Unit – I

Chemical Thermodynamics

1.1 - Basic definitions in Thermodynamics

1.1.1 Thermodynamic system
A system may be defined as the specified portion of matter under study which is separated
from the rest of the universe by a boundary.

Ex: A substance kept in a beaker.

1.1.2 Surroundings:

The remaining part of the universe which should be in a position to exchange energy and
matter with the system is called as surroundings.

Ex: All that is around the substance under study.

1.1.3 Types of System

1. Closed System:

A system which can exchange energy but not matter with its surroundings is called as closed
system.

Ex: A substance kept in a closed vessel, but not insulated, will be able to exchange energy but not
matter with its surroundings.

2. Open system:

A system, which can exchange energy as well as matter with its surroundings is said to be an
open system.

Ex: Water kept in an open beaker. The heat (energy) is absorbed from the surroundings and the
water vapour (matter) will escape into the surroundings.

3. Isolated system

A system which can exchange neither energy nor matter with its surroundings is called an
isolated system.

Ex: Hot water kept in a closed and insulated vessel. A substance kept in a perfect thermo flask
cannot exchange either energy or matter.
1.1.4 Properties of a system

The macroscopic or bulk properties of a system can be divided into two classes;
a) Intensive properties
b) Extensive properties

Intensive properties:

The properties which do not depend on the quantity of the substance present in a system is
called intensive properties.
Example: temperature, pressure, density, viscosity, surface tension, refractive index, freezing point
etc.

Extensive properties:

The properties which depend on the amount of the substance present in a system are called
extensive properties
Example: mass, volume, energy, internal energy, free energy, entropy, etc.
1.1.5 Thermodynamic Processes
Isothermal process
A process is said to be isothermal if the temperature of the system remains constant during each
stage of the process. Example: consider a chemical reaction taking place in a vessel which is not
insulated. The system is in thermal equilibrium with the surroundings. If the process is exothermic, the
heat is given out from the system to the surroundings at once (keeping temp constant). If the process
is endothermic, the required amount of heat is absorbed instantaneously by the system from the
surroundings.

Adiabatic process
A process is said to be adiabatic if no heat enters or leaves the system during the process. Example:
consider a chemical reaction taking place in an insulated vessel; no heat enters or leaves the system.
If the reaction is exothermic, the heat evolved increases the temperature of the system. If the reaction
is endothermic, the heat absorbed decreases the temperature of the system
Isobaric process
It is the process in which pressure is kept constant throughout.
Example: consider a reaction done in an open vessel which is always at atmospheric pressure. In
isobaric process volume changes may occur.

Isochoric process
It is the process in which the volume is kept constant during a reaction.
Example: Changes occurring in closed vessels.
Spontaneous and non-Spontaneous processes

Spontaneous Process:
A process which occurs by itself without the help of an external force is called a spontaneous process.
All spontaneous processes are irreversible. e.g., water flowing down the hill (all natural processes are
spontaneous).

Non – spontaneous process:

Any process which doesn’t proceed by itself is called as a non- spontaneous process. e.g., water
flowing up a hill
Reversible process
When a process is carried out infinitesimally slowly in such a way that the driving force is
infinitesimally greater than the opposing force it is called as a reversible process. If the opposing force
becomes slightly greater than the driving force, the process reverses itself.
Irreversible process
A process which cannot be reversed without spending large amount of energy is an irreversible
process. e.g., water flowing down the hill is an irreversible process. The reverse of this process namely
moving water up the hill can be achieved only if we spend large amount of energy on it. All irreversible
processes are spontaneous in nature.
Exothermic and Endothermic processes
Many processes are accompanied by energy changes. These changes appear in the form of either
evolution or absorption of heat. Exothermic process is accompanied by evolution of heat. Endothermic
process is accompanied by absorption of heat.

1.1.6 State function

It is a thermodynamic property which depends on the state of the system and it is independent of
the path followed by the system.

e.g., if the pressure and volume of the initial state of a system is P1and V1 and in the final state P2
and V2 respectively, then the differences,

ΔP &ΔV are state functions. Similarly, ΔS, ΔG & ΔE are also state functions.
1.1.7 Path function

Path function is also known as path variable. Properties which depend on the path followed to
bring about the change are called as path functions.
e.g., heat, work, etc.
1.2 - I Law of Thermodynamics.

a) Energy can neither be created nor destroyed, but it can be converted from one form to another
form.
b) The energy of an isolated system remains constant.
c) It is impossible for any machine to produce work without consuming energy. This law is a statement
of the principle of conservation of energy.
1.2.1 Mathematical expression of I Law of Thermodynamics

Consider a system to which a heat energy ‘q’ is supplied. It is used in two ways. One is to
increase the internal energy and the other is to do some useful work.
∴ q = ∆𝐸 + w
∆𝐸 = 𝑞 − w
𝑞 = ℎe𝑎𝑡 𝑎𝑏𝑠o𝑟𝑏e𝑑
W =Work done by the system

1.2.2 Internal energy

A substance is associated with different types of energies such as vibration energy (𝐸𝑣),
rotational energy (𝐸𝑟), translation energy (𝐸𝑡), electronic energy (𝐸e) and nuclear energy (𝐸𝑛).

Internal energy is the sum of all these energies present in a substance.

𝐸 𝐼𝑛𝑡e𝑟𝑛𝑎𝑙 = 𝐸𝑣 + 𝐸𝑟 + 𝐸𝑡 + 𝐸 e + 𝐸𝑛

1.2.3 Enthalpy

Enthalpy represents t h e total energy stored in a system i.e., the sum of internal energy and
pressure volume work of a system under a particular set of conditions.

It may be represented as, H=E+PV, change in enthalpy of a system at constant P can be written as

∆𝐻 = ∆𝐸 + 𝑃∆𝑉
1.2.4 Relationship between ∆𝐸 & ∆𝐻

By definition, ∆𝐻 = ∆𝐸 + 𝑃∆𝑉 ---------------- (1)

The ideal gas equation at constant pressure in two different states are

𝑃𝑉1 = 𝑛1𝑅𝑇 ------------------- (2)

𝑃𝑉2 = 𝑛2𝑅𝑇 ------------------- (3)

Subtracting eqn. (2) from eqn. (3),

(𝑉2 − 𝑉1) = (𝑛2 − 𝑛1) 𝑇
𝑃∆𝑉 = ∆𝑛𝑅𝑇
Substituting in eqn. (1),
 ∆𝐻 = ∆𝐸 + ∆𝑛𝑅𝑇 ------------- (4)

Where ∆𝑛 = 𝑛2 − 𝑛1

𝑛1=no. of moles of gaseous reactants

𝑛2=no. of moles of gaseous products

1.2.5 Limitations of the I law

a. I law is concerned only with the energy changes, but not the direction in which energy
changes take place
b. It does not tell about the feasibility of a reaction
c. It does not explain why the heat energy cannot be completely converted into work.
The above statement leads to the need for the II law of thermodynamics.

1.3 - II Law of Thermodynamics

Statements of II Law:
a) In terms of inter-conversion of heat and work: Heat cannot be completely converted into work
without producing changes elsewhere, either in the system or surroundings.
b) In terms of the flow of heat:
Heat never flows from a cooler to a hotter body on its own.
c) In terms of entropy:
The entropy of the universe is increasing continuously.
1.3.1 Concept of entropy

Entropy is a measure of degree of disorder or randomness in a given system. i.e., when a

system goes from a more orderly to a less orderly state, the randomness increases; hence entropy of
the system increases.

Ex: When a solid changes into a liquid, there is an increase in entropy since the arrangement of
atoms and molecules is less ordered in liquid.

1.3.2 Significance of Entropy

Entropy is very significant in thermodynamics. The significances are mentioned below:

a) Entropy is a physical quantity. It is equal to the ratio of heat absorbed or rejected to the
temperature.
b) It indicates the direction of heat flow. A spontaneous process is also known as an irreversible
process because these processes take place at a very fast rate. All the natural processes are
spontaneous processes.
c) It helps in determining the thermodynamic state of an object. A little consideration will show
that when a spontaneous process takes place it moves from less probable state to a more probable
state.
 d) Like temperature, pressure, volume, internal energy, magnetic behavior it expresses the state of
a body.
e) The orderliness of an object decreases with the increase of entropy. Hence spontaneous
processes are accompanied by an increase in entropy as well as an increase in the disorder of the
system.
f) Like temperature or pressure, it cannot be felt. Hence the state of the order of the molecules gets
disturbed and gives rise to greater disorder.
g) It is a measure of the disorder or randomness in the system. When a gas expands into a vacuum,
water flows out of a reservoir, spontaneous chain reaction takes place, an increase in the disorder occurs
and therefore entropy increases.

1.3.3 Mathematical expression of entropy:

If any process is carried out between the limits of initial state 1 and final state 2, with the
absorption of heat qrev at constant temperature then the entropy change is shown as,

Heat absorbed reversibly

∆𝑆 = 𝑆2 − 𝑆1 =
Temperature at which heat is absorbed
𝑞𝑟e𝑣
∆𝑆 =
𝑇

qrev/T is a state function which depends on the initial state (S1) and final state (S2)

If qrev is positive, (heat is absorbed) S is also positive indicating an increase in entropy. When heat is
evolved, qrev is negative and S is also negative indicating a decrease in entropy.
-1
SI units of entropy and change in entropy is Joules/ Kelvin (JK )

1.3.4 Gibbs free energy (G)

In a system, a part of the total energy supplied is converted into useful work and the rest is unavailable.
The part of energy which is converted into useful work is called the available energy, which is called
as the Gibbs free energy.
Available Energy = Total Energy-Unavailable Energy
Mathematical expression, 𝐺 = 𝐻 − 𝑇𝑆
1.3.5 Helmholtz Work Function (A)
We know that a part of internal energy of a system can be used at constant temperature to do
useful work. This part of the internal energy which is isothermally available to do useful work is called
the work function (A) of the system. It is mathematically defined as

A=E-TS
A=E-TS
1.3.6 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
ΔA=ΔE-TΔS -----------------------(2)
But by definition,
ΔS=qrev/T (or) TΔS= qrev -------------------------- (3)
Substituting TΔS in equation (2), we get
ΔA=ΔE- qrev ------------------------------------ (4)
But according to I law of thermodynamics
ΔE= q-W
(or) -----------------------------------(5)
ΔE- q= -W
Comparing equation (4) and (5)
ΔA= -W
(or)
ΔA= - 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.
1.3.7 Physical Significance of the Free Energy(G)
The free energy is a 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 a constant temperature

ΔG=ΔH-TΔS-------------------(2)

But, ΔH=ΔE+PΔV ----------------- (3)

Equation (3) is written as

ΔG=ΔE+PΔV-TΔS--------------- (4)

We know that

ΔA=ΔE-TΔS ------------------(5)

Hence equation (4) can be written as

 ΔG=ΔA+PΔV ------------------------(6)
Since ΔA=-Wmax -----------------------------(7)
Substitute equation (7) in equation (6)
ΔG= -Wmax +PΔV
-ΔG= Wmax -PΔV
Where PΔV is the work done by expansion and Wmax is the maximum work that can be obtained from
the system. Therefore,
Wmax –PΔV = Network or Useful work
Hence,
-ΔG= W useful
So, the decrease in free energy accompanying a process at constant temperature and pressure, is equal
to the useful work obtainable from the system.

1.3.8 Entropy changes in reversible isothermal expansion of an ideal gas.

Consider a certain mass of an ideal gas in a cylinder fitted with a frictionless and weightless piston.
The gas is allowed to expand isothermally and reversibly. As the expansion is carried out isothermally,
there will be no change of internal energy.

i.e. ∆𝐸 = 0

Hence from the I Law equation,

q-w=0
i.e., q=w
In such a case the work done in the expansion of one mole of a gas from volume V 1 to V2 at
constant temperature ‘T’ is given by

w = PdV

𝑞𝑟e𝑣 =PdV

For an ideal gas,

PV =nRT
 Therefore, 𝑃 = nRT
𝑉 𝑞𝑟ev nRT
= 𝑑𝑉
Integrating within the limits V2 and V1 𝑉

𝑞𝑟e𝑣 = 𝑛𝑅𝑇
𝑉1
𝑉2
𝑞𝑟ev = 𝑛𝑅𝑇𝑙𝑛
Change in entropy, ∆S is given as 𝑉1

𝑞𝑟e𝑣 1 𝑉2
∆𝑆 = = 𝑛𝑅𝑇 𝑙𝑛
𝑇 𝑇
𝑉1
ie, ∆𝑆 = 𝑛𝑅𝑙𝑛 𝑉2
𝑉1

∆𝑆 = 2.303 𝑛𝑅 𝑙og 𝑉2 / 𝑉1

1.3.9 Problems related to entropy

1. State which of the following will have more entropy. Explain why?
0 O
a) Ice and water b) Water at 100 and c) steam at 100 c

a) Water will have more entropy than ice

O O
b) Steam at 100 c will have more entropy than water at 100 c

Entropy increases as Solid changes to liquid and liquid in turn changes to gas since randomness or
disorderliness increases in the above order.
2. Calculate the entropy change in the melting of one mole of ice at 0oC. Latent heat
of fusion of ice = 80 cals.

∆𝐻ƒ 𝐿ƒ × 𝑀
∆𝑆 = =

𝑇 𝑇

80 × 18
∆𝑆 =
273
∆𝑆= ∆Hf = Lf X M
T T
∆𝑆 = 4.184 𝑐𝑎𝑙𝑠/𝑚o𝑙/𝑑e𝑔

[1 cal = 4.184 joules]

5.27 × 4.184 = 22.05 𝐽/𝐾/𝑚o𝑙e

3. Helium, weighing 4 gm, is expanded from 1 atm to one-tenth of the original pressure
at 300 C. Calculate the change in its entropy, assuming it to be an ideal gas.
Solution
We know that
∆𝑆=2.303 X n X R X log P1/P2
Number of moles, n = Weight (in gm) = 4 = 1 mole
Mol. Wt 4

R=1.987 cal. K-1 mol -1; P1 = 1 atm; P2=1/10 atm

∆𝑆=2.303 X 1 X 1.987 X log 1

1/10
∆𝑆 =4.57 e.u

4. One mole of an ideal gas expands isothermally to twice its original volume at 29 o C. Calculate the
entropy change during the process.
Entropy change in an isothermal expansion of an ideal gas is given by ∆𝑆= 2.303 nR log V2/V1

Given: V1 = 1; V2= 2; n=1; R=1.987 cals (known value)

∆𝑆= 2.303 X 1 X 1.987 X log 2/1

= 2.303 X 1.987 X 0.3010

= 1.377 e.u.

1.3.10. Criteria for spontaneity

We know that
∆G=G2-G1

Where G1 is the free energy of the initial state and G2 is the final state's free energy. We can easily visualize
the fact that when G1 > G2, the change would be spontaneous. Thus, the value of ΔG should be negative
for a spontaneous reaction.
The equation ΔG=ΔH-TΔS shows that ΔH and ΔS decide the value of ΔG.

Like ΔG, a negative value of ΔH will support spontaneous change. But increase of ΔS (a positive value)
will support spontaneous change. Conditions of spontaneity are as here under. When a system is at
equilibrium, ΔG=0. Then ΔH and ΔS will have same sign and equal magnitude.

S.NO ΔH value ΔS vlaue Condition ΔG value Result

1. - ve + ve - - ve Spontaneous

2. - ve - ve ΔH>TΔS - ve Spontaneous

3. + ve + ve ΔH<TΔS - ve Spontaneous

4. + ve - ve - + ve Non- spontaneous

5. 0 - ve - + ve Non- spontaneous

6. 0 + ve - - ve Spontaneous

7. - ve 0 - - ve Spontaneous

1.4 Gibbs-Helmholtz equation

The Gibbs free energy is given by,

We know that,
𝐺 = 𝐻 − 𝑇𝑆

i.e., 𝐺 = 𝐸 + 𝑃𝑉 − 𝑇𝑆 𝐻 = 𝐸 + 𝑃𝑉
on differentiation,

𝑑𝐺 = 𝑑𝐸 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 – 𝑆𝑑𝑇 ------------------------------ (1)

The first law equation for an infinitesimal change may be written as,

𝑑𝐸 = 𝑑𝑞 − 𝑑w (2)

𝑑𝑞 = 𝑑𝐸 + 𝑑w
If the work done is only due to expansion, then

𝑑𝑞 = 𝑑𝐸 + 𝑃𝑑𝑉

The mathematical expression for II-law is,

𝑑𝑞
𝑑𝑆 = (o𝑟) 𝑑𝑞 = 𝑇𝑑𝑆
𝑇
𝑑𝑞 = 𝑇𝑑𝑆 = 𝑑𝐸 + 𝑃𝑑𝑉

(or)

𝑑𝐸 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 ------------------------------------------(3)

Substituting this value in equation (1),

𝑑𝐺 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇

𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 ----------------------------------------- (4)

At constant pressure,

𝑑𝐺 = −𝑆𝑑𝑇 ----------------------------------------------- (5)

Let us consider a closed system. Let us assume that in the initial state, at temperature T, the
free energy of the system is G1. In the same initial state, at temperature T + dT, the free energy
of the system is G1 + dG1
In the final state, at temperature T, the free energy of the system is G2. In the same final state at the
same temperature T + dT, the free energy is G2 + dG2

Therefore, 𝑑𝐺1 and 𝑑𝐺2 can be written as

𝑑𝐺1 = – 𝑆1𝑑𝑇
𝑑𝐺2 = – 𝑆2𝑑𝑇
𝑑𝐺2 – 𝑑𝐺1 = – 𝑆2𝑑𝑇 – (– 𝑆1𝑑𝑇)

𝑑𝐺2 – 𝑑𝐺1 = – (𝑆2 – 𝑆1)

𝑑𝐺2 – 𝑑𝐺1 = – ∆𝑆𝑑𝑇
The difference in free energies of state 1 and state 2 is
𝐺2 − 𝐺1 = ∆𝐺
𝑑𝐺2 − 𝑑𝐺1 = 𝑑∆𝐺
d (∆G) = – ∆S dT

𝑑(∆𝐺)
= −∆𝑆
𝑑𝑇
Since this equation is obtained by considering the change in free energy at constant pressure, it can be
written as,

= −∆𝑆 ----------------- (7)

P
According to Gibb’s, G = H – TS
For an isothermal process,
∆𝐺 = ∆𝐻 − 𝑇∆𝑆

∆𝐺 − ∆𝐻
= −∆𝑆 ------------------- (8)
𝑇
Comparing equations (7) and (8),
 ∆G-∆H = - ∆S
T
∆G-∆H = T
P

T
∆G = ∆H + T
P (9)

This is one form of Gibbs – Helmholtz equation.

1.4.1 Applications:

(1) It is used to calculate the heat change H, for a process or a reaction taking place at
constant pressure provided the values of free energy change at two different temperatures
are known
(2) It is used to calculate H and S of a redox reaction taking place in a Galvanic
cell.
In a Galvanic cell electrical energy produced is equal to the free energy decrease
of the cell reaction.
Electrical energy produced = nFE
Where n is the no. of electrons
F is the Faraday, E is the emf

∆𝐺 = −𝑛𝐹𝐸 − − − − − − − −(1)

∆𝐺 = ∆𝐻 + 𝑇 P − − − − − − (2)

Substituting –nFE for ∆𝐺 We get

− − − − − − − −(3)
−𝑛𝐹𝐸 = ∆𝐻 + 𝑇 (6(−𝑛𝐹𝐸))
6𝑇 𝑃
dividing the above equation by –nF
𝑇∂𝐸
+
∆𝐻 ∂𝑇

𝐸=
−𝑛𝐹

𝑇∂𝐸 ∆𝐻
𝐸− =
∂𝑇 −𝑛𝐹

−𝑛𝐹 (𝐸 − 𝑇∂𝐸) = ∆𝐻 − − − − − − − − − (4)

6𝑇
∆𝐺 = ∆𝐻 − 𝑇∆𝑆 − − − − − − − − − − (5)
Comparing equations (3) and (5)
∂(−𝑛𝐹𝐸)
−∆𝑆 =
∂𝑇

∂(𝑛𝐹𝐸)
∆𝑆 =
∂𝑇
𝑛 𝐹∂(𝐸)
∆𝑆 =
∂𝑇
1.4.2 Gibbs – Helmholtz equation using work function ‘A’

We know that work function,

𝐴 = 𝐸 − 𝑇𝑆 - ----------------- (1)
On differentiation,
𝑑𝐴 = 𝑑𝐸 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 - -------------------- (2)

From I law we know that,

𝑑𝐸 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉

Substituting the value of dE in equation (2)

𝑑𝐴 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇 -----------------------------------------------------(3)

At constant volume, dV=0

𝑑𝐴 = −𝑆𝑑𝑇
For a given system at state1 and state2

𝑑𝐴1 = −𝑆1𝑑𝑇 ------------------- (4)

𝑑𝐴2 = −𝑆2𝑑𝑇 ------------------------- (5)

Subtracting the equation (4) from (5)

(𝐴2 − 𝐴1) = −(𝑆2 − 𝑆1)𝑑𝑇

𝑑(∆𝐴) = −(∆𝑆)𝑑𝑇
If the volume is constant,
(
V
= − (∆𝑆) ----------------------------- (6)
From the equation of work function,
𝐴 = 𝐸 − 𝑇𝑆

∆𝐴 = ∆𝐸 − 𝑇∆𝑆

−∆𝑆 = ∆A−∆𝐸 (7)

T
comparing the equation (6) and (7)
 − − − − − − − − − −(8
V =

= +T V

Equation (8) is another form of Gibbs-Helmholtz equation.

1.4.3 Problems based on the Relation between ∆G, ∆H and ∆S

1. ΔH and ΔS for a reaction at 270C are -10 kcals and 20 cals K-1 respectively. What is ΔG for the
reaction? Predict whether the reaction will be feasible or not.

Solution: The free energy change is expressed as

∆𝐺 = ∆𝐻 − 𝑇∆𝑆
Given: ∆𝐻=-10 kcals (or) -10,000 cals ; ∆𝑆= 20 cals K-1
T= 27+273 = 300 K
∆𝐺 = -10,000 – 300 (20)
∆𝐺 = -16,000 cals
∆𝐺 = -16 kcals
As ∆𝐺 is negative, the reaction is feasible.
2. Predict whether the following reaction is spontaneous at 250C. ΔH=31.4 kcals/mol,
ΔS=32 cals/deg at 250C.
C(s)+H2O(l) CO(g)+H2(g)
Given : ΔH=31.4 kcals/mol or 31.4 X 103 cals mol -1, ΔS=32 cals/deg at 250C,T= 27+273= 300 K
Solution: The free energy change is expressed as
∆𝐺 = ∆𝐻 − 𝑇∆𝑆
∆𝐺 = 31.4 X 103 - 298 (32)
∆𝐺= 21864
∆𝐺= 2.186 kcals.
Since ∆𝐺 is positive, the reaction is not spontaneous at 250C.
Problems based on the Applications of Gibbs-Helmholtz Equation
1.The free energy change, ∆𝐺 for a process is -138 KJ at 300C and -135 KJ at 400C. Calculate the
change in entropy and ∆𝐻 accompanying the process at 350C.
Solution: According to Gibbs-Helmholtz equation

∆𝐺 = ∆𝐻 + 𝑇 ( ∂(∆𝐺) ). P

∂𝑇
Here , d ∆𝐺 = ∆𝐺2 -∆𝐺1 and T = T2 - T1
∆𝐺1 = -138 KJ; ∆𝐺2 = -135 KJ
T1 = 300 C = 30+273 = 303 K
T2 = 400 C = 40+273 = 313 K
 So, ( ∂(∆𝐺) ) = -135 – (-138) = 3
∂𝑇 313 – 303 10

=0.3 KJ

The change in free energy ΔG at 350 C may be taken as the average value of ΔG at 300 C
.and 400 C.
i.e., T = 303+ 313
2
= 308 K
Hence ΔG at 308 K = -135 + (-138)
2
= - 136.5 KJ
Putting these values in the Gibbs-Helmholtz equation and simplifying for ΔH.

ΔG = ΔG - 𝑇 ( ∂(∆𝐺) ) . P

∂𝑇
= - 136.5 – 308 (0.3)
ΔG = - 228.9 KJ
Further ΔG = ΔH – TΔS
(Or)
ΔS = ΔH – ΔG
T
= -228.9 – (-136.5)
308
= - 92.4 / 308
ΔS = -300 J

1.5 Maxwell’s relations

A thermodynamic system is described by the state functions like P, V, T, S, E, H, A and G.

Using these functions, four important relations can be derived, which are known as Maxwell’s
relations.

We already know that,

𝐻= 𝐸 + 𝑃𝑉
𝐴= 𝐸 − 𝑇𝑆
𝐺= 𝐻 − 𝑇𝑆
∆𝐸 = 𝑞− W
 From these equations we have,
𝑑𝐸 = 𝑑𝑞 − 𝑑W = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 −I
Since, 𝑑𝑆 = 𝑑𝑞, 𝑑W = − 𝑃. 𝑑𝑉
𝑇
𝑑𝐻 = 𝑑𝐸 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 − II
𝑑𝐴 = 𝑑𝐸 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇 − III
𝑑𝐺 = 𝑑𝐻 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 − IV
The above four equations are called fundamental equation of Thermodynamics.
I – relation:
Consider the fundamental equation

If volume is kept constant,

Differentiate equation (2) with respect to (V) at constant entropy,

If entropy is kept constant,

Differentiating equation (4) with respect to (S) at constant volume,

Comparing equations (3) and (5)

Equation – I, states that the change of temperature with volume at constant entropy is negatively
equal to the change of pressure with entropy at constant volume. This is one form of Maxwell’s
relation

II – relation:

Consider the fundamental equation

If pressure is kept constant,

Differentiate equation (2) with respect to (P) at constant entropy,

 If entropy is kept constant,

Differentiating equation (4) with respect to (S) at constant pressure

Comparing equations (3) and (5)

This equation states that “the rate of change of temperature with pressure at constant entropy is equal
to the change of volume with entropy at constant pressure.

III – relation:

Consider another fundamental equation,

If volume is kept constant,

Differentiate equation (2) with respect to (V) at constant temperature,

If temperature is kept constant,

Differentiating equation (4) with respect to (T) at constant volume,

Comparing equations (3) and (5)

This is the third form of Maxwell’s relation which states that “the change of entropy with volume
at constant temperature is equal to the change of pressure with temperature at constant volume.

IV -relation
Consider another fundamental equation,

If pressure is kept constant,

Differentiate equation (2) with respect to (P) at constant temperature,

 If temperature is kept constant,dT

Differentiating equation (4) with respect to (T) at constant pressure,

Comparing equations (3) and (5)

This is the fourth form of Maxwell’s relation which states that “the change of volume with temperature at
constant pressure is negatively equal to the change of entropy with pressure at constant temperature.