1.

INTRODUCTION

Need of Second Law of Thermodynamics

1. First law states that “heat can be converted completely into work”. Actually, it is found that,
only a fraction of quantity of heat may be converted into work in a cyclic process (i.e.,
efficiency of such conversion is not 100%).
2. The second law provides a mean for calculating the efficiency of this conversion.
3. The second law of thermodynamics states that, work can always be converted into heat but
heat cannot be completely converted into work without leaving a permanent change in the
system or surroundings.

Limitations of First Law and Need of Second Law

1. The first law of thermodynamics states that “One form of energy can be converted into
another form but the total energy remains constant”. It does not indicate the direction of the
flow of energy. Further, it does not explain whether the conversion process / reaction will
occur spontaneously or non-spontaneously.
2. First law also states that “heat can be converted completely into work”. But actually, it is
found that only a fraction of quantity of heat may be converted into work in a cyclic process.
i.e., efficiency of such conversion is not 100%. The second law provide a mean for calculating
the efficiency of this conversion.

The Second Law of Thermodynamics

1. Clausius Statement: It is impossible to construct a machine which can transfer heat from a cold
reservoir to a hot reservoir in a cyclic process, unless some external work is done on the machine.

2. Kelvin–Planck Statement: It is impossible to take heat from a hot reservoir and convert it into
work in a cyclic process without transferring a part of heat to the cold reservoir.

3. Entropy Statement: Whenever a spontaneous process takes place, it is accompanied by an

increase in the total entropy of the universe (system and surroundings).

2. THE CARNOT CYCLE (THE CONCEPT OF ENTROPY)

The Carnot cycle is a reversible cycle which demonstrates the maximum convertibility of heat into
work.

The Carnot’s Reversible Engine

Sadi Carnot imagined a theoretical engine which is free from all defects of practical engines. Its
efficiency is maximum and it is an ideal heat engine. This ideal heat engine operating ideal conditions
can convert only a part of the absorbed heat into work. The fraction of the total heat converted into
work by an engine is considered as its efficiency.

It works on a cycle consisting of two reversible isothermal and two reversible adiabatic processes.
For carrying out this cycle change (Fig. 1.1):

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1. One mole on an ideal gas (working substance) is enclosed in the cylinder with the help of a
weightless and frictionless piston.

2. The source is kept at a fixed higher temperature T1 and from which any amount of heat can be
drawn.

3. The sink is kept at a lower temperature T2 to which any amount of heat can be rejected.

4. A perfectly insulated stand is also provided so that the working substance (1 mole of an ideal gas)
can undergo adiabatic change.

Cylinder
Working
Substance

Conducting Insulating Conducting

Source Stand Sink

At T1 At T2

Fig. 1.1: The Carnot’s Ideal Heat Engine

The Carnot Cycle

To prove that only a fraction of heat (absorbed at higher temperature) can be converted into work and
to get an expression for efficiency in terms of temperature of the source and the sink, we have to
consider a series of cyclic operations, called Carnot cycle.

The Carnot cycle consists of four steps (Fig. 1.2):

1. Isothermal reversible expansion

2. Adiabatic reversible expansion
3. Isothermal reversible compression
4. Adiabatic reversible compression

1. Isothermal Reversible Expansion

In the first part of the cycle, the cylinder is placed in a source at temperature T1. The gas is then
allowed to expand isothermally and reversibly until the gas expands from volume V1 to V2.
Meanwhile, the pressure changes from P1 to P2. During this isothermal expansion, let the amount of
heat absorbed be q1. In the pressure–volume graph the line AB represents this change.

During this part of the cycle, the change in internal energy is (as per the First law of
Thermodynamics):

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 ∆Ε1 = q1 – w1 …..(1)

Since the expansion is isothermal,

Work done, 𝑤1 = 𝑅𝑇1 𝑙𝑛 (𝑉2 ) …..(2)

𝑉 1

A(P1, V1)

T1 B (P2, V2)

(P4, V4) D
C(P3, V3)
T2
P

E F G H
V
Fig. 1.2: The Carnot Cycle

2. Adiabatic Reversible Expansion

In the second part of the cycle, the cylinder is placed on the insulated stand. The gas is allowed to
expand adiabatically and reversibly from the state P2, V2 at T1 to a new state P3, V3. In an adiabatic
change q=0 and all the work is done at the expense of internal energy of the system. Hence its
temperature falls. Let the temperature drop from T1 to T2. In the P-V graph, the line BC represents
this change.

For this adiabatic change, the change in internal energy is,

∆Ε2 = – w2 since q=0 …..(3)

Since the expansion is adiabatic,

Work done, 𝑤2 = −𝐶𝑉 (𝑇2 − 𝑇1 ) …..(4)

3. Isothermal Reversible Compression

In the third stage of the cycle, the cylinder is kept in a sink at temperature T2. The gas is isothermally
compressed to volume V4. During this isothermal compression, the amount of heat rejected to the
sink be q2.

During this part of the cycle, the change in internal energy is

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 ∆Ε3 = ‒q2 – w3 …..(5)

(since the heat is rejected to the sink, negative sign is given to the amount of heat)

Since, the compression is isothermal,

Work done, 𝑤3 = 𝑅𝑇 𝑙𝑛 (𝑉4 )

2 𝑉 3

Work done, 𝑤3 = −𝑅𝑇2 𝑙𝑛 (𝑉3 ) …..(6)

𝑉 4

4. Adiabatic Reversible Compression

In the last part of the cycle, the cylinder is placed on the insulated stand. The gas is compressed
adiabatically and reversibly from P4, V4 at T2 to its initial state P1, V1 at T1. In P-V graph, the line
DA represents this change.
Here again q=0.

Hence change in internal energy is

∆Ε4 = – w4 since q=0 …..(7)

Since, the compression is adiabatic

Work done, 𝑤4 = −𝐶𝑉 (𝑇1 − 𝑇2 )

Work done, 𝑤4 = 𝐶𝑉 (𝑇2 − 𝑇1 ) .....(8)

The total change in internal energy ΔE for the whole cycle must be zero, since the system comes back
to its initial state. Hence,

𝛥𝐸1 + 𝛥𝐸2 + 𝛥𝐸3 + 𝛥𝐸4 = 0

𝑞1 − 𝑤1 − 𝑤2 − 𝑞2 − 𝑤3 − 𝑤4 = 0
𝑞1 − 𝑞2 = 𝑤1 + 𝑤2 + 𝑤3 + 𝑤4
𝑞1 − 𝑞2 = 𝑊 …..(9)

Here W is the total work done in the cycle. Since all the steps are reversible, work done must be
maximum. i.e., The amount of heat converted into work is q1 ‒ q2.

Hence its efficiency (η) is,

Amount of heat converted into work (or) Maximum Workdone

𝜂=
Total heat absorbed
𝑞1 −𝑞2 𝑊
𝜂 = =𝑞 .....(10)
𝑞1 1

Where W is the maximum work done by the system; q1 is the amount of heat absorbed by the system
from the source at a higher temperature T1.

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To get an expression for efficiency in terms of temperature of the source and the sink,

𝑊 = 𝑤1 + 𝑤2 + 𝑤3 + 𝑤

𝜂 = 𝑉2 𝑉3
𝑅𝑇1 𝑙𝑛 ( ) − 𝐶𝑉 (𝑇2 − 𝑇1 ) − 𝑅𝑇2 𝑙𝑛 ( ) + 𝐶𝑉 (𝑇2 − 𝑇1 )
𝑉1 𝑉4

𝜂 = 𝑉 𝑉
𝑅𝑇1 𝑙𝑛 (𝑉2 ) − 𝑅𝑇2 𝑙𝑛 (𝑉3 ) .....(11)
1 4

For an isothermal process ∆E=0. Therefore, from the first law of thermodynamics,

∆Ε1 = q1 – w1

q1 = w1 Since ∆E=0 for an isothermal process

𝑉
𝑅𝑇1 𝑙𝑛 (𝑉2 ) .....(12)
q1 = 1

Therefore, efficiency (η) is written from equations as:

𝑉 𝑉
𝑅𝑇1 𝑙𝑛( 2 )−𝑅𝑇2 𝑙𝑛( 3 )
𝑉1 𝑉4
𝑊 𝑉
𝑅𝑇1 𝑙𝑛( 2 )
𝑉1
𝑞1 =
𝑉
𝑅𝑇2 𝑙𝑛( 3 )
𝑉4
𝑊 = 1− 𝑉 .....(13)
𝑅𝑇1 𝑙𝑛( 2 )
𝑉1
𝑞1

The expression for a reversible adiabatic process of an ideal gas in term of temperature and volume
is written as:
𝑇𝑉 𝛾−1 = a constant

For an adiabatic expansion (states 2 and 3, the temperature-volume expression is written as:
𝛾−1 = 𝑇2 𝑉3𝛾−1
𝑇1 𝑉2 .....(14)

For an adiabatic compression (states 4 and 1, the temperature-volume expression is written as:
𝛾−1 = 𝑇2 𝑉4𝛾−1
𝑇1 𝑉1 .....(15)

On dividing (14) by (15) and comparing the equations, we obtain:

𝑉2 𝑉3 .....(16)
=
𝑉1 𝑉14

Substituting (16) in equation (13), we get

𝜂 = 1 − 𝑇2 .....(17)
𝑇 1

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Comparison of equations (10) and (16) shows that:
𝑇1 −𝑇2
𝜂 = .....(18)
𝑇1

Equation (17) gives us the efficiency of Carnot’s engine in terms of the temperature of the source and
the sink. Equation (18) is the mathematical expression for the second law.

3. ENTROPY
1. Entropy Definitions

✓ Entropy is a measure of degree of disorder or randomness in the system.

✓ Entropy is also considered as a measure of unavailable form of energy.

Mathematical Statement: The change in entropy is equal to the ratio of heat change occurs to the
temperature in a reversible cyclic process.

𝒒𝒓𝒆𝒗
∆𝑺 =
𝑻

Where, q is the heat absorbed or evolved in calories and T is the temperature in degrees.

2. Characteristics of Entropy

✓ The unit of entropy is calories degree−1. It is also called as entropy unit (e.u). The unit of
entropy in S.I. unit is Joules per Kelvin (JK−1).

✓ Entropy is a state function. The entropy change of a system is determined by the initial and
final states only, and not on the path taken by the system.

✓ The entropy change is an extensive property. Its value depends upon the amount of substance
involved (in moles).

✓ So, the unit of entropy is also written as cals/deg/moles (or) in S.I. unit JK−1 mole−1.

3. Entropy and Disorder (Randomness)

Entropy is a measure of randomness or disorder in the system. Increase in entropy means change
from an ordered to less ordered or disordered state (Fig. 1.3).
SOLID LIQUID GAS

Entropy increases

Fig. 1.3: Physical Representation of the Degree of Disorder

There is always decrease in order and increase in disorder and therefore entropy increases.

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4. Entropy and Spontaneity

A spontaneous process is always accompanied by an increase in entropy.

Let us consider a molecular system in states A and B. In state A, all the molecules are arranged and
highly ordered while in state B, the molecules are present at random and it is highly disordered.

By definition, the entropy of state A is low and that of state B is high. Hence, an increase of entropy
occurs in the change from state A to state B.

According to the law of chance, state A is less probable and state B is more probable. ie. The change
from state A to state B is spontaneous (Fig. 1.4).

Hence, we can say that a change in a system which is accompanied by an increase in entropy tends
to be spontaneous.

SPONTANEOUS
CHANGE

STATE, A STATE, B
Highly ordered, low entropy Highly disordered, high entropy
(Less probable) (More probable)

Fig. 1.4: Entropy and Spontaneity

5. Entropy and Unavailable Energy

When heat is supplied to the system, some portion of the heat is used up in doing work. This portion
of heat is called workable or available energy. The remaining portion of heat which remains
uncovered called unavailable energy. The second law of thermodynamics says that entropy is a
measure of unavailable energy. Hence entropy can be defined as unavailable energy per unit
temperature.

𝑈𝑛𝑎𝑣𝑎𝑖𝑎𝑏𝑙𝑒 𝑒𝑛𝑒𝑟𝑔𝑦
𝐸𝑛𝑡𝑟𝑜𝑝𝑦 =
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒

6. Entropy Change in Reversible Process

Consider an isothermal reversible expansion of an ideal gas at temperature T.

During the expansion, let q be the amount of heat absorbed by system from the surroundings.
𝑞
Hence, the change in entropy of the system =
𝑇

At the same time, surroundings lose the same amount of heat (q) at the same temperature T. This
results in decrease of surroundings entropy.

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 −𝑞
Hence, the change in entropy of the surroundings =
𝑇

[𝑇𝑜𝑡𝑎𝑙 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑒𝑛𝑡𝑟𝑜𝑝𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠]∆𝑆𝑡𝑜𝑡𝑎𝑙

= [𝐸𝑛𝑡𝑟𝑜𝑝𝑦 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑠𝑦𝑠𝑡𝑒𝑚]∆𝑆𝑠𝑦𝑠 + [𝐸𝑛𝑡𝑟𝑜𝑝𝑦 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑠𝑢𝑟𝑟]∆𝑆𝑠𝑢𝑟𝑟

𝑞 −𝑞
𝛥𝑆𝑡𝑜𝑡𝑎𝑙 = +( )
𝑇 𝑇

𝛥𝑆𝑡𝑜𝑡𝑎𝑙 = 0

Therefore, the entropy change in a reversible isothermal process is zero. In other words, the entropy
remains constant during a reversible process.

7. Entropy Change in Irreversible Process (Entropy Change of the Universe)

Let a system be at higher temperature T1 and its surroundings at lower temperature T2. Consider a
quantity of heat q passes irreversibly from system to surroundings. Then,
−𝑞
Decrease in entropy of system, (∆𝑆)𝑠𝑦𝑠 =
𝑇1

+𝑞
Increase in entropy of surroundings, (∆𝑆)𝑠𝑢𝑟𝑟 =
𝑇2
𝑞 𝑞
Net entropy change of process, 𝛥𝑆𝑡𝑜𝑡𝑎𝑙 = − +
𝑇1 𝑇2
𝑞 𝑞
𝛥𝑆𝑡𝑜𝑡𝑎𝑙 = −
𝑇2 𝑇1

1 1
𝛥𝑆𝑡𝑜𝑡𝑎𝑙 = 𝑞 ( − )
𝑇2 𝑇1

𝑇1 − 𝑇2
𝛥𝑆𝑡𝑜𝑡𝑎𝑙 = 𝑞 ( )
𝑇1 𝑇2
But T1 > T2, and hence T1 − T2 is positive.

(𝑜𝑟) 𝑆𝑡𝑜𝑡𝑎𝑙 > 0

Hence during an irreversible process, the entropy of the system increases. The total change in entropy
of the system and its surroundings is called as entropy change of the Universe. Since all-natural
processes that take place spontaneously are irreversible processes, the entropy of the Universe always
increases.

4. ENTROPY CHANGE FOR AN IDEAL GAS (APPLICATIONS OF SECOND LAW

OF THERMODYNAMICS)

➢ Entropy is a state function. The entropy change of a system is determined by the initial and final
states only and not on the path taken by the system.

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➢ Entropy is an extensive property because its value depends upon the amount of substance
involved i.e., its value depends on any two of the three variables T, P and V.

1. Entropy Change as a Function of T and V

➢ According to the first law of thermodynamics:

dq = dE + PdV …(1)

By definition, dq = T dS

➢ Substituting the value of dq in equation (1), we have

T dS = dE + PdV …(2)

➢ By definition, dE
CV = dT

dE = C V dT

➢ Substituting the value of dE in equation (2), we have

T dS = C V dT + PdV …(3)

➢ For 1 mole of an ideal gas,

PV = RT

RT
P = V

➢ Substituting in equation (3), we have

RT
T dS = C V dT + dV
V

(or) dT dV
dS = CV +R …(4)
T V

➢ For a finite change of state of the system, the entropy change ∆S can be obtained by integrating
equation (4) between limits of initial state 1 and final state 2 i.e., between S1 and S2; T1 and T2
and V1 and V2 assuming that Cv remains constant over the temperature range involved.

S2 T2 V2
dT dV
 dS = Cv 
T
+ R  V
S1 T 1 V1

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 SSS12 = C v ln T TT12 + R ln V VV12

S2 − S1  = C v ln T2 − ln T1  + R ln V2 − ln V1 

T2 V2
S = C v ln + R ln
T1 V1

➢ For ‘n’ moles of an ideal gas,

T2 V2
S = nC v ln + nR ln ...(5)
T1 V1

T V
S = 2.303 n C V log 2 + 2.303 n R log 2
(or) T1 V…(6)
1

2. Entropy Change as a Function of T and P

➢ Let P1 be the pressure of the ideal gas in the initial state and P2 in the final state, then for 1 mole
of an ideal gas,
P1 V1 = R T1 and

P2 V2 = R T2

P1V1 P2 V2
(or) =
T1 T2

V2 P1T2
V1 = P2T1

V2
➢ Substituting the value in equation (5), we have
V1

T2 P1T2
S = C v ln + R ln
T1 P2T1

T2 P1 T
S = C v ln + R ln + R ln 2
T1 P2 T1

S = (C v + R ) ln T2 + R ln
P1
T1 P2

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 S = C P ln
T2
+ R ln
P1
 C P − CV = R
T1 P2

For ‘n’ moles of an ideal gas,

T2 P1
S = nC P ln + nR ln ...(7)
T1 P2

T2 P1
S = 2.303 n C P log + 2.303 n R log … (8)
(or) T1 P2

3. Entropy Change for an Isothermal Process

➢ Since an isothermal process is carried out at constant temperature, the change in temperature,
(∆T) is zero. Therefore,

T = T2 − T1 = 0
T1 = T2 ...(1)
➢ Entropy change as a function of T and V is given by the expression:

T2 V2
S = 2.303 n C v log + 2.303 n R log ...(2)
T1 V1

➢ For an isothermal process, T1 = T2 and the expression for the change in entropy for n moles of
ideal gas using the expression (2) is written as:

V2
S = 2.303 n R log
V1 ...(3)

➢ Entropy change as a function of T and P is given by the expression:

T P
S = 2.303 n C P log 2 + 2.303 n R log 1 ...(4)
T1 P2

➢ The expression for the change in entropy for an isothermal process (T1 = T2) for n moles of ideal
gas using the expression (4) is written as:

P
S = 2.303 n R log 1
P2 ...(5)

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4. Entropy Change for an Isobaric Process

Since the isobaric process is carried out at constant pressure, the change in pressure, (∆P) is zero.
Therefore,
P = P2 − P1 = 0

P1 = P2 …(1)

➢ Entropy change as a function of T and P is given by the expression:

T P
S = 2.303 n C P log 2 + 2.303 n R log 1 ...(2)
T1 P2

So, the entropy change for an isobaric process (P1 = P2) is written as:

T
S = 2.303 n C P log 2
T1 …(3)

5. Entropy Change for an Isochoric Process

Since an isochoric process is carried at constant volume, the change in volume, (∆V) is zero.
Therefore,
V = V2 − V1 = 0

V1 = V2

➢ Entropy change as a function of T and V is given by the expression:

T V
S = 2.303 n C V log 2 + 2.303 n R log 2 ...(1)
T1 V1

So, the entropy change for an isochoric process (V1 = V2) is written as:

T
S = 2.303 n C V log 2
T1 …(2)

6. Entropy Change of Phase Transitions

➢ The change of a substance from one form to another is known as phase transitions. Such changes
occur at definite temperatures and are accompanied by entropy change.

➢ During these transitions either heat is absorbed or evolved (ie: the entropy either increases or
decreases).

➢ The entropy change for these transformations is given by:

qrev
S trans =
T
13
 where,
✓ qrev is the heat absorbed or evolved

✓ T temperature of transition

✓ qrev is actually the molar enthalpy change of the substance

1. Entropy of Vapourisation

➢ It is defined as the change in entropy when one mole of a liquid substance change into vapours at
its boiling point.

H vapour
S vapour =
T

✓ where, H vapour is the latent heat of vaporization. Latent heat of vapourisation of water is 540
cals/gm.

2. Entropy Of Fusion

➢ It is defined as the change in entropy when one mole of a solid substance changes into liquid form
at its melting point.

H fusion
Sfusion =
T

✓ where, H fusion is the latent heat of fusion. Latent heat of fusion of ice at 0°C is 80 cals/gm.

Note:
L M
S =
T

✓ where, L is the latent heat in calories; M is the molecular weight in grams; T is the temperature in
Kelvin.

3. Entropy of Sublimation

➢ It is defined as the change in entropy when one mole of a solid substance changes into vapour at
a particular temperature.

Hsublimation
Ssublimation =
T

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 5. NEED FOR THE INTRODUCTION OF NEW THERMODYNAMIC
FUNCTIONS
➢ It is understood clearly that, for a process to be spontaneous ∆STotal should be greater than zero.

i.e., ∆STotal > 0 (or) ∆Ssys + ∆Ssurr > 0

➢ Hence, in order to decide the spontaneity of a process, we have to consider the change in entropy
of the system as well as surroundings.

➢ So, Gibbs free energy (G) and Helmholtz work function (A) are the thermodynamic functions
which can be applied only to system so that it can be used as criterion of spontaneity of a process.

1. Helmholtz Work Function (A)

➢ We also know that a part of internal energy of a system can be used at constant temperature to do
useful work.

➢ A part of the internal energy which is isothermally available to do useful work is called work
function (A) of the system.

➢ It is mathematically defined as:

A = E − ...(5)
TS
where,

✓ E is internal energy of the system

✓ S is the entropy of system and
✓ T is the temperature.

2. Physical Significance of the Work Function (A)

➢ The work function is given by

A = E – TS …..(1)

For a small change in a reversible system at constant temperature,

∆A = ∆E − T∆S …..(2)
But by definition,
q rev
∆S = T
 Equation (2) is written as

T∆S = qrev …..(3)

Substituting T∆S in equation (2), we get

15
 ∆A = ∆E − qrev …..(4)

But according to first law of thermodynamics:

∆E = q −w …..(5)

∆E− q = − wmax

Comparing equation (4) and (5),

∆A = − w

∆A = − wmax
[Since for an isothermal reversible process, work
obtained is maximum]

➢ So the decrease in the work function A in any process at constant temperature gives the maximum
work that can be obtained from the system.

3. Gibbs Free Energy (G)

➢ Gibbs free energy refers to “the capacity to do useful work”. We know that a part of the total
energy of a system is converted into work and the rest is unavailable. The part of energy which
is converted into useful work is called available energy.

➢ The isothermally available energy present in a system to do useful work is called as free energy
(G).

➢ It is mathematically defined as:

G = H – TS …(1)

where,

✓ H is enthalpy of the system

✓ S is the entropy of system and

✓ T is the temperature.

➢ For an isothermal process occurring at temperature T, if the system undergoes a change from the
initial state to final state, then

G1 = H1 – TS1 (for the initial state) …(2)

G2 = H2 – TS2 (for the initial state) ...(3)

Subtracting (3) from (2)

(G2−G1) = (H2 – TS2 ) – (H1 – TS1 )

16
 ∆G = ∆H − T∆S ...(4)

where,

✓ ∆G is the change in free energy of the system

✓ ∆H is the change in enthalpy of the system
✓ ∆S is the change in entropy of the system

4. Physical Significance of the Free Energy (G)

➢ The free energy is measure of the useful work obtainable from a system through a reversible,
isothermal process at constant pressure. It is given by

G = H – TS …..(1)

For a small change in a reversible system at constant temperature,

∆G = ∆H − T∆S …..(2)

But by definition, ∆H = ∆E + P∆V

 Equation (2) is written as

∆G = ∆E + P∆V − T∆S …..(3)

We know that, ∆A = ∆E − T∆S

Hence equation (3) can be written as:

∆G = ∆A + P∆V …..(4)

Since ∆A = − wmax

∆G = − wmax + P∆V

− ∆G = wmax − P∆V

➢ Where, P∆V is the work done by expansion and wmax is the maximum work that can be obtained
from the system.

➢ Therefore,
wmax − P∆V = Network or Useful work

Hence, − ∆G = wuseful

➢ So, the decrease in free energy accompanying a process at constant temperature and pressure is
equal to the useful work obtainable from the system.

17
6. THERMODYNAMIC CRITERION OF SPONTANEITY IN TERMS OF
FREE ENERGY CHANGE
➢ Consider a process which is carried out at constant temperature, T.

➢ Suppose q is the amount of heat lost by surroundings and gained by the system, then

STotal = S system + S surroundings …..(1)

The entropy change of the surroundings is given by:

q
S surr = −T …..(2)

(Negative sign indicates that the heat has been lost by the surroundings).

➢ Now heat gained by system at constant temperature represents its enthalpy change.

i.e., Heat gained by the system, q = (H )sys

From (2), q
−
S surr = T
(or) () sys
S surr = − [ q = (∆H)sys] ...(3)
T
Substituting the value ∆Ssurr in equation (1), we get

(H )sys
STotal = S sys −
T

Multiplying by T on both sides, we get

 (H )sys 
T STotal = T S sys − 
 T 

T STotal = T S sys − (H )sys

(H )sys − T S sys = − T STotal

(G )sys = − T STotal  G = H − TS  ...(4)

➢ Equation (4) is the basis for criterion of spontaneity in terms of free energy change of the system
only.

18
➢ We know that, for a process to be spontaneous ∆STotal should be positive.

➢ In other words, for a process to be spontaneous ∆Gsys should be negative.

➢ i.e., for a process at particular temperature and pressure to be spontaneous, the free energy change
of the system must be less than zero.

(G )T , P < 0 …..(5)

➢ From equation (4),

✓ If ∆STotal is positive, (∆G) T, P = −, then the process is spontaneous.

✓ If ∆S Total = 0, (∆G) T, P = 0, then the process is represents equilibrium.
✓ If ∆S Total is negative, (∆G) T, P = +, then the process is non-spontaneous.

➢ Hence for an irreversible or spontaneous process at constant temperature and pressure ∆G < 0,
and at equilibrium under isothermal and isobaric conditions ∆G = 0.

7. GIBB’S − HELMHOLTZ EQUATION

We know that, G = H – TS and H = E + PV

 G = E + PV – TS

Upon differentiation, dG = dE + P dV + V dP – T dS –S dT …..(1)

But according to first law and second law of thermodynamics,

dE = dq – P dV (First law)
dq = T dS (Second law)
 dE = T dS – P dV

Substituting dE value in equation (1), we get,

dG = T dS – P dV + P dV + V dP – T dS –S dT
dG = V dP–S dT …..(2)

At constant Pressure, dP = 0

dG = –S dT

For any two states of the system,

dG1 = –S1 dT
dG2 = –S2 dT
dG2 − dG1 = –S2 dT – ( –S1 dT )
d∆G = –S2 dT +S1 dT
d∆G = −(S2 − S1) dT
d∆G = −∆S dT

19
 dG = −∆S …..(3)
dT
But according to the definition of free energy change,

G = H − TS
− S = G − H
T
Substituting −∆S in to the equation (3), we have

G − H  dG 
T =  d 
p
 dG 
G − H = T  d 
p
 dG 
G H + T   …(4)
=  d  P

➢ The equation (4) is known as the Gibb’s – Helmholtz equation.

Variation of Free Energy with Temperature at Constant Pressure (Another form Gibbs
Helmholtz Equation)

The Gibbs free energy, G is defined as:

G = H – TS …..(1)
Upon differentiation,
dG = dH − TdS – SdT

dG d (E + PV) − TdS − SdT [ H = E + PV]

dG = dE + PdV + VdP − TdS – SdT

dG = TdS + VdP − TdS – SdT [ dE + PdV = TdS]

dG = VdP – SdT …..(2)

If the process is isobaric (constant pressure), dP = 0, therefore, equation (2) can be

written as:
 G 
  = −S …..(3)
 TP  P
Since entropy is always positive, the negative sign indicates that at constant pressure,
G decreases with rise in temperature.

If we substitute the value of S in equation (1), we get

 G 
G = H + T  T  …..(4)
P
Dividing by T2 on both sides gives,

20
 G H 1  G 
= +  
T 2
T 2 T  T  P
G 1  G  H
−   = T2 …..(5)
T 2 T  T  P

1  G  G   H
 − 
 T  T   = T2
T  P

 G  G   H
 − 
 T  T   = T
 P
On differentiating and neglecting higher terms, we get

 d (G / T )  H
= − T2
 dT 
P
…(6)

Equation (6) is another form of Gibb’s-Helmholtz equation.

Applications of Gibb’s-Helmholtz Equation

(i) Calculation of Enthalpy Change of the Reaction (Heat of Reaction) occurring in

Galvanic Cells

If a cell yields nF coulombs of electricity in a reversible manner, it must be equal to the decrease in
free energy, then

− ∆G◦ = nFE° …..(1)

Hence, Gibb’s-Helmholtz equation is given as:

 G 
∆G =  + T  T 
P
(or)   (−nFE ) 


− nFE  =  + T  T


 P

 E  
− nFE  =  − nFT  
 T 
 P
 E  
= − nFE + nFT  

  T 
 P
  E   
E  − T    …..(2)
 = − nF   T  
  P 
➢ Knowing the value of E° and the temperature coefficient ( E  / T ) of the cell reaction, it is
possible to evaluate the enthalpy change (∆H) of the reaction.

21
(ii) Calculation of Entropy Change

➢ ∆H and ∆S are related by the equation:

∆G = ∆H − T∆S …..(3)

➢ We know that ∆G = − nFE° and ∆H can be calculated by the above equation (2). Hence ∆S can
be calculated easily from the above equation (3).

8. CLAPEYRON EQUATION
➢ According to thermodynamics, the change of free energy with change of temperature and pressure
is expressed as:

 dG = VdP − SdT …(1)

➢ For two phases in equilibrium, we have

dG1 = V1dP − S1dT …(2)

dG 2 = V2 dP − S2 dT …(3)

➢ The free energy change for the process at equilibrium

dG1 = dG 2

 V1dP − S1dT = V2 dP − S2 dT

On rearranging
V1dP − V2 dP = S1dT − S2 dT

(or) (V1 − V2 )dP = (S1 − S2 )dT

dP (S1 − S2 )
dT = (V1 − V2 )
dP S
…..(4)
dT = V

When there is a change of state from solid to liquid (melting), or liquid to vapours (vapourisation),
or solid to vapours (sublimation), there is a change in entropy.

If one mole of liquid changes reversibly, it would absorb molar heat of vapourisation (HV) at a
temperature equal to its boiling point. In this case the entropy change is given by:

H
S = T

22
 Substituting S in equation (4), we get

dP H
dT = TV

dP H
(or) …(4)
dT = T(V2 − V1 )

This equation is known as Clapeyron equation.

9. CLAUSIUS–CLAPEYRON EQUATION

➢ The Clapeyron equation for a liquid – vapour system is written as:

dP H V
dT = T(V2 − V1 )

➢ This equation can be simplified by neglecting the small volume of liquid in comparison with the
volume of vapour. The equation in such a case becomes:
dP H V
= …(1)
dT TV2
Suppose the vapour obeys the ideal gas laws:

RT
V2 = P
Substituting V2 in equation (5), we have

dP H V
dT =  RT 
T 
 P 

dP = H V  P
…(2)
dT RT 2

The equation (2) is known as Clausius–Clapeyron equation.

Integrated Form of Clausius-Clapeyron Equation

By rearranging the above equation, we have

dP H V dT
=  2
P R T
If H is considered as constant, we may integrate the above equation between suitable initial and
final limits as:

23
 T2
P2 dP H V
P1 P =
R  T2
dT
T1
T
H V  1  2
ln P  P2 =  − 
P1 R  T  T1

H V  1 1
ln P2 − ln P1  = −  − 
R  T2 T1 

P2 H V  1 1 
2.303 log =  − 
P1 R  T1 T2 

P2 H V  T − T1 
log =  2 
P1 2.303R  T2 T1  …(3)

Equation (3) is known as integrated form of Clapeyron ‒ Clausius equation. It can be used to
calculate the heat of vapourisation from the vapour pressure data at two different temperatures.

10. SOLVED PROBLEMS

Entropy Change in Isothermal Process

1. One mole of an ideal gas expands isothermally to twice its original volume at 27°C.
Calculate the entropy change during the process.

Solution

➢ Entropy change in an isothermal expansion of an ideal gas is given by:

V2
∆S = 2.303 × n × R × log V
1
Given: n = 1 mol ; V1 = 1 ; R= 1.987 cal. K−1 mol−1 ; V2 = 2
2
∆S = 2.303 × 1 × 1.987 × log 1
∆S = 2.303 × 1.987 × 0.3010
∆S = 1.3773 e.u.

2. Calculate the entropy change in the thermodynamic expansion of 2 moles of an ideal gas
from a volume of 5 litres to a volume of 50 litres.

Solution

➢ Entropy change in an isothermal expansion of an ideal gas is given by:

V2
∆S = 2.303 × n × R × log V
1

24
 Given: 2 mol ; V1 = 5 litres ; R= 1.987 cal. K−1 mol−1 ; V2 = 50 litres
50
∆S = 2.303 × 2 × 1.987 × log 5
∆S = 2.303 × 2 × 1.987 × 1
∆S = 9.152 e.u.

3. Helium, weighing 4 gm, is expanded from 1 atm to one tenth to the original pressure at
30°C. Calculate the change in its entropy, assuming it to be an ideal gas.

Solution
➢ We know that:
P1
∆S = 2.303 × n × R × log
P 2
Number of moles, = Weight (in gm) 4
= = 1 mole
n Mol. Wt. 4
1
Given: R= 1.987 cal. K−1 mol−1 ; P1 = 1 atm ; P2 =
atm
10
1
2.303 × 1 × 1.987 × log
∆S = 1
10
∆S = 4.57 e.u.

Entropy of Phase Transitions

4. Calculate the entropy change when one mole of water is converted into steam, reversibly,
at its boiling point. Latent heat of vapourisation is 540 cal.g–1.

Solution

Given:
Lv = 540 cal.g–1; ∆Hv = Lv × Molecular weight of water
= 540 × 18 = 9720 cals.

Tb = 100 + 273 = 373 K

∆S for vaporization is given by:

 v
∆Sv = Tb

9720
∆Sv = 373

∆Sv = 26.06 e.u.

5. Calculate the entropy change involved when one mole of liquid oxygen is converted into
gaseous oxygen at its boiling point of −183°C. Entropy of vaporization of liquid oxygen is
6.82 J.

25
 Solution

Given:
∆Hv = 6.82 J; Tb = − 183 + 273 = 90 K

∆S for vaporization is given by:

 v
∆Sv = Tb

6.82
∆Sv = 90

∆Sv = 0.0757 e.u.

6. Calculate the entropy changes for the fusion and vaporization of one mole of water at
normal melting point (273 K) and at normal boiling point (373K). The molar enthalpy of
fusion = 6.01 kJ mol−1 and the molar enthalpy of vaporization = 40.79 kJ mol−1.

Given:
∆Hfusion = 6.01 kJ mol−1 or 6010 J mol−1; Tfusion = 273 K

∆Hv = 40.79 kJ mol−1 or 40790 J mol−1; Tv = 373 K

(i) ∆S for fusion is given by:
 fusion
∆Sf = Tfusion

6010
∆Sf = 273

∆Sf = 22.01 JK−1 mol−1.

(ii) ∆S for vaporization is given by:

 v
∆Sv = Tb

40790
∆Sv = 373

∆Sv = 109.3 JK−1 mol−1.

Free Energy Change and Spontaneity

7. Predict whether the following reaction is spontaneous at 25ºC.

C (g) + H2O (l)→CO (g) + H2 (g)
ΔH = 31.4 k cal / mol and ΔS = 32 cal / deg at 25ºC.

26
 Solution

Given:
∆H = 31.4 kcals (or) 31,400 cals; ∆S =32 cals deg−1; T =25+273 = 298 K

The free energy change is expressed as:

∆G = ∆H − T∆S
∆G = 31,400 – 298 (32)
∆G = 31,400 – 9,536
∆G = 21,864 cal mole–1 (or) 21.86 kcal mole–1.

Since ΔG is positive, the reaction is not spontaneous.

8. ∆H and ∆S for a reaction at 27°C are −10 kcals and 20 cals K −1 respectively. What is ∆G
for the reaction? Predict whether the reaction will be feasible or not?

Solution

Given:
∆H =−10 kcals (or) −10,000 cals; ∆S =20 cals K−1; T =27+273 = 300 K

The free energy change is expressed as:

∆G = ∆H − T∆S
∆G = −10,000 – 300 (20)
∆G = −16,000
∆G = −16 kcals

As ∆G is negative, the reaction is feasible.

9. ∆G for a reaction at 300 K is − 16 kcals. ∆H for the reaction is − 10 kcals. What is the
entropy of the reaction and what will be ∆G at 330 K?

Solution

Given:
∆G = −16 kcals; ∆H =−16 kcals; T = 300 K

The free energy change is expressed as:

∆G = ∆H − T∆S
∆S = H − G
T
∆S = − 10 − (− 16)
300
∆S = 0.02 kcals K-1.
At 330 K
∆G = ∆H − T∆S
∆G = −10 – 330 (0.02)
∆G = − 16.6 kcals.

27
Gibbs-Helmholtz Equation

10. The free energy change, ∆G for a process is −138 at 30°C and −135 kJ at 40°C. Calculate
the change in entropy and ∆H accompanying the process at 35°C.

Solution
∆G1 = −138 kJ; ∆G2 = −135 kJ; d∆G = ∆G2 − ∆G1 =−135 – (−138)= 3 kJ;

T1 = 30°C = 273 + 30 = 303 K; T2 = 40°C = 273 + 40 = 313 K;

dT = T2 − T1 = 313 – 303 =10 K

According to Gibbs-Helmholtz equation:

 dG 
H + T  
G =  d  P

The change in free energy ∆G at 35°C may be taken as the average value of ∆G at
30°C and 40°C.
 T1 + T2  303 + 313
T   = = 308 K
=
 2  2

∆G at 308 K =  G1 + G2  − 138 + (− 135) − 135 − 138

  = = = −136.5 kJ
 2  2 2
 3
H + 308   
−136.5 =  10 
−136.5 = H + 92.4
H = − 136.5 – 92.4
H = − 228.9 kJ

The free energy change is expressed as:

∆G = ∆H − T∆S
H − G
∆S = T
− 228.9 − (− 136.5)
∆S = 308
− 92.4
∆S = 308

∆S = − 0.3 kJ K-1
∆S = − 300 JK-1

11. Gibbs free energy of a reaction at 300 K and 310 K are −29 kcals and −29.5 kcals
respectively. Determine its ∆H and ∆S at 300 K.

Solution

Given:
∆G1 = −29 kcals; ∆G2 = −29.5 kcals; d∆G = ∆G2−∆G1=−29.5–(−29)

28
 = −0.5 kcals;
T1 = 300 K; T2 = 310 K; dT = T2 − T1 = 310 – 300 =10 K

According to Gibbs-Helmholtz equation:

 dG 
G = H + T  d 
 P
 ∆H at 300 K ,
 − 0.5 
− 29 = H + 300  10 
−29 = H −15
H = − 29 + 15
H = − 14 kcals

The free energy change is expressed as:

∆G = ∆H − T∆S

H − G
∆S = T

− 14 − (− 29)
∆S = 300
15
∆S = 300
∆S = 0.05 kcals K-1
∆S = 50 cals K-1

Applications of Gibbs-Helmholtz Equation

12. Calculate ∆G° for a Daniel cell, Zn/ZnSO4//CuSO4/Cu at 25°C. Given E° = 1.1V.

Solution

Given:
o
Ecell = +1.1 V ; n= 2; F = 96,500 Coulombs

We know that:
∆G = − nFE°cell

∆G = − 2 × 96500 × 1.1
∆G = − 212300 (Coulombs × Volts = Joules)
∆G = − 212.3 kJ

Since ∆G is negative, the reaction is spontaneous.

13. The emf of a standard cadmium cell at 298 K is 1.01832 V and the temperature coefficient
of emf of cell is –5.0 × 10–5 VK–1. Calculate the values of ∆G, ∆H and ∆S for the cell reaction.

29
 Solution

Given:
Ecell = 1.01832 V; n = 2;  Ecell  = –5.0 × 10–5 V K–1; T = 298 K
 T 

We know that:
∆G = – nFEcell
∆G = –2 × 96500 × 1.01832 (coulombs × volts = joules)
∆G = –19653 J (or) –196.53 kJ
From the Gibbs-Helmholtz equation:
   E  
∆H = − nF  E − T   
  T  P 
∆H = –2 × 96500 [1.01832 – (298 × –5 × 10–5)]
∆H = –2 × 96500 [1.01832 – (–0.0149)]
∆H = –2 × 96500 [1.01832 + 0.0149]
∆H = –2 × 96500 × 1.03322
∆H = – 199411.4 J (or) – 199.4 kJ

Further we know that:

∆G = ∆H – T∆S
 − G
∆S = T

− 199.4 − (− 196.5)
∆S = 298

− 2. 9
∆S = 298

∆S = – 0.0097 kJ. K–1 (or) – 9.7 J.K–1

14. Calculate ∆G° for the cell reaction at 25°C, Zn + FeSO4 → Fe + ZnSO4. The standard
reduction potentials are E°(Zn2+/ Zn) = −0.76 V and E° (Fe2+/ Fe) = −0.44 V. Predict whether the
reaction is spontaneous.

Given:
Eo 2+ = −0.76 V ; Eo 2+ = −0.44 V ; n= 2; F = 96,500 Coulombs
Zn / Zn Fe / Fe

In the given system, Zn acts as anode and Fe acts as cathode.

  
Ecell = Ecathode − Eanode


Ecell = Eo 2+ − Eo = − 0.44 − (− 0.76) = + 0.32 V
Fe / Fe Zn 2+ / Zn
We know that:
30
 ∆G = − nFE°cell
∆G = − 2 × 96500 × 0.32
∆G = − 61760 (Coulombs × Volts = Joules)
∆G = − 61.76 kJ

Since ∆G is negative, the reaction is spontaneous.

Clausius-Clapeyron Equation

15. The vapour pressure of water at 100ºC is 760 mm. What will be the vapour pressure at
95ºC? The heat of vapourisation of water in the temperature range is 41.27 kJ mol–1.

Solution

Given:
P1 = 760 mm; T1 = 100 + 273 = 373 K; T2 = 95 + 273 = 368 K;

∆HV = 41.27 kJ mol–1 or 41270 J mol–1; R = 8.314 JK–1 mol–1.

The Clapeyron-Clausius equation for liquid-vapour equilibria is given by:

P
log 2 HV  T2 − T1 
=  
P1 2.303  R  T1T2 

log
P2 41270  368 − 373 
760 = 2.303  8.314  368  373 

− 206350
log P2 − log 760 = 2628213

log P2 = – 0.0785 + log 760

log P2 = – 0.0785 + 2.8808

log P2 = 2.8023

P2 = antilog of 2.8023

P2 = 634.3 mm.

16. The vapour pressures of water at 95ºC and 100ºC are 634 and 760 mm, respectively.
Calculate the molar heat of vapourisation, ∆HV of water between 95ºC and 100ºC.

Solution

Given:
P1 = 634 mm; P2 = 760 mm; T1 = 95 + 273 = 368 K;

T2 = 100 + 273 = 373 K; R = 8.314 JK–1 mol–1.

31
 The vapour pressures at different temperatures and molar heat of vapourisation are
related by the equation:
P
log 2 = H v  T2 − T1 
 
P1 2.303  R  T1T2 
760 H v  373 − 368 
log
634 = 2.303  8.314  368  373 

 v  5 
0.0787 = 19.1471 137264 

0.0787  19.1471 137264

 v = 5

 v = 41368 Jmol–1 (or) 41.368 kJ mol–1.

[Link] POTENTIAL (or) PARTIAL MOLAR FREE ENERGY

Expression for Chemical Potential in terms of other Quantities

Let us consider the extensive property, free energy (G).

Suppose the system consists of ‘n’ constituents (in solution or in a heterogeneous system) and let the
amount of each constituent in the system be n1, n2, n3 … moles.

Therefore, the property G is a function of not only temperature and pressure but also the amounts of
different constituents present in the system. Hence, we have:

𝑮 = 𝒇(𝑻, 𝑷, 𝒏𝟏 , 𝒏𝟐 , 𝒏𝟑 . . . ) . . . (1)

If there is a small change in the temperature, pressure and the amounts of the different constituents,
then the change in the property G is given by:

𝜕𝐺 𝜕𝐺 𝜕𝐺
𝑑𝐺 = ( ) 𝑑𝑇 + ( ) 𝑑𝑃 + ( ) 𝑑𝑛 +. .. (2)
𝜕𝑇 𝑃,𝑛1,𝑛2,𝑛3 ... 𝜕𝑃 𝑇,𝑛1,𝑛2,𝑛3 ... 𝜕𝑛1 𝑇,𝑃,𝑛2 ,𝑛3 ... 1

In equation (2), the first term on the right hand side gives the change in the value of G with
temperature when pressure and compositions of different constituents are kept constant; the second
term gives the change in the value of G with pressure when the temperature and compositions of
different constituents are kept constant; and the remaining quantities in the right hand side gives the
change in the value of G with a change in the amount of a constituent when temperature, pressure
and the amounts of other constituents are kept constants.

If the temperature and pressure of the system are kept constant, then dT = 0 and dP = 0. Therefore,
the equation (2) becomes:

𝜕𝐺 𝜕𝐺 𝜕𝐺
(𝑑𝐺) 𝑇,𝑃 = ( ) 𝑑𝑛1 + ( ) 𝑑𝑛2 + ( ) 𝑑𝑛 +. .. (3)
𝜕𝑛1 𝑇,𝑃,𝑛2,𝑛3 ... 𝜕𝑛2 𝑇,𝑃,𝑛1,𝑛3 ... 𝜕𝑛3 𝑇,𝑃,𝑛1,𝑛2 ... 3

32
 1. INTRODUCTION
Electrochemistry is a branch of physical chemistry, which deals with the relationship between
chemical energy and electrical energy. The knowledge of electrochemistry is essential for
understanding various electrochemical processes such as Batteries and Fuel cells, Corrosion and its
prevention, Industrial metal finishing etc.

2. ELECTRODE POTENTIAL AND ELECTROCHEMICAL CELLS

An electrochemical cell is a device used to convert chemical energy into electrical energy. It
consists of two electrodes namely anode, cathode and an electrolyte. In this cell, electrons transfer
in the redox reaction is utilised as a source of producing electrical energy.

Galvanic Cell

In a galvanic cell, a zinc rod is partially immersed in 1M ZnSO4 solution and a copper rod is
partially immersed in 1M CuSO4 solution. The two solutions are interconnected by a salt bridge.
The salt bridge is a U-tube containing saturated KCl or NH4NO3 in agar-agar gel. The salt bridge
provides electrical contact between two compartments.

Fig. 2.1: Galvanic Cell

It also helps to maintain electrical neutrality by allowing the migration of ions. If zinc and
copper rods are connected from outside, electrons flow from zinc to copper since zinc atoms are
oxidised and copper atoms are reduced. The flow of electrons are indicated by ammeter placed in
the circuit (Fig. 2.1).

Daniel Cell

The practical application of an electrochemical cell is Daniel cell. It consists of zinc rod
dipped in ZnSO4 solution and a copper rod dipped in CuSO4 solution. The two solutions are separated
by a porous pot. The two solutions can seep through the pot and so come into contact with each other
automatically. Here the porous pot acts as salt bridge (Fig. 2.2).

The electrode reaction occurs in the Daniel cell are,

At anode (negative electrode) Zn → Zn2+ + 2e

At cathode (positive electrode) Cu2+ + 2e → Cu

41
 Fig. 2.2: Daniel Cell

Representation of a cell

(i) A cell consists of two electrodes namely anode and cathode

(ii) The anode half cell must be represented always on the left side while the cathode half
cell must be represented always on the right side.

(iii) The anode half cell must be written by writing metal first and then electrolyte. The
two must be separated by a vertical line or a semicolon

Example : M/Mn+ or M; Mn+

(iv) The cathode half cell must be written by writing electrolyte first and then the metal.
The two must be separated by a vertical line or a semicolon.

Example : Mn+/M or Mn+ ; M

(v) The electrolyte may be represented by whole formula or its ionic species. The
concentration of the electrolyte may also be represented in bracket.
(vi) A salt bridge is indicated by two vertical lines (║) separating the two half cells.

Applying the above rules to a galvanic cell, we can represent it as,

Zn / ZnSO4 (1M) ║ CuSO4 (1M) / Cu.

or Zn / Zn2+ (1M) ║ Cu2+ (1M) / Cu.

or Zn ; Zn2+ (1M) ║ Cu2+ (1M) ; Cu.

3. ORIGIN OF ELECTRODE POTENTIAL

All metals consist of positive metallic ions and their valency electrons. When a metal is
placed in a solution of its own salt, the positive metal ions pass into the solution leaving behind its
valency electrons on the metal itself and making it negatively charged. This tendency is known as
solution pressure of metal. Different metals have different solution pressures.

42
 The negative charge developed on the metal attracts positive metal ions from solution, and a
layer forms close to the metal. The layer formed around the negatively charged metal is called as
electrical double layer (edl). The edl prevents further transfer of positive metal ions from the metal
and the equilibrium state is reached with some definite value of potential difference. The potential
difference of edl formed at the interface of the metal and electrolyte is called electrode potential.

In certain cases, when a metal is placed in a solution on its own salt, the positive metal ions
from the solution deposit over the metal and gain electrons (remove the electrons from the metal) and
making it positively charged. [Metal = Positive ion + Electrons]. This tendency is known as osmotic
pressure of solution.

The positive charge developed on the metal attracts negative ions from solution, and forms a
layer close to the metal. This edl prevents further deposition of positive ions from the solution and
an equilibrium state is reached with some definite value of potential difference (Fig. 2.3). This
potential difference of edl is also known as electrode potential.

Fig. 2.3: Formation of Electrical Double Layer

Therefore, electrode potential is defined as “the measure of tendency of a metallic electrode

to loose or gain electrons when in contact with a solution of its own salt.”

According to Nernst’s solution pressure theory, if the solution pressure of metal is greater
than osmotic pressure of solution, the metal becomes negatively charged. This electrode is
called anode and the potential difference of the metal and solution is called as oxidation potential. If
the osmotic pressure of solution is greater than the solution pressure of metal, the metal becomes
positively charged. This electrode is called as cathode and the potential difference of the metal and
solution is called as reduction potential.

Single electrode potential (E)

It is defined as “the measure of tendency of a metallic electrode to loose electrons (oxidation

or decomposition) or gain electrons (reduction or discharged) when in contact with a solution of its
own salt is called single electrode potential of a metal”.

Standard electrode potential (E°)

It is defined as “the measure of tendency of a metallic electrode to lose or gain electrons

when in contact with a solution of its own salt of 1 molar concentration at 25°C”.

43
 4. REFERENCE ELECTRODES
To determine the electrode potential it is necessary to have another electrode whose single
electrode potential (half cell potential) is accurately known. This electrode is called “reference
electrode”. The two half cells can then be combined to form a Voltaic cell, the emf (electromotive
force or net cell potential) of which can be directly measured.

(i) Primary Reference Electrode

Eg: Standard Hydrogen Electrode (SHE)

The primary reference electrode is the normal or standard hydrogen electrode (NHE or SHE).
This can be prepared by bubbling hydrogen gas of 1 atmospheric pressure over platinised platinum,
immersed in a solution of HCl containing 1 M H+ ions of unit activity. The electrode potential of
SHE is zero at all temperatures (Fig. 2.4).

It is represented as

Pt, H2 (1 atm) / H+ (1 M) E°=0 Volt.

The cathodic reaction is

2H+ + 2e → H2

Fig. 2.4: Standard Hydrogen Electrode (SHE)

(ii) Secondary Reference Electrode

Eg: Saturated Calomel Electrode (SCE)

SCE is an example of secondary reference electrode. It is a glass tube containing mercury at

the bottom over which mercurous chloride is placed. The rest of the vessel is filled with saturated
solution of KCl. The bottom of the tube is sealed with a platinum wire. The upper end is closed with
cork (Fig. 2.5). Its electrode potential at 25° C is +0.2422 V. It is represented as

Hg / Hg2Cl2 , satd KCl E° = +0.2422 Volt

The cathodic reaction is

44
 Hg2Cl2 + 2e → 2Hg + 2Cl−

Fig. 2.5: Saturated Calomel Electrode (SCE)

The potentials of three calomel electrodes are

(i) Hg / Hg2Cl2 , 0.1 NKCl + 0.3350 V

(ii) Hg / Hg2Cl2 , 1 NKCl + 0.2810 V
(iii)Hg / Hg2Cl2 , Satd KCl + 0.2422 V

5. DETERMINATION OF SINGLE ELECTRODE POTENTIAL

Single electrode potential of a metal is defined as “the measure of its ability to loose or gain
electrons when in contact with a solution of its own salt”.

Absolute value of single electrode potential cannot be determined. However, potential

difference of two half cells i.e., emf of a cell can be determined by using a voltmeter. Therefore
single electrode potential of any electrode is obtained by coupling the electrode with standard
hydrogen electrode (SHE). Since single electrode potential of standard hydrogen electrode is zero at
all temperatures, the measured emf of the cell is the single electrode potential of the other electrode.

According to IUPAC convention, the term single electrode potential is reserved exclusively
for half cell reactions written as reduction direction and is generally reported as reduction potential.

Zn2+ + 2e  Zn ; EZn2+ / Zn
Fe2+ + 2e  Fe ; EFe2+ / Fe
Cu2+ + 2e  Cu ; ECu2+ / Cu
2H+ + 2e  H2 ; E 2 H + / H 2

According to IUPAC convention, during single electrode potential determination, reference

electrode, SHE should be kept at left and hence the single electrode potential of other electrodes are
reported as electrode reduction potentials.

Eright − Eleft =  emf

or
Eright =  emf [ Eleft = 0]

45
Since Eleft = 0, the measured emf is the reduction potential of the other electrode.

The positive sign of the measured emf indicates that the reaction proceeds in the forward
direction with respect to standard hydrogen electrode. i.e., The reduction reaction is feasible with
respect to SHE and hence the electrode acts as cathode with respect to SHE (SHE which acts as
anode). The negative sign of the measured emf indicates that the reaction proceeds in the opposite
direction with respect to SHE i.e., The reduction reaction is not feasible with respect to SHE, and
hence the electrode acts as anode while SHE acts as cathode.

Fig. 2.6a: Determination of Single Electrode Potential

Fig. 2.6b Determination of Single Electrode Potential

(i) If zinc electrode is coupled with SHE, keeping SHE in the left, emf is observed to be −0.76 V.
(Fig. 2.6a).

i.e., − 0.76 V = E  Zn2+ Zn − E° SHE

 E  Zn2+ / Zn = − 0.76 V [ E°SHE = 0]

(ii) If copper electrode is coupled with SHE, Keeping SHE in the left, emf is observed to be + 0.34
V. (Fig. 2.6b).
i.e., + 0.34 V = E  Cu 2+ / Cu − E° SHE

 E  Cu 2+ / Cu = + 0.34 V [ E°SHE = 0]

46
 6. ELECTROCHEMICAL SERIES (or) EMF SERIES
Electrochemical Series or Emf Series: The arrangement of various metals in the order of increasing
values of standard reduction potentials is called as electrochemical series.

Applications of Electrochemical Series

1. Relative ease of oxidation or reduction: Higher the value of standard reduction potential, the
greater is the tendency to get reduced form.

(a) The positive sign of reduction potential indicates that the electrode reaction occurs in
forward direction, i.e., reduction direction. The fluoride has higher positive value of standard
reduction potential (+2.65V) shows higher tendency towards reduction.

(b) The negative sign of reduction potential indicates that the electrode reaction occurs in
opposite direction i.e., backward direction. It means, the reduced form has a greater tendency to
loose electrons and get oxidised. Thus Lithium (−3.01 V) has highest negative reduction potential
and shows higher tendency to lose electrons.

. Displacement of one species by the other

The metal with more negative reduction potential can displace those metals with less negative
or positive potentials from their solution.

For example, we can know whether copper will displace zinc from solution or vice versa. We
know that E  Cu 2+ / Cu = + 0.34 V and E  Zn2+ / Zn = − 0.76 V. Therefore Cu2+ has much greater tendency
to get Cu-form than Zn2+, for getting Zn – form. In other words zinc will displace copper from its
solution.

3. Calculation of standard emf of the cell

Using E° of anode half cell and cathode half cell, the standard emf can be calculated.

E° cell or standard emf of a cell = E°Cathode − E°anode

4. Predicting feasibility or spontaneity of the cell

In a reversible cell, when the cell yields electrical energy, there is a fall in free energy (or) −
∆G = nFE..

(a) If ∆G = Negative; E = Positive. Then the cell reaction is feasible.

(b) If ∆G = Positive; E = Negative. Then the cell reaction is non spontaneous (not feasible).
(c) If ∆G = 0; E = 0. Then the cell reaction has the equilibrium.

5. Determination of equilibrium constant for the reaction

Standard electrode potential can be used to determine equilibrium constant for the reaction.
We know that
− ∆G° = RT In k = 2.303 RT log k

47
 - G 
log k =
2.303RT
nFE 
log k = [ −∆G° = nFE°]
2.303RT

So, from the value of E° for a cell reaction, its equilibrium constant can be calculated.

Table 2.1: Standard Electrode Potential (Half Cell Potential) of some Metals with respect to
SHE at 25°C

Half Cell Reaction E°, Volts Vs SHE Half cell Representa-tion

Li+ + e  Li − 3.01 Li+ / Li Anodic

Mg2+ + 2e  Mg − 2.37 Mg2+ / Mg

Al3+ + 3e  Al − 1.66 Al3+ / Al

Pb2+ + 2e  Pb − 1.12 Pb2+ / Pb

Zn2+ + 2e  Zn − 0.76 Zn2+ / Zn

Fe2+ + 2e  Fe − 0.44 Fe2+ / Fe

Cd2+ + 2e  Cd − 0.40 Cd2+ / Cd

Sn2+ + 2e  Sn − 0.13 Sn2+ / Sn

2H+ + 2e  H2 0.00 2H+ / Pt, H2 Reference

Cu2+ + 2e  Cu + 0.34 Cu2+ / Cu

Ag+ + 2e  Ag + 0.80 Ag+ / Ag

Pt4+ + 4e  Pt + 0.86 Pt4+ / Pt

Au+ + e  Au + 1.50 Au+ / Au

½ F2 + e  F − + 2.65 1/2 F2 / F − Cathodic

7. RELATION BETWEEN ELECTRICAL ENERGY AND FREE

ENERGY CHANGE IN A CELL
A galvanic cell is a source of electrical energy, and it can be quantitatively converted into
work. The electrical work or electrical energy is the product of emf of the cell and the electrical
charge that flows through the external wire.

If n is the number of electrons flowing through the wire and F is the 1 Faraday of electricity,
then the electrical charge flowing through the wire is equal to nF.

48
 If Ecell is the emf of the cell, then the electrical work or electrical energy is given by,

Welec = nFEcell

Since the electrical work is done by the system (ie: galvanic cell), by convention it is taken
as negative.

i.e.: – Welec = nFEcell

or Welec = – nFEcell

According to thermodynamics, the free energy change (ΔG) for a process occurring at
constant temperature and constant pressure is the measure of useful work. Therefore,

ΔG = Welec

where Welec is the useful work produced by the system.

or ΔG = – nFEcell

or – ΔG = nFEcell

8. NERNST EQUATIONS
1. Nernst Equation for Single Electrode Potential or Variation of Electrode Potential with
Concentration

Consider a general redox reaction

M n+ + ne  M

The electrode potential forms between the metal and the solution of its own salt of valency 'n'
be E. Now the electrical energy required to transfer 1 gm equivalent of metal ion from the metal to
solution of its own salt would be 'nFE' where F is 1 Faraday of electricity. That is, the decrease in
free energy of a metal produces “nFE” electrical energy.

– ∆G = nFE [∆G is free energy change]

According to Van't Hoff's reaction isotherm, at equilibrium this free energy change in terms
of concentration are inter related as

Pr oduct
∆G = ∆G º + 2.303 RT log
Re ac tan t

where ∆G º is the standard free energy change.

[M ]
or – nFE = – nFEº + 2.303 RT log
[M n+ ]

49
 2.303 RT [M ]
or E = Eº – log
nF [M n+ ]

2.303 RT [1]
or E = Eº – log
nF [M n+ ]

[ the activity of solid metal = 1 at a given temperature]

2.303 RT
or E = Eº + log [ M n + ]
nF

When R = 8.314 J/K/Mole; F = 96,500 Coulombs; T = 298º K then,

0.0591 n+
E = Eº + log [M ] at 25º C
n

where Eº is standard electrode potential and n is number of electrons transferred.

This equation is known as "Nernst equation for single electrode potential".

2. Nernst Equation for the Emf of a Complete Cell

Consider a general redox cell reaction involving the transfer of n electrons,

aA + bB  cC + dD …(1)

The decrease in free energy change, ∆G, accompanying the process is given by a well known
thermodynamic equation as

[Pr oducts]
∆G = ∆G˚ + 2.303 RT log
[Re ac tan ts]

[C ]c [ D]d
or ∆G = ∆G˚ + 2.303 RT log …(2)
[ A]a [ B]b

Since ∆G = – nFEcell, equation (2) can be written as

[C ]c [ D]d
– nFE cell = – nFE˚cell + 2.303 RT log
[ A]a [ B]b

2.303 RT [C ]c [ D] d
(or) Ecell = E˚cell – log …(3)
nF [ A] a [ B]b

This equation is often referred to as the Nernst equation for the emf of a complete cell.

At 25º C, the equation (3) can be written as

50
 0.0591 [C ]c [ D]d
Ecell = Eºcell – log
n [ A] a [ B]b

9. EMF OF A CELL
It is defined as "the difference of potential which causes the flow of current from an electrode
having higher potential to another having lower potential is known as emf of the cell". It is expressed
in Volts.

Emf of a cell (Ecell) is theoretically calculated by

Ecell = ERight side electrode ─ ELeft side electrode

Ecell = Ecathode ─ Eanode

1. Determination of Emf of a Cell by Poggendorff's Compensation Method (Potentiometric

Method)

The accurate emf of a cell can not be determined by voltmeter directly because (i) internal
resistance of cell may absorb a part of available potential difference and (ii) a part of cell current is
drawn from the cell during the process of measurement itself. To get accurate emf of a cell,
potentiometers are used which involves little flow of electricity.

Poggendorff's Method

Principle

In this method, the emf of the cell is compensated or balanced by an external emf so that no
current flows in the circuit. At this stage, the applied emf is equal to the magnitude of emf of the test
cell.

Description

The potentiometer circuit consists of a storage battery, P. The constant emf of the storage
battery must be larger than that of the cell under measurement. This sends a constant current I through
the uniform cross-section potentiometer wire AB. It is made of platinum-iridium and is stretched
over a meter scale (Fig. 2.7).

Now the cell whose emf is to be measured is also connected to A having the positive pole in the same
direction as the storage battery P and send current in the same direction. When the sliding contact C
is pressed on the potentiometer wire, the test cell opposes the flow of current through the
galvanometer. Adjust the sliding contact along the wire until the galvanometer G shows null
deflection. This is called the null point. At this point the emf of the cell is balanced by the potential
difference between the points AC of the potentiometer wire.

i.e.: Potential difference between A and C = i × Resistance of AC.

51
 Fig. 2.7: Poggendorff's Circuit for Emf Determination

Now the test cell is replaced by a standard cell in the circuit. The point of null deflection is
again determined. Now the balance length is AD.

i.e.: Potential difference between A and D = i × Resistance of AD.

As the wire AB is uniform and its resistance is proportional to its length,

 Emf of test cell α i × length AC and

Emf of standard cell α i × length AD

AC
 Emf of test cell = Emf of std. cell ×
AD

Standard Cell (Example: Weston-Cadmium cell)

Fig. 2.8: Weston-Cadmium Cell

It consists of a H-shaped glass vessel. The bottom of the glass tubes are sealed with platinum wire.
The positive electrode contains mercury over which mercurous sulphate is placed. The negative
electrode consists of an amalgam of Hg-Cd over which some crystals of CdSO4 8/3 H2O are
sprinkled. The rest of the vessel is filled with saturated solution of CdSO4. The upper end of the

52
arms are closed with either corks or sealing wax (Fig. 2.8). The purpose of solid crystals is to keep
the electrolyte saturated at all temperatures. The emf of the cell is 1.01807 V at 25˚C.

[Link] OF EMF MEASUREMENTS

1. Determination of pH of an Aqueous Solution

(A) The Glass Electrode

The most common standard electrode used in pH measurements is the glass electrode.

Fig. 2.9: Determination of pH by Glass Electrode

It consists of a thin glass bulb with a long neck. The glass bulb is made up of a special glass
having low melting point and high electrical conductivity. The glass bulb is filled with 0.1 N HCl
solution and silver wire coated with silver chloride is inserted to make the electrical contact (Fig.
2.9). This half cell glass electrode is represented as,

Ag, AgCl / HCl (0.1N) / Glass / Unknown solution

It has been observed that a potential difference exists at the interface between glass and
solution containing H+ ions. The magnitude of this difference of potential (single electrode potential)
at 25˚C is given by

EG = E˚G + 0.0591 log [H+]

EG = E˚G – 0.0591 pH [ pH = –log [H+]]

where E˚G is constant for the given glass electrode and it depends upon the nature and composition
of glass membrane

To carryout the determination of pH of a solution, the glass electrode is connected with a

saturated calomel electrode. The cell is therefore represented as

Ag, AgCl / HCl (0.1N) / Glass / Unknown solution ║SCE

Ecell = Eright ─ Eleft

= 0.2422 ─ (E˚G – 0.0591 pH)
53
 = 0.2422 ─ E˚G + 0.0591 pH

E cell − 0.2422 + E  G
or pH =
0.0591

Merits of Glass Electrode

(i) It can be used in any solutions.

(ii) A small quantity of solution is sufficient for the determination of

pH.

(iii) It can be used even in the presence of metallic ions and poisons.

Demerits of Glass Electrode

(i) Since the resistance of glass membrane used in the bulb is very high, electronic potentiometers
are needed for the measurement.

(ii) It can not be used in strongly alkaline solution (pH>10). In such cases, special type of glass must
be used.

(B) The Quinhydrone Electrode

The quinhydrone electrode is a good example of redox electrode, used for the measurement
of pH. The quinhydrone electrode consists of a platinum electrode dipped in the test solution,
quinhydrone (an equimolar compound of quinone, Q and hydroquinone, QH2). The half cell reaction
of the quinhydrone electrode is written as

O O + 2 H+ + 2e  HO HO OH

Quinone (Q) Hydroquinone(QH2) (QH2)

This redox electrode system is represented as

Pt / Q, QH2 / H+ (unknown concentration)

The potential developed on platinum electrode is given by Nernst equation as

2.303 RT [Pr oduct]

E = Eº – log
nF [Re ac tan t ]

2.303 RT [QH 2 ]
= Eº – log
2F [Q] [ H + ]2

54
 2.303 RT [Q] [ H + ] 2
= Eº + log
2F [QH 2 ]

2.303 RT [Q] 2.303 RT

= Eº + log + log [ H + ] 2
2F [QH 2 ] 2F

Since the concentration of hydroquinone [QH2] is same as that of quinone [Q], the quantity [Q] /
[QH2] is unity.

2.303 RT 2.303 RT
 E = E° + log 1 + log [ H + ] 2
2F 2F

2.303 RT
= E° + log [ H + ] [  log 1 = 0]
F

= E° + 0.0591 log [H+] at 25° C.

or E = E° − 0.0591 pH

[where E° is the standard electrode potential of quinhydrone electrode = 0.6996V]

or E = 0.6996 − 0.0591 pH

To carry out the determination of pH of a solution, the quinhydrone electrode is connected

with a saturated calomel electrode. This combination may be represented as

SCE ║ H+ (unknown) / Q, QH2 / Pt.

Ecell = Eright− Eleft

Ecell = 0.6996 − 0.0591 pH − 0.2422

0.6996 − 0.2422 − Ecell

pH =
0.0591

Merits of Quinhydrone Electrode

(i) It can work in the presence of oxidizing and reducing agents.

(ii) It can be used for pH measurements in non-aqueous media.

Demerits of Quinhydrone Electrode

(i) It cannot be used for solutions of pH more than 8.

(ii) It cannot be used in the presence of solutes that react with

hydroquinone.

55
2. Potentiometric Titrations

Potentiometric titration involves the measurement of the potential of a suitable indicator

electrode as a function of titrant volume. It is useful with coloured and turbid solution and for
detecting the presence of unsuspected species.

The electrode dipped in the test solution is called the indicator electrode, and the other
electrode is called the reference electrode, whose potential remains constant. Hence the potential of
the indicator electrode will change relative to that of reference electrode.

(i) Acid – Base Titration

A glass indicator electrode is used to carry out acid – base titration. The cell may be
constructed as:

Pt, H2 (1 atm) / H+ ║SCE

and its emf is given by Ecell = 0.2422 – EGO + 0.0591 pH

By measuring the emf of cell after each addition of alkali, and plotting against volume of alkali added,
the end point can be detected.

Fig. 2.10: Acid – Base Titration

(ii) Redox Titration

An inert electrode (platinum) is used to carry out redox titration. Both the oxidised and
reduced forms are usually soluble and their ratio varies throughout the titration. The potential of the
[reduced species]
indicator electrode will vary and directly proportional to log
[oxidised species]
For Fe −Fe system, the following cell may be constructed.
2+ 3+

SCE ║ Fe3+ −Fe2+ / Pt

and its emf is given by

 0.0591 [ Fe3+ ] 
Ecell =  E  + log  − 0.2422
 n [ Fe 2+ ] 

56
 The progressive addition of K2Cr2O7 will change in the emf of the cell. At the equivalence
point a sharp change in emf is observed. This is due to sudden oxidation of all the ferrous ions into
ferric ions. By plotting emf vs volume of K2Cr2O7 added, the end point is determined.

A still better result of end point can be obtained by plotting the differential change in emf
 E 
with volume  against volume of K2Cr2O7.
 V 

Fig. 2.11: Redox Titration

3. Determination of Solubility of a Sparingly Soluble Salt

The solubility and solubility product of a sparingly soluble salt can be calculated by measuring
emf of suitable concentration cell.

For example, to find out the solubility of AgCl, the following cell may be constructed.

Ag / AgCl (0.01 NKCl) ║ AgNO3 (0.01N) / Ag

[Ag+] = c [Ag+] = 0.01

The cell can be prepared by placing one of silver electrodes in contact with 0.01N solution of
AgNO3 and the other in contact with 0.01 N solution of KCl. The two half cells are connected by a
salt bridge. A drop of AgNO3 solution is added to KCl solution. A small amount of AgCl is produced
which is sufficient to give its saturated solution. The cell so constructed is a concentration cell with
respect to silver ions. The emf of such cell is given by

2303 RT 0.01
Ecell = log
nF c

Where c is the concentration of Ag+ ions furnished by AgCl in KCl solution. By measuring emf of
cell, the value ‘c’ can be calculated.

If 0.01N KCl is assumed to be completely dissociated, the activity of Cl− ion is equal to 0.01.

Therefore solubility product, Ksp = [Ag+] [Cl−]

KSP= c × 0.01

Solubility of AgCl = K sp = c  0.01 [Link]. / lit

57
 11. CONCENTRATION CELLS
In a concentration cell, electric energy is produced by transfer of matter or substance from
one half cell to the other because of difference in the concentration of the species involved.

There are two types of concentration cells.

(i) Electrode concentration cell.

(ii) Electrolyte concentration cell

1. Electrode Concentration Cell

An electrode concentration cell consists of two identical electrodes of different composition

dipped in a common electrolyte containing ions of the electrode material.

(i) A simple electrode concentration cell may be constructed by placing two hydrogen electrodes at
different pressures in the same solution of hydrochloric acid.

Pt, H2 (P1) / HCl (aq) / H2 (P2), Pt (P2 > P1)

(ii) Another commonly employed electrode concentration cell is cadmium – amalgam cell. It
consists of two amalgam electrodes at different activities in contact with a solution of an electrolyte
containing ions of the metal dissolved in amalgam.

Cd-Hg(a1) / CdSO4(aq) / Cd-Hg(a2) (a2 > a1)

2. Electrolyte Concentration Cell

In this type, the two electrodes of the same metal are in contact with same electrolyte of
different concentration.

Example: Copper ion concentration cell

Cu / Cu 2+ (c1) ║ Cu 2+ (c2) / Cu (c2 > c1)

Determination of Emf of a Concentration Cell

According to Nernst equation, when a metal is placed in a solution of its own salt of
concentration, c, the electrode potential

forms between the metal and the solution is determined by the equation
2.303 RT
E = E° + log c
nF

0.0591
At 25° C, E = E° + log c
n
Let us consider a general electrolyte concentration cell in which two half cells are made up of
similar electrodes and similar electrolytes. But the concentration of reactive ions around the
electrodes are different.

58
It may be represented as

M / Mn+ (c1) ║ Mn+ (c2) / M (c2 > c1)

where c1 and c2 are the concentration of reactive ions at the two electrodes (Fig. 2.12).

Fig. 2.12: Electrolyte Concentration Cell

Metal immersed in higher concentration acts as cathode because of high osmotic pressure of
solution whereas the metal immersed in lower concentration acts as anode.

The emf of cell is generally determined by

Emf of cell Ecell = Eright− Eleft = Ecathode− Eanode

where Ecathode and Eanode are half cell potential s of cathode and anode respectively.

The half cell potential can be determined by Nernst equation.

 0.0591 
Ecell =  E  M n + / M + log c 2  –
 n 

  n+ 0.0591 
 E M / M + n log c1  at 25°C.


0.0591 0.0591
= log c 2 − log c1
n n

0.0591 c2
Ecell = log at 25º C
n c1

The reactions occurring at the two half cells are,

At cathode M n+ (c2) + ne → M (reduction)

59
At anode M → M n+ (c1) + ne (oxidation)

Overall reaction M n+ (c2) → M n+ (c1)

It is clear from the above equation that there is no net chemical reaction. Therefore the emf
developed is due to the transfer of metal ions from the solution of higher concentration to the lower
concentration.

Applications of Concentration Cells

1. Determination of solubility of sparingly soluble salt

The solubility and solubility product of a sparingly soluble salt can be calculated by measuring emf
of suitable concentration cell.

For example, to find out the solubility of AgCl, the following cell may be constructed.

Ag / AgCl (0.01 NKCl) ║ AgNO3 (0.01N) / Ag

[Ag+] = c [Ag+] = 0.01

The cell can be prepared by placing one of silver electrodes in contact with 0.01N solution of
AgNO3 and the other in contact with 0.01 N solution of KCl. The two half cells are connected by a
salt bridge. A drop of AgNO3 solution is added to KCl solution. A small amount of AgCl is produced
which is sufficient to give its saturated solution. The cell so constructed is a concentration cell with
respect to silver ions. The emf of such cell is given by

2303 RT 0.01
Ecell = log
nF c

Where c is the concentration of Ag+ ions furnished by AgCl in KCl solution. By measuring emf of
cell, the value ‘c’ can be calculated.

If 0.01N KCl is assumed to be completely dissociated, the activity of Cl− ion is equal to 0.01.

Therefore solubility product, Ksp = [Ag+] [Cl−]

KSP= c × 0.01

Solubility of AgCl = K sp = c  0.01 [Link]. / lit

2. Determination of Valency of an Ion

By substituting the measured value of emf of a concentration cell, the values of c1 and c2 in
the equation.

0.0591 c2
Emf = log at 25 C
n c1

The value of n, the number of electrons involved in the cell reaction can be calculated.

60
 12. REVERSIBLE CELLS AND IRREVERSIBLE CELLS
1. Reversible Cells

Examples: Daniel cell, Secondary batteries

Cells which obey the conditions of thermodynamic reversibility are called as reversible cells.

Daniel cell is an example of reversible cell because it obeys the following conditions. Its emf
is 1.1 volt.

Zn / ZnSO 4 (1M) ║ CuSO 4 (1M) / Cu

(i) If an external emf of 1.1 volt is applied in the opposite direction from an external source,
the chemical reaction taking place in the cell stops i.e., no current flows.

(ii) If the external emf is slightly greater than 1.1 volt is applied, the current will begin to
flow in the opposite direction and hence the chemical reaction in the cell gets reversed.
Since the secondary batteries (Lead-acid battery, Nickel-Cadmium battery) obey these
conditions, they can be recharged and are called rechargeable batteries.

2. Irreversible Cells

Examples : Zinc-silver cell, Dry cell (Primary cells)

Cells which do not obey the conditions of thermodynamic reversibility are called irreversible
cells.

Zinc-Silver cell is an example of an irreversible cell. It may be represented as

Zn / H2SO4 (aq) / Ag

The cell reactions taking place at the anode and cathode are,

Zn + H2SO4 → ZnSO4 + H2 ↑ ( At anode )

2 Ag+ + 2e → 2 Ag ( At cathode )

When two electrodes are connected from outside, zinc dissolves with the liberation of
hydrogen gas.

When the external emf is slightly greater than the actual emf of the cell is applied to it, the
above chemical reactions are not reversed, since one of the products, H2 gas has already escaped.
Such a cell which does not obey the conditions of reversibility is called as irreversible cell.

Similarly primary cells (Eg: dry cell) do not obey the conditions of reversibility and hence
they are unchargeable.

61
 13. LIQUID JUNCTION POTENTIAL

• A liquid junction potential is developed when a cell contains two electrolytic solutions of
different concentration in contact with one another (Development of potential at the junction
of the two liquids).
• The more concentrated solution possesses a tendency to diffuse into the comparatively less
concentrated one.
• Large concentration difference between the liquid phases results in high liquid junction
potential.
• The rate of diffusion of an ion at the junction of the two solutions is proportional to its speed.
• The rate of diffusion of each ion ∝ its speed (ion mobility) in an electric field
• It may be regarded as a steady state where an effectively time-independent charge separation
is developed. It is non-equilibrium potential.
• The structure of the liquid junction may hardly change as diffusion tends to be a slow process
in it.
• The dilute solution always acquires the charge of faster moving ion.

If the cations (positively charged ions) move faster from concentrated solution to diluted solution
than anions (negatively charged ions), the (+)ve ions will diffuse ahead of the (-)ve ions in the dilute
solution. Thus the dilute solution will be (+)vely charged with respect to concentrated solution.
Similarly, if the anion (negatively charged ions) moves faster, it will diffuse rapidly than (+)ve ion
and the dilute solution will be (-)vely charged. In both the cases, an electrical double layer is formed
at the junction of solutions resulting potential difference. This potential difference developed at the
junction of two solutions is known as liquid junction potential (EL) or diffusion potential, the
magnitude which depends upon the relative speed of the ions. The electrical separation and potential
difference thus arises will continue to increase until the rates of diffusion of (-)ve and (+)ve ions are
equalized by electrical forces. If two ions are moving with the same speed there will be no liquid
junction potential.

Expression for Liquid Junction Potential

When different concentrations of same electrolytic solutions are in contact, liquid junction potential
can be measured. Let us consider the simplest case in which the junction is formed between two
solutions of the same uni-univalent electrolyte at activities a1 and a2.

KCl (a1) │KCl (a2)

Adopting the usual convention for a (+)ve emf, the left hand electrode is the source of electrons so
that (+)ve current flows through the interior of the cell from left to right. If one Faraday of electricity
is passed in the cell, nc gram ion of cation (i.e. K+ ion) migrates from left to right i.e., from solution
of activity a1 to a2. Likely, na gm ion of anion (i.e., Cl- ion) migrates from right to left. na and nc are
the transference numbers of anions and cations respectively. If transference number is assumed to be
independent of concentration, then the free energy change during the passage of one faraday of
electricity may be calculated.
𝑎+ 2
The free energy change for (+)ve ion in the left compartment = 𝑛𝑐 𝑅𝑇 𝑙𝑛 . . . .1
𝑎+ 1

𝑎− 1
The free energy change for (-)ve ion in the right compartment = 𝑛𝑎 𝑅𝑇 𝑙𝑛 . . . .2
𝑎− 2

62
Thus the total free energy change (ΔG ) is:
𝑎+ 2 𝑎− 1
∆𝐺 = 𝑛𝑐 𝑅𝑇 𝑙𝑛 + 𝑛𝑎 𝑅𝑇 𝑙𝑛 . . . . . .3
𝑎+ 1 𝑎− 2

Let EL be the liquid junction potential.

The electrical work done = -nELF

∆𝐺 = −nE𝐿 F (n = 1) . . . . . . .4

From equation (3) and (4)

𝑎+ 2 𝑎− 1
−E𝐿 F = 𝑛𝑐 𝑅𝑇 𝑙𝑛 + 𝑛𝑎 𝑅𝑇 𝑙𝑛
𝑎+ 1 𝑎− 2
𝑛𝑐 𝑅𝑇 𝑎+ 2 𝑛𝑎 𝑅𝑇 𝑎− 1
E𝐿 = − 𝑙𝑛 − 𝑙𝑛
𝐹 𝑎+ 1 𝐹 𝑎− 2
𝑛𝑐 𝑅𝑇 𝑎 +2 𝑛𝑎 𝑅𝑇 𝑎 −2
E𝐿 = − 𝑙𝑛 + 𝑙𝑛 . . . . .5
𝐹 𝑎+ 1 𝐹 𝑎− 1

Here a1 and a2 are the mean activities of the electrolyte in the two solutions. By making further
approximation of writing;
𝑎+ 2 𝑎2 𝑎− 2 𝑎2
= 𝑎𝑛𝑑 =
𝑎+ 1 𝑎1 𝑎− 1 𝑎1

Hence, equation (5) reduces to

𝑛𝑐 𝑅𝑇 𝑎2 𝑛𝑎 𝑅𝑇 𝑎2
E𝐿 = − 𝑙𝑛 + 𝑙𝑛
𝐹 𝑎1 𝐹 𝑎1

𝑅𝑇 𝑎2
E𝐿 = (−𝑛𝑐 + 𝑛𝑎 ) 𝑙𝑛 . . . . . . .6
𝐹 𝑎1
Since 𝑛𝑎 + 𝑛𝑐 = 1
𝑛𝑎 = 1 − 𝑛𝑐
Equation (6) may be written as
𝑅𝑇 𝑎2
E𝐿 = (−𝑛𝑐 + 1 − 𝑛𝑐 ) 𝑙𝑛
𝐹 𝑎1

𝑅𝑇 𝑎2
E𝐿 = (1 − 2𝑛𝑐 ) 𝑙𝑛 . . . . . . .7
𝐹 𝑎1

It is clear from equation (6) that the sign of liquid junction potential depends upon the relative values
of transfernce number of anion and cation.

If the liquid function potential under consideration forms part of the concentration cell

Ag/AgCl(s), KCl (a1) / KCl (a2), AgCl(s)/Aghe emf of the cell (Et) is given by

63
 𝑅𝑇 𝑎2
E𝑡 = − 2𝑛𝑐 𝑙𝑛 . . . . . . .8
𝐹 𝑎1
Dividing equation (7) by (8)

E𝐿 (1 − 2𝑛𝑐 )
=
E𝑡 − 2𝑛𝑐

(1 − 2𝑛𝑐 )
E𝐿 = E𝑡
− 2𝑛𝑐

This is the expression for liquid junction potential (diffusion potential).

14. SOLVED PROBLEMS

1. Determine the electrode potential of zinc electrode immersed in 0.1M ZnSO4 solution at
25°C. [ E  Zn2+ / Zn = − 0.763V ]

Given: Concentration ZnSO4 = 0.1M; E  Zn2+ / Zn = − 0.763V ;

E=?

Since this problem has concentration term, we must use Nernst equation for calculating electrode
potential
E = E° +
0.0591
2

log Zn 2+ at 25°C. 
0.0591
= − 0.763 + log (0.1)
2

= − 0.763 − 0.0295

E = − 0.7925V
2. Calculate the standard emf of a galvanic cell. The standard reduction potential of zinc
and copper are −0.76V and +0.34V respectively.

Given: E  Zn2 + / Zn = − 0.76V ; E  Cu 2+ / Cu = + 0.34V

E° cell = E° cathode − E° anode

= E  Cu 2+ / Cu − E  Zn2+ / Zn

= + 0.34 −(−0.76) = 0.34 + 0.76

E° cell = + 1.1V

3. The standard electrode potentials of lead and silver are − 0.13V and + 0.80 V
respectively. Write down the cell reaction and calculate the emf of the cell.

Given: E°Ag+/ Ag = + 0.80V; E°Pb2+/ Pb = − 0.13V

64
 We know that, E° cell = E° cathode − E° anode

= E  Ag + / Ag − E  Pb2+ / Pb

= + 0.80 − (− 0.13)

= + 0.080 + 0.13

= + 0.93V

The anode half cell reaction: Pb → Pb2+ + 2e

The cathode half cell reaction: Ag + + e → Ag

(or) 2Ag + + 2e → 2Ag

The net cell reaction: Pb + 2 Ag + → Pb 2+ + 2 Ag.

4. Calculate the emf of Daniel cell at 25°C when the concentration of ZnSO4 and CuSO4
are 0.01M and 0.1M respectively. Standard emf of the cell is 1.1V.

Given: Concentration of ZnSO4 = 0.01M; Concentration of CuSO4= 0.1M; Std. Emf of the cell =
1.1 V

Since the problem has the concentration terms, we must use Nernst equation to calculate electrode
potentials of zinc and copper.

We know that Ecell = Ecathode − Eanode

Ecell = E Cu 2+ / Cu − E Zn 2+ / Zn ...(1)
According to Nernst equation,

log 0.1 at 25°C

0.0591
E = E  Cu 2 + / Cu +
Cu 2+ / Cu
2

0.0591
E = E  Zn2+ / Zn + log [0.01] at 25°C
Zn 2+ / Zn
2

Substituting these values in equation (1), we get

 0.0591 
Ecell =  E  + log (0.1) −
 Cu 2 + / Cu 2 
  0.0591 
E 2 + + log (0.01)
 Zn / Zn 2 

0.0591 0.0591
= E − E + log(0.1)− log(0.01)
Cu 2 + / Cu Zn 2 + / Zn 2 2

65
= 1.1 +
0.0591
2
log
0 .1
0.01
 E 
Cu 2 + / Cu
− E  Zn2 + / Zn = 1.1V 
= 1.1 + 0.02955

= 1.12955V

5. Calculate the cell potential at 298K for the cell Zn(s)/Zn2+(0.1M)║Sn2+(0.001M)/Sn(s).

Given: E  Zn2+ / Zn = − 0.76V ; E  Sn2+ / Sn = − 0.1V

The reactions taking place in the cell are

Zn → Zn2+ (0.1M) + 2e ( Anode half cell reaction)

Sn2+ (0.001M) + 2e → Sn (Cathode half cell reaction)

Zn + Sn2+ (0.001M) → Zn2+ (0.1M) + Sn

The net cell reaction involves a transfer of 2 moles of electrons ie: n = 2. The Nernst equation for a
reversible complete cell is given by

0.0591 Zn  2+
Ecell = E° cell −
n
log
Sn  2+
at 298ºK

E° cell = − 0.14 − (− 0.76)

= 0.62 V

0.0591 0.1
 Ecell = 0.62 − log
2 0.001

= 0.62 − 0.0591

= 0.5609 V.

REFERENCES

1. B. R. Puri and L.R. Sharma, Principles of Physical Chemistry, Shoban Lal Nagin Chand and
Co. 23rd edition, 1993.
2. Arun Bahl, B. S. Bahl and G. D. Tuli, Essentials of Physical Chemistry, S. Chand publishing,
2012.
3. P.W. Atkins, Physical Chemistry, 7th Ed., Oxford university press, 2001.
4. Glasstone & Lewis, Physical Chemistry, 2nd Edition, McMillan publishers, 1973.
5. A.S. Negi and S. C. Anand, A Textbook of Physical Chemistry, New Age International, 2004.

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