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

3.10 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).

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