (s) (iv) 1 g of Cl2(g) 1.29 Calculate the molarity of a solution of ethanol in water, in which the mole fraction of ethanol is 0.040 (assume the density of water to be one). 1.30 What will be the mass of one 12C atom in g? 1.31 How many significant figures should be present in the answer of the following calculations? 0.02856 × 298.15 × 0.112 (i) (ii) 5 × 5.364 0 .5785 (iii) 0.0125 + 0.7864 + 0.0215 1.32 Use the data given in the following table to calculate the molar mass of naturally occuring argon isotopes: Isotope Isotopic molar mass Abundance 36Ar 35.96755 g mol–1 0.337% 38Ar 37.96272 g mol–1 0.063% 40Ar 39.9624 g mol–1 99.600% 1.33 Calculate the number of atoms in each of the following (i) 52 moles of Ar (ii) 52 u of He (iii) 52 g of He. 1.34 A welding fuel gas contains carbon and hydrogen only. Burning a small sample of it in oxygen gives 3.38 g carbon dioxide, 0.690 g of water and no other products. A volume of 10.0 L (measured at STP) of this welding gas is found to weigh 11.6 g. Calculate (i) empirical formula, (ii) molar mass of the gas, and (iii) molecular formula. 1.35 Calcium carbonate reacts with aqueous HCl to give CaCl2 and CO2 according to the reaction, CaCO3 (s) + 2 HCl (aq) → CaCl2 (aq) + CO2(g) + H2O(l) What mass of CaCO3 is required to react completely with 25 mL of 0.75 M HCl? 1.36 Chlorine is prepared in the laboratory by treating manganese dioxide (MnO2) with aqueous hydrochloric acid according to the reaction 4 HCl (aq) + MnO2(s) → 2H2O (l) + MnCl2(aq) + Cl2 (g) How many grams of HCl react with 5.0 g of manganese dioxide? Reprint 2025-26 Unit 2 structure of atom The rich diversity of chemical behaviour of different Objectives elementsstructure canof atomsbe tracedof theseto theelements.differences in the internal After studying this unit you will be able to • know about the discovery of The existence of atoms has been proposed since the time electron, proton and neutron and of early Indian and Greek philosophers (400 B.C.) who their characteristics; were of the view that atoms are the fundamental building • describe Thomson, Rutherford blocks of matter. According to them, the continued and Bohr atomic models; subdivisions of matter would ultimately yield atoms which would not be further divisible. The word ‘atom’ • understand the important features has been derived from the Greek word ‘a-tomio’ which of the quantum mechanical model means ‘uncut-able’ or ‘non-divisible’. These earlier ideas of atom; were mere speculations and there was no way to test • u n d e r s t a n d n a t u r e o f them experimentally. These ideas remained dormant for electromagnetic radiation and a very long time and were revived again by scientists in Planck’s quantum theory; the nineteenth century. • explain the photoelectric effect The atomic theory of matter was first proposed and describe features of atomic on a firm scientific basis by John Dalton, a British spectra; school teacher in 1808. His theory, called Dalton’s • state the de Broglie relation and atomic theory, regarded the atom as the ultimate Heisenberg u able to explain the law of conservation of mass, law of • define an atomic orbital in terms constant composition and law of multiple proportion of quantum numbers; very successfully. However, it failed to explain the results • state aufbau principle, Pauli of many experiments, for example, it was known that exclusion principle and Hund’s substances like glass or ebonite when rubbed with silk rule of maximum multiplicity; and or fur get electrically charged. • write the electronic configurations In this unit we start with the experimental observations of atoms. made by scientists towards the end of nineteenth and beginning of twentieth century. These established that atoms are made of sub-atomic particles, i.e., electrons, protons and neutrons — a concept very different from that of Dalton. Reprint 2025-26 30 chemistry

1.5 A solution of glucose in water is labelled as 10% w/w, what would be the molality and mole fraction of each component in the solution? If the density of solution is 1.2 g mL–1, then what shall be the molarity of the solution? 1.6 How many mL of 0.1 M HCl are required to react completely with 1 g mixture of Na2CO3 and NaHCO3 containing equimolar amounts of both? 1.7 A solution is obtained by mixing 300 g of 25% solution and 400 g of 40% solution by mass. Calculate the mass percentage of the resulting solution. 1.8 An antifreeze solution is prepared from 222.6 g of ethylene glycol (C2H6O2) and 200 g of water. Calculate the molality of the solution. If the density of the solution is 1.072 g mL–1, then what shall be the molarity of the solution? 1.9 A sample of drinking water was found to be severely contaminated with chloroform (CHCl3) supposed to be a carcinogen. The level of contamination was 15 ppm (by mass): (i) express this in percent by mass (ii) determine the molality of chloroform in the water sample. 1.10 What role does the molecular interaction play in a solution of alcohol and water? 1.11 Why do gases always tend to be less soluble in liquids as the temperature is raised? 1.12 State Henry’s law and mention some important applications. 1.13 The partial pressure of ethane over a solution containing 6.56 × 10–3 g of ethane is 1 bar. If the solution contains 5.00 × 10–2 g of ethane, then what shall be the partial pressure of the gas? 1.14 What is meant by positive and negative deviations from Raoult's law and how is the sign of DmixH related to positive and negative deviations from Raoult's law? 1.15 An aqueous solution of 2% non-volatile solute exerts a pressure of 1.004 bar at the normal boiling point of the solvent. What is the molar mass of the solute? 1.16 Heptane and octane form an ideal solution. At 373 K, the vapour pressures of the two liquid components are 105.2 kPa and 46.8 kPa respectively. What will be the vapour pressure of a mixture of 26.0 g of heptane and 35 g of octane? 1.17 The vapour pressure of water is 12.3 kPa at 300 K. Calculate vapour pressure of 1 molal solution of a non-volatile solute in it. 1.18 Calculate the mass of a non-volatile solute (molar mass 40 g mol–1) which should be dissolved in 114 g octane to reduce its vapour pressure to 80%. 1.19 A solution containing 30 g of non-volatile solute exactly in 90 g of water has a vapour pressure of 2.8 kPa at 298 K. Further, 18 g of water is then added to the solution and the new vapour pressure becomes 2.9 kPa at 298 K. Calculate: (i) molar mass of the solute (ii) vapour pressure of water at 298 K. 1.20 A 5% solution (by mass) of cane sugar in water has freezing point of 271K. Calculate the freezing point of 5% glucose in water if freezing point of pure water is 273.15 K. 1.21 Two elements A and B form compounds having formula AB2 and AB4. When dissolved in 20 g of benzene (C6H6), 1 g of AB2 lowers the freezing point by 2.3 K whereas 1.0 g of AB4 lowers it by 1.3 K. The molar depression constant for benzene is 5.1 K kg mol–1. Calculate atomic masses of A and B. Chemistry 28 Reprint 2025-26 1.22 At 300 K, 36 g of glucose present in a litre of its solution has an osmotic pressure of 4.98 bar. If the osmotic pressure of the solution is 1.52 bars at the same temperature, what would be its concentration?

3.6 VECTOR ADDITION – ANALYTICAL then, a vector T = a + b – c has components : METHOD T x = a x + b x − c x Although the graphical method of adding vectors Ty = a y + b y − c y (3.23b) helps us in visualising the vectors and the T z = a z + b z − c z .resultant vector, it is sometimes tedious and has limited accuracy. It is much easier to add vectors ⊳ Example 3.2 Find the magnitude andby combining their respective components. direction of the resultant of two vectors AConsider two vectors A and B in x-y plane with and B in terms of their magnitudes and components Ax, Ay and Bx, By : angle θ between them. ɵ ɵ A = A x i + A y j (3.18) * Note that angles α, β, and γ are angles in space. They are between pairs of lines, which are not coplanar. Reprint 2025-26 34 PHYSICS ⊳ Example 3.3 A motorboat is racing towards north at 25 km/h and the water current in that region is 10 km/h in the direction of 60° east of south. Find the resultant velocity of the boat. Answer The vector vb representing the velocity of the motorboat and the vector vc representing Fig. 3.10 the water current are shown in Fig. 3.11 in Answer Let OP and OQ represent the two vectors directions specified by the problem. Using the A and B making an angle θ (Fig. 3.10). Then, parallelogram method of addition, the resultant using the parallelogram method of vector R is obtained in the direction shown in the addition, OS represents the resultant vector R : figure. R = A + B SN is normal to OP and PM is normal to OS. From the geometry of the figure, OS2 = ON2 + SN2 but ON = OP + PN = A + B cos θ SN = B sin θ OS2 = (A + B cos θ)2 + (B sin θ)2 or, R2 = A2 + B2 + 2AB cos θ R = A 2 + B 2 + 2AB cosθ (3.24a) In ∆ OSN, SN = OS sinα = R sinα, and in ∆ PSN, SN = PS sin θ = B sin θ Therefore, R sin α = B sin θ R B or, = (3.24b) sin θ sin α Fig. 3.11 Similarly, PM = A sin α = B sin β We can obtain the magnitude of R using the Law A B or, = (3.24c) of cosine : sin β sin α Combining Eqs. (3.24b) and (3.24c), we get R = v 2b + v c2 + 2v bv c cos120 o R A B = = (3.24d) = 25 2 + 10 2 + 2 × 25 × 10 ( -1/2 ) ≅ 22 km/h sin θ sin β sin α To obtain the direction, we apply the Law of sines Using Eq. (3.24d), we get: R vc v c B = sin θ or, sin φ = sin α = sin θ (3.24e) sin θ sin φ R R where R is given by Eq. (3.24a). 10 × sin120 10 3 = = ≅ 0.397 SN B sin θ 21.8 2 × 21.8or, tan α= = (3.24f) OP + PN A + B cos θ φ ≅ 23.4 ⊳ Equation (3.24a) gives the magnitude of the 3.7 MOTION IN A PLANEresultant and Eqs. (3.24e) and (3.24f) its direction. Equation (3.24a) is known as the Law of cosines In this section we shall see how to describe and Eq. (3.24d) as the Law of sines. ⊳ motion in two dimensions using vectors. Reprint 2025-26 MOTION IN A PLANE 35 3.7.1 Position Vector and Displacement Suppose a particle moves along the curve shown The position vector r of a particle P located in a by the thick line and is at P at time t and P′ at plane with reference to the origin of an x-y time t′ [Fig. 3.12(b)]. Then, the displacement is : reference frame (Fig. 3.12) is given by ∆r = r′ – r (3.25) ɵ ɵ and is directed from P to P′. r = x i + y j We can write Eq. (3.25) in a component form: where x and y are components of r along x-, and y- axes or simply they are the coordinates of ɵ ɵ ɵ ɵ ∆r = x' i + y' j − x i + y j ( ) ( )the object. ɵ ɵ = i ∆ x + j ∆ y where ∆x = x ′ – x, ∆y = y′ – y (3.26) Velocity v The average velocity ( ) of an object is the ratio of the displacement and the corresponding time interval : ɵ ɵ ∆ r ∆ x i + ∆y j ɵ ∆ x ɵ ∆ y v = = = i + j (3.27) ∆ t ∆ t ∆ t ∆ t Or, v = v x ˆi + v y j (a) ∆ r Since v = , the direction of the average velocity ∆t is the same as that of ∆r (Fig. 3.12). The velocity (instantaneous velocity) is given by the limiting value of the average velocity as the time interval approaches zero : ∆ r d r v = lim = (3.28) ∆ t → 0 ∆ t d t The meaning of the limiting process can be easily understood with the help of Fig 3.13(a) to (d). In these figures, the thick line represents the path of an object, which is at P at time t. P1, P2 and (b) P3 represent the positions of the object after Fig. 3.12 (a) Position vector r. (b) Displacement ∆r and times ∆t1,∆t2, and ∆t3. ∆r1, ∆r2, and ∆r3 are the average velocity v of a particle. displacements of the object in times ∆t1, ∆t2, and Fig. 3.13 As the time interval ∆t approaches zero, the average velocity approaches the velocity v. The direction of v is parallel to the line tangent to the path. Reprint 2025-26 36 PHYSICS ∆t3, respectively. The direction of the average velocity v is shown in figures (a), (b) and (c) for three decreasing values of ∆t, i.e. ∆t1,∆t2, and ∆t3, (∆t1 > ∆t2 > ∆t3). As ∆t → 0, ∆r → 0 and is along the tangent to the path [Fig. 3.13(d)]. Therefore, the direction of velocity at any point on the path of an object is tangential to the path at that point and is in the direction of motion. We can express v in a component form : Fig. 3.14 The components vx and vy of velocity v and the angle θ it makes with x-axis. Note that dr vx = v cos θ, vy = v sin θ. v = dt The acceleration (instantaneous acceleration)  ∆x ɵ ∆y ɵ  is the limiting value of the average acceleration = lim  i + j  (3.29) ∆t → 0 ∆t ∆t  as the time interval approaches zero : ∆ v ∆x ∆y ɵ ɵ a = lim (3. 32a) + = i lim j lim ∆t → 0 ∆t ∆t → 0 ∆t ∆ t → 0 ∆ t ɵ ɵ ɵ dx ɵ dy ɵ ɵ Since ∆ v = ∆ v x i + ∆ v y j, we have + jOr, v = i = v x i + v y j . dt dt ɵ ∆ v x ɵ ∆ v y dx dy a = i lim + j lim ∆ t → 0 ∆ t ∆ t → 0 ∆ twhere v x = dt , v y = dt (3.30a) ɵ ɵ So, if the expressions for the coordinates x and Or, a = a x i + a y j (3.32b) y are known as functions of time, we can use d v y d v xthese equations to find vx and vy. (3.32c)* where, a x = , a y = The magnitude of v is then d t d t 2 2 As in the case of velocity, we can understand v = v x + v y (3.30b) graphically the limiting process used in defining and the direction of v is given by the angle θ : acceleration on a graph showing the path of the object’s motion. This is shown in Figs. 3.15(a) to  v y  (d). P represents the position of the object at v y −1 tanθ = , θ = tan     (3.30c) time t and P1, P2, P3 positions after time ∆t1, ∆t2,  v x  v x ∆t3, respectively (∆t 1> ∆t2>∆t3). The velocity vectors vx, vy and angle θ are shown in Fig. 3.14 for a at points P, P1, P2, P3 are also shown in Figs. 3.15 velocity vector v at point p. (a), (b) and (c). In each case of ∆t, ∆v is obtained using the triangle law of vector addition. ByAcceleration definition, the direction of average acceleration The average acceleration a of an object for a is the same as that of ∆v. We see that as ∆t time interval ∆t moving in x-y plane is the change decreases, the direction of ∆v changes and in velocity divided by the time interval : consequently, the direction of the acceleration ɵ ɵ changes. Finally, in the limit ∆t g0 [Fig. 3.15(d)], j v x i + v y ∆ v ∆ ( ∆ v y ɵ ) ∆ v x ɵ a = = = i + j (3.31a) the average acceleration becomes the ∆ t ∆ t ∆ t ∆ t instantaneous acceleration and has the direction ɵ ɵ as shown. Or, a = a x i + a y j . (3.31b) * In terms of x and y, ax and ay can be expressed as Reprint 2025-26 MOTION IN A PLANE 37 x (m) Fig. 3.15 The average acceleration for three time intervals (a) ∆t1, (b) ∆t2, and (c) ∆t3, (∆t1> ∆t2> ∆t3). (d) In the limit ∆t g0, the average acceleration becomes the acceleration. Note that in one dimension, the velocity and the acceleration of an object are always along -1  v y  − 1  4  ° θ = tan   = tan   ≅ 53 with x-axis. the same straight line (either in the same  v x   3  direction or in the opposite direction). ⊳ However, for motion in two or three dimensions, velocity and acceleration vectors may have any angle between 0° and 180° 3.8 MOTION IN A PLANE WITH CONSTANT between them. ACCELERATION ⊳ Suppose that an object is moving in x-y plane Example 3.4 The position of a particle is and its acceleration a is constant. Over an given by interval of time, the average acceleration will r = 3.0t ˆi + 2 .0t 2 ˆj + 5 .0 kˆ equal this constant value. Now, let the velocity where t is in seconds and the of the object be v0 at time t = 0 and v at time t. coefficients have the proper units for r to Then, by definition be in metres. (a) Find v(t) and a(t) of the v − v 0 v − v 0 particle. (b) Find the magnitude and a = = t − 0 t direction of v(t) at t = 1.0 s. Or, v = v 0 + a t (3.33a) Answer In terms of components : v x = v ox + a x t dr d ɵ ɵ ɵ v ( t ) = = 3.0 t i + 2.0t2 j + 5.0 k ( ) v y = v oy + a y t (3.33b) d t dt ɵ ɵ = 3.0 i + 4.0t j Let us now find how the position r changes with d v time. We follow the method used in the one- a ( t ) = = +4.0ɵj dt dimensional case. Let ro and r be the position a = 4.0 m s–2 along y- direction vectors of the particle at time 0 and t and let the velocities at these instants be vo and v. Then,At t = 1.0 s, v = 3.0ˆi + 4.0 ˆj over this time interval t, the average velocity is 2 2 -1 (vo + v)/2. The displacement is the average It’s magnitude is v = 3 + 4 = 5.0 m s velocity multiplied by the time interval : and direction is Reprint 2025-26 38 PHYSICS ˆ  v + v 0   ( v 0 + at ) + v 0  = 5.0 t + 1.5 t 2 i + 1.0 t 2 ˆj ( ) t t = r − r0 = 2  2    2 Therefore, x (t ) = 5.0 t + 1.5 t 1 2 y (t ) = +1.0 t 2 at = v 0 t + 2 Given x (t) = 84 m, t = ? 1 2 5.0 t + 1.5 t 2 = 84 ⇒ t = 6 s Or, r = r0 + v 0t + at (3.34a) At t = 6 s, y = 1.0 (6)2 = 36.0 m 2 d r 2.0 t ˆjIt can be easily verified that the derivative of Now, the velocity v = = ( 5.0 + 3.0 t ) ˆi + d t d r ɵ ɵEq. (3.34a), i.e. gives Eq.(3.33a) and it also At t = 6 s, v = 23.0 i + 12.0 j d t satisfies the condition that at t=0, r = ro. speed = v = 232 + 122 ≅ 26 m s−1 . ⊳Equation (3.34a) can be written in component form as 3.9 PROJECTILE MOTION 1 2 x = x 0 + v ox t + a x t As an application of the ideas developed in the 2 previous sections, we consider the motion of a 1 2 projectile. An object that is in flight after being y = y 0 + v oy t + a y t (3.34b) thrown or projected is called a projectile. Such 2 a projectile might be a football, a cricket ball, a One immediate interpretation of Eq.(3.34b) is that baseball or any other object. The motion of a the motions in x- and y-directions can be treated projectile may be thought of as the result of two independently of each other. That is, motion in separate, simultaneously occurring components a plane (two-dimensions) can be treated as two of motions. One component is along a horizontal separate simultaneous one-dimensional direction without any acceleration and the other motions with constant acceleration along two along the vertical direction with constant perpendicular directions. This is an important acceleration due to the force of gravity. It was result and is useful in analysing motion of objects Galileo who first stated this independency of the in two dimensions. A similar result holds for three horizontal and the vertical components ofdimensions. The choice of perpendicular projectile motion in his Dialogue on the greatdirections is convenient in many physical world systems (1632).situations, as we shall see in section 3.9 for In our discussion, we shall assume that theprojectile motion. air resistance has negligible effect on the motion ⊳ Example 3.5 A particle starts from origin of the projectile. Suppose that the projectile is launched with velocity vo that makes an angle at t = 0 with a velocity 5.0 î m/s and moves in x-y plane under action of a force which θo with the x-axis as shown in Fig. 3.16. produces a constant acceleration of (3.0iɵ+2.0jɵ) m/s 2. (a) What is the After the object has been projected, the acceleration acting on it is that due to gravity y-coordinate of the particle at the instant which is directed vertically downward: its x-coordinate is 84 m ? (b) What is the ɵ speed of the particle at this time ? a = −g j Or, ax = 0, ay = – g (3.35) Answer From Eq. (3.34a) for r0 = 0, the position The components of initial velocity vo are : of the particle is given by 1 at 2 vox = vo cos θo r (t ) = v 0 t + 2 2 voy= vo sin θo (3.36) t 3.0ˆi + 2.0 ˆj = 5.0 ˆi t + (1/2 )( ) Reprint 2025-26 MOTION IN A PLANE 39 Now, since g, θo and vo are constants, Eq. (3.39) is of the form y = a x + b x2, in which a and b are constants. This is the equation of a parabola, i.e. the path of the projectile is a parabola (Fig. 3.17). Fig 3.16 Motion of an object projected with velocity vo at angle θ0. If we take the initial position to be the origin of the reference frame as shown in Fig. 3.16, we have : xo = 0, yo = 0 Then, Eq.(3.34b) becomes : x = vox t = (vo cos θo ) t and y = (vo sin θo ) t – ( ½ )g t2 (3.37) Fig. 3.17 The path of a projectile is a parabola. The components of velocity at time t can be Time of maximum height obtained using Eq.(3.33b) : How much time does the projectile take to reach the vx = vox = vo cos θo maximum height ? Let this time be denoted by tm. Since at this point, vy= 0, we have from Eq. (3.38): vy = vo sin θo – g t (3.38) vy = vo sinθo – g tm = 0 Equation (3.37) gives the x-, and y-coordinates Or, tm = vo sinθo /g (3.40a) of the position of a projectile at time t in terms of The total time Tf during which the projectile is two parameters — initial speed vo and projection in flight can be obtained by putting y = 0 in angle θo. Notice that the choice of mutually Eq. (3.37). We get : perpendicular x-, and y-directions for the analysis of the projectile motion has resulted in Tf = 2 (vo sin θo )/g (3.40b) a simplification. One of the components of Tf is known as the time of flight of the projectile. velocity, i.e. x-component remains constant We note that Tf = 2 tm , which is expected throughout the motion and only the because of the symmetry of the parabolic path. y- component changes, like an object in free fall Maximum height of a projectile in vertical direction. This is shown graphically The maximum height hm reached by theat few instants in Fig. 3.17. Note that at the point projectile can be calculated by substituting of maximum height, vy= 0 and therefore, t = tm in Eq. (3.37) : -1 v y 2 = oθ = tan    g  v 0 sinθ0 v 0 sinθ0 v x y = h m = ( v 0 sinθ0 )  −   Equation of path of a projectile  g  2  g  What is the shape of the path followed by the ( v 0 sinθ0 ) 2 projectile? This can be seen by eliminating the Or, h m = (3.41) 2gtime between the expressions for x and y as given in Eq. (3.37). We obtain: Horizontal range of a projectile g 2 The horizontal distance travelled by a projectile from x y = ( tan θo ) x − (3.39) its initial position (x = y = 0) to the position where it 2 (v o cosθo )2 passes y = 0 during its fall is called the horizontal Reprint 2025-26 40 PHYSICS range, R. It is the distance travelled during the time y (t) = yo + voy t +(1/2) ay t2 of flight Tf . Therefore, the range R is Here, xo = yo = 0, voy = 0, ay = –g = –9.8 m s-2, R = (vo cos θo) (Tf ) vox = 15 m s-1. The stone hits the ground when y(t) = – 490 m. =(vo cos θo) (2 vo sin θo)/g – 490 m = –(1/2)(9.8) t2. 2 sin 2θ0 This gives t =10 s. v 0 Or, R = (3.42a) The velocity components are vx = vox and g vy = voy – g t Equation (3.42a) shows that for a given so that when the stone hits the ground : projection velocity vo , R is maximum when sin vox = 15 m s–1 2θ0 is maximum, i.e., when θ0 = 450. voy = 0 – 9.8 × 10 = – 98 m s–1 The maximum horizontal range is, therefore, Therefore, the speed of the stone is 2 v 0 v 2x + v y2 = 15 2 + 98 2 = 99 m s −1 ⊳ R m = (3.42b) g ⊳ ⊳ Example 3.6 Galileo, in his book Two new Example 3.8 A cricket ball is thrown at a sciences, stated that “for elevations which speed of 28 m s–1 in a direction 30° above exceed or fall short of 45° by equal amounts, the horizontal. Calculate (a) the maximum the ranges are equal”. Prove this statement. height, (b) the time taken by the ball to return to the same level, and (c) the distance from the thrower to the point Answer For a projectile launched with velocity where the ball returns to the same level. vo at an angle θo , the range is given by v 02 sin2θ0 R = Answer (a) The maximum height is given by g 2 2 sin sin 30 ( 28 ( v 0 θo ) ° ) m = m =Now, for angles, (45° + α) and ( 45° – α), 2θo is h 2 2 g ( 9.8 )(90° + 2α) and ( 90° – 2α) , respectively. The values of sin (90° + 2α) and sin (90° – 2α) are 14 × 14 = = 10.0 mthe same, equal to that of cos 2α. Therefore, 2 × 9.8 ranges are equal for elevations which exceed or fall short of 45° by equal amounts α. ⊳ (b) The time taken to return to the same level is Tf = (2 vo sin θo )/g = (2× 28 × sin 30° )/9.8 ⊳ = 28/9.8 s = 2.9 s Example 3.7 A hiker stands on the edge (c) The distance from the thrower to the point of a cliff 490 m above the ground and where the ball returns to the same level is throws a stone horizontally with an initial speed 2 of 15 m s-1. Neglecting air resistance, v o sin2θo 28 × 28 × sin60o ( ) = = 69 m ⊳ find the time taken by the stone to reach R = g 9.8 the ground, and the speed with which it hits the ground. (Take g = 9.8 m s-2 ). 3.10 UNIFORM CIRCULAR MOTION Answer We choose the origin of the x-,and y- When an object follows a circular path at a axis at the edge of the cliff and t = 0 s at the constant speed, the motion of the object is called instant the stone is thrown. Choose the positive uniform circular motion. The word “uniform” direction of x-axis to be along the initial velocity refers to the speed, which is uniform (constant) and the positive direction of y-axis to be the throughout the motion. Suppose an object is vertically upward direction. The x-, and y- moving with uniform speed v in a circle of radius components of the motion can be treated R as shown in Fig. 3.18. Since the velocity of the independently. The equations of motion are : object is changing continuously in direction, the x (t) = xo + vox t object undergoes acceleration. Let us find the magnitude and the direction of this acceleration. Reprint 2025-26 MOTION IN A PLANE 41 Fig. 3.18 Velocity and acceleration of an object in uniform circular motion. The time interval ∆t decreases from (a) to (c) where it is zero. The acceleration is directed, at each point of the path, towards the centre of the circle. Let r and r′ be the position vectors and v and r′ be ∆θ. Since the velocity vectors v and v′ are v′ the velocities of the object when it is at point P always perpendicular to the position vectors, the and P′ as shown in Fig. 3.18(a). By definition, angle between them is also ∆θ . Therefore, the velocity at a point is along the tangent at that triangle CPP′ formed by the position vectors and point in the direction of motion. The velocity the triangle GHI formed by the velocity vectors vectors v and v′ are as shown in Fig. 3.18(a1). v, v′ and ∆v are similar (Fig. 3.18a). Therefore, ∆v is obtained in Fig. 3.18 (a2) using the triangle the ratio of the base-length to side-length for law of vector addition. Since the path is circular, one of the triangles is equal to that of the other v is perpendicular to r and so is v′ to r′. triangle. That is : Therefore, ∆v is perpendicular to ∆r. Since  ∆v  ∆ v ∆ r average acceleration is along ∆v  a =  , the =  ∆t  v R average acceleration a is perpendicular to ∆r. If we place ∆v on the line that bisects the angle ∆ r Or, ∆ v = v between r and r′, we see that it is directed towards R the centre of the circle. Figure 3.18(b) shows the Therefore, same quantities for smaller time interval. ∆v and ∆ v v ∆ r v ∆r hence a is again directed towards the centre. a = lim = lim = lim t ∆ t → 0 R ∆ t R ∆ t → 0 ∆ tIn Fig. 3.18(c), ∆tŽ 0 and the average ∆ t → 0 ∆ acceleration becomes the instantaneous If ∆t is small, ∆θ will also be small and then arc acceleration. It is directed towards the centre*. PP′ can be approximately taken to be|∆r|: Thus, we find that the acceleration of an object ∆ r ≅v∆ t in uniform circular motion is always directed ∆r towards the centre of the circle. Let us now find ≅ v the magnitude of the acceleration. ∆ t The magnitude of a is, by definition, given by ∆ r lim = v ∆v Or, ∆ t → 0 ∆ t a = lim ∆ t → 0 ∆t Let the angle between position vectors r and Therefore, the centripetal acceleration ac is : * In the limit ∆tŽ0, ∆r becomes perpendicular to r. In this limit ∆v→ 0 and is consequently also perpendicular to V. Therefore, the acceleration is directed towards the centre, at each point of the circular path. Reprint 2025-26 42 PHYSICS 2 2 2  v  v R ω 2  R ac = = = ω a c =  R v = v2/R (3.43) R R Thus, the acceleration of an object moving with 2 a c = ω R (3.46) speed v in a circle of radius R has a magnitude v 2/R and is always directed towards the centre. The time taken by an object to make one revolution This is why this acceleration is called centripetal is known as its time period T and the number ofacceleration (a term proposed by Newton). A revolution made in one second is called itsthorough analysis of centripetal acceleration was frequency ν (=1/T). However, during this timefirst published in 1673 by the Dutch scientist the distance moved by the object is s = 2πR.Christiaan Huygens (1629-1695) but it was probably known to Newton also some years earlier. Therefore, v = 2πR/T =2πRν (3.47) “Centripetal” comes from a Greek term which means In terms of frequency ν, we have ‘centre-seeking’. Since v and R are constant, the ω = 2πν magnitude of the centripetal acceleration is also v = 2πRν constant. However, the direction changes — ac = 4π2 ν2R (3.48)pointing always towards the centre. Therefore, a ⊳centripetal acceleration is not a constant vector. Example 3.9 An insect trapped in a We have another way of describing the circular groove of radius 12 cm moves along velocity and the acceleration of an object in the groove steadily and completes 7 uniform circular motion. As the object moves revolutions in 100 s. (a) What is the from P to P′ in time ∆t (= t′ – t), the line CP angular speed, and the linear speed of the (Fig. 3.18) turns through an angle ∆θ as shown motion? (b) Is the acceleration vector a in the figure. ∆θ is called angular distance. We constant vector ? What is its magnitude ? define the angular speed ω (Greek letter omega) as the time rate of change of angular Answer This is an example of uniform circular displacement : motion. Here R = 12 cm. The angular speed ω is ∆θ given by ω = ∆t (3.44) ω = 2π/T = 2π × 7/100 = 0.44 rad/s The linear speed v is :Now, if the distance travelled by the object during the time ∆t is ∆s, i.e. PP′ is ∆s, then : v =ω R = 0.44 s-1 × 12 cm = 5.3 cm s-1 ∆ s The direction of velocity v is along the tangent v = ∆t to the circle at every point. The acceleration is directed towards the centre of the circle. Sincebut ∆s = R ∆θ. Therefore : this direction changes continuously, ∆θ v = R = R ω acceleration here is not a constant vector. ∆ t However, the magnitude of acceleration is v = R ω (3.45) constant: a = ω2 R = (0.44 s–1)2 (12 cm)We can express centripetal acceleration ac in terms of angular speed : = 2.3 cm s-2 ⊳ Reprint 2025-26 MOTION IN A PLANE 43 SUMMARY 1. Scalar quantities are quantities with magnitudes only. Examples are distance, speed, mass and temperature. 2. Vector quantities are quantities with magnitude and direction both. Examples are displacement, velocity and acceleration. They obey special rules of vector algebra. 3. A vector A multiplied by a real number λ is also a vector, whose magnitude is λ times the magnitude of the vector A and whose direction is the same or opposite depending upon whether λ is positive or negative. 4. Two vectors A and B may be added graphically using head-to-tail method or parallelogram method. 5. Vector addition is commutative : A + B = B + A It also obeys the associative law : (A + B) + C = A + (B + C) 6. A null or zero vector is a vector with zero magnitude. Since the magnitude is zero, we don’t have to specify its direction. It has the properties : A + 0 = A λ0 = 0 0 A = 0 7. The subtraction of vector B from A is defined as the sum of A and –B : A – B = A+ (–B) 8. A vector A can be resolved into component along two given vectors a and b lying in the same plane : A = λ a + µ b where λ and µ are real numbers. 9. A unit vector associated with a vector A has magnitude 1 and is along the vector A: A ˆn = A ɵ ɵ ɵ The unit vectors i, j, k are vectors of unit magnitude and point in the direction of the x-, y-, and z-axes, respectively in a right-handed coordinate system. 10. A vector A can be expressed as ɵ ɵ A = A x i + Ay j where Ax, Ay are its components along x-, and y -axes. If vector A makes an angle θ A y 2 2 with the x-axis, then Ax = A cos θ, Ay=A sin θ and A = A = A x + A y , tanθ = . A x 11. Vectors can be conveniently added using analytical method. If sum of two vectors A and B, that lie in x-y plane, is R, then : ɵ R = R x i + Ry ɵ,j where, Rx = Ax + Bx, and Ry = Ay + By ɵ ɵ 12. The position vector of an object in x-y plane is given by r = x i + y j and the displacement from position r to position r’ is given by ∆r = r′− r ɵ ɵ = ( x ′ − x ) i + (y ′ − y ) j ɵ ɵ = ∆x i + ∆y j 13. If an object undergoes a displacement ∆r in time ∆t, its average velocity is given by ∆ r v = . The velocity of an object at time t is the limiting value of the average velocity ∆t as ∆t tends to zero : Reprint 2025-26 44 PHYSICS ∆ r d r v = lim = . It can be written in unit vector notation as : ∆ t →0 ∆ t dt ɵ ɵ ɵ dx dy dz = y v = v x i + v y j + v z k where v x = dt , v dt , v z = dt When position of an object is plotted on a coordinate system, v is always tangent to the curve representing the path of the object. 14. If the velocity of an object changes from v to v′in time ∆t, then its average acceleration v − v' ∆ v is given by: a = = ∆ t ∆t The acceleration a at any time t is the limiting value of a as ∆t Ž0 : ∆ v dv a = lim = ∆ t → 0 ∆ t dt ɵ ɵ ɵ In component form, we have : a = a x i + a y j + a z k dvy dv x dv z where, a x = , a y = , a z = dt dt dt 15. If an object is moving in a plane with constant acceleration a = a = a x2 + a y2 and its position vector at time t = 0 is ro, then at any other time t, it will be at a point given by: 1 2 r = ro + v o t + at 2 and its velocity is given by : v = vo + a t where vo is the velocity at time t = 0 In component form : 1 2 x = x o + v ox t + a x t 2 1 2 y = yo + v oy t + a y t 2 v x = v ox + a x t v y = v oy + a y t Motion in a plane can be treated as superposition of two separate simultaneous one- dimensional motions along two perpendicular directions 16. An object that is in flight after being projected is called a projectile. If an object is projected with initial velocity vo making an angle θo with x-axis and if we assume its initial position to coincide with the origin of the coordinate system, then the position and velocity of the projectile at time t are given by : x = (vo cos θo) t y = (vo sin θo) t − (1/2) g t2 vx = vox = vo cos θo vy = vo sin θo − g t The path of a projectile is parabolic and is given by : 2 gx y = ( tanθ0 ) x – 2 2 (v o cosθo ) The maximum height that a projectile attains is : Reprint 2025-26 MOTION IN A PLANE 45 (v o sinq o )2 h m = 2g The time taken to reach this height is : v o sinθo t m = g The horizontal distance travelled by a projectile from its initial position to the position it passes y = 0 during its fall is called the range, R of the projectile. It is : v o2 R = sin2θo g 17. When an object follows a circular path at constant speed, the motion of the object is called uniform circular motion. The magnitude of its acceleration is ac = v2 /R. The direction of ac is always towards the centre of the circle. The angular speed ω, is the rate of change of angular distance. It is related to velocity v by v = ω R. The acceleration is ac = ω 2R. If T is the time period of revolution of the object in circular motion and ν is its frequency, we have ω = 2π ν, v = 2πνR, ac = 4π2ν2R Reprint 2025-26 46 PHYSICS POINTS TO PONDER 1. The path length traversed by an object between two points is, in general, not the same as the magnitude of displacement. The displacement depends only on the end points; the path length (as the name implies) depends on the actual path. The two quantities are equal only if the object does not change its direction during the course of motion. In all other cases, the path length is greater than the magnitude of displacement. 2. In view of point 1 above, the average speed of an object is greater than or equal to the magnitude of the average velocity over a given time interval. The two are equal only if the path length is equal to the magnitude of displacement. 3. The vector equations (3.33a) and (3.34a) do not involve any choice of axes. Of course, you can always resolve them along any two independent axes. 4. The kinematic equations for uniform acceleration do not apply to the case of uniform circular motion since in this case the magnitude of acceleration is constant but its direction is changing. 5. An object subjected to two velocities v1 and v2 has a resultant velocity v = v1 + v2. Take care to distinguish it from velocity of object 1 relative to velocity of object 2 : v12= v1 − v2. Here v1 and v2 are velocities with reference to some common reference frame. 6. The resultant acceleration of an object in circular motion is towards the centre only if the speed is constant. 7. The shape of the trajectory of the motion of an object is not determined by the acceleration alone but also depends on the initial conditions of motion ( initial position and initial velocity). For example, the trajectory of an object moving under the same acceleration due to gravity can be a straight line or a parabola depending on the initial conditions. EXERCISES 3.1 State, for each of the following physical quantities, if it is a scalar or a vector : volume, mass, speed, acceleration, density, number of moles, velocity, angular frequency, displacement, angular velocity. 3.2 Pick out the two scalar quantities in the following list : force, angular momentum, work, current, linear momentum, electric field, average velocity, magnetic moment, relative velocity. 3.3 Pick out the only vector quantity in the following list : Temperature, pressure, impulse, time, power, total path length, energy, gravitational potential, coefficient of friction, charge. 3.4 State with reasons, whether the following algebraic operations with scalar and vector physical quantities are meaningful : (a) adding any two scalars, (b) adding a scalar to a vector of the same dimensions , (c) multiplying any vector by any scalar, (d) multiplying any two scalars, (e) adding any two vectors, (f) adding a component of a vector to the same vector. 3.5 Read each statement below carefully and state with reasons, if it is true or false : (a) The magnitude of a vector is always a scalar, (b) each component of a vector is always a scalar, (c) the total path length is always equal to the magnitude of the displacement vector of a particle. (d) the average speed of a particle (defined as total path length divided by the time taken to cover the path) is either greater or equal to the magnitude of average velocity of the particle over the same interval of time, (e) Three vectors not lying in a plane can never add up to give a null vector. 3.6 Establish the following vector inequalities geometrically or otherwise : (a) |a+b| < |a| + |b| (b) |a+b| > ||a| −|b|| Reprint 2025-26 MOTION IN A PLANE 47 (c) |a−b| < |a| + |b| (d) |a−b| > ||a| − |b|| When does the equality sign above apply? 3.7 Given a + b + c + d = 0, which of the following statements are correct : Q (a) a, b, c, and d must each be a null vector, (b) The magnitude of (a + c) equals the magnitude of ( b + d), (c) The magnitude of a can never be greater than the sum of the magnitudes of b, c, and d, (d) b + c must lie in the plane of a and d if a and d are not collinear, and in the line of a and d, if they are collinear ? 3.8 Three girls skating on a circular ice ground of radius 200 m start from a point P on the edge of the ground and reach a point Q diametrically opposite to P following different paths as shown in Fig. 3.19. What is the magnitude of the displacement vector for each ? For Fig. 3.19 which girl is this equal to the actual length of path skate ? 3.9 A cyclist starts from the centre O of a circular park of radius 1 km, reaches the edge P of the park, then cycles along the circumference, and returns to the centre along QO as shown in Fig. 3.20. If the round trip takes 10 min, what is the (a) net displacement, (b) average velocity, and (c) average speed of the cyclist ? Fig. 3.20 3.10 On an open ground, a motorist follows a track that turns to his left by an angle of 600 after every 500 m. Starting from a given turn, specify the displacement of the motorist at the third, sixth and eighth turn. Compare the magnitude of the displacement with the total path length covered by the motorist in each case. 3.11 A passenger arriving in a new town wishes to go from the station to a hotel located 10 km away on a straight road from the station. A dishonest cabman takes him along a circuitous path 23 km long and reaches the hotel in 28 min. What is (a) the average speed of the taxi, (b) the magnitude of average velocity ? Are the two equal ? 3.12 The ceiling of a long hall is 25 m high. What is the maximum horizontal distance that a ball thrown with a speed of 40 m s-1 can go without hitting the ceiling of the hall ? 3.13 A cricketer can throw a ball to a maximum horizontal distance of 100 m. How much high above the ground can the cricketer throw the same ball ? Reprint 2025-26 48 PHYSICS 3.14 A stone tied to the end of a string 80 cm long is whirled in a horizontal circle with a constant speed. If the stone makes 14 revolutions in 25 s, what is the magnitude and direction of acceleration of the stone ? 3.15 An aircraft executes a horizontal loop of radius 1.00 km with a steady speed of 900 km/h. Compare its centripetal acceleration with the acceleration due to gravity. 3.16 Read each statement below carefully and state, with reasons, if it is true or false : (a) The net acceleration of a particle in circular motion is always along the radius of the circle towards the centre (b) The velocity vector of a particle at a point is always along the tangent to the path of the particle at that point (c) The acceleration vector of a particle in uniform circular motion averaged over one cycle is a null vector 3.17 The position of a particle is given by r = 3.0t ˆi − 2.0t 2 ˆj + 4.0 kˆ m where t is in seconds and the coefficients have the proper units for r to be in metres. (a) Find the v and a of the particle? (b) What is the magnitude and direction of velocity of the particle at t = 2.0 s ? 3.18 A particle starts from the origin at t = 0 s with a velocity of 10.0 jɵ m/s and moves in ɵ ɵ the x-y plane with a constant acceleration of 8.0 i + 2.0 j m s-2. (a) At what time is ( ) the x- coordinate of the particle 16 m? What is the y-coordinate of the particle at that time? (b) What is the speed of the particle at the time ? 3.19 ɵi and ɵj are unit vectors along x- and y- axis respectively. What is the magnitude ɵ ɵ ɵ ɵ and direction of the vectors i + j , and i − j ? What are the components of a vector ɵ ɵ ɵ ɵ ɵ ɵ A= 2 i + 3 j along the directions of i + j and i −?j [You may use graphical method] 3.20 For any arbitrary motion in space, which of the following relations are true : (a) vaverage = (1/2) (v (t1) + v (t2)) (b) v average = [r(t2) - r(t1) ] /(t2 – t1) (c) v (t) = v (0) + a t (d) r (t) = r (0) + v (0) t + (1/2) a t2 (e) a average =[ v (t2) - v (t1 )] /( t2 – t1) (The ‘average’ stands for average of the quantity over the time interval t1 to t2) 3.21 Read each statement below carefully and state, with reasons and examples, if it is true or false : A scalar quantity is one that (a) is conserved in a process (b) can never take negative values (c) must be dimensionless (d) does not vary from one point to another in space (e) has the same value for observers with different orientations of axes. 3.22 An aircraft is flying at a height of 3400 m above the ground. If the angle subtended at a ground observation point by the aircraft positions 10.0 s a part is 30°, wat is the speed of the aircraft ? Reprint 2025-26 CHAPTER FOUR LAWS OF MOTION 4.1 INTRODUCTION In the preceding Chapter, our concern was to describe the motion of a particle in space quantitatively. We saw that 4.1 Introduction uniform motion needs the concept of velocity alone whereas 4.2 Aristotle’s fallacy non-uniform motion requires the concept of acceleration in 4.3 The law of inertia addition. So far, we have not asked the question as to what governs the motion of bodies. In this chapter, we turn to this4.4 Newton’s first law of motion basic question.4.5 Newton’s second law of Let us first guess the answer based on our common motion experience. To move a football at rest, someone must kick it.4.6 Newton’s third law of motion To throw a stone upwards, one has to give it an upward

3.2 A battery of emf 10 V and internal resistance 3 Ω is connected to a resistor. If the current in the circuit is 0.5 A, what is the resistance of the resistor? What is the terminal voltage of the battery when the circuit is closed?

3.7 and are in the direction specified by the problem. Using the rule of vector addition, we see that the resultant of vr and vw is R as shown in the figure. The magnitude of R is 2 2 2 2 −1 −1 R = v r + v w = 35 + 12 m s = 37 m s The direction θ that R makes with the vertical is given by v w 12 tan θ = = = 0.343 Fig. 3.8 (a) Two non-colinear vectors a and b. v r 35 (b) Resolving a vector A in terms of vectors Or, θ = tan-1 ( 0.343 ) = 19° a and b. Therefore, the boy should hold his umbrella We say that A has been resolved into two in the vertical plane at an angle of about 19o component vectors λ a and µ b along a and b with the vertical towards the east. ⊳ Reprint 2025-26 32 PHYSICS respectively. Using this method one can resolve and A2 is parallel to ɵj, we have :a given vector into two component vectors along a set of two vectors – all the three lie in the same A1= Ax ɵi , A2 = Ay ɵj (3.11) plane. It is convenient to resolve a general vector where Ax and Ay are real numbers.along the axes of a rectangular coordinate system using vectors of unit magnitude. These Thus, A = Ax ɵi + Ay ɵj (3.12) are called unit vectors that we discuss now. A unit vector is a vector of unit magnitude and This is represented in Fig. 3.9(c). The quantities points in a particular direction. It has no Ax and Ay are called x-, and y- components of the dimension and unit. It is used to specify a vector A. Note that Ax is itself not a vector, but direction only. Unit vectors along the x-, y- and ɵi is a vector, and so is Ay ɵj. Using simplez-axes of a rectangular coordinate system are Ax trigonometry, we can express Ax and Ay in terms denoted by ɵi , ɵj and ˆk , respectively, as shown of the magnitude of A and the angle θ it makes in Fig. 3.9(a). with the x-axis : Since these are unit vectors, we have Ax = A cos θ Ay = A sin θ (3.13) ˆi  = ˆj  = ˆk =1 (3.9) As is clear from Eq. (3.13), a component of a These unit vectors are perpendicular to each vector can be positive, negative or zero other. In this text, they are printed in bold face depending on the value of θ. with a cap (^) to distinguish them from other Now, we have two ways to specify a vector A vectors. Since we are dealing with motion in two in a plane. It can be specified by : dimensions in this chapter, we require use of (i) its magnitude A and the direction θ it makes only two unit vectors. If we multiply a unit vector, with the x-axis; or say ˆn by a scalar, the result is a vector (ii) its components Ax and Ay λ = λ ˆn. In general, a vector A can be written as If A and θ are given, Ax and Ay can be obtained using Eq. (3.13). If Ax and Ay are given, A and θ A = |A| ˆn (3.10) can be obtained as follows : where ˆn is a unit vector along A. 2 2 2 2 2 2 A x + A y = A cos θ + A sin θ We can now resolve a vector A in terms = A2 of component vectors that lie along unit vectors iˆ and ɵj. Consider a vector A that lies in x-y Or, A = A 2x + Ay2 (3.14) plane as shown in Fig. 3.9(b). We draw lines from the head of A perpendicular to the coordinate Ay A y tan θ = , θ = tan− 1 axes as in Fig. 3.9(b), and get vectors A1 and A2 And A x A x (3.15) such that A1 + A2 = A. Since A1 is parallel to ɵi Fig. 3.9 (a) Unit vectors ɵi , ɵj and ɵk lie along the x-, y-, and z-axes. (b) A vector A is resolved into its components Ax and Ay along x-, and y- axes. (c) A1 and A2 expressed in terms of ɵi and ɵj . Reprint 2025-26 MOTION IN A PLANE 33 So far we have considered a vector lying in ɵ ɵ B = B x i + B y jan x-y plane. The same procedure can be used Let R be their sum. We haveto resolve a general vector A into three components along x-, y-, and z-axes in three R = A + B dimensions. If α, β, and γ are the angles* ɵ ɵ ɵ ɵ = + (3.19a) ( A x i + A y j ) ( B x i + B y j )between A and the x-, y-, and z-axes, respectively [Fig. 3.9(d)], we have Since vectors obey the commutative and associative laws, we can arrange and regroup the vectors in Eq. (3.19a) as convenient to us : ɵ ɵ j (3.19b) R = ( A x + B x ) i + ( A y + B y ) ɵ ɵ SinceR = R x i + R y j (3.20) we have, R x = A x + B x , R y = A y + B y (3.21) Thus, each component of the resultant vector R is the sum of the corresponding components of A and B. In three dimensions, we have ɵ ɵ ɵ A = A x i + Ay j + A z k ɵ ɵ ɵ B = B x i + B y j + B z k (d) ɵ ɵ ɵ R = A + B = R x i + R y j + R z kFig. 3.9 (d) A vector A resolved into components along x-, y-, and z-axes with R x = A x + B x y = A y + B yA x = A cos α, A y = A cos β, A z = A cos γ (3.16a) R In general, we have R z = A z + B z (3.22) A = Ax ˆi + Ay ˆj + Az kˆ (3.16b) This method can be extended to addition and The magnitude of vector A is subtraction of any number of vectors. For A = A x2 + Ay2 + A z2 (3.16c) example, if vectors a, b and c are given as ɵ ɵ ɵ A position vector r can be expressed as a = a x i + a y j + a z k ɵ ɵ ɵ r = x i + y j + z k (3.17) ɵ ɵ ɵ b = b x i + b y j + b z k where x, y, and z are the components of r along ɵ ɵ ɵ x-, y-, z-axes, respectively. c = c x i + c y j + c z k (3.23a)

3.1 The storage battery of a car has an emf of 12 V. If the internal resistance of the battery is 0.4 Ω, what is the maximum current that can be drawn from the battery?

3.3 At room temperature (27.0 °C) the resistance of a heating element is 100 Ω. What is the temperature of the element if the resistance is found to be 117 Ω, given that the temperature coefficient of the material of the resistor is 1.70 × 10–4 °C–1. 105 Reprint 2025-26 Physics 3.4 A negligibly small current is passed through a wire of length 15 m and uniform cross-section 6.0 × 10–7 m2, and its resistance is measured to be 5.0 W. What is the resistivity of the material at the temperature of the experiment? 3.5 A silver wire has a resistance of 2.1 W at 27.5 °C, and a resistance of 2.7 W at 100 °C. Determine the temperature coefficient of resistivity of silver. 3.6 A heating element using nichrome connected to a 230 V supply draws an initial current of 3.2 A which settles after a few seconds to a steady value of 2.8 A. What is the steady temperature of the heating element if the room temperature is 27.0 °C? Temperature coefficient of resistance of nichrome averaged over the temperature range involved is 1.70 × 10–4 °C–1. 3.7 Determine the current in each branch of the network shown in Fig. 3.20: FIGURE 3.20 3.8 A storage battery of emf 8.0 V and internal resistance 0.5 W is being charged by a 120 V dc supply using a series resistor of 15.5 W. What is the terminal voltage of the battery during charging? What is the purpose of having a series resistor in the charging circuit? 3.9 The number density of free electrons in a copper conductor estimated in Example 3.1 is 8.5 × 1028 m–3. How long does an electron take to drift from one end of a wire 3.0 m long to its other end? The area of cross-section of the wire is 2.0 × 10–6 m2 and it is carrying a current of 3.0 A. Reprint 2025-26 Chapter Four MOVING CHARGES AND MAGNETISM 4.1 INTRODUCTION Both Electricity and Magnetism have been known for more than 2000 years. However, it was only about 200 years ago, in 1820, that it was realised that they were intimately related. During a lecture demonstration in the summer of 1820, Danish physicist Hans Christian Oersted noticed that a current in a straight wire caused a noticeable deflection in a nearby magnetic compass needle. He investigated this phenomenon. He found that the alignment of the needle is tangential to an imaginary circle which has the straight wire as its centre and has its plane perpendicular to the wire. This situation is depicted in Fig.4.1(a). It is noticeable when the current is large and the needle sufficiently close to the wire so that the earth’s magnetic field may be ignored. Reversing the direction of the current reverses the orientation of the needle [Fig. 4.1(b)]. The deflection increases on increasing the current or bringing the needle closer to the wire. Iron filings sprinkled around the wire arrange themselves in concentric circles with the wire as the centre [Fig. 4.1(c)]. Oersted concluded that moving charges or currents produced a magnetic field in the surrounding space. Following this, there was intense experimentation. In 1864, the laws obeyed by electricity and magnetism were unified and formulated by Reprint 2025-26 Physics James Maxwell who then realised that light was electromagnetic waves. Radio waves were discovered by Hertz, and produced by J.C.Bose and G. Marconi by the end of the 19th century. A remarkable scientific and technological progress took place in the 20th century. This was due to our increased understanding of electromagnetism and the invention of devices for production, amplification, transmission and detection of electromagnetic waves. FIGURE 4.1 The magnetic field due to a straight long current-carrying wire. The wire is perpendicular to the plane of the paper. A ring of compass needles surrounds the wire. The orientation of the needles is shown when (a) the current emerges out of the plane of the paper, (b) the current moves into the plane of the paper. (c) The arrangement of iron filings around the wire. The darkened ends of the needle represent north poles. The effect of the earth’s magnetic field is neglected. In this chapter, we will see how magnetic field exerts forces on moving charged particles, like electrons, protons, and current-carrying wires. We shall also learn how currents produce magnetic fields. We shall see how particles can be accelerated to very high energies in a cyclotron. We shall study how currents and voltages are detected by a galvanometer.(1777–1851) In this and subsequent Chapter on magnetism, we adopt the following convention: A current or a field (electric or magnetic) emerging out of the plane of the paper is depicted by a dot (¤). A current or a field going into the plane of the paper is depicted by a cross ()*. Hans Christian Oersted Figures. 4.1(a) and 4.1(b) correspond to these twoOERSTED (1777–1851) Danish situations, respectively. physicist and chemist, professor at Copenhagen. 4.2 MAGNETIC FORCE He observed that a compass needle suffers a 4.2.1 Sources and fields deflection when placed Before we introduce the concept of a magnetic field B, weCHRISTIAN near a wire carrying an electric current. This shall recapitulate what we have learnt in Chapter 1 about discovery gave the first the electric field E. We have seen that the interaction empirical evidence of a between two charges can be considered in two stages.HANS connection between electric The charge Q, the source of the field, produces an electric and magnetic phenomena. field E, where * A dot appears like the tip of an arrow pointed at you, a cross is like the feathered 108 tail of an arrow moving away from you. Reprint 2025-26 Moving Charges and Magnetism E = Q ˆr / (4pe0)r2 (4.1) where ˆr is unit vector along r, and the field E is a vector field. A charge q interacts with this field and experiences a force F given by F = q E = q Q ˆr / (4pe0) r 2 (4.2) As pointed out in the Chapter 1, the field E is not just an artefact but has a physical role. It can convey energy and momentum and is not established instantaneously but takes finite time to propagate. The concept of a field was specially stressed by Faraday and was incorporated by Maxwell in his unification of electricity and magnetism. In addition to depending on each point in space, it can also vary with time, i.e., be a function of time. In our Hendrik Antoon Lorentz discussions in this chapter, we will assume that the fields (1853 – 1928) Dutch do not change with time. theoretical physicist, The field at a particular point can be due to one or professor at Leiden. He investigated themore charges. If there are more charges the fields add HENDRIK relationship between vectorially. You have already learnt in Chapter 1 that this electricity, magnetism, and is called the principle of superposition. Once the field is mechanics. In order to known, the force on a test charge is given by Eq. (4.2). explain the observed effect Just as static charges produce an electric field, the of magnetic fields on ANTOONcurrents or moving charges produce (in addition) a emitters of light (Zeeman magnetic field, denoted by B (r), again a vector field. It effect), he postulated the existence of electric chargeshas several basic properties identical to the electric field. in the atom, for which he It is defined at each point in space (and can in addition was awarded the Nobel Prize depend on time). Experimentally, it is found to obey the in 1902. He derived a set of LORENTZprinciple of superposition: the magnetic field of several transformation equations sources is the vector addition of magnetic field of each (known after him, as individual source. Lorentz transformation equations) by some tangled (1853 4.2.2 Magnetic Field, Lorentz Force mathematical arguments, – but he was not aware thatLet us suppose that there is a point charge q (moving these equations hinge on a with a velocity v and, located at r at a given time t) in new concept of space andpresence of both the electric field E (r) and the magnetic 1928) time. field B (r). The force on an electric charge q due to both of them can be written as F = q [ E (r) + v × B (r)] º Felectric +Fmagnetic (4.3) This force was given first by H.A. Lorentz based on the extensive experiments of Ampere and others. It is called the Lorentz force. You have already studied in detail the force due to the electric field. If we look at the interaction with the magnetic field, we find the following features. (i) It depends on q, v and B (charge of the particle, the velocity and the magnetic field). Force on a negative charge is opposite to that on a positive charge. (ii) The magnetic force q [ v × B ] includes a vector product of velocity 109 and magnetic field. The vector product makes the force due to magnetic Reprint 2025-26 Physics field vanish (become zero) if velocity and magnetic field are parallel or anti-parallel. The force acts in a (sideways) direction perpendicular to both the velocity and the magnetic field. Its direction is given by the screw rule or right hand rule for vector (or cross) product as illustrated in Fig. 4.2. (iii) The magnetic force is zero if charge is not moving (as then |v|= 0). Only a moving charge feels the magnetic force. The expression for the magnetic force helps us to define the unit of the magnetic field, if one FIGURE 4.2 The direction of the magnetic takes q, F and v, all to be unity in the force force acting on a charged particle. (a) The equation F = q [ v × B] =q v B sin q ˆn , where q is force on a positively charged particle with the angle between v and B [see Fig. 4.2 (a)]. The velocity v and making an angle q with the magnitude of magnetic field B is 1 SI unit, when magnetic field B is given by the right-hand the force acting on a unit charge (1 C), moving rule. (b) A moving charged particle q is perpendicular to B with a speed 1m/s, is one deflected in an opposite sense to –q in the newton. presence of magnetic field. Dimensionally, we have [B] = [F/qv] and the unit of B are Newton second / (coulomb metre). This unit is called tesla (T) named after Nikola Tesla (1856 – 1943). Tesla is a rather large unit. A smaller unit (non-SI) called gauss (=10–4 tesla) is also often used. The earth’s magnetic field is about 3.6 × 10–5 T. 4.2.3 Magnetic force on a current-carrying conductor We can extend the analysis for force due to magnetic field on a single moving charge to a straight rod carrying current. Consider a rod of a uniform cross-sectional area A and length l. We shall assume one kind of mobile carriers as in a conductor (here electrons). Let the number density of these mobile charge carriers in it be n. Then the total number of mobile charge carriers in it is nlA. For a steady current I in this conducting rod, we may assume that each mobile carrier has an average drift velocity vd (see Chapter 3). In the presence of an external magnetic field B, the force on these carriers is: F = (nlA)q vd ´ B where q is the value of the charge on a carrier. Now nq vd is the current density j and |(nq vd)|A is the current I (see Chapter 3 for the discussion of current and current density). Thus, F = [(nq vd )lA] × B = [ jAl ] ´ B = Il ´ B (4.4) where l is a vector of magnitude l, the length of the rod, and with a direction identical to the current I. Note that the current I is not a vector. In the last step leading to Eq. (4.4), we have transferred the vector sign from j to l. Equation (4.4) holds for a straight rod. In this equation, B is the external magnetic field. It is not the field produced by the current-carrying rod. If the wire has an arbitrary shape we can calculate the Lorentz force on it by considering it as a collection of linear strips dlj and summing F  Idl j × B j This summation can be converted to an integral in most cases. Reprint 2025-26 Moving Charges and Magnetism Example 4.1 A straight wire of mass 200 g and length 1.5 m carries a current of 2 A. It is suspended in mid-air by a uniform horizontal magnetic field B (Fig. 4.3). What is the magnitude of the magnetic field? FIGURE 4.3 Solution From Eq. (4.4), we find that there is an upward force F, of magnitude IlB,. For mid-air suspension, this must be balanced by the force due to gravity: m g = I lB m g B = I l Interactive Charged 0.2 × 9.8 = = 0.65 T 2 × 1.5 Note that it would have been sufficient to specify m/l, the mass per EXAMPLE particles unit length of the wire. The earth’s 4 × 10–5 T and we have ignored it. magnetic field is approximately 4.1 moving demonstration: in a Example 4.2 If the magnetic field is parallel to the positive y-axis and the charged particle is moving along the positive x-axis (Fig. 4.4), which way would the Lorentz force be for (a) an electron (negative magnetic charge), (b) a proton (positive charge). field. http://www.phys.hawaii.edu/~teb/optics/java/partmagn/index.html FIGURE 4.4 Solution The velocity v of particle is along the x-axis, while B, the magnetic field is along the y-axis, so v × B is along the z-axis (screw rule or right-hand thumb rule). So, (a) for electron it will be along –z EXAMPLE axis. (b) for a positive charge (proton) the force is along +z axis. 4.2 111 Reprint 2025-26 Physics 4.3 MOTION IN A MAGNETIC FIELD We will now consider, in greater detail, the motion of a charge moving in a magnetic field. We have learnt in Mechanics (see Class XI book, Chapter 5) that a force on a particle does work if the force has a component along (or opposed to) the direction of motion of the particle. In the case of motion of a charge in a magnetic field, the magnetic force is perpendicular to the velocity of the particle. So no work is done and no change in the magnitude of the velocity is produced (though the direction of momentum may be changed). [Notice that this is unlike the force due to an electric field, qE, which can have a component parallel (or antiparallel) to motion and thus can transfer energy in addition to momentum.] We shall consider motion of a charged particle in a uniform magnetic field. First consider the case of v perpendicular to B. The perpendicular force, q v × B, acts as a centripetal force and produces a circular motion perpendicular to the magnetic field. The particle will describe a circle if v and B are perpendicular to each other (Fig. 4.5). If velocity has a component along B, this component remains unchanged as the motion along the magnetic field will not be affected by the magnetic field. The motion in a plane perpendicular to B is as before a circular one, thereby producing a helical motion (Fig. 4.6). You have already learnt in earlier classes (See Class XI, Chapter 3) that if r is the radius of the circular path of a particle, then a force of m v2 / r, acts perpendicular to the path towards the centre of the circle, and is called the centripetal force. If the FIGURE 4.5 Circular motion velocity v is perpendicular to the magnetic field B, the magnetic force is perpendicular to both v and B and acts like a centripetal force. It has a magnitude q v B. Equating the two expressions for centripetal force, m v 2/r = q v B, which gives r = m v / qB (4.5) for the radius of the circle described by the charged particle. The larger the momentum, the larger is the radius and bigger the circle described. If w is the angular frequency, then v = w r. So, w = 2p n = q B/ m [4.6(a)] which is independent of the velocity or energy . Here n is the frequency of rotation. The independence of n from energy has important application in the design of a cyclotron. The time taken for one revolution is T= 2p/ w º 1/n. If there is a component of the velocity FIGURE 4.6 Helical motion parallel to the magnetic field (denoted by v||), 112 it will make the particle move along the field and the path of the Reprint 2025-26 Moving Charges and Magnetism particle would be a helical one (Fig. 4.6). The distance moved along the magnetic field in one rotation is called pitch p. Using Eq. [4.6 (a)], we have p = v||T = 2pm v|| / q B [4.6(b)] The radius of the circular component of motion is called the radius of the helix. Example 4.3 What is the radius of the path of an electron (mass 9 × 10-31 kg and charge 1.6 × 10–19 C) moving at a speed of 3 ×107 m/s in a magnetic field of 6 × 10–4 T perpendicular to it? What is its frequency? Calculate its energy in keV. ( 1 eV = 1.6 × 10–19 J). Solution Using Eq. (4.5) we find r = m v / (qB) = 9 ×10–31 kg × 3 × 107 m s–1 / ( 1.6 × 10–19 C × 6 × 10–4 T) = 28 × 10–2 m = 28 cm n = v / (2 pr) = 17×106 s–1 = 17×106 Hz =17 MHz. 2 EXAMPLE E = (½ )mv = (½ ) 9 × 10–31 kg × 9 × 1014 m2/s2 = 40.5 ×10–17 J ≈ 4×10–16 J = 2.5 keV. 4.3

12.5 A hydrogen atom initially in the ground level absorbs a photon, which excites it to the n = 4 level. Determine the wavelength and frequency of photon.

12.7 The radius of the innermost electron orbit of a hydrogen atom is 5.3×10–11 m. What are the radii of the n = 2 and n =3 orbits?

12.3 BEHAVIOUR OF GASES where M is the mass of the gas containing N Properties of gases are easier to understand than molecules, M0 is the molar mass and NA the those of solids and liquids. This is mainly Avogadro’s number. Using Eqs. (12.4) and (12.3) because in a gas, molecules are far from each can also be written as other and their mutual interactions are PV = kB NT or P = kB nT negligible except when two molecules collide. Gases at low pressures and high temperatures much above that at which they liquefy (or solidify) approximately satisfy a simple relation ) between their pressure, temperature and volume –1 given by (see Chapter 10) K –1 PV = KT (12.1) mol Jfor a given sample of the gas. Here T is the ( temperature in kelvin or (absolute) scale. K is a T pV µ constant for the given sample but varies with the volume of the gas. If we now bring in the idea of atoms or molecules, then K is proportional to the number of molecules, (say) N in the sample. We can write K = N k . Observation tells P (atm) us that this k is same for all gases. It is called Fig.12.1 Real gases approach ideal gas behaviour at Boltzmann constant and is denoted by k B. low pressures and high temperatures. P1V1 P2 V2 where n is the number density, i.e. number ofAs = = constant = kB (12.2) N 1 T1 N 2 T2 molecules per unit volume. kB is the Boltzmann constant introduced above. Its value in SI unitsif P, V and T are same, then N is also same for all is 1.38 × 10–23 J K–1.gases. This is Avogadro’s hypothesis, that the Another useful form of Eq. (12.3) isnumber of molecules per unit volume is ρRT the same for all gases at a fixed temperature and P = (12.5) pressure. The number in 22.4 litres of any gas M 0 Reprint 2025-26 KINETIC THEORY 247 where ρ is the mass density of the gas. etc. in a vessel of volume V at temperature T and A gas that satisfies Eq. (12.3) exactly at all pressure P. It is then found that the equation of pressures and temperatures is defined to be an state of the mixture is : ideal gas. An ideal gas is a simple theoretical PV = ( µ1 + µ2 +… ) RT (12.7)model of a gas. No real gas is truly ideal. Fig. 12.1 shows departures from ideal gas RT RT i.e. P = µ1 + µ2 + ... (12.8)behaviour for a real gas at three different V V temperatures. Notice that all curves approach = P1 + P2 + … (12.9)the ideal gas behaviour for low pressures and high temperatures. Clearly P1 = µ1 R T/V is the pressure that At low pressures or high temperatures the gas 1 would exert at the same conditions of molecules are far apart and molecular volume and temperature if no other gases were interactions are negligible. Without interactions present. This is called the partial pressure of the the gas behaves like an ideal one. gas. Thus, the total pressure of a mixture of ideal If we fix µ and T in Eq. (12.3), we get gases is the sum of partial pressures. This is Dalton’s law of partial pressures. PV = constant (12.6) i.e., keeping temperature constant, pressure of a given mass of gas varies inversely with volume. This is the famous Boyle’s law. Fig. 12.2 shows comparison between experimental P-V curves and the theoretical curves predicted by Boyle’s law. Once again you see that the agreement is good at high temperatures and low pressures. Next, if you fix P, Eq. (12.1) shows that V ∝ T i.e., for a fixed pressure, the volume of a gas is proportional to its absolute temperature T (Charles’ law). See Fig. 12.3. Fig. 12.3 Experimental T-V curves (solid lines) for CO2 at three pressures compared with Charles’ law (dotted lines). T is in units of 300 K and V in units of 0.13 litres. We next consider some examples which give us information about the volume occupied by the molecules and the volume of a single molecule. ⊳ Example 12.1 The density of water is 1000 kg m–3. The density of water vapour at 100 °C and 1 atm pressure is 0.6 kg m–3. The volume of a molecule multiplied by the total Fig.12.2 Experimental P-V curves (solid lines) for number gives ,what is called, molecular steam at three temperatures compared with volume. Estimate the ratio (or fraction) of Boyle’s law (dotted lines). P is in units of 22 the molecular volume to the total volume atm and V in units of 0.09 litres. occupied by the water vapour under the Finally, consider a mixture of non-interacting above conditions of temperature and pressure.ideal gases: µ moles of gas 1, µ moles of gas 2, 1 2 Reprint 2025-26 248 PHYSICS Answer For a given mass of water molecules, number of molecules and (ii) mass density the density is less if volume is large. So the of neon and oxygen in the vessel. Atomic volume of the vapour is 1000/0.6 = 1/(6 × 10 -4 ) mass of Ne = 20.2 u, molecular mass of O2times larger. If densities of bulk water and water = 32.0 u. molecules are same, then the fraction of molecular volume to the total volume in liquid Answer Partial pressure of a gas in a mixture is state is 1. As volume in vapour state has the pressure it would have for the same volume increased, the fractional volume is less by the and temperature if it alone occupied the vessel. same amount, i.e. 6×10-4. ⊳ (The total pressure of a mixture of non-reactive ⊳ gases is the sum of partial pressures due to its Example 12.2 Estimate the volume of a constituent gases.) Each gas (assumed ideal) water molecule using the data in Example obeys the gas law. Since V and T are common to 12.1. the two gases, we have P1V = µ 1 RT and P2V = Answer In the liquid (or solid) phase, the µ2 RT, i.e. (P1/P2) = (µ1 / µ2). Here 1 and 2 refer to neon and oxygen respectively. Since (P1/P2) =molecules of water are quite closely packed. The (3/2) (given), (µ1/ µ2) = 3/2.density of water molecule may therefore, be (i) By definition µ1 = (N1/NA ) and µ2 = (N2/NA)regarded as roughly equal to the density of bulk where N1 and N2 are the number of moleculeswater = 1000 kg m–3. To estimate the volume of of 1 and 2, and NA is the Avogadro’s number.a water molecule, we need to know the mass of Therefore, (N1/N2) = (µ1 / µ2) = 3/2.a single water molecule. We know that 1 mole (ii) We can also write µ1 = (m1/M1) and µ2 =of water has a mass approximately equal to (2 + 16)g = 18 g = 0.018 kg. (m2/M2) where m1 and m2 are the masses of 1 and 2; and M1 and M2 are their molecular Since 1 mole contains about 6 × 1023 masses. (Both m1 and M1; as well as m2 andmolecules (Avogadro’s number), the mass of a molecule of water is (0.018)/(6 × 1023) kg = M2 should be expressed in the same units). If ρ1 and ρ2 are the mass densities of 1 and3 × 10–26 kg. Therefore, a rough estimate of the 2 respectively, we havevolume of a water molecule is as follows : Volume of a water molecule ρ1 m 1 / V m 1 µ1  M 1  = (3 × 10–26 kg)/ (1000 kg m–3) = = = × ρ2 m 2 / V m 2 µ2  M 2  = 3 × 10–29 m3 = (4/3) π (Radius)3 3 20.2 Hence, Radius ≈ 2 ×10-10 m = 2 Å ⊳ = × = 0.947 2 32.0 ⊳ ⊳ Example 12.3 What is the average distance between atoms (interatomic distance) in water? Use the data given in 12.4 KINETIC THEORY OF AN IDEAL GAS Examples 12.1 and 12.2. Kinetic theory of gases is based on the molecular picture of matter. A given amount of gas is a Answer : A given mass of water in vapour state collection of a large number of molecules has 1.67×103 times the volume of the same mass (typically of the order of Avogadro’s number) that of water in liquid state (Ex. 12.1). This is also are in incessant random motion. At ordinary the increase in the amount of volume available pressure and temperature, the average distance for each molecule of water. When volume between molecules is a factor of 10 or more than increases by 103 times the radius increases by the typical size of a molecule (2 Å). Thus, V1/3 or 10 times, i.e., 10 × 2 Å = 20 Å. So the interaction between molecules is negligible and average distance is 2 × 20 = 40 Å. ⊳ we can assume that they move freely in straight lines according to Newton’s first law. However,⊳ Example 12.4 A vessel contains two non- occasionally, they come close to each other, reactive gases : neon (monatomic) and experience intermolecular forces and their oxygen (diatomic). The ratio of their partial velocities change. These interactions are called pressures is 3:2. Estimate the ratio of (i) collisions. The molecules collide incessantly against each other or with the walls and change Reprint 2025-26 KINETIC THEORY 249 their velocities. The collisions are considered to the wall. Thus, the number of molecules with be elastic. We can derive an expression for the velocity (vx, vy, vz ) hitting the wall in time ∆t is pressure of a gas based on the kinetic theory. ½A vx ∆t n, where n is the number of molecules We begin with the idea that molecules of a per unit volume. The total momentum gas are in incessant random motion, colliding transferred to the wall by these molecules in against one another and with the walls of the time ∆t is: container. All collisions between molecules Q = (2mvx) (½ n A vx ∆t ) (12.10) among themselves or between molecules and the The force on the wall is the rate of momentum walls are elastic. This implies that total kinetic transfer Q/∆t and pressure is force per unit energy is conserved. The total momentum is area : conserved as usual. P = Q /(A ∆t) = n m vx 2 (12.11) Actually, all molecules in a gas do not have 12.4.1 Pressure of an Ideal Gas the same velocity; there is a distribution in velocities. The above equation, therefore, standsConsider a gas enclosed in a cube of side l. Take for pressure due to the group of molecules withthe axes to be parallel to the sides of the cube, speed vx in the x-direction and n stands for theas shown in Fig. 12.4. A molecule with velocity number density of that group of molecules. The (vx, vy, vz ) hits the planar wall parallel to yz- total pressure is obtained by summing over theplane of area A (= l2). Since the collision is elastic, contribution due to all groups:the molecule rebounds with the same velocity; its y and z components of velocity do not change P = n m v x2 (12.12) in the collision but the x-component reverses where v 2x is the average of vx 2 . Now the gas sign. That is, the velocity after collision is is isotropic, i.e. there is no preferred direction (-vx, vy, vz ) . The change in momentum of the of velocity of the molecules in the vessel. molecule is: –mvx – (mvx) = – 2mvx . By the Therefore, by symmetry, principle of conservation of momentum, the momentum imparted to the wall in the collision v 2x = v y2 = v z2 = 2mvx . 2 2 2 2 = (1/3) [ v x + v y + v z ] = (1/3) v (12.13) where v is the speed and v 2 denotes the mean of the squared speed. Thus P = (1/3) n m v 2 (12.14) Some remarks on this derivation. First, though we choose the container to be a cube, the shape of the vessel really is immaterial. For a vessel of arbitrary shape, we can always choose a small infinitesimal (planar) area and carry through the steps above. Notice that both A and ∆t do not appear in the final result. By Pascal’s law, given in Ch. 9, pressure in one portion of Fig. 12.4 Elastic collision of a gas molecule with the the gas in equilibrium is the same as anywhere wall of the container. else. Second, we have ignored any collisions in To calculate the force (and pressure) on the the derivation. Though this assumption is wall, we need to calculate momentum imparted difficult to justify rigorously, we can qualitatively to the wall per unit time. In a small time interval see that it will not lead to erroneous results. The ∆t, a molecule with x-component of velocity vx number of molecules hitting the wall in time ∆t will hit the wall if it is within the distance vx ∆t was found to be ½ n Avx ∆t. Now the collisions from the wall. That is, all molecules within the are random and the gas is in a steady state. volume Avx ∆t only can hit the wall in time ∆t. Thus, if a molecule with velocity (vx, vy, vz ) But, on the average, half of these are moving acquires a different velocity due to collision with towards the wall and the other half away from some molecule, there will always be some other Reprint 2025-26 250 PHYSICS molecule with a different initial velocity which P = (1/3) [n1m1 v1 2 + n2 m2 v 22 +… ] (12.20) after a collision acquires the velocity (vx, vy, vz ). In equilibrium, the average kinetic energy of If this were not so, the distribution of velocities the molecules of different gases will be equal. would not remain steady. In any case we are That is, finding v x2 . Thus, on the whole, molecular ½ m1 v1 2 = ½ m2 v 22 = (3/2) kB Tcollisions (if they are not too frequent and the so thattime spent in a collision is negligible compared to time between collisions) will not affect the P = (n1 + n2 +… ) kB T (12.21) calculation above. which is Dalton’s law of partial pressures. From Eq. (12.19), we can get an idea of the12.4.2 Kinetic Interpretation of Temperature typical speed of molecules in a gas. At a Equation (13.14) can be written as temperature T = 300 K, the mean square speed PV = (1/3) nV m v 2 (12.15a) of a molecule in nitrogen gas is : PV = (2/3) N x ½ m v 2 (12.15b) M N 2 28 –26 where N (= nV) is the number of molecules in m = = 26 = 4.65 × 10 kg. N A 6.02 × 10the sample. The quantity in the bracket is the average v 2 = 3 kB T / m = (516)2 m2s-2 translational kinetic energy of the molecules in 2 The square root of v is known as root mean the gas. Since the internal energy E of an ideal square (rms) speed and is denoted by vrms,gas is purely kinetic*, 2 ( We can also write v 2 as < v2 >.) E = N × (1/2) m v (12.16) vrms = 516 m s-1 Equation (12.15) then gives : The speed is of the order of the speed of sound PV = (2/3) E (12.17) in air. It follows from Eq. (12.19) that at the same We are now ready for a kinetic interpretation temperature, lighter molecules have greater rms of temperature. Combining Eq. (12.17) with the speed. ⊳ideal gas Eq. (12.3), we get Example 12.5 A flask contains argon and E = (3/2) kB NT (12.18) chlorine in the ratio of 2:1 by mass. The or E/ N = ½ m v 2 = (3/2) kBT (12.19) temperature of the mixture is 27 °C. Obtain i.e., the average kinetic energy of a molecule is the ratio of (i) average kinetic energy per proportional to the absolute temperature of the molecule, and (ii) root mean square speed gas; it is independent of pressure, volume or vrms of the molecules of the two gases. the nature of the ideal gas. This is a fundamental Atomic mass of argon = 39.9 u; Molecular result relating temperature, a macroscopic mass of chlorine = 70.9 u. measurable parameter of a gas (a thermodynamic variable as it is called) to a Answer The important point to remember is thatmolecular quantity, namely the average kinetic the average kinetic energy (per molecule) of anyenergy of a molecule. The two domains are connected by the Boltzmann constant. We note (ideal) gas (be it monatomic like argon, diatomic in passing that Eq. (12.18) tells us that internal like chlorine or polyatomic) is always equal to energy of an ideal gas depends only on (3/2) kBT. It depends only on temperature, and temperature, not on pressure or volume. With is independent of the nature of the gas. this interpretation of temperature, kinetic theory (i) Since argon and chlorine both have the same of an ideal gas is completely consistent with the temperature in the flask, the ratio of average ideal gas equation and the various gas laws kinetic energy (per molecule) of the two gasesbased on it. is 1:1. For a mixture of non-reactive ideal gases, the total pressure gets contribution from each gas (ii) Now ½ m vrms2 = average kinetic energy per in the mixture. Equation (12.14) becomes molecule = (3/2) ) kBT where m is the mass * E denotes the translational part of the internal energy U that may include energies due to other degrees of freedom also. See section 12.5. Reprint 2025-26 KINETIC THEORY 251 of a molecule of the gas. Therefore, v 2 ( rms ) Ar (m )Cl ( M )Cl 70.9 = = 2 v rms (m ) Ar ( M ) Ar = 39.9 =1.77 ( )Cl where M denotes the molecular mass of the gas. (For argon, a molecule is just an atom of argon.) Taking square root of both sides, v ( rms ) Ar ( vrms )Cl = 1.33 You should note that the composition of the mixture by mass is quite irrelevant to the above calculation. Any other proportion by mass of argon and chlorine would give the same answers to (i) and (ii), provided the temperature remains Fig. 12.5 Molecules going through a porous wall. unaltered. ⊳ ⊳ ⊳ Example 12.7 (a) When a molecule (or an Example 12.6 Uranium has two isotopes elastic ball) hits a ( massive) wall, it of masses 235 and 238 units. If both are rebounds with the same speed. When a ball present in Uranium hexafluoride gas which hits a massive bat held firmly, the same would have the larger average speed ? If thing happens. However, when the bat is atomic mass of fluorine is 19 units, moving towards the ball, the ball rebounds estimate the percentage difference in with a different speed. Does the ball move speeds at any temperature. faster or slower? (Ch.5 will refresh your Answer At a fixed temperature the average memory on elastic collisions.) energy = ½ m <v2 > is constant. So smaller the (b) When gas in a cylinder is compressed mass of the molecule, faster will be the speed. by pushing in a piston, its temperature The ratio of speeds is inversely proportional to rises. Guess at an explanation of this in the square root of the ratio of the masses. The terms of kinetic theory using (a) above. masses are 349 and 352 units. So (c) What happens when a compressed gas v349 / v352 = ( 352/ 349)1/2 = 1.0044 . pushes a piston out and expands. What ∆ V would you observe ? Hence difference = 0.44 %. (d) Sachin Tendulkar used a heavy cricket V bat while playing. Did it help him in [235U is the isotope needed for nuclear fission. anyway ?To separate it from the more abundant isotope 238U, the mixture is surrounded by a porous cylinder. The porous cylinder must be thick and Answer (a) Let the speed of the ball be u relative narrow, so that the molecule wanders through to the wicket behind the bat. If the bat is moving individually, colliding with the walls of the long towards the ball with a speed V relative to the pore. The faster molecule will leak out more than wicket, then the relative speed of the ball to bat the slower one and so there is more of the lighter is V + u towards the bat. When the ball rebounds molecule (enrichment) outside the porous (after hitting the massive bat) its speed, relative cylinder (Fig. 12.5). The method is not very to bat, is V + u moving away from the bat. So efficient and has to be repeated several times relative to the wicket the speed of the rebounding for sufficient enrichment.]. ⊳ ball is V + (V + u) = 2V + u, moving away from the When gases diffuse, their rate of diffusion is wicket. So the ball speeds up after the collision inversely proportional to square root of the with the bat. The rebound speed will be less than masses (see Exercise 12.12 ). Can you guess the u if the bat is not massive. For a molecule this explanation from the above answer? would imply an increase in temperature. Reprint 2025-26 252 PHYSICS You should be able to answer (b) (c) and (d) to the axis joining the two oxygen atoms about based on the answer to (a). which the molecule can rotate*. The molecule (Hint: Note the correspondence, pistonà bat, thus has two rotational degrees of freedom, each of which contributes a term to the total energycylinder à wicket, molecule à ball.) ⊳ consisting of translational energy tε and rotational energy εr.12.5 LAW OF EQUIPARTITION OF ENERGY The kinetic energy of a single molecule is εt + εr = 1 mv x2 + 1 mv y2 + 1 mv z2 + 1 I 1ω12 + 1 I 2ω22 (12.25) 2 2 2 2 2 1 2 1 2 1 2 εt = mv x + mv y + mv z (12.22) 2 2 2 For a gas in thermal equilibrium at temperature T the average value of energy denoted by < tε > is 1 2 1 2 1 2 3 εt = mv x + mv y + mv z = k B T (12.23) 2 2 2 2 Since there is no preferred direction, Eq. (12.23) implies 1 2 1 1 2 1 mv x = k B T , mv y = k B T , 2 2 2 2 Fig. 12.6 The two independent axes of rotation of a diatomic molecule 1 2 1 mv z = k B T (12.24) 2 2 where ω1 and ω2 are the angular speeds about A molecule free to move in space needs three the axes 1 and 2 and I1, I2 are the corresponding coordinates to specify its location. If it is moments of inertia. Note that each rotational constrained to move in a plane it needs two; and degree of freedom contributes a term to the if constrained to move along a line, it needs just energy that contains square of a rotational one coordinate to locate it. This can also be variable of motion. expressed in another way. We say that it has We have assumed above that the O2 molecule one degree of freedom for motion in a line, two is a ‘rigid rotator’, i.e., the molecule does not for motion in a plane and three for motion in vibrate. This assumption, though found to be space. Motion of a body as a whole from one true (at moderate temperatures) for O2, is notpoint to another is called translation. Thus, a always valid. Molecules, like CO, even at molecule free to move in space has three moderate temperatures have a mode of translational degrees of freedom. Each vibration, i.e., its atoms oscillate along the translational degree of freedom contributes a interatomic axis like a one-dimensional term that contains square of some variable of 2 oscillator, and contribute a vibrational energymotion, e.g., ½ mvx and similar terms in term εv to the total energy:vy and vz. In, Eq. (12.24) we see that in thermal equilibrium, the average of each such term is 1  d y  2 1 2 εv = m + ky½ kBT . 2  d t  2 Molecules of a monatomic gas like argon have only translational degrees of freedom. But what ε = εt + εr + ε v (12.26) about a diatomic gas such as O2 or N2? A where k is the force constant of the oscillator molecule of O2 has three translational degrees and y the vibrational co-ordinate. of freedom. But in addition it can also rotate Once again the vibrational energy terms in about its centre of mass. Figure 12.6 shows the Eq. (12.26) contain squared terms of vibrational two independent axes of rotation 1 and 2, normal variables of motion y and dy/dt . * Rotation along the line joining the atoms has very small moment of inertia and does not come into play for quantum mechanical reasons. See end of section 12.6. Reprint 2025-26 KINETIC THEORY 253 At this point, notice an important feature in where Cp is the molar specific heat at constant Eq.(12.26). While each translational and pressure. Thus, rotational degree of freedom has contributed only 5 one ‘squared term’ in Eq.(12.26), one vibrational Cp = R (12.30) mode contributes two ‘squared terms’ : kinetic 2 and potential energies. C p 5 The ratio of specific heats γ = = (12.31) Each quadratic term occurring in the C v 3 expression for energy is a mode of absorption of energy by the molecule. We have seen that in 12.6.2 Diatomic Gases thermal equilibrium at absolute temperature T, As explained earlier, a diatomic molecule treated for each translational mode of motion, the as a rigid rotator, like a dumbbell, has 5 degrees average energy is ½ kBT. The most elegant of freedom: 3 translational and 2 rotational. principle of classical statistical mechanics (first Using the law of equipartition of energy, the total proved by Maxwell) states that this is so for each internal energy of a mole of such a gas is mode of energy: translational, rotational and 5 5 vibrational. That is, in equilibrium, the total U = k B T × N A = RT (12.32) 2 2 energy is equally distributed in all possible The molar specific heats are then given by energy modes, with each mode having an average energy equal to ½ kBT. This is known as the law 5 7 Cv (rigid diatomic) = R, Cp = R (12.33)of equipartition of energy. Accordingly, each 2 2 translational and rotational degree of freedom 7 of a molecule contributes ½ kBT to the energy, γ (rigid diatomic) = (12.34) while each vibrational frequency contributes 5 If the diatomic molecule is not rigid but has 2 × ½ kBT = kBT , since a vibrational mode has in addition a vibrational mode both kinetic and potential energy modes.  5  7 The proof of the law of equipartition of energy U =  k B T + k B T  N A = RT is beyond the scope of this book. Here, we shall  2  2 apply the law to predict the specific heats of gases 7 9 9 theoretically. Later, we shall also discuss briefly, C v = R , C p = R , γ = R (12.35) 2 2 7 the application to specific heat of solids. 12.6.3 Polyatomic Gases 12.6 SPECIFIC HEAT CAPACITY In general a polyatomic molecule has 3 12.6.1 Monatomic Gases translational, 3 rotational degrees of freedom and a certain number ( f ) of vibrational modes.The molecule of a monatomic gas has only three According to the law of equipartition of energy,translational degrees of freedom. Thus, the it is easily seen that one mole of such a gas hasaverage energy of a molecule at temperature 3T is (3/2)kBT . The total internal energy of a mole  3 U = kBT + kBT + f kBT  NA of such a gas is  2 2 3 3 U = k B T × N A = RT (12.27) i.e.,Cv = (3 + f ) R, Cp = (4 + f ) R, 2 2 ( 4 + f ) γ = (12.36) The molar specific heat at constant volume, ( 3 + f ) Cv, is Note that Cp – Cv = R is true for any ideal d U 3 gas, whether mono, di or polyatomic. Cv (monatomic gas) = = RT (12.28) d T 2 Table 12.1 summarises the theoretical For an ideal gas, predictions for specific heats of gases ignoring Cp – Cv = R (12.29) any vibrational modes of motion. The values are Reprint 2025-26 254 PHYSICS in good agreement with experimental values of Answer Using the gas law PV = µRT, you can specific heats of several gases given in Table 12.2. easily show that 1 mol of any (ideal) gas at Of course, there are discrepancies between standard temperature (273 K) and pressure predicted and actual values of specific heats of (1 atm = 1.01 × 105 Pa) occupies a volume of 22.4 several other gases (not shown in the table), such litres. This universal volume is called molar volume. Thus the cylinder in this exampleas Cl2, C2H6 and many other polyatomic gases. contains 2 mol of helium. Further, since heliumUsually, the experimental values for specific is monatomic, its predicted (and observed) molar heats of these gases are greater than the specific heat at constant volume, Cv = (3/2) R,predicted values as given in Table12.1 suggesting and molar specific heat at constant pressure, that the agreement can be improved by including Cp = (3/2) R + R = (5/2) R. Since the volume of vibrational modes of motion in the calculation. the cylinder is fixed, the heat required is The law of equipartition of energy is, thus, well determined by Cv. Therefore, verified experimentally at ordinary temperatures. Heat required = no. of moles × molar specific heat × rise in temperature Table 12.1 Predicted values of specific heat = 2 × 1.5 R × 15.0 = 45 R capacities of gases (ignoring vibrational modes) = 45 × 8.31 = 374 J. ⊳ 12.6.4 Specific Heat Capacity of Solids Nature of Cv Cp Cp - Cv g Gas (J mol-1 K-1) (J mol-1 K-1) (J mol-1 K-1) We can use the law of equipartition of energy to determine specific heats of solids. Consider a Monatomic 12.5 20.8 8.31 1.67 solid of N atoms, each vibrating about its mean Diatomic 20.8 29.1 8.31 1.40 position. An oscillation in one dimension has average energy of 2 × ½ kBT = kBT . In three Triatomic 24.93 33.24 8.31 1.33 dimensions, the average energy is 3 kBT. For a mole of solid, N = NA, and the total energy is Table12.2 Measured values of specific heat U = 3 kBT × NA = 3 RT capacities of some gases Now at constant pressure ∆Q = ∆U + P∆V = ∆U, since for a solid ∆V is negligible. Hence, ∆Q ∆ U C = = = 3 R (12.37) ∆T ∆T Table 12.3 Specific Heat Capacity of some solids at room temperature and atmospheric pressure As Table 12.3 shows the prediction generally ⊳ Example 12.8 A cylinder of fixed capacity agrees with experimental values at ordinary 44.8 litres contains helium gas at standard temperature (Carbon is an exception). temperature and pressure. What is the amount of heat needed to raise the 12.7 MEAN FREE PATH temperature of the gas in the cylinder by Molecules in a gas have rather large speeds of 15.0 °C ? (R = 8.31 J mo1–1 K–1). the order of the speed of sound. Yet a gas leaking Reprint 2025-26 KINETIC THEORY 255 from a cylinder in a kitchen takes considerable are moving and the collision rate is determined time to diffuse to the other corners of the room. by the average relative velocity of the molecules. The top of a cloud of smoke holds together for Thus we need to replace <v> by <v r> in Eq. hours. This happens because molecules in a gas (12.38). A more exact treatment gives have a finite though small size, so they are bound 2 2 nπd (12.40)to undergo collisions. As a result, they cannot l = 1/ ( ) move straight unhindered; their paths keep Let us estimate l and τ for air molecules with getting incessantly deflected. average speeds <v> = ( 485m/s). At STP 0.02 × 1023 ( ) n = –3 22.4 × 10 ( ) = 2.7 × 10 25 m -3. Taking, d = 2 × 10–10 m, τ = 6.1 × 10–10 s t and l = 2.9 × 10–7 m ≈ 1500 d (12.41) v As expected, the mean free path given by d Eq. (12.40) depends inversely on the number density and the size of the molecules. In a highly evacuated tube n is rather small and the mean d free path can be as large as the length of the tube. ⊳ Example 12.9 Estimate the mean free path for a water molecule in water vapour at 373 K. Use information from Exercises 12.1 and Eq. Fig. 12.7 The volume swept by a molecule in time ∆t (12.41) above. in which any molecule will collide with it. Answer The d for water vapour is same as that Suppose the molecules of a gas are spheres of of air. The number density is inverselydiameter d. Focus on a single molecule with the proportional to absolute temperature.average speed <v>. It will suffer collision with any molecule that comes within a distance d 25 273 25 –3 So n = 2.7 × 10 × = 2 × 10 mbetween the centres. In time ∆t, it sweeps a 373 volume πd2 <v> ∆t wherein any other molecule –7 Hence, mean free path l = 4 × 10 m ⊳will collide with it (see Fig. 12.7). If n is the number of molecules per unit volume, the Note that the mean free path is 100 times the molecule suffers nπd2 <v> ∆t collisions in time interatomic distance ~ 40 Å = 4 × 10-9 m calculated ∆t. Thus the rate of collisions is nπd2 <v> or the earlier. It is this large value of mean free path that time between two successive collisions is on the leads to the typical gaseous behaviour. Gases can average, not be confined without a container. τ = 1/(nπ <v> d2 ) (12.38) Using, the kinetic theory of gases, the bulk The average distance between two successive measurable properties like viscosity, heat collisions, called the mean free path l, is : conductivity and diffusion can be related to the l = <v> τ = 1/(nπd2) (12.39) microscopic parameters like molecular size. It is In this derivation, we imagined the other through such relations that the molecular sizes molecules to be at rest. But actually all molecules were first estimated. Reprint 2025-26 256 PHYSICS SUMMARY 1. The ideal gas equation connecting pressure (P), volume (V) and absolute temperature (T ) is PV = µ RT = kB NT where µ is the number of moles and N is the number of molecules. R and kB are universal constants. R R = 8.314 J mol–1 K–1, kB = N A = 1.38 × 10–23 J K–1 Real gases satisfy the ideal gas equation only approximately, more so at low pressures and high temperatures. 2. Kinetic theory of an ideal gas gives the relation 1 2 P = n m v 3 where n is number density of molecules, m the mass of the molecule and v 2 is the mean of squared speed. Combined with the ideal gas equation it yields a kinetic interpretation of temperature. 1 2 3 2 1/2 3k B T m v = k B T , v rms = v = 2 2 ( ) m This tells us that the temperature of a gas is a measure of the average kinetic energy of a molecule, independent of the nature of the gas or molecule. In a mixture of gases at a fixed temperature the heavier molecule has the lower average speed. 3. The translational kinetic energy 3 E = kB NT. 2 This leads to a relation 2 PV = E 3 4. The law of equipartition of energy states that if a system is in equilibrium at absolute temperature T, the total energy is distributed equally in different energy modes of absorption, the energy in each mode being equal to ½ kB T. Each translational and rotational degree of freedom corresponds to one energy mode of absorption and has energy ½ kB T. Each vibrational frequency has two modes of energy (kinetic and potential) with corresponding energy equal to 2 × ½ kB T = kB T. 5. Using the law of equipartition of energy, the molar specific heats of gases can be determined and the values are in agreement with the experimental values of specific heats of several gases. The agreement can be improved by including vibrational modes of motion. 6. The mean free path l is the average distance covered by a molecule between two successive collisions : 1 l = 2 2 n πd where n is the number density and d the diameter of the molecule. Reprint 2025-26 KINETIC THEORY 257 POINTS TO PONDER 1. Pressure of a fluid is not only exerted on the wall. Pressure exists everywhere in a fluid. Any layer of gas inside the volume of a container is in equilibrium because the pressure is the same on both sides of the layer. 2. We should not have an exaggerated idea of the intermolecular distance in a gas. At ordinary pressures and temperatures, this is only 10 times or so the interatomic distance in solids and liquids. What is different is the mean free path which in a gas is 100 times the interatomic distance and 1000 times the size of the molecule. 3. The law of equipartition of energy is stated thus: the energy for each degree of freedom in thermal equilibrium is ½ k T. Each quadratic term in the total energy expression of a molecule is to be counted asB a degree of freedom. Thus, each vibrational mode gives 2 (not 1) degrees of freedom (kinetic and potential energy modes), corresponding to the energy 2 × ½ k T = k T. B B 4. Molecules of air in a room do not all fall and settle on the ground (due to gravity) because of their high speeds and incessant collisions. In equilibrium, there is a very slight increase in density at lower heights (like in the atmosphere). The effect is small since the potential energy (mgh) for ordinary heights is much less than the average kinetic energy ½ mv2 of the molecules. 5. < v2 > is not always equal to ( < v >)2. The average of a squared quantity is not necessarily the square of the average. Can you find examples for this statement. EXERCISESEXERCISESEXERCISESEXERCISESEXERCISES 12.112.112.112.112.1 Estimate the fraction of molecular volume to the actual volume occupied by oxygen gas at STP. Take the diameter of an oxygen molecule to be 3 Å. 12.212.212.212.212.2 Molar volume is the volume occupied by 1 mol of any (ideal) gas at standard temperature and pressure (STP : 1 atmospheric pressure, 0 °C). Show that it is 22.4 litres. 12.312.312.312.312.3 Figure 12.8 shows plot of PV/T versus P for 1.00×10–3 kg of oxygen gas at two different temperatures. y T1 PV –1 T2 (J K ) T x P Fig.Fig.Fig.Fig.Fig. 12.812.812.812.812.8 (a) What does the dotted plot signify? (b) Which is true: T1 > T2 or T1 < T2? (c) What is the value of PV/T where the curves meet on the y-axis? Reprint 2025-26 258 PHYSICS (d) If we obtained similar plots for 1.00×10–3 kg of hydrogen, would we get the same value of PV/T at the point where the curves meet on the y-axis? If not, what mass of hydrogen yields the same value of PV/T (for low pressure high temperature region of the plot) ? (Molecular mass of H2 = 2.02 u, of O2 = 32.0 u, R = 8.31 J mo1–1 K–1.) 12.412.412.412.412.4 An oxygen cylinder of volume 30 litre has an initial gauge pressure of 15 atm and a temperature of 27 °C. After some oxygen is withdrawn from the cylinder, the gauge pressure drops to 11 atm and its temperature drops to 17 °C. Estimate the mass of oxygen taken out of the cylinder (R = 8.31 J mol–1 K–1, molecular mass of O2 = 32 u). 12.512.512.512.512.5 An air bubble of volume 1.0 cm3 rises from the bottom of a lake 40 m deep at a temperature of 12 °C. To what volume does it grow when it reaches the surface, which is at a temperature of 35 °C ? 12.612.612.612.612.6 Estimate the total number of air molecules (inclusive of oxygen, nitrogen, water vapour and other constituents) in a room of capacity 25.0 m3 at a temperature of 27 °C and 1 atm pressure. 12.712.712.712.712.7 Estimate the average thermal energy of a helium atom at (i) room temperature (27 °C), (ii) the temperature on the surface of the Sun (6000 K), (iii) the temperature of 10 million kelvin (the typical core temperature in the case of a star). 12.812.812.812.812.8 Three vessels of equal capacity have gases at the same temperature and pressure. The first vessel contains neon (monatomic), the second contains chlorine (diatomic), and the third contains uranium hexafluoride (polyatomic). Do the vessels contain equal number of respective molecules ? Is the root mean square speed of molecules the same in the three cases? If not, in which case is vrms the largest ? 12.912.912.912.912.9 At what temperature is the root mean square speed of an atom in an argon gas cylinder equal to the rms speed of a helium gas atom at – 20 °C ? (atomic mass of Ar = 39.9 u, of He = 4.0 u). 12.1012.1012.1012.1012.10 Estimate the mean free path and collision frequency of a nitrogen molecule in a cylinder containing nitrogen at 2.0 atm and temperature 17 0C. Take the radius of a nitrogen molecule to be roughly 1.0 Å. Compare the collision time with the time the molecule moves freely between two successive collisions (Molecular mass of N2 = 28.0 u). Reprint 2025-26 CHAPTER THIRTEEN OSCILLATIONS 13.1 INTRODUCTION In our daily life we come across various kinds of motions. You have already learnt about some of them, e.g., rectilinear 13.1 Introduction motion and motion of a projectile. Both these motions are non-repetitive. We have also learnt about uniform circular13.2 Periodic and oscillatory motions motion and orbital motion of planets in the solar system. In 13.3 Simple harmonic motion these cases, the motion is repeated after a certain interval of 13.4 Simple harmonic motion time, that is, it is periodic. In your childhood, you must have and uniform circular enjoyed rocking in a cradle or swinging on a swing. Both motion these motions are repetitive in nature but different from the 13.5 Velocity and acceleration periodic motion of a planet. Here, the object moves to and fro in simple harmonic motion about a mean position. The pendulum of a wall clock executes 13.6 Force law for simple a similar motion. Examples of such periodic to and fro harmonic motion motion abound: a boat tossing up and down in a river, the

12.4 The ground state energy of hydrogen atom is –13.6 eV. What are the kinetic and potential energies of the electron in this state?

12.3 A difference of 2.3 eV separates two energy levels in an atom. What is the frequency of radiation emitted when the atom make a transition from the upper level to the lower level?

14.2 Which of the statements given in Exercise 14.1 is true for p-type semiconductos.

14.1 In an n-type silicon, which of the following statement is true: (a) Electrons are majority carriers and trivalent atoms are the dopants. (b) Electrons are minority carriers and pentavalent atoms are the dopants. (c) Holes are minority carriers and pentavalent atoms are the dopants. (d) Holes are majority carriers and trivalent atoms are the dopants.

14.3 Carbon, silicon and germanium have four valence electrons each. These are characterised by valence and conduction bands separated 341 Reprint 2025-26 Physics by energy band gap respectively equal to (Eg)C, (Eg)Si and (Eg)Ge. Which of the following statements is true? (a) (Eg)Si < (Eg)Ge < (Eg)C (b) (Eg)C < (Eg)Ge > (Eg)Si (c) (Eg)C > (Eg)Si > (Eg)Ge (d) (Eg)C = (Eg)Si = (Eg)Ge 14.4 In an unbiased p-n junction, holes diffuse from the p-region to n-region because (a) free electrons in the n-region attract them. (b) they move across the junction by the potential difference. (c) hole concentration in p-region is more as compared to n-region. (d) All the above. 14.5 When a forward bias is applied to a p-n junction, it (a) raises the potential barrier. (b) reduces the majority carrier current to zero. (c) lowers the potential barrier. (d) None of the above. 14.6 In half-wave rectification, what is the output frequency if the input frequency is 50 Hz. What is the output frequency of a full-wave rectifier for the same input frequency. Reprint 2025-26 Notes Reprint 2025-26 Physics APPENDICES APPENDIX A 1 THE GREEK ALPHABET APPENDIX A 2 COMMON SI PREFIXES AND SYMBOLS FOR MULTIPLES AND SUB-MULTIPLES Reprint 2025-26 AppendicesAnswers APPENDIX A 3 SOME IMPORTANT CONSTANTS OTHER USEFUL CONSTANTS 345 Reprint 2025-26 Physics ANSWERS CHAPTER 9 9.1 v = –54 cm. The image is real, inverted and magnified. The size of the image is 5.0 cm. As u ® f, v ® ¥; for u < f, image is virtual. 9.2 v = 6.7 cm. Magnification = 5/9, i.e., the size of the image is 2.5 cm. As u ® ¥; v ® f (but never beyond) while m ® 0. 9.3 1.33; 1.7 cm 9.4 nga = 1.51; nwa = 1.32; ngw = 1.144; which gives sin r = 0.6181 i.e., r ~ 38°. 9.5 r = 0.8 × tan ic and sin ci = 1/1.33 ≅ 0.75 , where r is the radius (in m) of the largest circle from which light comes out and ic is the critical angle for water-air interface, Area = 2.6 m2 9.6 n ≅ 1.53 and Dm for prism in water ≅ 10° 9.7 R = 22 cm 9.8 Here the object is virtual and the image is real. u = +12 cm (object on right; virtual) (a) f = +20 cm. Image is real and at 7.5 cm from the lens on its right side. (b) f = –16 cm. Image is real and at 48 cm from the lens on its right side. 9.9 v = 8.4 cm, image is erect and virtual. It is diminished to a size 1.8 cm. As u ® ¥, v ® f (but never beyond f while m ® 0). Note that when the object is placed at the focus of the concave lens (21 cm), the image is located at 10.5 cm (not at infinity as one might wrongly think). 9.10 A diverging lens of focal length 60 cm 9.11 (a) ve = –25 cm and fe = 6.25 cm give ue = –5 cm; vO = (15 – 5) cm = 10 cm, fO = uO = – 2.5 cm; Magnifying power = 20 (b) uO = – 2.59 cm. Magnifying power = 13.5. 9.12 Angular magnification of the eye-piece for image at 25 cm 25 25   1  11; | u e |= cm = 2 .27cm ; vO = 7.2 cm 2.5 11 Separation = 9.47 cm; Magnifying power = 88 9.13 24; 150 cm 9.14 (a) Angular magnification = 1500 346 (b) Diameter of the image = 13.7 cm. Reprint 2025-26 Answers

8.17 Complete each synthesis by giving missing starting material, reagent or products

8.4 Write the IUPAC names of the following ketones and aldehydes. Wherever possible, give also common names. (i) CH3CO(CH2)4CH3 (ii) CH3CH2CHBrCH2CH(CH3)CHO (iii) CH3(CH2)5CHO (iv) Ph-CH=CH-CHO CHO (v) (vi) PhCOPh

8.2 Name the following compounds according to IUPAC system of nomenclature: (i) CH3CH(CH3)CH2CH2CHO (ii) CH3CH2COCH(C2H5)CH2CH2Cl (iii) CH3CH=CHCHO (iv) CH3COCH2COCH3 (v) CH3CH(CH3)CH2C(CH3)2COCH3 (vi) (CH3)3CCH2COOH (vii) OHCC6H4CHO-p

13.5 VELOCITY AND ACCELERATION IN SIMPLE HARMONIC MOTION The speed of a particle v in uniform circular motion is its angular speed ω times the radius of the circle A. v = ω A (13.8) The direction of velocity v at a time t is along the tangent to the circle at the point where the particle is located at that instant. From the Fig. 13.12 The acceleration, a(t), of the particle P′ isgeometry of Fig. 13.11, it is clear that the velocity the projection of the acceleration a of theof the projection particle P′ at time t is reference particle P. v(t) = –ωA sin (ωt + φ ) (13.9) Eq. (13.11) gives the acceleration of a particle in SHM. The same equation can again be obtained directly by differentiating velocity v(t) given by Eq. (13.9) with respect to time: d a (t ) = v (t ) (13.12) d t We note from Eq. (13.11) the important Fig. 13.11 The velocity, v (t), of the particle P′ is property that acceleration of a particle in SHM the projection of the velocity v of the is proportional to displacement. For x(t) > 0, reference particle, P. a(t) < 0 and for x(t) < 0, a(t) > 0. Thus, whatever Reprint 2025-26 OSCILLATIONS 267 the value of x between –A and A, the acceleration (b) Using Eq. (13.9), the speed of the body a(t) is always directed towards the centre. = – (5.0 m)(2π s–1) sin [(2π s–1) ×1.5 s For simplicity, let us put φ = 0 and write the + π/4] expression for x (t), v (t) and a(t) = – (5.0 m)(2π s–1) sin [(3π + π/4)] x(t) = A cos ωt, v(t) = – ω Asin ωt, a(t)=–ω2 A cos ωt = 10π × 0.707 m s–1 The corresponding plots are shown in Fig. 13.13. = 22 m s–1 All quantities vary sinusoidally with time; only (c) Using Eq.(13.10), the acceleration of the their maxima differ and the different plots differ body in phase. x varies between –A to A; v(t) varies = –(2π s–1)2 × displacement from –ωA to ωA and a(t) from –ω2A to ω2A. With = – (2π s–1)2 × (–3.535 m) respect to displacement plot, velocity plot has a = 140 m s–2 ⊳ phase difference of π/2 and acceleration plot has a phase difference of π. 13.6 FORCE LAW FOR SIMPLE HARMONIC MOTION Using Newton’s second law of motion, and the expression for acceleration of a particle undergoing SHM (Eq. 13.11), the force acting on a particle of mass m in SHM is F (t ) = ma = –mω2 x (t) i.e., F (t) = –k x (t) (13.13) where k = mω2 (13.14a) k or ω = (13.14b) m Like acceleration, force is always directed towards the mean position—hence it is sometimes called the restoring force in SHM. To summarise the discussion so far, simple harmonic motion can be defined in two equivalent ways, either by Eq. (13.4) for displacement or by Eq. (13.13) that gives Fig. 13.13 Displacement, velocity and acceleration of its force law. Going from Eq. (13.4) to Eq. (13.13) a particle in simple harmonic motion have required us to differentiate two times. Likewise, the same period T, but they differ in phase by integrating the force law Eq. (13.13) two times, we can get back Eq. (13.4). u Example 13.5 A body oscillates with SHM Note that the force in Eq. (13.13) is linearly according to the equation (in SI units), proportional to x(t). A particle oscillating under x = 5 cos [2π t + π/4]. such a force is, therefore, calling a linear harmonic oscillator. In the real world, the force At t = 1.5 s, calculate the (a) displacement, may contain small additional terms proportional (b) speed and (c) acceleration of the body. to x2, x3, etc. These then are called non-linear oscillators. Answer The angular frequency ω of the body = 2π s–1 and its time period T = 1 s. u Example 13.6 Two identical springs of At t = 1.5 s spring constant k are attached to a block (a) displacement = (5.0 m) cos [(2π s–1)× of mass m and to fixed supports as shown 1.5 s + π/4] in Fig. 13.14. Show that when the mass is = (5.0 m) cos [(3π + π/4)] displaced from its equilibrium position on = –5.0 × 0.707 m either side, it executes a simple harmonic = –3.535 m motion. Find the period of oscillations. Reprint 2025-26 268 PHYSICS 13.7 ENERGY IN SIMPLE HARMONIC MOTION Both kinetic and potential energies of a particle in SHM vary between zero and their maximum values. In section 13.5 we have seen that the velocity of a particle executing SHM, is a periodic Fig. 13.14 function of time. It is zero at the extreme positions of displacement. Therefore, the kinetic energy (K) Answer Let the mass be displaced by a small of such a particle, which is defined as distance x to the right side of the equilibrium position, as shown in Fig. 13.15. Under this 1 2 K = mv situation the spring on the left side gets 2 1 2 2 2 = m ω A sin (ωt + φ) 2 1 2 2 = k A sin (ωt + φ) (13.15) 2 is also a periodic function of time, being zero when the displacement is maximum and maximum when the particle is at the mean Fig. 13.15 position. Note, since the sign of v is immaterial in K, the period of K is T/2. elongated by a length equal to x and that on What is the potential energy (U) of a particle the right side gets compressed by the same executing simple harmonic motion? In length. The forces acting on the mass are Chapter 6, we have seen that the concept of then, potential energy is possible only for conservative forces. The spring force F = –kx is a conservative F1 = –k x (force exerted by the spring on force, with associated potential energy the left side, trying to pull the mass towards the mean 1 2 U = k x position) (13.16) 2 F2 = –k x (force exerted by the spring on Hence the potential energy of a particle the right side, trying to push the executing simple harmonic motion is, mass towards the mean position) 1 2 The net force, F, acting on the mass is then U(x) = k x given by, 2 F = –2kx 1 2 2 Hence the force acting on the mass is = k A cos (ωt + φ) (13.17) 2proportional to the displacement and is directed towards the mean position; therefore, the motion Thus, the potential energy of a particle executed by the mass is simple harmonic. The executing simple harmonic motion is also time period of oscillations is, periodic, with period T/2, being zero at the mean m position and maximum at the extreme T = 2 π displacements. 2k ⊳ Reprint 2025-26 OSCILLATIONS 269 It follows from Eqs. (13.15) and (13.17) that Observe that both kinetic energy and the total energy, E, of the system is, potential energy in SHM are seen to be always positive in Fig. 13.16. Kinetic energy can, of E = U + K course, be never negative, since it is proportional to the square of speed. Potential 1 1 = k A 2 cos 2 (ωt + φ) + k A 2 sin 2 (ωt + φ) energy is positive by choice of the undermined 2 2 constant in potential energy. Both kinetic energy and potential energy peak twice during each period of SHM. For x = 0, the energy is 1 2 2 2 = k A cos (ωt + φ) + sin (ωt + φ)  kinetic; at the extremes x = ±A, it is all   2 potential energy. In the course of motion Using the familiar trigonometric identity, the between these limits, kinetic energy increases value of the expression in the brackets is unity. at the expense of potential energy or Thus, vice-versa. 1 2 E = k A (13.18) u Example 13.7 A block whose mass is 1 kg 2 is fastened to a spring. The spring has a The total mechanical energy of a harmonic spring constant of 50 N m–1. The block is pulled to a distance x = 10 cm from itsoscillator is thus independent of time as equilibrium position at x = 0 on a frictionlessexpected for motion under any conservative surface from rest at t = 0. Calculate the force. The time and displacement dependence kinetic, potential and total energies of the of the potential and kinetic energies of a block when it is 5 cm away from the mean linear simple harmonic oscillator are shown position. in Fig. 13.16. Answer The block executes SHM, its angular frequency, as given by Eq. (13.14b), is k ω = m 1 50 N m– = 1kg = 7.07 rad s–1 Its displacement at any time t is then given by, x(t) = 0.1 cos (7.07t) Fig. 13.16 Kinetic energy, potential energy and total energy as a function of time [shown in (a)] Therefore, when the particle is 5 cm away from and displacement [shown in (b)] of a particle in SHM. The kinetic energy and potential the mean position, we have energy both repeat after a period T/2. The total energy remains constant at all t or x. 0.05 = 0.1 cos (7.07t) Reprint 2025-26 270 PHYSICS let it go. The stone executes a to and fro motion,Or cos (7.07t) = 0.5 and hence it is periodic with a period of about two seconds. 3 We shall show that this periodic motion is sin (7.07t) = = 0.866 2 simple harmonic for small displacements from Then, the velocity of the block at x = 5 cm is = 0.1 × 7.07 × 0.866 m s–1 = 0.61 m s–1 Hence the K.E. of the block, 1 2 = m v 2 = ½[1kg × (0.6123 m s–1 )2 ] = 0.19 J (a) The P.E. of the block, 1 2 = k x 2 = ½(50 N m–1 × 0.05 m × 0.05 m) = 0.0625 J The total energy of the block at x = 5 cm, = K.E. + P.E. = 0.25 J we also know that at maximum displacement, K.E. is zero and hence the total energy of the (b) system is equal to the P.E. Therefore, the total Fig. 13.17 (a) A bob oscillating about its mean position. (b) The radial force T-mg cosθ energy of the system, provides centripetal force but no torque = ½(50 N m–1 × 0.1 m × 0.1 m ) about the support. The tangential force mg sinθ provides the restoring torque. = 0.25 J which is same as the sum of the two energies at the mean position. Consider simple pendulum a displacement of 5 cm. This is in conformity — a small bob of mass m tied to an inextensible with the principle of conservation of energy. ⊳ massless string of length L. The other end of the string is fixed to a rigid support. The bob13.8 The Simple Pendulum oscillates in a plane about the vertical lineIt is said that Galileo measured the periods of a through the support. Fig. 13.17(a) shows thisswinging chandelier in a church by his pulse system. Fig. 13.17(b) is a kind of ‘free-body’beats. He observed that the motion of the chandelier was periodic. The system is a kind diagram of the simple pendulum showing the of pendulum. You can also make your own forces acting on the bob. pendulum by tying a piece of stone to a long Let θ be the angle made by the string with unstretchable thread, approximately 100 cm the vertical. When the bob is at the mean long. Suspend your pendulum from a suitable position, θ = 0 support so that it is free to oscillate. Displace There are only two forces acting on the bob; the stone to one side by a small distance and the tension T along the string and the vertical Reprint 2025-26 OSCILLATIONS 271 force due to gravity (=mg). The force mg can be Table 13.1 sin θ as ma function of angle θ resolved into the component mg cosθ along the string and mg sinθ perpendicular to it. Since (degrees) (radians) sin the motion of the bob is along a circle of length L and centre at the support point, the bob has a radial acceleration (ω2L) and also a tangental acceleration; the latter arises since motion along the arc of the circle is not uniform. The radial acceleration is provided by the net radial force T –mg cosθ, while the tangential acceleration is provided by mg sinθ. It is more convenient to Equation (13.24) is mathematically, identical towork with torque about the support since the radial force gives zero torque. Torque τ about Eq. (13.11) except that the variable is angular displacement. Hence we have proved that forthe support is entirely provided by the tangental small q, the motion of the bob is simple harmonic.component of force From Eqs. (13.24) and (13.11), τ = –L (mg sinθ ) (13.19) This is the restoring torque that tends to reduce mgL ω =angular displacement — hence the negative Isign. By Newton’s law of rotational motion, τ = I α (13.20) and where I is the moment of inertia of the system about the support and α is the angular I T = 2π (13.25)acceleration. Thus, mgL I α = –m g sin θ L (13.21) Now since the string of the simple pendulum is massless, the moment of inertia I is simply mL2. Eq. (13.25) then gives the well-known Or, formula for time period of a simple pendulum. m g L α = − sin θ (13.22) L I T = 2π (13.26) g We can simplify Eq. (13.22) if we assume that the displacement θ is small. We know that sin θ u Example 13.8 What is the length of a can be expressed as, simple pendulum, which ticks seconds ? θ3 θ5 Answer From Eq. (13.26), the time period of a sin θ = θ− + ± ... (13.23) 3! 5! simple pendulum is given by, L where θ is in radians. T = 2π Now if θ is small, sin θ can be approximated g by θ and Eq. (13.22) can then be written as, From this relation one gets, gT 2 mgL L = 2 θ α = − (13.24) 4π I The time period of a simple pendulum, which In Table 13.1, we have listed the angle θ in ticks seconds, is 2 s. Therefore, for g = 9.8 m s–2 degrees, its equivalent in radians, and the value of the function sin θ . From this table it and T = 2 s, L is can be seen that for θ as large as 20 degrees, 9.8(m s –2 ) × 4(s 2 ) = sin θ is nearly the same as θ expressed 2 4π in radians. = 1 m ⊳ Reprint 2025-26 272 PHYSICS SUMMARY 1. The motion that repeats itself is called periodlic motion. 2. The period T is the time reequired for one complete oscillation, or cycle. It is related to the frequency v by, 1 T = v The frequency ν of periodic or oscillatory motion is the number of oscillations per unit time. In the SI, it is measured in hertz : 1 hertz = 1 Hz = 1 oscillation per second = 1s–1 3. In simple harmonic motion (SHM), the displacement x (t) of a particle from its equilibrium position is given by, x (t) = A cos (ωt + φ ) (displacement), in which A is the amplitude of the displacement, the quantity (ωt + φ ) is the phase of the motion, and φ is the phase constant. The angular frequency ω is related to the period and frequency of the motion by, 2π ω= = 2πν (angular frequency). T 4. Simple harmonic motion can also be viewed as the projection of uniform circular motion on the diameter of the circle in which the latter motion occurs. 5. The particle velocity and acceleration during SHM as functions of time are given by, v (t) = –ωA sin (ωt + φ ) (velocity), a (t) = –ω2A cos (ωt + φ ) = –ω2x (t) (acceleration), Thus we see that both velocity and acceleration of a body executing simple harmonic motion are periodic functions, having the velocity amplitude vm=ω A and acceleration amplitude am =ω 2A, respectively. 6. The force acting in a simple harmonic motion is proportional to the displacement and is always directed towards the centre of motion. 7. A particle executing simple harmonic motion has, at any time, kinetic energy K = ½ mv2 and potential energy U = ½ kx2. If no friction is present the mechanical energy of the system, E = K + U always remains constant even though K and U change with time. 8. A particle of mass m oscillating under the influence of Hooke’s law restoring force given by F = – k x exhibits simple harmonic motion with k ω = (angular frequency) m m T = 2π (period) k Such a system is also called a linear oscillator. 9. The motion of a simple pendulum swinging through small angles is approximately simple harmonic. The period of oscillation is given by, L T = 2π g Reprint 2025-26 OSCILLATIONS 273 POINTS TO PONDER 1. The period T is the least time after which motion repeats itself. Thus, motion repeats itself after nT where n is an integer. 2. Every periodic motion is not simple harmonic motion. Only that periodic motion governed by the force law F = – k x is simple harmonic. 3. Circular motion can arise due to an inverse-square law force (as in planetary motion) as well as due to simple harmonic force in two dimensions equal to: –mω2r. In the latter case, the phases of motion, in two perpendicular directions (x and y) must differ by π/2. Thus, for example, a particle subject to a force –mω2r with initial position (0, A) and velocity (ωA, 0) will move uniformly in a circle of radius A. 4. For linear simple harmonic motion with a given ω, two initial conditions are necessary and sufficient to determine the motion completely. The initial conditions may be (i) initial position and initial velocity or (ii) amplitude and phase or (iii) energy and phase. 5. From point 4 above, given amplitude or energy, phase of motion is determined by the initial position or initial velocity. 6. A combination of two simple harmonic motions with arbitrary amplitudes and phases is not necessarily periodic. It is periodic only if frequency of one motion is an integral multiple of the other’s frequency. However, a periodic motion can always be expressed as a sum of infinite number of harmonic motions with appropriate amplitudes. 7. The period of SHM does not depend on amplitude or energy or the phase constant. Contrast this with the periods of planetary orbits under gravitation (Kepler’s third law). 8. The motion of a simple pendulum is simple harmonic for small angular displacement. 9. For motion of a particle to be simple harmonic, its displacement x must be expressible in either of the following forms : x = A cos ωt + B sin ωt x = A cos (ωt + α ), x = B sin (ωt + β ) The three forms are completely equivalent (any one can be expressed in terms of any other two forms). Thus, damped simple harmonic motion is not strictly simple harmonic. It is approximately so only for time intervals much less than 2m/b where b is the damping constant. Reprint 2025-26 274 PHYSICS Exercises 13.1 Which of the following examples represent periodic motion? (a) A swimmer completing one (return) trip from one bank of a river to the other and back. (b) A freely suspended bar magnet displaced from its N-S direction and released. (c) A hydrogen molecule rotating about its centre of mass. (d) An arrow released from a bow. 13.2 Which of the following examples represent (nearly) simple harmonic motion and which represent periodic but not simple harmonic motion? (a) the rotation of earth about its axis. (b) motion of an oscillating mercury column in a U-tube. (c) motion of a ball bearing inside a smooth curved bowl, when released from a point slightly above the lower most point. (d) general vibrations of a polyatomic molecule about its equilibrium position. 13.3 Fig. 13.18 depicts four x-t plots for linear motion of a particle. Which of the plots represent periodic motion? What is the period of motion (in case of periodic motion) ? Fig. 18.18 Reprint 2025-26 OSCILLATIONS 275 13.4 Which of the following functions of time represent (a) simple harmonic, (b) periodic but not simple harmonic, and (c) non-periodic motion? Give period for each case of periodic motion (ω is any positive constant): (a) sin ωt – cos ωt (b) sin3 ωt (c) 3 cos (π/4 – 2ωt) (d) cos ωt + cos 3ωt + cos 5ωt (e) exp (–ω2t2) (f) 1 + ωt + ω2t2 13.5 A particle is in linear simple harmonic motion between two points, A and B, 10 cm apart. Take the direction from A to B as the positive direction and give the signs of velocity, acceleration and force on the particle when it is (a) at the end A, (b) at the end B, (c) at the mid-point of AB going towards A, (d) at 2 cm away from B going towards A, (e) at 3 cm away from A going towards B, and (f) at 4 cm away from B going towards A. 13.6 Which of the following relationships between the acceleration a and the displacement x of a particle involve simple harmonic motion? (a) a = 0.7x (b) a = –200x2 (c) a = –10x (d) a = 100x3 13.7 The motion of a particle executing simple harmonic motion is described by the displacement function, x(t) = A cos (ωt + φ ). If the initial (t = 0) position of the particle is 1 cm and its initial velocity is ω cm/s, what are its amplitude and initial phase angle ? The angular frequency of the particle is π s–1. If instead of the cosine function, we choose the sine function to describe the SHM : x = B sin (ωt + α), what are the amplitude and initial phase of the particle with the above initial conditions. 13.8 A spring balance has a scale that reads from 0 to 50 kg. The length of the scale is 20 cm. A body suspended from this balance, when displaced and released, oscillates with a period of 0.6 s. What is the weight of the body ? 13.9 A spring having with a spring constant 1200 N m–1 is mounted on a horizontal table as shown in Fig. 13.19. A mass of 3 kg is attached to the free end of the spring. The mass is then pulled sideways to a distance of 2.0 cm and released. Fig. 13.19 Determine (i) the frequency of oscillations, (ii) maximum acceleration of the mass, and (iii) the maximum speed of the mass. Reprint 2025-26 276 PHYSICS 13.10 In Exercise 13.9, let us take the position of mass when the spring is unstreched as x = 0, and the direction from left to right as the positive direction of x-axis. Give x as a function of time t for the oscillating mass if at the moment we start the stopwatch (t = 0), the mass is (a) at the mean position, (b) at the maximum stretched position, and (c) at the maximum compressed position. In what way do these functions for SHM differ from each other, in frequency, in amplitude or the initial phase? 13.11 Figures 13.20 correspond to two circular motions. The radius of the circle, the period of revolution, the initial position, and the sense of revolution (i.e. clockwise or anti-clockwise) are indicated on each figure. Fig. 13.20 Obtain the corresponding simple harmonic motions of the x-projection of the radius vector of the revolving particle P, in each case. 13.12 Plot the corresponding reference circle for each of the following simple harmonic motions. Indicate the initial (t =0) position of the particle, the radius of the circle, and the angular speed of the rotating particle. For simplicity, the sense of rotation may be fixed to be anticlockwise in every case: (x is in cm and t is in s). (a) x = –2 sin (3t + π/3) (b) x = cos (π/6 – t) (c) x = 3 sin (2πt + π/4) (d) x = 2 cos πt 13.13 Figure 13.21(a) shows a spring of force constant k clamped rigidly at one end and a mass m attached to its free end. A force F applied at the free end stretches the spring. Figure 13.21 (b) shows the same spring with both ends free and attached to a mass m at either end. Each end of the spring in Fig. 13.21(b) is stretched by the same force F. Fig. 13.21 (a) What is the maximum extension of the spring in the two cases ? (b) If the mass in Fig. (a) and the two masses in Fig. (b) are released, what is the period of oscillation in each case ? Reprint 2025-26 OSCILLATIONS 277 13.14 The piston in the cylinder head of a locomotive has a stroke (twice the amplitude) of 1.0 m. If the piston moves with simple harmonic motion with an angular frequency of 200 rad/min, what is its maximum speed ? 13.15 The acceleration due to gravity on the surface of moon is 1.7 m s–2. What is the time period of a simple pendulum on the surface of moon if its time period on the surface of earth is 3.5 s ? (g on the surface of earth is 9.8 m s–2) 13.16 A simple pendulum of length l and having a bob of mass M is suspended in a car. The car is moving on a circular track of radius R with a uniform speed v. If the pendulum makes small oscillations in a radial direction about its equilibrium position, what will be its time period ? 13.17 A cylindrical piece of cork of density of base area A and height h floats in a liquid of density ρl. The cork is depressed slightly and then released. Show that the cork oscillates up and down simple harmonically with a period hρ T = 2π ρ1 g where ρ is the density of cork. (Ignore damping due to viscosity of the liquid). 13.18 One end of a U-tube containing mercury is connected to a suction pump and the other end to atmosphere. A small pressure difference is maintained between the two columns. Show that, when the suction pump is removed, the column of mercury in the U-tube executes simple harmonic motion. Reprint 2025-26 CHAPTER FOURTEEN WAVES 14.1 INTRODUCTION In the previous Chapter, we studied the motion of objects oscillating in isolation. What happens in a system, which is a collection of such objects? A material medium provides

13.5 The Q value of a nuclear reaction A + b ® C + d is defined by Q = [ mA + mb – mC – md]c2 where the masses refer to the respective nuclei. Determine from the given data the Q-value of the following reactions and state whether the reactions are exothermic or endothermic. (i) 11 H+13 H →12 H+12 H (ii) 126 C+126 C →1020 Ne+ 24 He Atomic masses are given to be m ( 12 H ) = 2.014102 u m ( 13 H) = 3.016049 u m ( 126 C ) = 12.000000 u m ( 1020 Ne ) = 19.992439 u

13.2 Obtain the binding energy of the nuclei 5626Fe and 20983 Bi in units of MeV from the following data: m ( 5626Fe ) = 55.934939 u m ( 20983 Bi ) = 208.980388 u

13.2 PERIODIC AND OSCILLATORY MOTIONS Very often, the body undergoing periodic motion has an equilibrium position somewhereFig. 13.1 shows some periodic motions. Suppose inside its path. When the body is at this positionan insect climbs up a ramp and falls down, it no net external force acts on it. Therefore, if it iscomes back to the initial point and repeats the left there at rest, it remains there forever. If the process identically. If you draw a graph of its body is given a small displacement from the height above the ground versus time, it would position, a force comes into play which tries to look something like Fig. 13.1 (a). If a child climbs bring the body back to the equilibrium point, up a step, comes down, and repeats the process giving rise to oscillations or vibrations. For identically, its height above the ground would example, a ball placed in a bowl will be in look like that in Fig. 13.1 (b). When you play the equilibrium at the bottom. If displaced a little game of bouncing a ball off the ground, between from the point, it will perform oscillations in the your palm and the ground, its height versus time bowl. Every oscillatory motion is periodic, but graph would look like the one in Fig. 13.1 (c). every periodic motion need not be oscillatory. Note that both the curved parts in Fig. 13.1 (c) Circular motion is a periodic motion, but it is are sections of a parabola given by the Newton’s not oscillatory. equation of motion (see section 2.6), There is no significant difference between 1 2 oscillations and vibrations. It seems that when h = ut + gt for downward motion, and 2 the frequency is small, we call it oscillation (like, the oscillation of a branch of a tree), while when 1 2 h = ut – gt for upward motion, the frequency is high, we call it vibration (like, 2 the vibration of a string of a musical instrument). with different values of u in each case. These Simple harmonic motion is the simplest form are examples of periodic motion. Thus, a motion of oscillatory motion. This motion arises when that repeats itself at regular intervals of time is the force on the oscillating body is directly called periodic motion. proportional to its displacement from the mean position, which is also the equilibrium position. Further, at any point in its oscillation, this force is directed towards the mean position. In practice, oscillating bodies eventually (a) come to rest at their equilibrium positions because of the damping due to friction and other dissipative causes. However, they can be forced to remain oscillating by means of some external periodic agency. We discuss the phenomena of damped and forced oscillations later in the chapter. Any material medium can be pictured as a (b) collection of a large number of coupled oscillators. The collective oscillations of the constituents of a medium manifest themselves as waves. Examples of waves include water waves, seismic waves, electromagnetic waves. We shall study the wave phenomenon in the next chapter. (c) 13.2.1 Period and frequency We have seen that any motion that repeats itself at regular intervals of time is called periodic motion. The smallest interval of time after which the motion is repeated is called its Fig. 13.1 Examples of periodic motion. The period T period. Let us denote the period by the symbol is shown in each case. T. Its SI unit is second. For periodic motions, Reprint 2025-26 OSCILLATIONS 261 which are either too fast or too slow on the scale as a displacement variable [see Fig.13.2(b)]. The of seconds, other convenient units of time are term displacement is not always to be referred used. The period of vibrations of a quartz crystal is expressed in units of microseconds (10–6 s) abbreviated as µs. On the other hand, the orbital period of the planet Mercury is 88 earth days. The Halley’s comet appears after every 76 years. The reciprocal of T gives the number of repetitions that occur per unit time. This quantity is called the frequency of the periodic motion. It is represented by the symbol ν. The relation between ν and T is Fig. 13.2(a) A block attached to a spring, the other ν = 1/T (13.1) end of which is fixed to a rigid wall. The block moves on a frictionless surface. The The unit of ν is thus s–1. After the discoverer of motion of the block can be described in radio waves, Heinrich Rudolph Hertz (1857–1894), terms of its distance or displacement x a special name has been given to the unit of from the equilibrium position. frequency. It is called hertz (abbreviated as Hz). Thus, 1 hertz = 1 Hz =1 oscillation per second =1 s–1 (13.2) Note, that the frequency, ν, is not necessarily an integer. u Example 13.1 On an average, a human heart is found to beat 75 times in a minute. Calculate its frequency and period. Fig.13.2(b) An oscillating simple pendulum; its Answer The beat frequency of heart = 75/(1 min) motion can be described in terms of = 75/(60 s) angular displacement θ from the vertical. = 1.25 s–1 = 1.25 Hz in the context of position only. There can be The time period T = 1/(1.25 s–1) many other kinds of displacement variables. The = 0.8 s ⊳ voltage across a capacitor, changing with time in an AC circuit, is also a displacement variable.13.2.2 Displacement In the same way, pressure variations in time inIn section 3.2, we defined displacement of a the propagation of sound wave, the changingparticle as the change in its position vector. In electric and magnetic fields in a light wave arethis chapter, we use the term displacement examples of displacement in different contexts.in a more general sense. It refers to change The displacement variable may take bothwith time of any physical property under positive and negative values. In experiments onconsideration. For example, in case of rectilinear oscillations, the displacement is measured formotion of a steel ball on a surface, the distance different times.from the starting point as a function of time is The displacement can be represented by a its position displacement. The choice of origin mathematical function of time. In case of periodic is a matter of convenience. Consider a block motion, this function is periodic in time. One of attached to a spring, the other end of the spring the simplest periodic functions is given by is fixed to a rigid wall [see Fig.13.2(a)]. Generally, it is convenient to measure displacement of the f (t) = A cos ωt (13.3a) body from its equilibrium position. For an If the argument of this function, ωt, is oscillating simple pendulum, the angle from the increased by an integral multiple of 2π radians, vertical as a function of time may be regarded the value of the function remains the same. The Reprint 2025-26 262 PHYSICS function f (t) is then periodic and its period, T, (ii) This is an example of a periodic motion. It is given by can be noted that each term represents a 2 π periodic function with a different angular T = (13.3b) frequency. Since period is the least interval ω of time after which a function repeats its Thus, the function f (t) is periodic with period T, value, sin ωt has a period T0= 2π/ω ; cos 2 ωt f (t) = f (t+T ) has a period π/ω =T0/2; and sin 4 ωt has a period 2π/4ω = T0/4. The period of the firstThe same result is obviously correct if we term is a multiple of the periods of the lastconsider a sine function, f (t ) = A sin ωt. Further, two terms. Therefore, the smallest intervala linear combination of sine and cosine functions of time after which the sum of the threelike, terms repeats is T0, and thus, the sum is a f (t) = A sin ωt + B cos ωt (13.3c) periodic function with a period 2π/ω. is also a periodic function with the same period (iii) The function e–ωt is not periodic, itT. Taking, decreases monotonically with increasing A = D cos φ and B = D sin φ time and tends to zero as t → ∞ and thus, Eq. (13.3c) can be written as, never repeats its value. (iv) The function log(ωt) increases f (t) = D sin (ωt + φ ) , (13.3d) monotonically with time t. It, therefore, Here D and φ are constant given by never repeats its value and is a non- periodic function. It may be noted that as  B  t → ∞, log(ωt) diverges to ∞. It, therefore, 2 2 – 1 D = A + B and φ= tan  A  cannot represent any kind of physical displacement. ⊳ The great importance of periodic sine and cosine functions is due to a remarkable result 13.3 SIMPLE HARMONIC MOTION proved by the French mathematician, Jean Consider a particle oscillating back and forth Baptiste Joseph Fourier (1768–1830): Any about the origin of an x-axis between the limits periodic function can be expressed as a +A and –A as shown in Fig. 13.3. This oscillatory superposition of sine and cosine functions motion is said to be simple harmonic if the of different time periods with suitable displacement x of the particle from the origin coefficients. varies with time as : x (t) = A cos (ω t + φ) (13.4) u Example 13.2 Which of the following functions of time represent (a) periodic and (b) non-periodic motion? Give the period for each case of periodic motion [ω is any positive constant]. (i) sin ωt + cos ωt Fig. 13.3 A particle vibrating back and forth about the origin of x-axis, between the limits +A (ii) sin ωt + cos 2 ωt + sin 4 ωt and –A. (iii) e–ωt (iv) log (ωt) where A, ω and φ are constants. Thus, simple harmonic motion (SHM) is not Answer any periodic motion but one in which displacement is a sinusoidal function of time.(i) sin ωt + cos ωt is a periodic function, it can Fig. 13.4 shows the positions of a particle also be written as 2 sin (ωt + π/4). executing SHM at discrete value of time, each Now 2 sin (ωt + π/4)= 2 sin (ωt + π/4+2π) interval of time being T/4, where T is the period of motion. Fig. 13.5 plots the graph of x versus t, = 2 sin [ω (t + 2π/ω) + π/4] which gives the values of displacement as a The periodic time of the function is 2π/ω. continuous function of time. The quantities A, Reprint 2025-26 OSCILLATIONS 263 any loss of generality]. As the cosine function of time varies from +1 to –1, the displacement varies between the extremes A and – A. Two simple harmonic motions may have same ω and φ but different amplitudes A and B, as shown in Fig. 13.7 (a). While the amplitude A is fixed for a given SHM, the state of motion (position and velocity) of the particle at any time t is determined by the Fig. 13.4 The location of the particle in SHM at the discrete values t = 0, T/4, T/2, 3T/4, T, 5T/4. The time after which motion repeats itself is T. T will remain fixed, no matter what location you choose as the initial (t = Fig. 13.7 (a) A plot of displacement as a function of 0) location. The speed is maximum for zero time as obtained from Eq. (14.4) with displacement (at x = 0) and zero at the φ = 0. The curves 1 and 2 are for two extremes of motion. different amplitudes A and B. ω and φ which characterize a given SHM have standard names, as summarised in Fig. 13.6. argument (ωt + φ) in the cosine function. This Let us understand these quantities. time-dependent quantity, (ωt + φ) is called the The amplitutde A of SHM is the magnitude phase of the motion. The value of plase at t = 0 of maximum displacement of the particle. is φ and is called the phase constant (or phase [Note, A can be taken to be positive without angle). If the amplitude is known, φ can be determined from the displacement at t = 0. Two simple harmonic motions may have the same A and ω but different phase angle φ, as shown in Fig. 13.7 (b). Finally, the quantity ω can be seen to be related to the period of motion T. Taking, for simplicity, φ = 0 in Eq. (13.4), we have Fig. 13.5 Displacement as a continuous function of time for simple harmonic motion. x (t) : displacement x as a function of time t A : amplitude ω : angular frequency ωt + φ : phase (time-dependent) φ : phase constant Fig. 13.7 (b) A plot obtained from Eq. (13.4). The curves 3 and 4 are for φ = 0 and -π/4 respectively. The amplitude A is same for Fig. 13.6 The meaning of standard symbols both the plots. in Eq. (13.4) Reprint 2025-26 264 PHYSICS x(t) = A cos ωt (13.5) This function represents a simple harmonic motion having a period T = 2π/ω and a Since the motion has a period T, x (t) is equal to phase angle (–π/4) or (7π/4) x (t + T). That is, (b) sin2 ωt = ½ – ½ cos 2 ωt A cos ωt = A cos ω (t + T ) (13.6) The function is periodic having a period Now the cosine function is periodic with period T = π/ω. It also represents a harmonic 2π, i.e., it first repeats itself when the argument motion with the point of equilibrium ½ instead of zero. ⊳changes by 2π. Therefore, occurring at ω(t + T ) = ωt + 2π 13.4 SIMPLE HARMONIC MOTION AND UNIFORM CIRCULAR MOTION that is ω = 2π/ T (13.7) In this section, we show that the projection of uniform circular motion on a diameter of the ω is called the angular frequency of SHM. Its circle follows simple harmonic motion. A S.I. unit is radians per second. Since the simple experiment (Fig. 13.9) helps us visualise frequency of oscillations is simply 1/T, ω is 2π this connection. Tie a ball to the end of a string times the frequency of oscillation. Two simple and make it move in a horizontal plane about harmonic motions may have the same A and φ, a fixed point with a constant angular speed. but different ω, as seen in Fig. 13.8. In this plot The ball would then perform a uniform circular the curve (b) has half the period and twice the motion in the horizontal plane. Observe the frequency of the curve (a). ball sideways or from the front, fixing your attention in the plane of motion. The ball will appear to execute to and fro motion along a horizontal line with the point of rotation as the midpoint. You could alternatively observe the shadow of the ball on a wall which is perpendicular to the plane of the circle. In this process what we are observing is the motion of the ball on a diameter of the circle normal to the direction of viewing. Fig. 13.8 Plots of Eq. (13.4) for φ = 0 for two different periods. u Example 13.3 Which of the following functions of time represent (a) simple Fig. 13.9 Circular motion of a ball in a plane viewed harmonic motion and (b) periodic but not edge-on is SHM. simple harmonic? Give the period for each case. Fig. 13.10 describes the same situation (1) sin ωt – cos ωt mathematically. Suppose a particle P is moving (2) sin2 ωt uniformly on a circle of radius A with angular Answer speed ω. The sense of rotation is anticlockwise. (a) sin ωt – cos ωt The initial position vector of the particle, i.e., = sin ωt – sin (π/2 – ωt) the vector OP at t = 0 makes an angle of φ with = 2 cos (π/4) sin (ωt – π/4) the positive direction of x-axis. In time t, it will = √2 sin (ωt – π/4) cover a further angle ωt and its position vector Reprint 2025-26 OSCILLATIONS 265 u Example 13.4 The figure given below depicts two circular motions. The radius of the circle, the period of revolution, the initial position and the sense of revolution are indicated in the figures. Obtain the simple harmonic motions of the x-projection of the radius vector of the rotating particle P in each case. Fig. 13.10 will make an angle of ωt + φ with the +ve x-axis. Next, consider the projection of the position vector OP on the x-axis. This will be Answer OP′. The position of P′ on the x-axis, as the (a) At t = 0, OP makes an angle of 45o = π/4 rad particle P moves on the circle, is given by with the (positive direction of) x-axis. After x(t) = A cos (ωt + φ ) 2 π time t, it covers an angle t in thewhich is the defining equation of SHM. This T shows that if P moves uniformly on a circle, anticlockwise sense, and makes an angle its projection P′ on a diameter of the circle executes SHM. The particle P and the circle of 2 πt + π with the x-axis. on which it moves are sometimes referred to T 4 as the reference particle and the reference circle, The projection of OP on the x-axis at time t respectively. is given by, We can take projection of the motion of P on any diameter, say the y-axis. In that case, the  2π π  x (t) = A cos t +displacement y(t) of P′ on the y-axis is given by  T 4  y = A sin (ωt + φ) For T = 4 s, which is also an SHM of the same amplitude as that of the projection on x-axis, but differing  2π π  x(t) = A cos t +by a phase of π/2.  4 4  In spite of this connection between circular motion and SHM, the force acting on a particle which is a SHM of amplitude A, period 4 s, in linear simple harmonic motion is very πdifferent from the centripetal force needed to and an initial phase* = . keep a particle in uniform circular motion. 4 * The natural unit of angle is radian, defined through the ratio of arc to radius. Angle is a dimensionless quantity. Therefore it is not always necessary to mention the unit ‘radian’ when we use π, its multiples or submultiples. The conversion between radian and degree is not similar to that between metre and centimetre or mile. If the argument of a trigonometric function is stated without units, it is understood that the unit is radian. On the other hand, if degree is to be used as the unit of angle, then it must be shown explicitly. For example, sin(150) means sine of 15 degree, but sin(15) means sine of 15 radians. Hereafter, we will often drop ‘rad’ as the unit, and it should be understood that whenever angle is mentioned as a numerical value, without units, it is to be taken as radians. Reprint 2025-26 266 PHYSICS (b) In this case at t = 0, OP makes an angle of where the negative sign shows that v (t) has a π direction opposite to the positive direction of 90o = with the x-axis. After a time t, it x-axis. Eq. (13.9) gives the instantaneous 2 2π velocity of a particle executing SHM, where covers an angle of t in the clockwise T displacement is given by Eq. (13.4). We can, of  π 2π  course, obtain this equation without using sense and makes an angle of  2 − T t  geometrical argument, directly by differentiating (Eq. 13.4) with respect of t: with the x-axis. The projection of OP on the x-axis at time t is given by d v(t) = x (t ) (13.10)  π 2π  d t x(t) = B cos  2 − T t  The method of reference circle can be similarly used for obtaining instantaneous acceleration  2π  of a particle undergoing SHM. We know that the = B sin  T t  centripetal acceleration of a particle P in uniform For T = 30 s, circular motion has a magnitude v2/A or ω2A, and it is directed towards the centre i.e., the  π  direction is along PO. The instantaneous x(t) = B sin  15 t  acceleration of the projection particle P′ is then (See Fig. 13.12)  π π  a (t) = –ω2A cos (ωt + φ) Writing this as x (t) = B cos  15 t − 2 , and comparing with Eq. (13.4). We find that this = –ω2x (t) (13.11) represents a SHM of amplitude B, period 30 s, π and an initial phase of − . ⊳ 2

13.4 1.23 351 Reprint 2025-26 Physics 13.5 (i) Q = –4.03 MeV; endothermic (ii) Q = 4.62 MeV; exothermic 56 – 2m 28 Al = 26.90 MeV; not possible. 13.6 Q = m ( 26 Fe ) ( 13 ) 13.7 4.536 × 1026 MeV 13.8 About 4.9 × 104 y 13.9 360 KeV CHAPTER 14 14.1 (c) 14.2 (d) 14.3 (c) 14.4 (c) 14.5 (c) 14.6 50 Hz for half-wave, 100 Hz for full-wave Reprint 2025-26 Bibligraphy BIBLIOGRAPHY TEXTBOOKS For additional reading on the topics covered in this book, you may like to consult one or more of the following books. Some of these books however are more advanced and contain many more topics than this book. 1 Ordinary Level Physics, A.F. Abbott, Arnold-Heinemann (1984). 2 Advanced Level Physics, M. Nelkon and P. Parker, 6th Edition, Arnold-Heinemann (1987). 3 Advanced Physics, Tom Duncan, John Murray (2000). 4 Fundamentals of Physics, David Halliday, Robert Resnick and Jearl Walker, 7th Edition John Wily (2004). 5 University Physics (Sears and Zemansky’s), H.D. Young and R.A. Freedman, 11th Edition, Addison—Wesley (2004). 6 Problems in Elementary Physics, B. Bukhovtsa, V. Krivchenkov, G. Myakishev and V. Shalnov, MIR Publishers, (1971). 7 Lectures on Physics (3 volumes), R.P. Feynman, Addision – Wesley (1965). 8 Berkeley Physics Course (5 volumes) McGraw Hill (1965). a. Vol. 1 – Mechanics: (Kittel, Knight and Ruderman) b. Vol. 2 – Electricity and Magnetism (E.M. Purcell) c. Vol. 3 – Waves and Oscillations (Frank S. Crawford) d. Vol. 4 – Quantum Physics (Wichmann) e. Vol. 5 – Statistical Physics (F. Reif ) 9 Fundamental University Physics, M. Alonso and E. J. Finn, Addison – Wesley (1967). 10 College Physics, R.L. Weber, K.V. Manning, M.W. White and G.A. Weygand, Tata McGraw Hill (1977). 11 Physics: Foundations and Frontiers, G. Gamow and J.M. Cleveland, Tata McGraw Hill (1978). 12 Physics for the Inquiring Mind, E.M. Rogers, Princeton University Press (1960). 13 PSSC Physics Course, DC Heath and Co. (1965) Indian Edition, 14 Physics Advanced Level, Jim Breithampt, Stanley Thornes Publishers (2000). 15 Physics, Patrick Fullick, Heinemann (2000). 16 Conceptual Physics, Paul G. Hewitt, Addision—Wesley (1998). 17 College Physics, Raymond A. Serway and Jerry S. Faughn, Harcourt Brace and Co. (1999). 18 University Physics, Harris Benson, John Wiley (1996). 19 University Physics, William P. Crummet and Arthur B. Western, Wm.C. Brown (1994). 20 General Physics, Morton M. Sternheim and Joseph W. Kane, John Wiley (1988). 21 Physics, Hans C. Ohanian, W.W. Norton (1989). Reprint 2025-26 Physics 22 Advanced Physics, Keith Gibbs, Cambridge University Press (1996). 23 Understanding Basic Mechanics, F. Reif, John Wiley (1995). 24 College Physics, Jerry D. Wilson and Anthony J. Buffa, Prentice Hall (1997). 25 Senior Physics, Part – I, I.K. Kikoin and A.K. Kikoin, MIR Publishers (1987). 26 Senior Physics, Part – II, B. Bekhovtsev, MIR Publishers (1988). 27 Understanding Physics, K. Cummings, Patrick J. Cooney, Priscilla W. Laws and Edward F. Redish, John Wiley (2005). 28 Essentials of Physics, John D. Cutnell and Kenneth W. Johnson, John Wiley (2005). GENERAL BOOKS For instructive and entertaining general reading on science, you may like to read some of the following books. Remember however, that many of these books are written at a level far beyond the level of the present book. 1 Mr. Tompkins in paperback, G. Gamow, Cambridge University Press (1967). 2 The Universe and Dr. Einstein, C. Barnett, Time Inc. New York (1962). 3 Thirty years that Shook Physics, G. Gamow, Double Day, New York (1966). 4 Surely You’re Joking, Mr. Feynman, R.P. Feynman, Bantam books (1986). 5 One, Two, Three… Infinity, G. Gamow, Viking Inc. (1961). 6 The Meaning of Relativity, A. Einstein, (Indian Edition) Oxford and IBH Pub. Co. (1965). 7 Atomic Theory and the Description of Nature, Niels Bohr, Cambridge (1934). 8 The Physical Principles of Quantum Theory, W. Heisenberg, University of Chicago Press (1930). 9 The Physics—Astronomy Frontier, F. Hoyle and J.V. Narlikar, W.H. Freeman (1980). 10 The Flying Circus of Physics with Answer, J. Walker, John Wiley and Sons (1977). 11 Physics for Everyone (series), L.D. Landau and A.I. Kitaigorodski, MIR Publisher (1978). Book 1: Physical Bodies Book 2: Molecules Book 3: Electrons Book 4: Photons and Nuclei. 12 Physics can be Fun, Y. Perelman, MIR Publishers (1986). 13 Power of Ten, Philip Morrison and Eames, W.H. Freeman (1985). 14 Physics in your Kitchen Lab., I.K. Kikoin, MIR Publishers (1985). 15 How Things Work: The Physics of Everyday Life, Louis A. Bloomfield, John Wiley (2005). 16 Physics Matters: An Introduction to Conceptual Physics, James Trefil and Robert M. Hazen, John Wiley (2004). 354 Reprint 2025-26

6.11 Dynamics of rotational the motion of extended bodies. motion about a fixed axis A large class of problems with extended bodies can be

6.12 ANGULAR MOMENTUM IN CASE OF For computing the total angular momentum ROTATION ABOUT A FIXED AXIS of the whole rigid body, we add up the contribution of each particle of the body. We have studied in section 6.7, the angular momentum of a system of particles. We already Thus know from there that the time rate of total We denote by L ⊥ and L z the components of angular momentum of a system of particles L respectively perpendicular to the z-axis andabout a point is equal to the total external torque along the z-axis;on the system taken about the same point. When OC i × m i v i (6.42a)the total external torque is zero, the total angular L ⊥= ∑ momentum of the system is conserved. where mi and vi are respectively the mass and We now wish to study the angular momentum the velocity of the ith particle and Ci is the centrein the special case of rotation about a fixed axis. of the circle described by the particle; The general expression for the total angular momentum of the system of n particles is N and ˆ (6.42b) L = =∑i 1 ri × p i (6.25b) or L z = Iωk We first consider the angular momentum of The last step follows since the perpendicular a typical particle of the rotating rigid body. We distance of the ith particle from the axis is ri; andthen sum up the contributions of individual by definition the moment of inertia of the body particles to get L of the whole body. m i ri2 . For a typical particle l = r × p. As seen in the about the axis of rotation is I =∑ last section r = OP = OC + CP [Fig. 6.17(b)]. With Note L = L z + L ⊥ (6.42c)p = m v , l = ( OC × m v ) + ( CP × m v ) The rigid bodies which we have mainly considered in this chapter are symmetric about The magnitude of the linear velocity v of the the axis of rotation, i.e. the axis of rotation is particle at P is given by v = ωr⊥ where r⊥ is the one of their symmetry axes. For such bodies, for length of CP or the perpendicular distance of P a given OCi, for every particle which has a from the axis of rotation. Further, v is tangential velocity vi , there is another particle of velocity at P to the circle which the particle describes. –vi located diametrically opposite on the circle Using the right-hand rule one can check that with centre Ci described by the particle. TogetherCP × v is parallel to the fixed axis. The unit vector along the fixed axis (chosen as the z-axis) such pairs will contribute zero to L ⊥ and as a is ˆk . Hence result for symmetric bodies L ⊥ is zero, and CP × m v = r⊥ (mv ) kˆ hence z = Iωkˆ (6.42d) = mr⊥2ω kˆ (since υ = ωr⊥ ) L = L Similarly, we can check that OC × v is For bodies, which are not symmetric about perpendicular to the fixed axis. Let us denote the axis of rotation, L is not equal to Lz and hence the part of l along the fixed axis (i.e. the z-axis) L does not lie along the axis of rotation. by lz, then Referring to Table 6.1, can you tell in which l z = CP × m v = mr⊥2ωkˆ cases L = Lz will not apply? Let us differentiate Eq. (6.42b). Since ˆk is a and l = l z + OC × m v fixed (constant) vector, we get We note that lz is parallel to the fixed axis, ˆbut l is not. In general, for a particle, the angular I ω) k d ( L z ) =  d (  d t momentum l is not along the axis of rotation, d t i.e. for a particle, l and ω are not necessarily Now, Eq. (6.28b) states parallel. Compare this with the corresponding dL fact in translation. For a particle, p and v are = τ dtalways parallel to each other. Reprint 2025-26 122 PHYSICS As we have seen in the last section, only We have already derived this equation using those components of the external torques which the work - kinetic energy route. are along the axis of rotation, need to be taken into account, when we discuss rotation about a 6.12.1 Conservation of angular momentum fixed axis. This means we can take τ = τkˆ . We are now in a position to revisit the principle of conservation of angular momentum in the Since L = L z + L ⊥ and the direction of Lz (vector context of rotation about a fixed axis. From Eq. ˆk ) is fixed, it follows that for rotation about a (6.43c), if the external torque is zero, fixed axis, Lz = Iω = constant (6.44) For symmetric bodies, from Eq. (6.42d), Lz d L z = τkˆ (6.43a) may be replaced by L .(L and Lz are respectively d t the magnitudes of L and Lz.) This then is the required form, for fixed axis d L rotation, of Eq. (6.29a), which expresses theand ⊥= 0 (6.43b) dt general law of conservation of angular momentum Thus, for rotation about a fixed axis, the of a system of particles. Eq. (6.44) applies to many component of angular momentum perpendicular situations that we come across in daily life. You may do this experiment with your friend. Sit on a to the fixed axis is constant. As L z = Iωkˆ , we swivel chair (a chair with a seat, free to rotate get from Eq. (6.43a), about a pivot) with your arms folded and feet not resting on, i.e., away from, the ground. Ask your d ( Iω) = τ (6.43c) friend to rotate the chair rapidly. While the chair d t is rotating with considerable angular speed If the moment of inertia I does not change with stretch your arms horizontally. What happens? time, Your angular speed is reduced. If you bring back d dω your arms closer to your body, the angular speed ( Iω) = I = Iα increases again. This is a situation where thed t d t principle of conservation of angular momentumand we get from Eq. (6.43c), is applicable. If friction in the rotational τ = I α (6.41) Fig 6.32 (a) A demonstration of conservation of Fig 6.32 (b) An acrobat employing the principle of angular momentum. A girl sits on a conservation of angular momentum in swivel chair and stretches her arms/ her performance. brings her arms closer to the body. Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 123 mechanism is neglected, there is no external A circus acrobat and a diver take advantage torque about the axis of rotation of the chair and of this principle. Also, skaters and classical, hence Iω is constant. Stretching the arms Indian or western, dancers performing a increases I about the axis of rotation, resulting in pirouette (a spinning about a tip–top) on the toes decreasing the angular speed ω. Bringing the of one foot display ‘mastery’ over this principle. arms closer to the body has the opposite effect. Can you explain? SUMMARY 1. Ideally, a rigid body is one for which the distances between different particles of the body do not change, even though there are forces on them. 2. A rigid body fixed at one point or along a line can have only rotational motion. A rigid body not fixed in some way can have either pure translational motion or a combination of translational and rotational motions. 3. In rotation about a fixed axis, every particle of the rigid body moves in a circle which lies in a plane perpendicular to the axis and has its centre on the axis. Every Point in the rotating rigid body has the same angular velocity at any instant of time. 4. In pure translation, every particle of the body moves with the same velocity at any instant of time. 5. Angular velocity is a vector. Its magnitude is ω = dθ/dt and it is directed along the axis of rotation. For rotation about a fixed axis, this vector ω has a fixed direction. 6. The vector or cross product of two vector a and b is a vector written as a×b. The magnitude of this vector is absinθ and its direction is given by the right handed screw or the right hand rule. 7. The linear velocity of a particle of a rigid body rotating about a fixed axis is given by v = ω × r, where r is the position vector of the particle with respect to an origin along the fixed axis. The relation applies even to more general rotation of a rigid body with one point fixed. In that case r is the position vector of the particle with respect to the fixed point taken as the origin. 8. The centre of mass of a system of n particles is defined as the point whose position vector is ri ∑m i R = M 9. Velocity of the centre of mass of a system of particles is given by V = P/M, where P is the linear momentum of the system. The centre of mass moves as if all the mass of the system is concentrated at this point and all the external forces act at it. If the total external force on the system is zero, then the total linear momentum of the system is constant. 10. The angular momentum of a system of n particles about the origin is n L = ri × pi i =∑1 The torque or moment of force on a system of n particles about the origin is τ = ∑ri × Fi 1 The force Fi acting on the ith particle includes the external as well as internal forces. Assuming Newton’s third law of motion and that forces between any two particles act along the line joining the particles, we can show τint = 0 and Reprint 2025-26 124 PHYSICS dL = τ ext dt 11. A rigid body is in mechanical equilibrium if (1) it is in translational equilibrium, i.e., the total external force on it is zero : Fi = 0 , ∑ and (2) it is in rotational equilibrium, i.e. the total external torque on it is zero : Fi = 0 . ∑ τi = ∑ri × 12. The centre of gravity of an extended body is that point where the total gravitational torque on the body is zero. 13. The moment of intertia of a rigid body about an axis is defined by the formula I m i ri2 =∑ where ri is the perpendicular distance of the ith point of the body from the axis. The 1 2 kinetic energy of rotation is K = Iω . 2 POINTS TO PONDER 1. To determine the motion of the centre of mass of a system no knowledge of internal forces of the system is required. For this purpose we need to know only the external forces on the body. 2. Separating the motion of a system of particles as the motion of the centre of mass, (i.e., the translational motion of the system) and motion about (i.e. relative to) the centre of mass of the system is a useful technique in dynamics of a system of particles. One example of this technique is separating the kinetic energy of a system of particles K as the kinetic energy of the system about its centre of mass K′ and the kinetic energy of the centre of mass MV2/2, K = K′ + MV2/2 3. Newton’s Second Law for finite sized bodies (or systems of particles) is based in Newton’s Second Law and also Newton’s Third Law for particles. 4. To establish that the time rate of change of the total angular momentum of a system of particles is the total external torque in the system, we need not only Newton’s second law for particles, but also Newton’s third law with the provision that the forces between any two particles act along the line joining the particles. 5. The vanishing of the total external force and the vanishing of the total external torque are independent conditions. We can have one without the other. In a couple, total external force is zero, but total torque is non-zero. 6. The total torque on a system is independent of the origin if the total external force is zero. 7. The centre of gravity of a body coincides with its centre of mass only if the gravitational field does not vary from one part of the body to the other. Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 125 8. The angular momentum L and the angular velocity ω are not necessarily parallel vectors. However, for the simpler situations discussed in this chapter when rotation is about a fixed axis which is an axis of symmetry of the rigid body, the relation L = Iω holds good, where I is the moment of the inertia of the body about the rotation axis. EXERCISES 6.1 Give the location of the centre of mass of a (i) sphere, (ii) cylinder, (iii) ring, and (iv) cube, each of uniform mass density. Does the centre of mass of a body necessarily lie inside the body ? 6.2 In the HCl molecule, the separation between the nuclei of the two atoms is about 1.27 Å (1 Å = 10-10 m). Find the approximate location of the CM of the molecule, given that a chlorine atom is about 35.5 times as massive as a hydrogen atom and nearly all the mass of an atom is concentrated in its nucleus. 6.3 A child sits stationary at one end of a long trolley moving uniformly with a speed V on a smooth horizontal floor. If the child gets up and runs about on the trolley in any manner, what is the speed of the CM of the (trolley + child) system ? 6.4 Show that the area of the triangle contained between the vectors a and b is one half of the magnitude of a × b. 6.5 Show that a.(b × c) is equal in magnitude to the volume of the parallelepiped formed on the three vectors , a, b and c. 6.6 Find the components along the x, y, z axes of the angular momentum l of a particle, whose position vector is r with components x, y, z and momentum is p with components px, py and pz. Show that if the particle moves only in the x-y plane the angular momentum has only a z-component. 6.7 Two particles, each of mass m and speed v, travel in opposite directions along parallel lines separated by a distance d. Show that the angular momentum vector of the two particle system is the same whatever be the point about which the angular momentum is taken. 6.8 A non-uniform bar of weight W is suspended at rest by two strings of negligible weight as shown in Fig.6.33. The angles made by the strings with the vertical are 36.9° and 53.1° respectively. The bar is 2 m long. Calculate the distance d of the centre of gravity of the bar from its left end. Fig. 6.33 6.9 A car weighs 1800 kg. The distance between its front and back axles is 1.8 m. Its centre of gravity is 1.05 m behind the front axle. Determine the force exerted by the level ground on each front wheel and each back wheel. Reprint 2025-26 126 PHYSICS 6.10 Torques of equal magnitude are applied to a hollow cylinder and a solid sphere, both having the same mass and radius. The cylinder is free to rotate about its standard axis of symmetry, and the sphere is free to rotate about an axis passing through its centre. Which of the two will acquire a greater angular speed after a given time. 6.11 A solid cylinder of mass 20 kg rotates about its axis with angular speed 100 rad s-1. The radius of the cylinder is 0.25 m. What is the kinetic energy associated with the rotation of the cylinder? What is the magnitude of angular momentum of the cylinder about its axis? 6.12 (a) A child stands at the centre of a turntable with his two arms outstretched. The turntable is set rotating with an angular speed of 40 rev/min. How much is the angular speed of the child if he folds his hands back and thereby reduces his moment of inertia to 2/5 times the initial value ? Assume that the turntable rotates without friction. (b) Show that the child’s new kinetic energy of rotation is more than the initial kinetic energy of rotation. How do you account for this increase in kinetic energy? 6.13 A rope of negligible mass is wound round a hollow cylinder of mass 3 kg and radius 40 cm. What is the angular acceleration of the cylinder if the rope is pulled with a force of 30 N ? What is the linear acceleration of the rope ? Assume that there is no slipping. 6.14 To maintain a rotor at a uniform angular speed of 200 rad s-1, an engine needs to transmit a torque of 180 N m. What is the power required by the engine ? (Note: uniform angular velocity in the absence of friction implies zero torque. In practice, applied torque is needed to counter frictional torque). Assume that the engine is 100% efficient. 6.15 From a uniform disk of radius R, a circular hole of radius R/2 is cut out. The centre of the hole is at R/2 from the centre of the original disc. Locate the centre of gravity of the resulting flat body. 6.16 A metre stick is balanced on a knife edge at its centre. When two coins, each of mass 5 g are put one on top of the other at the 12.0 cm mark, the stick is found to be balanced at 45.0 cm. What is the mass of the metre stick? 6.17 The oxygen molecule has a mass of 5.30 × 10-26 kg and a moment of inertia of 1.94 ×10-46 kg m2 about an axis through its centre perpendicular to the lines joining the two atoms. Suppose the mean speed of such a molecule in a gas is 500 m/s and that its kinetic energy of rotation is two thirds of its kinetic energy of translation. Find the average angular velocity of the molecule. Reprint 2025-26 CHAPTER SEVEN GRAVITATION 7.1 INTRODUCTION Early in our lives, we become aware of the tendency of all material objects to be attracted towards the earth. Anything

6.4 LINEAR MOMENTUM OF A SYSTEM OF Eq. (6.15), this also means that when the PARTICLES total external force on the system is zero the velocity of the centre of mass remainsLet us recall that the linear momentum of a constant. (We assume throughout the particle is defined as discussion on systems of particles in this p = m v (6.12) chapter that the total mass of the system Let us also recall that Newton’s second law remains constant.) written in symbolic form for a single particle is Note that on account of the internal forces, dp i.e. the forces exerted by the particles on one F = (6.13) another, the individual particles may have dt Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 101 complicated trajectories. Yet, if the total external force acting on the system is zero, the centre of mass moves with a constant velocity, i.e., moves uniformly in a straight line like a free particle. The vector Eq. (6.18a) is equivalent to three scalar equations, Px = c1, Py = c2 and Pz = c3 (6.18 b) (a) (b) Here Px, Py and Pz are the components of the total linear momentum vector P along the x–, y– Fig. 6.14 (a) Trajectories of two stars, S1 (dotted line) and z–axes respectively; c1, c2 and c3 are and S2 (solid line) forming a binary constants. system with their centre of mass C in uniform motion. (b) The same binary system, with the centre of mass C at rest. move back to back with their centre of mass remaining at rest as shown in Fig.6.13 (b). In many problems on the system of particles, as in the above radioactive decay problem, it is convenient to work in the centre of mass frame rather than in the laboratory frame of reference. (a) (b) In astronomy, binary (double) stars is a common occurrence. If there are no external forces, the centre of mass of a double star Fig. 6.13 (a) A heavy nucleus radium (Ra) splits into moves like a free particle, as shown in Fig.6.14 a lighter nucleus radon (Rn) and an alpha (a). The trajectories of the two stars of equal particle (nucleus of helium atom). The CM mass are also shown in the figure; they look of the system is in uniform motion. complicated. If we go to the centre of mass (b) The same spliting of the heavy nucleus radium (Ra) with the centre of mass at frame, then we find that there the two stars rest. The two product particles fly back are moving in a circle, about the centre of to back. mass, which is at rest. Note that the position of the stars have to be diametrically opposite As an example, let us consider the to each other [Fig. 6.14(b)]. Thus in our frame radioactive decay of a moving unstable particle, of reference, the trajectories of the stars are a combination of (i) uniform motion in a straightlike the nucleus of radium. A radium nucleus line of the centre of mass and (ii) circulardisintegrates into a nucleus of radon and an orbits of the stars about the centre of mass.alpha particle. The forces leading to the decay As can be seen from the two examples,are internal to the system and the external separating the motion of different parts of aforces on the system are negligible. So the total system into motion of the centre of mass andlinear momentum of the system is the same motion about the centre of mass is a verybefore and after decay. The two particles useful technique that helps in understanding produced in the decay, the radon nucleus and the motion of the system. the alpha particle, move in different directions in such a way that their centre of mass moves 6.5 VECTOR PRODUCT OF TWO VECTORS along the same path along which the original decaying radium nucleus was moving We are already familiar with vectors and their [Fig. 6.13(a)]. use in physics. In chapter 5 (Work, Energy, Power) If we observe the decay from the frame of we defined the scalar product of two vectors. An reference in which the centre of mass is at rest, important physical quantity, work, is defined as the motion of the particles involved in the decay a scalar product of two vector quantities, force looks particularly simple; the product particles and displacement. Reprint 2025-26 102 PHYSICS We shall now define another product of two A simpler version of the right hand rule is vectors. This product is a vector. Two important the following : Open up your right hand palm quantities in the study of rotational motion, and curl the fingers pointing from a to b. Your namely, moment of a force and angular stretched thumb points in the direction of c. momentum, are defined as vector products. It should be remembered that there are two angles between any two vectors a and b . In Definition of Vector Product Fig. 6.15 (a) or (b) they correspond to θ(as shown) A vector product of two vectors a and b is a and (3600– θ). While applying either of the above vector c such that rules, the rotation should be taken through the (i) magnitude of c = c = ab sinθ where a and b smaller angle (<1800) between a and b. It is θ are magnitudes of a and b and θ is the here. angle between the two vectors. Because of the cross (×) used to denote the (ii) c is perpendicular to the plane containing vector product, it is also referred to as cross product. a and b. • Note that scalar product of two vectors is (iii) if we take a right handed screw with its head commutative as said earlier, a.b = b.a lying in the plane of a and b and the screw The vector product, however, is not perpendicular to this plane, and if we turn commutative, i.e. a × b ≠ b × a the head in the direction from a to b, then The magnitude of both a × b and b × a is the the tip of the screw advances in the direction same ( ab sin θ ); also, both of them are of c. This right handed screw rule is perpendicular to the plane of a and b. But the illustrated in Fig. 6.15a. rotation of the right-handed screw in case of Alternately, if one curls up the fingers of a × b is from a to b, whereas in case of b × a it right hand around a line perpendicular to the is from b to a. This means the two vectors are plane of the vectors a and b and if the fingers in opposite directions. We have are curled up in the direction from a to b, then a × b = − b × a the stretched thumb points in the direction of • Another interesting property of a vector c, as shown in Fig. 6.15b. product is its behaviour under reflection. Under reflection (i.e. on taking the plane mirror image) we have x →− x , y →−y and z →− z . As a result all the components of a vector change sign and thus a →−a , b →−b . What happens to a × b under reflection? a × b →−( a ) × ( − b ) = a × b Thus, a × b does not change sign under reflection. • Both scalar and vector products are distributive with respect to vector addition. Thus, a.( b + c ) = a.b + a.c a × ( b + c ) = a × b + a × c (a) (b) • We may write c = a × b in the component form. For this we first need to obtain some elementary cross products: Fig. 6.15 (a) Rule of the right handed screw for (i) a × a = 0 (0 is a null vector, i.e. a vector defining the direction of the vector with zero magnitude) product of two vectors. This follows since magnitude of a × a is (b) Rule of the right hand for defining the direction of the vector product. a 2 sin0° = 0 . Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 103 From this follow the results ˆ ˆ ˆ i j k (i) ˆi × ˆi = 0, ˆj × ˆj = 0, kˆ × kˆ = 0 a × b = 3 − 4 5 = 7 ˆi − ˆj − 5 kˆ (ii) ˆi × ˆj = kˆ − 2 1 − 3 Note that the magnitude of ˆi × ˆj is sin900 Note b × a = −7ˆi + ˆj + 5 kˆ ⊳ or 1, since ˆi and ˆj both have unit magnitude and the angle between them is 900. 6.6 ANGULAR VELOCITY AND ITS RELATION WITH LINEAR VELOCITY Thus, ˆi × ˆj is a unit vector. A unit vector In this section we shall study what is angular perpendicular to the plane of ˆi and ˆj and velocity and its role in rotational motion. We related to them by the right hand screw rule is have seen that every particle of a rotating body moves in a circle. The linear velocity of the ˆk . Hence, the above result. You may verify particle is related to the angular velocity. The similarly, relation between these two quantities involves ˆ j × kˆ = ˆi and kˆ × ˆi = ˆj a vector product which we learnt about in the last section. From the rule for commutation of the cross Let us go back to Fig. 6.4. As said above, inproduct, it follows: rotational motion of a rigid body about a fixed ˆ j × ˆi = − kˆ , kˆ × ˆj = − ˆi, ˆi × kˆ = − ˆj axis, every particle of the body moves in a circle, Note if ˆi, ˆj, kˆ occur cyclically in the above vector product relation, the vector product is positive. If ˆi, ˆj, kˆ do not occur in cyclic order, the vector product is negative. Now, a × b = (a x ˆi + a y ˆj + a z kˆ ) × (b x ˆi + b y ˆj + b z kˆ ) = a x b y kˆ − a x b z ˆj − a y b x kˆ + a y b z ˆi + a z b x ˆj − a z b y ˆi = (a y b z − a z b y )i + (a z b x − a x b z ) j + (a x b y − a y b x )k We have used the elementary cross products in obtaining the above relation. The expression for a × b can be put in a determinant form which is easy to remember. ˆ ˆ ˆ i j k a × b = a x a y a z b x b y b z u Example 6.4 Find the scalar and vector Fig. 6.16 Rotation about a fixed axis. (A particle (P) of the rigid body rotating about the fixed products of two vectors. a = (z-) axis moves in a circle with centre (C) and b = on the axis.) Answer which lies in a plane perpendicular to the axis a i b = (3ˆi − 4 ˆj + 5 kˆ )i( − 2ˆi + ˆj − 3 kˆ ) and has its centre on the axis. In Fig. 6.16 we redraw Fig. 6.4, showing a typical particle (at a = −6 − 4 − 15 point P) of the rigid body rotating about a fixed = −25 axis (taken as the z-axis). The particle describes Reprint 2025-26 104 PHYSICS a circle with a centre C on the axis. The radius and points out in the direction in which a right of the circle is r, the perpendicular distance of handed screw would advance, if the head of the the point P from the axis. We also show the screw is rotated with the body. (See Fig. 6.17a). linear velocity vector v of the particle at P. It is The magnitude of this vector is ω = d θ dt along the tangent at P to the circle. referred as above. Let P′ be the position of the particle after an interval of time ∆t (Fig. 6.16). The angle PCP′ describes the angular displacement ∆θ of the particle in time ∆t. The average angular velocity of the particle over the interval ∆t is ∆θ/∆t. As ∆t tends to zero (i.e. takes smaller and smaller values), the ratio ∆θ/∆t approaches a limit which is the instantaneous angular velocity dθ/dt of the particle at the position P. We denote the instantaneous angular velocity by ω (the Greek letter omega). We know from our study Fig. 6.17 (a) If the head of a right handed screw of circular motion that the magnitude of linear rotates with the body, the screw velocity v of a particle moving in a circle is advances in the direction of the angular related to the angular velocity of the particle ω velocity ω. If the sense (clockwise or by the simple relation υ = ωr , where r is the anticlockwise) of rotation of the body changes, so does the direction of ω.radius of the circle. We observe that at any given instant the relation v = ωr applies to all particles of the rigid body. Thus for a particle at a perpendicular distance ri from the fixed axis, the linear velocity at a given instant vi is given by v i = ωri (6.19) The index i runs from 1 to n, where n is the total number of particles of the body. For particles on the axis, r = 0 , and hence v = ω r = 0. Thus, particles on the axis are stationary. This verifies that the axis is fixed. Note that we use the same angular velocity ω for all the particles. We therefore, refer to ω as the angular velocity of the whole body. We have characterised pure translation of a body by all parts of the body having the same Fig. 6.17 (b) The angular velocity vector ω is directed velocity at any instant of time. Similarly, we along the fixed axis as shown. The linear may characterise pure rotation by all parts of velocity of the particle at P is v = ω × r. the body having the same angular velocity at It is perpendicular to both ωωωωω and r and any instant of time. Note that this is directed along the tangent to the circle described by the particle. characterisation of the rotation of a rigid body about a fixed axis is just another way of saying We shall now look at what the vector as in Sec. 6.1 that each particle of the body moves product ω × r corresponds to. Refer to Fig. in a circle, which lies in a plane perpendicular 6.17(b) which is a part of Fig. 6.16 reproduced to the axis and has the centre on the axis. to show the path of the particle P. The figure In our discussion so far the angular velocity shows the vector ω directed along the fixed (z–) appears to be a scalar. In fact, it is a vector. We axis and also the position vector r = OP of the shall not justify this fact, but we shall accept particle at P of the rigid body with respect to it. For rotation about a fixed axis, the angular the origin O. Note that the origin is chosen to velocity vector lies along the axis of rotation, be on the axis of rotation. Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 105 Now ω × r = ω × OP = ω × (OC + CP) If the axis of rotation is fixed, the direction But ω × OC = 00000 as ωωωωω is along OC of ωωωωω and hence, that of α is fixed. In this case Hence ω × r = ω × CP the vector equation reduces to a scalar equation dω α = (6.22) The vector ω × CP is perpendicular to ω, i.e. dt to the z-axis and also to CP, the radius of the circle described by the particle at P. It is 6.7 TORQUE AND ANGULAR MOMENTUM therefore, along the tangent to the circle at P. In this section, we shall acquaint ourselves with Also, the magnitude of ω × CP is ω (CP) since two physical quantities (torque and angular ω and CP are perpendicular to each other. We momentum) which are defined as vector products shall denote CP by ⊥r and not by r, as we did of two vectors. These as we shall see, are earlier. especially important in the discussion of motion Thus, ω × r is a vector of magnitude ωr⊥ of systems of particles, particularly rigid bodies. and is along the tangent to the circle described by the particle at P. The linear velocity vector v 6.7.1 Moment of force (Torque) at P has the same magnitude and direction. We have learnt that the motion of a rigid body, Thus, in general, is a combination of rotation and v = ωωωωω × r (6.20) translation. If the body is fixed at a point or along In fact, the relation, Eq. (6.20), holds good a line, it has only rotational motion. We know even for rotation of a rigid body with one point that force is needed to change the translationalfixed, such as the rotation of the top [Fig. 6.6(a)]. In this case r represents the position vector of state of a body, i.e. to produce linear the particle with respect to the fixed point taken acceleration. We may then ask, what is the as the origin. analogue of force in the case of rotational We note that for rotation about a fixed motion? To look into the question in a concrete axis, the direction of the vector ω does not situation let us take the example of opening or change with time. Its magnitude may, closing of a door. A door is a rigid body which however, change from instant to instant. For can rotate about a fixed vertical axis passing the more general rotation, both the magnitude and the direction of ωωωωω may change through the hinges. What makes the door from instant to instant. rotate? It is clear that unless a force is applied the door does not rotate. But any force does not 6.6.1 Angular acceleration do the job. A force applied to the hinge line You may have noticed that we are developing cannot produce any rotation at all, whereas a the study of rotational motion along the lines force of given magnitude applied at right angles of the study of translational motion with which to the door at its outer edge is most effective in we are already familiar. Analogous to the kinetic producing rotation. It is not the force alone, but variables of linear displacement (s) and velocity how and where the force is applied is important (v) in translational motion, we have angular in rotational motion. displacement (θ) and angular velocity (ω) in The rotational analogue of force in linear rotational motion. It is then natural to define motion is moment of force. It is also referred to in rotational motion the concept of angular as torque or couple. (We shall use the words acceleration in analogy with linear acceleration moment of force and torque interchangeably.) defined as the time rate of change of velocity in We shall first define the moment of force for the translational motion. We define angular special case of a single particle. Later on we acceleration α as the time rate of change of shall extend the concept to systems of particles angular velocity. Thus, including rigid bodies. We shall also relate it to d ω a change in the state of rotational motion, i.e. is α = (6.21) dt angular acceleration of a rigid body. Reprint 2025-26 106 PHYSICS of the line of action of F from the origin and F⊥=( F sin θ) is the component of F in the direction perpendicular to r. Note that τ = 0 if r = 0, F = 0 or θ = 00 or 1800 . Thus, the moment of a force vanishes if either the magnitude of the force is zero, or if the line of action of the force passes through the origin. One may note that since r × F is a vector product, properties of a vector product of two vectors apply to it. If the direction of F is reversed, the direction of the moment of force is reversed. If directions of both r and F are reversed, the direction of the moment of force remains the same. 6.7.2 Angular momentum of a particle Just as the moment of a force is the rotational analogue of force in linear motion, the quantity angular momentum is the rotational analogue Fig. 6.18 τττττ ===== r × F, τττττ is perpendicular to the plane of linear momentum. We shall first define containing r and F, and its direction is angular momentum for the special case of a given by the right handed screw rule. single particle and look at its usefulness in the context of single particle motion. We shall then If a force acts on a single particle at a point extend the definition of angular momentum to P whose position with respect to the origin O is systems of particles including rigid bodies. given by the position vector r (Fig. 6.18), the Like moment of a force, angular momentum moment of the force acting on the particle with is also a vector product. It could also be referred respect to the origin O is defined as the vector to as moment of (linear) momentum. From this product term one could guess how angular momentum τ = r × F (6.23) is defined. The moment of force (or torque) is a vector Consider a particle of mass m and linear quantity. The symbol τττττ stands for the Greek momentum p at a position r relative to the origin letter tau. The magnitude of τττττ is O. The angular momentum l of the particle with τ = r F sinθ (6.24a) respect to the origin O is defined to be l = r × p (6.25a)where r is the magnitude of the position vector r, i.e. the length OP, F is the magnitude of force The magnitude of the angular momentum F and θ is the angle between r and F as vector is shown. l = r p sinθ (6.26a) Moment of force has dimensions M L2 T -2. where p is the magnitude of p and θ is the angle Its dimensions are the same as those of work between r and p. We may write or energy. It is, however, a very different physical l = r p⊥ or r ⊥ p (6.26b)quantity than work. Moment of a force is a vector, while work is a scalar. The SI unit of where r⊥ (= r sinθ) is the perpendicular distance moment of force is newton metre (N m). The of the directional line of p from the origin and magnitude of the moment of force may be p ⊥=( p sin θ) is the component of p in a directionwritten perpendicular to r. We expect the angular τ = (r sin θ)F = r⊥ F (6.24b) momentum to be zero (l = 0), if the linear or τ = r F sin θ = rF ⊥ (6.24c) momentum vanishes (p = 0), if the particle is at the origin (r = 0), or if the directional line of p where r⊥ = r sinθ is the perpendicular distance passes through the origin θ = 00 or 1800. Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 107 The physical quantities, moment of a force and angular momentum, have an important An experiment with the bicycle rim relation between them. It is the rotational Take a analogue of the relation between force and linear bicycle rim momentum. For deriving the relation in the and extend context of a single particle, we differentiate its axle on l = r × p with respect to time, both sides. Tie two d l d = ( r × p ) s t r i n g s d t d t at both ends Applying the product rule for differentiation A and B, to the right hand side, as shown in the d d r d p ( r × p ) = × p + r × a d j o i n i n g d t d t d t figure. Hold Now, the velocity of the particle is v = dr/dt both the and p = m v Initially After s t r i n g s together in dr one hand such that the rim is vertical. If you Because of this × p = v × m v = 0, dt leave one string, the rim will tilt. Now keeping the rim in vertical position with both the stringsas the vector product of two parallel vectors in one hand, put the wheel in fast rotation vanishes. Further, since dp / dt = F, around the axle with the other hand. Then leave d p one string, say B, from your hand, and observe r × = r × F = t dt what happens. The rim keeps rotating in a vertical plane d and the plane of rotation turns around the string Hence ( r × p ) = τ A which you are holding. We say that the axis dt of rotation of the rim or equivalently or (6.27) its angular momentum precesses about the string A. Thus, the time rate of change of the angular The rotating rim gives rise to an angular momentum of a particle is equal to the torque momentum. Determine the direction of this acting on it. This is the rotational analogue of angular momentum. When you are holding the the equation F = dp/dt, which expresses rotating rim with string A, a torque is generated. (We leave it to you to find out how the torque isNewton’s second law for the translational motion generated and what its direction is.) The effect of a single particle. of the torque on the angular momentum is to make it precess around an axis perpendicular Torque and angular momentum for a system to both the angular momentum and the torque. of particles Verify all these statements. To get the total angular momentum of a system of particles about a given point we need to add vectorially the angular momenta of individual particles. Thus, for a system of n particles, particle has mass mi and velocity vi) We may write the total angular momentum of a system of particles as (6.25b) The angular momentum of the ith particle is given by li = ri × pi This is a generalisation of the definition of angular momentum (Eq. 6.25a) for a singlewhere ri is the position vector of the ith particle particle to a system of particles.with respect to a given origin and p = (mivi) is Using Eqs. (6.23) and (6.25b), we getthe linear momentum of the particle. (The Reprint 2025-26 108 PHYSICS d L d d l Note that like Eq.(6.17), Eq.(6.28b) holds = ( l ) = ∑ = ∑ τ (6.28a) good for any system of particles, whether it is a d t d t i d t i rigid body or its individual particles have all where τi is the torque acting on the ith particle; kinds of internal motion. τi = ri × Fi Conservation of angular momentum The force Fi on the ith particle is the vector ext If τext = 0, Eq. (6.28b) reduces to Fi sum of external forces acting on the particle d L = 0 and the internal forces iFint exerted on it by the dt other particles of the system. We may therefore or L = constant. (6.29a) separate the contribution of the external and Thus, if the total external torque on a system the internal forces to the total torque of particles is zero, then the total angular momentum of the system is conserved, i.e. τ = ∑ τ i = ∑ ri × Fi as remains constant. Eq. (6.29a) is equivalent to i i three scalar equations, τ = τext + τ int , Lx = K1, Ly = K2 and Lz = K3 (6.29 b) Here K1, K2 and K3 are constants; Lx, Ly and τ ext = ∑ri × Fi ext Lz are the components of the total angular where i momentum vector L along the x,y and z axes respectively. The statement that the total i × Fiint τ int = ∑r and angular momentum is conserved means that i each of these three components is conserved. We shall assume not only Newton’s third law Eq. (6.29a) is the rotational analogue of of motion, i.e. the forces between any two particles Eq. (6.18a), i.e. the conservation law of the total of the system are equal and opposite, but also that linear momentum for a system of particles. these forces are directed along the line joining the Like Eq. (6.18a), it has applications in many two particles. In this case the contribution of the practical situations. We shall look at a few of internal forces to the total torque on the system is the interesting applications later on in zero, since the torque resulting from each action- this chapter. reaction pair of forces is zero. We thus have, τint = 0 and therefore τ = τττext.ττ u Example 6.5 Find the torque of a force Since τ = ∑ τ i , it follows from Eq. (6.28a) + – about the origin. The force acts on a particle whose position vector is .that d L = τ ext (6.28 b) Answer Here r = ˆi − ˆj + kˆ d t and F = 7 ˆi + 3 ˆj − 5 kˆ . Thus, the time rate of the total angular We shall use the determinant rule to find themomentum of a system of particles about a τ = r × Fpoint (taken as the origin of our frame of torque reference) is equal to the sum of the external torques (i.e. the torques due to external forces) acting on the system taken about the same point. Eq. (6.28 b) is the generalisation of the single particle case of Eq. (6.23) to a system of particles. Note that when we have only one or ⊳ particle, there are no internal forces or torques. Eq.(6.28 b) is the rotational analogue of Example 6.6 Show that the angular u momentum about any point of a single d P = Fext (6.17) particle moving with constant velocity d t remains constant throughout the motion. Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 109 Answer Let the particle with velocity v be at acceleration nor angular acceleration. This means point P at some instant t. We want to calculate (1) the total force, i.e. the vector sum of the the angular momentum of the particle about an forces, on the rigid body is zero; arbitrary point O. n F1 + F2 + ... + Fn = =∑i 1 Fi = 0 (6.30a) If the total force on the body is zero, then the total linear momentum of the body does not change with time. Eq. (6.30a) gives the condition for the translational equilibrium of the body. (2) The total torque, i.e. the vector sum of the torques on the rigid body is zero, n τ + τ i = 0 (6.30b) 1 2 + ... + τ n = =∑i 1 τ Fig 6.19 If the total torque on the rigid body is zero, The angular momentum is l = r × mv. Its the total angular momentum of the body does magnitude is mvr sinθ, where θ is the angle not change with time. Eq. (6.30 b) gives the between r and v as shown in Fig. 6.19. Although condition for the rotational equilibrium of the the particle changes position with time, the line body. of direction of v remains the same and hence One may raise a question, whether theOM = r sin θ. is a constant. rotational equilibrium condition [Eq. 6.30(b)] Further, the direction of l is perpendicular remains valid, if the origin with respect to whichto the plane of r and v. It is into the page of the the torques are taken is shifted. One can showfigure.This direction does not change with time. Thus, l remains the same in magnitude and that if the translational equilibrium condition direction and is therefore conserved. Is there [Eq. 6.30(a)] holds for a rigid body, then such a any external torque on the particle? ⊳ shift of origin does not matter, i.e. the rotational equilibrium condition is independent of the 6.8 EQUILIBRIUM OF A RIGID BODY location of the origin about which the torques are taken. Example 6.7 gives a proof of this result We are now going to concentrate on the motion in a special case of a couple, i.e. two forcesof rigid bodies rather than on the motion of acting on a rigid body in translationalgeneral systems of particles. equilibrium. The generalisation of this result to We shall recapitulate what effect the external forces have on a rigid body. (Henceforth n forces is left as an exercise. we shall omit the adjective ‘external’ because Eq. (6.30a) and Eq. (6.30b), both, are vector unless stated otherwise, we shall deal with only equations. They are equivalent to three scalar external forces and torques.) The forces change equations each. Eq. (6.30a) corresponds to the translational state of the motion of the rigid n n n body, i.e. they change its total linear =∑i 1 Fix = 0 , =∑i 1 Fiy = 0 and =∑i 1 Fiz = 0 (6.31a)momentum in accordance with Eq. (6.17). But this is not the only effect the forces have. The where Fix, Fiy and Fiz are respectively the x, y and total torque on the body may not vanish. Such z components of the forces Fi. Similarly, Eq. a torque changes the rotational state of motion (6.30b) is equivalent to three scalar equations of the rigid body, i.e. it changes the total angular n n 0momentum of the body in accordance with τix = 0 , τiy = and (6.31b) =∑i 1 =∑i 1 Eq. (6.28 b). where τix, τiy and τiz are respectively the x, y and A rigid body is said to be in mechanical z components of the torque τi .equilibrium, if both its linear momentum and Eq. (6.31a) and (6.31b) give six independentangular momentum are not changing with time, conditions to be satisfied for mechanicalor equivalently, the body has neither linear Reprint 2025-26 110 PHYSICS equilibrium of a rigid body. In a number of problems all the forces acting on the body are coplanar. Then we need only three conditions to be satisfied for mechanical equilibrium. Two of these conditions correspond to translational equilibrium; the sum of the components of the forces along any two perpendicular axes in the plane must be zero. The third condition corresponds to rotational equilibrium. The sum of the components of the torques along any axis Fig. 6.20 (b) perpendicular to the plane of the forces must be zero. The force at B in Fig. 6.20(a) is reversed in Fig. 6.20(b). Thus, we have the same rod with The conditions of equilibrium of a rigid body two forces of equal magnitude but acting inmay be compared with those for a particle, which opposite diretions applied perpendicular to the we considered in earlier chapters. Since rod, one at end A and the other at end B. Here consideration of rotational motion does not apply the moments of both the forces are equal, but to a particle, only the conditions for translational they are not opposite; they act in the same sense equilibrium (Eq. 6.30 a) apply to a particle. Thus, and cause anticlockwise rotation of the rod. The for equilibrium of a particle the vector sum of total force on the body is zero; so the body is in all the forces on it must be zero. Since all these translational equilibrium; but it is not in forces act on the single particle, they must be rotational equilibrium. Although the rod is not fixed in any way, it undergoes pure rotation (i.e.concurrent. Equilibrium under concurrent rotation without translation).forces was discussed in the earlier chapters. A pair of forces of equal magnitude but acting A body may be in partial equilibrium, i.e., it in opposite directions with different lines of may be in translational equilibrium and not in action is known as a couple or torque. A couple rotational equilibrium, or it may be in rotational produces rotation without translation. equilibrium and not in translational When we open the lid of a bottle by turning equilibrium. it, our fingers are applying a couple to the lid Consider a light (i.e. of negligible mass) rod [Fig. 6.21(a)]. Another known example is a compass needle in the earth’s magnetic field as(AB) as shown in Fig. 6.20(a). At the two ends (A shown in the Fig. 6.21(b). The earth’s magneticand B) of which two parallel forces, both equal field exerts equal forces on the north and southin magnitude and acting along same direction poles. The force on the North Pole is towards are applied perpendicular to the rod. the north, and the force on the South Pole is toward the south. Except when the needle points in the north-south direction; the two forces do not have the same line of action. Thus there is a couple acting on the needle due to the earth’s magnetic field. Fig. 6.20 (a) Let C be the midpoint of AB, CA = CB = a. the moment of the forces at A and B will both be equal in magnitude (aF ), but opposite in sense as shown. The net moment on the rod will be zero. The system will be in rotational equilibrium, but it will not be in translational fingers apply a couple to turnequilibrium; F ≠ 0 Fig. 6.21(a) Our ∑ the lid. Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 111 length. This point is called the fulcrum. A see- saw on the children’s playground is a typical example of a lever. Two forces F1 and F2, parallel to each other and usually perpendicular to the lever, as shown here, act on the lever at distances d1 and d2 respectively from the fulcrum as shown in Fig. 6.23. Fig. 6.21(b) The Earth’s magnetic field exerts equal and opposite forces on the poles of a Fig. 6.23 compass needle. These two forces form a couple. The lever is a system in mechanical equilibrium. Let R be the reaction of the supportu Example 6.7 Show that moment of a at the fulcrum; R is directed opposite to the couple does not depend on the point about forces F1 and F2. For translational equilibrium, which you take the moments. R – F1 – F2 = 0 (i) Answer For considering rotational equilibrium we take the moments about the fulcrum; the sum of moments must be zero, d1F1 – d2F2 = 0 (ii) Normally the anticlockwise (clockwise) moments are taken to be positive (negative). Note R acts at the fulcrum itself and has zero moment about the fulcrum. Fig. 6.22 In the case of the lever force F1 is usually Consider a couple as shown in Fig. 6.22 some weight to be lifted. It is called the load and acting on a rigid body. The forces F and -F act its distance from the fulcrum d1 is called the respectively at points B and A. These points have load arm. Force F2 is the effort applied to lift the position vectors r1 and r2 with respect to origin load; distance d2 of the effort from the fulcrum O. Let us take the moments of the forces about is the effort arm. the origin. Eq. (ii) can be written as The moment of the couple = sum of the d1F1 = d2 F2 (6.32a) moments of the two forces making the couple or load arm × load = effort arm × effort = r1 × (–F) + r2 × F The above equation expresses the principle = r2 × F – r1 × F of moments for a lever. Incidentally the ratio = (r2–r1) × F F1/F2 is called the Mechanical Advantage (M.A.); But r1 + AB = r2, and hence AB = r2 – r1. F1 d 2 The moment of the couple, therefore, is M.A. = = (6.32b) F2 d1AB × F. Clearly this is independent of the origin, the If the effort arm d2 is larger than the load point about which we took the moments of the arm, the mechanical advantage is greater than forces. ⊳ one. Mechanical advantage greater than one means that a small effort can be used to lift a 6.8.1 Principle of moments large load. There are several examples of a lever An ideal lever is essentially a light (i.e. of around you besides the see-saw. The beam of a negligible mass) rod pivoted at a point along its balance is a lever. Try to find more such Reprint 2025-26 112 PHYSICS examples and identify the fulcrum, the effort and The CG of the cardboard is so located that effort arm, and the load and the load arm of the the total torque on it due to the forces m1g, m2g lever in each case. …. etc. is zero. You may easily show that the principle of If ri is the position vector of the ith particle moment holds even when the parallel forces F1 of an extended body with respect to its CG, then and F2 are not perpendicular, but act at some the torque about the CG, due to the force of angle, to the lever. gravity on the particle is τi = ri × mi g. The total gravitational torque about the CG is zero, i.e. 6.8.2 Centre of gravity i × m i g = 0 (6.33) τ g = ∑ τ i = ∑r Many of you may have the experience of We may therefore, define the CG of a body balancing your notebook on the tip of a finger. as that point where the total gravitational torque Figure 6.24 illustrates a similar experiment that on the body is zero. you can easily perform. Take an irregular- We notice that in Eq. (6.33), g is the same shaped cardboard having mass M and a narrow for all particles, and hence it comes out of the tipped object like a pencil. You can locate by trial summation. This gives, since g is non-zero, and error a point G on the cardboard where it ir = 0. Remember that the position vectorscan be balanced on the tip of the pencil. (The ∑mi cardboard remains horizontal in this position.) (ri) are taken with respect to the CG. Now, in This point of balance is the centre of gravity (CG) accordance with the reasoning given below of the cardboard. The tip of the pencil provides Eq. (6.4a) in Sec. 6.2, if the sum is zero, the origin a vertically upward force due to which the must be the centre of mass of the body. Thus, cardboard is in mechanical equilibrium. As the centre of gravity of the body coincides with shown in the Fig. 6.24, the reaction of the tip is the centre of mass in uniform gravity or gravity- equal and opposite to Mg and hence the cardboard is in translational equilibrium. It is also in rotational equilibrium; if it were not so, due to the unbalanced torque it would tilt and fall. There are torques on the card board due to the forces of gravity like m1g, m2g …. etc, acting on the individual particles that make up the cardboard. Fig. 6.25 Determining the centre of gravity of a body Fig. 6.24 Balancing a cardboard on the tip of a of irregular shape. The centre of gravity G pencil. The point of support, G, is the lies on the vertical AA1 through the point centre of gravity. of suspension of the body A. Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 113 free space. We note that this is true because = 30 cm, PG = 5 cm, AK1= BK2 = 10 cm and K1G = the body being small, g does not K2G = 25 cm. Also, W= weight of the rod = 4.00 vary from one point of the body to the other. If kg and W 1= suspended load = 6.00 kg; the body is so extended that g varies from part R1 and R2 are the normal reactions of the to part of the body, then the centre of gravity support at the knife edges. and centre of mass will not coincide. Basically, For translational equilibrium of the rod, the two are different concepts. The centre of R1+R2 –W1 –W = 0 (i) mass has nothing to do with gravity. It depends Note W1 and W act vertically down and R1 only on the distribution of mass of the body. and R2 act vertically up. In Sec. 6.2 we found out the position of the For considering rotational equilibrium, we centre of mass of several regular, homogeneous take moments of the forces. A convenient point objects. Obviously the method used there gives to take moments about is G. The moments of us also the centre of gravity of these bodies, if R2 and W1 are anticlockwise (+ve), whereas the they are small enough. moment of R1 is clockwise (-ve). Figure 6.25 illustrates another way of For rotational equilibrium, determining the CG of an irregular shaped body –R1 (K1G) + W1 (PG) + R2 (K2G) = 0 (ii) like a cardboard. If you suspend the body from It is given that W = 4.00g N and W1 = 6.00g some point like A, the vertical line through A N, where g = acceleration due to gravity. We passes through the CG. We mark the vertical take g = 9.8 m/s2. AA1. We then suspend the body through other With numerical values inserted, from (i) points like B and C. The intersection of the R1 + R2 – 4.00g – 6.00g = 0 verticals gives the CG. Explain why the method or R1 + R2 = 10.00g N (iii) works. Since the body is small enough, the = 98.00 N method allows us to determine also its centre From (ii), – 0.25 R1 + 0.05 W1 + 0.25 R2 = 0 of mass. or R1 – R2 = 1.2g N = 11.76 N (iv) From (iii) and (iv), R1 = 54.88 N, u Example 6.8 A metal bar 70 cm long and R2 = 43.12 N 4.00 kg in mass supported on two knife- Thus the reactions of the support are about edges placed 10 cm from each end. A 6.00 55 N at K1 and 43 N at K2. ⊳ kg load is suspended at 30 cm from one end. Find the reactions at the knife-edges. u Example 6.9 A 3m long ladder weighing (Assume the bar to be of uniform cross 20 kg leans on a frictionless wall. Its feet section and homogeneous.) rest on the floor 1 m from the wall as shown in Fig.6.27. Find the reaction forces of the Answer wall and the floor. Answer Fig. 6.26 Figure 6.26 shows the rod AB, the positions of the knife edges K1 and K2 , the centre of gravity of the rod at G and the suspended load at P. Note the weight of the rod W acts at its centre of gravity G. The rod is uniform in cross section and homogeneous; hence G is at the centre of the rod; AB = 70 cm. AG = 35 cm, AP Fig. 6.27 Reprint 2025-26 114 PHYSICS The ladder AB is 3 m long, its foot A is at from the axis, the linear velocity is υi = ir ω. The distance AC = 1 m from the wall. From kinetic energy of motion of this particle is Pythagoras theorem, BC = 2 2 m. The forces 1 2 1 2 2 on the ladder are its weight W acting at its centre k i = m i υi = m i ri ω 2 2 of gravity D, reaction forces F1 and F2 of the wall where mi is the mass of the particle. The totaland the floor respectively. Force F1 is kinetic energy K of the body is then given byperpendicular to the wall, since the wall is the sum of the kinetic energies of individualfrictionless. Force F2 is resolved into two particles,components, the normal reaction N and the force of friction F. Note that F prevents the ladder n 1 n 2 2 from sliding away from the wall and is therefore K = ∑ k i = ∑ (m i ri ω ) i =1 2 i =1 directed toward the wall. For translational equilibrium, taking the Here n is the number of particles in the body. forces in the vertical direction, Note ωis the same for all particles. Hence, taking N – W = 0 (i) ω out of the sum, Taking the forces in the horizontal direction, n 1 2 2 i ri ) F – F1 = 0 (ii) K = 2 ω ( ∑i =1 m For rotational equilibrium, taking the We define a new parameter characterisingmoments of the forces about A, the rigid body, called the moment of inertia I , 2 2 F1 −(1/2) W = 0 (iii) given by Now W = 20 g = 20 × 9.8 N = 196.0 N n 2 I = ∑ m i ri (6.34)From (i) N = 196.0 N i =1 With this definition,From (iii) F1 = W 4 2 = 196.0/4 2 = 34.6 N 1 2 From (ii) F = F1 = 34.6 N K = Iω (6.35) 2 2 2 Note that the parameter I is independent of F2 = F + N = 199.0 N the magnitude of the angular velocity. It is a The force F2 makes an angle α with the characteristic of the rigid body and the axis horizontal, about which it rotates. −1 Compare Eq. (6.35) for the kinetic energy oftan α = N F = 4 2 , α = tan (4 2) ≈ 80 ⊳ a rotating body with the expression for the kinetic energy of a body in linear (translational)6.9 MOMENT OF INERTIA motion, We have already mentioned that we are 1 2developing the study of rotational motion parallel K = m υ 2to the study of translational motion with which Here, m is the mass of the body and v is itswe are familiar. We have yet to answer one major velocity. We have already noted the analogy question in this connection. What is the between angular velocity ω (in respect of analogue of mass in rotational motion? We shall rotational motion about a fixed axis) and linear attempt to answer this question in the present velocity v (in respect of linear motion). It is then section. To keep the discussion simple, we shall evident that the parameter, moment of inertia consider rotation about a fixed axis only. Let us I, is the desired rotational analogue of mass in try to get an expression for the kinetic energy of linear motion. In rotation (about a fixed axis), a rotating body. We know that for a body rotating the moment of inertia plays a similar role as about a fixed axis, each particle of the body moves mass does in linear motion. We now apply the definition Eq. (6.34), toin a circle with linear velocity given by Eq. (6.19). calculate the moment of inertia in two simple cases.(Refer to Fig. 6.16). For a particle at a distance Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 115 (a) Consider a thin ring of radius R and mass change in its rotational motion, it can be M, rotating in its own plane around its centre regarded as a measure of rotational inertia of with angular velocity ω. Each mass element the body; it is a measure of the way in which of the ring is at a distance R from the axis, different parts of the body are distributed at and moves with a speed Rω. The kinetic different distances from the axis. Unlike the energy is therefore, mass of a body, the moment of inertia is not a fixed quantity but depends on distribution of 1 2 1 2 2 K = M υ = MR ω mass about the axis of rotation, and the 2 2 orientation and position of the axis of rotation Comparing with Eq. (6.35) we get I = MR 2 with respect to the body as a whole. As a for the ring. measure of the way in which the mass of a rotating rigid body is distributed with respect to the axis of rotation, we can define a new parameter, the radius of gyration. It is related to the moment of inertia and the total mass of the body. Notice from the Table 6.1 that in all cases, we can write I = Mk2, where k has the dimension of length. For a rod, about the perpendicular axis at its midpoint, k 2 = L2 12, i.e. k = L 12 . Similarly, k = R/2 for the circular disc about its diameter. The length k is a geometric property of the body and axis of rotation. It is called the radius of Fig. 6.28 A light rod of length l with a pair of gyration. The radius of gyration of a body masses rotating about an axis through about an axis may be defined as the distance the centre of mass of the system and perpendicular to the rod. The total mass from the axis of a mass point whose mass is of the system is M. equal to the mass of the whole body and whose moment of inertia is equal to the moment of (b) Next, take a rigid rod of negligible mass of inertia of the body about the axis. length of length l with a pair of small masses, Thus, the moment of inertia of a rigid body rotating about an axis through the centre of depends on the mass of the body, its shape and mass perpendicular to the rod (Fig. 6.28). size; distribution of mass about the axis of Each mass M/2 is at a distance l/2 from rotation, and the position and orientation of the the axis. The moment of inertia of the masses axis of rotation. is therefore given by From the definition, Eq. (6.34), we can infer (M/2) (l/2)2 + (M/2)(l/2)2 that the dimensions of moments of inertia are Thus, for the pair of masses, rotating about ML2 and its SI units are kg m2. the axis through the centre of mass The property of this extremely important perpendicular to the rod 2 quantity I, as a measure of rotational inertia of I = Ml / 4 the body, has been put to a great practical use. Table 6.1 simply gives the moment of inertia of The machines, such as steam engine and thevarious familiar regular shaped bodies about automobile engine, etc., that produce rotationalspecific axes. (The derivations of these motion have a disc with a large moment ofexpressions are beyond the scope of this inertia, called a flywheel. Because of its largetextbook and you will study them in higher classes.) moment of inertia, the flywheel resists the As the mass of a body resists a change in its sudden increase or decrease of the speed of the state of linear motion, it is a measure of its inertia vehicle. It allows a gradual change in the speed in linear motion. Similarly, as the moment of and prevents jerky motions, thereby ensuring inertia about a given axis of rotation resists a a smooth ride for the passengers on the vehicle. Reprint 2025-26 116 PHYSICS Table 6.1 Moments of inertia of some regular shaped bodies about specific axes Z Body Axis Figure I (1) Thin circular Perpendicular to M R 2 ring, radius R plane, at centre (2) Thin circular Diameter M R2/2 ring, radius R (3) Thin rod, Perpendicular to M L2/12 length L rod, at mid point (4) Circular disc, Perpendicular to M R2/2 radius R disc at centre (5) Circular disc, Diameter M R2/4 radius R (6) Hollow cylinder, Axis of cylinder M R2 radius R (7) Solid cylinder, Axis of cylinder M R2/2 radius R (8) Solid sphere, Diameter 2 M R2/5 radius R 6.10 KINEMATICS OF ROTATIONAL MOTION translation. We wish to take this analogy further. ABOUT A FIXED AXIS In doing so we shall restrict the discussion only We have already indicated the analogy between to rotation about fixed axis. This case of motion rotational motion and translational motion. For involves only one degree of freedom, i.e., needs example, the angular velocity ω plays the same only one independent variable to describe the role in rotation as the linear velocity v in motion. This in translation corresponds to linear Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 117 motion. This section is limited only to kinematics. We shall turn to dynamics in later sections. We recall that for specifying the angular displacement of the rotating body we take any particle like P (Fig.6.29) of the body. Its angular displacement θ in the plane it moves is the angular displacement of the whole body; θ is measured from a fixed direction in the plane of motion of P, which we take to be the x′-axis, chosen parallel to the x-axis. Note, as shown, the axis of rotation is the z – axis and the plane of the motion of the particle is the x - y plane. Fig. 6.29 also shows θ0, the angular displacement at t = 0. We also recall that the angular velocity is the time rate of change of angular displacement, ω = dθ/dt. Note since the axis of rotation is fixed, there is no need to treat angular velocity as a Fig.6.29 Specifying the angular position of a rigid vector. Further, the angular acceleration, α = body. dω/dt. u Example 6.10 Obtain Eq. (6.36) from first The kinematical quantities in rotational principles. motion, angular displacement (θ), angular velocity (ω) and angular acceleration (α) Answer The angular acceleration is uniform, respectively are analogous to kinematic hence quantities in linear motion, displacement (x), dω velocity (v) and acceleration (a). We know the = α = constant (i) kinematical equations of linear motion with d t uniform (i.e. constant) acceleration: Integrating this equation, α dt + c v = v0 + at (a) ω = ∫ 1 2 x = x 0 + υ0t + at (b) = αt + c (as α is constant) 2 At t = 0, ω = ω0 (given) 2 2 υ = υ0 + 2ax (c) From (i) we get at t = 0, ω = c = ω0 Thus, ω = αt + ω0 as required. where x0 = initial displacement and v0= initial With the definition of ω = dθ/dt we may velocity. The word ‘initial’ refers to values of the integrate Eq. (6.36) to get Eq. (6.37). This quantities at t = 0 derivation and the derivation of Eq. (6.38) is left The corresponding kinematic equations for as an exercise. rotational motion with uniform angular acceleration are: u Example 6.11 The angular speed of a motor wheel is increased from 1200 rpm to ω= ω0 + αt (6.36) 3120 rpm in 16 seconds. (i) What is its angular acceleration, assuming the 1 2 θ = θ0 + ω0t + αt (6.37) acceleration to be uniform? (ii) How many 2 revolutions does the engine make during and ω2 = ω0 2 + 2α(θ– θ0 ) (6.38) this time? Answer where θ0= initial angular displacement of the (i) We shall use ω = ω0 + αt rotating body, and ω0 = initial angular velocity ω0 = initial angular speed in rad/s of the body. Reprint 2025-26 118 PHYSICS = 2π × angular speed in rev/s It is, however, necessary that these correspondences are established on sound 2π × angular speed in rev/min dynamical considerations. This is what we now = 60 s/min turn to. Before we begin, we note a simplification 2π × 1200 that arises in the case of rotational motion = rad/s 60 about a fixed axis. Since the axis is fixed, only those components of torques, which are along = 40π rad/s the direction of the fixed axis need to be Similarly ω = final angular speed in rad/s considered in our discussion. Only these 2π × 3120 components can cause the body to rotate about = rad/s the axis. A component of the torque 60 perpendicular to the axis of rotation will tend to = 2π × 52 rad/s turn the axis from its position. We specifically = 104 π rad/s assume that there will arise necessary forces of constraint to cancel the effect of the ∴Angular acceleration perpendicular components of the (external) torques, so that the fixed position of the axis ω − ω will be maintained. The perpendicular α = 0 = 4 π rad/s2 t components of the torques, therefore need not be taken into account. This means that for our The angular acceleration of the engine calculation of torques on a rigid body: = 4π rad/s2 (1) We need to consider only those forces that (ii) The angular displacement in time t is lie in planes perpendicular to the axis. given by Forces which are parallel to the axis will give torques perpendicular to the axis and need 1 2 θ = ω0 t + αt not be taken into account. 2 (2) We need to consider only those components 1 2 of the position vectors which are = (40π × 16 + × 4π × 16 ) rad 2 perpendicular to the axis. Components of position vectors along the axis will result in = (640π + 512π) rad torques perpendicular to the axis and need = 1152π rad not be taken into account. 1152π = 576 ⊳ Work done by a torqueNumber of revolutions = 2π

6.12 Angular momentum in case solved by considering them to be rigid bodies. Ideally a of rotation about a fixed axis rigid body is a body with a perfectly definite and unchanging shape. The distances between all pairs of Summary particles of such a body do not change. It is evident from Points to Ponder this definition of a rigid body that no real body is truly rigid, Exercises since real bodies deform under the influence of forces. But in many situations the deformations are negligible. In a number of situations involving bodies such as wheels, tops, steel beams, molecules and planets on the other hand, we can ignore that they warp (twist out of shape), bend or vibrate and treat them as rigid. 6.1.1 What kind of motion can a rigid body have? Let us try to explore this question by taking some examples of the motion of rigid bodies. Let us begin with a rectangular Reprint 2025-26 SYSTEMS OF PARTICLES AND ROTATIONAL MOTION 93 most common way to constrain a rigid body so that it does not have translational motion is to fix it along a straight line. The only possible motion of such a rigid body is rotation. The line or fixed axis about which the body is rotating is its axis of rotation. If you look around, you will come across many examples of rotation about an axis, a ceiling fan, a potter’s wheel, a giant wheel in a fair, a merry-go-round and so on (Fig Fig 6.1 Translational (sliding) motion of a block down 6.3(a) and (b)). an inclined plane. (Any point like P1 or P2 of the block moves with the same velocity at any instant of time.) block sliding down an inclined plane without any sidewise movement. The block is taken as a rigid body. Its motion down the plane is such that all the particles of the body are moving together, i.e. they have the same velocity at any instant of time. The rigid body here is in pure translational motion (Fig. 6.1). In pure translational motion at any instant of time, all particles of the body have the same velocity. Consider now the rolling motion of a solid metallic or wooden cylinder down the same (a) inclined plane (Fig. 6.2). The rigid body in this problem, namely the cylinder, shifts from the top to the bottom of the inclined plane, and thus, seems to have translational motion. But as Fig.

9.15 Apply mirror equation and the condition: (a) f < 0 (concave mirror); u < 0 (object on left) (b) f > 0; u < 0 (c) f > 0 (convex mirror) and u < 0 (d) f < 0 (concave mirror); f < u < 0 to deduce the desired result.

9.17 (a) sin i¢c = 1.44/1.68 which gives i¢c = 59°. Total internal reflection takes place when i > 59° or when r < rmax = 31°. Now, (sin i /sin r max max ) = 1.68 , which gives imax ~ 60°. Thus, all incident rays of angles in the range 0 < i < 60° will suffer total internal reflections in the pipe. (If the length of the pipe is finite, which it is in practice, there will be a lower limit on i determined by the ratio of the diameter to the length of the pipe.) (b) If there is no outer coating, i¢c = sin–1(1/1.68) = 36.5°. Now, i = 90° will have r = 36.5° and i¢ = 53.5° which is greater than i¢c. Thus, all incident rays (in the range 53.5° < i < 90°) will suffer total internal reflections.

9.8 A beam of light converges at a point P. Now a lens is placed in the path of the convergent beam 12cm from P. At what point does the beam converge if the lens is (a) a convex lens of focal length 20cm, and (b) a concave lens of focal length 16cm?

1.3 SIGNIFICANT FIGURES figures in a measurement. This important remark makes most of the followingAs discussed above, every measurement observations clear:involves errors. Thus, the result of (1) For example, the length 2.308 cm has fourmeasurement should be reported in a way that significant figures. But in different units, theindicates the precision of measurement. same value can be written as 0.02308 m or 23.08Normally, the reported result of measurement is a number that includes all digits in the mm or 23080 µm. number that are known reliably plus the first All these numbers have the same number of digit that is u Reprint 2025-26 4 PHYSICS This shows that the location of decimal point is negative exponent (or power) of 10. In order to of no consequence in determining the number get an approximate idea of the number, we may of significant figures. round off the number a to 1 (for a ≤5) and to 10 The example gives the following rules : (for 5<a ≤10). Then the number can be • All the non-zero digits are significant. expressed approximately as 10b in which the • All the zeros between two non-zero digits exponent (or power) b of 10 is called order of magnitude of the physical quantity. When only are significant, no matter where the an estimate is required, the quantity is of the decimal point is, if at all. order of 10b. For example, the diameter of the • If the number is less than 1, the zero(s) earth (1.28×107m) is of the order of 107m with on the right of decimal point but to the the order of magnitude 7. The diameter of left of the first non-zero digit are not hydrogen atom (1.06 ×10–10m) is of the order of significant. [In 0.00 2308, the underlined 10–10m, with the order of magnitude zeroes are not significant]. –10. Thus, the diameter of the earth is 17 orders • The terminal or trailing zero(s) in a of magnitude larger than the hydrogen atom. It is often customary to write the decimal after number without a decimal point are not the first digit. Now the confusion mentioned in significant. (a) above disappears : [Thus 123 m = 12300 cm = 123000 mm has 4.700 m = 4.700 × 102 cm three significant figures, the trailing zero(s) = 4.700 × 103 mm = 4.700 × 10–3 km being not significant.] However, you can also The power of 10 is irrelevant to the see the next observation. determination of significant figures. However, all • The trailing zero(s) in a number with a zeroes appearing in the base number in the decimal point are significant. scientific notation are significant. Each number [The numbers 3.500 or 0.06900 have four in this case has four significant figures. significant figures each.] Thus, in the scientific notation, no confusion (2) There can be some confusion regarding the arises about the trailing zero(s) in the base trailing zero(s). Suppose a length is reported to number a. They are always significant. be 4.700 m. It is evident that the zeroes here (4) The scientific notation is ideal for reporting are meant to convey the precision of measurement. But if this is not adopted, we use measurement and are, therefore, significant. [If the rules adopted in the preceding example : these were not, it would be superfluous to write • For a number greater than 1, without anythem explicitly, the reported measurement decimal, the trailing zero(s) are notwould have been simply 4.7 m]. Now suppose we change units, then significant. • For a number with a decimal, the trailing4.700 m = 470.0 cm = 4700 mm = 0.004700 km zero(s) are significant. Since the last number has trailing zero(s) in a number with no decimal, we would conclude (5) The digit 0 conventionally put on the left of a erroneously from observation (1) above that the decimal for a number less than 1 (like 0.1250) number has two significant figures, while in is never significant. However, the zeroes at the fact, it has four significant figures and a mere end of such number are significant in a change of units cannot change the number of measurement. significant figures. (6) The multiplying or dividing factors which are (3) To remove such ambiguities in neither rounded numbers nor numbers determining the number of significant representing measured values are exact and figures, the best way is to report every have infinite number of significant digits. For measurement in scientific notation (in the dpower of 10). In this notation, every number is example in r = or s = 2πr, the factor 2 is an expressed as a × 10b, where a is a number 2 between 1 and 10, and b is any positive or exact number and it can be written as 2.0, 2.00 Reprint 2025-26 UNITS AND MEASUREMENT 5 decimal place. The final result should, therefore, t or 2.0000 as required. Similarly, in T = , n is be rounded off to 663.8 g. n Similarly, the difference in length can be an exact number. expressed as : 1.3.1 Rules for Arithmetic Operations with 0.307 m – 0.304 m = 0.003 m = 3 ×10–3 m. Significant Figures Note that we should not use the rule (1) applicable The result of a calculation involving approximate for multiplication and division and write 664 g as measured values of quantities (i.e. values with the result in the example of addition and limited number of significant figures) must 3.00 × 10–3 m in the example of subtraction. They reflect the umeasured values. It cannot be more accurate properly. For addition and subtraction, the rule than the original measured values themselves is in terms of decimal places. on which the result is based. In general, the final result should not have more significant 1.3.2 Rounding off the Ufigures than the original data from which it was The result of computation with approximate obtained. Thus, if mass of an object is measured numbers, which contain more than one to be, say, 4.237 g (four significant figures) and uits volume is measured to be 2.51 cm3, then its for rounding off numbers to the appropriate density, by mere arithmetic division, is significant figures are obvious in most cases. A 1.68804780876 g/cm3 upto 11 decimal places. number 2.746 rounded off to three significant It would be clearly absurd and irrelevant to figures is 2.75, while the number 1.743 would record the calculated value of density to such a be 1.74. The rule by convention is that the precision when the measurements on which the preceding digit is raised by 1 if the value is based, have much less precision. The insignificant digit to be dropped (the following rules for arithmetic operations with underlined digit in this case) is more than significant figures ensure that the final result 5, and is left unchanged if the latter is less of a calculation is shown with the precision that than 5. But what if the number is 2.745 in is consistent with the precision of the input which the insignificant digit is 5. Here, themeasured values : convention is that if the preceding digit is(1) In multiplication or division, the final even, the insignificant digit is simplyresult should retain as many significant dropped and, if it is odd, the preceding digitfigures as are there in the original number with the least significant figures. is raised by 1. Then, the number 2.745 rounded Thus, in the example above, density should off to three significant figures becomes 1.74. On be reported to three significant figures. the other hand, the number 2.735 rounded off to three significant figures becomes 1.74 since 4.237g -3 Density = = 1.69 g cm the preceding digit is odd. 3 2.51 cm In any involved or complex multi-step Similarly, if the speed of light is given as calculation, you should retain, in intermediate 3.00 × 108 m s-1 (three significant figure) and steps, one digit more than the significant digits one year (1y = 365.25 d) has 3.1557 × 107 s (five and round off to proper significant figures at the significant figures), the light year is 9.47 × 1015 m end of the calculation. Similarly, a number (three significant figures). known to be within many significant figures, such as in 2.99792458 × 108 m/s for the speed (2) In addition or subtraction, the final result of light in vacuum, is rounded off to anshould retain as many decimal places as are approximate value 3 × 108 m/s , which is oftenthere in the number with the least employed in computations. Finally, rememberdecimal places. that exact numbers that appear in formulae like For example, the sum of the numbers 436.32 g, 227.2 g and 0.301 g by mere arithmetic L addition, is 663.821 g. But the least precise 2 π in T = 2π , have a large (infinite) number measurement (227.2 g) is correct to only one g Reprint 2025-26 6 PHYSICS of significant figures. The value of π = = 16.2 cm ± 0.6 %. 3.1415926.... is known to a large number of significant figures. You may take the value as Similarly, the breadth b may be written as 3.142 or 3.14 for π, with limited number of b = 10.1 ± 0.1 cm significant figures as required in specific = 10.1 cm ± 1 % cases. Then, the error of the product of two (or more)⊳ Example 1.1 Each side of a cube is experimental values, using the combination of measured to be 7.203 m. What are the errors rule, will be total surface area and the volume of the l b = 163.62 cm2 + 1.6% cube to appropriate significant figures? = 163.62 + 2.6 cm2 Answer The number of significant figures in the measured length is 4. The calculated area This leads us to quote the final result as and the volume should therefore be rounded off l b = 164 + 3 cm2 to 4 significant figures. Here 3 cm2 is the uSurface area of the cube = 6(7.203)2 m2 estimation of area of rectangular sheet. = 311.299254 m2 (2) If a set of experimental data is specified = 311.3 m2 to n significant figures, a result obtained by combining the data will also be valid to n Volume of the cube = (7.203)3 m3 significant figures. = 373.714754 m3 However, if data are subtracted, the number of = 373.7 m3 ⊳ significant figures can be reduced. ⊳ Example 1.2 5.74 g of a substance For example, 12.9 g – 7.06 g, both specified to occupies 1.2 cm3. Express its density by three significant figures, cannot properly be keeping the significant figures in view. evaluated as 5.84 g but only as 5.8 g, as u in a different fashion (smallest number ofmeasured mass whereas there are only 2 decimal places rather than the number of significant figures in the measured volume. significant figures in any of the number added Hence the density should be expressed to only or subtracted). 2 significant figures. (3) The relative error of a value of number 5.74 −3 specified to significant figures depends not Density = g cm 1.2 only on n but also on the number itself. = 4.8 g cm--3 . ⊳ For example, the accuracy in measurement of mass 1.02 g is ± 0.01 g whereas another 1.3.3 Rules for Determining the U in the Results of Arithmetic The relative error in 1.02 g is Calculations = (± 0.01/1.02) × 100 % = ± 1%The rules for determining the u Similarly, the relative error in 9.89 g iserror in the number/measured quantity in = (± 0.01/9.89) × 100 %arithmetic operations can be understood from = ± 0.1 %the following examples. Finally, remember that intermediate results in(1) If the length and breadth of a thin rectangular sheet are measured, using a metre a multi-step computation should be scale as 16.2 cm and, 10.1 cm respectively, there calculated to one more significant figure in are three significant figures in each every measurement than the number of measurement. It means that the length l may digits in the least precise measurement. be written as These should be justified by the data and then l = 16.2 ± 0.1 cm the arithmetic operations may be carried out; Reprint 2025-26 UNITS AND MEASUREMENT 7 otherwise rounding errors can build up. For mass, one dimension in length, and –2 example, the reciprocal of 9.58, calculated (after dimensions in time. The dimensions in all other rounding off) to the same number of significant base quantities are zero. figures (three) is 0.104, but the reciprocal of Note that in this type of representation, the magnitudes are not considered. It is the quality0.104 calculated to three significant figures is of the type of the physical quantity that enters. 9.62. However, if we had written 1/9.58 = 0.1044 Thus, a change in velocity, initial velocity, and then taken the reciprocal to three significant average velocity, final velocity, and speed are figures, we would have retrieved the original all equivalent in this context. Since all these value of 9.58. quantities can be expressed as length/time, This example justifies the idea to retain one their dimensions are [L]/[T] or [L T–1]. more extra digit (than the number of digits in the least precise measurement) in intermediate 1.5 DIMENSIONAL FORMULAE AND steps of the complex multi-step calculations in DIMENSIONAL EQUATIONS order to avoid additional errors in the process The expression which shows how and which of of rounding off the numbers. the base quantities represent the dimensions of a physical quantity is called the dimensional

1.14 Consider a uniform electric field E = 3 × 103 î N/C. (a) What is the flux of this field through a square of 10 cm on a side whose plane is parallel to the yz plane? (b) What is the flux through the same square if the normal to its plane makes a 60° angle with the x-axis?

1.18 A point charge of 2.0 mC is at the centre of a cubic Gaussian surface 9.0 cm on edge. What is the net electric flux through the surface?

1.00 nF for two values of R: (i) R = 100 W and (ii) R = 200 W. For the source applied vm = 1 100 V. w0 for this case is = 1.00×106 LC FIGURE 7.14 Variation of im with w for tworad/s. cases: (i) R = 100 W, (ii) R = 200 W, We see that the current amplitude is L = 1.00 mH. maximum at the resonant frequency. Since im = vm / R at resonance, the current amplitude for case (i) is twice to that for case (ii). Resonant circuits have a variety of applications, for example, in the tuning mechanism of a radio or a TV set. The antenna of a radio accepts signals from many broadcasting stations. The signals picked up in the antenna acts as a source in the tuning circuit of the radio, so the circuit can be driven at many frequencies. But to hear one particular radio station, we tune the radio. In tuning, we vary the capacitance of a capacitor in the tuning circuit such that the resonant frequency of the circuit becomes nearly equal to the frequency of the radio signal received. When this happens, the amplitude of the current with the frequency of the signal of the particular radio station in the circuit is maximum. It is important to note that resonance phenomenon is exhibited by a circuit only if both L and C are present in the circuit. Only then do the voltages across L and C cancel each other (both being out of phase) and the current amplitude is vm/R, the total source voltage appearing across R. This means that we cannot have resonance in a RL or RC circuit. 189 Reprint 2025-26 Physics Example 7.6 A resistor of 200 W and a capacitor of 15.0 mF are connected in series to a 220 V, 50 Hz ac source. (a) Calculate the current in the circuit; (b) Calculate the voltage (rms) across the resistor and the capacitor. Is the algebraic sum of these voltages more than the source voltage? If yes, resolve the paradox. Solution Given R = 200 Ω, C = 15.0 µF = 15.0 × 10 −6 F V = 220 V, ν = 50Hz (a) In order to calculate the current, we need the impedance of the circuit. It is Z = R 2 + X C2 = R 2 + (2πνC )− 2 = (200 Ω )2 + (2 × 3.14 × 50 × 15.0 × 10 −6 F )−2 = (200 Ω )2 + (212.3 Ω )2 = 291.67 Ω Therefore, the current in the circuit is V 220 V I = = = 0.755 A Z 291.5 Ω (b) Since the current is the same throughout the circuit, we have V R = I R = (0.755 A)(200 Ω=) 151V VC = I X C = (0.755 A)(212.3 Ω=) 160.3 V The algebraic sum of the two voltages, VR and VC is 311.3 V which is more than the source voltage of 220 V. How to resolve this paradox? As you have learnt in the text, the two voltages are not in the same phase. Therefore, they cannot be added like ordinary numbers. The two voltages are out of phase by ninety degrees. Therefore, the total of these voltages must be obtained using the Pythagorean theorem: V R +C = V R2 + VC2 7.6 = 220 V Thus, if the phase difference between two voltages is properly taken into account, the total voltage across the resistor and the capacitor EXAMPLE is equal to the voltage of the source. 7.7 POWER IN AC CIRCUIT: THE POWER FACTOR We have seen that a voltage v = vm sinwt applied to a series RLC circuit drives a current in the circuit given by i = im sin(wt + f) where v m − 1  X C − X L  i m = Z and φ = tan  R  190 Therefore, the instantaneous power p supplied by the source is Reprint 2025-26 Alternating Current p = v i = (v m sin ωt ) × [ i m sin(ωt + φ)] v m i m = [ cosφ− cos(2ωt + φ)] (7.29) 2 The average power over a cycle is given by the average of the two terms in R.H.S. of Eq. (7.29). It is only the second term which is time-dependent. Its average is zero (the positive half of the cosine cancels the negative half). Therefore, v m i m v m i m P = cos φ = cos φ 2 2 2 = V I cos φ [7.30(a)] This can also be written as, P = I 2 Z cos φ [7.30(b)] So, the average power dissipated depends not only on the voltage and current but also on the cosine of the phase angle φ between them. The quantity cosφ is called the power factor. Let us discuss the following cases: CaseCaseCaseCaseCase (i)(i)(i)(i)(i) Resistive circuit: If the circuit contains only pure R, it is called resistive. In that case φ = 0, cos φ = 1. There is maximum power dissipation. CaseCaseCaseCaseCase (ii)(ii)(ii)(ii)(ii) Purely inductive or capacitive circuit: If the circuit contains only an inductor or capacitor, we know that the phase difference between voltage and current is π/2. Therefore, cos φ = 0, and no power is dissipated even though a current is flowing in the circuit. This current is sometimes referred to as wattless current. CaseCaseCaseCaseCase (iii)(iii)(iii)(iii)(iii) LCR series circuit: In an LCR series circuit, power dissipated is given by Eq. (7.30) where φ = tan–1 (Xc – XL )/ R. So, φ may be non-zero in a RL or RC or RCL circuit. Even in such cases, power is dissipated only in the resistor. CaseCaseCaseCaseCase (iv)(iv)(iv)(iv)(iv) Power dissipated at resonance in LCR circuit: At resonance Xc – XL= 0, and φ = 0. Therefore, cosφ = 1 and P = I2Z = I2 R. That is, maximum power is dissipated in a circuit (through R) at resonance. ExampleExampleExampleExampleExample 7.77.77.77.77.7 (a) For circuits used for transporting electric power, a low power factor implies large power loss in transmission. Explain. (b) Power factor can often be improved by the use of a capacitor of appropriate capacitance in the circuit. Explain. SolutionSolutionSolutionSolutionSolution (a) We know that P = I V cosφ where cosφ is the power factor. To supply a given power at a given voltage, if cosφ is small, we have to increase current accordingly. But this will lead to large power loss (I2R) in transmission. EEEE (b)Suppose in a circuit, current I lags the voltage by an angle φ. Then power factor cosφ =R/Z. EXAMPLEXAMPLEXAMPLEXAMPLEXAMPLE We can improve the power factor (tending to 1) by making Z tend to 7.77.77.77.77.7 us understand, with the help of a phasor diagram (Fig. 7.15) R. Let 191 Reprint 2025-26 Physics FIGURE 7.15 how this can be achieved. Let us resolve I into two components. Ip along the applied voltage V and Iq perpendicular to the applied voltage. Iq as you have learnt in Section 7.7, is called the wattless component since corresponding to this component of current, there is no power loss. IP is known as the power component because it is in phase with the voltage and corresponds to power loss in the circuit. It’s clear from this analysis that if we want to improve power factor, 7.7 we must completely neutralize the lagging wattless current Iq by an equal leading wattless current I¢q. This can be done by connecting a capacitor of appropriate value in parallel so that Iq and I¢q cancel EXAMPLE each other and P is effectively Ip V. Example 7.8 A sinusoidal voltage of peak value 283 V and frequency 50 Hz is applied to a series LCR circuit in which R = 3 W, L = 25.48 mH, and C = 796 mF. Find (a) the impedance of the circuit; (b) the phase difference between the voltage across the source and the current; (c) the power dissipated in the circuit; and (d) the power factor. Solution (a) To find the impedance of the circuit, we first calculate XL and XC. XL = 2 pnL = 2 × 3.14 × 50 × 25.48 × 10–3 W = 8 W 1 X C = 2 π νC 1 = 6 = 4 Ω 2 × 3.14 × 50 × 796 × 10− Therefore, Z = R 2 + ( X L − X C )2 = 3 2 + (8 − 4)2 = 5 W X C − X L 7.8 (b) Phase difference, f = tan–1 R −1  4 − 8  EXAMPLE = tan  3 = −53. 1°192 Reprint 2025-26 Alternating Current Since f is negative, the current in the circuit lags the voltage across the source. (c) The power dissipated in the circuit is P = I 2 R im 1  283  = Now, I = 2 2  5 = 40A EXAMPLE Therefore, P = (40 A )2 × 3 Ω= 4800 W (d) Power factor = cos cos –53.1 0.6 7.8 Example 7.9 Suppose the frequency of the source in the previous example can be varied. (a) What is the frequency of the source at which resonance occurs? (b) Calculate the impedance, the current, and the power dissipated at the resonant condition. Solution (a) The frequency at which the resonance occurs is 1 1 ω0 = = LC 25.48 × 10 −3 × 796 × 10 −6 = 222.1rad/s ω0 221.1 νr = = Hz = 35.4Hz 2 π 2 × 3.14 (b) The impedance Z at resonant condition is equal to the resistance: Z = R = 3 Ω The rms current at resonance is V V  283  1 = = = = 66.7 A Z R  2  3 The power dissipated at resonance is P = I 2 × R = (66.7)2 × 3 = 13.35 kW EXAMPLE You can see that in the present case, power dissipated at resonance is more than the power dissipated in Example 7.8. 7.9 Example 7.10 At an airport, a person is made to walk through the doorway of a metal detector, for security reasons. If she/he is carrying anything made of metal, the metal detector emits a sound. On what principle does this detector work? Solution The metal detector works on the principle of resonance in ac circuits. When you walk through a metal detector, you are, in fact, walking through a coil of many turns. The coil is connected to a capacitor tuned so that the circuit is in resonance. When you walk through with metal in your pocket, the impedance of the EXAMPLE circuit changes – resulting in significant change in current in the circuit. This change in current is detected and the electronic circuitry causes a sound to be emitted as an alarm. 7.10 193 Reprint 2025-26 Physics 7.8 TRANSFORMERS For many purposes, it is necessary to change (or transform) an alternating voltage from one to another of greater or smaller value. This is done with a device called transformer using the principle of mutual induction. A transformer consists of two sets of coils, insulated from each other. They are wound on a soft-iron core, either one on top of the other as in Fig. 7.16(a) or on separate limbs of the core as in Fig. 7.16(b). One of the coils called the primary coil has Np turns. The other coil is called the secondary coil; it has Ns turns. Often the primary coil is the input coil and the secondary coil is the output coil of the transformer. FIGURE 7.16 Two arrangements for winding of primary and secondary coil in a transformer: (a) two coils on top of each other, (b) two coils on separate limbs of the core. When an alternating voltage is applied to the primary, the resulting current produces an alternating magnetic flux which links the secondary and induces an emf in it. The value of this emf depends on the number of turns in the secondary. We consider an ideal transformer in which the primary has negligible resistance and all the flux in the core links both primary and secondary windings. Let f be the flux in each turn in the core at time t due to current in the primary when a voltage vp is applied to it. Then the induced emf or voltage es, in the secondary with Ns turns is dφ εs = − N s (7.31) d t The alternating flux f also induces an emf, called back emf in the primary. This is dφ εp = − N p (7.32) d t But ep = vp. If this were not so, the primary current would be infinite since the primary has zero resistance (as assumed). If the secondary is an open circuit or the current taken from it is small, then to a good approximation es = vs Reprint 2025-26 Alternating Current where vs is the voltage across the secondary. Therefore, Eqs. (7.31) and (7.32) can be written as dφ v s = − N s [7.31(a)] d t dφ v p = − N p [7.32(a)] d t From Eqs. [7.31 (a)] and [7.32 (a)], we have v s N s = (7.33) v p N p Note that the above relation has been obtained using three assumptions: (i) the primary resistance and current are small; (ii) the same flux links both the primary and the secondary as very little flux escapes from the core, and (iii) the secondary current is small. If the transformer is assumed to be 100% efficient (no energy losses), the power input is equal to the power output, and since p = i v, ipvp = isvs (7.34) Although some energy is always lost, this is a good approximation, since a well designed transformer may have an efficiency of more than 95%. Combining Eqs. (7.33) and (7.34), we have i p v s N s = = (7.35) i s v p N p Since i and v both oscillate with the same frequency as the ac source, Eq. (7.35) also gives the ratio of the amplitudes or rms values of corresponding quantities. Now, we can see how a transformer affects the voltage and current. We have:  N s   N p  Vs = V p and I s = I p (7.36)  N p   N s  That is, if the secondary coil has a greater number of turns than the primary (Ns > Np), the voltage is stepped up (Vs > Vp). This type of arrangement is called a step-up transformer. However, in this arrangement, there is less current in the secondary than in the primary (Np/Ns < 1 and Is < Ip). For example, if the primary coil of a transformer has 100 turns and the secondary has 200 turns, Ns/Np = 2 and Np/Ns=1/2. Thus, a 220V input at 10A will step-up to 440 V output at 5.0 A. If the secondary coil has less turns than the primary (Ns < Np), we have a step-down transformer. In this case, Vs < Vp and Is > Ip. That is, the voltage is stepped down, or reduced, and the current is increased. The equations obtained above apply to ideal transformers (without any energy losses). But in actual transformers, small energy losses do occur due to the following reasons: (i) Flux Leakage: There is always some flux leakage; that is, not all of the flux due to primary passes through the secondary due to poor 195 Reprint 2025-26 Physics design of the core or the air gaps in the core. It can be reduced by winding the primary and secondary coils one over the other. (ii) Resistance of the windings: The wire used for the windings has some resistance and so, energy is lost due to heat produced in the wire (I 2R). In high current, low voltage windings, these are minimised by using thick wire. (iii) Eddy currents: The alternating magnetic flux induces eddy currents in the iron core and causes heating. The effect is reduced by using a laminated core. (iv) Hysteresis: The magnetisation of the core is repeatedly reversed by the alternating magnetic field. The resulting expenditure of energy in the core appears as heat and is kept to a minimum by using a magnetic material which has a low hysteresis loss. The large scale transmission and distribution of electrical energy over long distances is done with the use of transformers. The voltage output of the generator is stepped-up (so that current is reduced and consequently, the I 2R loss is cut down). It is then transmitted over long distances to an area sub-station near the consumers. There the voltage is stepped down. It is further stepped down at distributing sub-stations and utility poles before a power supply of 240 V reaches our homes. SUMMARY 1. An alternating voltage v = v m sin ω t applied to a resistor R drives a v m current i = im sinwt in the resistor, i m = . The current is in phase with R the applied voltage. 2. For an alternating current i = im sin wt passing through a resistor R, the average power loss P (averaged over a cycle) due to joule heating is ( 1/2 )i 2mR. To express it in the same form as the dc power (P = I 2R), a special value of current is used. It is called root mean square (rms) current and is donoted by I: i m I = = 0.707 i m 2 Similarly, the rms voltage is defined by vm V = = 0.707 v m 2 We have P = IV = I 2R 3. An ac voltage v = vm sin wt applied to a pure inductor L, drives a current in the inductor i = im sin (wt – p/2), where im = vm/XL. XL = wL is called inductive reactance. The current in the inductor lags the voltage by p/2. The average power supplied to an inductor over one complete cycle is zero. Reprint 2025-26 Alternating Current 4. An ac voltage v = vm sinwt applied to a capacitor drives a current in the capacitor: i = im sin (wt + p/2). Here, v m 1 i m = , X C = is called capacitive reactance. X C ωC The current through the capacitor is p/2 ahead of the applied voltage. As in the case of inductor, the average power supplied to a capacitor over one complete cycle is zero. 5. For a series RLC circuit driven by voltage v = vm sin wt, the current is given by i = im sin (wt + f) v m where i m = R 2 + ( X C − X L )2 −1 X C − X L and φ = tan R is called the impedance of the circuit. Z = R 2 + ( X C − X L )2 The average power loss over a complete cycle is given by P = V I cosf The term cosf is called the power factor. 6. In a purely inductive or capacitive circuit, cosf = 0 and no power is dissipated even though a current is flowing in the circuit. In such cases, current is referred to as a wattless current. 7. The phase relationship between current and voltage in an ac circuit can be shown conveniently by representing voltage and current by rotating vectors called phasors. A phasor is a vector which rotates about the origin with angular speed w. The magnitude of a phasor represents the amplitude or peak value of the quantity (voltage or current) represented by the phasor. The analysis of an ac circuit is facilitated by the use of a phasor diagram. 8. A transformer consists of an iron core on which are bound a primary coil of Np turns and a secondary coil of Ns turns. If the primary coil is connected to an ac source, the primary and secondary voltages are related by  N s  Vs =  N p  V p and the currents are related by  N p  Is = I p  N s  If the secondary coil has a greater number of turns than the primary, the voltage is stepped-up (Vs > Vp). This type of arrangement is called a step- up transformer. If the secondary coil has turns less than the primary, we have a step-down transformer. 197 Reprint 2025-26 Physics Physical quantity Symbol Dimensions Unit Remarks 2 –3 v m rms voltage V [M L T A –1] V V = , v m is the 2 amplitude of the ac voltage. i m rms current I [ A] A I = , im is the amplitude of 2 the ac current. Reactance: Inductive XL [M L2 T –3 A–2] XL = L Capacitive XC [M L2 T –3 A–2] XC = 1/C Impedance Z [M L2 T –3 A–2] Depends on elements present in the circuit. 1 Resonant wr or w0 [T –1] Hz w0  for a frequency LC series RLC circuit ω0 L 1 Quality factor Q Dimensionless Q = = for a series R ω0 C R RLC circuit. Power factor Dimensionless = cosf, f is the phase difference between voltage applied and current in the circuit. POINTS TO PONDER 1. When a value is given for ac voltage or current, it is ordinarily the rms value. The voltage across the terminals of an outlet in your room is normally 240 V. This refers to the rms value of the voltage. The amplitude of this voltage is v m = 2V = 2(240) = 340 V 2. The power rating of an element used in ac circuits refers to its average power rating. 3. The power consumed in an ac circuit is never negative. 4. Both alternating current and direct current are measured in amperes. But how is the ampere defined for an alternating current? It cannot be derived from the mutual attraction of two parallel wires carrying ac 198 currents, as the dc ampere is derived. An ac current changes direction Reprint 2025-26 Alternating Current with the source frequency and the attractive force would average to zero. Thus, the ac ampere must be defined in terms of some property that is independent of the direction of the current. Joule heating is such a property, and there is one ampere of rms value of alternating current in a circuit if the current produces the same average heating effect as one ampere of dc current would produce under the same conditions. 5. In an ac circuit, while adding voltages across different elements, one should take care of their phases properly. For example, if VR and VC are voltages across R and C, respectively in an RC circuit, then the total voltage across RC combination is V RC = VR2 + VC2 and not VR + VC since VC is p/2 out of phase of VR. 6. Though in a phasor diagram, voltage and current are represented by vectors, these quantities are not really vectors themselves. They are scalar quantities. It so happens that the amplitudes and phases of harmonically varying scalars combine mathematically in the same way as do the projections of rotating vectors of corresponding magnitudes and directions. The ‘rotating vectors’ that represent harmonically varying scalar quantities are introduced only to provide us with a simple way of adding these quantities using a rule that we already know as the law of vector addition. 7. There are no power losses associated with pure capacitances and pure inductances in an ac circuit. The only element that dissipates energy in an ac circuit is the resistive element. 8. In a RLC circuit, resonance phenomenon occur when XL = XC or 1 ω0 = . For resonance to occur, the presence of both L and C LC elements in the circuit is a must. With only one of these (L or C ) elements, there is no possibility of voltage cancellation and hence, no resonance is possible. 9. The power factor in a RLC circuit is a measure of how close the circuit is to expending the maximum power. 10. In generators and motors, the roles of input and output are reversed. In a motor, electric energy is the input and mechanical energy is the output. In a generator, mechanical energy is the input and electric energy is the output. Both devices simply transform energy from one form to another. 11. A transformer (step-up) changes a low-voltage into a high-voltage. This does not violate the law of conservation of energy. The current is reduced by the same proportion. 199 Reprint 2025-26 Physics EXERCISES 7.1 A 100 W resistor is connected to a 220 V, 50 Hz ac supply. (a) What is the rms value of current in the circuit? (b) What is the net power consumed over a full cycle? 7.2 (a) The peak voltage of an ac supply is 300 V. What is the rms voltage? (b) The rms value of current in an ac circuit is 10 A. What is the peak current? 7.3 A 44 mH inductor is connected to 220 V, 50 Hz ac supply. Determine the rms value of the current in the circuit. 7.4 A 60 mF capacitor is connected to a 110 V, 60 Hz ac supply. Determine the rms value of the current in the circuit. 7.5 In Exercises 7.3 and 7.4, what is the net power absorbed by each circuit over a complete cycle. Explain your answer. 7.6 A charged 30 mF capacitor is connected to a 27 mH inductor. What is the angular frequency of free oscillations of the circuit? 7.7 A series LCR circuit with R = 20 W, L = 1.5 H and C = 35 mF is connected to a variable-frequency 200 V ac supply. When the frequency of the supply equals the natural frequency of the circuit, what is the average power transferred to the circuit in one complete cycle? 7.8 Figure 7.17 shows a series LCR circuit connected to a variable frequency 230 V source. L = 5.0 H, C = 80mF, R = 40 W. FIGURE 7.17 (a) Determine the source frequency which drives the circuit in resonance. (b) Obtain the impedance of the circuit and the amplitude of current at the resonating frequency. (c) Determine the rms potential drops across the three elements of the circuit. Show that the potential drop across the LC combination is zero at the resonating frequency. Reprint 2025-26 Chapter Eight ELECTROMAGNETIC WAVES 8.1 INTRODUCTION In Chapter 4, we learnt that an electric current produces magnetic field and that two current-carrying wires exert a magnetic force on each other. Further, in Chapter 6, we have seen that a magnetic field changing with time gives rise to an electric field. Is the converse also true? Does an electric field changing with time give rise to a magnetic field? James Clerk Maxwell (1831-1879), argued that this was indeed the case – not only an electric current but also a time-varying electric field generates magnetic field. While applying the Ampere’s circuital law to find magnetic field at a point outside a capacitor connected to a time-varying current, Maxwell noticed an inconsistency in the Ampere’s circuital law. He suggested the existence of an additional current, called by him, the displacement current to remove this inconsistency. Maxwell formulated a set of equations involving electric and magnetic fields, and their sources, the charge and current densities. These equations are known as Maxwell’s equations. Together with the Lorentz force formula (Chapter 4), they mathematically express all the basic laws of electromagnetism. The most important prediction to emerge from Maxwell’s equations is the existence of electromagnetic waves, which are (coupled) time- varying electric and magnetic fields that propagate in space. The speed of the waves, according to these equations, turned out to be very close to Reprint 2025-26 Physics the speed of light( 3 ×108 m/s), obtained from optical measurements. This led to the remarkable conclusion that light is an electromagnetic wave. Maxwell’s work thus unified the domain of electricity, magnetism and light. Hertz, in 1885, experimentally demonstrated the existence of electromagnetic waves. Its technological use by Marconi and others led in due course to the revolution in communication that we are witnessing today. In this chapter, we first discuss the need for displacement current and its consequences. Then we present a descriptive account of electromagnetic waves. James Clerk Maxwell The broad spectrum of electromagnetic waves, (1831 – 1879) Born in stretching from g rays (wavelength ~10–12 m) to long Edinburgh, Scotland, radio waves (wavelength ~106 m) is described. was among the greatest physicists of the nineteenth century. He 8.2 DISPLACEMENT CURRENT derived the thermal We have seen in Chapter 4 that an electrical current velocity distribution of produces a magnetic field around it. Maxwell showed molecules in a gas and that for logical consistency, a changing electric field must was among the first to obtain reliable also produce a magnetic field. This effect is of great estimates of molecular importance because it explains the existence of radio parameters from waves, gamma rays and visible light, as well as all other measurable quantities forms of electromagnetic waves. like viscosity, etc. To see how a changing electric field gives rise to Maxwell’s greatest a magnetic field, let us consider the process of acheivement was the unification of the laws of charging of a capacitor and apply Ampere’s circuital electricity and law given by (Chapter 4) magnetism (discovered by Coulomb, Oersted, “B.dl = m0 i (t) (8.1)(1831–1879) Ampere and Faraday) to find magnetic field at a point outside the capacitor. into a consistent set of Figure 8.1(a) shows a parallel plate capacitor C which equations now called Maxwell’s equations. is a part of circuit through which a time-dependent From these he arrived at current i (t) flows . Let us find the magnetic field at a the most important point such as P, in a region outside the parallel plateMAXWELL conclusion that light is capacitor. For this, we consider a plane circular loop of an electromagnetic radius r whose plane is perpendicular to the direction wave. Interestingly, of the current-carrying wire, and which is centred Maxwell did not agree symmetrically with respect to the wire [Fig. 8.1(a)]. FromCLERK with the idea (strongly suggested by the symmetry, the magnetic field is directed along the Faraday’s laws of circumference of the circular loop and is the same in electrolysis) that magnitude at all points on the loop so that if B is theJAMES electricity was magnitude of the field, the left side of Eq. (8.1) is B (2p r). particulate in nature. So we have B (2pr) = m0i (t) (8 .2) 202 Reprint 2025-26 Electromagnetic Waves Now, consider a different surface, which has the same boundary. This is a pot like surface [Fig. 8.1(b)] which nowhere touches the current, but has its bottom between the capacitor plates; its mouth is the circular loop mentioned above. Another such surface is shaped like a tiffin box (without the lid) [Fig. 8.1(c)]. On applying Ampere’s circuital law to such surfaces with the same perimeter, we find that the left hand side of Eq. (8.1) has not changed but the right hand side is zero and not m0i, since no current passes through the surface of Fig. 8.1(b) and (c). So we have a contradiction; calculated one way, there is a magnetic field at a point P; calculated another way, the magnetic field at P is zero. Since the contradiction arises from our use of Ampere’s circuital law, this law must be missing something. The missing term must be such that one gets the same magnetic field at point P, no matter what surface is used. We can actually guess the missing term by looking carefully at Fig. 8.1(c). Is there anything passing through the surface S between the plates of the capacitor? Yes, of course, the electric field! If the plates of the capacitor have an area A, and a total charge Q, the magnitude of the electric field E between the plates is (Q/A)/e0 (see Eq. 2.41). The field is perpendicular to the surface S of Fig. 8.1(c). It has the same magnitude over the area A of the capacitor plates, and vanishes outside it. So what is the electric flux FE through the surface S ? Using Gauss’s law, it is 1 Q Q ΦE = E A = A = (8.3) ε0 A ε0 Now if the charge Q on the capacitor plates changes with time, there is a current i = (dQ/dt), so that using Eq. (8.3), we have dΦE d  Q  1 d Q = FIGURE 8.1 A d t d t  ε0 = ε0 d t parallel plate capacitor C, as part of This implies that for consistency, a circuit through which a time  dΦE  dependent current i (t) flows, (a) a loop of ε0  d t  = i (8.4) radius r, to determine This is the missing term in Ampere’s circuital law. If we generalise magnetic field at a this law by adding to the total current carried by conductors through point P on the loop; the surface, another term which is e0 times the rate of change of electric (b) a pot-shaped surface passingflux through the same surface, the total has the same value of current i through the interior for all surfaces. If this is done, there is no contradiction in the value of B between the capacitor obtained anywhere using the generalised Ampere’s law. B at the point P plates with the loop shown in (a) as itsis non-zero no matter which surface is used for calculating it. B at a rim; (c) a tiffin- point P outside the plates [Fig. 8.1(a)] is the same as at a point M just shaped surface with inside, as it should be. The current carried by conductors due to flow of the circular loop as charges is called conduction current. The current, given by Eq. (8.4), is a its rim and a flat circular bottom S new term, and is due to changing electric field (or electric displacement, between the capacitor an old term still used sometimes). It is, therefore, called displacement plates. The arrows show uniform electriccurrent or Maxwell’s displacement current. Figure 8.2 shows the electric field between the and magnetic fields inside the parallel plate capacitor discussed above. capacitor plates. The generalisation made by Maxwell then is the following. The source of a magnetic field is not just the conduction electric current due to flowing 203 Reprint 2025-26 Physics charges, but also the time rate of change of electric field. More precisely, the total current i is the sum of the conduction current denoted by ic, and the displacement current denoted by id (= ✒0 (d✂E/dt)). So we have dΦE i = i c + i d = i c + ε0 (8.5) d t In explicit terms, this means that outside the capacitor plates, we have only conduction current ic = i, and no displacement current, i.e., id = 0. On the other hand, inside the capacitor, there is no conduction current, i.e., ic = 0, and there is only displacement current, so that id = i. The generalised (and correct) Ampere’s circuital law has the same form as Eq. (8.1), with one difference: “the total current passing through any surface of which the closed loop is the perimeter” is the sum of the conduction current and the displacement current. The generalised law is dΦE B idl = µ0 i c + µ0 ε0 (8.6) Ñ∫ dt and is known as Ampere-Maxwell law. In all respects, the displacement current has the same physical effects as the conduction current. In some cases, for example, steady electric fields in a conducting wire, the displacement current may be zero since the electric field E does not change with time. In other FIGURE 8.2 (a) The cases, for example, the charging capacitor above, both conduction electric and magnetic and displacement currents may be present in different regions of fields E and B between space. In most of the cases, they both may be present in the same the capacitor plates, at region of space, as there exist no perfectly conducting or perfectly the point M. (b) A cross insulating medium. Most interestingly, there may be large regions sectional view of Fig. (a). of space where there is no conduction current, but there is only a displacement current due to time-varying electric fields. In such a region, we expect a magnetic field, though there is no (conduction) current source nearby! The prediction of such a displacement current can be verified experimentally. For example, a magnetic field (say at point M) between the plates of the capacitor in Fig. 8.2(a) can be measured and is seen to be the same as that just outside (at P). The displacement current has (literally) far reaching consequences. One thing we immediately notice is that the laws of electricity and magnetism are now more symmetrical*. Faraday’s law of induction states that there is an induced emf equal to the rate of change of magnetic flux. Now, since the emf between two points 1 and 2 is the work done per unit charge in taking it from 1 to 2, the existence of an emf implies the existence of an electric field. So, we can rephrase Faraday’s law of electromagnetic induction by saying that a magnetic field, changing with time, gives rise to an electric field. Then, the fact that an electric field changing with time gives rise to a magnetic field, is the symmetrical counterpart, and is * They are still not perfectly symmetrical; there are no known sources of magnetic field (magnetic monopoles) analogous to electric charges which are sources of 204 electric field. Reprint 2025-26 Electromagnetic Waves a consequence of the displacement current being a source of a magnetic field. Thus, time- dependent electric and magnetic fields give rise to each other! Faraday’s law of electromagnetic induction and Ampere-Maxwell law give a quantitative expression of this statement, with the current being the total current, as in Eq. (8.5). One very important consequence of this symmetry is the existence of electromagnetic waves, which we discuss qualitatively in the next section. MAXWELL’S EQUATIONS IN VACUUM 1. “E.dA = Q/✒0 (Gauss’s Law for electricity) 2. “B.dA = 0 (Gauss’s Law for magnetism) –dΦB 3. “E.dl == (Faraday’s Law) d t d ΦE + µ0 ε0 (Ampere – Maxwell Law) 4. “B.dl = µ0 i c d t

1.4 DIMENSIONS OF PHYSICAL QUANTITIES formula of the given physical quantity. For example, the dimensional formula of the volume The nature of a physical quantity is described is [M° L3 T°], and that of speed or velocity is by its dimensions. All the physical quantities [M° L T-1]. Similarly, [M° L T–2] is the dimensional represented by derived units can be expressed formula of acceleration and [M L–3 T°] that of in terms of some combination of seven mass density. fundamental or base quantities. We shall call An equation obtained by equating a physical these base quantities as the seven dimensions quantity with its dimensional formula is called of the physical world, which are denoted with the dimensional equation of the physical square brackets [ ]. Thus, length has the quantity. Thus, the dimensional equations are dimension [L], mass [M], time [T], electric current the equations, which represent the dimensions [A], thermodynamic temperature [K], luminous of a physical quantity in terms of the base intensity [cd], and amount of substance [mol]. quantities. For example, the dimensional The dimensions of a physical quantity are the equations of volume [V], speed [v], force [F ] and powers (or exponents) to which the base mass density [ρ] may be expressed as quantities are raised to represent that [V] = [M0 L3 T0] quantity. Note that using the square brackets [v] = [M0 L T–1] [ ] round a quantity means that we are dealing [F] = [M L T–2] with ‘the dimensions of’ the quantity. [ρ] = [M L–3 T0] In mechanics, all the physical quantities can be written in terms of the dimensions [L], [M] The dimensional equation can be obtained and [T]. For example, the volume occupied by from the equation representing the relations between the physical quantities. Thean object is expressed as the product of length, dimensional formulae of a large number andbreadth and height, or three lengths. Hence the wide variety of physical quantities, derived fromdimensions of volume are [L] × [L] × [L] = [L]3 = [L3]. the equations representing the relationships As the volume is independent of mass and time, among other physical quantities and expressed it is said to possess zero dimension in mass [M°], in terms of base quantities are given in zero dimension in time [T°] and three Appendix 9 for your guidance and ready dimensions in length. reference. Similarly, force, as the product of mass and acceleration, can be expressed as 1.6 DIMENSIONAL ANALYSIS AND ITS Force = mass × acceleration APPLICATIONS = mass × (length)/(time)2 The recognition of concepts of dimensions, which The dimensions of force are [M] [L]/[T]2 = guide the description of physical behaviour is [M L T–2]. Thus, the force has one dimension in of basic importance as only those physical Reprint 2025-26 8 PHYSICS quantities can be added or subtracted which such as angle as the ratio (length/length), have the same dimensions. A thorough refractive index as the ratio (speed of light in understanding of dimensional analysis helps us vacuum/speed of light in medium) etc., has no in deducing certain relations among different dimensions. physical quantities and checking the derivation, Now we can test the dimensional consistency accuracy and dimensional consistency or or homogeneity of the equation homogeneity of various mathematical 2expressions. When magnitudes of two or more x = x 0 + v 0 t + (1/2 ) a t physical quantities are multiplied, their units for the distance x travelled by a particle or body should be treated in the same manner as in time t which starts from the position x0 with ordinary algebraic symbols. We can cancel an initial velocity v0 at time t = 0 and has uniformidentical units in the numerator and acceleration a along the direction of motion. denominator. The same is true for dimensions The dimensions of each term may be written as of a physical quantity. Similarly, physical [x] = [L] quantities represented by symbols on both sides of a mathematical equation must have the same [x0 ] = [L] dimensions. [v0 t] = [L T–1] [T] = [L] [(1/2) a t2] = [L T–2] [T2]1.6.1 Checking the Dimensional Consistency of Equations = [L] As each term on the right hand side of this The magnitudes of physical quantities may be equation has the same dimension, namely that added together or subtracted from one another of length, which is same as the dimension of only if they have the same dimensions. In other left hand side of the equation, hence this words, we can add or subtract similar physical equation is a dimensionally correct equation. quantities. Thus, velocity cannot be added to It may be noted that a test of consistency of force, or an electric current cannot be subtracted dimensions tells us no more and no less than a from the thermodynamic temperature. This test of consistency of units, but has the simple principle called the principle of advantage that we need not commit ourselves homogeneity of dimensions in an equation is to a particular choice of units, and we need not extremely useful in checking the correctness of worry about conversions among multiples and an equation. If the dimensions of all the terms sub-multiples of the units. It may be borne in are not same, the equation is wrong. Hence, if mind that if an equation fails this consistency we derive an expression for the length (or test, it is proved wrong, but if it passes, it is distance) of an object, regardless of the symbols not proved right. Thus, a dimensionally correct appearing in the original mathematical relation, equation need not be actually an exact when all the individual dimensions are (correct) equation, but a dimensionally wrong simplified, the remaining dimension must be (incorrect) or inconsistent equation must be that of length. Similarly, if we derive an equation wrong. of speed, the dimensions on both the sides of ⊳equation, when simplified, must be of length/ Example 1.3 Let us consider an equation time, or [L T–1]. Dimensions are customarily used as a 1 2 m v = m g h preliminary test of the consistency of an 2 equation, when there is some doubt about the where m is the mass of the body, v its correctness of the equation. However, the velocity, g is the acceleration due to dimensional consistency does not guarantee gravity and h is the height. Check correct equations. It is uof dimensionless quantities or functions. The correct. arguments of special functions, such as the trigonometric, logarithmic and exponential Answer The dimensions of LHS are functions must be dimensionless. A pure [M] [L T–1 ]2 = [M] [ L2 T–2] number, ratio of similar physical quantities, = [M L2 T–2] Reprint 2025-26 UNITS AND MEASUREMENT 9 The dimensions of RHS are string, that oscillates under the action of [M][L T–2] [L] = [M][L2 T–2] the force of gravity. Suppose that the period = [M L2 T–2] of oscillation of the simple pendulum depends on its length (l), mass of the bobThe dimensions of LHS and RHS are the same and hence the equation is dimensionally correct. ⊳ (m) and acceleration due to gravity (g). Derive the expression for its time period ⊳ using method of dimensions. Example 1.4 The SI unit of energy is J = kg m2 s–2; that of speed v is m s–1 and Answer The dependence of time period T on of acceleration a is m s–2. Which of the the quantities l, g and m as a product may be formulae for kinetic energy (K) given below written as : can you rule out on the basis of T = k lx gy mz dimensional arguments (m stands for the mass of the body) : where k is dimensionless constant and x, y (a) K = m2 v3 and z are the exponents. (b) K = (1/2)mv2 By considering dimensions on both sides, we (c) K = ma have (d) K = (3/16)mv2 o o 1 1 x 1 –2 y 1 z [L M T ]=[L ] [L T ] [M ] (e) K = (1/2)mv2 + ma = Lx+y T–2y Mz Answer Every correct formula or equation must On equating the dimensions on both sides, have the same dimensions on both sides of the we have equation. Also, only quantities with the same x + y = 0; –2y = 1; and z = 0 physical dimensions can be added or 1 1 subtracted. The dimensions of the quantity on So that x = , y = – , z = 0 2 2the right side are [M2 L3 T–3] for (a); [M L2 T–2] for (b) and (d); [M L T–2] for (c). The quantity on the Then, T = k l½ g–½ right side of (e) has no proper dimensions since two quantities of different dimensions have been l or, T = kadded. Since the kinetic energy K has the g dimensions of [M L2 T–2], formulas (a), (c) and (e) Note that value of constant k can not be obtainedare ruled out. Note that dimensional arguments by the method of dimensions. Here it does notcannot tell which of the two, (b) or (d), is the matter if some number multiplies the right sidecorrect formula. For this, one must turn to the of this formula, because that does not affect itsactual definition of kinetic energy (see dimensions.Chapter 5). The correct formula for kinetic energy is given by (b). ⊳ l Actually, k = 2π so that T = 2π ⊳ 1.6.2 Deducing Relation among the g Physical Quantities The method of dimensions can sometimes be Dimensional analysis is very useful in deducing used to deduce relation among the physical relations among the interdependent physical quantities. For this we should know the quantities. However, dimensionless constants dependence of the physical quantity on other cannot be obtained by this method. The method quantities (upto three physical quantities or of dimensions can only test the dimensional linearly independent variables) and consider it validity, but not the exact relationship between as a product type of the dependence. Let us take physical quantities in any equation. It does not an example. distinguish between the physical quantities having same dimensions.⊳ Example 1.5 Consider a simple A number of exercises at the end of this pendulum, having a bob attached to a chapter will help you develop skill in dimensional analysis. Reprint 2025-26 10 PHYSICS SUMMARY 1. Physics is a quantitative science, based on measurement of physical quantities. Certain physical quantities have been chosen as fundamental or base quantities (such as length, mass, time, electric current, thermodynamic temperature, amount of substance, and luminous intensity). 2. Each base quantity is defined in terms of a certain basic, arbitrarily chosen but properly standardised reference standard called unit (such as metre, kilogram, second, ampere, kelvin, mole and candela). The units for the fundamental or base quantities are called fundamental or base units. 3. Other physical quantities, derived from the base quantities, can be expressed as a combination of the base units and are called derived units. A complete set of units, both fundamental and derived, is called a system of units. 4. The International System of Units (SI) based on seven base units is at present internationally accepted unit system and is widely used throughout the world. 5. The SI units are used in all physical measurements, for both the base quantities and the derived quantities obtained from them. Certain derived units are expressed by means of SI units with special names (such as joule, newton, watt, etc). 6. The SI units have well defined and internationally accepted unit symbols (such as m for metre, kg for kilogram, s for second, A for ampere, N for newton etc.). 7. Physical measurements are usually expressed for small and large quantities in scientific notation, with powers of 10. Scientific notation and the prefixes are used to simplify measurement notation and numerical computation, giving indication to the precision of the numbers. 8. Certain general rules and guidelines must be followed for using notations for physical quantities and standard symbols for SI units, some other units and SI prefixes for expressing properly the physical quantities and measurements. 9. In computing any physical quantity, the units for derived quantities involved in the relationship(s) are treated as though they were algebraic quantities till the desired units are obtained. 10. In measured and computed quantities proper significant figures only should be retained. Rules for determining the number of significant figures, carrying out arithmetic operations with them, and ‘rounding off ‘ the u 11. The dimensions of base quantities and combination of these dimensions describe the nature of physical quantities. Dimensional analysis can be used to check the dimensional consistency of equations, deducing relations among the physical quantities, etc. A dimensionally consistent equation need not be actually an exact (correct) equation, but a dimensionally wrong or inconsistent equation must be wrong. EXERCISES Note : In stating numerical answers, take care of significant figures. 1.1 Fill in the blanks (a) The volume of a cube of side 1 cm is equal to .....m3 (b) The surface area of a solid cylinder of radius 2.0 cm and height 10.0 cm is equal to ...(mm)2 (c) A vehicle moving with a speed of 18 km h–1 covers....m in 1 s (d) The relative density of lead is 11.3. Its density is ....g cm–3 or ....kg m–3. 1.2 Fill in the blanks by suitable conversion of units (a) 1 kg m2 s–2 = ....g cm2 s–2 (b) 1 m = ..... ly (c) 3.0 m s–2 = .... km h–2 (d) G = 6.67 × 10–11 N m2 (kg)–2 = .... (cm)3 s–2 g–1. Reprint 2025-26 UNITS AND MEASUREMENT 11 1.3 A calorie is a unit of heat (energy in transit) and it equals about 4.2 J where 1J = 1 kg m2 s–2. Suppose we employ a system of units in which the unit of mass equals α kg, the unit of length equals β m, the unit of time is γ s. Show that a calorie has a magnitude 4.2 α–1 β–2 γ 2 in terms of the new units. 1.4 Explain this statement clearly : “To call a dimensional quantity ‘large’ or ‘small’ is meaningless without specifying a standard for comparison”. In view of this, reframe the following statements wherever necessary : (a) atoms are very small objects (b) a jet plane moves with great speed (c) the mass of Jupiter is very large (d) the air inside this room contains a large number of molecules (e) a proton is much more massive than an electron (f) the speed of sound is much smaller than the speed of light. 1.5 A new unit of length is chosen such that the speed of light in vacuum is unity. What is the distance between the Sun and the Earth in terms of the new unit if light takes 8 min and 20 s to cover this distance ? 1.6 Which of the following is the most precise device for measuring length : (a) a vernier callipers with 20 divisions on the sliding scale (b) a screw gauge of pitch 1 mm and 100 divisions on the circular scale (c) an optical instrument that can measure length to within a wavelength of light ? 1.7 A student measures the thickness of a human hair by looking at it through a microscope of magnification 100. He makes 20 observations and finds that the average width of the hair in the field of view of the microscope is 3.5 mm. What is the estimate on the thickness of hair ? 1.8 Answer the following : (a)You are given a thread and a metre scale. How will you estimate the diameter of the thread ? (b)A screw gauge has a pitch of 1.0 mm and 200 divisions on the circular scale. Do you think it is possible to increase the accuracy of the screw gauge arbitrarily by increasing the number of divisions on the circular scale ? (c) The mean diameter of a thin brass rod is to be measured by vernier callipers. Why is a set of 100 measurements of the diameter expected to yield a more reliable estimate than a set of 5 measurements only ? 1.9 The photograph of a house occupies an area of 1.75 cm2 on a 35 mm slide. The slide is projected on to a screen, and the area of the house on the screen is 1.55 m2. What is the linear magnification of the projector-screen arrangement. 1.10 State the number of significant figures in the following : (a) 0.007 m2 (b) 2.64 × 1024 kg (c) 0.2370 g cm–3 (d) 6.320 J (e) 6.032 N m–2 (f) 0.0006032 m2 1.11 The length, breadth and thickness of a rectangular sheet of metal are 4.234 m, 1.005 m, and 2.01 cm respectively. Give the area and volume of the sheet to correct significant figures. 1.12 The mass of a box measured by a grocer’s balance is 2.30 kg. Two gold pieces of masses 20.15 g and 20.17 g are added to the box. What is (a) the total mass of the box, (b) the difference in the masses of the pieces to correct significant figures ? 1.13 A famous relation in physics relates ‘moving mass’ m to the ‘rest mass’ mo of a particle in terms of its speed v and the speed of light, c. (This relation first arose as a consequence of special relativity due to Albert Einstein). A boy recalls the relation almost correctly but forgets where to put the constant c. He writes : m 0 m = 2 1/2 . 1 − v ( ) Guess where to put the missing c. Reprint 2025-26 12 PHYSICS 1.14 The unit of length convenient on the atomic scale is known as an angstrom and is denoted by Å: 1 Å = 10–10 m. The size of a hydrogen atom is about 0.5 Å. What is the total atomic volume in m3 of a mole of hydrogen atoms ? 1.15 One mole of an ideal gas at standard temperature and pressure occupies 22.4 L (molar volume). What is the ratio of molar volume to the atomic volume of a mole of hydrogen ? (Take the size of hydrogen molecule to be about 1 Å). Why is this ratio so large ? 1.16 Explain this common observation clearly : If you look out of the window of a fast moving train, the nearby trees, houses etc. seem to move rapidly in a direction opposite to the train’s motion, but the distant objects (hill tops, the Moon, the stars etc.) seem to be stationary. (In fact, since you are aware that you are moving, these distant objects seem to move with you). 1.17 The Sun is a hot plasma (ionized matter) with its inner core at a temperature exceeding 107 K, and its outer surface at a temperature of about 6000 K. At these high temperatures, no substance remains in a solid or liquid phase. In what range do you expect the mass density of the Sun to be, in the range of densities of solids and liquids or gases ? Check if your guess is correct from the following data : mass of the Sun = 2.0 ×1030 kg, radius of the Sun = 7.0 × 108 m. Reprint 2025-26 CHAPTER TWO MOTION IN A STRAIGHT LINE 2.1 INTRODUCTION Motion is common to everything in the universe. We walk, run and ride a bicycle. Even when we are sleeping, air moves 2.1 Introduction into and out of our lungs and blood flows in arteries and 2.2 Instantaneous velocity and veins. We see leaves falling from trees and water flowing speed down a dam. Automobiles and planes carry people from one 2.3 Acceleration place to the other. The earth rotates once every twenty-four 2.4 Kinematic equations for hours and revolves round the sun once in a year. The sun uniformly accelerated motion itself is in motion in the Milky Way, which is again moving

5.2 NOTIONS OF WORK AND KINETIC to be proportional to the speed of the drop ENERGY: THE WORK-ENERGY THEOREM but is otherwise undetermined. Consider The following relation for rectilinear motion under a drop of mass 1.00 g falling from a height constant acceleration a has been encountered 1.00 km. It hits the ground with a speed of in Chapter 3, 50.0 m s-1. (a) What is the work done by the v2 − u2 = 2 as (5.2) gravitational force ? What is the work done where u and v are the initial and final speeds by the unknown resistive force? and s the distance traversed. Multiplying both Answer (a) The change in kinetic energy of the sides by m/2, we have drop is 1 2 1 2 1 2 mv − mu = mas = Fs (5.2a) ∆ K = m v − 0 2 2 2 where the last step follows from Newton’s Second 1 -3 = × 10 × 50 × 50 Law. We can generalise Eq. (5.2) to three 2 dimensions by employing vectors = 1.25 J v2 − u2 = 2 a.d where we have assumed that the drop is initially at rest. Here a and d are acceleration and displacement Assuming that g is a constant with a value vectors of the object respectively. 10 m/s2, the work done by the gravitational force Once again multiplying both sides by m/2 , we obtain is, 1 1 mv 2 − mu 2 = m a.d = F.d (5.2b) Wg = mgh 2 2 = 10-3 ×10 ×103 The above equation provides a motivation for = 10.0 J the definitions of work and kinetic energy. The (b) From the work-energy theorem left side of the equation is the difference in the quantity ‘half the mass times the square of the ∆ K = W g + W r speed’ from its initial value to its final value. We where Wr is the work done by the resistive force call each of these quantities the ‘kinetic energy’, on the raindrop. Thus denoted by K. The right side is a product of the Wr = ∆K − Wg displacement and the component of the force = 1.25 −10 along the displacement. This quantity is called = − 8.75 J ‘work’ and is denoted by W. Eq. (5.2b) is then is negative. ⊳ Kf − Ki = W (5.3) 5.3 WORK where Ki and Kf are respectively the initial and As seen earlier, work is related to force and the final kinetic energies of the object. Work refers displacement over which it acts. Consider a to the force and the displacement over which it constant force F acting on an object of mass m. acts. Work is done by a force on the body over The object undergoes a displacement d in the a certain displacement. positive x-direction as shown in Fig. 5.2. Equation (5.2) is also a special case of the work-energy (WE) theorem : The change in kinetic energy of a particle is equal to the work done on it by the net force. We shall generalise the above derivation to a varying force in a later section. ⊳ Example 5.2 It is well known that a raindrop falls under the influence of the Fig. 5.2 An object undergoes a displacement d downward gravitational force and the under the influence of the force F. opposing resistive force. The latter is known Reprint 2025-26 74 PHYSICS The work done by the force is defined to be Table 5.1 Alternative Units of Work/Energy in J the product of component of the force in the direction of the displacement and the magnitude of this displacement. Thus W = (F cos θ)d = F.d (5.4) We see that if there is no displacement, there is no work done even if the force is large. Thus, when you push hard against a rigid brick wall, ⊳ the force you exert on the wall does no work. Yet Example 5.3 A cyclist comes to a skidding your muscles are alternatively contracting and stop in 10 m. During this process, the force relaxing and internal energy is being used up on the cycle due to the road is 200 N and and you do get tired. Thus, the meaning of work is directly opposed to the motion. (a) How in physics is different from its usage in everyday much work does the road do on the cycle ? language. (b) How much work does the cycle do on the road ? No work is done if : (i) the displacement is zero as seen in the example above. A weightlifter holding a 150 Answer Work done on the cycle by the road is kg mass steadily on his shoulder for 30 s the work done by the stopping (frictional) force does no work on the load during this time. on the cycle due to the road. (ii) the force is zero. A block moving on a smooth (a) The stopping force and the displacement make horizontal table is not acted upon by a an angle of 180o (π rad) with each other. horizontal force (since there is no friction), but Thus, work done by the road, may undergo a large displacement. Wr = Fd cosθ (iii) the force and displacement are mutually = 200 × 10 × cos π perpendicular. This is so since, for θ= π/2 rad = – 2000 J (= 90o), cos (π/2) = 0. For the block moving on It is this negative work that brings the cycle a smooth horizontal table, the gravitational to a halt in accordance with WE theorem. force mg does no work since it acts at right (b) From Newton’s Third Law an equal and angles to the displacement. If we assume that opposite force acts on the road due to the the moon’s orbits around the earth is cycle. Its magnitude is 200 N. However, the perfectly circular then the earth’s road undergoes no displacement. Thus, gravitational force does no work. The moon’s work done by cycle on the road is zero. ⊳ instantaneous displacement is tangential while the earth’s force is radially inwards and The lesson of Example 5.3 is that though the θ = π/2. force on a body A exerted by the body B is always Work can be both positive and negative. If θ is equal and opposite to that on B by A (Newton’s between 0o and 90o, cos θ in Eq. (5.4) is positive. Third Law); the work done on A by B is not If θ is between 90o and 180o, cos θ is negative. necessarily equal and opposite to the work done In many examples the frictional force opposes on B by A. displacement and θ = 180o. Then the work done 5.4 KINETIC ENERGY by friction is negative (cos 180o = –1). As noted earlier, if an object of mass m has From Eq. (5.4) it is clear that work and energy velocity v, its kinetic energy K ishave the same dimensions, [ML2T–2]. The SI unit of these is joule (J), named after the famous British 1 1 2physicist James Prescott Joule (1811-1869). Since K = m v. v = mv (5.5) 2 2work and energy are so widely used as physical concepts, alternative units abound and some of Kinetic energy is a scalar quantity. The kinetic these are listed in Table 5.1. energy of an object is a measure of the work an Reprint 2025-26 WORK, ENERGY AND POWER 75 Table 5.2 Typical kinetic energies (K) object can do by the virtue of its motion. This This is illustrated in Fig. 5.3(a). Adding notion has been intuitively known for a long time. successive rectangular areas in Fig. 5.3(a) we The kinetic energy of a fast flowing stream get the total work done as has been used to grind corn. Sailing x f ships employ the kinetic energy of the wind. Table W ≅ F (x )∆x (5.6) ∑

5.2 lists the kinetic energies for various x i objects. where the summation is from the initial position ⊳ xi to the final position xf. Example 5.4 In a ballistics demonstration a police officer fires a bullet of mass 50.0 g If the displacements are allowed to approach with speed 200 m s-1 (see Table 5.2) on soft zero, then the number of terms in the sum plywood of thickness 2.00 cm. The bullet increases without limit, but the sum approaches emerges with only 10% of its initial kinetic a definite value equal to the area under the curve energy. What is the emergent speed of the in Fig. 5.3(b). Then the work done is bullet ? xf W = lim F (x )∆xAnswer The initial kinetic energy of the bullet ∆ x → 0 ∑ x i is mv2/2 = 1000 J. It has a final kinetic energy xfof 0.1×1000 = 100 J. If vf is the emergent speed x ) d x (5.7)of the bullet, = ∫F ( i 1 2 x mv f = 100 J where ‘lim’ stands for the limit of the sum when 2 ∆x tends to zero. Thus, for a varying force 2 × 100 J the work done can be expressed as a definite v f = 0. 05 kg integral of force over displacement (see also Appendix 3.1). = 63.2 m s–1 The speed is reduced by approximately 68% (not 90%). ⊳

5.8 THE CONSERVATION OF MECHANICAL a ball of mass m being dropped from a cliff of ENERGY height H. For simplicity we demonstrate this important principle for one-dimensional motion. Suppose that a body undergoes displacement ∆x under the action of a conservative force F. Then from the WE theorem we have, ∆K = F(x) ∆x If the force is conservative, the potential energy function V(x) can be defined such that − ∆V = F(x) ∆x The above equations imply that Fig. 5.5 The conversion of potential energy to kinetic ∆K + ∆V = 0 energy for a ball of mass m dropped from a ∆(K + V ) = 0 (5.10) height H. Reprint 2025-26 WORK, ENERGY AND POWER 79 The total mechanical energies E0, Eh, and EH Answer (i) There are two external forces on of the ball at the indicated heights zero (ground the bob : gravity and the tension (T ) in the level), h and H, are string. The latter does no work since the displacement of the bob is always normal to the EH = mgH (5.11 a) string. The potential energy of the bob is thus 1 2 E h = mgh + mv h (5.11 b) associated with the gravitational force only. The 2 2 total mechanical energy E of the system is E0 = (1/2) mvf (5.11 c) conserved. We take the potential energy of the The constant force is a special case of a spatially system to be zero at the lowest point A. Thus, dependent force F(x). Hence, the mechanical at A : energy is conserved. Thus EH = E0 1 2 1 2 E = mv0 (5.12) or, mgH = mv f 2 2 v f = 2 gH [Newton’s Second Law] a result that was obtained in section 5.7 for a where TA is the tension in the string at A. At thefreely falling body. highest point C, the string slackens, as the Further, tension in the string (TC) becomes zero. EH = Eh Thus, at Cwhich implies, 2 1 2 v h = 2 g(H − h) (5.11 d) E = mv c + 2mgL (5.13) 2 and is a familiar result from kinematics. At the height H, the energy is purely potential. mvc2It is partially converted to kinetic at height h and mg = [Newton’s Second Law] (5.14) L is fully kinetic at ground level. This illustrates the conservation of mechanical energy. where vC is the speed at C. From Eqs. (5.13) ⊳ and (5.14) Example 5.7 A bob of mass m is suspended 5 by a light string of length L . It is imparted a E = mgL horizontal velocity vo at the lowest point A 2 such that it completes a semi-circular Equating this to the energy at A trajectory in the vertical plane with the string 5 m 2 becoming slack only on reaching the topmost mgL = v 0 point, C. This is shown in Fig. 5.6. Obtain an 2 2 expression for (i) vo; (ii) the speeds at points or, v 0 = 5 gL B and C; (iii) the ratio of the kinetic energies (ii) It is clear from Eq. (5.14) (KB/KC) at B and C. Comment on the nature of the trajectory of the bob after it reaches vC = gL the point C. At B, the energy is 1 2 E = mv B + mgL 2 Equating this to the energy at A and employing the result from (i), namely v 02 = 5 gL , 1 2 1 2 mv B + mgL = mv 0 2 2 5 = m g L Fig. 5.6 2 Reprint 2025-26 80 PHYSICS ∴ vB = 3 gL k x m2 W = + (5.16) 2 (iii) The ratio of the kinetic energies at B and C is : 1 2 mv B K B 2 3 = = 2 1 K C 1 mvC 2 At point C, the string becomes slack and the velocity of the bob is horizontal and to the left. If the connecting string is cut at this instant, the bob will execute a projectile motion with horizontal projection akin to a rock kicked horizontally from the edge of a cliff. Otherwise the bob will continue on its circular path and complete the revolution. ⊳

11.6 SPECIFIC HEAT CAPACITY average energy of 2 × ½ kBT = kBT. In three dimensions, the average energy is 3 kBT.Suppose an amount of heat ∆Q supplied to a For a mole of a solid, the total energy is substance changes its temperature from T to T + ∆T. We define heat capacity of a substance U = 3 kBT × NA = 3 RT (∵kBT × NA = R) (see Chapter 10) to be Now, at constant pressure, ∆Q = ∆U + P ∆V ≅ ∆ Q ∆U, since for a solid ∆V is negligible. Therefore, S = (11.4) ∆ T ∆ Q ∆U C = = = 3 R (11.7) We expect ∆Q and, therefore, heat capacity S ∆ T ∆ T to be proportional to the mass of the substance. Table 11.1 Specific and molar heat capacities Further, it could also depend on the of some solids at room temperature, i.e., a different amount of heat may temperature and atmospheric be needed for a unit rise in temperature at pressure different temperatures. To define a constant –v Speci"c heat Molar speci"c characteristic of the substance and Substance –1 –1 –1 –1 (J kg K ) heat (J mol K ) independent of its amount, we divide S by the mass of the substance m in kg : S  1  ∆Q s = (11.5) m =  m  ∆T s is known as the specific heat capacity of the substance. It depends on the nature of the As Table 11.1 shows, the experimentally substance and its temperature. The unit of measured values which generally agrees withspecific heat capacity is J kg–1 K–1. Reprint 2025-26 232 PHYSICS predicted value 3R at ordinary temperatures. ideal gas, we have a simple relation. (Carbon is an exception.) The agreement is known to break down at low temperatures. Cp – Cv = R (11.8) Specific heat capacity of water where Cp and Cv are molar specific heat capacities of an ideal gas at constant pressure The old unit of heat was calorie. One calorie and volume respectively and R is the universal was earlier defined to be the amount of heat gas constant. To prove the relation, we begin required to raise the temperature of 1g of water with Eq. (11.3) for 1 mole of the gas : by 1°C. With more precise measurements, it was found that the specific heat of water varies ∆Q = ∆U + P ∆V slightly with temperature. Figure 11.5 shows If ∆Q is absorbed at constant volume, ∆V = 0this variation in the temperature range 0 to 100 °C.  ∆Q   ∆ U   ∆ U  (11.9) C v =  ∆T  v =  ∆T  v =  ∆T  where the subscript v is dropped in the last step, since U of an ideal gas depends only on temperature. (The subscript denotes the quantity kept fixed.) If, on the other hand, ∆Q is absorbed at constant pressure,  ∆ Q   ∆ U   ∆V  (11.10) C p =  ∆T  p =  ∆T  p + P  ∆ T  p The subscript p can be dropped from the Fig. 11.5 Variation of specific heat capacity of first term since U of an ideal gas depends only water with temperature. on T. Now, for a mole of an ideal gas For a precise definition of calorie, it was, PV = RTtherefore, necessary to specify the unit temperature interval. One calorie is defined which gives to be the amount of heat required to raise the temperature of 1g of water from 14.5 °C to  ∆ V  P = R (11.11)15.5 °C. Since heat is just a form of energy,  ∆ T  p it is preferable to use the unit joule, J. In SI units, the specific heat capacity of water Equations (11.9) to (11.11) give the desired is 4186 J kg–1 K–1 i.e. 4.186 J g–1 K–1. The so relation, Eq. (11.8). called mechanical equivalent of heat defined 11.7THERMODYNAMIC STATE VARIABLES as the amount of work needed to produce AND EQUATION OF STATE 1 cal of heat is in fact just a conversion factor between two different units of energy : calorie Every equilibrium state of a thermodynamic to joule. Since in SI units, we use the unit joule system is completely described by specific for heat, work or any other form of energy, the values of some macroscopic variables, also term mechanical equivalent is now called state variables. For example, an superfluous and need not be used. equilibrium state of a gas is completely As already remarked, the specific heat specified by the values of pressure, volume, capacity depends on the process or the temperature, and mass (and composition if conditions under which heat capacity transfer there is a mixture of gases). A thermodynamic takes place. For gases, for example, we can system is not always in equilibrium. For example, define two specific heats : specific heat a gas allowed to expand freely against vacuum capacity at constant volume and specific is not an equilibrium state [Fig. 11.6(a)]. During heat capacity at constant pressure. For an the rapid expansion, pressure of the gas may Reprint 2025-26 THERMODYNAMICS 233 not be uniform throughout. Similarly, a mixture temperature do not. To decide which variable is of gases undergoing an explosive chemical extensive and which intensive, think of a reaction (e.g. a mixture of petrol vapour and relevant system in equilibrium, and imagine that air when ignited by a spark) is not an it is divided into two equal parts. The variables that remain unchanged for each part areequilibrium state; again its temperature and intensive. The variables whose values get halvedpressure are not uniform [Fig. 11.6(b)]. in each part are extensive. It is easily seen, forEventually, the gas attains a uniform example, that internal energy U, volume V, total temperature and pressure and comes to mass M are extensive variables. Pressure P, thermal and mechanical equilibrium with its temperature T, and density ρ are intensive surroundings. variables. It is a good practice to check the consistency of thermodynamic equations using this classification of variables. For example, in the equation ∆Q = ∆U + P ∆V quantities on both sides are extensive*. (The product of an intensive variable like P and an extensive quantity ∆V is extensive.) 11.8 THERMODYNAMIC PROCESSES 11.8.1 Quasi-static process Consider a gas in thermal and mechanical equilibrium with its surroundings. The pressure of the gas in that case equals the external Fig. 11.6 (a) The partition in the box is suddenly pressure and its temperature is the same as removed leading to free expansion of the that of its surroundings. Suppose that the gas. (b) A mixture of gases undergoing an external pressure is suddenly reduced (say by explosive chemical reaction. In both lifting the weight on the movable piston in the situations, the gas is not in equilibrium and container). The piston will accelerate outward. cannot be described by state variables. During the process, the gas passes through In short, thermodynamic state variables states that are not equilibrium states. The non- describe equilibrium states of systems. The equilibrium states do not have well-defined various state variables are not necessarily pressure and temperature. In the same way, if independent. The connection between the state a finite temperature difference exists between variables is called the equation of state. For the gas and its surroundings, there will be a example, for an ideal gas, the equation of state rapid exchange of heat during which the gas is the ideal gas relation will pass through non-equilibrium states. In due course, the gas will settle to an equilibrium P V = µ R T state with well-defined temperature and For a fixed amount of the gas i.e. given µ, there pressure equal to those of the surroundings. The are thus, only two independent variables, say P free expansion of a gas in vacuum and a mixture and V or T and V. The pressure-volume curve of gases undergoing an explosive chemical for a fixed temperature is called an isotherm. reaction, mentioned in section 11.7 are also Real gases may have more complicated examples where the system goes through non- equations of state. equilibrium states. The thermodynamic state variables are of two Non-equilibrium states of a system are difficult kinds: extensive and intensive. Extensive to deal with. It is, therefore, convenient to variables indicate the ‘size’ of the system. imagine an idealised process in which at every Intensive variables such as pressure and stage the system is an equilibrium state. Such a * As emphasised earlier, Q is not a state variable. However, ∆Q is clearly proportional to the total mass of system and hence is extensive. Reprint 2025-26 234 PHYSICS process is, in principle, infinitely slow, hence the A process in which the temperature of the name quasi-static (meaning nearly static). The system is kept fixed throughout is called an system changes its variables (P, T, V ) so slowly isothermal process. The expansion of a gas in that it remains in thermal and mechanical a metallic cylinder placed in a large reservoir of equilibrium with its surroundings throughout. fixed temperature is an example of an isothermal In a quasi-static process, at every stage, the process. (Heat transferred from the reservoir to difference in the pressure of the system and the the system does not materially affect the external pressure is infinitesimally small. The temperature of the reservoir, because of its very large heat capacity.) In isobaric processes thesame is true of the temperature difference pressure is constant while in isochoricbetween the system and its surroundings processes the volume is constant. Finally, if the(Fig.11.7). To take a gas from the state (P, T ) to another state (P ′, T ′ ) via a quasi-static process, system is insulated from the surroundings and no heat flows between the system and thewe change the external pressure by a very small surroundings, the process is adiabatic. The amount, allow the system to equalise its pressure definitions of these special processes are with that of the surroundings and continue the summarised in Table. 11.2 process infinitely slowly until the system achieves the pressure P ′. Similarly, to change Table 11.2 Some special thermodynamic the temperature, we introduce an infinitesimal processes temperature difference between the system and the surrounding reservoirs and by choosing reservoirs of progressively different temperatures T to T ′, the system achieves the temperature T ′. We now consider these processes in some detail : 11.8.2 Isothermal process For an isothermal process (T fixed), the ideal gas equation gives PV = constant i.e., pressure of a given mass of gas varies inversely as its volume. This is nothing but Boyle’s Law. Suppose an ideal gas goes isothermally (at temperature T ) from its initial state (P1, V1) to Fig. 11.7 In a quasi-static process, the temperature the final state (P2, V 2). At any intermediate stage of the surrounding reservoir and the with pressure P and volume change from V to external pressure differ only infinitesimally V + ∆V (∆V small) from the temperature and pressure of the system. ∆W = P ∆ V A quasi-static process is obviously a Taking (∆V → 0) and summing the quantity hypothetical construct. In practice, processes ∆W over the entire process, that are sufficiently slow and do not involve V2 accelerated motion of the piston, large W = ∫ P d V temperature gradient, etc., are reasonably V1 approximation to an ideal quasi-static process. V2 d V V2We shall from now on deal with quasi-static = µ RT = µRT In ∫ (11.12) Vprocesses only, except when stated otherwise. V1 V 1 Reprint 2025-26 THERMODYNAMICS 235 where in the second step we have made use of We can calculate, as before, the work done in the ideal gas equation PV = µ RT and taken the an adiabatic change of an ideal gas from the constants out of the integral. For an ideal gas, state (P1, V1, T1) to the state (P2, V2, T2). internal energy depends only on temperature. V 2Thus, there is no change in the internal energy W = ∫ P d Vof an ideal gas in an isothermal process. The V1First Law of Thermodynamics then implies that heat supplied to the gas equals the work done by the gas : Q = W. Note from Eq. (11.12) that for V2 > V1, W > 0; and for V2 < V1, W < 0. That is, in an isothermal expansion, the gas absorbs heat and does work while in an isothermal (11.15) compression, work is done on the gas by the environment and heat is released. From Eq. (11.14), the constant is P1V1γ or P2V2γ 11.8.3 Adiabatic process γ  γ  P2 V 2 P1V 1In an adiabatic process, the system is insulated W = 1 − 1   −1 γ γ − from the surroundings and heat absorbed or 1 − γ  V2 V1  released is zero. From Eq. (11.1), we see that work done by the gas results in decrease in its 1 µR(T1 − T2 ) = [ P2 V2 − P1V1 ] = (11.16)internal energy (and hence its temperature for 1 − γ γ − 1 an ideal gas). We quote without proof (the result that you will learn in higher courses) that for As expected, if work is done by the gas in an an adiabatic process of an ideal gas. adiabatic process (W > 0), from Eq. (11.16), P V γ = const (11.13) T2 < T1. On the other hand, if work is done on the gas (W < 0), we get T2 > T1 i.e., thewhere γ is the ratio of specific heats (ordinary temperature of the gas rises. or molar) at constant pressure and at constant volume. 11.8.4 Isochoric process Cp In an isochoric process, V is constant. No work γ = Cv is done on or by the gas. From Eq. (11.1), the heat absorbed by the gas goes entirely to change Thus if an ideal gas undergoes a change in its internal energy and its temperature. The its state adiabatically from (P1, V1) to (P2, V2) : change in temperature for a given amount of γ = P2 V2γ (11.14) heat is determined by the specific heat of the P1 V1 gas at constant volume. Figure11.8 shows the P-V curves of an ideal gas for two adiabatic processes connecting two 11.8.5 Isobaric process isotherms. In an isobaric process, P is fixed. Work done by the gas is W = P (V2 – V1) = µ R (T2 – T1) (11.17) Since temperature changes, so does internal energy. The heat absorbed goes partly to increase internal energy and partly to do work. The change in temperature for a given amount of heat is determined by the specific heat of the gas at constant pressure. 11.8.6 Cyclic process In a cyclic process, the system returns to its initial state. Since internal energy is a stateFig. 11.8 P-V curves for isothermal and adiabatic variable, ∆U = 0 for a cyclic process. From processes of an ideal gas. Reprint 2025-26 236 PHYSICS Eq. (11.1), the total heat absorbed equals the 11.10 REVERSIBLE AND IRREVERSIBLE work done by the system. PROCESSES Imagine some process in which a thermodynamic11.9 SECOND LAW OF THERMODYNAMICS system goes from an initial state i to a final state The First Law of Thermodynamics is the f. During the process the system absorbs heat Q principle of conservation of energy. Common from the surroundings and performs work W on experience shows that there are many it. Can we reverse this process and bring both conceivable processes that are perfectly the system and surroundings to their initial allowed by the First Law and yet are never states with no other effect anywhere ? Experience observed. For example, nobody has ever seen suggests that for most processes in nature this a book lying on a table jumping to a height by is not possible. The spontaneous processes ofitself. But such a thing would be possible if nature are irreversible. Several examples can bethe principle of conservation of energy were cited. The base of a vessel on an oven is hotterthe only restriction. The table could cool than its other parts. When the vessel is removed,spontaneously, converting some of its internal heat is transferred from the base to the otherenergy into an equal amount of mechanical parts, bringing the vessel to a uniformenergy of the book, which would then hop to a height with potential energy equal to the temperature (which in due course cools to the mechanical energy it acquired. But this never temperature of the surroundings). The process happens. Clearly, some additional basic cannot be reversed; a part of the vessel will not principle of nature forbids the above, even get cooler spontaneously and warm up the base. though it satisfies the energy conservation It will violate the Second Law of Thermodynamics, principle. This principle, which disallows if it did. The free expansion of a gas is irreversible. many phenomena consistent with the First The combustion reaction of a mixture of petrol Law of Thermodynamics is known as the and air ignited by a spark cannot be reversed. Second Law of Thermodynamics. Cooking gas leaking from a gas cylinder in the The Second Law of Thermodynamics gives kitchen diffuses to the entire room. The diffusion a fundamental limitation to the efficiency of a process will not spontaneously reverse and bring heat engine and the co-efficient of the gas back to the cylinder. The stirring of a performance of a refrigerator. In simple terms, liquid in thermal contact with a reservoir will it says that efficiency of a heat engine can convert the work done into heat, increasing the never be unity. For a refrigerator, the Second internal energy of the reservoir. The process Law says that the co-efficient of performance cannot be reversed exactly; otherwise it would can never be infinite. The following two amount to conversion of heat entirely into work, statements, one due to Kelvin and Planck violating the Second Law of Thermodynamics. denying the possibility of a perfect heat engine, Irreversibility is a rule rather an exception and another due to Clausius denying the in nature. possibility of a perfect refrigerator or heat Irreversibility arises mainly from two causes: pump, are a concise summary of these one, many processes (like a free expansion, or observations. an explosive chemical reaction) take the system Kelvin-Planck statement to non-equilibrium states; two, most processes No process is possible whose sole result is the involve friction, viscosity and other dissipative absorption of heat from a reservoir and the effects (e.g., a moving body coming to a stop and complete conversion of the heat into work. losing its mechanical energy as heat to the floor and the body; a rotating blade in a liquid coming Clausius statement to a stop due to viscosity and losing its No process is possible whose sole result is the mechanical energy with corresponding gain in transfer of heat from a colder object to a the internal energy of the liquid). Since hotter object. dissipative effects are present everywhere and It can be proved that the two statements can be minimised but not fully eliminated, most above are completely equivalent. processes that we deal with are irreversible. Reprint 2025-26 THERMODYNAMICS 237 A thermodynamic process (state i → state f ) in a reversible heat engine operating between is reversible if the process can be turned back two temperatures, heat should be absorbed such that both the system and the surroundings (from the hot reservoir) isothermally and return to their original states, with no other released (to the cold reservoir) isothermally. We change anywhere else in the universe. From the thus have identified two steps of the reversible preceding discussion, a reversible process is an heat engine : isothermal process at temperature idealised notion. A process is reversible only if T1 absorbing heat Q1 from the hot reservoir, and another isothermal process at temperature T2it is quasi-static (system in equilibrium with the releasing heat Q2 to the cold reservoir. Tosurroundings at every stage) and there are no complete a cycle, we need to take the systemdissipative effects. For example, a quasi-static from temperature T1 to T2 and then back fromisothermal expansion of an ideal gas in a temperature T2 to T1. Which processes shouldcylinder fitted with a frictionless movable piston we employ for this purpose that are reversible?is a reversible process. A little reflection shows that we can only adopt Why is reversibility such a basic concept in reversible adiabatic processes for these thermodynamics ? As we have seen, one of the purposes, which involve no heat flow from any concerns of thermodynamics is the efficiency reservoir. If we employ any other process that is with which heat can be converted into work. not adiabatic, say an isochoric process, to take The Second Law of Thermodynamics rules out the system from one temperature to another, we the possibility of a perfect heat engine with 100% shall need a series of reservoirs in the efficiency. But what is the highest efficiency temperature range T2 to T1 to ensure that at each possible for a heat engine working between two stage the process is quasi-static. (Remember reservoirs at temperatures T1 and T2? It turns again that for a process to be quasi-static and out that a heat engine based on idealised reversible, there should be no finite temperature reversible processes achieves the highest difference between the system and the reservoir.) efficiency possible. All other engines involving But we are considering a reversible engine that irreversibility in any way (as would be the case operates between only two temperatures. Thus for practical engines) have lower than this adiabatic processes must bring about the limiting efficiency. temperature change in the system from T1 to T2 and T2 to T1 in this engine.11.11 CARNOT ENGINE Suppose we have a hot reservoir at temperature T1 and a cold reservoir at temperature T2. What is the maximum efficiency possible for a heat engine operating between the two reservoirs and what cycle of processes should be adopted to achieve the maximum efficiency ? Sadi Carnot, a French engineer, first considered this question in 1824. Interestingly, Carnot arrived at the correct answer, even though the basic concepts of heat and thermodynamics had yet to be firmly established. We expect the ideal engine operating between two temperatures to be a reversible engine. Irreversibility is associated with dissipative Fig. 11.9 Carnot cycle for a heat engine with an effects, as remarked in the preceding section, ideal gas as the working substance. and lowers efficiency. A process is reversible if it is quasi-static and non-dissipative. We have A reversible heat engine operating between seen that a process is not quasi-static if it two temperatures is called a Carnot engine. We involves finite temperature difference between have just argued that such an engine must have the system and the reservoir. This implies that the following sequence of steps constituting one Reprint 2025-26 238 PHYSICS cycle, called the Carnot cycle, shown in Fig. 11.9. We have taken the working substance In  V 3  of the Carnot engine to be an ideal gas. T2   V4  = 1 −  T1   V2  (11.23)(a) Step 1 → 2 Isothermal expansion of the gas In  V1  taking its state from (P1, V1, T1) to (P2, V2, T1). Now since step 2 → 3 is an adiabatic process, The heat absorbed by the gas (Q1) from the γ −1 γ −1 reservoir at temperature T1 is given by T1 V 2 = T2 V3 Eq. (11.12). This is also the work done (W1 → 2) by the gas on the environment. 1 /( γ −1 ) V2  T2   V2  i.e. = (11.24) 3  T1  W1 → 2 = Q1 = µ R T1 ln  V1  (11.18) V (b) Step 2 → 3 Adiabatic expansion of the gas Similarly, since step 4 → 1 is an adiabatic from (P2, V2, T1) to (P3, V3, T2) process Work done by the gas, using γ −1 γ −1 Eq. (11.16), is T2 V 4 = T1 V1 µR ( T1 − T2 ) 1 /γ −1 W2 →=3 (11.19) V1  T2  γ − 1 i.e. = (11.25) V4  T1  (c) Step 3 → 4 Isothermal compression of the gas from (P3, V3, T2) to (P4, V4, T2). From Eqs. (11.24) and (11.25), 2 Heat released (Q2) by the gas to the reservoir V3 = V (11.26) at temperature T2 is given by Eq. (11.12). This V4 V1 is also the work done (W3 → 4) on the gas by the environment. Using Eq. (11.26) in Eq. (11.23), we get  V 3  2 W 3 → 4 = Q2 = µRT2 ln η = 1 −T (Carnot engine) (11.27)  V 4  (11.20) T1 (d) Step 4 → 1 Adiabatic compression of the gas from (P4, V4, T2) to (P1,V1, T1). We have already seen that a Carnot engine is a reversible engine. Indeed it is the only Work done on the gas, [using Eq.(11.16), is reversible engine possible that works between two reservoirs at different temperatures. Each  T1 − T2  W4 → 1 = µR (11.21) step of the Carnot cycle given in Fig. 11.9 can  γ -1  be reversed. This will amount to taking heat Q2 from the cold reservoir at T2, doing work W on From Eqs. (11.18) to (11.21) total work done by the gas in one complete cycle is the system, and transferring heat Q1 to the hot reservoir. This will be a reversible refrigerator. W = W1 → 2 + W2 → 3 – W3 → 4 – W4 → 1 We next establish the important result  V2   V3  (sometimes called Carnot’s theorem) that = µ RT1 ln  V1  – µ RT2 ln  V4  (11.22) (a) working between two given temperatures T1 and T2 of the hot and cold reservoirs respectively, The efficiency η of the Carnot engine is no engine can have efficiency more than that of the Carnot engine and (b) the efficiency of the W Q 2 η = = 1 − Carnot engine is independent of the nature of Q1 Q1 the working substance. Reprint 2025-26 THERMODYNAMICS 239 To prove the result (a), imagine a reversible reservoir and delivers the same amount of work (Carnot) engine R and an irreversible engine I in one cycle, without any change in the source working between the same source (hot reservoir) or anywhere else. This is clearly against the and sink (cold reservoir). Let us couple the Kelvin-Planck statement of the Second Law of engines, I and R, in such a way so that I acts Thermodynamics. Hence the assertion ηI > ηR like a heat engine and R acts as a refrigerator. is wrong. No engine can have efficiency greater Let I absorb heat Q1 from the source, deliver than that of the Carnot engine. A similar work W ′ and release the heat Q1- W′ to the sink. argument can be constructed to show that a We arrange so that R returns the same heat Q1 reversible engine with one particular substance to the source, taking heat Q2 from the sink and cannot be more efficient than the one using requiring work W = Q1 – Q2 to be done on it. another substance. The maximum efficiency of Now suppose ηR < ηI i.e. if R were to act a Carnot engine given by Eq. (11.27) is as an engine it would give less work output independent of the nature of the system performing the Carnot cycle of operations. Thus we are justified in using an ideal gas as a system in the calculation of efficiency η of a Carnot engine. The ideal gas has a simple equation of I state, which allows us to readily calculate η, but the final result for η, [Eq. (11.27)], is true for any Carnot engine. R This final remark shows that in a Carnot cycle, Q1 T1 = W (11.28) T2 Q 2 is a universal relation independent of the natureFig. 11.10 An irreversible engine (I) coupled to a reversible refrigerator (R). If W ′ > W, this of the system. Here Q1 and Q2 are respectively, would amount to extraction of heat the heat absorbed and released isothermally W′ – W from the sink and its full (from the hot and to the cold reservoirs) in a conversion to work, in contradiction with Carnot engine. Equation (11.28), can, therefore, the Second Law of Thermodynamics. be used as a relation to define a truly universal thermodynamic temperature scale that is than that of I i.e. W < W ′ for a given Q1. With R independent of any particular properties of the acting like a refrigerator, this would mean system used in the Carnot cycle. Of course, for Q2 = Q1 – W > Q1 – W ′. Thus, on the whole, an ideal gas as a working substance, this the coupled I-R system extracts heat universal temperature is the same as the ideal (Q1 – W) – (Q1 – W ′) = (W ′ – W ) from the cold gas temperature introduced in section 11.9. SUMMARY 1. The zeroth law of thermodynamics states that ‘two systems in thermal equilibrium with a third system separately are in thermal equilibrium with each other’. The Zeroth Law leads to the concept of temperature. 2. Internal energy of a system is the sum of kinetic energies and potential energies of the molecular constituents of the system. It does not include the over-all kinetic energy of the system. Heat and work are two modes of energy transfer to the system. Heat is the energy transfer arising due to temperature difference between the system and the surroundings. Work is energy transfer brought about by other means, such as moving the piston of a cylinder containing the gas, by raising or lowering some weight connected to it. Reprint 2025-26 240 PHYSICS 3. The first law of thermodynamics is the general law of conservation of energy applied to any system in which energy transfer from or to the surroundings (through heat and work) is taken into account. It states that ∆Q = ∆U + ∆W where ∆Q is the heat supplied to the system, ∆W is the work done by the system and ∆U is the change in internal energy of the system. 4. The specific heat capacity of a substance is defined by 1 ∆Q s = m ∆T where m is the mass of the substance and ∆Q is the heat required to change its temperature by ∆T. The molar specific heat capacity of a substance is defined by 1 ∆ Q C = µ ∆T where µ is the number of moles of the substance. For a solid, the law of equipartition of energy gives C = 3 R which generally agrees with experiment at ordinary temperatures. Calorie is the old unit of heat. 1 calorie is the amount of heat required to raise the temperature of 1 g of water from 14.5 °C to 15.5 °C. 1 cal = 4.186 J. 5. For an ideal gas, the molar specific heat capacities at constant pressure and volume satisfy the relation Cp – Cv = R where R is the universal gas constant. 6. Equilibrium states of a thermodynamic system are described by state variables. The value of a state variable depends only on the particular state, not on the path used to arrive at that state. Examples of state variables are pressure (P ), volume (V ), temperature (T ), and mass (m ). Heat and work are not state variables. An Equation of State (like the ideal gas equation PV = µ RT ) is a relation connecting different state variables. 7. A quasi-static process is an infinitely slow process such that the system remains in thermal and mechanical equilibrium with the surroundings throughout. In a quasi-static process, the pressure and temperature of the environment can differ from those of the system only infinitesimally. 8. In an isothermal expansion of an ideal gas from volume V1 to V2 at temperature T the heat absorbed (Q) equals the work done (W ) by the gas, each given by  V 2   Q = W = µ R T ln   V1  9. In an adiabatic process of an ideal gas γ PV = constant C p where γ = C v Work done by an ideal gas in an adiabatic change of state from (P1, V1, T1) to (P2, V2, T2) is µR ( T1 − T2 ) W = γ – 1 Reprint 2025-26 THERMODYNAMICS 241 10. The second law of thermodynamics disallows some processes consistent with the First Law of Thermodynamics. It states Kelvin-Planck statement No process is possible whose sole result is the absorption of heat from a reservoir and complete conversion of the heat into work. Clausius statement No process is possible whose sole result is the transfer of heat from a colder object to a hotter object. Put simply, the Second Law implies that no heat engine can have efficiency η equal to 1 or no refrigerator can have co-efficient of performance α equal to infinity. 11. A process is reversible if it can be reversed such that both the system and the surroundings return to their original states, with no other change anywhere else in the universe. Spontaneous processes of nature are irreversible. The idealised reversible process is a quasi-static process with no dissipative factors such as friction, viscosity, etc. 12. Carnot engine is a reversible engine operating between two temperatures T1 (source) and T2 (sink). The Carnot cycle consists of two isothermal processes connected by two adiabatic processes. The efficiency of a Carnot engine is given by T 2 η= 1 − (Carnot engine) T1 No engine operating between two temperatures can have efficiency greater than that of the Carnot engine. 13. If Q > 0, heat is added to the system If Q < 0, heat is removed to the system If W > 0, Work is done by the system If W < 0, Work is done on the system Quantity Symbol Dimensions Unit Remark Co-efficienty of volume αv [K–1] K–1 αv = 3 α1 expansion Heat supplied to a system ∆Q [ML2 T–2] J Q is not a state variable Specific heat capacity s [L2 T–2 K–1] J kg–1 K–1 dt Thermal Conductivity K [MLT–3 K–1] J s–1 K–1 H = – KA dx POINTS TO PONDER 1. Temperature of a body is related to its average internal energy, not to the kinetic energy of motion of its centre of mass. A bullet fired from a gun is not at a higher temperature because of its high speed. 2. Equilibrium in thermodynamics refers to the situation when macroscopic variables describing the thermodynamic state of a system do not depend on time. Equilibrium of a system in mechanics means the net external force and torque on the system are zero. Reprint 2025-26 242 PHYSICS 3. In a state of thermodynamic equilibrium, the microscopic constituents of a system are not in equilibrium (in the sense of mechanics). 4. Heat capacity, in general, depends on the process the system goes through when heat is supplied. 5. In isothermal quasi-static processes, heat is absorbed or given out by the system even though at every stage the gas has the same temperature as that of the surrounding reservoir. This is possible because of the infinitesimal difference in temperature between the system and the reservoir. EXERCISES 11.1 A geyser heats water flowing at the rate of 3.0 litres per minute from 27 °C to 77 °C. If the geyser operates on a gas burner, what is the rate of consumption of the fuel if its heat of combustion is 4.0 × 104 J/g ? 11.2 What amount of heat must be supplied to 2.0 × 10–2 kg of nitrogen (at room temperature) to raise its temperature by 45 °C at constant pressure ? (Molecular mass of N2 = 28; R = 8.3 J mol–1 K–1.) 11.3 Explain why (a) Two bodies at different temperatures T1 and T2 if brought in thermal contact do not necessarily settle to the mean temperature (T1 + T2 )/2. (b) The coolant in a chemical or a nuclear plant (i.e., the liquid used to prevent the different parts of a plant from getting too hot) should have high specific heat. (c) Air pressure in a car tyre increases during driving. (d) The climate of a harbour town is more temperate than that of a town in a desert at the same latitude. 11.4 A cylinder with a movable piston contains 3 moles of hydrogen at standard temperature and pressure. The walls of the cylinder are made of a heat insulator, and the piston is insulated by having a pile of sand on it. By what factor does the pressure of the gas increase if the gas is compressed to half its original volume ? 11.5 In changing the state of a gas adiabatically from an equilibrium state A to another equilibrium state B, an amount of work equal to 22.3 J is done on the system. If the gas is taken from state A to B via a process in which the net heat absorbed by the system is 9.35 cal, how much is the net work done by the system in the latter case ? (Take 1 cal = 4.19 J) 11.6 Two cylinders A and B of equal capacity are connected to each other via a stopcock. A contains a gas at standard temperature and pressure. B is completely evacuated. The entire system is thermally insulated. The stopcock is suddenly opened. Answer the following : (a) What is the final pressure of the gas in A and B ? (b) What is the change in internal energy of the gas ? (c) What is the change in the temperature of the gas ? (d) Do the intermediate states of the system (before settling to the final equilibrium state) lie on its P-V-T surface ? 11.7 An electric heater supplies heat to a system at a rate of 100W. If system performs work at a rate of 75 joules per second. At what rate is the internal energy increasing? Reprint 2025-26 THERMODYNAMICS 243 11.8 A thermodynamic system is taken from an original state to an intermediate state by the linear process shown in Fig. (11.13) Fig. 11.11 Its volume is then reduced to the original value from E to F by an isobaric process. Calculate the total work done by the gas from D to E to F Reprint 2025-26 CHAPTER TWELVE KINETIC THEORY 12.1 INTRODUCTION Boyle discovered the law named after him in 1661. Boyle, Newton and several others tried to explain the behaviour of 12.1 Introduction gases by considering that gases are made up of tiny atomic 12.2 Molecular nature of matter particles. The actual atomic theory got established more than 12.3 Behaviour of gases 150 years later. Kinetic theory explains the behaviour of gases 12.4 Kinetic theory of an ideal gas based on the idea that the gas consists of rapidly moving 12.5 Law of equipartition of energy atoms or molecules. This is possible as the inter-atomic forces, 12.6 Specific heat capacity which are short range forces that are important for solids and liquids, can be neglected for gases. The kinetic theory12.7 Mean free path was developed in the nineteenth century by Maxwell, Summary Boltzmann and others. It has been remarkably successful. It Points to ponder gives a molecular interpretation of pressure and temperature Exercises of a gas, and is consistent with gas laws and Avogadro’s hypothesis. It correctly explains specific heat capacities of many gases. It also relates measurable properties of gases such as viscosity, conduction and diffusion with molecular parameters, yielding estimates of molecular sizes and masses. This chapter gives an introduction to kinetic theory. 12.2 MOLECULAR NATURE OF MATTER Richard Feynman, one of the great physicists of 20th century considers the discovery that “Matter is made up of atoms” to be a very significant one. Humanity may suffer annihilation (due to nuclear catastrophe) or extinction (due to environmental disasters) if we do not act wisely. If that happens, and all of scientific knowledge were to be destroyed then Feynman would like the ‘Atomic Hypothesis’ to be communicated to the next generation of creatures in the universe. Atomic Hypothesis: All things are made of atoms - little particles that move around in perpetual motion, attracting each other when they are a little distance apart, but repelling upon being squeezed into one another. Speculation that matter may not be continuous, existed in many places and cultures. Kanada in India and Democritus Reprint 2025-26 KINETIC THEORY 245 Atomic Hypothesis in Ancient India and Greece Though John Dalton is credited with the introduction of atomic viewpoint in modern science, scholars in ancient India and Greece conjectured long before the existence of atoms and molecules. In the Vaiseshika school of thought in India founded by Kanada (Sixth century B.C.) the atomic picture was developed in considerable detail. Atoms were thought to be eternal, indivisible, infinitesimal and ultimate parts of matter. It was argued that if matter could be subdivided without an end, there would be no difference between a mustard seed and the Meru mountain. The four kinds of atoms (Paramanu — Sanskrit word for the smallest particle) postulated were Bhoomi (Earth), Ap (water), Tejas (fire) and Vayu (air) that have characteristic mass and other attributes, were propounded. Akasa (space) was thought to have no atomic structure and was continuous and inert. Atoms combine to form different molecules (e.g. two atoms combine to form a diatomic molecule dvyanuka, three atoms form a tryanuka or a triatomic molecule), their properties depending upon the nature and ratio of the constituent atoms. The size of the atoms was also estimated, by conjecture or by methods that are not known to us. The estimates vary. In Lalitavistara, a famous biography of the Buddha written mainly in the second century B.C., the estimate is close to the modern estimate of atomic size, of the order of 10 –10 m. In ancient Greece, Democritus (Fourth century B.C.) is best known for his atomic hypothesis. The word ‘atom’ means ‘indivisible’ in Greek. According to him, atoms differ from each other physically, in shape, size and other properties and this resulted in the different properties of the substances formed by their combination. The atoms of water were smooth and round and unable to ‘hook’ on to each other, which is why liquid /water flows easily. The atoms of earth were rough and jagged, so they held together to form hard substances. The atoms of fire were thorny which is why it caused painful burns. These fascinating ideas, despite their ingenuity, could not evolve much further, perhaps because they were intuitive conjectures and speculations not tested and modified by quantitative experiments - the hallmark of modern science. in Greece had suggested that matter may consist of matter. The theory is now well accepted by of indivisible constituents. The scientific ‘Atomic scientists. However even at the end of the Theory’ is usually credited to John Dalton. He nineteenth century there were famous scientists proposed the atomic theory to explain the laws who did not believe in atomic theory ! of definite and multiple proportions obeyed by From many observations, in recent times we elements when they combine into compounds. now know that molecules (made up of one or The first law says that any given compound has, more atoms) constitute matter. Electron a fixed proportion by mass of its constituents. microscopes and scanning tunnelling The second law says that when two elements microscopes enable us to even see them. The form more than one compound, for a fixed mass size of an atom is about an angstrom (10 -10 m). of one element, the masses of the other elements In solids, which are tightly packed, atoms are are in ratio of small integers. spaced about a few angstroms (2 Å) apart. In To explain the laws Dalton suggested, about liquids the separation between atoms is also 200 years ago, that the smallest constituents about the same. In liquids the atoms are not of an element are atoms. Atoms of one element as rigidly fixed as in solids, and can move are identical but differ from those of other around. This enables a liquid to flow. In gases elements. A small number of atoms of each the interatomic distances are in tens of element combine to form a molecule of the angstroms. The average distance a molecule compound. Gay Lussac’s law, also given in early can travel without colliding is called the mean 19th century, states: When gases combine free path. The mean free path, in gases, is of chemically to yield another gas, their volumes the order of thousands of angstroms. The atoms are in the ratios of small integers. Avogadro’s are much freer in gases and can travel long law (or hypothesis) says: Equal volumes of all distances without colliding. If they are not gases at equal temperature and pressure have enclosed, gases disperse away. In solids and the same number of molecules. Avogadro’s law, liquids the closeness makes the interatomic force when combined with Dalton’s theory explains important. The force has a long range attraction Gay Lussac’s law. Since the elements are often and a short range repulsion. The atoms attract in the form of molecules, Dalton’s atomic theory when they are at a few angstroms but repel when can also be referred to as the molecular theory they come closer. The static appearance of a gas Reprint 2025-26 246 PHYSICS is misleading. The gas is full of activity and the is 6.02 × 1023. This is known as Avogadro number equilibrium is a dynamic one. In dynamic and is denoted by NA. The mass of 22.4 litres of equilibrium, molecules collide and change their any gas is equal to its molecular weight in grams speeds during the collision. Only the average at S.T.P (standard temperature 273 K and properties are constant. pressure 1 atm). This amount of substance is Atomic theory is not the end of our quest, but called a mole (see Chapter 1 for a more precise the beginning. We now know that atoms are not definition). Avogadro had guessed the equality of indivisible or elementary. They consist of a numbers in equal volumes of gas at a fixed nucleus and electrons. The nucleus itself is made temperature and pressure from chemical up of protons and neutrons. The protons and reactions. Kinetic theory justifies this hypothesis. neutrons are again made up of quarks. Even The perfect gas equation can be written as quarks may not be the end of the story. There PV = µ RT (12.3)may be string like elementary entities. Nature always has surprises for us, but the search for where µ is the number of moles and R = NA truth is often enjoyable and the discoveries kB is a universal constant. The temperature T is absolute temperature. Choosing kelvin scale forbeautiful. In this chapter, we shall limit ourselves absolute temperature, R = 8.314 J mol–1K–1.to understanding the behaviour of gases (and a Herelittle bit of solids), as a collection of moving molecules in incessant motion. M N µ = = (12.4) M 0 N A

11.3 The photoelectric cut-off voltage in a certain experiment is 1.5 V. What is the maximum kinetic energy of photoelectrons emitted?

11.4 HEAT, INTERNAL ENERGY AND WORK associated with various random motions of its The Zeroth Law of Thermodynamics led us to molecules. We will see in the next chapter that the concept of temperature that agrees with our in a gas this motion is not only translational commonsense notion. Temperature is a marker (i.e. motion from one point to another in the of the ‘hotness’ of a body. It determines the volume of the container); it also includes rotational and vibrational motion of thedirection of flow of heat when two bodies are molecules (Fig. 11.3).placed in thermal contact. Heat flows from the body at a higher temperature to the one at lower temperature. The flow stops when the temperatures equalise; the two bodies are then in thermal equilibrium. We saw in some detail how to construct temperature scales to assign temperatures to different bodies. We now describe the concepts of heat and other relevant quantities like internal energy and work. Fig. 11.3 (a) Internal energy U of a gas is the sum of the kinetic and potential energies of its The concept of internal energy of a system is molecules when the box is at rest. Kinetic not difficult to understand. We know that every energy due to various types of motion bulk system consists of a large number of (translational, rotational, vibrational) is to molecules. Internal energy is simply the sum of be included in U. (b) If the same box is the kinetic energies and potential energies of moving as a whole with some velocity, these molecules. We remarked earlier that in the kinetic energy of the box is not to be thermodynamics, the kinetic energy of the included in U. system, as a whole, is not relevant. Internal energy is thus, the sum of molecular kinetic and potential energies in the frame of reference relative to which the centre of mass of the system is at rest. Thus, it includes only the (disordered) energy associated with the random motion of molecules of the system. We denote the internal energy of a system by U. Though we have invoked the molecular picture to understand the meaning of internal energy, as far as thermodynamics is concerned, U is simply a macroscopic variable of the system. The important thing about internal energy is that it depends only on the state of the system, not on how that state was achieved. Internal energy U of a system is an example of a thermodynamic ‘state variable’ – its value depends only on the given state of the system, not on history i.e. not on the ‘path’ taken to arrive at that state. Thus, the internal energy of a given mass of gas depends on its state described by Fig. 11.4 Heat and work are two distinct modes of specific values of pressure, volume and energy transfer to a system that results in temperature. It does not depend on how this change in its internal energy. (a) Heat is energy transfer due to temperaturestate of the gas came about. Pressure, volume, difference between the system and the temperature, and internal energy are surroundings. (b) Work is energy transfer thermodynamic state variables of the system brought about by means (e.g. moving the (gas) (see section 11.7). If we neglect the small piston by raising or lowering some weight intermolecular forces in a gas, the internal connected to it) that do not involve such a energy of a gas is just the sum of kinetic energies temperature difference. Reprint 2025-26 230 PHYSICS What are the ways of changing internal 11.5 FIRST LAW OF THERMODYNAMICS energy of a system ? Consider again, for We have seen that the internal energy U of a simplicity, the system to be a certain mass of system can change through two modes of energy gas contained in a cylinder with a movable transfer : heat and work. Let piston as shown in Fig. 11.4. Experience shows ∆Q = Heat supplied to the system by thethere are two ways of changing the state of the surroundingsgas (and hence its internal energy). One way is to put the cylinder in contact with a body at a ∆W = Work done by the system on the higher temperature than that of the gas. The surroundings temperature difference will cause a flow of ∆U = Change in internal energy of the system energy (heat) from the hotter body to the gas, The general principle of conservation of thus increasing the internal energy of the gas. energy then implies that The other way is to push the piston down i.e. to ∆Q = ∆U + ∆W (11.1) do work on the system, which again results in i.e. the energy (∆Q) supplied to the system goesincreasing the internal energy of the gas. Of in partly to increase the internal energy of thecourse, both these things could happen in the system (∆U) and the rest in work on thereverse direction. With surroundings at a lower environment (∆W). Equation (11.1) is known astemperature, heat would flow from the gas to the First Law of Thermodynamics. It is simplythe surroundings. Likewise, the gas could push the general law of conservation of energy applied the piston up and do work on the surroundings. to any system in which the energy transfer from In short, heat and work are two different modes or to the surroundings is taken into account. of altering the state of a thermodynamic system Let us put Eq. (11.1) in the alternative form and changing its internal energy. The notion of heat should be carefully ∆Q – ∆W = ∆U (11.2) distinguished from the notion of internal energy. Heat is certainly energy, but it is the energy in Now, the system may go from an initial state transit. This is not just a play of words. The to the final state in a number of ways. For distinction is of basic significance. The state of example, to change the state of a gas from a thermodynamic system is characterised by its (P1, V1) to (P2, V2), we can first change the volume of the gas from V1 to V2, keeping itsinternal energy, not heat. A statement like ‘a pressure constant i.e. we can first go the stategas in a given state has a certain amount of heat’ is as meaningless as the statement that (P1, V2) and then change the pressure of the gas from P1 to P2, keeping volume constant, to‘a gas in a given state has a certain amount take the gas to (P2, V2). Alternatively, we canof work’. In contrast, ‘a gas in a given state first keep the volume constant and then keep has a certain amount of internal energy’ is a the pressure constant. Since U is a state perfectly meaningful statement. Similarly, the variable, ∆U depends only on the initial and statements ‘a certain amount of heat is final states and not on the path taken by the supplied to the system’ or ‘a certain amount gas to go from one to the other. However, ∆Q of work was done by the system’ are perfectly and ∆W will, in general, depend on the path meaningful. taken to go from the initial to final states. From To summarise, heat and work in the First Law of Thermodynamics, Eq. (11.2), thermodynamics are not state variables. They it is clear that the combination ∆Q – ∆W, is are modes of energy transfer to a system however, path independent. This shows that resulting in change in its internal energy, if a system is taken through a process in which ∆U = 0 (for example, isothermal expansion ofwhich, as already mentioned, is a state variable. an ideal gas, see section 11.8), In ordinary language, we often confuse heat with internal energy. The distinction between ∆Q = ∆W them is sometimes ignored in elementary physics books. For proper understanding of i.e., heat supplied to the system is used up thermodynamics, however, the distinction is entirely by the system in doing work on the crucial. environment. Reprint 2025-26 THERMODYNAMICS 231 If the system is a gas in a cylinder with a If the amount of substance is specified in movable piston, the gas in moving the piston does terms of moles µ (instead of mass m in kg ), we work. Since force is pressure times area, and can define heat capacity per mole of the area times displacement is volume, work done substance by by the system against a constant pressure P is S 1 ∆Q C = = (11.6) ∆W = P ∆V µ µ ∆T C is known as molar specific heat capacity of where ∆V is the change in volume of the gas. the substance. Like s, C is independent of the Thus, for this case, Eq. (11.1) gives amount of substance. C depends on the nature ∆Q = ∆U + P ∆V (11.3) of the substance, its temperature and the conditions under which heat is supplied. The As an application of Eq. (11.3), consider the unit of C is J mo1–1 K–1. As we shall see later (in change in internal energy for 1 g of water when connection with specific heat capacity of gases), we go from its liquid to vapour phase. The additional conditions may be needed to define measured latent heat of water is 2256 J/g. i.e., C or s. The idea in defining C is that simple for 1 g of water ∆Q = 2256 J. At atmospheric predictions can be made in regard to molar pressure, 1 g of water has a volume 1 cm3 in specific heat capacities. liquid phase and 1671 cm3 in vapour phase. Table 11.1 lists measured specific and molar heat capacities of solids at atmospheric pressure Therefore, and ordinary room temperature. ∆W =P (Vg –Vl ) = 1.013 ×105 × (1671 × 10–6) =169.2 J We will see in Chapter 12 that predictions of specific heats of gases generally agree with Equation (11.3) then gives experiment. We can use the same law of equipartition of energy that we use there to ∆U = 2256 – 169.2 = 2086.8 J predict molar specific heat capacities of solids We see that most of the heat goes to increase (See Section 12.5 and 12.6). Consider a solid of the internal energy of water in transition from N atoms, each vibrating about its mean the liquid to the vapour phase. position. An oscillator in one dimension has

11.3 ZEROTH LAW OF THERMODYNAMICS (a) Imagine two systems A and B, separated by an adiabatic wall, while each is in contact with a third system C, via a conducting wall [Fig. 11.2(a)]. The states of the systems (i.e., their macroscopic variables) will change until both A and B come to thermal equilibrium with C. After this is achieved, suppose that the adiabatic wall between A and B is replaced by a conducting wall and C is insulated from A and B by an adiabatic wall [Fig.11.2(b)]. It is found that the states of A and B change no (b) further i.e. they are found to be in thermal Fig. 11.2 (a) Systems A and B are separated by an equilibrium with each other. This observation adiabatic wall, while each is in contact forms the basis of the Zeroth Law of with a third system C via a conducting Thermodynamics, which states that ‘two wall. (b) The adiabatic wall between A systems in thermal equilibrium with a third and B is replaced by a conducting wall, system separately are in thermal equilibrium while C is insulated from A and B by an adiabatic wall.with each other’. R.H. Fowler formulated this * Both the variables need not change. It depends on the constraints. For instance, if the gases are in containers of fixed volume, only the pressures of the gases would change to achieve thermal equilibrium. Reprint 2025-26 THERMODYNAMICS 229

7.21 Name the reagents used in the following reactions: (i) Oxidation of a primary alcohol to carboxylic acid. (ii) Oxidation of a primary alcohol to aldehyde. (iii) Bromination of phenol to 2,4,6-tribromophenol. (iv) Benzyl alcohol to benzoic acid. (v) Dehydration of propan-2-ol to propene. (vi) Butan-2-one to butan-2-ol.

7.7 Predict the major product of acid catalysed dehydration of (i) 1-methylcyclohexanol and (ii) butan-1-ol

7.17 Give equations of the following reactions: (i) Oxidation of propan-1-ol with alkaline KMnO4 solution. (ii) Bromine in CS2 with phenol. (iii) Dilute HNO3 with phenol. (iv) Treating phenol wih chloroform in presence of aqueous NaOH.

2.1 Arrange the following metals in the order in which they displace each other from the solution of their salts. Al, Cu, Fe, Mg and Zn.

2.10 The conductivity of sodium chloride at 298 K has been determined at different concentrations and the results are given below: Concentration/M 0.001 0.010 0.020 0.050 0.100 102 × k/S m–1 1.237 11.85 23.15 55.53 106.74 Calculate Λm for all concentrations and draw a plot between Λm and c½. Find the value of 0m . 2.11 Conductivity of 0.00241 M acetic acid is 7.896 × 10–5 S cm–1. Calculate its molar conductivity. If 0m for acetic acid is 390.5 S cm2 mol–1, what is its dissociation constant? 2.12 How much charge is required for the following reductions: (i) 1 mol of Al3+ to Al? (ii) 1 mol of Cu2+ to Cu? (iii) 1 mol of MnO4– to Mn2+? 2.13 How much electricity in terms of Faraday is required to produce (i) 20.0 g of Ca from molten CaCl2? (ii) 40.0 g of Al from molten Al2O3? 2.14 How much electricity is required in coulomb for the oxidation of (i) 1 mol of H2O to O2? (ii) 1 mol of FeO to Fe2O3? 2.15 A solution of Ni(NO3)2 is electrolysed between platinum electrodes using a current of 5 amperes for 20 minutes. What mass of Ni is deposited at the cathode? 2.16 Three electrolytic cells A,B,C containing solutions of ZnSO4, AgNO3 and CuSO4, respectively are connected in series. A steady current of 1.5 amperes was passed through them until 1.45 g of silver deposited at the cathode of cell B. How long did the current flow? What mass of copper and zinc were deposited? 2.17 Using the standard electrode potentials given in Table 3.1, predict if the reaction between the following is feasible: (i) Fe3+(aq) and I–(aq) (ii) Ag+ (aq) and Cu(s) (iii) Fe3+ (aq) and Br– (aq) (iv) Ag(s) and Fe 3+ (aq) (v) Br2 (aq) and Fe2+ (aq). 2.18 Predict the products of electrolysis in each of the following: (i) An aqueous solution of AgNO3 with silver electrodes. (ii) An aqueous solution of AgNO3 with platinum electrodes. (iii) A dilute solution of H2SO4 with platinum electrodes. (iv) An aqueous solution of CuCl2 with platinum electrodes. Answers to Some Intext Questions 2.5 E(cell) = 0.91 V 2.6 ∆ rG o = −45.54 kJ mol −1 , Kc = 9.62 ×107 2.9 0.114, 3.67 × 10–4 mol L–1 Chemistry 60 Reprint 2025-26 UnitUnitUnit Unit33Unit Objectives ChemicalChemical KineticsKinetics After studying this Unit, you will be able to · define the average and Chemical Kinetics helps us to understand how chemical reactions instantaneous rate of a reaction; occur. · express the rate of a reaction in terms of change in concentration Chemistry, by its very nature, is concerned with change. of either of the reactants or Substances with well defined properties are converted products with time; by chemical reactions into other substances with · distinguish between elementary different properties. For any chemical reaction, chemists and complex reactions; try to find out · differentiate between the (a) the feasibility of a chemical reaction which can be molecularity and order of a reaction; predicted by thermodynamics ( as you know that a · define rate constant; reaction with DG < 0, at constant temperature and pressure is feasible);· discuss the dependence of rate of reactions on concentration, (b) extent to which a reaction will proceed can be temperature and catalyst; determined from chemical equilibrium; · derive integrated rate equations (c) speed of a reaction i.e. time taken by a reaction to for the zero and first order reach equilibrium. reactions; Along with feasibility and extent, it is equally · determine the rate constants for important to know the rate and the factors controlling zeroth and first order reactions; the rate of a chemical reaction for its complete · describe collision theory. understanding. For example, which parameters determine as to how rapidly food gets spoiled? How to design a rapidly setting material for dental filling? Or what controls the rate at which fuel burns in an auto engine? All these questions can be answered by the branch of chemistry, which deals with the study of reaction rates and their mechanisms, called chemical kinetics. The word kinetics is derived from the Greek word ‘kinesis’ meaning movement. Thermodynamics tells only about the feasibility of a reaction whereas chemical kinetics tells about the rate of a reaction. For example, thermodynamic data indicate that diamond shall convert to graphite but in reality the conversion rate is so slow that the change is not perceptible at all. Therefore, most people think Reprint 2025-26 that diamond is forever. Kinetic studies not only help us to determine the speed or rate of a chemical reaction but also describe the conditions by which the reaction rates can be altered. The factors such as concentration, temperature, pressure and catalyst affect the rate of a reaction. At the macroscopic level, we are interested in amounts reacted or formed and the rates of their consumption or formation. At the molecular level, the reaction mechanisms involving orientation and energy of molecules undergoing collisions, are discussed. In this Unit, we shall be dealing with average and instantaneous rate of reaction and the factors affecting these. Some elementary ideas about the collision theory of reaction rates are also given. However, in order to understand all these, let us first learn about the reaction rate. 3.13.13.13.13.1 RateRateRateRateRate ofofofofof aaaaa Some reactions such as ionic reactions occur very fast, for example, ChemicalChemicalChemicalChemicalChemical precipitation of silver chloride occurs instantaneously by mixing of aqueous solutions of silver nitrate and sodium chloride. On the other ReactionReactionReactionReactionReaction hand, some reactions are very slow, for example, rusting of iron in the presence of air and moisture. Also there are reactions like inversion of cane sugar and hydrolysis of starch, which proceed with a moderate speed. Can you think of more examples from each category? You must be knowing that speed of an automobile is expressed in terms of change in the position or distance covered by it in a certain period of time. Similarly, the speed of a reaction or the rate of a reaction can be defined as the change in concentration of a reactant or product in unit time. To be more specific, it can be expressed in terms of: (i) the rate of decrease in concentration of any one of the reactants, or (ii) the rate of increase in concentration of any one of the products. Consider a hypothetical reaction, assuming that the volume of the system remains constant. R ® P One mole of the reactant R produces one mole of the product P. If [R]1 and [P]1 are the concentrations of R and P respectively at time t1 and [R]2 and [P]2 are their concentrations at time t2 then, Dt = t2 – t1 D[R] = [R]2 – [R]1 D [P] = [P]2 – [P]1 The square brackets in the above expressions are used to express molar concentration. Rate of disappearance of R Decrease in concentration of R ∆ [ R ] = = − (3.1) Time taken ∆ t Chemistry 62 Reprint 2025-26 Rate of appearance of P Increase in concentration of P ∆ [ P ] = = + (3.2) Time taken ∆t Since, D[R] is a negative quantity (as concentration of reactants is decreasing), it is multiplied with –1 to make the rate of the reaction a positive quantity. Equations (3.1) and (3.2) given above represent the average rate of a reaction, rav. Average rate depends upon the change in concentration of reactants or products and the time taken for that change to occur (Fig. 3.1). { } Fig. 3.1: Instantaneous and average rate of a reaction Units of rate of a reaction From equations (3.1) and (3.2), it is clear that units of rate are concentration time–1. For example, if concentration is in mol L–1 and time is in seconds then the units will be mol L-1s–1. However, in gaseous reactions, when the concentration of gases is expressed in terms of their partial pressures, then the units of the rate equation will be atm s–1. From the concentrations of C4H9Cl (butyl chloride) at different times given ExampleExampleExampleExampleExample 3.13.13.13.13.1 below, calculate the average rate of the reaction: C4H9Cl + H2O ® C4H9OH + HCl during different intervals of time. t/s 0 50 100 150 200 300 400 700 800 [C4H9Cl]/mol L–1 0.100 0.0905 0.0820 0.0741 0.0671 0.0549 0.0439 0.0210 0.017 We can determine the difference in concentration over different intervals SolutionSolutionSolutionSolutionSolution of time and thus determine the average rate by dividing D[R] by Dt (Table 3.1). 63 Chemical Kinetics Reprint 2025-26 Table 3.1: Average rates of hydrolysis of butyl chloride [C4H9CI]t1 / [C4H9CI]t2 / t1/s t2/s rav × 104/mol L–1s–1 × 10 4 mol L–1 mol L–1 = – / ( t 2 − t1 ) C 4 H 9 Cl ]t 2 – [ C 4 H 9 Cl ]t1 {[ } 0.100 0.0905 0 50 1.90 0.0905 0.0820 50 100 1.70 0.0820 0.0741 100 150 1.58 0.0741 0.0671 150 200 1.40 0.0671 0.0549 200 300 1.22 0.0549 0.0439 300 400 1.10 0.0439 0.0335 400 500 1.04 0.0210 0.017 700 800 0.4 It can be seen (Table 3.1) that the average rate falls from 1.90 × 0-4 mol L-1s-1 to 0.4 × 10-4 mol L-1s-1. However, average rate cannot be used to predict the rate of a reaction at a particular instant as it would be constant for the time interval for which it is calculated. So, to express the rate at a particular moment of time we determine the instantaneous rate. It is obtained when we consider the average rate at the smallest time interval say dt ( i.e. when Dt approaches zero). Hence, mathematically for an infinitesimally small dt instantaneous rate is given by −∆ [ R ] ∆ [ P ] rav = = (3.3) ∆t ∆ t  d  R  d P As Dt ® 0 or rinst   d t d t Fig 3.2 Instantaneous rate of hydrolysis of butyl chloride(C4H9Cl) Chemistry 64 Reprint 2025-26 It can be determined graphically by drawing a tangent at time t on either of the curves for concentration of R and P vs time t and calculating its slope (Fig. 3.1). So in problem 3.1, rinst at 600s for example, can be calculated by plotting concentration of butyl chloride as a function of time. A tangent is drawn that touches the curve at t = 600 s (Fig. 3.2). The slope of this tangent gives the instantaneous rate. So, rinst at 600 s = – mol L–1 = 5.12 × 10–5 mol L–1s–1 At t = 250 s rinst = 1.22 × 10–4 mol L–1s–1 t = 350 s rinst = 1.0 × 10–4 mol L–1s–1 t = 450 s rinst = 6.4 ×× 10–5 mol L–1s–1 Now consider a reaction Hg(l) + Cl2 (g) ® HgCl2(s) Where stoichiometric coefficients of the reactants and products are same, then rate of the reaction is given as ∆ [ Hg ] ∆ [ Cl 2 ] ∆ [ HgCl 2 ] Rate of reaction = – = – = ∆t ∆t ∆ t i.e., rate of disappearance of any of the reactants is same as the rate of appearance of the products. But in the following reaction, two moles of HI decompose to produce one mole each of H2 and I2, 2HI(g) ® H2(g) + I2(g) For expressing the rate of such a reaction where stoichiometric coefficients of reactants or products are not equal to one, rate of disappearance of any of the reactants or the rate of appearance of products is divided by their respective stoichiometric coefficients. Since rate of consumption of HI is twice the rate of formation of H2 or I2, to make them equal, the term D[HI] is divided by 2. The rate of this reaction is given by 1 ∆ [ HI ] ∆ [ H 2 ] ∆ [ I 2 ] Rate of reaction = − = = 2 ∆ t ∆ t ∆ t Similarly, for the reaction 5 Br- (aq) + BrO3– (aq) + 6 H+ (aq) ® 3 Br2 (aq) + 3 H2O (l) − − + 1 ∆ [ Br BrO 3 1 ∆ [ H ] 1 ∆ [ Br2 ] 1 ∆ [ H 2 O ] ] ∆  Rate = − = − = − = = 5 ∆ t ∆ t 6 ∆t 3 ∆ t 3 ∆t For a gaseous reaction at constant temperature, concentration is directly proportional to the partial pressure of a species and hence, rate can also be expressed as rate of change in partial pressure of the reactant or the product. 65 Chemical Kinetics Reprint 2025-26 ExampleExampleExampleExampleExample 3.23.23.23.23.2 The decomposition of N2O5 in CCl4 at 318K has been studied by monitoring the concentration of N2O5 in the solution. Initially the concentration of N2O5 is 2.33 mol L–1 and after 184 minutes, it is reduced to 2.08 mol L–1. The reaction takes place according to the equation 2 N2O5 (g) ® 4 NO2 (g) + O2 (g) Calculate the average rate of this reaction in terms of hours, minutes and seconds. What is the rate of production of NO2 during this period? 1  ( 2.08 − 2 .33 ) mol L−1  1 ∆ [ N 2 O5 ] SolutionSolutionSolutionSolutionSolution Average Rate = − = − 184 min 2  ∆t  2   = 6.79 × 10–4 mol L–1/min = (6.79 × 10–4 mol L–1 min–1) × (60 min/1h) = 4.07 × 10–2 mol L–1/h = 6.79 × 10–4 mol L–1 × 1min/60s = 1.13 × 10–5 mol L–1s–1 It may be remembered that 1 ∆ [ NO 2 ] Rate = 4  ∆t  ∆ [ NO 2 ] = 6.79 × 10–4 × 4 mol L–1 min–1 = 2.72 × 10–3 mol L–1min–1 ∆t IntextIntextIntextIntextIntext QuestionsQuestionsQuestionsQuestionsQuestions 3.1 For the reaction R ® P, the concentration of a reactant changes from 0.03M to 0.02M in 25 minutes. Calculate the average rate of reaction using units of time both in minutes and seconds. 3.2 In a reaction, 2A ® Products, the concentration of A decreases from 0.5 mol L–1 to 0.4 mol L–1 in 10 minutes. Calculate the rate during this interval? 3.23.23.23.23.2 FactorsFactorsFactorsFactorsFactors InfluencingInfluencingInfluencingInfluencingInfluencing Rate of reaction depends upon the experimental conditions such RateRateRateRateRate ofofofofof aaaaa ReactionReactionReactionReactionReaction as concentration of reactants (pressure in case of gases), temperature and catalyst. 3.2.1 Dependence The rate of a chemical reaction at a given temperature may depend on of Rate on the concentration of one or more reactants and products. The Concentration representation of rate of reaction in terms of concentration of the reactants is known as rate law. It is also called as rate equation or rate expression. 3.2.2 Rate The results in Table 3.1 clearly show that rate of a reaction decreases with Expression the passage of time as the concentration of reactants decrease. Conversely, and Rate rates generally increase when reactant concentrations increase. So, rate of Constant a reaction depends upon the concentration of reactants. Chemistry 66 Reprint 2025-26 Consider a general reaction aA + bB ® cC + dD where a, b, c and d are the stoichiometric coefficients of reactants and products. The rate expression for this reaction is Rate µ [A] x [B] y (3.4) where exponents x and y may or may not be equal to the stoichiometric coefficients (a and b) of the reactants. Above equation can also be written as Rate = k [A] x [B] y (3.4a) d [ R ] x y − = k [ A ] [ B ] (3.4b) d t This form of equation (3.4 b) is known as differential rate equation, where k is a proportionality constant called rate constant. The equation like (3.4), which relates the rate of a reaction to concentration of reactants is called rate law or rate expression. Thus, rate law is the expression in which reaction rate is given in terms of molar concentration of reactants with each term raised to some power, which may or may not be same as the stoichiometric coefficient of the reacting species in a balanced chemical equation. For example: 2NO(g) + O2(g) ® 2NO2 (g) We can measure the rate of this reaction as a function of initial concentrations either by keeping the concentration of one of the reactants constant and changing the concentration of the other reactant or by changing the concentration of both the reactants. The following results are obtained (Table 3.2). Table 3.2: Initial rate of formation of NO2 Experiment Initial [NO]/ mol L-1 Initial [O2]/ mol L-1 Initial rate of formation of NO2/ mol L-1s-1 1. 0.30 0.30 0.096 2. 0.60 0.30 0.384 3. 0.30 0.60 0.192 4. 0.60 0.60 0.768 It is obvious, after looking at the results, that when the concentration of NO is doubled and that of O2 is kept constant then the initial rate increases by a factor of four from 0.096 to 0.384 mol L–1s–1. This indicates that the rate depends upon the square of the concentration of NO. When concentration of NO is kept constant and concentration of O2 is doubled the rate also gets doubled indicating that rate depends on concentration of O2 to the first power. Hence, the rate equation for this reaction will be Rate = k [NO] 2[O2] 67 Chemical Kinetics Reprint 2025-26 The differential form of this rate expression is given as d [ R ] 2 − = k [ NO ] [ O 2 ] d t Now, we observe that for this reaction in the rate equation derived from the experimental data, the exponents of the concentration terms are the same as their stoichiometric coefficients in the balanced chemical equation. Some other examples are given below: Reaction Experimental rate expression 1. CHCl3 + Cl2 ® CCl4 + HCl Rate = k [CHCl3 ] [Cl2]1/2 2. CH3COOC2H5 + H2O ® CH3COOH + C2H5OH Rate = k [CH3COOC2H5]1 [H2O]0 In these reactions, the exponents of the concentration terms are not the same as their stoichiometric coefficients. Thus, we can say that: Rate law for any reaction cannot be predicted by merely looking at the balanced chemical equation, i.e., theoretically but must be determined experimentally. 3.2.3 Order of a In the rate equation (3.4) Reaction Rate = k [A]x [B]y x and y indicate how sensitive the rate is to the change in concentration of A and B. Sum of these exponents, i.e., x + y in (3.4) gives the overall order of a reaction whereas x and y represent the order with respect to the reactants A and B respectively. Hence, the sum of powers of the concentration of the reactants in the rate law expression is called the order of that chemical reaction. Order of a reaction can be 0, 1, 2, 3 and even a fraction. A zero order reaction means that the rate of reaction is independent of the concentration of reactants. ExampleExampleExampleExampleExample 3.33.33.33.33.3 Calculate the overall order of a reaction which has the rate expression (a) Rate = k [A]1/2 [B]3/2 (b) Rate = k [A]3/2 [B]–1 SolutionSolutionSolutionSolutionSolution (a) Rate = k [A]x [B]y order = x + y So order = 1/2 + 3/2 = 2, i.e., second order (b) order = 3/2 + (–1) = 1/2, i.e., half order. A balanced chemical equation never gives us a true picture of how a reaction takes place since rarely a reaction gets completed in one step. The reactions taking place in one step are called elementary reactions. When a sequence of elementary reactions (called mechanism) gives us the products, the reactions are called complex reactions. Chemistry 68 Reprint 2025-26 These may be consecutive reactions (e.g., oxidation of ethane to CO2 and H2O passes through a series of intermediate steps in which alcohol, aldehyde and acid are formed), reverse reactions and side reactions (e.g., nitration of phenol yields o-nitrophenol and p-nitrophenol). Units of rate constant For a general reaction aA + bB ® cC + dD Rate = k [A]x [B]y Where x + y = n = order of the reaction Rate k = x [A] [B]y concentration 1 = × n ( where [A] = [B]) time ( concentration ) Taking SI units of concentration, mol L –1 and time, s, the units of k for different reaction order are listed in Table 3.3 Table 3.3: Units of rate constant Reaction Order Units of rate constant mol L−1 1 −1 − 1 × 0 = mol L s −1 Zero order reaction 0 s ( mol L ) −1 mol L 1 −1 × = s − 1 1 First order reaction 1 s ( mol L ) − 1 mol L 1 − 1 −1 × = mol L s −1 2 Second order reaction 2 s ( mol L ) Identify the reaction order from each of the following rate constants. ExampleExampleExampleExampleExample 3.43.43.43.43.4 (i) k = 2.3 × 10–5 L mol–1 s–1 (ii) k = 3 × 10–4 s–1 (i) The unit of second order rate constant is L mol–1 s–1, therefore SolutionSolutionSolutionSolutionSolution k = 2.3 × 10–5 L mol–1 s–1 represents a second order reaction. (ii) The unit of a first order rate constant is s–1 therefore k = 3 × 10–4 s–1 represents a first order reaction. 3.2.4 Molecularity Another property of a reaction called molecularity helps in of a understanding its mechanism. The number of reacting species Reaction (atoms, ions or molecules) taking part in an elementary reaction, which must collide simultaneously in order to bring about a chemical reaction is called molecularity of a reaction. The reaction can be unimolecular when one reacting species is involved, for example, decomposition of ammonium nitrite. 69 Chemical Kinetics Reprint 2025-26 NH4NO2 ® N2 + 2H2O Bimolecular reactions involve simultaneous collision between two species, for example, dissociation of hydrogen iodide. 2HI ® H2 + I2 Trimolecular or termolecular reactions involve simultaneous collision between three reacting species, for example, 2NO + O2 ® 2NO2 The probability that more than three molecules can collide and react simultaneously is very small. Hence, reactions with the molecularity three are very rare and slow to proceed. It is, therefore, evident that complex reactions involving more than three molecules in the stoichiometric equation must take place in more than one step. KClO3 + 6FeSO4 + 3H2SO4 ® KCl + 3Fe2(SO4)3 + 3H2O This reaction which apparently seems to be of tenth order is actually a second order reaction. This shows that this reaction takes place in several steps. Which step controls the rate of the overall reaction? The question can be answered if we go through the mechanism of reaction, for example, chances to win the relay race competition by a team depend upon the slowest person in the team. Similarly, the overall rate of the reaction is controlled by the slowest step in a reaction called the rate determining step. Consider the decomposition of hydrogen peroxide which is catalysed by iodide ion in an alkaline medium. -I 2H2O2  2H2O + O2 Alkaline medium The rate equation for this reaction is found to be d  H 2 O 2   Rate  k  H2 O 2 I dt This reaction is first order with respect to both H2O2 and I–. Evidences suggest that this reaction takes place in two steps (1) H2O2 + I– ® H2O + IO– (2) H2O2 + IO– ® H2O + I– + O2 Both the steps are bimolecular elementary reactions. Species IO- is called as an intermediate since it is formed during the course of the reaction but not in the overall balanced equation. The first step, being slow, is the rate determining step. Thus, the rate of formation of intermediate will determine the rate of this reaction. Thus, from the discussion, till now, we conclude the following: (i) Order of a reaction is an experimental quantity. It can be zero and even a fraction but molecularity cannot be zero or a non integer. (ii) Order is applicable to elementary as well as complex reactions whereas molecularity is applicable only for elementary reactions. For complex reaction molecularity has no meaning. Chemistry 70 Reprint 2025-26 (iii) For complex reaction, order is given by the slowest step and molecularity of the slowest step is same as the order of the overall reaction. IntextIntextIntextIntextIntext QuestionsQuestionsQuestionsQuestionsQuestions 3.3 For a reaction, A + B ® Product; the rate law is given by, r = k [ A]1/2 [B]2. What is the order of the reaction? 3.4 The conversion of molecules X to Y follows second order kinetics. If concentration of X is increased to three times how will it affect the rate of formation of Y ? 3.33.33.33.33.3 IntegratedIntegratedIntegratedIntegratedIntegrated We have already noted that the concentration dependence of rate is RateRateRateRateRate called differential rate equation. It is not always convenient to determine the instantaneous rate, as it is measured by determination EquationsEquationsEquationsEquationsEquations of slope of the tangent at point ‘t’ in concentration vs time plot (Fig. 3.1). This makes it difficult to determine the rate law and hence the order of the reaction. In order to avoid this difficulty, we can integrate the differential rate equation to give a relation between directly measured experimental data, i.e., concentrations at different times and rate constant. The integrated rate equations are different for the reactions of different reaction orders. We shall determine these equations only for zero and first order chemical reactions. 3.3.1 Zero Order Zero order reaction means that the rate of the reaction is proportional Reactions to zero power of the concentration of reactants. Consider the reaction, R ® P d  R  Rate =   k  R 0 d t As any quantity raised to power zero is unity d  R  Rate =   k × 1 d t d[R] = – k dt Integrating both sides [R] = – k t + I (3.5) where, I is the constant of integration. At t = 0, the concentration of the reactant R = [R]0, where [R]0 is initial concentration of the reactant. Substituting in equation (3.5) [R]0 = –k × 0 + I [R]0 = I Substituting the value of I in the equation (3.5) [R] = -kt + [R]0 (3.6) 71 Chemical Kinetics Reprint 2025-26 Comparing (3.6) with equation of a straight line, y = mx + c, if we plot [R] against t, we get a straight [R0 ] line (Fig. 3.3) with slope = –k and intercept equal to [R]0. Further simplifying equation (3.6), we get the rateR k = -slope constant, k as of [ R ]0 − [ R ] k = (3.7) t Zero order reactions are relatively uncommon but they occur under special conditions. Some enzyme Concentration catalysed reactions and reactions which occur on metal surfaces are a few examples of zero order 0 Time reactions. The decomposition of gaseous ammonia on a hot platinum surface is a zero order reaction at Fig. 3.3: Variation in the concentration high pressure. vs time plot for a zero order 1130K reaction 2NH 3 ( g ) →Pt catalyst N 2 ( g ) +3H 2 ( g ) Rate = k [NH3]0 = k In this reaction, platinum metal acts as a catalyst. At high pressure, the metal surface gets saturated with gas molecules. So, a further change in reaction conditions is unable to alter the amount of ammonia on the surface of the catalyst making rate of the reaction independent of its concentration. The thermal decomposition of HI on gold surface is another example of zero order reaction. 3.3.2 First Order In this class of reactions, the rate of the reaction is proportional to the Reactions first power of the concentration of the reactant R. For example, R ® P d [ R ] Rate = − = k [ R ] d t d [ R ] or = – kdt [ R ] Integrating this equation, we get ln [R] = – kt + I (3.8) Again, I is the constant of integration and its value can be determined easily. When t = 0, R = [R]0, where [R]0 is the initial concentration of the reactant. Therefore, equation (3.8) can be written as ln [R]0 = –k × 0 + I ln [R]0 = I Substituting the value of I in equation (3.8) ln[R] = –kt + ln[R]0 (3.9) Chemistry 72 Reprint 2025-26 Rearranging this equation [ R ] ln = −kt [ R ]0 1 R 0 or k  ln (3.10) t R At time t1 from equation (3.8) *ln[R]1 = – kt1 + *ln[R]0 (3.11) At time t2 ln[R]2 = – kt2 + ln[R]0 (3.12) where, [R]1 and [R]2 are the concentrations of the reactants at time t1 and t2 respectively. Subtracting (3.12) from (3.11) ln[R]1– ln[R]2 = – kt1 – (–kt2) [ R ]1 ln = k (t 2 − t 1 ) [ R ]2 1 [ R ]1 k = ln (t 2 − t 1 ) [ R ]2 (3.13) Equation (3.9) can also be written as [ R ] ln = −kt [ R ]0 Taking antilog of both sides [R] = [R]0 e–kt (3.14) Comparing equation (3.9) with y = mx + c, if we plot ln [R] against t (Fig. 3.4) we get a straight line with slope = –k and intercept equal to ln [R]0 The first order rate equation (3.10) can also be written in the form 2.303 [ R ]0 k = log (3.15) t [ R ] [ R ]0 kt * log = [ R ] 2.303 If we plot a graph between log [R]0/[R] vs t, (Fig. 3.5), the slope = k/2.303 Hydrogenation of ethene is an example of first order reaction. C2H4(g) + H2 (g) ® C2H6(g) Rate = k [C2H4] All natural and artificial radioactive decay of unstable nuclei take place by first order kinetics. * Refer to Appendix-IV for ln and log (logarithms). 73 Chemical Kinetics Reprint 2025-26 /[R]) 0] Slope = k /2.303 ([R log 0 Time Fig. 3.4: A plot between ln[R] and t Fig. 3.5: Plot of log [R]0/[R] vs time for a for a first order reaction first order reaction 226 88 Ra  24 He  22286 Rn Rate = k [Ra] Decomposition of N2O5 and N2O are some more examples of first order reactions. ExampleExampleExampleExampleExample 3.53.53.53.53.5 The initial concentration of N2O5 in the following first order reaction N2O5(g) ® 2 NO2(g) + 1/2O2 (g) was 1.24 × 10–2 mol L–1 at 318 K. The concentration of N2O5 after 60 minutes was 0.20 × 10–2 mol L–1. Calculate the rate constant of the reaction at 318 K. SolutionSolutionSolutionSolutionSolution For a first order reaction  R 1 k t 2  t 1  log =  R 2 2.303 2.303  R 1 log k =  t 2  t 1   R 2 2.303 1.24  10  2 mol L1 log  2  1 =  60 min  0 min  0.20  10 mol L 2.303  1 = log 6.2 min 60 k = 0.0304 min-1 Let us consider a typical first order gas phase reaction A(g) ® B(g) + C(g) Let pi be the initial pressure of A and pt the total pressure at time ‘t’. Integrated rate equation for such a reaction can be derived as Total pressure pt = pA + pB + pC (pressure units) Chemistry 74 Reprint 2025-26 pA, pB and pC are the partial pressures of A, B and C, respectively. If x atm be the decrease in pressure of A at time t and one mole each of B and C is being formed, the increase in pressure of B and C will also be x atm each. A(g) ® B(g) + C(g) At t = 0 pi atm 0 atm 0 atm At time t (pi–x) atm x atm x atm where, pi is the initial pressure at time t = 0. pt = (pi – x) + x + x = pi + x x = (pt - pi) where, pA = pi – x = pi – (pt – pi) = 2pi – pt  2.303   p i  k =   log  (3.16)  t  p A  2.303 p i log = t  2 p i  p t  The following data were obtained during the first order thermal ExampleExampleExampleExampleExample 3.63.63.63.63.6 decomposition of N2O5 (g) at constant volume: 2N 2 O5 ( g ) → 2N 2 O 4 ( g ) + O 2 ( g ) S.No. Time/s Total Pressure/(atm) 1. 0 0.5 2. 100 0.512 Calculate the rate constant. Let the pressure of N2O5(g) decrease by 2x atm. As two moles of SolutionSolutionSolutionSolutionSolution N2O5 decompose to give two moles of N2O4(g) and one mole of O2 (g), the pressure of N2O4 (g) increases by 2x atm and that of O2 (g) increases by x atm. 2N 2 O5 ( g ) → 2N 2 O 4 ( g ) + O 2 ( g ) Start t = 0 0.5 atm 0 atm 0 atm At time t (0.5 – 2x) atm 2x atm x atm pt = p N 2 O 5  p N 2 O 4  p O 2 = (0.5 – 2x) + 2x + x = 0.5 + x x = tp − 0.5 p N 2 O5 = 0.5 – 2x = 0.5 – 2 (pt – 0.5) = 1.5 – 2pt At t = 100 s; pt = 0.512 atm 75 Chemical Kinetics Reprint 2025-26 p N 2 O 5 = 1.5 – 2 × 0.512 = 0.476 atm Using equation (3.16) 2.303 p i 2.303 0.5 atm k  log  log t p A 100s 0.476 atm 2.303  4 1   0.0216  4.98  10 s 100s 3.3.3 Half-Life of The half-life of a reaction is the time in which the concentration of a a Reaction reactant is reduced to one half of its initial concentration. It is represented as t1/2. For a zero order reaction, rate constant is given by equation 3.7. [ R ]0 − [ R ] k = t 1 [ R ]0 At t = t 1/2 , [ R ] = 2 The rate constant at t1/2 becomes [ R ]0 − 1/2 [ R ]0 k = t 1/2 [ R ]0 t 1/2 = 2k It is clear that t1/2 for a zero order reaction is directly proportional to the initial concentration of the reactants and inversely proportional to the rate constant. For the first order reaction, 2.303 [ R ]0 k = log (3.15) t [ R ] [ R ]0 at t1/2 [ R ] = (3.16) 2 So, the above equation becomes 2.303 [ R ]0 k = log t 1/2 [ R ] /2 2.303 or t1/2  log 2 k 2.303 t 1/2 = × 0.301 k 0.693 t 1/2 = (3.17) k Chemistry 76 Reprint 2025-26 It can be seen that for a first order reaction, half-life period is constant, i.e., it is independent of initial concentration of the reacting species. The half-life of a first order equation is readily calculated from the rate constant and vice versa. For zero order reaction t1/2 µ [R]0. For first order reaction t1/2 is independent of [R]0. A first order reaction is found to have a rate constant, k = 5.5 × 10-14 s-1. ExampleExampleExampleExampleExample 3.73.73.73.73.7 Find the half-life of the reaction. Half-life for a first order reaction is SolutionSolutionSolutionSolutionSolution 0.693 t 1/2 = k 0.693 t 1/2 = –14 –1 = 1.26 × 1013s 5.5×10 s Show that in a first order reaction, time required for completion of 99.9% is 10 times of half-life (t1/2) of the reaction. When reaction is completed 99.9%, [R]n = [R]0 – 0.999[R]0 ExampleExampleExampleExampleExample 3.83.83.83.83.8 2.303  R 0 log k = SolutionSolutionSolutionSolutionSolution t  R  2.303  R 0 2.303 3 log = = log10 t  R 0  0.999  R 0 t t = 6.909/k For half-life of the reaction t1/2 = 0.693/k t 6.909 k =   10 t1/2 k 0.693 Table 3.4 summarises the mathematical features of integrated laws of zero and first order reactions. Table 3.4: Integrated Rate Laws for the Reactions of Zero and First Order Order Reaction Differential Integrated Straight Half- Units of k type rate law rate law line plot life 0 R® P d[R]/dt = -k kt = [R]0-[R] [R] vs t [R]0/2k conc time-1 or mol L–1s–1 1 R® P d[R]/dt = -k[R] [R] = [R]0e-kt ln[R] vs t ln 2/k time-1 or s–1 or kt = ln{[R]0/[R]} 77 Chemical Kinetics Reprint 2025-26 The order of a reaction is sometimes altered by conditions. There are many reactions which obey first order rate law although they are higher order reactions. Consider the hydrolysis of ethyl acetate which is a chemical reaction between ethyl acetate and water. In reality, it is a second order reaction and concentration of both ethyl acetate and water affect the rate of the reaction. But water is taken in large excess for hydrolysis, therefore, concentration of water is not altered much during the reaction. Thus, the rate of reaction is affected by concentration of ethyl acetate only. For example, during the hydrolysis of 0.01 mol of ethyl acetate with 10 mol of water, amounts of the reactants and products at the beginning (t = 0) and completion (t) of the reaction are given as under. H CH3COOH + C2H5OH CH3COOC2H5 + H2O  t = 0 0.01 mol 10 mol 0 mol 0 mol t 0 mol 9.99 mol 0.01 mol 0.01 mol The concentration of water does not get altered much during the course of the reaction. So, the reaction behaves as first order reaction. Such reactions are called pseudo first order reactions. Inversion of cane sugar is another pseudo first order reaction. C12H22O11 + H2O →H+ C6H12O6 + C6H12O6 Cane sugar Glucose Fructose Rate = k [C12H22O11] IntextIntextIntextIntextIntext QuestionsQuestionsQuestionsQuestionsQuestions 3.5 A first order reaction has a rate constant 1.15 × 10-3 s-1. How long will 5 g of this reactant take to reduce to 3 g? 3.6 Time required to decompose SO2Cl2 to half of its initial amount is 60 minutes. If the decomposition is a first order reaction, calculate the rate constant of the reaction. 3.43.43.43.43.4 TemperatureTemperatureTemperatureTemperatureTemperature Most of the chemical reactions are accelerated by increase in temperature. For example, in decomposition of N2O5, the time taken for half of the DependenceDependenceDependenceDependenceDependence ofofofofof original amount of material to decompose is 12 min at 50oC, 5 h at thethethethethe RateRateRateRateRate ofofofofof aaaaa 25oC and 10 days at 0oC. You also know that in a mixture of potassium ReactionReactionReactionReactionReaction permanganate (KMnO4) and oxalic acid (H2C2O4), potassium permanganate gets decolourised faster at a higher temperature than that at a lower temperature. It has been found that for a chemical reaction with rise in temperature by 10°, the rate constant is nearly doubled. The temperature dependence of the rate of a chemical reaction can be accurately explained by Arrhenius equation (3.18). It was first proposed by Dutch chemist, J.H. van’t Hoff but Swedish chemist, Arrhenius provided its physical justification and interpretation. Chemistry 78 Reprint 2025-26 k = A e -Ea /RT (3.18) where A is the Arrhenius factor or the frequency factor. It is also called pre-exponential factor. It is a constant specific to a particular reaction. R is gas constant and Ea is activation energy measured in joules/mole (J mol –1). It can be understood clearly using the following simple reaction H 2 g  I 2 g  2HI g According to Arrhenius, this reaction can take place only when a molecule of hydrogen and a molecule of iodine Intermediate collide to form an unstable intermediate (Fig. 3.6). It exists for a very short time and then breaks up to form two Fig. 3.6: Formation of HI through molecules of hydrogen iodide. the intermediate The energy required to form this intermediate, called activated complex (C), is known as activation energy (Ea). Fig. 3.7 is obtained by plotting potential energy vs reaction coordinate. Reaction coordinate represents the profile of energy change when reactants change into products. Some energy is released when the complex decomposes to form products. So, the final enthalpy of the reaction depends upon the nature of reactants and products. All the molecules in the reacting species do not have the same kinetic Fig. 3.7: Diagram showing plot of potential energy. Since it is difficult to predict the energy vs reaction coordinate behaviour of any one molecule with precision, Ludwig Boltzmann and James Clark Maxwell used statistics to predict the behaviour of large number of molecules. According to them, the distribution of kinetic energy may be described by plotting the fraction of molecules (NE/NT) with a given kinetic energy (E) vs kinetic energy (Fig. 3.8). Here, NE is the number of molecules with energy E and NT is total number of molecules. The peak of the curve corresponds to the most probable kinetic energy, i.e., kinetic energy of maximum fraction of molecules. There are decreasing number Fig. 3.8: Distribution curve showing energies of molecules with energies higher or among gaseous molecules lower than this value. When the 79 Chemical Kinetics Reprint 2025-26 temperature is raised, the maximum of the curve moves to the higher energy value (Fig. 3.9) and the curve broadens out, i.e., spreads to the right such that there is a greater proportion of molecules with much higher energies. The area under the curve must be constant since total probability must be one at all times. We can mark the position of Ea on Fig. 3.9: Distribution curve showing temperature Maxwell Boltzmann distribution curve dependence of rate of a reaction (Fig. 3.9). Increasing the temperature of the substance increases the fraction of molecules, which collide with energies greater than Ea. It is clear from the diagram that in the curve at (t + 10), the area showing the fraction of molecules having energy equal to or greater than activation energy gets doubled leading to doubling the rate of a reaction. In the Arrhenius equation (3.18) the factor e -Ea /RT corresponds to the fraction of molecules that have kinetic energy greater than Ea. Taking natural logarithm of both sides of equation (3.18) E a ln k = – + ln A (3.19) RT The plot of ln k vs 1/T gives a straight line according to the equation (3.19) as shown in Fig. 3.10. Thus, it has been found from Arrhenius equation (3.18) that increasing the temperature or decreasing the activation energy will result in an increase in the rate of the reaction and an exponential increase in the rate constant. E a In Fig. 3.10, slope = – and intercept = ln R A. So we can calculate Ea and A using these values. At temperature T1, equation (3.19) is E a ln k1 = – RT1 + ln A (3.20) At temperature T2, equation (3.19) is E a ln k2 = – RT2 + ln A (3.21) (since A is constant for a given reaction) k1 and k2 are the values of rate constants at temperatures T1 and T2 respectively. Fig. 3.10: A plot between ln k and 1/T Chemistry 80 Reprint 2025-26 Subtracting equation (3.20) from (3.21), we obtain E a E a ln k2 – ln k1 = RT1 – RT2 k 2 E a  1 1  ln = − k1 R  T1 T2  k 2 E a  1 1  log = − (3.22) k1 2.303 R  T1 T2  k 2 E a  T2 − T1  log = k1 2. 303R  T1T2  ExampleExampleExampleExampleExample 3.93.93.93.93.9 The rate constants of a reaction at 500K and 700K are 0.02s–1 and 0.07s–1 respectively. Calculate the values of Ea and A. k 2 E a  T2  T1 SolutionSolutionSolutionSolutionSolution log =   k1 2.303 R  T1T2  0.07  E a   700  500  log =      700  500 0.02  2.303  8.314 JK  1 mol  1  0.544 = Ea × 5.714 × 10-4/19.15 Ea = 0.544 × 19.15/5.714 × 10–4 = 18230.8 J Since k = Ae-Ea/RT × 500 0.02 = Ae-18230.8/8.314 A = 0.02/0.012 = 1.61 ExampleExampleExampleExampleExample 3.103.103.103.103.10 The first order rate constant for the decomposition of ethyl iodide by the reaction C2H5I(g) ® C2H4 (g) + HI(g) at 600K is 1.60 × 10–5 s–1. Its energy of activation is 209 kJ/mol. Calculate the rate constant of the reaction at 700K. SolutionSolutionSolutionSolutionSolution We know that E a  1 1     log k2 – log k1 = 2.303R  T1 T2  81 Chemical Kinetics Reprint 2025-26 E a  1 1  log k2 = log k1     2.303R  T1 T2  209000 J mol L 1  1 1  5 = log 1.60  10     1  1    2.303  8.314 J mol L K  600 K 700K  log k2 = – 4.796 + 2.599 = – 2.197 k2 = 6.36 × 10–3 s–1 3.4.1 Effect of A catalyst is a substance which increases the rate of a reaction without Catalyst itself undergoing any permanent chemical change. For example, MnO2 catalyses the following reaction so as to increase its rate considerably. 2KClO3 MnO2 2 KCl + 3O2 The word catalyst should not be used when the added substance reduces the rate of raction. The substance is then called inhibitor. The action of the catalyst can be explained by intermediate complex theory. According to this theory, a catalyst participates in a chemical reaction by forming temporary bonds with the reactants resulting in an intermediate complex. This has a transitory existence and decomposes to yield products and the catalyst. It is believed that the catalyst provides an alternate pathway or reaction mechanism by reducing the activation energy between reactants and products and hence lowering the potential energy barrier as shown in Fig. 3.11. It is clear from Arrhenius equation (3.18) that lower the value of activation energy faster will be the rate of a reaction. A small amount of the catalyst can catalyse a large amount of reactants. A catalyst does Fig. 3.11: Effect of catalyst on activation energy not alter Gibbs energy, DG of a reaction. It catalyses the spontaneous reactions but does not catalyse non-spontaneous reactions. It is also found that a catalyst does not change the equilibrium constant of a reaction rather, it helps in attaining the equilibrium faster, that is, it catalyses the forward as well as the backward reactions to the same extent so that the equilibrium state remains same but is reached earlier. 3.53.53.53.53.5 CollisionCollisionCollisionCollisionCollision Though Arrhenius equation is applicable under a wide range of TheoryTheoryTheoryTheoryTheory ofofofofof circumstances, collision theory, which was developed by Max Trautz ChemicalChemicalChemicalChemicalChemical and William Lewis in 1916 -18, provides a greater insight into the energetic and mechanistic aspects of reactions. It is based on kinetic ReactionsReactionsReactionsReactionsReactions theory of gases. According to this theory, the reactant molecules are Chemistry 82 Reprint 2025-26 assumed to be hard spheres and reaction is postulated to occur when molecules collide with each other. The number of collisions per second per unit volume of the reaction mixture is known as collision frequency (Z). Another factor which affects the rate of chemical reactions is activation energy (as we have already studied). For a bimolecular elementary reaction A + B ® Products rate of reaction can be expressed as a / RT (3.23) Rate = Z AB e − E where ZAB represents the collision frequency of reactants, A and B and e-Ea /RT represents the fraction of molecules with energies equal to or greater than Ea. Comparing (3.23) with Arrhenius equation, we can say that A is related to collision frequency. Equation (3.23) predicts the value of rate constants fairly accurately for the reactions that involve atomic species or simple molecules but for complex molecules significant deviations are observed. The reason could be that all collisions do not lead to the formation of products. The collisions in which molecules collide with sufficient kinetic energy (called threshold energy*) and proper orientation, so as to facilitate breaking of bonds between reacting species and formation of new bonds to form products are called as effective collisions. For example, formation of methanol from bromoethane depends upon the orientation of reactant molecules as shown in Fig. 3.12. The proper orientation of reactant molecules lead to bond formation whereas improper orientation makes them simply bounce back and no products are formed. Fig. 3.12: Diagram showing molecules having proper and To account for effective collisions, improper orientation another factor P, called the probability or steric factor is introduced. It takes into account the fact that in a collision, molecules must be properly oriented i.e., − E a / RT Rate = PZ AB e Thus, in collision theory activation energy and proper orientation of the molecules together determine the criteria for an effective collision and hence the rate of a chemical reaction. Collision theory also has certain drawbacks as it considers atoms/ molecules to be hard spheres and ignores their structural aspect. You will study details about this theory and more on other theories in your higher classes. * Threshold energy = Activation Energy + energy possessed by reacting species. 83 Chemical Kinetics Reprint 2025-26 IntextIntextIntextIntextIntext QuestionsQuestionsQuestionsQuestionsQuestions 3.7 What will be the effect of temperature on rate constant ? 3.8 The rate of the chemical reaction doubles for an increase of 10K in absolute temperature from 298K. Calculate Ea. 3.9 The activation energy for the reaction 2 HI(g) ® H2 + I2 (g) is 209.5 kJ mol–1 at 581K.Calculate the fraction of molecules of reactants having energy equal to or greater than activation energy? SummarySummarySummarySummarySummary Chemical kinetics is the study of chemical reactions with respect to reaction rates, effect of various variables, rearrangement of atoms and formation of intermediates. The rate of a reaction is concerned with decrease in concentration of reactants or increase in the concentration of products per unit time. It can be expressed as instantaneous rate at a particular instant of time and average rate over a large interval of time. A number of factors such as temperature, concentration of reactants, catalyst, affect the rate of a reaction. Mathematical representation of rate of a reaction is given by rate law. It has to be determined experimentally and cannot be predicted. Order of a reaction with respect to a reactant is the power of its concentration which appears in the rate law equation. The order of a reaction is the sum of all such powers of concentration of terms for different reactants. Rate constant is the proportionality factor in the rate law. Rate constant and order of a reaction can be determined from rate law or its integrated rate equation. Molecularity is defined only for an elementary reaction. Its values are limited from 1 to 3 whereas order can be 0, 1, 2, 3 or even a fraction. Molecularity and order of an elementary reaction are same. Temperature dependence of rate constants is described by Arrhenius equation (k = Ae–Ea/RT). Ea corresponds to the activation energy and is given by the energy difference between activated complex and the reactant molecules, and A (Arrhenius factor or pre-exponential factor) corresponds to the collision frequency. The equation clearly shows that increase of temperature or lowering of Ea will lead to an increase in the rate of reaction and presence of a catalyst lowers the activation energy by providing an alternate path for the reaction. According to collision theory, another factor P called steric factor which refers to the orientation of molecules which collide, is important and contributes to effective collisions, thus, modifying the Arrhenius equation to k  P Z AB e  E a / RT . Chemistry 84 Reprint 2025-26 ExercisesExercisesExercisesExercisesExercises 3.1 From the rate expression for the following reactions, determine their order of reaction and the dimensions of the rate constants. (i) 3NO(g) ® N2O (g) Rate = k[NO]2 (ii) H2O2 (aq) + 3I– (aq) + 2H+ ® 2H2O (l) + 3I Rate = k[H2O2][I-] (iii) CH3CHO (g) ® CH4 (g) + CO(g) Rate = k [CH3CHO]3/2 (iv) C2H5Cl (g) ® C2H4 (g) + HCl (g) Rate = k [C2H5Cl] 3.2 For the reaction: 2A + B ® A2B the rate = k[A][B]2 with k = 2.0 × 10–6 mol–2 L2 s–1. Calculate the initial rate of the reaction when [A] = 0.1 mol L–1, [B] = 0.2 mol L–1. Calculate the rate of reaction after [A] is reduced to 0.06 mol L–1. 3.3 The decomposition of NH3 on platinum surface is zero order reaction. What are the rates of production of N2 and H2 if k = 2.5 × 10–4 mol–1 L s–1? 3.4 The decomposition of dimethyl ether leads to the formation of CH4, H2 and CO and the reaction rate is given by Rate = k [CH3OCH3]3/2 The rate of reaction is followed by increase in pressure in a closed vessel, so the rate can also be expressed in terms of the partial pressure of dimethyl ether, i.e., 3/2 Rate = k ( p CH 3 OCH 3 ) If the pressure is measured in bar and time in minutes, then what are the units of rate and rate constants? 3.5 Mention the factors that affect the rate of a chemical reaction. 3.6 A reaction is second order with respect to a reactant. How is the rate of reaction affected if the concentration of the reactant is (i) doubled (ii) reduced to half ? 3.7 What is the effect of temperature on the rate constant of a reaction? How can this effect of temperature on rate constant be represented quantitatively? 3.8 In a pseudo first order reaction in water, the following results were obtained: t/s 0 30 60 90 [A]/ mol L–1 0.55 0.31 0.17 0.085 Calculate the average rate of reaction between the time interval 30 to 60 seconds.

2.2 Given the standard electrode potentials, K+/K = –2.93V, Ag+/Ag = 0.80V, Hg2+/Hg = 0.79V Mg2+/Mg = –2.37 V, Cr3+/Cr = – 0.74V Arrange these metals in their increasing order of reducing power.

4.4 A horizontal overhead power line carries a current of 90 A in east to west direction. What is the magnitude and direction of the magnetic field due to the current 1.5 m below the line?

4.10 Two moving coil meters, M1 and M2 have the following particulars: R1 = 10 Ω, N1 = 30, A1 = 3.6 × 10–3 m2, B1 = 0.25 T R2 = 14 Ω, N2 = 42, A2 = 1.8 × 10–3 m2, B2 = 0.50 T (The spring constants are identical for the two meters). Determine the ratio of (a) current sensitivity and (b) voltage sensitivity of M2 and M1.

4.16 Describe the preparation of potassium permanganate. How does the acidified permanganate solution react with (i) iron(II) ions (ii) SO2 and (iii) oxalic acid? Write the ionic equations for the reactions. 4.17 For M2+/M and M3+/M 2+ systems the E o values for some metals are as follows: Cr2+/Cr -0.9V Cr3/Cr2+ -0.4 V Mn 2+/Mn -1.2V Mn3+/Mn2+ +1.5 V Fe2+/Fe -0.4V Fe3+/Fe2+ +0.8 V Use this data to comment upon: (i) the stability of Fe3+ in acid solution as compared to that of Cr3+ or Mn3+ and (ii) the ease with which iron can be oxidised as compared to a similar process for either chromium or manganese metal. 4.18 Predict which of the following will be coloured in aqueous solution? Ti 3+, V3+, Cu+, Sc3+, Mn 2+, Fe3+ and Co 2+. Give reasons for each. 4.19 Compare the stability of +2 oxidation state for the elements of the first transition series. 4.20 Compare the chemistry of actinoids with that of the lanthanoids with special reference to: (i) electronic configuration (iii) oxidation state (ii) atomic and ionic sizes and (iv) chemical reactivity. 4.21 How would you account for the following: (i) Of the d4 species, Cr2+ is strongly reducing while manganese(III) is strongly oxidising. (ii) Cobalt(II) is stable in aqueous solution but in the presence of complexing reagents it is easily oxidised. (iii) The d1 configuration is very unstable in ions. 4.22 What is meant by ‘disproportionation’? Give two examples of disproportionation reaction in aqueous solution. 4.23 Which metal in the first series of transition metals exhibits +1 oxidation state most frequently and why? 4.24 Calculate the number of unpaired electrons in the following gaseous ions: Mn3+, Cr3+, V3+ and Ti3+. Which one of these is the most stable in aqueous solution? 4.25 Give examples and suggest reasons for the following features of the transition metal chemistry: (i) The lowest oxide of transition metal is basic, the highest is amphoteric/acidic. (ii) A transition metal exhibits highest oxidation state in oxides and fluorides. (iii) The highest oxidation state is exhibited in oxoanions of a metal. 4.26 Indicate the steps in the preparation of: (i) K2Cr2O7 from chromite ore. (ii) KMnO4 from pyrolusite ore. 4.27 What are alloys? Name an important alloy which contains some of the lanthanoid metals. Mention its uses. 4.28 What are inner transition elements? Decide which of the following atomic numbers are the atomic numbers of the inner transition elements : 29, 59, 74, 95, 102, 104. 4.29 The chemistry of the actinoid elements is not so smooth as that of the lanthanoids. Justify this statement by giving some examples from the oxidation state of these elements. 4.30 Which is the last element in the series of the actinoids? Write the electronic configuration of this element. Comment on the possible oxidation state of this element. Chemistry 116 Reprint 2025-26 4.31 Use Hund’s rule to derive the electronic configuration of Ce3+ ion, and calculate its magnetic moment on the basis of ‘spin-only’ formula. 4.32 Name the members of the lanthanoid series which exhibit +4 oxidation states and those which exhibit +2 oxidation states. Try to correlate this type of behaviour with the electronic configurations of these elements. 4.33 Compare the chemistry of the actinoids with that of lanthanoids with reference to: (i) electronic configuration (ii) oxidation states and (iii) chemical reactivity. 4.34 Write the electronic configurations of the elements with the atomic numbers 61, 91, 101, and 109. 4.35 Compare the general characteristics of the first series of the transition metals with those of the second and third series metals in the respective vertical columns. Give special emphasis on the following points: (i) electronic configurations (ii) oxidation states (iii) ionisation enthalpies and (iv) atomic sizes. 4.36 Write down the number of 3d electrons in each of the following ions: Ti 2+, V 2+, Cr3+, Mn 2+, Fe2+, Fe3+, Co2+, Ni2+ and Cu2+. Indicate how would you expect the five 3d orbitals to be occupied for these hydrated ions (octahedral). 4.37 Comment on the statement that elements of the first transition series possess many properties different from those of heavier transition elements. 4.38 What can be inferred from the magnetic moment values of the following complex species ? Example Magnetic Moment (BM) K4[Mn(CN)6) 2.2 [Fe(H2O)6]2+ 5.3 K2[MnCl4] 5.9 Answers to Some Intext Questions 4.1 Silver (Z = 47) can exhibit +2 oxidation state wherein it will have incompletely filled d-orbitals (4d), hence a transition element. 4.2 In the formation of metallic bonds, no eletrons from 3d-orbitals are involved in case of zinc, while in all other metals of the 3d series, electrons from the d-orbitals are always involved in the formation of metallic bonds. 4.3 Manganese (Z = 25), as its atom has the maximum number of unpaired electrons. 4.5 Irregular variation of ionisation enthalpies is mainly attributed to varying degree of stability of different 3d-configurations (e.g., d 0, d 5, d 10 are exceptionally stable). 4.6 Because of small size and high electronegativity oxygen or fluorine can oxidise the metal to its highest oxidation state. 4.7 Cr 2+ is stronger reducing agent than Fe 2+ Reason: d 4  d 3 occurs in case of Cr 2+ to Cr 3+ But d 6  d 5 occurs in case of Fe2+ to Fe 3+ In a medium (like water) d 3 is more stable as compared to d 5 (see CFSE) 4.9 Cu + in aqueous solution underoes disproportionation, i.e., 2Cu +(aq) ® Cu 2+(aq) + Cu(s) The E0 value for this is favourable.

6.7 Relationship between to such a small degree that only a very Equilibrium Constant K, minute quantity of product is formed. Reaction Quotient Q and Gibbs Energy G Problem 6.10 The value of Kc for a reaction does not depend The value of ∆G  for the phosphorylation of on the rate of the reaction. However, as you glucose in glycolysis is 13.8 kJ/mol. Find have studied in Unit 5, it is directly related the value of Kc at 298 K. to the thermodynamics of the reaction and Solutionin particular, to the change in Gibbs energy, ∆G. If, ∆G  = 13.8 kJ/mol = 13.8 × 103J/mol • ∆G is negative, then the reaction is Also, ∆G  = – RT lnKc spontaneous and proceeds in the forward Hence, ln Kc = –13.8 × 103J/mol direction. (8.314 J mol–1K–1 × 298 K) • ∆G is positive, then reaction is considered ln Kc = – 5.569 non-spontaneous. Instead, as reverse reaction would have a negative ∆G, the Kc = e–5.569 products of the forward reaction shall be Kc = 3.81 × 10–3 converted to the reactants. Problem 6.11• ∆G is 0, reaction has achieved equilibrium; Hydrolysis of sucrose gives, at this point, there is no longer any free energy left to drive the reaction. Sucrose + H2O Glucose + Fructose A mathematical expression of this Equilibrium constant Kc for the reaction is thermodynamic view of equilibrium can be 2 ×1013 at 300K. Calculate ∆G  at 300K. described by the following equation: Solution ∆G = ∆G + RT lnQ (6.21) ∆G  = – RT lnKcwhere, G is standard Gibbs energy. ∆G  = – 8.314J mol–1K–1× At equilibrium, when ∆G = 0 and Q = Kc, 300K × ln(2×1013) the equation (6.21) becomes, ∆G  = – 7.64 ×104 J mol–1 ∆G = ∆G + RT ln K = 0 6.8 FACTORS AFFECTING EQUILIBRIA ∆G = – RT lnK (6.22) One of the principal goals of chemical lnK = – ∆G / RT synthesis is to maximise the conversion of the Reprint 2025-26 EQUILIBRIUM 185 reactants to products while minimising the “When the concentration of any of the expenditure of energy. This implies maximum reactants or products in a reaction at yield of products at mild temperature and equilibrium is changed, the composition pressure conditions. If it does not happen, of the equilibrium mixture changes so as then the experimental conditions need to be to minimize the effect of concentration adjusted. For example, in the Haber process changes”. for the synthesis of ammonia from N2 and Let us take the reaction, H2, the choice of experimental conditions is of real economic importance. Annual world H2(g) + I2(g) 2HI(g) production of ammonia is about hundred If H2 is added to the reaction mixture million tones, primarily for use as fertilisers. at equilibrium, then the equilibrium of the reaction is disturbed. In order to restore it, Equilibrium constant, Kc is independent the reaction proceeds in a direction whereinof initial concentrations. But if a system at equilibrium is subjected to a change in the H2 is consumed, i.e., more of H2 and I2 react to form HI and finally the equilibrium shiftsconcentration of one or more of the reacting in right (forward) direction (Fig.6.8). This is insubstances, then the system is no longer at accordance with the Le Chatelier’s principleequilibrium; and net reaction takes place in which implies that in case of addition of asome direction until the system returns to reactant/product, a new equilibrium willequilibrium once again. Similarly, a change be set up in which the concentration of thein temperature or pressure of the system may reactant/product should be less than what italso alter the equilibrium. In order to decide was after the addition but more than what itwhat course the reaction adopts and make was in the original mixture.a qualitative prediction about the effect of a change in conditions on equilibrium we use Le Chatelier’s principle. It states that a change in any of the factors that determine the equilibrium conditions of a system will cause the system to change in such a manner so as to reduce or to counteract the effect of the change. This is applicable to all physical and chemical equilibria. We shall now be discussing factors which can influence the equilibrium. 6.8.1 Effect of Concentration Change In general, when equilibrium is disturbed by the addition/removal of any reactant/ products, Le Chatelier’s principle predicts that: • The concentration stress of an added reactant/product is relieved by net Fig. 6.8 Effect of addition of H2 on change reaction in the direction that consumes of concentration for the reactants the added substance. and products in the reaction, • The concentration stress of a removed H2(g) + I2 (g) 2HI(g) reactant/product is relieved by net reaction in the direction that replenishes The same point can be explained in terms the removed substance. of the reaction quotient, Qc, or in other words, Qc = [HI]2/ [H2][I2] Reprint 2025-26 186 chemistry Addition of hydrogen at equilibrium concentration of [Fe(SCN)]2+ decreases, the results in value of Qc being less than Kc . Thus, intensity of red colour decreases. in order to attain equilibrium again reaction Addition of aq. HgCl2 also decreases redmoves in the forward direction. Similarly, colour because Hg2+ reacts with SCN– ions to we can say that removal of a product also form stable complex ion [Hg(SCN)4]2–. Removalboosts the forward reaction and increases of free SCN– (aq) shifts the equilibrium the concentration of the products and this in equation (6.24) from right to left to has great commercial application in cases replenish SCN– ions. Addition of potassium of reactions, where the product is a gas or a thiocyanate on the other hand increases the volatile substance. In case of manufacture of colour intensity of the solution as it shift the ammonia, ammonia is liquified and removed equilibrium to right. from the reaction mixture so that reaction keeps moving in forward direction. Similarly, 6.8.2 Effect of Pressure Change in the large scale production of CaO (used A pressure change obtained by changing the as important building material) from CaCO3, volume can affect the yield of products in constant removal of CO2 from the kiln drives case of a gaseous reaction where the total the reaction to completion. It should be number of moles of gaseous reactants and remembered that continuous removal of a total number of moles of gaseous products are product maintains Qc at a value less than Kc different. In applying Le Chatelier’s principle and reaction continues to move in the forward to a heterogeneous equilibrium the effect direction. of pressure changes on solids and liquids can be ignored because the volume (and Effect of Concentration – An experiment concentration) of a solution/liquid is nearly This can be demonstrated by the following independent of pressure. reaction: Consider the reaction, Fe3+(aq)+ SCN–(aq) [Fe(SCN)]2+(aq) (6.24) CO(g) + 3H2(g) CH4(g) + H2O(g)yellow colourless deep red Here, 4 mol of gaseous reactants (CO + 3H2) become 2 mol of gaseous products (CH4 + H2O). Suppose equilibrium mixture (for above (6.25) reaction) kept in a cylinder fitted with a piston at constant temperature is compressed to A reddish colour appears on adding two one half of its original volume. Then, totaldrops of 0.002 M potassium thiocynate solution pressure will be doubled (according to to 1 mL of 0.2 M iron(III) nitrate solution due pV = constant). The partial pressure and to the formation of [Fe(SCN)]2+. The intensity therefore, concentration of reactants and of the red colour becomes constant on products have changed and the mixture is no attaining equilibrium. This equilibrium can be longer at equilibrium. The direction in which shifted in either forward or reverse directions the reaction goes to re-establish equilibrium depending on our choice of adding a reactant can be predicted by applying the Le Chatelier’s or a product. The equilibrium can be shifted principle. Since pressure has doubled, in the opposite direction by adding reagents the equilibrium now shifts in the forward that remove Fe3+ or SCN– ions. For example, direction, a direction in which the number oxalic acid (H2C2O4), reacts with Fe3+ ions of moles of the gas or pressure decreases (we to form the stable complex ion [Fe(C2O4)3]3–, know pressure is proportional to moles of the thus decreasing the concentration of free gas). This can also be understood by using Fe3+(aq). In accordance with the Le Chatelier’s reaction quotient, Qc. Let [CO], [H2], [CH4] principle, the concentration stress of removed and [H2O] be the molar concentrations at Fe3+ is relieved by dissociation of [Fe(SCN)]2+ equilibrium for methanation reaction. When to replenish the Fe3+ ions. Because the volume of the reaction mixture is halved, the Reprint 2025-26 EQUILIBRIUM 187 partial pressure and the concentration are Production of ammonia according to the doubled. We obtain the reaction quotient by reaction, replacing each equilibrium concentration by N2(g) + 3H2(g) 2NH3(g);double its value. ∆H= – 92.38 kJ mol–1  CH 4 ( g )  H 2 O ( g ) is an exothermic process. According to Qc = 3  CO ( g )  H 2 ( g ) Le Chatelier’s principle, raising the temperature shifts the equilibrium to left As Qc < Kc , the reaction proceeds in the and decreases the equilibrium concentration forward direction. of ammonia. In other words, low temperature is favourable for high yield of ammonia, but In reaction C(s) + CO2(g) 2CO(g), when practically very low temperatures slow downpressure is increased, the reaction goes in the the reaction and thus a catalyst is used.reverse direction because the number of moles of gas increases in the forward direction. Effect of Temperature – An experiment Effect of temperature on equilibrium can6.8.3 Effect of Inert Gas Addition be demonstrated by taking NO2 gas (brown If the volume is kept constant and an inert gas in colour) which dimerises into N2O4 gas such as argon is added which does not take (colourless). part in the reaction, the equilibrium remains 2NO2(g) N2O4(g); ∆H = –57.2 kJ mol–1undisturbed. It is because the addition of an inert gas at constant volume does not NO2 gas prepared by addition of Cu change the partial pressures or the molar turnings to conc. HNO3 is collected in two 5 mL test tubes (ensuring same intensityconcentrations of the substance involved in of colour of gas in each tube) and stopperthe reaction. The reaction quotient changes sealed with araldite. Three 250 mL beakersonly if the added gas is a reactant or product 1, 2 and 3 containing freesing mixture, waterinvolved in the reaction. at room temperature and hot water (363K), 6.8.4 Effect of Temperature Change respectively, are taken (Fig. 6.9). Both the test tubes are placed in beaker 2 for 8-10 minutes.Whenever an equilibrium is disturbed by After this one is placed in beaker 1 and thea change in the concentration, pressure or other in beaker 3. The effect of temperaturevolume, the composition of the equilibrium on direction of reaction is depicted very wellmixture changes because the reaction in this experiment. At low temperatures inquotient, Qc no longer equals the equilibrium beaker 1, the forward reaction of formation ofconstant, Kc. However, when a change in temperature occurs, the value of equilibrium N2O4 is preferred, as reaction is exothermic, and thus, intensity of brown colour dueconstant, Kc is changed. to NO2 decreases. While in beaker 3, high In general, the temperature dependence temperature favours the reverse reaction of of the equilibrium constant depends on the sign of ∆H for the reaction. • The equilibrium constant for an exothermic reaction (negative ∆H) decreases as the temperature increases. • The equilibrium constant for an endothermic reaction (positive ∆H) increases as the temperature increases. Temperature changes affect the Fig. 6.9 Effect of temperature on equilibrium for the reaction, 2NO2 (g) N2O4 (g)equilibrium constant and rates of reactions. Reprint 2025-26 188 chemistry formation of NO2 and thus, the brown colour Similarly, in manufacture of sulphuric intensifies. acid by contact process, Effect of temperature can also be seen in 2SO2(g) + O2(g) 2SO3(g); Kc = 1.7 × 1026 an endothermic reaction, though the value of K is suggestive of reaction [Co(H2O)6]3+(aq) + 4Cl–(aq) [CoCl4]2–(aq) + going to completion, but practically the 6H2O(l) oxidation of SO2 to SO3 is very slow. Thus, pink colourless blue platinum or divanadium penta-oxide (V2O5) is used as catalyst to increase the rate of the At room temperature, the equilibrium reaction.mixture is blue due to [CoCl4]2–. When cooled Note: If a reaction has an exceedingly smallin a freesing mixture, the colour of the mixture K, a catalyst would be of little help.turns pink due to [Co(H2O)6]3+. 6.9 IONIC EQUILIBRIUM IN SOLUTION6.8.5 Effect of a Catalyst Under the effect of change of concentrationA catalyst increases the rate of the chemical on the direction of equilibrium, you havereaction by making available a new low energy pathway for the conversion of reactants to incidently come across with the following products. It increases the rate of forward equilibrium which involves ions: and reverse reactions that pass through the Fe3+(aq) + SCN–(aq) [Fe(SCN)]2+(aq) same transition state and does not affect There are numerous equilibria that involve equilibrium. Catalyst lowers the activation ions only. In the following sections we will energy for the forward and reverse reactions study the equilibria involving ions. It is well by exactly the same amount. Catalyst does known that the aqueous solution of sugar not affect the equilibrium composition of does not conduct electricity. However, when a reaction mixture. It does not appear in common salt (sodium chloride) is added the balanced chemical equation or in the to water it conducts electricity. Also, the equilibrium constant expression. conductance of electricity increases with an Let us consider the formation of NH3 increase in concentration of common salt. from dinitrogen and dihydrogen which is Michael Faraday classified the substances highly exothermic reaction and proceeds into two categories based on their ability with decrease in total number of moles to conduct electricity. One category of formed as compared to the reactants. substances conduct electricity in their Equilibrium constant decreases with increase aqueous solutions and are called electrolytes in temperature. At low temperature rate while the other do not and are thus, referred to decreases and it takes long time to reach at as non-electrolytes. Faraday further classified equilibrium, whereas high temperatures give electrolytes into strong and weak electrolytes. satisfactory rates but poor yields. Strong electrolytes on dissolution in water German chemist, Fritz Haber discovered are ionized almost completely, while the weak that a catalyst consisting of iron catalyse electrolytes are only partially dissociated. the reaction to occur at a satisfactory rate For example, an aqueous solution of at temperatures, where the equilibrium sodium chloride is comprised entirely of concentration of NH3 is reasonably favourable. sodium ions and chloride ions, while that Since the number of moles formed in the of acetic acid mainly contains unionized reaction is less than those of reactants, the acetic acid molecules and only some acetate yield of NH3 can be improved by increasing ions and hydronium ions. This is because the pressure. there is almost 100% ionization in case Optimum conditions of temperature of sodium chloride as compared to less and pressure for the synthesis of NH3 using than 5% ionization of acetic acid which is catalyst are around 500°C and 200 atm. a weak electrolyte. It should be noted Reprint 2025-26 EQUILIBRIUM 189 that in weak electrolytes, equilibrium is exists in solid state as a cluster of positively established between ions and the unionized charged sodium ions and negatively charged molecules. This type of equilibrium involving chloride ions which are held together due to ions in aqueous solution is called ionic electrostatic interactions between oppositely equilibrium. Acids, bases and salts come charged species (Fig.6.10). The electrostatic under the category of electrolytes and may act forces between two charges are inversely as either strong or weak electrolytes. proportional to dielectric constant of the medium. Water, a universal solvent, possesses

6.6 APPLICATIONS OF EQUILIBRIUM in the denominator). This implies that a high value of K is suggestive of a high concentration CONSTANTS of products and vice-versa.Before considering the applications of We can make the following generalisationsequilibrium constants, let us summarise the concerning the composition of equilibriumimportant features of equilibrium constants mixtures:as follows: 1. Expression for equilibrium constant is • If Kc > 103, products predominate over applicable only when concentrations of reactants, i.e., if Kc is very large, the the reactants and products have attained reaction proceeds nearly to completion. constant value at equilibrium state. Consider the following examples: 2. The value of equilibrium constant is (a) The reaction of H2 with O2 at 500 K independent of initial concentrations of has a very large equilibrium constant, the reactants and products. Kc = 2.4 × 1047. 3. Equilibrium constant is temperature (b) H2(g) + Cl2(g) 2HCl(g) at 300K has dependent having one unique value for Kc = 4.0 × 1031. a particular reaction represented by a (c) H2(g) + Br2(g) 2HBr (g) at 300 K, balanced equation at a given temperature. Kc = 5.4 × 1018 4. The equilibrium constant for the reverse • If Kc < 10–3, reactants predominate over reaction is equal to the inverse of the products, i.e., if Kc is very small, the equilibrium constant for the forward reaction proceeds rarely. Consider the reaction. following examples: Reprint 2025-26 182 chemistry (a) The decomposition of H2O into H2 and If Qc = Kc, the reaction mixture is already O2 at 500 K has a very small equilibrium at equilibrium. constant, Kc = 4.1 × 10–48 Consider the gaseous reaction of H2 (b) N2(g) + O2(g) 2NO(g), with I2, at 298 K has Kc = 4.8 ×10–31. H2(g) + I2(g) 2HI(g); Kc = 57.0 at 700 K. • If Kc is in the range of 10 – 3 to 103, Suppose we have molar concentrations appreciable concentrations of both [H2]t=0.10M, [I2]t = 0.20 M and [HI]t = 0.40 M. reactants and products are present. (the subscript t on the concentration symbols Consider the following examples: means that the concentrations were measured at some arbitrary time t, not necessarily at(a) For reaction of H2 with I2 to give HI, equilibrium). Kc = 57.0 at 700K. Thus, the reaction quotient, Qc at this(b) Also, gas phase decomposition of N2O4 stage of the reaction is given by, to NO2 is another reaction with a value 2 –3 Qc = [HI]t / [H2]t [I2]t = (0.40)2/ (0.10)×(0.20) of Kc = 4.64 × 10 at 25°C which is neither too small nor too large. Hence, = 8.0 equilibrium mixtures contain appreciable Now, in this case, Qc (8.0) does not equal concentrations of both N2O4 and NO2. Kc (57.0), so the mixture of H2(g), I2(g) and HI(g) These generarlisations are illustrated in is not at equilibrium; that is, more H2(g) and Fig. 6.6 I2(g) will react to form more HI(g) and their concentrations will decrease till Qc = Kc. The reaction quotient, Qc is useful in predicting the direction of reaction by comparing the values of Qc and Kc. Thus, we can make the following generalisations concerning the direction of the reaction (Fig. 6.7) :Fig.6.6 Dependence of extent of reaction on Kc 6.6.2 Predicting the Direction of the Reaction The equilibrium constant helps in predicting the direction in which a given reaction will proceed at any stage. For this purpose, we calculate the reaction quotient Q. The reaction quotient, Q (Qc with molar Fig. 6.7 Predicting the direction of the reactionconcentrations and QP with partial pressures) is defined in the same way as the equilibrium • If Qc < Kc, net reaction goes from left to constant Kc except that the concentrations right in Qc are not necessarily equilibrium values. • If Qc > Kc, net reaction goes from right to For a general reaction: left. a A + b B c C + d D (6.19) • If Qc = Kc, no net reaction occurs. Qc = [C]c[D]d / [A]a[B]b (6.20) Problem 6.7 Then, The value of Kc for the reaction If Qc > Kc, the reaction will proceed in the 2A B + C is 2 × 10–3. At a given time, direction of reactants (reverse reaction). the composition of reaction mixture is [A] = [B] = [C] = 3 × 10–4 M. In which direction If Qc < Kc, the reaction will proceed in the the reaction will proceed?direction of the products (forward reaction). Reprint 2025-26 EQUILIBRIUM 183 Solution The total pressure at equilbrium was For the reaction the reaction quotient Qc is found to be 9.15 bar. Calculate Kc, Kp and given by, partial pressure at equilibrium. Qc = [B][C]/ [A]2 Solution as [A] = [B] = [C] = 3 × 10–4M Qc = (3 ×10–4)(3 × 10–4) / (3 ×10–4)2 = 1 We know pV = nRT as Qc > Kc so the reaction will proceed in the Total volume (V ) = 1 L reverse direction. Molecular mass of N2O4 = 92 g 6.6.3 Calculating Equilibrium Number of moles = 13.8g/92 g = 0.15 Concentrations of the gas (n) In case of a problem in which we know the Gas constant (R) = 0.083 bar L mol–1K–1 initial concentrations but do not know any of Temperature (T ) = 400 K the equilibrium concentrations, the following pV = nRTthree steps shall be followed: Step 1. Write the balanced equation for the p × 1L = 0.15 mol × 0.083 bar L mol–1K–1 × 400 Kreaction. Step 2. Under the balanced equation, make p = 4.98 bar a table that lists for each substance involved N2O4 2NO2 in the reaction: Initial pressure: 4.98 bar 0 (a) the initial concentration, At equilibrium: (4.98 – x) bar 2x bar (b) the change in concentration on going to Hence, equilibrium, and ptotal at equilibrium = pN2O4 + pNO2(c) the equilibrium concentration. 9.15 = (4.98 – x) + 2x In constructing the table, define x as the 9.15 = 4.98 + xconcentration (mol/L) of one of the substances that reacts on going to equilibrium, then use x = 9.15 – 4.98 = 4.17 bar the stoichiometry of the reaction to determine Partial pressures at equilibrium are, the concentrations of the other substances in terms of x. pN2O4 = 4.98 – 4.17 = 0.81bar Step 3. Substitute the equilibrium pNO2 = 2x = 22 × 4.17 = 8.34 bar concentrations into the equilibrium equation K p = p N 2O 4  p NO 2 / for the reaction and solve for x. If you are = (8.34)2/0.81 = 85.87to solve a quadratic equation choose the mathematical solution that makes chemical Kp = Kc(RT)∆n sense. 85.87 = Kc(0.083 × 400)1 Step 4. Calculate the equilibrium Kc = 2.586 = 2.6 concentrations from the calculated value of x. Problem 6.9Step 5. Check your results by substituting them into the equilibrium equation. 3.00 mol of PCl5 kept in 1L closed reaction vessel was allowed to attain equilibrium at 380K. Calculate composition of the Problem 6.8 mixture at equilibrium. Kc= 1.80 13.8g of N2O4 was placed in a 1L reaction Solution vessel at 400K and allowed to attain PCl5 PCl3 + Cl2 equilibrium Initial N2O4 (g) 2NO2 (g) concentration: 3.0 0 0 Reprint 2025-26 184 chemistry Taking antilog of both sides, we get, Let x mol per litre of PCl5 be dissociated, K = e–∆G/RT (6.23) At equilibrium: (3-x) x x Hence, using the equation (6.23), the reaction spontaneity can be interpreted in Kc = [PCl3][Cl2]/[PCl5] terms of the value of ∆G . 1.8 = x2/ (3 – x) • If ∆G  < 0, then –∆G /RT is positive, x2 + 1.8x – 5.4 = 0 and e –∆DG /RT>1, making K >1, which x = [–1.8 ± √(1.8)2 – 4(–5.4)]/2 implies a spontaneous reaction or the x = [–1.8 ± √3.24 + 21.6]/2 reaction which proceeds in the forward direction to such an extent that the x = [–1.8 ± 4.98]/2 products are present predominantly. x = [–1.8 + 4.98]/2 = 1.59 • If ∆G  > 0, then –∆G /RT is negative, and [PCl5] = 3.0 – x = 3 –1.59 = 1.41 M e –∆G </RT 1, that is , K < 1, which implies [PCl3] = [Cl2] = x = 1.59 M a non-spontaneous reaction or a reaction which proceeds in the forward direction

8.2 A parallel plate capacitor (Fig. 8.6) made of circular plates each of radius R = 6.0 cm has a capacitance C = 100 pF. The capacitor is connected to 213 a 230 V ac supply with a (angular) frequency of 300 rad s–1. Reprint 2025-26 Physics (a) What is the rms value of the conduction current? (b) Is the conduction current equal to the displacement current? (c) Determine the amplitude of B at a point 3.0 cm from the axis between the plates. FIGURE 8.6 8.3 What physical quantity is the same for X-rays of wavelength 10–10 m, red light of wavelength 6800 Å and radiowaves of wavelength 500m? 8.4 A plane electromagnetic wave travels in vacuum along z-direction. What can you say about the directions of its electric and magnetic field vectors? If the frequency of the wave is 30 MHz, what is its wavelength? 8.5 A radio can tune in to any station in the 7.5 MHz to 12 MHz band. What is the corresponding wavelength band? 8.6 A charged particle oscillates about its mean equilibrium position with a frequency of 10 9 Hz. What is the frequency of the electromagnetic waves produced by the oscillator? 8.7 The amplitude of the magnetic field part of a harmonic electromagnetic wave in vacuum is B0 = 510 nT. What is the amplitude of the electric field part of the wave? 8.8 Suppose that the electric field amplitude of an electromagnetic wave is E0 = 120 N/C and that its frequency is n = 50.0 MHz. (a) Determine, B0,w, k, and l. (b) Find expressions for E and B. 8.9 The terminology of different parts of the electromagnetic spectrum is given in the text. Use the formula E = hn (for energy of a quantum of radiation: photon) and obtain the photon energy in units of eV for different parts of the electromagnetic spectrum. In what way are the different scales of photon energies that you obtain related to the sources of electromagnetic radiation? 8.10 In a plane electromagnetic wave, the electric field oscillates sinusoidally at a frequency of 2.0 × 1010 Hz and amplitude 48 V m–1. (a) What is the wavelength of the wave? (b) What is the amplitude of the oscillating magnetic field? (c) Show that the average energy density of the E field equals the average energy density of the B field. [c = 3 × 108 m s–1.] Reprint 2025-26

7.5 ACCELERATION DUE TO GRAVITY OF THE EARTH 4π 3 density and hence its mass is M E = R E ρ 3 The earth can be imagined to be a sphere made where ME is the mass of the earth RE is its radiusof a large number of concentric spherical shells and ρ is the density. On the other hand thewith the smallest one at the centre and the largest one at its surface. A point outside the 4π 3 ρr and mass of the sphere Mr of radius r isearth is obviously outside all the shells. Thus, 3 Reprint 2025-26 GRAVITATION 133 hence its distance from the centre of the earth is (RE + h ). If F (h) denoted the magnitude of the force on the point mass m , we get from G m M E Eq. (7.5) : = 3 r (7.10) R E If the mass m is situated on the surface of GM E m F (h ) = earth, then r = RE and the gravitational force on ( R E + h )2 (7.13) it is, from Eq. (7.10) The acceleration experienced by the point M E m F = G 2 (7.11) mass is F (h )/ m ≡ g (h ) and we get R E The acceleration experienced by the mass F (h ) GM E . g (h ) = = (7.14)m, which is usually denoted by the symbol g is m ( R E + h )2 related to F by Newton’s 2nd law by relation This is clearly less than the value of g on the F = mg. Thus GM E . g = surface of earth : GM F For h << R E , we can E R E2 g = = 2 (7.12) m R E expand the RHS of Eq. (7.14) : E Acceleration g is readily measurable. RE is a g (h ) = 2 GM 2 = g (1 + h / R E )−2known quantity. The measurement of G by R E (1 + h / R E ) Cavendish’s experiment (or otherwise), combined h << 1 , using binomial expression,with knowledge of g and RE enables one to For R E estimate ME from Eq. (7.12). This is the reason  2h why there is a popular statement regarding g (h ) ≅ g 1 − . (7.15)Cavendish : “Cavendish weighed the earth”.  RE  7.6 ACCELERATION DUE TO GRAVITY BELOW Equation (7.15) thus tells us that for small AND ABOVE THE SURFACE OF EARTH heights h above the value of g decreases by a factor (1 − 2h / R E ).Consider a point mass m at a height h above the Now, consider a point mass m at a depthsurface of the earth as shown in Fig. 7.8(a). The d below the surface of the earth (Fig. 7.8(b)),radius of the earth is denoted by RE . Since this so that its distance from the centre of thepoint is outside the earth, earth is ( R E − d ) as shown in the figure. The earth can be thought of as being composed of a smaller sphere of radius (RE – d ) and a spherical shell of thickness d. The force on m due to the outer shell of thickness d is zero because the result quoted in the previous section. As far as the smaller sphere of radius ( RE – d ) is concerned, the point mass is outside it and hence according to the result quoted earlier, the force due to this smaller sphere is just as if the entire mass of the smaller sphere is concentrated at the centre. If Ms is the mass of the smaller sphere, then, Ms/ME = ( RE – d)3 / RE3 ( 7.16) Since mass of a sphere is proportional to be Fig. 7.8 (a) g at a height h above the surface of the cube of its radius. earth. Reprint 2025-26 134 PHYSICS close to the surface of earth, at distances from the surface much smaller than the radius of the earth. In such cases, the force of gravity is practically a constant equal to mg, directed towards the centre of the earth. If we consider a Ms ME point at a height h1 from the surface of the earth and another point vertically above it at a height h2 from the surface, the work done in lifting the particle of mass m from the first to the second position is denoted by W12 Fig. 7.8 (b) g at a depth d. In this case only the smaller W12 = Force × displacement = mg (h2 – h1) (7.20) sphere of radius (RE–d) contributes to g. Thus the force on the point mass is If we associate a potential energy W(h) at a point at a height h above the surface such that F (d) = G Ms m / (RE – d ) 2 (7.17) W(h) = mgh + Wo (7.21) Substituting for Ms from above , we get (where Wo = constant) ; F (d) = G ME m ( RE – d ) / RE 3 (7.18) then it is clear that and hence the acceleration due to gravity at W12 = W(h2) – W(h1) (7.22) a depth d, The work done in moving the particle is just the difference of potential energy between its F ( d ) final and initial positions.Observe that the g(d) = is m constant Wo cancels out in Eq. (7.22). Setting h = 0 in the last equation, we get W ( h = 0 ) = Wo. F (d ) GM E g ( d ) = = 3 ( R E − d ) . h = 0 means points on the surface of the earth. m R E Thus, Wo is the potential energy on the surface of the earth. R E − d = g = g (1 − d / R E ) (7.19) If we consider points at arbitrary distance R E from the surface of the earth, the result just Thus, as we go down below earth’s surface, derived is not valid since the assumption that the acceleration due gravity decreases by a factor the gravitational force mg is a constant is no (1 − d / R E ). The remarkable thing about longer valid. However, from our discussion we know that a point outside the earth, the force of acceleration due to earth’s gravity is that it is gravitation on a particle directed towards the maximum on its surface decreasing whether you centre of the earth is go up or down. G ME m F = 2 (7.23)7.7 GRAVITATIONAL POTENTIAL ENERGY r where ME = mass of earth, m = mass of theWe had discussed earlier the notion of potential particle and r its distance from the centre of theenergy as being the energy stored in the body at earth. If we now calculate the work done inits given position. If the position of the particle lifting a particle from r = r1 to r = r2 (r2 > r1) alongchanges on account of forces acting on it, then a vertical path, we get instead of Eq. (7.20) the change in its potential energy is just the amount of work done on the body by the force. r2 G M m W12 2 d rAs we had discussed earlier, forces for which the =∫r1 r work done is independent of the path are the conservative forces.  1 1  = − G M E m − (7.24) The force of gravity is a conservative force  r2 r1  and we can calculate the potential energy of a In place of Eq. (7.21), we can thus associate body arising out of this force, called the a potential energy W(r) at a distance r, such that gravitational potential energy. Consider points Reprint 2025-26 GRAVITATION 135 G M E m W (r ) =− + W1 , (7.25) r valid for r > R , so that once again W12 = W(r2) – W(r1). Setting r = infinity in the last equation, we get W ( r = infinity ) = W1 . Thus, W1 is the potential energy at infinity. One should note that only the difference of potential energy between two points has a definite meaning from Eqs. (7.22) and (7.24). One conventionally sets W1 equal to zero, so that the potential energy at a point is just the amount of work done in displacing the particle from infinity to that point. We have calculated the potential energy at a point of a particle due to gravitational forces Fig. 7.9 on it due to the earth and it is proportional to the mass of the particle. The gravitational The gravitational potential at the centre of potential due to the gravitational force of the the square r = 2 l/2 is ( )earth is defined as the potential energy of a particle of unit mass at that point. From the G m U (r ) = − 4 2 . ⊳earlier discussion, we learn that the gravitational l potential energy associated with two particles of masses m1 and m2 separated by distance by a 7.8 ESCAPE SPEED distance r is given by If a stone is thrown by hand, we see it falls back Gm 1m 2 to the earth. Of course using machines we can V = – (if we choose V = 0 as r →∞) r shoot an object with much greater speeds and It should be noted that an isolated system of with greater and greater initial speed, the object particles will have the total potential energy that scales higher and higher heights. A natural equals the sum of energies (given by the above query that arises in our mind is the following: equation) for all possible pairs of its constituent ‘can we throw an object with such high initial particles. This is an example of the application speeds that it does not fall back to the earth?’ of the superposition principle. The principle of conservation of energy helps us to answer this question. Suppose the object ⊳ Example 7.3 Find the potential energy of did reach infinity and that its speed there was a system of four particles placed at the Vf. The energy of an object is the sum of potential vertices of a square of side l. Also obtain and kinetic energy. As before W1 denotes that the potential at the centre of the square. gravitational potential energy of the object at infinity. The total energy of the projectile at infinity then is Answer Consider four masses each of mass m at the corners of a square of side l; See Fig. 7.9. 2 mV fWe have four mass pairs at distance l and two E ( ∞=) W1 + (7.26) 2 diagonal pairs at distance 2 l If the object was thrown initially with a speed Hence, Vi from a point at a distance (h+RE) from the G m 2 G m 2 centre of the earth (RE = radius of the earth), its W (r ) = − 4 − 2 l 2 l energy initially was 2 2 1 2 GmM E 2 G m  1  G m E (h + R E ) = mVi – + W1 (7.27) 5.41 = − 2 (h + R E ) 2 +  = − l  l  2  Reprint 2025-26 136 PHYSICS By the principle of energy conservation ⊳ Eqs. (7.26) and (7.27) must be equal. Hence Example 7.4 Two uniform solid spheres 2 2 of equal radii R, but mass M and 4 M have mV f mVi GmM E a centre to centre separation 6 R, as shown – = (7.28) 2 (h + R E ) 2 in Fig. 7.10. The two spheres are held fixed. The R.H.S. is a positive quantity with a A projectile of mass m is projected from the minimum value zero hence so must be the L.H.S. surface of the sphere of mass M directly Thus, an object can reach infinity as long as Vi towards the centre of the second sphere. is such that Obtain an expression for the minimum speed v of the projectile so that it reaches mVi 2 GmM E the surface of the second sphere. – ≥ 0 (7.29) 2 (h + R E ) The minimum value of Vi corresponds to the case when the L.H.S. of Eq. (7.29) equals zero. Thus, the minimum speed required for an object to reach infinity (i.e. escape from the earth) Fig. 7.10corresponds to 1 2 GmM E Answer The projectile is acted upon by two m = (7.30) mutually opposing gravitational forces of the two ( Vi )min 2 h + R E spheres. The neutral point N (see Fig. 7.10) is defined as the position where the two forces If the object is thrown from the surface of cancel each other exactly. If ON = r, we have the earth, h = 0, and we get G M m 4 G M m = 2GM E r 2 (6 R −r )2 (Vi )min = (7.31) (6R – r)2 = 4r2 R E 6R – r = ±2r r = 2R or – 6R. 2 The neutral point r = – 6R does not concern Using the relation g = GM E / R E , we get us in this example. Thus ON = r = 2R. It is sufficient to project the particle with a speed (Vi )min = 2 gR E (7.32) which would enable it to reach N. Thereafter, the greater gravitational pull of 4M would suffice. The mechanical energy at the surface Using the value of g and RE, numerically of M is (Vi)min≈11.2 km/s. This is called the escape 1 2 G M m 4 G M mspeed, sometimes loosely called the escape E i = m v − − . velocity. 2 R 5 R Equation (7.32) applies equally well to an At the neutral point N, the speed approaches object thrown from the surface of the moon with zero. The mechanical energy at N is purely g replaced by the acceleration due to Moon’s potential. gravity on its surface and rE replaced by the G M m 4 G M m − EN = − .radius of the moon. Both are smaller than their 2 R 4 R values on earth and the escape speed for the From the principle of conservation of moon turns out to be 2.3 km/s, about five times mechanical energy smaller. This is the reason that moon has no atmosphere. Gas molecules if formed on the 1 2 GM 4GM GM GMsurface of the moon having velocities larger than v − − = − − this will escape the gravitational pull of the 2 R 5 R 2R R moon. or Reprint 2025-26 GRAVITATION 137 + h) with speed V. Its 2 2 G M  4 1  traverses a distance 2π(RE v = − time period T therefore is R  5 2  2π( R E + h ) 2π( R E + h )3 / 2 T = = (7.37)  3 G M 1/2 V ⊳ G M E v =  5 R  on substitution of value of V from Eq. (7.35). A point to note is that the speed of the projectile Squaring both sides of Eq. (7.37), we get is zero at N, but is nonzero when it strikes the 2 T = k ( RE + h)3 (where k = 4 π2 / GME) (7.38)heavier sphere 4 M. The calculation of this speed is left as an exercise to the students. which is Kepler’s law of periods, as applied to motion of satellites around the earth. For a 7.9 EARTH SATELLITES satellite very close to the surface of earth h can be neglected in comparison to RE in Eq. (7.38). Earth satellites are objects which revolve around Hence, for such satellites, T is To, where the earth. Their motion is very similar to the motion of planets around the Sun and hence T 0 = 2π R E / g (7.39) Kepler’s laws of planetary motion are equally If we substitute the numerical values applicable to them. In particular, their orbits g ≃ 9.8 m s-2 and RE = 6400 km., we get around the earth are circular or elliptic. Moon is the only natural satellite of the earth with a near 6.4 × 10 6 T 0 = 2π s circular orbit with a time period of approximately 9.8

10.5 In Young’s double-slit experiment using monochromatic light of wavelength l, the intensity of light at a point on the screen where path difference is l, is K units. What is the intensity of light at a point where path difference is l/3?

9.9 Give the structures of A, B and C in the following reactions: B NaOH  Br 2 C (i) CH 3 CH 2 I NaCN A Partial OHhydrolysis CuCN H 2 O/H  NH 3 (ii) C 6 H 5 N 2 Cl  A  B  C 4 B HNO 2 C (iii) CH 3 CH 2 Br KCN A LiAlH 0  C  2  2 O/H HCl B H C  (iv) C6 H 5 NO 2 Fe/HCl A NaNO273 K 3 A NaOBr B NaNO 2 /HCl C (v) CH 3 COOH NH 2 B C 6 H 5 OH C (vi) C6 H 5 NO 2 Fe/HCl A HNO273K 279 Amines Reprint 2025-26