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

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

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%). ⊳