Physical Chemistry

Chemical Thermodynamics

Dr. R. R. Misra
Reader in Chemistry
Hindu College, Delhi – 110007
E- mail: rrmisra@hotmail.com

CONTENTS

Thermodynamics
Thermodynamic process
Isothermal process
Adiabatic process
Isobaric process
Reversible process
Irreversible process
Cyclic process
Concept of internal energy, work and heat
Concept of internal energy
Concept of work in thermodynamics
Concept of heat in thermodynamics
Thermal equilibrium
The first law of thermodynamics
Definition of enthalpy
Characteristics of enthalpy
Heat capacity
Joule’s Law
Joule – Thomson Coefficient
Carnot theorem
Thermochemistry
Enthalpy of reaction
Enthalpy of combustion
Enthalpy of neutralization
Bond enthalpy
Kirchhoff’s equation
Second law of thermodynamics
Concept of entropy
Third law of thermodynamics
Nernst heat theorem
Concept of residual entropy
Evaluation of absolute entropy
Need of a new thermodynamic property
Gibbs energy
Gibbs energy change and useful work
Helmholtz energy
Introduction

In the study of chemistry the following fundamental questions need to be answered.

(i) Why does a reaction occur? That is, what is the driving force of a reaction?

(ii) How far a reaction can occur? That is, what is the extent (or progress) of the reaction?

(iii) How fast a reaction can occur? That is, what is the rate of the reaction?

We get the answer of the first two questions by the study of thermodynamics, while third
question forms the domain of the study of chemical kinetics. In this unit we shall focus our
attention mainly on thermodynamics while the study of chemical kinetics will be taken up in
other unit of the book

Thermodynamics

The branch of science dealing with the relations between energy, heat, work and
accompanying changes in the nature and behaviour of various substances around us is called
thermodynamics. The principles of thermodynamics have been enunciated in the form of a
few laws of thermodynamics called zeroth law, first law, second law and third law. These
laws find applications in physics, chemistry, engineering, medicine, biotechnology,
biochemistry, geology and space sciences. The branch of chemistry dealing with the
investigation of energetics and feasibility of chemical reactions and physical changes is called
chemical thermodynamics. Its principles are simple, and its predictions are powerful and
extensive.

The predictive power of chemical thermodynamics is based on the characteristics of

thermodynamic properties namely internal energy (U), enthalpy (H), entropy (S) and free
energy functions (A and G) and their variations with variables like temperature, pressure,
volume and amount. The changes in these properties depend only on the initial and final
states of the system, and are independent of the path followed for the system Therefore, these
thermodynamic properties are called state functions. This aspect will be discussed later in
this unit.

Aim of the study of chemical thermodynamics

The main aim of the study of chemical thermodynamics is to learn (i) transformation of
energy from one form into another form, (ii) utilization of various forms of energy and (iii)
changes in the properties of systems produced by chemical or physical effects. Therefore, this
branch of science is called chemical energetics also.

Various forms of energy involved in the study of chemical thermodynamics

In the study of chemical thermodynamics most frequently we deal with the interconversions
of four forms of energy namely, electrical energy, thermal energy, mechanical energy, and
chemical energy. The energy involved in the chemical processes is called chemical energy.
That is, it is the energy liberated or absorbed when chemical bonds are formed, broken or
rearranged. For example, when hydrogen and oxygen combine water is formed and a large
quantity of chemical energy is released. When one mole H–H and half mole O = O bonds are
broken, two moles of O–H bonds are formed as H–O–H. In the process energy is required to
break

1
H – H and O = O bonds whereas energy is liberated in the formation of O – H bonds. As a
result of breaking and formation of bonds the energy equivalent to 286 kJ is released. The
changes are described by the equation.

H – H + ½ O = O ⎯⎯→ H – O – H + 286 kJ

Conversion of chemical energy into other forms

Depending upon the conditions under which the reaction proceeds, the chemical energy
released can be made to appear as thermal energy, mechanical energy or electrical energy.

™ If the reaction takes place in a closed vessel immersed in a water bath, the chemical
energy will appear as thermal energy (heat), which would warm the vessel, the reaction
mixture and the bath.

™ If the reaction proceeds in a cylinder fitted with a movable piston, the chemical energy
released can be made to produce mechanical work (work of expansion) by forcing the piston
to move in the cylinder against an external pressure.

™ If the reaction is allowed to take place in an appropriate electrochemical cell, the

chemical energy can be converted into electrical energy.

Thermodynamic terms

In order to understand and appreciate the power of thermodynamics it is necessary to become

familiar with the commonly used terms in thermodynamics.

System. A system is a portion of the universe which is selected for investigations. The
system may be water taken in a beaker, a balloon filled with air, an aqueous solution of
glucose, a seed, a plant, a flower, a bird, animal cell etc.

Surroundings. The rest of the universe, which can interact with the system, is called
surroundings. For practical purposes the environment in the immediate vicinity of the system
is called the surroundings. The boundary may be real or even imaginary

Boundary. The space that separates the system and the surroundings is called the boundary.
The system and surroundings interact across the boundary.

Surroundings
(Thermostat)

Boundary
System

Fig. 1. Illustration of system, surroundings and boundary

2
Let us suppose that water is taken in a beaker and kept in a constant temperature bath (called
thermostat) as shown in Fig. 1. Here water is the system. Each wall of the beaker is a
boundary (water-air surface is another boundary). The constant temperature bath is the
surroundings.

Types of boundary: Depending upon the nature of the walls of the container boundary can
be classified as follows.

(a) Rigid boundary. It is a wall whose shape and position are fixed

(b) Impermeable boundary: It is a wall that prevents the passage of the matter but
permits the passage of energy.

(c) Permeable boundary. It is a wall that permits the passage of matter and energy

(d) Adiabatic boundary. It is a wall that prevents the passage of mass or energy.

(e) Diathermic boundary. It is a wall that allows the passage of energy but prevents the
passage of matter. That is, a diathermic boundary is impermeable but not adiabatic

Types of system

Depending upon the nature of the boundary the system can be identified as open, closed
or isolated.

(i) An open system. It is a system which has permeable boundary across which the
system can exchange both the mass (m) and energy (U) with the surroundings.
Thus in an open system mass and energy may change. In terms of symbolic
notation it may be stated that in an open system ∆m ≠ 0 and ∆U ≠0

(ii) A closed system. It is a system with impermeable boundary across which the
system cannot exchange the mass (m) but it can exchange energy (U) with the
surroundings. Thus in a closed system mass remains constant but energy may
change. In terms of symbolic notation it may be stated that in an open system ∆m
= 0 but ∆U ≠0

Open system Closed system Isolated system

Fig. 2. Types of systems

3
 (iii) An isolated system. It is a system with rigid and adiabatic boundary across which
neither exchange of mass (m) nor energy (U) between the system and the
surroundings is not permissible. Thus in an isolated system mass and energy
remain unchanged. In terms of symbolic notation it may be stated that in an
isolated system ∆m = 0 and ∆U =0 Milk kept in a thermos flask is an example of
an isolated system.

Extensive and intensive properties

Some of the properties of a system depend on its size whereas others do not depend on its
size. Therefore, the properties of a system are grouped as extensive property and intensive
property.

Extensive property. A property which depends directly on the size of the system is called
extensive property. Volume, mass and amount (mole) are extensive properties.

Characteristics of an extensive property

™ An extensive property of the entire system is greater than any of its smaller parts.

™ The sum of the properties of subsystems is equal to the same property of the entire
system. This means that the extensive properties are additive.

Intensive property. A property which does not depend on the size of the system is called
intensive property. Density, temperature and molarity are intensive properties.

Characteristics of an intensive property

™ An intensive property of a homogeneous system is the same as that of any of its smaller
parts.

™ The intensive properties are nonadditive.

Illustration that volume is an extensive property but temperature is an intensive

property

Take 100 mL of water in a beaker (main system A) and note its temperature (say it is 25
°C). Now divide water (the main system) into four parts as subsystems A1 (10 mL), A2 (20
mL), A3 (30 mL), and A4 (40 mL). Here we observe that the volume of the main system A is
larger than the volume of any individual subsystem. But the sum of the volumes of
subsystems (10 mL + 20 mL + 30 mL+ 40 mL) is equal to the volume of the main system
(100 mL). So volume is an extensive property.

Record the temperature of each subsystem. It is observed that the temperature of each
subsystem A1, A2, A3, and A4 is the same as it was for the main system. Therefore,
temperature is an intensive property.

4
List of extensive and intensive properties

Extensive properties Intensive properties

Volume, mass, amount (mole), Molar volume, density, molar

energy, enthalpy, entropy, free mass, molarity, mole fraction,
energy, heat capacity molality, specific heat capacity

A general statement: The ratio of two extensive properties is an intensive property. For
example:

(1) Density is an intensive property

Mass (extensive property)

= Density (intensive property)
Volume (extensive property)

(2) Molarity is an intensive property

Mole of the solute (extensive property)

= Molarity (intensive property)
Volume of solution (extensive property)

Logical explanation that molarity of solution is an intensive property

When we prepare 100 mL of 0.1 molar solution of Mohr salt in a measuring flask, we

say that its molarity is 0.1 mol/L (0.1 M). Now, if we take 20 mL or 10 mL of this solution,
its molarity is still 0.1 mol/L. Thus, the molarity does not depend on the size (volume) of the
system (solution) and it is an intensive property.

State variables of the system

A system can be described by its measurable properties such as temperature (T), pressure (P),
volume (V) and amount (n = moles of various species present in the system). These
measurable properties (T, P, V, n) are called state variables.

Reason: If the state variables are fixed, the other properties of the system are also fixed. If
the state variables are changed the properties of the system are accordingly changed. This
implies that all the state variables are not independent. That is, the state of the system may be
defined by fixing a certain minimum number of variables depending on the nature of the
system.

State properties of the system and state functions

A property of the system which depends only on the state variables is called state property or
state function. The change in a state property depends only on the initial and final states of
the system. A state property is independent of the manner in which the change is brought
about. This means that the state property does not depend on the path followed by the
system.

Thermodynamic properties namely energy (U), enthalpy (H), entropy (S), work function (A)

5
free energy (G), volume (V), pressure (P) and temperature (T) are state functions. A state
function say energy (U) may be mathematically represented as U = U (T, V, n). The
mathematical representation is stated as U is a function of T, V, and n. That is, energy of the
system depends on the state variables T, V and n. Similarly; volume of the system is a
function of temperature (T), pressure (P) and amount (n). That is, V = V (T, P, n). For a
system of constant composition (for a constant value of n) the volume of a gas is a function of
temperature and pressure only i.e., V = V (T, P).

We can understand the meaning of state functions and state property by taking an analogy.
Suppose that one wants to climb a. mountain peak l km above ground level. This decision
defines the initial state (ground where h = 0) and the final state (peak where h = h). There
may be various paths up to the mountain peak but the vertical height (h) of the peak from the
ground is 1 km. The height of the mountain peak cannot be altered by choosing different
paths though the actual distance travelled and the amount of work put in will be different if
different paths are followed. Vertical distance in this analogy corresponds to a
thermodynamic function.

Mathematical formulation of state property (Φ)

A thermodynamic property (Φ) of the system is called state function if it can be expressed in
terms of state variables say x and y as

Φ = Φ (x, y)

The function Φ can represent any thermodynamic state property namely P, V, T U, H, S, A,

and G

The total differential of a state function is an exact differential. It is expressed in terms of

partial derivatives as follows.

⎛ ∂φ ⎞ ⎛ ∂φ ⎞
d Φ =⎜ ⎟ dx + ⎜⎜ ⎟⎟ dy
⎝ ∂x ⎠ y ⎝ ∂y ⎠ x

⎛
∂φ ⎞ ∂φ
Or, d Φ = ⎜⎜ ⎟⎟ dy + ⎛⎜ ⎞⎟ dx
⎝ ∂y ⎠ x ⎝ ∂x ⎠ y

In the expression for total differential

⎛ ∂φ ⎞
⎜ ⎟ = Partial derivative of Φ with respect to x at constant y and dx is the small change in
⎝ ∂x ⎠ y
the variable x. Therefore,

⎛ ∂φ ⎞
⎜ ⎟ dx = Change in the function Φ due to change in the variable x
⎝ ∂x ⎠ y

Similarly,

⎛ ∂φ ⎞
⎜⎜ ⎟⎟ = Partial derivative of Φ with respect to y at constant x and dy is the small change in
⎝ ∂y ⎠ x

6
 ⎛ ∂φ ⎞
the variable y and ⎜⎜ ⎟⎟ dy = Change in the function Φ due to change in the variable y
⎝ ∂y ⎠ x

The expression for total differential implies that d Φ is the same whether Φ is
differentiated first with respect x at constant y then with respect to y at constant x or first with
respect to y at constant x then with respect to x at constant y. This implies that the order of
differentiation of a state function is immaterial. That is,

∂ ⎡⎛ ∂φ ⎞ ⎤ ∂ ⎡⎛ ∂φ ⎞ ⎤
⎢⎜ ⎟ ⎥ = ⎢⎜ ⎟ ⎥
∂y ⎢⎣⎝ ∂x ⎠ y ⎥⎦ ∂x ⎢⎣⎜⎝ ∂y ⎟⎠ x ⎥⎦
x y

∂ 2φ ∂ 2φ
=
∂y∂x ∂x∂y

The above relation is called Euler’s reciprocity relation.

Simplified form of Euler’s reciprocity relation

⎛ ∂φ ⎞ ⎛ ∂φ ⎞
In equation for total differentia Φ = ⎜ ⎟ dx + ⎜⎜ ⎟⎟ dy , let us suppose that
⎝ ∂x ⎠ y ⎝ ∂y ⎠ x

⎛ ∂φ ⎞
⎜ ⎟ = M (x, y)
⎝ ∂x ⎠ y

⎛ ∂φ ⎞
and ⎜⎜ ⎟⎟ = N (x, y)
⎝ ∂y ⎠ x

Now the total differential d Φ can be written as

d Φ = M(x, y) dx + N(x, y) dy

and Euler’s reciprocity relation can be written as

⎛ ∂M ⎞ ⎛ ∂N ⎞
⎜⎜ ⎟⎟ = ⎜ ⎟
⎝ ∂y ⎠ x ⎝ ∂x ⎠ y

Exercise for proficiency. Describe the method to write the total differential and Euler’s
reciprocity relation for the volume of a fixed amount of a system.

The volume of a fixed amount of a gas is a function of temperature and pressure. That
is, V = V (T, P). Total differential of V is written as

∂V ⎞ ⎛ ∂V ⎞
dV = ⎛⎜ ⎟ dT + ⎜ ⎟ dP
⎝ ∂T ⎠ P ⎝ ∂P ⎠T

(i) In the above equation

dV = Total small change in the volume when temperature and pressure are changed by dT
and dP respectively

7
⎛ ∂V ⎞
⎜ ⎟ = Rate of change of volume with temperature at constant pressure and therefore,
⎝ ∂T ⎠ P

⎛ ∂V ⎞
⎜ ⎟ dT = Change in volume due to change in temperature only
⎝ ∂T ⎠ P

⎛ ∂V ⎞
⎜ ⎟ = Rate of change of volume with pressure at constant temperature and therefore,
⎝ ∂P ⎠ T

⎛ ∂V ⎞
⎜ ⎟ dP = Change in volume due to change in pressure only
⎝ ∂P ⎠ T

Euler’s reciprocity relation for volume is written as

∂ ⎡⎛ ∂V ⎞ ⎤ ∂ ⎡⎛ ∂V ⎞ ⎤
⎢⎜ ⎟ ⎥ = ⎢⎜ ⎟ ⎥
∂P ⎣⎝ ∂T ⎠ P ⎦ T ∂T ⎣⎝ ∂P ⎠ T ⎦ P

∂ 2V ∂ 2V
Or, =
∂P∂T ∂T∂P

Illustration of total differential and exact differential of volume of an ideal gas

The volume of an ideal gas is expressed by the equation PV = nRT or, V = nRT/P. For
one mole of a gas, n = 1 and

RT
V= (i)
P

On differentiating equation (i) we get

R RT
dV = dT − dP (ii)
P P2

This equation implies that the volume of a given amount of the gas is a function of
temperature and pressure

V = V (T, P) (iii)

Total differential of V is written as

∂V ⎞ ⎛ ∂V ⎞
dV = ⎛⎜ ⎟ dT + ⎜ ⎟ dP (iv)
⎝ ∂T ⎠ P ⎝ ∂P ⎠T

The differential dV given by equation (ii) is the same as that given by equation (iv). Thus on
comparing the coefficients of dT and dP of the two equations, we get

⎛ ∂V ⎞ R
⎜ ⎟ = (v)
⎝ ∂T ⎠ P P

8
 ⎛ ∂V ⎞ RT
and ⎜ ⎟ =– 2 (vi)
⎝ ∂P ⎠ T P

On differentiating equation (v) with respect to P at constant T we get

∂ ⎡⎛ ∂V ⎞ ⎤ ∂ ⎛R⎞ R
⎢⎜ ⎟ ⎥ = ⎜ ⎟ =– 2 (vii)
P ⎣⎝ ∂T ⎠ P ⎦ T P ⎝ P ⎠T P

On differentiating equation (vi) with respect to T at constant P we get

∂ ⎡⎛ ∂V ⎞ ⎤ ∂ ⎛ RT ⎞ R
⎢⎜ ⎟ ⎥ = ⎜− 2 ⎟ = – (viii)
T ⎣⎝ ∂P ⎠ T ⎦P T ⎝ P ⎠P P2

Comparison of equations (vii) and (viii) gives

∂ ⎡⎛ ∂V ⎞ ⎤ R ∂ ⎡⎛ ∂V ⎞ ⎤
⎢⎜ ⎟ ⎥ = – = ⎢⎜ ⎟ ⎥
P ⎣⎢⎝ ∂T ⎠ P ⎦⎥ T P 2 T ⎣⎝ ∂P ⎠ T ⎦ P

∂ 2V ∂ 2V
Or, =
∂P∂T ∂T∂P

Conclusion: The total differential of V is an exact differential because it satisfies the Euler’s
reciprocity relation. Thus volume (V) is a state function.

General statements

™ Total differential of a state function is an exact differential.

™ An exact differential follows Euler’s reciprocity relation

Conversely

™ If a total differential follows Euler’s reciprocity relation, it is an exact differential

™ If the total differential of a function is exact, then that function must represent a state
property

Physical interpretation of Euler’s reciprocity relation

The Euler’s reciprocity relation implies that the total change in a state property is
independent of the path (method) followed.

We shall illustrate this aspect by taking an example of change of volume (V) of a given
amount of gas with the change of the temperature and pressure from T1 , P1 to T2 , P2. This
change in volume may be carried by any of the following methods.

Method I: Both the temperature and pressure are simultaneously changed from T1, P1 to T2,
P2

Gas (T1, P1) ⎯simultaneous change of temperature and pressure

⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯⎯→ Gas (T2, P2)

9
 Initial state Final state

Volume change = Final volume of the gas – Initial volume of the gas

∆V (I) = V (T2, P2) – V (T1, P1)

Method II: First the temperature is changed from T1 to T2 at constant pressure (P1), and then
the pressure is changed from P1 to P2 at constant temperature (T2)

Gas (T1, P1) ⎯constant

⎯⎯⎯⎯⎯
pressure constant temperature
⎯→ Gas (T2, P1) ⎯⎯ ⎯ ⎯ ⎯ ⎯ ⎯⎯→ Gas (T2, P2)

Initial state Intermediate state Final state

∆V (II) = [V (T2, P1) – V (T1, P1) ] + [V (T2, P2) – V (T2, P1) ]

= V (T2, P2) – V (T1, P1)

Thus, Volume change = Final volume of the gas – Initial volume of the gas

Method III: First the pressure is changed from P1 to P2 at constant temperature (T1), and
then the temperature is changed from T1 to T2 at constant pressure (P2)

Gas (T1, P1) ⎯constant

⎯⎯⎯⎯⎯⎯
temperature constant pressure
⎯→ Gas (T1, P2) ⎯⎯ ⎯ ⎯ ⎯ ⎯ ⎯→ Gas (T2, P2)

Initial state Intermediate state Final state

∆V (III) = [V (T1, P2) – V (T1, P1) ] + [V (T2, P2) – V (T1, P2) ]

= V (T2, P2) – V (T1, P1)

Thus, Volume change = Final volume of the gas – Initial volume of the gas

Experimentally it has been observed that total change in the volume of the gas is the
same in all the three cases, i.e.,

∆V (I) = ∆V (II) =. ∆V (III)

Thus volume is a state property.

VOLUME IS A STATE PROPERTY– demonstration by calculation

Consider a given amount of an ideal gas in its initial state TI = 300 K, PI = 1 bar, VI = 20 dm3.
Let us suppose that the state variables of the gas are changed to a final state T2 = 600 K, P2 =
0.8 bar, so that its final volume is V2. The change in the state of the gas (system) may be made
in the following ways.

Method 1. The gas is heated and allowed to expand simultaneously from the initial state T1 =
300 K, P1 = 1 bar, V1= 20 dm3 to the final state T2 = 600 K, P2 = 0.8 bar, so that final volume
is V2. Now in this case the gas equation P1 V1/ T1 = P2 V2 /T2 gives

P1V1T2 1 bar × 20 dm 3 × 600 K

V2 = = = 50 dm3
P2T1 0.8 bar × 300 K

10
 Thus change of volume = ∆V (1) = V2 – V1 = 50 dm3 – 20 dm3 = 30 dm3

Method 2. Step (a). The gas is heated at constant pressure from 300 K, 1 bar, 20 dm3 to 600
K, 1 bar so that its volume is Va as given by Charles’s law:

600 K
Va = × 20 dm 3 = 40 dm3
300 K

∆V (2 a) = (40 – 20) dm3 = 20 dm3

Step 2(b) The gas is allowed to expand at constant temperature from 600 K, 1 bar, 40 dm3 to
600 K, 0.8 bar so that its final volume is V2 as given by Boyle's law

1 bar × 40 dm 3
V2 = = 50 dm3
0.8 bar

∆V (2 b) = (50 dm3 – 40 dm3) = 10 dm3

Net change of volume in step 2 =∆V (2 ) = ∆V (2a) + ∆V (2b)

= (20 dm3 + 10 dm3) = 30 dm3

Method 3. Step (a) The gas is allowed to expand at constant temperature from 300 K, 1 bar,
20 dm3 to 300 K, 0.8 bar so that its final volume is Va as given by Boyle's law

1 bar × 20 dm 3
Va = = 25 dm3
0.8 bar

∆V (3a) =(25 dm3– 20 dm3 = 5 dm3

Step 3(b) The gas is heated at constant pressure from 300 K, 0.8 bar, 25 dm3 to 600 K, 0.8
bar so that its final volume V2 is given by Charles’s law:

600 K
V2 = × 25 dm 3 = 50 dm3
300 K

∆V (3b) =(50 dm3 – 25 dm3) = 25 dm3

Net change of volume in step 3 =∆V (3 ) = ∆V (3a) + ∆V (3b)

=(5 dm3 + 25 dm3) dm3= 30 dm3

Discussion: The final state of the system is reached in three different ways but the final
volume in each process is the same V2 = 50 dm3 and the net volume change for all the three
paths is also the same. This proves that volume is a state function and V = V (T, P)

Other characteristics of partial derivatives of a state function (for example V)

(i) Reciprocal of a partial derivative of a state function leads to the reversal of the
differentiation, i.e.,

11
 1 ⎛ ∂T ⎞
= ⎜ ⎟
⎛ ∂V ⎞ ⎝ ∂V ⎠P
⎜ ⎟
⎝ ∂T ⎠P

(2) Two partial derivatives of a state function can be multiplied and their numerators and

denominators can be cancelled provided their constraints (subscripts) are the same. For
example

⎛ ∂V ⎞ ⎛ ∂P ⎞ ⎛ ∂V ⎞
⎜ ⎟ ×⎜ ⎟ = ⎜ ⎟ =1
⎝ ∂P ⎠T ⎝ ∂V ⎠ T ⎝ ∂V ⎠ T

(3) Partial derivatives of a state function obey cyclic rule. For example

⎛ ∂P ⎞ ⎛ ∂V ⎞ ⎛ ∂T ⎞
⎜ ⎟ ×⎜ ⎟ × ⎜ ⎟ +1=0
⎝ ∂V ⎠T ⎝ ∂T ⎠ P ⎝ ∂P ⎠V

⎛ ∂P ⎞ ⎛ ∂V ⎞ ⎛ ∂T ⎞
Or, ⎜ ⎟ ×⎜ ⎟ × ⎜ ⎟ =–1
⎝ ∂V ⎠T ⎝ ∂T ⎠ P ⎝ ∂P ⎠V

Note: To remember the cyclic rule write PVT in a line and differentiate P with respect to V at
constant T (remember PVT), differentiate V with respect to T at constant P (remember VTP),
differentiate T with respect to P at constant V (remember TPV), multiply these derivative and
equate to –1.

Physical significance of partial derivatives of volume

∂V
(i) ⎛⎜ ⎞⎟ = Rate of change of volume with change of temperature at constant pressure
⎝ ∂T ⎠ P

= αV

1 ⎛ ∂V ⎞
Or, α= ⎜ ⎟
V ⎝ ∂T ⎠ P

where α is called isobaric coefficient of thermal expansion, its dimension is T–1

∂V
(ii) ⎛⎜ ⎞⎟ = Rate of hange of volume with change of pressure at constant temperature
⎝ ∂P ⎠ T

= –k V

1 ⎛ ∂V ⎞
Or, k =– ⎜ ⎟
V ⎝ ∂P ⎠ T

where k is called isothermal compressibility coefficient, its dimension is P–1

A negative sign with the derivative tells that volume of the system decreases with increase of
pressure at constant temperature.

Relation between α and k

12
 α ∂P ⎞
(a) = ⎛⎜ ⎟
κ ⎝ ∂T ⎠V

⎛ ∂α ⎞ ⎛ ∂κ ⎞
(b) ⎜ ⎟ =– ⎜ ⎟
⎝ ∂P ⎠T ⎜ ∂T ⎟
⎝ ⎠P

Path dependent function and its differential

A thermodynamic quantity is called a path function if its value depends on the path followed.
For example, work done depends on the path followed by the system. For the same initial and
final states of a system the work done is different under reversible and irreversible conditions
as given below.

(i) wreversible (ideal gas) = –2.303 nRT ln (P1/P2)

P2
(ii) wirreversible (ideal gas) = – nRT (1– )
P1

It is clear from the above relations that w (reversible) ≠ w (irreversible)

Differential of a path function is inexact and it does not follow Euler’s reciprocity
relation. For example, work (w) is a path dependent quantity and its differential is inexact and
is represented by đw

Justification that đw is an inexact differential (Optional)

The work done is given by

đw = – PdV (i)

But V is a state function V= V (T, P) and its total differential is given by

∂V ⎞ ⎛ ∂V ⎞
dV = ⎛⎜ ⎟ dT + ⎜ ⎟ dP (ii)
⎝ ∂T ⎠ P ⎝ ∂P ⎠T

From equations (i) and (ii), we have

∂V ∂V
đw = – P ⎛⎜ ⎞⎟ dT – P ⎛⎜ ⎞⎟ dP (iii)
⎝ ∂T ⎠ P ⎝ ∂P ⎠T

At constant T, dT = 0 and therefore, equation (iii) gives

⎛ ∂w ⎞ ⎛ ∂V ⎞
⎜ ⎟ =–P ⎜ ⎟ (iv)
⎝ ∂P ⎠T ⎝ ∂P ⎠ T

Differentiation of equation (iv) with respect to T at constant P gives

∂2w ⎛ ∂ 2V ⎞
= – P ⎜⎜ ⎟
⎟
(v)
∂T∂P ⎝ ∂T ∂P ⎠

13
At constant P, dP = 0 and therefore, equation (iii) gives

⎛ ∂w ⎞ ⎛ ∂V ⎞
⎜ ⎟ =– P ⎜ ⎟ (vi)
⎝ ∂T ⎠P ⎝ ∂T ⎠ P

Differentiation of equation (vi) with respect to P at constant T gives

∂2w ∂V ⎛ ∂ 2V ⎞
= – ⎛⎜ ⎞⎟ – P ⎜⎜ ⎟
⎟
(vi)
∂P∂T ⎝ ∂T ⎠ P ⎝ ∂P∂T ⎠

Let us suppose that w were state function and dw were exact differential. In such a case
Euler’s reciprocity relation should be valid and

∂2w ∂2w
=
∂T∂P ∂P∂T

⎛ ∂ 2V ⎞ ∂V ⎛ ∂ 2V ⎞
Or, – P ⎜⎜ ⎟
⎟ = – ⎛⎜ ⎞⎟ – P ⎜⎜ ⎟
⎟ (vii)
⎝ ∂T∂P ⎠ ⎝ ∂T ⎠ P ⎝ ∂P∂T ⎠

But V is a state function and dV is exact differential therefore,

∂ 2V ∂ 2V
= (viii)
∂P∂T ∂T∂P

From equations (vii) and (viii) we should have

⎛ ∂V ⎞
⎜ ⎟ =0 (ix)
⎝ ∂T ⎠P

The above equation implies that volume is independent of temperature at constant pressure.
But this result is against the experimental observation (Charles’s law requires that volume of
a given amount of a gas is directly

proportional to absolute temperature at constant pressure).

Conclusion

ƒ We arrived at a wrong result because of the wrong assumption of considering work as

state function and dw as exact differential. Hence đw is inexact differential and w is a path
dependent quantity.

ƒ In the same way it can be proved that đq is inexact differential and heat (q) is path
dependent quantity.

Thermodynamic process

The method of operation which can bring about the change in the system is called
thermodynamic process. Heating, cooling, expansion, compression, fusion, vaporization etc.,
are some examples of thermodynamic process.

Types of process

14
 A change can be carried in different ways and under different conditions. Therefore,
the processes can be classified as follows:

Isothermal process. A process is said to be isothermal when the temperature of the system is
kept constant

during various operations. That is, there is no change of temperature (dT = 0) in an isothermal
process. Isothermal condition is attained either by supplying heat to the system or by
removing heat from the system. For this purpose the experiment is performed in a thermostat
(constant temperature bath).

Adiabatic process. A process is said to be adiabatic if there is no exchange of heat (q)

between the system and surroundings during various operations. That is, q = 0 in an adiabatic
process. This condition is attained by thermally insulating the system. In an adiabatic process
if work is done by the system its temperature decreases, if work is done on the system its
temperature increases.

Isobaric process. A process is said to be isobaric if the pressure remains constant during the
change. That is, dP = 0 in an isobaric process. (bar is the SI unit of pressure, therefore,
isobaric means same pressure))

Isochoric process. A process is said to be isochoric if the volume of the system remains
constant during the change. That is, dV = 0 in an isochoric process. Combustion of a fuel in a
bomb calorimeter is an example of isochoric process.(the term chore is used for space,
therefore, isochoric means same space or same volume)

Quick view of the process and its condition

Process Isothermal Adiabatic Isobaric Isochoric

Condition dT = 0 q=0 dP = 0 dV = 0

Reversible process. A process is said to be reversible if the change can take place in both the
forward and back directions by a small change in its state variables. In a reversible change
the system can be brought back to its initial state without altering the properties of
surroundings to an appreciable extent. In a reversible process the change takes place very
slowly so that the system and surroundings are nearly at equilibrium (called
quasiequilibrium).

Illustrations of a reversible process

Let us consider a gas taken in a cylinder which is fitted with a movable piston. Suppose that
an external pressure (Pext) is applied on the gas by keeping sufficient quantity of sand grains
on the piston. In this situation the pressure of the gas (P1) is balanced by the external pressure
on the gas, that is, P1 = Pext

15
 Fig. 3 Illustration of reversible process

Suppose that one grain of the sand is removed from the piston. The removal of the sand grain
will cause a very small decrease in the external pressure. Now the pressure of the gas
becomes slightly greater than the external pressure. Because of this difference of pressure the
gas will expand till the pressure of the gas becomes equal to the pressure on the gas. This
expansion will result in an infinitesimally small work done by the gas on the surroundings.
The work is so small that no appreciable change is observed in the properties of the system or
surroundings. On the other hand, if the same grain of sand is placed again on the piston, the
external pressure will increase and the gas will be compressed to its initial stage. In this case
also infinitesimally small work will be done by the surroundings on the system, which will
not cause any appreciable change in the properties of the system and surroundings. Therefore,
the change is said to be reversible. However, by removing the sand grains continuously from
the piston (by lowering the pressure) the gas will expand by a definite volume

Irreversible process. A process is said to be irreversible if the change takes place in one
direction. In an irreversible process the system cannot be brought back to its original state
without affecting the surroundings. All the natural changes are irreversible and hence
spontaneous.

Cyclic process. It is a process in which the initial state of the system is restored after
undergoing a series of changes

Path. Path is the representation of steps of changes starting from initial state and then
reaching the final state through various intermediate states (if any).

Concept of internal energy, work and heat

Thermodynamics has been defined as the branch of science wherein we study the
interconversions of heat, work and energy and various possible relations between these
quantities. Therefore, it is essential to learn the meaning of these terms.

Concept of internal energy (U)

Internal energy is a characteristic property of a system which decides its nature and
behaviour. It is denoted by symbol U. Internal energy of a system is equal to the energy
possessed by all its constituents namely atoms, ions and molecules. The energy of a molecule
is equal to translational energy (Ut), vibrational energy (Uv), rotational energy (Ur), bond
energy (Ub), electronic energy (Ue), energy due to molecular interactions (VT) and the

16
relativistic energy (U = ∆m× c2 which is very large and hence it is not considered in chemical
reactions). Thus:

U = Ut + U v + Ur + Ub + Ue + VT

The total energy of all the molecules of the system is called internal energy or intrinsic
energy. The internal energy is the cause of existence of various types of distinct substances.
In thermodynamic studies one is more concerned with the change in internal energy (∆U)
rather than the absolute value of energy.

Importance of internal energy: The internal energy possessed by a substance differentiates

it from other substances. For example, the allotropes of carbon namely graphite (C) and
diamond (C), differ from each other because they possess different internal energies and have
different structures. This is the reason that internal energy is also called inherent energy or
hidden energy or more appropriately intrinsic energy.

Characteristics of internal energy

™ Internal energy of a system is an extensive property. It depends on the amount of the

substances present in the system. If the amount is doubled, energy is also doubled.

™ Internal energy of a system is a state property. It depends only upon the state variables (T,
P, V, n) of the system. The change in internal energy of a fixed amount the system is
expressed as:

∆U = U2 (T2, P2, V2) – U1 (T1, P1, V1)

2

Or, ∆U = U 2 − U 1 = ∫ dU
1

™ The change in internal energy does not depend on the path by which the final state is
reached.

™ In a cyclic process, there is no energy change. ∆U (cycle) = 0

Or, ∫ dU = 0
Methods by which the energy of a system can be changed. The energy of a system can be
changed by all or any of the following processes:

™ The system undergoes either a chemical change or a physical change.

™ Heat is given to the system or heat is removed from the system.

™ Work is done by the system or work is done on the system. Therefore, internal
energy of a system is also defined as its capacity to do work

Concept of work in thermodynamics

Work is a result of action against an opposing force. It is equal to the force multiplied by

17
displacement

w = –F× ∆x

where ∆x is the path length over which action is taken and F is the force against which work
has to be done.

™ If F = 0, then w = 0. That is, if there is no opposing force, then the motion itself cannot
produce any work.

™ If ∆x = 0, then w = 0. That is, if there is no motion, even the strongest opposing force
cannot generate any work.

Mechanical work involving gas

In a system when gases are involved, the mechanical work is equal to pressure (P)
multiplied by change of volume (∆V).

w = –F×∆x

F
= × A×∆x
A

= –P×∆x

F
Here P= = Force per unit area = pressure
A

and ∆V = A ×∆x = Area × displacement = change of volume

Significance of minus sign in the expression w = – P×∆V

™ As per IUPAC recommendations the symbol w has to be used for work done on the
system.

™ During compression work is done on the system thus volume decreases and ∆V is
negative. Therefore, work done on the system is positive as is clear from the relation w = –P
× ∆V

™ During expansion volume increases and ∆V is positive so the work done on the system is
negative as is clear from the relation w = –P × ∆V. But in this case work done by the system
is positive during expansion as given by –w = P × ∆V..

Characteristics of w

™ A system does not possess any work. Work appears across the boundary during

change only.

™ The work is zero if there is no change.

™ Work is path dependent quantity.

18
 ™ Work is manifestation of energy.

™ When work is done by the system its energy decreases.

™ When work is done on the system its energy increases.

Illustration of work and sign of its value

(i) w = + 200 kJ implies that 200 kJ work is done on the system. This will increase
the energy of the system. Since the work done on the system is positive, it
represents compression.

(ii) w = –250 kJ implies that - 250 kJ work is done on the system. That is, in the
process the energy of the system would decrease. A decrease in energy suggests
that the work is done by the system. Thus w = - 240 kJ stands for - w = 240 kJ =
work done by the system and the given value corresponds to a process of
expansion.

An analogy of sign of work done on the system and work done by the system

It is the recommendation of the IUPAC that the symbol w should be used for the work done on the
system by the surrounding. Therefore, for the work done by the surrounding on the system the symbol –
w can be used. Let us understand it by an analogy of an account in a bank.

Suppose a person deposits a sum of Rs. 400. 00 on December 2005 and withdraws a sum of Rs. 150.00
on December 8, 2005. Now these statements can be shown as follows

–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––

Particulars Amount deposited Amount withdrawn Balance

Rs. Paise Rs. Paise Rs. Paise

2 - 12 - 2005 400 00 nil 400 00

8 - 12 - 2005 nil 150 00 250 00

––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––

Suppose that in the register of bank there is column for amount deposited only and there is no column
for amount withdrawn. In that case the amount withdrawn will be indicated as – 150.00 under the
amount deposited and the above statement of account may be shown as follows:

Expressions for work under different conditions

It has been stated that work is a path dependent quantity. It has different values if the change
is brought under different experimental conditions. For example, for the changes between the
same initial state and same final state of a system

(i) work done under isothermal condition is different from the work done under
adiabatic condition.

(ii) work done under isothermal reversible condition is different from the work done

19
 under isothermal irreversible condition.

(iii) work done for free expansion is different from the work done under any other
condition

(A) Work done under isothermal reversible condition

Let us consider n moles of a gas in a cylinder confined by a frictionless and weightless

movable piston. Let us suppose that

Pext = External pressure acting on the gas

Pint = Internal pressure of the gas.

The change in the state of the gas will depend on the relative values of Pext and Pint. Thus

(a) When Pext > Pint the gas will be compressed

(b) When Pint > Pext the gas will expand

When Pext = Pint ±dP, where dP is a small change in the pressure then the change is
reversible. This type of situation is shown in Fig. 4. (a) for the expansion of a gas. In the
figure the dotted lines show the position of the piston for a small volume change dV of the
gas.

Fig. 4 (a) Reversible - isothermal expansion of an Fig. 4 (b) Pressure versus volume indicator diagram
ideal gas in a cylinder fitted with a movable piston for reversible - isothermal expansion of an
. ideal gas. Work = Area ABCD
Calculation of work done for isothermal reversible process from P versus V indicator
diagram

When the change is isothermal and reversible the pressure and volume both are changed
slowly so that equilibrium is maintained between the system and surrounding at each stage of
the change. For such a process the variation of volume with pressure is shown by an indicator
diagram in Fig. 4 (b).

Suppose that the pressure is slightly lowered by dP (from c to d) so that there is

infinitesimally small increase in volume by dV (from a to d). For such a small volume change

20
the small work done by the gas is given by

đw (rev) = (P– dP) dV

The change of pressure from point c to point d is very small as it is clear from the indicator
diagram.

Therefore, it can be assumed that pressure on the gas (P– dP) is very near to the pressure of
the gas (P). That is,

P– dP ≈ P and thus work done by the gas is given by

– đw (rev) = P dV

From the indicator diagram it is seen that

P dV = ac×ab = Area of the thin strip abcd

–dw(rev) = P dV = Area abcd

For a finite isothermal reversible change of state of the system, the total work done is equal to
the sum of the areas of all such thin strips as abcd. Now the reversible change is very slow
and continuous therefore, the work done by the gas is equal to the integral of PdV. Thus
V2

– w(rev) = ∫ PdV = Area ABCD refer to Fig. 5 (a)

V1

Comments. Reversible work of expansion is the maximum work which can be obtained
from a system. Let us see how and why? For expansion the pressure on the gas should be less
than pressure of the gas. That is Pext < Pint and work done by the gas is given by

– đw = Pext× dV

In a reversible change the internal pressure is only slightly greater that the external pressure

Pext = Pint – dP ≈ Pint

Now to cause expansion, Pext cannot be greater than Pint. At most these two pressures may
approach each other. In other words, it may be stated that Pext is the limiting maximum
pressure against which the gas can expand. If the external pressure exceeds this limiting value
the gas will not expand rather it will be compressed. Therefore, the product Pext× dV = Pint
×dV should have the maximum possible value and thus the reversible work of expansion is
maximum.

(B) Work done under isothermal irreversible condition

Let us consider n moles of a gas in a cylinder confined by a frictionless and weightless

movable piston. Let us suppose that the piston is held in position by a pin Fig. 5 (a) and the
internal pressure of the gas is greater than the external pressure on the gas.

21
Fig. 5 (a) Irreversible-isothermal expansion of an Fig. 5 (b) Pressure versus volume indicator diagram for
ideal gas i n a cylinder fitted with a piston irreversible-isothermal expansion of an ideal gas.
Initial state: Piston held by a pin (Pint > Pext) Work = Area BCDE
Final state: When pin is removed the gas expands
so that Pint = Pext

Calculation of work done for isothermal irreversible process from P versus V indicator
diagram

In an irreversible process the pressure is suddenly released from initial value of P1 to a final
value of P2. Therefore, the gas expands from initial volume V1 to final volume V2 against the
new lower constant pressure P2 Thus
V2

–w(irr) = ∫ PdV
V1

Since final pressure is constant and P = P2 , therefore,

V2

– w(irr) = P2 ∫ dV
V1

= P2 [V2 – V1]

=DE×DC = Area BCDE refer to Fig 5 (b)

Conclusions: From the above illustrations it is quite clear that area ABCD is larger than the
area BCDE. Therefore

(a) Work done is different under different conditions for the same initial state and same
final state.

(b) Isothermal reversible work is greater than isothermal irreversible work.

22
Concept of heat in thermodynamics

The change in the internal energy of the system due to difference of temperature of the
system and its surroundings is called heat. The symbol of heat is q. Heat flows from higher
temperature towards lower temperature. The energy of the system increases when it is
brought into contact with the surroundings which is at a higher temperature. On the other
hand, when the temperature of the system is higher than that of the surroundings the heat
flows from the system to the surroundings and the internal energy of the system decreases.
Thus:

™ When heat is absorbed by the system its energy increases. That is, ∆U is positive. Such a
change is called endothermic.

™ When heat is given out by the system its energy decreases. That is, ∆U is negative. Such a
change is called exothermic.

Characteristics of heat

™ A system does not possess any heat. It possesses only energy

™ The concept of heat comes into picture across the boundary during the change only.

™ If there is no difference of temperature between the system and surroundings there is no

flow of heat.

™ Heat is a path dependent quantity.

™ Heat is manifestation of energy.

™ When heat flows into the system its energy increases.

™ When heat flows out of the system its energy decreases.

Sign conventions for heat (q)

™ When q has a positive value, then we say that heat is absorbed by the system from the
surroundings. This change is endothermic

™ When q has a negative value, then we say that heat is given out by the system to the
surroundings. This change is exothermic

Illustration

(i) q = +200 kJ implies that 200 kJ heat is absorbed by the system from the surroundings

(ii) q = – 300 kJ implies that 300 kJ heat is given out by the system to the surroundings

Discussion

™ Heat is not a material or fluid.

™ A system does not possess heat and work.

23
™ When it is stated that heat flows it means that the energy is exchanged between the
system and surroundings due to temperature difference

™ When it is stated that mechanical work is done it means that energy is exchanged because
of pressure gradient between the system and the surroundings.

™ In reality the heat and work are manifestation of energy.

Units of energy, heat and work

™ The energy of a system is expressed as joules (J) or kilojoules (kJ). The change of energy
is also expressed in J or kJ. Since heat and work are manifestation of energy, these are also
expressed in the units of J or kJ.

™ Calories (cal) and kilocalories (kcal) are non-SI units of energy

™ These units are related as follows:

(i) 1000 J = 1 kJ or 10–3 kJ = 1 J

(ii) 1000 cal = 1 kcal or 10–3 kcal = 1 cal

(iii) 1 cal = 4.198 J = 4.2 J (for approximate

calculations)

A molecular picture of flow of heat or exchange of heat. The internal energy of the
system can be changed by supplying heat to the system or by removing heat from the system.
The energy of the system increases when it is brought into contact with the surroundings
which is at a higher temperature.

Explanation. In this case heat energy flows from the surroundings into the system because
of temperature difference. The flow of heat from the surroundings to the system continues
until both attain the same temperature. The exchange of heat between the system and
surroundings is due to the collisions of the molecules on the walls of the system. The
molecules in the surroundings have more energy because they are at higher
temperature.When these energetic molecules hit the boundary they transfer their energy
which is transmitted to the system. This causes an increase in the internal energy of the
system.

When the temperature of the system is higher its molecules hit the boundary and transfer
their energy to the surroundings. Thus, the heat flows from the system to the surroundings
and the internal energy of the system decreases.

Example. State which of the following will cause decrease and increase of the internal
energy of the system:

(a) Heat transferred to the surroundings

(b) Work done by the system

24
(c) Work done on the system.

Solution.

(a) Heat transferred to the surroundings will cause a decrease in the energy of the system.

(b) Work done by the system will cause a decrease in its energy.

(c) Work done on the system will cause an increase in is energy.

THERMAL EQUILIBRIUM

The law of thermal equilibrium is called the zeroth law of thermodynamics. This law states
that if two systems A and B are separately in thermal equilibrium with a third system C, then
A and B will also be in the thermal equilibrium with each other. That is,

If A = C ... thermal equilibrium between A and C

and B = C ... thermal equilibrium between B and C

Then A = B ... thermal equilibrium between A and B

Zeroth law of thermodynamics forms the basis of measurement of temperature of a system by

a thermometer. When a thermometer is brought in contact with a system both attain thermal
equilibrium. Thus, the thermometer records a constant temperature of the system

25
 CONFIDENCE BUILDING QUESTIONS ON FUNDAMENTAL TERMS

(A) Complete the following statements using a correct word/term from the list given
below:

[zero, extensive, boumdary, volume, temperature, isobaric, adiabatic, isothermal, closed,

intensive, path dependent, cyclic, state, on]

1. The space separating the system from the surroundings is called the --------------

2. Temperature is kept constant in an ------------------ process

3. In an isothermal process ------------------- remains constant.

4. In an adiabatic process ------------- is not exchanged between the system and the
surroundings.

5. In -------------- process heat is not exchanged between the system and surroundings.

6. An ------------- property is independent of the amount of substance.

7. An ------------- property depends on the amount of substance.

8. A --------------- property is independent of the path

9. Change of internal energy is ------------ in a cyclic process

10. In an isochoric process ------------- is constant.

11. Pressure is constant in an ------------- process

12. Mass cannot be exchanged between the system and surroundings in a -------------- system

13. Work is a ------------------ property

14. The change of a state property in a --------------process must be zero.

15. The sign of work is positive when work is done ---------- the system.

(B) Give a very brief answer of the following questions.

1.Write the main aim of the study of thermodynamics.

2. Define an extensive property.

3. Volume is an extensive property. Give reason.

4. Define an intensive property.

5. Density is an intensive property. Explain.

6. Use the relation PV = nRT to prove that volume is a state function.

26
7. Select intensive and extensive properties from the following:

volume, pressure, density, mass, internal energy, heat capacity, mole, mole fraction,
molarity, molar mass

8. State the condition under which a thermodynamic property Φ(x, y ) is a state function and
d Φ is an exact differential.

(C) Select true and false statements

1. In an adiabatic process volume is kept constant.

2. In an isothermal process temperature is kept constant

3. Density is an intensive property.

4. Both heat and matter are exchanged between the system and surroundings in an isolated
system.

5. Total differential of a state function is an exact differential.

6. Heat is state property of the system.

7. The internal energy is a state function.

8. In an open system both heat and matter are exchanged with the surroundings.

9. State functions are perfect differentials.

10. All natural processes are irreversible.

Answers

True: 2, 3, 5,7, 9, 10 False 1, 4, 6, 8:

27
THE FIRST LAW OF THERMODYNAMICS

The first law of thermodynamics is popularly called the law of conservation of energy. This
law is stated as follows:

Energy can be neither created nor destroyed. If it disappears in

one form it must reappear in some other equivalent form.

This statement also implies that the energy of the universe is constant. If there is an increase
in the energy of the system, there must be a decrease in the energy of the surroundings and
vice versa.

Statement of the first law of thermodynamics

Mathematical formulation of the law of conservation of energy is called the first law of
thermodynamics. In terms of energy, heat and work the first law of thermodynamics is
written as:

∆U = q + w

Here: ∆U = Change in the internal energy of the system

= U (final) – U (initial)

q = Heat absorbed by the system

w = Work done on the system (it includes all possible types of work)

Formulation of the relation ∆U = q + w

Let us suppose that U1 is the initial internal energy of the system. Again let us suppose that
work (w) is done on the system and at the same time heat (q) is supplied to the system so that
its energy is increased from initial value U1 to a final value U2. According to the law of
conservation of energy, the final energy of the system is equal to the sum of its initial energy
(U1), work done on it (w) and heat absorbed by it (q).

Final energy = Initial energy + Heat absorbed by the system +Work done on the
system

U2 = U1 + q + w (i)

Or, U2 – U1 = q + w

∆U = q + w

That is, increase in internal energy = Heat absorbed by the system + Work done on the system

The equation ∆U = q + w is a mathematical statement of the first law of thermodynamics. In

this equation ∆U is the change in the internal energy of the system, q is the heat absorbed by
the system and w is the work done on the system.

Meaning of symbol ∆ in ∆U. Symbol ∆ is called delta. It signifies a change. Thus, ∆U is

28
the change in the internal energy of the system and ∆U = U2 – U1.

Delta (∆) is not used before q and w

Reason. q and w depend on path and there is no initial and final heat or work of the system.
The concept of heat or work comes into picture only during the change. If there is no change,
there is no heat or work. But the system has energy.

Important information derived from the first law of thermodynamics (∆U = q + w)

™ If no work is done, w = 0, and first law of thermodynamics reduces to

∆U = q when w = 0

This relation tells that change in internal energy is equal to the heat exchanged between the
system and the surroundings. That is, if heat is absorbed by the system there is increase in its
internal energy. On the other hand, if heat is released by the system there is decrease in its
internal energy

™ If there is no exchange of heat between the system and surroundings, q = 0 and the first
law reduces to

∆U = w when q = 0

This relation is true for adiabatic process. It implies that if work is done on the system its
internal energy will increase. On the other hand, if work is done by the system its internal
energy will decrease. That is, in an adiabatic process work is done by the system at the
expense of its internal energy. This is the reason that in adiabatic expansion of a gas cooling
effect is observed and during adiabatic compression heating effect is observed.

™ If there is no change in the internal energy of the system, ∆U = 0 and the first law may be
written as

q=–w when ∆U = 0

But –w represents the work done by the system. Thus, when the energy of the system is kept
constant then heat absorbed by the system is equal to the work done by the system.

The relation q = – w may also be written as w = – q. Thus when the energy of the system is
kept constant and work is done on the system, then heat must flow from the system to the
surroundings.

Change in internal energy and heat exchanged in an isochoric process

The change in internal energy is equal to the heat exchanged between the system and
surrounding at constant volume. Let us prove it.

The first law of thermodynamics states that ∆U = q + w where ∆U is the change of internal
energy, q is the heat exchanged between the system and surroundings and w is the work done
against an opposing force. The mechanical work at constant pressure due to volume change is
given by

29
 w = –P ×∆V

where ∆V is the volume change and P is the constant pressure. For such a case the first law of
thermodynamics can be written as:

∆U = q + w = q – P× ∆V

In an isochoric process volume is constant and ∆V = 0, therefore, the product P×∆V is also
zero. Thus, for an isochoric process the first law of thermodynamics can be written as

∆U = q at constant volume

Or ∆U = qv

Here subscript 'V' in qv indicates that volume (V) is constant. The relation ∆U = qv is a link
between the chemical energy (∆U) and thermal energy (q).

Example: In an experiment 400 kJ heat is absorbed by the system so that its internal
energy increases by 250 kJ. How would you apply the law of conservation of energy to this
system?

Solution. Law of conservation of energy in the form of first law of thermodynamics requires
that

∆U = q + w

Or, – w = q – ∆U

= 400 kJ – 250 kJ

= 150 kJ = work done by the system

Measurement of ∆U

The energy change in a chemical reaction is measured in a bomb calorimeter. Fig. 6

illustrates an experimental set up.

Fig. 6. Measurement of ∆U in a bomb calorimeter

30
In this experiment a known mass of the combustible material and sufficient quantity of an
oxidizer are taken in the bomb. The bomb is immersed in a vessel containing known mass of
water (it will act as surroundings). The water is stirred by rotating blades and its initial
temperature (ti) is recorded.

An electric current is passed to ignite the mixture taken in the bomb. As the reaction takes
place, chemical energy is released which is used to warm water and the calorimeter. When
the temperature of water reaches a constant value, the final reading of thermometer (t2) is
noted. Thus, change in temperature (∆T = t2 – t1) of water and the calorimeter (surroundings)
is recorded.

The heat exchanged between the system (reaction) and surroundings (water + calorimeter) is
calculated from the equation

q (water + calorimeter) = (m × s+ C) × ∆T = q (surroundings)

In the above equation

m =mass of water

s = specific heat capacity of water

C = heat capacity of the calorimeter

The heat liberated in the reaction is calculated as heat appearing in the surroundings. Thus

∆U = q (system) = – q (surroundings) at constant volume

Difficulties in the experimental determination of ∆U

When the experiment is performed at constant volume in a bomb calorimeter and if a large
quantity of heat is liberated in a reaction then there is a danger of explosion. Why? Because
the heat liberated during the reaction will make the gaseous products to expand. Since the
vessel is closed the gas cannot expand. This will cause a build up of high pressure inside the
bomb calorimeter. If the walls of the vessel are not strong enough to withstand the high
pressure developed, an explosion may take place.

Need of a new thermodynamic property- the enthalpy

In the laboratory usually the experiments are performed at constant atmospheric pressure and
the volume is allowed to change. So the measured value of ∆U cannot account for the actual
heat exchanged between the system and surroundings at constant pressure. Hence, there is a
need of new function that can account for the total heat content. That is, we need a function
that must reflect as to how much heat is absorbed or liberated in the process at constant
pressure. This new property is called heat content or enthalpy.

Definition of enthalpy (H)

The enthalpy (H) is defined by

31
 H = U + PV

where U is the internal energy, P is the pressure and V is the volume.

Comments:

(i) The enthalpy is a Greek word which means heat in (en = in, thalpos = heat) and
was formerly called heat content. The symbol of enthalpy is H. Why? Because H
is the first letter of heat content.

(ii) The name heat content was dropped to avoid confusion with heat capacity but the
symbol H is retained to represent enthalpy.

Characteristics of enthalpy

™ Enthalpy is an extensive property. Its value depends on the amount of the substances
present in the system. Larger the amount larger is the value of H.

™ Enthalpy of a system is a state property. For a given amount of the system it depends only
on the state variables (T, P, V). If the state variables are changed from T1, P1, V1 to T2, P2,
V2 the enthalpy of a given amount (fixed n) of the system is changed from H1 to H2. The
change in enthalpy is represented as:

∆H = H (T2, P2, V2) – H (TI, P1, V1) when n = constant

Since T, P, V are related by a suitable equation of state, out of T, P, V, if two are known the
third is also known for a constant amount of the system. Therefore, enthalpy is considered as
a function of T and P for a fixed amount, i.e.,

H = H (T, P)

and ∆H = H (T2, P2) – H (TI, P1)

™ The change in enthalpy (∆H) does not depend on the path by which the final state of the
system is reached.

Sign conventions of ∆JI

™ When heat is absorbed by the system at constant pressure its enthalpy is increased so the
value of ∆H is positive. When ∆H is positive, the process is said to be endothermic.

™ When heat is liberated by the system at constant pressure its enthalpy is decreased so the
value of ∆H is negative. When ∆H is negative, the process is said to be exothermic.

Illustration:

(i) ∆H = 310 kJ implies that during the change 310 kJ heat is absorbed by the system from
the surroundings at constant pressure. The process is endothermic. Since heat absorbed by
the system is heat lost by surroundings, a cooling effect is observed in the surroundings.

(ii) ∆H = – 175 kJ implies that during the change 175 kJ heat is released by the system into
the surroundings at constant pressure. The process is exothermic. Since heat released by the

32
system is heat gained by the surroundings, a heating effect is observed in the surroundings.

Relation between ∆H and q

The enthalpy is defined by

H = U + PV

For a change in the states of the system

∆H =∆ (U + PV)

= ∆U + (P× ∆V+ V× ∆P) (i)

First law of thermodynamics states that

∆U = q + w = q – P× ∆V (ii)

From equations (i) and (ii), we get

∆H = (q – P×∆ V) + (P× ∆V+ V× ∆P)

= q + V×∆P

When pressure is constant, ∆P = 0, and thus V × ∆P = 0, therefore

∆H = q . .. at constant pressure

Or, ∆H = qp

Here subscript 'P' in qp is used to state that pressure is constant in the process.

Comparison of ∆H and ∆U

(i) The change of enthalpy (∆H) of the system accounts for both the energy change (∆U) and
the pressure-volume changes of the system. ∆ H = ∆U + P× ∆V + V× ∆P

(ii) ∆H and ∆U have different values for different types of changes. Enthalpy change is equal
to the heat exchanged between the system and the surroundings at constant pressure ∆H = qp
whereas energy change is equal to the heat exchanged between the system and surroundings
at constant volume ∆U = qv

(iii) If the experiment is performed at constant pressure and at the same time there is no
volume change then

P× ∆V + V× ∆P = 0 and ∆H = ∆U.

Illustration of enthalpy change and heat exchanged at constant pressure

Consider water taken in a cylinder which is fitted with a movable piston. When water is
heated its temperature increases and thus the energy of each molecule of water increases.
Consequently water vaporizes. The energetic molecules of water vapour hit the piston which

33
is pushed and thus vapour expands against the constant atmospheric pressure (P) (Fig. 7).

(a) Heating of a liquid (b) Expansion of vapour

Fig.7. Illustration of enthalpy change in terms of heat absorbed at constant pressure

During expansion work is done by the vapour and at the same time energy is increased
from U1 to U2

Work done by vapour = – w = P× (V2 – V1) = P×∆V

Suppose qp is the heat absorbed by the system at constant pressure, so that there is an increase
in the energy of the system by ∆U and P×∆V work is done by the system. For this process the
law of conservation of energy (first law of thermodynamics) requires that

Heat absorbed = Increase in energy + work done by vapour

qp = ∆U + P × ∆V

Now, ∆U = U2 – U1

and ∆V = V2 – V1

Therefore, qp = U2 – U1 + P V2 – PV1

= (U2 + PV2) – (U1 + PVI)

The relation H = U + PV, guides us to write

H2 = U2 + PV2

and H1 = UI + PVt

Thus qp = H2 – HI = ∆H

34
 qp = Total heat absorbed by water at constant pressure

But H2 = U2 + PV2 = Enthalpy of the vapour after expansion

and H1 = UI + PVt = Enthalpy of water before heating

Therefore, ∆H = H2 – H1 = Difference of enthalpies of water vapour and liquid water

= Change of enthalpy of the system

The relation ∆H = qp is a link between the chemical energy (∆H) and thermal energy (qp).

Heat capacity

The quantity of heat needed to cause unit rise in the temperature of a substance is called
its heat capacity. It is denoted by symbol C and defined by.

Heat needed
Heat capacity =
Increase of temperature

q
C=
∆T

Units of heat capacity. Heat (q) is expressed in joules (J) and temperature in kelvin (K).
Therefore, heat capacity is expressed in the units of joules per kelvin (J K–1). Heat capacity is
an extensive property because the heat needed to raise the temperature of the system depends
on its size.

Note: Change of temperature expressed in kelvin is equal to the change of temperature

expressed in degree celsius. How? Suppose that the initial temperature of a system is 25 °C
and its final temperature is 32 °C, then

The change of temperature in degree celsius = 32 °C – 25 °C = 7 °C

The change of temperature in kelvin = (32 + 273) K – (25 + 273) K

= 305 K – 298 K = 7 K

Molar heat capacity. It is defined as the quantity of heat needed to cause unit rise in the

temperature of one mole of a substance. Molar heat capacity is denoted by Cm. Thus,

Heat capacity of the substance

Molar heat capacity =
Amount of the substsnce

C
Cm =
n

Units of molar heat capacity. Heat capacity is expressed as J K–1 and the amount is
expressed as mol. Therefore, molar heat capacity is expressed as J K–1 mol–1 (pronounced as
joule per Kelvin per mol). It should never be written as J/K/mol.

Molar heat capacity is an intensive property, because it is a ratio of two extensive properties.

35
Specific heat capacity. It is defined as the quantity of heat needed to cause unit rise in the
temperature of unit mass of a substance. Specific heat capacity is denoted by small c or small
s. It is expressed in the units of J K–1 g–1

Example. Calculate the thermal energy needed to raise the temperature of 10.0 g of iron
from 298 K to 773 K. It is given that the specific heat capacity of iron is 0.45 J K −1 g −1

Solution. Data given:

Mass of iron = m = 10 g

Specific heat capacity of iron = Cs = 0.45 JK−1 g−1

Temperature change = ∆T = 773 K − 298 K = 475 K

Therefore, q = m × Cs × ∆T

=10 g × 0.45 JK−1 g−1 × 475 K = 2173.5 J = 2.1 kJ

Heat capacity at constant volume and at constant pressure

From the first law of thermodynamics we know that the heat exchanged between the
system and surroundings depends on the experimental conditions, For example,

(i) Heat exchanged at constant volume = qV = ∆U

(ii) Heat exchanged at constant pressure = qP = ∆H

Therefore, depending on the experimental conditions the following two types of heat
capacities are defined.

(1) Heat capacity at constant volume

qv ∆U
CV = =
∆T ∆T

For small temperature change the heat capacity at constant volume is expressed as

∂U ⎞
CV = ⎛⎜ ⎟
⎝ ∂T ⎠ V

CV
Molar heat capacity at constant volume = CV,m =
n

and CV = n× CV,m

(2) Heat capacity at constant pressure

qP ∆H
CP = =
∆T ∆T

For small temperature change the heat capacity at constant pressure is expressed as

36
 ∂H ⎞
CP = ⎛⎜ ⎟
⎝ ∂T ⎠ P

CP
Molar heat capacity at constant pressure = CP,m =
n

and CP = n× CP, m

Relation between CP and CV

(i) Ratio of heat capacities = CP,m/CV, m = 

(a) For monotomic gas such as He: CP, m /CV, m =  = 1.67

(b) For diatomic gas such as H2: CP, m /CV, m =  = 1.40

(c) For triatomic gas such as CO2: CP, m /CV, m =  = 1.33

(ii) Difference between CP and CV

(a) For an ideal gas: CP – CV = nR where R is gas constant and n is the amount
of the substance.

(b) For 1 mole of an ideal gas: CP, m – CV, m = R

(c) For a solid or a liquid: CP, m CV, m

Derivation of the relation between CP and CV

H = U + PV Definition of enthalpy

Differentiation of above equation with respect to T an constant P gives

⎛ ∂H ⎞ ⎛ ∂U ⎞ ⎛ ∂V ⎞
⎜ ⎟ = ⎜ ⎟ + P⎜ ⎟ (i)
⎝ ∂T ⎠ P ⎝ ∂T ⎠P ⎝ ∂T ⎠P

Heat capacity at constant pressure is defined by

∂H
CP = ⎛⎜ ⎞
⎟ (ii)
⎝ ∂T ⎠P

For an ideal gas

⎛ ∂U ⎞ ⎛ ∂U ⎞
⎜ ⎟ = ⎜ ⎟ = CV (iii)
⎝ ∂T ⎠ P ⎝ ∂T ⎠V

where, CV = Heat capacity at constant volume

Differentiation of ideal gas equation of state PV = nRT with respect to T at constant P, gives

37
 ∂V ∂T
P ⎛⎜ ⎞⎟ = nR ⎛⎜ ⎞⎟ = nR×1 = nR (iv)
⎝ ∂T ⎠P ⎝ ∂T ⎠ P

On putting the expressions for various derivatives in to equation (i) we get

Cp = CV + nR

Cp – CV = nR

Variation of heat capacity with temperature

The variation of heat capacity with temperature are given by the following general equations

(i) CP, m = α + βT + γT2

(ii) CV, m = α’ + β’T + γ’ T2

where values of the parameters α, β, γ… α’, β’, γ’ are characteristics of a substance. These
values are available in the thermodynamic tables.

Variation of internal energy with temperature and volume

Internal energy of given amount of system is a function of temperature and volume

U = U (T, V)

For a small change in T and V the change in internal energy is expressed as its total
differential

∂U ∂U
dU = ⎛⎜ ⎞⎟ dT + ⎛⎜ ⎞⎟ dV
⎝ ∂T ⎠V ⎝ ∂V ⎠ T

∂U
= CV dT + ⎛⎜ ⎞⎟ dV
⎝ ∂V ⎠ T

∂U ⎞
where, CV = ⎛⎜ ⎟ = Heat capacity at constant volume
⎝ ∂T ⎠ V

The change in internal energy can be calculated provided the values of CV and (∂U/∂V)T of
the system are known. The value of CV is obtained by calorimetric method and the value of
(∂U/∂V)T is given by Joule’s law.

Joule’s Law

Joule’s law states that the internal energy of an ideal gas is independent of its volume at a
constant temperature. Mathematically it is expressed as

⎛ ∂U ⎞
⎜ ⎟ =0 … Joule’s law
⎝ ∂V ⎠T

This law also means that internal energy of a given amount of an ideal gas depends on its

38
temperature only. Thus at a constant temperature there is no change in the internal energy of
an ideal gas as the volume is changed.

Experimental verification of Joule’s law

Joule performed an experiment to demonstrate the law that for a gas (∂U/∂V)T = 0. The
experimental setup is sown in Fig.8.

Fig. 8. Joule’s experiment of expansion of air from

vessel A into an evacuated vessel B

A glass bulb A was filled with air and connected through a stopcock to an evacuated bulb B.
The assembly was placed in a water bath and its initial temperature was recorded. When the
stopcock was opened the gas expanded into the bulb B and thus occupied both the bulbs. The
final temperature of the water bath was recorded but no change in the temperature was
observed.

Interpretation of the observations: From this experiment Joule argued as follows.

(i) There is no change of temperature showing that there is no exchange of heat

between the system and surroundings. That is, q = 0.

(ii) The gas expands into an evacuated vessel where Pext = 0. Therefore, no work is
done in the process and w = – Pext× ∆V = –0 × ∆V = 0.

(iii) From the first law of thermodynamics, therefore, it is obvious that ∆U = q + w = 0

+0 =0 or dU = 0. Thus

∂U
dU = CV dT + ⎛⎜ ⎞⎟ dV = 0
⎝ ∂V ⎠ T

⎛ ∂U ⎞
Or, ⎜ ⎟ dV = – CV dT
⎝ ∂V ⎠ T

Now, dT = 0 (because there is no change of temperature in Joule’s experiment) but CV ≠0,

therefore, CV dT = 0. Thus

39
 ⎛ ∂U ⎞
⎜ ⎟ dV = 0
⎝ ∂V ⎠ T

Now, dV≠0 (as the gas expands and occupies both the bulbs). Therefore, the above equation
is valid only when

⎛ ∂U ⎞
⎜ ⎟ =0 … Joule’s law
⎝ ∂V ⎠ T

Physical interpretation of Joule’s law: The derivative (∂U/∂V)T is called internal pressure
( T). It is a measure of the molecular force of attraction. For a nonideal gas obeying van der
Waals equation of state the internal pressure is given by (∂U/∂V)T = a/V2. When the
molecular force of attraction is strong, the internal pressure is large. In an ideal gas the
molecular force of attraction is absent, therefore, its internal pressure is zero. Thus (∂U/∂V)T
=0 is a thermodynamic definition of an ideal gas.

Variation of enthalpy with temperature and pressure

Enthalpy of given amount of system is a function of temperature and pressure

H = H (T, P)

For a small change in T and P the change in enthalpy is expressed as its total differential

∂H ∂H
dH = ⎛⎜ ⎞⎟ dT + ⎛⎜ ⎞⎟ dP
⎝ ∂T ⎠ P ⎝ ∂P ⎠ T

∂H
= CP dT + ⎛⎜ ⎞⎟ dP
⎝ ∂P ⎠ T

∂H ⎞
where, CP = ⎛⎜ ⎟ = Heat capacity at constant pressure
⎝ ∂T ⎠ P

The change in enthalpy can be calculated provided the values of CP and (∂H/∂P)T of the
system are known. The value of Cp is obtained by calorimetric method and the value of
(∂H/∂P)T can be calculated from Joule- Thomson coefficient.

Joule – Thomson Coefficient

The change of temperature with change of pressure of a gas at constant enthalpy is

called Joule – Thomson coefficient. It is denoted by the symbol J-T and defined as

µJ-T = (∂T/∂P)H

Measurement of µJ-T

Joule in collaboration with Thomson performed porous plug experiment to study the
change of temperature with change of pressure of a gas at constant enthalpy. Fig. 9 shows the
experimental setup.

40
 Fig. 9. Joule – Thomson porous plug experiment (Dotted lines represent
the final position of piston in each compartment)

The entire experimental assembly is insulated from the surroundings so that adiabatic
condition is maintained. In this experiment the gas is compressed by applying a high pressure
(P1) and forced to pass through the pores of porous plug. The gas escaping through the
porous plug is allowed to expand against a constant pressure (P2). The change of temperature
with the change of pressure is recorded and thus Joule-Thomson coefficient (∂T/∂P)H is
determined.

Justification of isenthalpic condition in Joule-Thomson experiment

In J-T experiment the enthalpy of the system remains constant (H2 – H1 = ∆H = 0)

though there is change of temperature and pressure. It is explained below.

In the left chamber the gas is compressed at a constant pressure P1 from initial volume V1 to a
state that the piston touches the porous plug and thus final volume of the gas in the left
chamber is zero (because the gas passes into the right chamber). Thus

Work done on the gas in the left chamber = w1 = P1V1

In the right chamber the gas expands against a constant external pressure P2 from zero initial
volume to a final volume V2. Thus

Work done by the gas in the right chamber = w2 = – P2V2

Total work done in the process = w = w1+ w2 = P1V1 – P2V2

Joule – Thomson experiment is carried adiabatically and thus q = 0. Therefore, the first law
of thermodynamics gives

∆U = q + w = 0 + w = w

or, ∆U – w = 0

or, (U2 – U1) – (P1V1 – P2V2) = 0

41
 (U2 + P2V2) – (U1+ P1V1) = 0

But H = U + PV, therefore

∆H = H2 – H1 =0

Significance of Joule – Thomson coefficient µJ-T = (∂T/∂P)H

™ Joule-Thomson effect and the value of µJ-T form the basis of liquefaction of gases.

™ A positive value of the Joule-Thomson coefficient (µJ-T) corresponds to a cooling effect

when a compressed gas is allowed to pass through small holes

™ A negative value of the Joule-Thomson coefficient (µJ-T) corresponds to a heating effect

when a compressed gas is allowed to pass through small holes

™ A zero value of the Joule-Thomson coefficient (µJ-T) corresponds to no thermal change

when a compressed gas is allowed to pass through small holes

Summary of the significance of the values of

Joule – Thomson coefficient(µJ-T)

Sign of the Value of µJ -T Effect observed

™ Positive Cooling

™ Negative Heating

™ Zero Neither heating nor cooling

Inversion temperature: The temperature at which the Joule-Thomson coefficient is zero is

called the inversion temperature. At this temperature neither cooling nor heating effect is
observed during Joule Thomson expansion, below this temperature, cooling effect is
observed while above this temperature, heating effect is observed.

Evaluation of (∂H/∂P)T from Joule-Thomson coefficient

The change of enthalpy is given by

∂H
dH = CP dT + ⎛⎜ ⎞⎟ dP
⎝ ∂P ⎠ T

Joule – Thomson experiment is isenthalpic process (constant enthalpy) , that is, dH = 0 and
thus

∂H
CP dT + ⎛⎜ ⎞⎟ dP = 0 when H is constant
⎝ ∂P ⎠ T

42
 ⎛ ∂H ⎞
or, ⎜ ⎟ dP = – CP dT
⎝ ∂P ⎠ T

⎛ ∂H ⎞ ⎛ ∂T ⎞
⎜ ⎟ = – CP ⎜ ⎟
⎝ ∂P ⎠ T ⎝ ∂P ⎠ H

⎛ ∂T ⎞
But ⎜ ⎟ = J-T = Joule-Thomson coefficient
⎝ ∂P ⎠ H

⎛ ∂H ⎞
⎜ ⎟ = – CP ×µJ-T
⎝ ∂P ⎠ T

™ The value of (∂H/∂P)T can be calculated if the values of CP and µJ-T are known.

™ For an ideal gas µJ-T is zero. Therefore, (∂H/∂P)T is also zero. This implies that the
enthalpy of a given amount of an ideal gas is independent of pressure and it depends on
temperature only. Thus at a constant temperature there is no change in the enthalpy of an
ideal gas as the pressure is changed.

Calculation of thermodynamic preperties from first law

(A) Calculation of w, q, ∆U and ∆H for isothermal and reversible changes in the states
of an Ideal gas

Points to be remembered

™ Isothermal change: Temperature is constant

™ Reversible change: Change is slow but pressure and volume both are changed

™ Ideal gas: PV = n RT

(1) Calculation of w

For an infinitesimally small change in volume (dV) of a gas the small quantity of mechanical
work (đw) is defined by

đw = – PdV (i)

For an ideal gas PV = nRT and P = nRT/V. Thus

nRT
đw = – dV = – nRT d ln V
V

For a finite reversible change of volume of a fixed amount of the gas from an initial volume
of V1 to a final volume V2 at a constant temperature, the work is obtained by integrating
equation (ii)
V2

w = – nRT ∫ d ln V
V1

43
 = – nRT ln[V] VV2
1

V V
= – nRT ln 2 = nRT ln 1
V1 V2

For an ideal gas at constant temperature, P1V1 = P2V2 and V2/V1 = P1/P2. Thus

P1 P2
w = – 2.303 nRT log = 2.303 nRT log
P2 P1

The value of w can be calculated on substituting the values of n, R, T, V1,,V2 ( or P1, P2) in the
above equation.

(2) Calculation of ∆U

The internal energy (U) of an ideal gas is a function of temperature only and is
independent of volume (Joule’s law). Therefore, for an isothermal process when temperature
is constant internal energy of an ideal gas is also constant. Thus

U2 – U1 = ∆U = 0 … for an ideal gas at constant T

(3) Calculation of q

From the first law of thermodynamics we have

∆U = q + w

For isothermal change, ∆U = 0 for an ideal gas, therefore,

V2 P1
q = – w = 2.303 nRT log = 2.303 nRT log
V1 P2

(4) Calculation of ∆H

Change of enthalpy = Final enthalpy – Initial enthalpy

∆H = H2 – H1

= (U2 + P2V2) – (U1 + P1V1 )

= U2 – U1 + (P2V2 – P1V1)

For an ideal gas at constant temperature

U2 – U1 = ∆U = 0

and P2V2 = P1V1

Therefore, ∆H = 0

Summary : For isothermal reversible change of states of an ideal gas

44
 V2 P1
(i) w = – 2.303 nRT log = –2.303 nRT log
V1 P2

(ii) q = – w (iii) ∆U = 0 and (iv) ∆H = 0

Example: Two moles of an ideal gas undergo the following changes:

(a) Reversible isobaric expansion from state x (1.0 bar, 20.0 dm3) to state y (1.0 bar, 40.0
dm3)

(b) Reversible isochoric change from state y (1.0 bar, 40.0 dm3) to state z (0.5 bar, 40.0
dm3)

(c) Reversible isothermal compression from state z (0.5 bar, 40.0 dm3) to x (1.0 bar,
20.0 dm3).

Calculate

(i) The work done in each step and the total work (w) done

(ii) Total heat exchanged (q) in the above processes

(iii) The values of ∆U and ∆H for the overall process.

Solution.

(i) Calculation of work (w)

Process (a):

2 mol Ideal gas (1.0 bar, 20.0 dm3) → 2 mol Ideal gas (1.0 bar, 40.0 dm3)

For a reversible isobaric process

Work done = w = – P× ∆V = – P(V2 –V1) when P is constant

Therefore, w(a) = – 1 bar ( 40 dm3 – 20 dm3) = – 20 bar dm3

Since 1 bar dm3 =101.325 J

Therefore, w(a) = –20 bar dm3×101.325 J/bar dm3 = –2026.5 J

In this process the work done on the system is negative thus the work is done by the system

Process (b) : 2 mol Ideal gas (1.0 bar, 40.0 dm3) → 2 mol Ideal gas (0.5 bar, 40.0 dm3)

w(b) = – 0.5 bar ( 40 L – 40 L) = – 0,5 bar× 0 = 0

In this process no work is done because the volume is constant

Process (c) 2 mol Ideal gas (0.5, 40.0 L) → 2 mol Ideal gas (1.0 bar, 20.0 L)

For an isothermal reversible process

45
 w = – nRT ln (V2/V1).

But for an ideal gas nRT =PV

Therefore, w(c) = – nRT ln (V2/V1) = – PV ln (V2/V1)

On substituting the values of various quantities in the above equation, we have

w(c) = – ( 0.5 bar× 40 dm3) ln (20 L/40 dm3)

= 13.86 bar dm3

= (13.86 bar L)× (101.325 J/ bar dm3)

= 1404.4 J

In this process, the work is done on the system.

Total work done = w = w(a) + w(b) + w(c)

= –2026.5 J + 0 J + 1404.4 J

= – 622.1 J

(ii) Calculation of heat exchanged (q)

From the first law of thermodynamics we know that∆U = q + w. Now the given
processes constitute a cycle for which the internal energy is constant. That is, ∆U is zero for
the cyclic process x y z x. Thus

∆U = q + w = 0

and q = – w = – (– 622.1 J) = 622.1 J

In the given cyclic process heat is absorbed by the system

(iii) Calculation of ∆U and ∆H

U and H are state functions and depend only on the initial and final states of the system.
Now, in the give processes a, b and c the system is restored to its initial state. Therefore, there
is no change in U and H. Thus ∆U (cycle) = 0 and ∆H(cycle) = 0

(B) Calculation of w, q, ∆U and ∆H for adiabatic and reversible changes in the states of
an Ideal gas

Points to remember

™ Adiabatic change: q = 0

™ Reversible change: Change is slow and T, P, and V are changed

™ Ideal gas: PV = n RT

46
(1) Calculation of q

The change is adiabatic, therefore, q = 0

(2) Calculation of ∆U

In adiabatic process there is change of temperature and for a small change of

temperature (dT) the change of internal energy is given by

dU = Cv dT

For a finite change of temperature of a fixed amount of the gas from an initial value of
T1 to a final value of T2 the change of internal energy is obtained on integrating equation.
Thus when Cv is constant

U2 – U1 = Cv (T2 – T1)

Or, ∆U = Cv × ∆T= n Cv. m × ∆T

where, CV. m = molar heat capacity of the gas at constant volume and n is the amount of the
gas

(3) Calculation of w

For a small change in volume (dV) of a gas the small quantity of mechanical work (dw) is
given by dw = – PdV

For an ideal gas PV = nRT and P = nRT/V. Thus

nRT
dw = – dV
V

A direct calculation of work (w) is not possible because the integration of the above equations
is difficult as in an adiabatic reversible process each one of T, P and V will change.

Calculation of w from ∆U: For adiabatic process q = 0 and first law of thermodynamic gives
∆U = w. Thus

w = ∆U = Cv × ∆T = n Cv. m × ∆T

(4) Calculation of ∆H

∆H = H2 – H1

= (U2 + P2V2) – (U1 + P1V1 )

= (U2 – U1)+ (P2V2 – P1V1)

Since, U2 – U1=∆U = CV (T2 – T1)

and (P2V2 – P1V1) = (n RT2 – n RT1)

47
Therefore,

∆H = CV (T2 – T1) + n R(T2 – T1)

= (CV + n R) (T2 – T1)

= CP (T2 – T1)

= n CP, m (T2 – T1)

Here, (CV + n R) = CP = n CP. m

Derivation of T–P–V relations for adiabatic and reversible process

Purpose of derivation: The relation w=∆U = CV (T2 – T1) is used to calculate the desired
quantities when T2 and T1 are known. When instead of T2 the values of P1, V1, T1 and P2 , V2
are given, we need relations between T, P and V.

Main equations to be remembered

™ CV dT = – PdV

™ PV = n RT

(1) T – V relation: For an adiabatic process

CV dT = – PdV

nRT
Now, P=
V

nRT
CV dT = – dV
V

dT nR dV
or, = –
T CV V

d ln T = –( γ – 1) d ln V

or, d ln T = – d ln (V )γ −1

where γ = CPCV and γ – 1 = nR / CV = (CP – CV )/ CV

On integrating between the limits T = T 1 , T = T 2 and V = V1, V = V2 , we get

γ −1
T2 ⎛V ⎞
ln = ln ⎜⎜ 1 ⎟
⎟
T1 ⎝ V2 ⎠

On taking antilog we shall get

48
 γ −1
T2 V⎛ ⎞
= ⎜⎜ 1 ⎟⎟
T1 ⎝ V2 ⎠

γ −1
⎛V ⎞
or, T2 = T1 ⎜⎜ 1 ⎟
⎟
⎝ V2 ⎠

(2) T – P relation: For an adiabatic process

CV dT = – PdV … (i)

For ideal gas PV = n RT

and P dV + V dP = n R dT

nRT
or, – PdV = V dP – n R dT = dP – n R dT … (ii)
P

From equations (i) and (ii) we get

dT dP
(CV + n R) = nR
T P

nR
or, d ln T = d ln P = d ln (P ) (γ –1) / γ
CV + nR

where γ = CP/CV and γ – 1 = nR / CV = (CP – CV )/ CV

On integrating between the limits T = T 1 , T = T 2 and P = P1, P = P2 ,we get

( γ −1) / γ
T2 ⎛P ⎞
ln = ln ⎜⎜ 2 ⎟
⎟
T1 ⎝ P1 ⎠

On taking antilog we shall get

( γ −1) / γ
T2 ⎛ P2 ⎞
= ⎜ ⎟
T1 ⎜P ⎟
⎝ 1 ⎠

( γ −1) / γ
⎛ P2 ⎞
T2 = T1 ⎜⎜ ⎟
⎟
⎝ P1 ⎠

(3) P – V relation: For an adiabatic process

CV dT = – PdV … (i)

For ideal gas PV = n RT

and P dV + V dP = n R dT

49
 nRT nRT
dV + dP = n R dT
V P

dV dP
or, dT = T +T = T (d ln V + d ln P)
V P

On substituting dT in to equation (i) we get

nRT
CV × T (d ln V + d ln P) = – PdV = – dV = – nRT d ln V
V

or, (CV + nRT) d ln V = – CV d ln P

or, d ln (V) γ = – d ln P

On integrating between the limits V = V1 , V = V2 and P = P1, P = P2 then taking

antilog we shall get
γ
⎛ V2 ⎞ P1
⎜ ⎟ =
⎜V ⎟ P2
⎝ 1 ⎠

and P1 V1γ = P2 V2γ = constant

or, PV γ = constant

EXPRESSIONS FOR REVERSIBLE ADIABATIC WORK UNDER DIFFERENT

CONDITIONS

(A) When T1, V1 and V2 are given

w = ∆ U = n Cv, m (T2 – T1)

⎛ T2 ⎞
= n Cv, m T1 ⎜⎜ − 1⎟
⎟
⎝ T1 ⎠

γ −1
T2 ⎛ V1 ⎞
But = ⎜ ⎟
T1 ⎜V ⎟
⎝ 2 ⎠

⎡ γ −1 ⎤
⎛V ⎞
Therefore, w = n Cv, m T1 ⎢⎜⎜ 1 ⎟⎟ − 1⎥
⎢ V ⎥
⎣⎢⎝ 2 ⎠ ⎥⎦

(B) When T1, P1 and P2 are given

w = ∆ U = n Cv, m (T2 – T1)

⎛ T2 ⎞
= n Cv, m T1 ⎜⎜ − 1⎟
⎟
⎝ T1 ⎠

50
 γ −1 / γ
T2 ⎛ P2 ⎞
But = ⎜⎜ ⎟
⎟
T1 ⎝ P1 ⎠

⎡⎛ P ⎞( γ −1) / γ ⎤
Therefore, w = n Cv, m T1 ⎢⎜⎜ 2 ⎟⎟ − 1⎥
⎢ P ⎥
⎣⎝ 1 ⎠ ⎦

(C) When P1, V1 and P2, V2 are given

w=∆U

= n Cv, m (T2 – T1)

For an ideal gas P1V1 = nRT1 and P2V2 = nRT2

Or, T1 = P1V1/nR

and T2 = P2V2/nR

With these values of T1 and T2 in the expression for w is written as

CV ,m
Therefore, w= (P2V2 – P1V1)
R

CV ,m CV ,m 1
But, = =
R C P,m − CV ,m γ −i

P2V2 - P1V1
Therefore, w=
γ−i

Note: In the same way the values of ∆U and ∆H can be calculated for reversible adiabatic
process under different conditions.

Example: One mole of an ideal gas at 300 K and 1 bar is allowed to expand under
reversible and adiabatic conditions to 0. 1 bar. Calculate the final temperature (T2), w,
∆U, ∆H when CV,m = 1.5 R.

Solution. Data given:

n = 1 mol, Cv, m = 1.5 R , T1 =300 K, P1 = 1 bar and P2 = 0.1 bar

γ −1 / γ
⎛P ⎞
Final temperature = T2 =T1 ⎜⎜ 2 ⎟
⎟
⎝ P1 ⎠

 γ = CP,m / CV, m = (1.5 P +  R) / 1.5R = 2.5/1.5

γ −1 (2.5 / 1.5) − 1
and  = = 0.4
γ 2.5 / 1.5

Therefore, T2 = 300 K× [(0.1 bar/ 1 bar)0.4 –1]

51
 = 120 K

The change is adiabatic. Therefore, q = 0 and thus from the first law of thermodynamics we
have

w = ∆U = nCV, m (T2 – T1)

= n× 1.5 R ×(120 K – 300 K)

= –1 mol ×1.5 × 8.314 JK–1 mol–1 × 180 K

= – 2245 J

∆H = CP, m (T2 – T1)

= n×2.5 R(T2 – T1)

= 1 mol×2.5 × 8.314 J K–1- mol–1 (120 K – 300 K)

= – 3741 J

Example: One mole of a gas at 2 bar occupies a volume of 100 cm3 and kept in an
adiabatic container. Its pressure increases steeply to 100 bar followed by a decrease of
volume to 98 cm3 at a constant pressure of 100 bar. Calculate the values of ∆U and ∆H
for the change of state.

Solution. (a) Adiabatic and isochoric change of pressure

1 mol gas (2 bar, 100 cm3) ⎯⎯→ 1 mole gas (100 bar, 100 cm3)

Work done = w = – P × ∆V = –100 bar × 0 mL = 0

For adiabatic process, q = 0 Therefore, from the first law of thermodynamics we have

∆U(a)= q+ w = 0 + 0 = 0

(b) Adiabatic isobaric volume change

1 mol gas ( 100 bar, 100 cm3) ⎯⎯→ 1 mole gas (100 bar, 96 cm3)

Work done = w = – P × ∆V = –100 bar ×(98 cm3 –100 cm3) = 200 bar cm3

For adiabatic process, q = 0, therefore, from the first law of thermodynamics we have

∆U(b) = q + w = 0 + 200 bar cm3 = 200 bar cm3

= 200 bar cm3 ×(105 N m--2 / bar) (10—6 m3 / cm3) = 20 N m = 20 J

(c) Calculation of ∆U and ∆H for the change of state

∆U = ∆U(a) + ∆U(b) = 0 + 20 J = 20 J

52
 ∆H = ∆U + ∆PV)

= ∆U + P2V2 — P1V1)

= 200 bar mL + (100 bar ×98 cm3 — 2 bar × 100 cm3)

= 200 bar cm3 + 9600 bar cm3 = 9800 bar cm3

= 9800 bar cm3 ×(105 N m--2 / bar) (10—6 m3 / cm3)

= 980 N m = 980 J

Example. When one mole of a monotomic ideal gas initially at a temperature of T K

undergoes adiabatic expansion under a constant external pressure of 1 atm the volume
changes from 1 L to 2 L. Which one of the following options would be a correct
expression for the final temperature of the gas when R = 0.0821 atm L K−1 mol−1.

T
(A) (B) T
2 273

2 2
(C) T + (D) T −
3 × 0.0821 3 × 0.0821

Solution. Option (D) is correct

Justification. For an adiabatic process, q = 0 and therefore, from the first law of
thermodynamics we have

∆U = q + w = 0 + w = w

For one mole of a monotomic ideal gas

∆U = Cv, m (Tfinal − Tinitial) = (3/2) R(Tfinal − Tinitial)

and w = − Pext(V2 − V1) = − 1 atm (2 L mol−1 − 1 L mol−1) = − 1 atm L mol−1

Therefore, 3/2 R (Tfinal − Tinitial) = − Pext(V2 − V1)

− Pext (V 2 − V1 )
Tfinal = + Tinitial
(3 / 2) R

On substituting the known data we get

− 1 atm L mol -1
T final = +TK
(3/2) × 0.0821 atm L K -1 mol -1

2
=T +
3 × 0.0821

Discussion. In adiabatic expansion the final temperature is lower than the initial temperature.
Therefore, options (B) and (C) are not possible. Out of the others, option (A) is valid if the
adiabatic change is reversible and option (D) is correct if the adiabatic change is irreversible.

53
Now, the given problem refers to an irreversible adiabatic volume change at a constant
pressure. therefore, option (D) is correct..

Comparison of isothermal and adiabatic reversible expansion of an ideal gas

An indicator diagram of the variation of volume with pressure for an ideal gas under
iothermal and adiabatic reversible conditions is shown in Fig. 10.

Fig. 10. Comparison of isothermal and adiabatic

reversible expansion of an ideal gas

Form the figure it is observed that:

ƒ The final volume (V2) in isothermal reversible expansion is greater than that of adiabatic
expansion for the same final pressure (refer to Fig. 10).

Explanation: For isothermal change PisoViso = constant

For adiabatic change Pad Vad γ = constant

Or, PisoViso = Pad Vad γ

Since Piso= Pad = Final pressure. Therefore,

Viso = Vad γ

Now, γ >1, therefore. Viso > Vad

ƒ Isothermal reversible work of expansion is greater than adiabatic reversible work of

expansion as shown in Fig, 10 (area under isothermal curve is greater than the area under
adiabatic curve).

Isothermal irreversible changes in the states of an ideal gas

54
 In an irreversible change the pressure acting on the gas is suddenly released and then
the gas expands against the constant pressure Pext. Due to expansion the state variables of the
gas are changed from P1, V1 to P2, V2

(1) Calculation of w

The work done on the gas is given by

V2 V2
w= – ∫
V1
Pext dV = –Pext ∫ V1
dV

= –Pext (V2 – V1)

For an ideal gas PV = nRT and V = nRT/P. Therefore, for an isothermal process

⎛ nRT nRT ⎞
w = –Pext ⎜⎜ − ⎟
⎟
⎝ P2 P1 ⎠

⎛ Pext Pext ⎞
= –nRT ⎜⎜ − ⎟
⎝ P2 P1 ⎟⎠

When Pext = P2 = final pressure of the gas, the work done is given by

w = –P2 (V2 – V1)

⎛ P2 ⎞
= –nRT ⎜⎜1 − ⎟
⎝ P1 ⎟⎠

Work of compression under isothermal irreversible condition

To bring back the gas to its initial state (P1, V1) from the expanded state (P2, V2) it must be
compressed by applying pressure higher than P2 and equal to P1. Thus, work of compression
is given by
V1 V
w= – ∫ V2
Pext dV = – Pext ∫ 1 dV
V2

⎛ Pext Pext ⎞
= –Pext (V1 – V2) = – nRT ⎜⎜ − ⎟
⎝ P1 P2 ⎟⎠

When Pext = P1 = pressure of the compressed gas

w = –P1 (V1 – V2)

⎛ P1 ⎞
= – nRT ⎜⎜1 − ⎟ (ii)
⎝ P2 ⎟⎠

Comparison of irreversible work due to expansion and compression

In an irreversible process the work obtained from the system (work of expansion) is

55
smaller than the work done on the system (work of compression). That is, to bring back the
gas to its initial state more work has to be done than the work produced on expansion.

Jusification:

wby(exp) = P2 (V2 – V1)

and won (com) = –P1 (V1 – V2)

Since P1 > P2 and (V2 – V1) = – (V1 – V2)

Therefore, – P1 (V1 – V2) > P2 (V2 – V1)

and won(com) > wby(exp)

(2) Calculation of ∆U

The internal energy (U) of an ideal gas is a function of temperature only and is
independent of volume (Joule’s law). Therefore, for an isothermal process when temperature
is constant internal energy of an ideal gas is also constant. Thus

U2 – U1 = ∆U = 0 … for an ideal gas at constant T

(3) Calculation of q

From the first law of thermodynamics we have

∆U = q + w

For isothermal change, ∆U = 0 for an ideal gas, therefore,

⎛ Pt ⎞
q = – w = nRT ⎜⎜1 − ⎟
⎝ P1 ⎟⎠

(4) Calculation of ∆H

H = U + PV … definition of enthalpy

Change of enthalpy = Final enthalpy – Initial enthalpy

∆H = H2 – H1

= (U2 + P2V2) – (U1 + P1V1 )

= U2 – U1 + (P2V2 – P1V1)

For an ideal gas at constant temperature

U2 – U1 = ∆U = 0 and P2V2 = P1V1

Therefore, ∆H = 0

56
(D) Isothermal free expansion of an ideal gas

Free expansion is a process in which the gas is allowed to expand against zero external
pressure into an evacuated vessel (as in Joule’s experiment).

(1) Calculation of w

The work done by the gas is given by

V2 V2
–w= ∫V
1
Pext dV = Pext ∫
V1
dV

Since Pext = 0, therefore,

V2
Therefore, –w= 0× ∫V1
dV =0

(2) Calculation of ∆U

The internal energy (U) of an ideal gas is a function of temperature only and is independent
of volume (Joule’s law). Therefore, for an isothermal process when temperature is constant
internal energy of an ideal gas is also constant. Thus

U2 – U1 = ∆U = 0 … for an ideal gas at constant T

(3) Calculation of q

From the first law of thermodynamics we have

q = ∆U – w= 0 – 0 = 0

(4) Calculation of ∆H

H = U + PV … definition of enthalpy

Change of enthalpy = Final enthalpy – Initial enthalpy

∆H = H2 – H1

= (U2 + P2V2) – (U1 + P1V1 )

= U2 – U1 + (P2V2 – P1V1)

For an ideal gas at constant temperature

U2 – U1 = ∆U = 0

and P2V2 = P1V1

Therefore, ∆H = 0

Summary: In an isothermal free expansion of an ideal gas

57
 (i) w = 0 (ii) q = 0 (iii) ∆U = 0 (iv) ∆H = 0

Example: One mole of an ideal gas is held under a piston in a cylinder at a pressure of 10
bar and 300 K. The pressure is suddenly released to 0.5 bar and the gas expands
isothermally.

(i) Calculate w, q, ∆U and ∆H

(ii) Calculate the work required to bring back the gas to its initial state.

Solution. Sudden release of pressure implies that the expansion is irreversible.

(i) Data give: n = 1 mol, P1= 10 bar, Pext = 0.5 bar = P2, T = 300 K

⎛ P2 ⎞
w = –nRT ⎜⎜1 − ⎟
⎝ P1 ⎟⎠

= –1 mol× 8.314 J K–1 mol–1 × 300 K ⎛⎜1 −

0.5 bar ⎞
⎟
⎝ 10 bar ⎠

= – 2369.49 J

For isothermal change of an ideal gas

∆U= 0 and ∆H = 0

From the first law of thermodynamics ∆U= q + w =0 and

q = –w =2369.49 J

(ii) For isothermal irreversible compressible

⎛ P1 ⎞
w = –nRT ⎜⎜1 − ⎟
⎝ P2 ⎟⎠

= – 1 mol× 8.314 J K–1 mol–1 × 300 K ⎛⎜1 −

10 bar ⎞
⎟
⎝ 0.5 bar ⎠

= 47389.8 J

Note: From this calculation it is observed that the work done by the surroundings on system
(47389.8 J) during compression is much greater than the work done by the system on
surroundings (2369.49 J) during expansion.

First law of thermodynamic applied to Carnot cycle

A cyclic process in which each step operates under reversible conditions is called a
Carnot cycle (pronounce Carnot as Karno). With the help of paper and pencil, Sadi Carnot
(an engineer by profession) explained that a reversible engine should have the highest
efficiency. Four steps of Carnot cycle. The Carnot cycle for a fluid involves the following
four reversible operations which are shown in Fig. also as P-V indicator diagram for a gas.

58
 1. Isothermal reversible expansion along path AB

2. Adiabatic reversible expansion along path BD

3. Isothermal reversible compression along path CD

Adiabatic reversible compression along path DA

Fig. 11. Pressure – volume indicator diagram of the four steps of Carnot
cycle (shaded area gives the work for the corresponding change)

Example. One mole of an ideal gas undergoes reversible changes in a Carnot cycle.
Without doing calculations, predict the sign of each one of ∆T, ∆V, ∆P, ∆U and ∆H in
each step of the cycle.

Solution. The four steps of Carnot cycle and the corresponding changes are given below

Step ∆T ∆V ∆P ∆U ∆H

(a) Isothermal reversible expansion 0 + – 0 0

(b) Adiabatic reversible expansion – + – – –

(c) Isothermal reversible compression 0 – + 0 0

(d) Adiabatic reversible compression + – + + +

59
Efficiency of Carnot cycle

The efficiency of Carnot cycle is defined as the fraction of the heat q2 absorbed at the higher
temperature which is converted into work in the cycle. It is denoted by symbol (eta) and
expressed as

Net work done by the system W by (cycle)

η= =
Total heat absobed by the system q2

A machine that converts heat into work is called heat engine. Suppose that a heat
engine absorbs heat q2 from a source at a higher temperature T2 and reject a part q1 to the
surroundings at a lower temperature T1. Since in a cyclic process ∆U = 0, therefore, from the
first law of thermodynamics we have q2 – q1 = wby (cycle) and

q 2 − q1 q1
η = = 1−
q2 q2

From the above equation it is clear that efficiency of a machine is always less than one.

Calculation of work and heat for each step of Carnot cycle involving an ideal gas

1. Isothermal reversible expansion. The gas absorbs heat q2 and expands reversibly at a
higher temperature T2 so that its volume changes from V1 to V2 along path AB of the indicator
diagram. The work done by the gas (– w1) is given by

(– w1) = nRT2 ln (V2/V1) = Area A'ABA`

or, w1 = – nRT2 ln (V2/V1)

For an ideal gas at constant temperature, ∆U1 = 0, therefore, first law of thermodynamics
gives

q2 = (– w1) = nRT2 ln (V2/V1)

2. Adiabatic reversible expansion. The gas expands reversibly and adiabatically so that its
volume changes from V2 to V3 along path BC of the indicator diagram. In this step no heat is
exchanged and q = 0 thus temperature falls

from T2 to T1. Therefore, according to the first law of thermodynamics the work done by the
gas (– w2) is equal to decrease of internal energy. That is,

–w2 = ∆U2 = CV (T1 – T2) or w2 = CV (T1 – T2)

3. Isothermal reversible compression. The gas is compressed reversibly and isothermally at

lower temperature T1 so that its volume changes from V3 to V4 along path CD of the indicator
diagram. During isothermal compression heat q1 is given out by the system and work (w3) is
done on the system. Thus ∆U3 = 0 and from first law of thermodynamics we have.

w3 = – q1 = – nRT1 ln (V4/V3)

60
4. Adiabatic reversible compression. The gas is compressed reversibly and adiabatically so
that its volume changes from V4 to V1 along path DA of the indicator diagram and the system
reaches its original state. In this step no heat is exchanged and q = 0 thus temperature
increases from T1 to T2. Therefore, according to the first law of thermodynamics the work
done on the gas (w4) is equal to increase of internal energy. That is,

w4 = ∆U4 = CV (T2 – T1)

In the Carnot cycle

Net heat absorbed = Q (cycle)

= Heat taken from the hot source – Heat rejected to the surroundings

= q2 – q1

Net work done = W (cycle)

= w1 + w2 + w3 + w4

= – nRT2 ln (V2/V1) + CV (T1 – T2) – nRT1 ln (V4/V3) + CV (T2 – T1)

For second and fourth steps of Carnot cycle CV (T1 – T2) = – CV (T2 – T1)

Therefore, W (cycle) = – nRT2 ln (V2/V1)– nRT1 ln (V4/V3)

Or, Wby (cycle) = – Wby (cycle) = nRT2 ln (V2/V1) + nRT1 ln (V4/V3) (i)

For adiabatic changes along BC and DA

γ −1 γ −1
T1 ⎛ V2 ⎞ ⎛ V1 ⎞
= ⎜ ⎟ = ⎜ ⎟
T2 ⎜V ⎟ ⎜V ⎟
⎝ 3 ⎠ ⎝ 4 ⎠

V1 V4
Or, =
V2 V3

V4 V1 V2
and ln = ln = – ln
V3 V2 V1

On substituting the above equality in equation (i), we get

V2
Wby (cycle) = nRT2 ln (V2/V1) – nRT1 ln
V1

V2
= nR (T2 – T1) ln
V1

Net energy change =∆U (cycle) = 0 since internal energy is a state function

From the first law of thermodynamics we have

61
 ∆U (cycle) = Q (cycle) + W (cycle) = 0

Q (cycle) = – W (cycle) = Wby (cycle)

Or, Wby (cycle) = Q (cycle) = q2 – q1

Wby (cycle)
Efficiency = η = =
q2

nR (T2 − T1 ) ln (V 2 / V1 )
=
nRT2 ln (V 2 / V1 )

T2 − T1 T1
= =1 –
T2 T2

Example. One mole of an ideal gas undergoes reversible changes in a Carnot cycle.First it
expands isothermally from a most compressed state of 10 bar and 600 K to a pressure of 1
bar then adiabatically to most expanded state at 300 K. Finally it is brought back to its
initial state via isothermal compression and adiabatic compression respectively. Calculate
q, w and ∆U for each step and the efficiency of the cycle. CV, m= 25 JK–1 mol–1

Solution: Data given:

T1 = 300 K, T2 = 600 K, CV, m= 25 JK–1 mol–1

(a) Step 1: Reversible isothermal expansion at 600 K from a pressure of 10 bar to a pressure
of 1 bar

P1
w1 = –2.303 n RT2 log
P2

10 bar
= –2.303×1 mol × 8.314 JK–1 mol–1× 600 K× log
1 bar

= –11488 J

and q2 = – w1 = 11488 J since ∆U = 0

(b) Step 2. Reversible adiabatic expansion so that temperature decreases from 600 K to 300
K

q=0

and from the first law of thermodynamics we have

w2 = ∆U2 =n CV, m (T1 – T2)

=1 mol× 25 JK–1 mol–1 ×(300 K – 600 K)

= – 7500 J

62
(c) Step 3: Reversible isothermal compression at 300 K from a pressure of 1 bar to a pressure
of 10 bar

P1
w3 = –2.303 nRT1 log
P2

1 bar
= –2.303 ×1 mol× 8.314 JK–1 mol–1× 300 K× log
10 bar

= 5744 J

and q1 = – w3 = –5744 J since ∆U3 = 0

(d) Step 4. Reversible adiabatic compression so that temperature increases from 300 K to 600
K

q=0

and from the first law of thermodynamics we have

w4 = ∆U4 =n CV, m (T2 – T1)

=1 mol× 25 JK–1 mol–1 ×(600 K – 300 K)

= + 7500 J

For the entire cycle

∆U(cycle) =∆U1 +∆U2 +∆U3 + ∆U4

1
= 0 +(–7500 J ) + 0 + 7500 J =0

W(cycle) = w1 + w2 + w3 + w4
1
= – 11488 J –7500 J –5744 J + 7500 J

= – 5744 J

Wby(cycle) = – W(cycle) =5744 J

Wby (cycle)
Efficiency = η = =
q2

5744 J
= = 0.5
11488 J

Comments: The efficiency is also calculated by

Tl 300 K
η = 1− = 1− = 1 – 0.5 = 0.5
T2 600 K

63
A critical discussion: It is observed that in a cyclic process the total heat absorbed is not
converted in to work. Why? Where has that remaining heat been utilized? We can explain this
aspect of the subject by the study of the second law of thermodynamics which introduces the
concept of entropy a measure of randomness and unavailable energy.

Carnot theorem

(i) Carnot theorem states that the efficiency of a reversible engine depends only on
the higher temperature (T2) and lower temperature (T1) and is independent of the
nature of the substance. Therefore, efficiency of a reversible engine may be
expressed as

W by (cycle)
Efficiency = η =
q2

q 2 − q1 T2 − T1
= =
q2 T2

(ii) Carnot theorem may also be stated that for the same higher and same lower
temperatures all reversible engines should have same efficiency.

Further discussion of Carnot theorem

Tl
The relation η = 1 − suggests that
T2

(1) The efficiency of an engine is less than 1

(2) The efficiency will be equal to 1 only when T1/T2 = 0. It is possible only when
either.Tl = 0, or T2 = ∞ But both these conditions are impossible to achieve
experimentally.

(3) The efficiency of an engine can be increased by increasing the difference of the
temperature of the source and the sink

(4) The efficiency of a machine operating in Carnot cycle is maximum because the work
obtained from the system under reversible conditions is the highest possible work
which a system can perform.

Thermodynamic scale of temperature

Lord Kelvin defined the thermodynamic scale of temperature by assigning the triple
point of water exactly equal to 273.16 K. On this scale one kelvin (1 K) is defined as the
fraction 1/273.16 of the thermodynamic temperature of triple point of water. This temperature
can be conveniently realized, maintained and measured in the laboratory. The measurement
of temperature is independent of the method followed. That is, the temperature of a system is
the same whether it is measured using a mercury thermometer or thermocouple or thermistor.
The temperature on thermodynamic scale (kelvin scale) is always positive. There is no
negative value of temperature on kelvin scale

64
Comments: Triple point of water is the state when the three phases of water namely, solid
(ice), liquid (water) and gas (vapour) exist together in equilibrium. The triple point of water is
273.16 K, which is greater than its melting point.

Zero value of kelvin temperature in terms of efficiency of Carnot cycle

Zero value of kelvin temperature is defined in terms of the efficiency ( , which is

independent of the working substance in the cycle) of Carnot cycle as

T1 = T2 ( 1 – η)

When η=1

T1 = T2 ( 1 – ) = 0 K

That is, the efficiency of the Carnot cycle is unity if the temperature of the surroundings
(sink) is 0 K. In other words, we may state that the lowest temperature of thermodynamic
scale corresponds to unit efficiency of Carnot cycle. This lowest temperature is written as T =
0 K which is equal to –273.16 oC.

65
CONFIDENCE BUILDING QUESTIONS ON THE FIRST LAW OF
THERMODYNAMICS

(A) Complete the following statements using a correct word/term from the list:

[by, increases, first, internal energy, adiabatic, enthalpy, constant, greater, zero, lower,
adiabatic]

1. The relation ∆ U = q + w represents the ………….law of thermodynamics

2. Work done on the system ………….. its internal energy.

3. Work done … the system decreases its internal energy.

4. In the equation H = U + PV, the term H is called --------------

5. The relation PVγ tant is valid when an ideal gas undergoes ………….. reversible process..

6. In an adiabatic reversible process for an ideal gas TVγ–1 = ---------------

7. The value of w is ------------- in an adiabatic process than that in an isothermal process.

8. The value of w is ------------- in an isothermal reversible process than that in an isothermal

irreversible process.

9. The efficiency of a Carnot cycle is one when T1/T2 is ------------

10. ∆ U = w for an ------------- process

(B) Short Answer Questions:

1. Write the mathematical statement of the first law of thermodynamics.

2. Write the relation between work, heat and change in internal energy.

3. Write the first law of thermodynamics for an adiabatic process.

4. Name the process for which the first law of thermodynamics is written as ∆ U = w

5. Write the missing terms in the equation H = U + --------

6. Mention the conditions when (a) ∆ U = qV and (b) ∆ H = qP

7. Mention the conditions when ∆ U = ∆ H

8. Define heat capacity, specific heat capacity and molar heat capacity.

9. Write the relation between CP and CV for an ideal gas.

10. The relation CP – CV = nR is valid for which type of system?

11. State Joule’s law.

66
 12. The relation ( ∂ U/ ∂ V)T = 0 is known as which law?

13. A positive value of Joule-Thomson coefficient corresponds to which type of effect

cooling or heating or no thermal change?

14. A zero value of Joule-Thomson coefficient corresponds to which type of effect cooling
or heating or no thermal change ?

15. A negative value of Joule-Thomson coefficient corresponds to which type of effect

cooling or heating or no thermal change ?

16. Derive an expression for work (w) when an ideal gas undergoes isothermal and
reversible volume change.

17. Derive the expressions for w, q, ∆U and ∆H when n mol of an ideal gas undergoes
adiabatic and reversible expansion.

18. Derive a relation between temperature and volume in adiabatic reversible expansion of
an ideal gas.

19. Derive a relation between temperature and pressure in adiabatic reversible expansion of
an ideal gas.

20. Name the system and conditions when PV is constant.

21. Derive the following relation for an ideal gas undergoing adiabatic reversible process

(a) TVγ–1 = constant (b) TP –R/Cp = constant

22. What is the value of work (w) when an ideal gas is allowed to expand in to an evacuated
vessel?

23. In which type of process adiabatic or isothermal the value of work (w) done is more?

24. Calculate the value of ∆U and ∆H in the isothermal and reversible expansion of 4 g of
hydrogen gas at 300 K from an initial volume of 20 dm3 to a final volume of 60 dm3.
Assume that hydrogen gas obeys ideal gas law.

(C) Numerical problems

1. One mole of an ideal gas is heated at constant pressure from 273 K to 373 K. Calculate w,
q ∆U and ∆H when Cp,. m = 3.5 R [Ans: w= – Pext (V2 – V1) = – nR(T2 – T1) = – 831.4
J. ∆U = 2078.5 J, q = 2909.9 J = ∆H ]

2. One mole of an ideal gas at 300 K and 106 Pa expands to 105 Pa under isothermal and
reversible conditions. Calculate w, q ∆U and ∆H .[Ans: w= –5744 J q = 5744 J. ∆U
= 0, ∆H = 0

3. One mole of an ideal gas at 300 K and 106 Pa expands to 105 Pa under isothermal and
irreversible conditions Calculate w, q ∆U and ∆H .[Ans: w= –2245 J q = 2245 J. ∆U
= 0, ∆H = 0]

67
4. One mole of an ideal gas at 300 K and 106 Pa expands to 105 Pa under adiabatic and
reversible conditions. Calculate final temperature, w, q ∆U and ∆H (Given that CV,. m =
1.5 R)..[Ans:Final temperature = 119.4 K, q = 0 ∆U = w= –2252 J, ∆H = – 3753 J]

5. A sample of 1.6 mole of an ideal gas ( CV, .m = 2.5 R) at 300 K were allowed to expand
adiabatically from 5 bar to a final pressure of 2 bar against a constant external pressure of
1 bar. Calculate final temperature, q, w, ∆U and ∆H . [Ans: Final temperature = 270 K
, q = 0, w= ∆U = – 997.68 J. ∆H = –1396.7]

6. A sample of 0.175 mol of an ideal gas is allowed to expand under adiabatic and reversible
conditions from a volume of 5.0 dm3 at a pressure of 303975 N/m2 and 298 K until the
volume becomes 10.0 dm3. Calculate the final pressure and final temperature of the gas
and the values of q, w, ∆U and ∆H . for the process. (Given that Cp,. m = 29.1 JK–1 mol–
1
)..[Ans: Final pressure = 115186.5 N/m2, final temperature = 226 K , q = 0, w = ∆U
= – 261.9 J. ∆H = –366.6 J]

7. One mole of an ideal gas is held by a piston at 0 oC and under a pressure of 10 kPa. The
pressure is suddenly released to 0. 4 kPa and the gas is allowed to expand isothermally.
Calculate q, w, ∆U and ∆H . for the process. Hint: The change is irreversible. [Ans: ∆U
= 0, ∆H = 0, w = –2179 J =q]

68
Thermochemistry

The branch of chemistry dealing with the measurement and computation of energy changes
(∆U) and enthalpy changes (∆H) of various types of physical transformations and chemical
reactions is called thermachemistry. Now ∆U and ∆H are related to the heat exchanged
between the system and the surroundings, Therefore, these properties are also called as heat
of reactions.

Types of heat of a reaction

Depending on the experimentsl conditionsthe heat of a reaction is classified as follows.

™ When the reaction is performed at constant volume the accompanying energy change
(∆U) is called heat af reaction at canstant volume (qv)

∆U = qv = Heat of reaction at constant volume

™ When the reaction takes place at constant pressure the accompanying enthalpy change
(∆.H) is called the heat af reactian at canstant pressure

∆H = qp = Heat of reaction at constant pressure

Since most of the experiments are performed at constant pressure, the enthalpy change
(∆H) is used to describe the thermal changes in various types of chemical reactions and
physical transformations.

Type of enthalpy changes. The enthalpy changes are classified as follows

(1) Enthalpy changes in (2) Enthalpy changes in chemical

reactions (∆rH) physical transformation (∆trssH)

(a) Enthalpy of formation (∆fH) (i) Enthalpy of vaporization (∆vapH)

(b) Enthalpy of combustion (∆cH) (ii) Enthalpy of fusion (∆fusH)

(c) Bond enthalpy ∆H( A –B) (iii) Enthalpy of sublimation (∆subH)

(d) Enthalpy of neutralization (∆nH) (iv) Enthalpy of solution (∆solH)

Enthalpy of reaction (∆rH)

The enthalpy of a reaction is defined as the heat absorbed or liberated when the
reactants are completely converted into products as represented by the balanced chemical
equation at a given temperature and pressure.. It is also called as the heat of reaction at
constant pressure. Enthalpy of reaction is denoted by ∆rH and expressed in the units of kJ
mol–1. For example,

(i) When hydrogen gas is burnt in oxygen, a chemical reaction takes place. As a result of the
reaction water is formed and 285.8 kJ heat is liberated. The reaction is represented by the
equation

69
 H2 g) + ½ O2 (g) ⎯
⎯→ H2 O(l) ∆rH = – 285.8 kJ mol–1

Interpretation of the above equation : The above equation tells that 286 kJ heat is liberated
when 1 mole (2 g) of hydrogen gas completely reacts with half mole (16 g) of oxygen gas so
that 1 mole (18 g) of water is formed. Thus heat of the reaction as represented by the above
balanced chemical equation is –285.8 kJ mol–1

(ii) When methane gas is burnt in oxygen, a chemical reaction takes place. As a result of the
reaction carbon dioxide and water are formed and 890 kJ heat is liberated. The reaction is
represented by the equation

CH4(g) + 2O2 (g) ⎯

⎯→ CO2(g) + 2H2O(l) ∆rH = – 890 kJ mol–1

Interpretation of the above equation : The above equation tells that 890 kJ heat is liberated
when 1 mole (16 g) of methane gas completely reacts with 2 moles (64 g) of oxygen gas so
that 1 mole CO2 (44 g) and 2 moles (36 g) of water are formed. Thus heat of the reaction as
represented by the above balanced chemical equation is -890 kJ mol–1

Role of mole to report the value of the enthalpy of reaction

–1 –1
™ Enthalpy of reaction is always reported as kJ mol . Here per mole (mol ) corresponds to
per mole of the extent (progress) of reaction. Thus ∆rH is the change of enthalpy with the
extent of reaction. For example,

(i) The enthalpy of reaction

CH4(g) + 2O2 (g) ⎯

⎯→ CO2(g) + 2H2O(l)

is –890 kJ mol–1. This value tells that when one mole of methane gas reacts completely with 2
moles of oxygen gas to produce one mole of CO2 (g) and 2 moles of H2O(l) then progress of
reaction is said to be hundred percent. In this case we state that one mole of reaction has
occurred

(ii) The enthalpy of reaction

2 CH4g) + 4 O2(g) ⎯
⎯→ 2 CO2 (g) + 4 H2O(l)

is –1780 kJ mol–1 This value tells that when two moles of methane react completely with 4
moles of oxygen to produce two moles of CO2 and 4 moles H2O then progress of this reaction
is hundred percent. In this case we state that one mole of reaction as represented by the
balanced chemical equation has occurred.

Notes:

(i) While reporting the enthalpy of combustion of a fuel, the value is given as kJ per mole of
the substance burnt. In the given example the enthalpy of combustion is 890 kJ mol–1 of
methane

(ii) Enthalpies of formation, vaporisation, fusion etc. are reported as kilojoules per mole (kJ
mol–1) of the substance concerned.

70
Standard state

The enthalpy change depends on temperature, pressure and the physical states of the reactants
and products. Therefore, it is the recommendation of the IUPAC to mention the standard
experimental condition while reporting the values of the enthalpy changes.

Standard states of different forms of matter

Physical state Notatio Conditions of standard states

n

(1) Gas (g) Ideal gas at 1 bar at the specified temperature*

(2) Liquid (l) Pure liquid at 1 bar at the specified temperature*

(3) Solid (s) Pure crystalline and reactive form# at 1 bar and
temperature T
(4) Solution in (aq)
water Unit molarity (1 mol /dm3) at 1 bar and temperature T

*The conventional temperature for thermodynamic tables is specified as 298.15 K

#graphite is taken as the standard state of carbon

#rhombic form is taken as the standard state of sulphur

Standard enthalpy of formation (∆fHυ)

Standard enthalpy of formation is defined as the heat absorbed or liberated when one
mole of a substance is formed from its constituent elements in their respective standard
states. Standard enthalpy of formation is denoted by ∆fHυ .and it is called standard heat of
formation also. It is expressed in the units of kJ mol–1. For example, the standard enthalpy of
formation of water is – 285.8 kJ mol–1. It is written as ∆fHυ (H2O) = – 285.8 kJ mol–1. This
enthalpy change is described as follows:

H2(g) + ½ O2 (g) ⎯
⎯→ H2O (l) ∆fHυ (H2O) = – 285.8 kJ mol–1

Ideal gas Ideal gas Pure liquid

1 bar, 298 K 1 bar, 298 K 1 bar, 298 K

Notes:

(i) It is not always necessary to mention the standard conditions with the reactants
and products in the balanced chemical equation, because ∆fHυ itself tells that the
value refers to standard state

The values of standard enthalpy of formation of some substances are given in table 1

71
Table 1- a. Standard enthalpy of formation ( ∆ f H Θ ) of some inorganic compounds

Substance ∆ f H Θ /kJ mol–1 Substance ∆ f H Θ /kJ mol–1

H2O (l) - 285.8 NO (g) 90.4

H2O (g) - 241.8 N2O (g) 81.5

H2O2 (l) - 188.0 N2O4 (g) 9.6

HF (g) - 268.6 NO2 (g) 33.8

HCl (g) -92.3 NH3 (g) -46.2

HBr (g) -36.2 HNO3 (l) - 173.2

HI (g) 25.9 NH4Cl (s) -315.4

HIO3(s) - 238.6 LiCl(s) - 408.8

H2S (g) - 20.1 NaCl(s) - 411.0

H2SO4 (l) - 814.0 KCl (s) - 435.8

SO2 (g) - 296.9 AgCl (s) - 127.0

SO3 (g) - 395.2 Br2 (g) 30.7

CO (g) - 110.5 O3 (g) + 142.3

CO2 (g) - 393.5 Na2CO3 -1131.0

72
Table 1-b. Standard enthalpy of formation ( ∆ f H Θ ) of some organic compounds

Compound
Formula ∆ f H Θ / kJ mol–1
Methane CH4 (g) - 74.85

Ethane C2H6 (g) - 84.67

Propane C3H8 (g) - 103.50

n-Butane C4H10 (g) - 124.30

Ethene C2H4 (g) + 52.30

Ethyne C2H2 (g) + 226.70

Benzene C6H6 (l) + 49.03

Benzene C6H6 (g) + 82.93

Methanol CH3OH (l) - 238.6

Ethanol C2H5OH (l) - 227.6

Ethanal CH3CHO (l) - 166.3

Tetrachloromethane CCI4 (l) - 139.8

Trichloromethane CHCI3 (l) - 131.8

Urea (NH2)2CO (s) - 333.2

Glucose C6H12O6 (s) - 1270.0

Cyclohexane C6H12 (l) - 123.1

(A) Standard enthalpy of formation of an element

The standard enthalpy of formation of an element is taken as zero.. That is, ∆f Hυ

(element) = 0

Reason: An element can not be synthesized or decomposed by chemical or physical methods.

For example, let us suppose that we want to represent the standard enthalpy of formation of
element H2(g) by a balanced chemical equation. Now, according to the definition of ∆fHθit
will be represented by

H2(g, 1 bar, 298 K) ⎯

⎯→ H2(g, 1 bar,298 K) ∆rH = ∆fHθ (H2, g) = 0

(reactant) (product)

It is quite clear that there will not be any change of enthalpy for the formation of H2(g) from
H2(g). It is to be kept in mind that ∆fHθ (H2, g) = 0, but ∆fHθ (H, g) ≠ 0. That is, the standard
enthalpy of formation of hydrogen atom is not zero because atomic hydrogen is not the
standard state of H2. Similarly, we can write that:

73
(1) ∆fHυ (O2, g) = 0 (2) ∆fH υ (N2, g) = 0 (3) ∆fH υ
(I2, s)) = 0 but ∆fH υ
(I2, g)) ≠ 0
because gaseous iodine is not its standard state.

(B) Standard enthalpy of formation of a gaseous atom

The heat absorbed when 1 mole of a gaseous atom is formed from its element in its standard
state is called the standard enthalpy of formation of that atom. For example:

™ The standard enthalpy of formation of gaseous hydrogen atom is equal to the enthalpy
change for the following reaction.

½ H2(g) ⎯
⎯→ H(g) ∆rHθ= ∆fHθ (H, g) = 218 kJ mol–1

™ The standard enthalpy of formation of gaseous carbon atom is equal to the enthalpy
change for the following reaction.

C(graphite) ⎯
⎯→ C(g) ∆rHθ= ∆fHθ (C, g) = 716.67 kJ mol–1

Enthalpy of combustion (∆cH)

The enthalpy of combustion is the heat liberated at a constant pressure when one mole of a
fuel is completely burnt in oxygen. It is denoted by notation ∆cH and expressed in the units
of kJ mol-1. Enthalpy of combustion is called heat of combustion also.

A combustion reaction is always exothermic. For example, when one mole of methane burns
completely in the presence of oxygen, one mole of CO2 and two moles of H2O are formed
and 890 kJ heat is liberated.

CH4 (g) + 2 O2 (g) ⎯

⎯→ CO2 (g) + 2 H2O (l) ∆rH = ∆ cH (CH4, g) = – 890 kJ
mol–1

Relation between standard enthalpy of reaction and standard enthalpy of formation

Standard enthalpy of reaction (∆rHθ) and standard enthalpy of formation (∆fHθ) are related by

(∆rHθ) = ΣVp ∆fHθ (products) – Σ V r ∆rHθ (reactant)

where,

Vp = Stoichiometric coefficient of product

Vr = Stoichiometric coefficient of reactant

For a general chemical reaction

aA + bB ⎯
⎯→ c C + d D

Σ p ∆fHυ (products) =c ∆fHυ (C) + d ∆fHυ (D)

Σ vr ∆fHθ (reactants) =a ∆fHθ (A) + b ∆fHθ (B)

74
Thus

(∆rHθ ) = [c ∆fHθ (C) + d ∆fHθ (D)] – [a ∆fHθ (A) + b ∆fHθ (B)]

Comments:

™ The above equation can be used to calculate any one of the quantities if others are known

θ
™ In the calculation it is assumed that ∆fH (element) = 0

θ
™ The values of ∆fH for other substances are taken from the table of thermodynamic data.

Example: Use the given values of ∆fHθ to calculate the enthalpy of the following reaction

2 H2S (g) + 3 O2 (g) ⎯

⎯→ 2 SO2(g) + 2 H2O (l)

Substance H2S (g) SO2(g) H2O (l)

∆fHθ /kJ mol–1 – 20.1 –296.9 – 285.8

Solution: Enthalpy of a reaction is related to the standard enthalpy of formation as

(∆rHθ ) = Σ vp ∆fHθ (products) – Σ vr ∆rHθ (reactant)

For the given reaction

(∆rHθ) = [ 2 ∆fHθ (SO2, g) + 2 ∆fHθ (H2O, l)] – [2 ∆fHθ (H2S, g) + 3 ∆fHθ (O2, g)]

On substituting the given ∆fHθ values and assuming ∆fHθ (O2, g) = 0, we get

(∆rHθ) = 2×(–296.9 kJ mol–1)+ 2×(– 285.8 kJ mol–1) – [2×(– 20.1 kJ mol–1) – 3×0 kJ mol–1)

= – 1125.2 kJ mol–1

Example: Use the standard enthalpies of formation of various species to calculate the
enthalpy change (∆r H0) for the reaction CH2Cl2 —→ C(g) + 2 H (g) + 2 Cl(g)

Species CH2Cl2 (g) C(g) H(g) Cl(g)

∆ fHυ/ kJ mol -1 − 1162.4 715.0 218.0 121.3

Solution. For the reaction CH2Cl2 —→ C(g) + 2 H (g) + 2 Cl(g)

∆rHθ = [∆f Hθ (C, g) + 2∆f Hθ (H, g) + 2 ∆f Hθ (Cl, g)] − ∆f Hθ (CH2Cl2, g)

= [ 715.0 + 2×218.0 + 2×121.3] kJ mol−1 − (−1162.4 kJ mol−1)

= 1556.0 kJ mol−1

75
Difference between the enthalpy of formation and enthalpy of reaction

™ The enthalpy change accompanying the formation of one mole of a compound from its
constituent elements in their respective standard stable states is called standard enthalpy
of formation . It is denoted by ∆fH Θ .

™ The enthalpy change in any type of chemical reaction namely combination, combustion,
hydrogenation, bond dissociation or neutralization is called the enthalpy of reaction. It is
denoted by ∆ rH Θ.

Important statements: Enthalpy of formation is always equal to the enthalpy of reaction

representing the formation of that compound. But the enthalpy of every reaction need not
be the enthalpy of formation For example,

• Reaction H2 (g) + 1/2 O2(g) ⎯ ⎯→ H2O (l) describes the formation of one mole of liquid
water from its constituent elements. It also describes the combustion of hydrogen gas in
the presence of oxygen to produce one mole of liquid water. Therefore, the enthalpy
change of this reaction is equal to the enthalpy of combustion of hydrogen and also the
standard enthalpy of formation of H2O (l). Thus

∆ rH Θ = ∆ CH Θ (H2, g).= ∆ fH Θ (H2O, l)

• The enthalpy of the reaction

⎯→ NH4Cl (s) ∆ rH Θ = –178.9 kJ mol -1

NH3 (g) + HCl (g) ⎯

does not represent the standard enthalpy of formation of NH4Cl (s). That is,

∆ rH Θ ≠ ∆ fH Θ (NH4Cl, s)

Reason. The reactants NH3 (g) and HCl (g) are not elements.

• The enthalpy change for the reaction

C(g) + 4H(g) ⎯
⎯→ CH4 (g) ∆ rH Θ = –1664 kJ mol -1

does not represent the standard enthalpy of formation of one mole of methane. That is,

∆ rH Θ ≠ ∆ fH Θ (CH4, g)

Reason. The reactants C (g) and H(g) are not the elements in their standard states.

Exercise. Identify and justify the thermochemical equations representing standard

enthalpy of formation and standard enthalpy of reaction in the following list.

(1) H2 (g) + 1/2 O2(g) ⎯

⎯→ H2O (l) ∆ H Θ = -286 kJ mol -1

(2) C(g) + 4 H(g) ⎯

⎯→ CH4 (g) ∆ H Θ = –1664 kJ mol -1

(3) 2H2(g) + O2(g) ⎯

⎯→ 2 H2O (l) ∆ H Θ = –572 kJ mol -1

76
 (4) C2H4 (g) + H2(g) ⎯
⎯→ C2H6(g) ∆ H Θ = -137 kJ mol -1

(5) C (graphite) + 2 H2(g) ⎯

⎯→ CH4 (g) ∆ H Θ = -74.8 kJ mol -1

(6) CaO(s) + CO2 (g) ⎯

⎯→ CaCO3(s) ∆ H Θ = -178.3 kJ mol -1

(7) NH3 (g) + HCl (g) ⎯

⎯→ NH4Cl (s) ∆ H Θ = -178.9 kJ mol -1

(8) C (graphite) + O2(g) ⎯

⎯→ CO2 (g) ∆ H Θ = - 393.5 kJ mol -1

Hint: (i) Enthalpy of formation : (1), (5), (8) (ii) Enthalpy of reaction: Each one
including 1, 5 and 8

Enthalpy of neutralization

The heat liberated when one mole of hydrogen ions (H+) is completely neutralized by a base
in dilute aqueous solution at constant temperature and constant pressure is called enthalpy
of neutralization. It is called the heat of neutralization also.

H+ (aq) + Base ⎯
⎯→ Salt + Water + Heat

For example, at 25 °C and 1 atm when one mole HCl (aq) and one mole NaOH (aq) react, 57
kJ heat is liberated as represented by

HCl (aq) + NaOH (aq) ⎯

⎯→ NaCl (aq) + H2O (1) ∆H = – 57 kJ mol–1

In aqueous solution each one of HCl (aq), NaOH (aq) and NaCl (aq) is completely ionized.
Therefore, the neutralization reaction may be represented as

H+(aq) + Cl –(aq) + Na+(aq) + OH –(aq) ⎯

⎯→ Na+(aq) + Cl– (aq)+ H2O(l) ∆H = – 57
kJ mol–1

Since equal number of Na+ (aq) and Cl–(aq) ions appear on both the aides of the
neutralization reaction they may be dropped while writing the balanced chemical equation
so that we have

H+(aq) + OH–(aq) ⎯
⎯→ H2O (l) ∆H = – 57 kJ mol–1

That is, the neutralization reaction between HCl (aq) and NaOH (aq) is essentially the
reaction between H+ (aq) and OH– (aq) to form unionized H2O This is exclusively valid for
strong and strong base pair.

Comments:

(i) It is true that the neutralization reaction between a strong acid-base pair is the
combination of H + (aq) and OH– (aq) ions to form H2O (l). But the value of heat of
neutralization is different for various acid-base pairs at different concentrations. For
example, the heat of neutralization of sulphuric acid and NaOH is 62 kJ at 25 °C and 1
atm.

77
(ii) In very dilute solutions the heat of neutralization of strong acid and strong base pair is
constant and equal to about 57 kJ mol–1 at 298 K and 1 atm. If the acid and base are of
appreciable concentrations (more than 1.0 M), then ∆H value is different.

(iii) For weak acid and strong base pair (CH3COOH + NaOH), or strong acid and weak base
pair (HCl + NH4OH), the heat of neutralization is less than 57 kJ. Why? Because part of
the heat liberated is utilized to cause the ionization of the weak acid or weak base.

Example: The enthalpy of neutralization of ethanoic acid and NaOH is – 55.8 kJ mol –1
and that of hydrochloric acid and NaOH is – 57.3 kJ mol –1. Give a suitable reason for
the difference in the two values.

Solution. The enthalpy changes may be represented by the following equations.

(i) Na+ OH− (aq) + H+ Cl− (aq) ⎯

⎯→ Na+Cl− (aq) + H2O (l) ∆H = − 57.3 kJ
mol−1

Or, OH−(aq) + H+(aq) ⎯

⎯→ H2O ∆H = − 57.3 kJ mol−1

(ii) Na+OH− (aq) + CH3COOH(aq) ⎯

⎯→ CH3COO− Na+ (aq) + H2O(l) ∆H = − 55.8 kJ
mol−1

Or, OH−(aq) + CH3COOH(aq) ⎯

⎯→ CH3COO−(aq) + H2O(l) ∆H = − 55.8
kJ mol−1

Ethanoic acid is a weak acid and is only partially ionized. Therefore, a part of the
enthalpy change on neutralization is used in the ionization of CH3COOH. Thus the magnitude
of ∆H for the reaction (ii) is lower than that for the reaction (i)

Calculation of enthalpy of ionization of CH3COOH

(i) Na+ OH− (aq) + H+ Cl− (aq) ⎯

⎯→ Na+Cl− (aq) + H2O (l) ∆H(i) = − 57.3 kJ
mol−1

(ii) Na+OH− (aq) + CH3COOH(aq) ⎯

⎯→ CH3COO− Na+ (aq) + H2O(l) ∆H(ii) = − 55.8 kJ
mol−1

On subtracting equation (i) from equation (ii) we get

⎯→ CH3COO−(aq) + H+(aq)
(A) CH3COOH (aq) ⎯

∆H(A) = ∆H(ii) − ∆H(i) = − 55.8 kJ mol−1 − (−57.3 kJ mol−1) = +1.8 kJ mol−1

Enthalpy on ionization of CH3COOH = 1.8 kJ mol−1

Hess's law of constant heats summation

This law was formulated in 1840 by the Swiss-Russian chemist Germain Henri Hess and is
stated as follows

78
 The heat of a reaction (reaction enthalpy) is the same whether the reaction

takes place in one step or in several steps under the same conditions.

Illustration of the statement of the Hess’s law

Let us consider the calculation of the standard enthalpy of formation of carbon dioxide.
The formation of CO2 may be described in the following two ways:

Method 1. A calculated quantity of carbon (graphite) is burnt directly in the presence of

oxygen to form carbon dioxide

(i) C (graphite) + O2(g) ⎯

⎯→ CO2 (g) ∆H°(i) = –395 kJ mol–1

Method 2. A calculated quantity of carbon (graphite) is burnt in limited supply of oxygen to

form cabron monoxide: then allowing CO to combine with oxygen and form carbon dioxide

(ii) C (graphite) + ½ O2(g) ⎯

⎯→ CO(g) ∆H°(ii) = –110 kJ mol–1

(iii) CO(g) + ½ O2(g) ⎯

⎯→ CO2 (g) ∆H°(iii) = – 285 kJ mol–1

On adding equations (ii) and (iii) alongwith the ∆Hθ values we get

C (graphite) + ½ O2( g) + CO(g) + O2( g) ⎯

⎯→ CO(g) + CO2( g)

and ∆Hθ (ii) + ∆Hθ (iii) = – 110 kJ mol—1 + ( – 285 kJ mol–1 ) = – 395 kJ mol–1

On cancelling the common species on both the sides of the above equation we have

(iv) C (graphite) + O2(g) ⎯

⎯→ CO2(g) ∆Hθ (iv) = – 395 kJ mol–1

Since the chemical equations (i) and (iv) are the same, their enthalpy changes are also the
same. Thus

∆Hθ (i) = ∆Hθ (ii) + ∆Hθ (iii) = ∆Hθ (iv) = – 395 kJ mol–1

Conclusion: From this illustration it is concluded that the standard enthalpy of formation of
carbon dioxide is the same whether it is produced by burning graphite in sufficient quantity
of oxygen or first burning graphite in limited supply of oxygen to form carbon monoxide then
burning carbon monoxide to produce carbon dioxide

Discussion

(1) Hess's law is a direct consequence of the law of conservation of energy. Suppose in the
above reaction the enthalpy changes in the two steps of the second method were greater than
that of the first method i.e., ∆Hθ (ii) + ∆Hθ (iii) > ∆Hθ (i). This would mean that energy is not
conserved though the amounts of the reactants and the product are the same in both the
methods of performing the experiments. This would be contrary to the conservation law.
Thus the enthalpy changes estimated by the two should be the same.

(2) Hess's law is also in line with the fact that enthalpy is a state function. Therefore, the

79
change of enthalpy will depend only on the initial and final states, and not on the path
followed by the change. It implies that we cannot alter the enthalpy of a reaction by choosing
different paths.

Applications of Hess’s law of constant heat summation

(i) This law provides a practical method for computing the enthalpy change of a
reaction from the enthalpy changes of other reactions.

(ii) Hess’s law is used to calculate the reaction enthalpies even for those reactions
which are otherwise difficult to carry out in the laboratory

(iii) According to Hess's law the thermochemical equations may be treated as algebraic
equations.

Working rules of applications of Hess’s law

™ When a chemical equations is reversed, the sign of the enthalpy change is also reversed
but magnitude remains the same.. For example, the standard enthalpy of formation of
H2O is given by the reaction

. H2 (g) + ½ O2(g) ⎯
⎯→ H2O (l) ∆fHθ (H2O) = –285.8 kJ mol –1

Now, according to the Hess’s law, the enthalpy of decomposition of H2O is represented by

H2O (l) ⎯
⎯→ H2 (g) + ½ O2(g) ∆dHθ (H2O) = – ∆fHθ (H2O) = + 285.8
kJ mol –1

™ When an equation is multiplied by a number, the enthalpy change is also multiplied by

the same number. For example

If H2 (g) + ½ O2(g) ⎯
⎯→ H2O (l) ∆rHθ (i) = –285.8 kJ mol –1

then 2 H2 (g) + O2(g) ⎯

⎯→ 2 H2O (l)

∆Hθ (ii) = 2 × ∆rHθ (i) = 2×(–285.8 kJ mol –1) = –571.6 kJ mol–1

™ When equations are added, the enthalpy changes are also added accordingly with
proper signs. For example

(a) C (graphite) + ½ O2(g) ⎯

⎯→ CO(g) ∆Hθ (a) = –110 kJ mol–1

(b) CO(g) + ½ O2(g) ⎯

⎯→ CO2 (g) ∆Hθ (b) = – 285 kJ mol–1

On adding equations (a) and (b) we get

C (graphite) + O2(g) ⎯
⎯→ CO2(g)

According to the Hess’s law the enthalpy of reaction (c) is given by

80
 ∆Hυ (c) = ∆Hυ °(a) + ∆Hυ(b)

= – 110 kJ mol –1+ (– 285 kJ mol–1)

= – 395 kJ mol–1

Example: Apply Hess’s law to calculate the enthalpy change (∆rHθ) of the following
reaction

C (graphite) + 2 H2(g) ⎯
⎯→ CH4(g)

Data given:

(i) C (graphite) + O2(g) ⎯

⎯→ CO2(g) ∆rHθ (i) = – 393.5 kJ mol–1

(ii) H2 (g) + 0.5 O2(g) ⎯

⎯→ H2O(l) ∆rHθ (ii) = – 285.8 kJ mol–1

(iii) CH4 (g) + 2 O2(g) ⎯

⎯→ CO2(g) +2 H2O(l) ∆rHθ (iii) = – 890.3 kJ mol–1

Solution. Our aim

(A) C (graphite) + 2 H2(g) ⎯

⎯→ CH4(g) ∆rHθ (A) = ?

Operations: On multiplying equation (ii) by 2 and reversing equation (iii) we get

(iv) 2H2 (g) + O2(g) ⎯

⎯→ 2H2O(l) ∆rHθ (iv) = – 2×285.8 kJ mol–1

(v) CO2(g) + H2O(l) ⎯

⎯→ CH4 (g) + 2 O2(g) ∆rHθ (v) = + 890.3 kJ mol–1

On adding equations (i), (iv) and (v) along with corresponding ∆rHυ values, we get equation
(vi)

(vi) [C (graphite) + O2(g)] + [2H2 (g) + O2(g)] + [CO2(g) +2 H2O(l) ]

⎯
⎯→ CO2 (g) + 2 H2O(l) +[ CH4(g) + 2 O2(g) ]

∆rHθ (vi) = ∆rHθ (iv) + ∆rHθ (v) + ∆rHθ (i)

= (– 393.5 + ( – 2×285.8 + 890.3) kJ mol–1

= –74.8 kJ mol–1

On canceling the common terms on the two sides of equation (vi), we get equation (vii)

⎯→ CH4(g) ∆rHυ (vii) = –74.8 kJ mol–1

(vii) C (graphite) + 2H2 (g) ⎯

It is observed that equations (A) and (vii) are the same. Therefore, according to Hess’s law
their enthalpies should also be the same. Thus

81
 ∆rHυ (A) = ∆rHυ (vii) = –74.8 kJ mol–1

Example. Use the following combustion data to calculate the enthalpy change for the
hydrogenation of ethene as represented by the reaction C2H4 (g) + H2 (g) —→ C2H6(g)

Combustion data:

(i) C2H4 (g) + 3O2 (g) —→ 2CO2 + 2H2O(g) ∆cH0 = – 1410 kJ mol −1

(ii ) C2H6 (g) + 3.5 O2 (g) —→ 2CO2 + 3H2O(g) ∆cH0 = – 1550 kJ mol −1

(iii) H2 (g) + 0.5O2 (g) —→ H2O(l) ∆cH0 = – 286.0 kJ mol −1

Solution. Our aim is to calculate ∆Hυ for the reaction

C2H4 (g) + H2 (g) —→ C2H6 (g) ∆Hυ (A) = ?

Operations: Subtract equation (ii) from the sum of equations (i) and (iii) to get

eq (i) + eq (iii) − eq (ii)

[C2H4 (g) + 3O2 (g)] + [H2 (g) + 0.5O2 (g)] — [C2H6 (g) + 3.5 O2 (g)]

→[2 CO2 + 2H2O(g)] + H2O(l) —[2CO2 + 3H2O(g)]

On canceling the common terms on the two sides of the above equation we get

C2H4 (g) + H2 (g) —→ C2H6 (g)

and ∆r Hυ (A) = ∆rHυ (i) + ∆rHυ (iii) − ∆Hυ (ii)

= – 1410 kJ mol −1+ (– 286 kJ mol −1) − (– 1550 kJ mol −1)

= – 137 kJ mol −1

Relation between ∆rH AND ∆rU

H = U + PV Definition of enthalpy

∆H = ∆U + P ∆V + V ∆P For changes in the states of the system

= ∆U + P ∆V At constant pressure

And for a chemical reaction the above relation can be written as ∆rH = ∆ rU + P ∆rV

(i) For solids and liquids, the volume change in the reaction (∆rV) is generally very small.
Therefore, under atmospheric pressure P∆rV is negligible as compared to ∆ rH and ∆ rU.
Hence,

∆ rH = ∆ rU For reactions involving solids and liquids only

(ii) For gases ∆ rV is large and hence P ∆rV has appreciable value. Thus

82
 ∆ rH = ∆ rU + P ∆ rV For gases at constant pressure

(iii) In a chemical reaction involving gases

∆rV = Σvolume of products – Σvolume of reactants

= ΣV (products) – ΣV (reactants)

For a general reaction involving gases

aA (g) + bB(g) ⎯
⎯→ cC (g) + dD (g)

Reactants ⎯
⎯→ Products

ΣV (reactants) = aVm (A) + bVm (B)

ΣV (products) = cVm (C) + dVm (D)

Where, Vm = Molar volume of gas

For an ideal gas PV = nRT and V/n = RT/P. Therefore, Vm =RT/P. .

If temperature (T) and pressure (P) are kept constant, we shall have

RT RT RT
ΣV (reactants) = a × + b× = (a +b )
P P P

RT RT RT
ΣV (products) =c× + d× = (c + d)
P P P

∆rV = ΣV (products) – ΣV (reactants)

RT
= [(c + d) – (a +b )]
P

RT
Therefore, P ∆rV = P × [(c + d) – (a +b )]
P

= RT[(c + d) – (a +b )]

= ∆ng RT

Where, ∆ng = (c + d) – (a +b )

=Σcoefficients of gaseous products – Σ coefficients of gaseous reactants

Thus ∆rH = ∆rU + P ∆V = ∆rU + ∆ng RT

Or, ∆rU = ∆rH – ∆ng RT

For the reaction N2 (g) + 3 H2 (g) ⎯

⎯→ 2 NH3 (g)

83
 ∆ng = 2 – (1 + 3) = –2

and ∆rH = ∆rU – 2 RT

Or, ∆rU = ∆rH + 2 RT

Remarks:

(i) It must be noted that ∆ng is a number and it is not mole because it is the change in the
moles of the substances per mole of the reaction occurred. Thus mole divided by
mole is a number.

(ii) For a reaction ∆rH = qp and ∆rU = qv, thus, the relation ∆rH = ∆rU + ∆ng RT may be
written as

qp = qv + ∆ng RT

(iii) For a reaction such as H2(g) + I2(g) ⎯

⎯→ 2 HI(g), ∆ng = 0. Therefore, ∆rH = ∆rU
and qp = qv

Example: For a reaction CH4 (g) + 2 O2 (g) ⎯ ⎯→ CO2(g) + 2 H2O(l), ∆rH≡ = – 890.3
kJ mol–1 at 298 K and 1 bar. Find the value of ∆rU for the same reaction at the same
temperature and pressure.

Solution: For the reaction CH4 (g) + 2 O2 (g) ⎯

⎯→ CO2(g) + 2 H2O (l)

∆ng =1 – (1 + 2) = –2

Therefore, ∆rH≡ = ∆rU≡ – 2 RT

Or, ∆rU≡ = ∆rH≡ + 2 RT

= – 890. 35 kJ mol–1 + 2 × 8.314 × 10–3 kJ mol–1 K–1 × 298 K

= – 890. 35 kJ mol–1 + 4.95 kJ mol–1

= – 885.4 kJ mol–1

Example. The enthalpy change (∆rH) for the reaction N2(g) + 3 H2(g) → 2 NH3(g) is –
92.38 kJ mol−1 at 298 K. Calculate the value of ∆rU at 298 K.

Solution. For the reaction N2(g) + 3 H2(g) → 2 NH3(g)

∆ν =2 - (1 + 3) = − 2

∆rH = − 92.38 kJ mol−1 at 298 K

Therefore, ∆rU = ∆rH − ∆ν RT

= − 92.38 kJ mol−1 − (−2)×8,314×10−3 kJ K−1 mol−1×298 K

84
 = −92.38 kJ mol−1 + 4.95 kJ mol−1

= − 87.43 kJ mol−1

Example. Calculate the value of ∆rH at 298 K for the reaction OF2 (g) + H2O(g) → 2
HF(g) + O2(g). It is given that the value of ∆rU is −320.9 kJ mol−1 at 298 K.

Solution. For the reaction OF2(g) + H2O(g) → 2 HF(g) + O2 (g)

∆ν =(2+ 1) - (1 + 1) = 1

∆rU = − 320.9 kJ mol−1 at 298 K

Therefore, ∆rH = ∆rU + ∆ν RT

= − 320.9 kJ mol−1 + 1 × 8.314×10−3 kJ K−1 mol−1×298 K

= −92.38 kJ mol−1 + 2.477 kJ mol−1

= − 318.423 kJ mol−1

Example. When a sample of 1.25 g of gaseous chlorofluorocarbon (C2Cl2F2) at a

constant atmospheric pressure of 1 atm was cooled from 320 K to 293 K there was a
decrease in its volume from 274 cm3 to 248 cm3. Calculate the values of ∆rH and ∆rU for
the process. The molar heat capacity of C2Cl2F2 is 80.7 JK - 1 mol - 1.

Solution. Data given :

Heat capacity of C2Cl2F2 at constant pressure = Cp = 80.7 JK - 1 mol −1

Initial temperature =T1 = 320 K , Final temperature = T2 = 293 K

Therefore, ∆T = T2 − T1 = 293 K – 320 K = −27 K

(i) Calculation of ∆H

∆Hm = Cp ×∆T

= 80.7 JK - 1 mol - 1. × ( – 27 K)

= – 2178.9 J mol --1

∆H (to cool 1.25 g of C2Cl2F2)

= ∆H per mole of C2Cl2F2 × mole of C2Cl2F2 in 1.25 g

Mass of C 2 Cl 2 F2 1,25 g
Mole of C2Cl2F2 = =
Molar mass of C 2 Cl 2 F2 133 g/mol

1,25 g
Therefore, ∆H = −2178.9 kJ mol --1 × = –- 20.478 J
133 g/mol

85
(ii) Calculation of ∆U

∆H = ∆U + P∆V gives

∆U = ∆H – P∆V

Data given

P = 1 atm = 101325 N / m2

V1 = 274 cm3 = 274 ×10− 6 m3

V2 = 248 cm3 = 248 ×10 − 6 m3

Therefore, ∆V = V2 − V1 = 248 ×10 − 6 m3 – 274 ×10− 6 m3 = – 26 ×10 −6 m3

and P ×∆V = 101325 N m−2 × ( –26 x 10 −6

m3) = –-2.634 N m−2 = 2.364 J

Thus

∆U = ∆H – P∆V

= – 20.478 J –- (– 2.364 J )

= – 20.478 J + 2.364 J = – 18.114 J

Example. When the sample of 0.562 g of graphite was burnt in a bomb calorimeter in
the presence of excess of oxygen at 298 K and 1 bar pressure the following reaction took
place C (s) + O2(g) → CO2 (g). During the reaction an increase of temperature from
298 K to 298.8 K was observed. Calculate the molar enthalpy change for the above
reaction. It is given that the heat capacity of the calorimeter and its content is 20.7 kJ
K −1 .

Solution. q (calorimeter) = C(calorimeter) × ∆T

= 20.7 kJ K−1 × (298.8 K − 298.0 K)

= 18.423 kJ

q (reaction) = − q(calorimeter)

= − 18.423 kJ

= Heat liberated on burning 0.562 g of graphite

q(reaction)
Heat liberated per mole of graphite =
mole of graphite

−18.423 kJ
=
0.562 g/12 g mol -1

= − 393.378 kJ mol−1

86
(i) Calculation of ∆U: The experiment is carried in a bomb calorimeter

Therefore, q (reaction) /mol = ∆U (reaction)./mol = − 393.378 kJ mol−1

(ii) Calculation of ∆H = ∆U + ∆ g RT

For the reaction C (s) + O2(g) → CO2 (g

∆νg = 1 − 1 = 0

Therefore, ∆νg RT = 0× RT = 0

and ∆H = ∆U = − 393.378 kJ mol−1

Bond enthalpy

When a chemical bond is formed heat is liberated. This heat liberated at constant pressure is
referred to as enthalpy of bond formation. On the other hand, the heat needed to cause the
breaking of a chemical bond at a constant pressure is called the bond dissociation enthalpy.
Thus, the bond formation is an exothermic process whereas bond dissociation is an
endothermic process. For example:

When two hydrogen atoms unite to form a covalent bond in hydrogen molecule as H–H,
the heat liberated is 436 kilo joule per mole of bond formed. That is, the enthalpy of
formation of one mole of H–H bond is – 436 kJ. It is written as follows

H (g) + H(g) ⎯
⎯→ H – H(g) ∆Hυ = – 436 kJ mol–1

On the other hand, when one mole of H – H covalent bonds are broken, 436 kJ heat is
absorbed and is given as

H – H (g) ⎯
⎯→ 2H (g) ∆Hυ = + 436 kJ mol–1

The enthalpy of dissociation of one mole of H–H bonds is 436 kJ mol–1

Preference of bond dissociation enthalpy over bond formation enthalpy

Bond formation enthalpy is a conceptual term. It is not possible to estimate directly its
experimental value. Why? Because we cannot isolate the free gaseous atoms and force them
to combine. On the other hand, bond dissociation enthalpy is an operational term. It is
convenient to collect a sample of the substance and fragment (atomize) its molecules to
produce the constituent atoms and then to estimate the heat needed to break the bonds.

Bond enthalpy of a diatomic molecule

. The bond dissociation enthalpy of a diatomic molecule is equal to the heat needed to break
the bonds in one mole of molecules so that free gaseous atoms are produced. For example:

(i) The bond enthalpy of H –H bond is equal to the enthalpy change for breaking one mole of
H–H bonds in H2 molecules and to produce free gaseous H atoms

87
 H – H (g) ⎯
⎯→ 2 H(g) ∆H (H–H) = 436 kJ mol–1

(ii) The bond enthalpy of O = O bond is equal to the enthalpy change for breaking one mole
O = O bonds in O2 molecules and to produce free gaseous O atoms.

O = O (g) ⎯
⎯→ 2 O (g) ∆H (O=O) = 498 kJ mol–1

(iii) The bond enthalpy of H–Cl bond is equal to the enthalpy change in breaking one mole
H–Cl bonds in HCl molecules so that 1 mole H atoms and 1 mole Cl atoms are produced.

⎯→ H(g) + Cl(g) ∆H (H–Cl) = 432 kJ mol–1

H– Cl (g) ⎯

Enthalpy of bond dissociation in polyatomic molecules

In a polyatomic molecule the energy needed to break the same type of bond is different in
different chemical situations. For example, in H2O there are two O–H bonds written as H–O–
H (simplified). Both the O–H bonds are equivalent in length and strength. But, the
experiment shows that the enthalpy change to break one mole O – H bonds in H – O –H is
498 kJ mol–1. On the other hand, the enthalpy change to break one mole O – H bond in
hydroxyl group (OH) is 430 kJ mol–1

H–OH (g) ⎯
⎯→ H(g) + OH(g) ∆H = 498 kJ mol–1

and O–H (g) ⎯

⎯→ O(g) + H(g) ∆H = 430 kJ mol–1

Thus the enthalpy of bond dissociation is defined as the enthalpy change to breaking a given
bond in specified chemical environment.

Bond enthalpy. Average of bond dissociation enthalpies of a given bond in different

dissociating species is called its bond enthalpy. For example, in water molecule (H–O–H) the
average of the two O–H bond dissociation enthalpies is called O–H bond enthalpy.

498 kJ mol -1 + 430 kJ mol -1

∆H (O – H) = = 464 kJ mol–1
2

Illustrative examples: Use the following bond dissociation enthalpies to compute the C–H
bond enthalpy in methane (CH4)

(i) CH4 (g) ⎯

⎯→ CH3 (g) + H(g) ∆H(i) = 425 kJ mol–1

(ii) CH3(g) ⎯
⎯→ CH2 (g) + H(g) ∆H(ii) = 470 kJ mol–1

(iii) CH2 (g) ⎯

⎯→ CH(g) + H(g) ∆H(iii) = 416 kJ mol–1

(iv) CH(g) ⎯
⎯→ C(g) + H(g ∆H(iv) = 335 kJ mol–1

On adding equations (i), (ii), (iii) and (iv) and canceling the common terms on the two sides,
we get

CH4 (g) ⎯
⎯→ C (g) + 4 H(g)) ∆H = 1646 kJ mol–1

88
This is the sum of the individual C–H bond dissociation enthalpies. But bond enthalpy is
equal to the average of the bond dissociation enthalpies. Therefore, the C–H bond enthalpy is
given by

(425 + 470 + 416 + 335) kJ mol -1

∆H (C–H) = = 411.5 kJ mol–1
4

A discussion of bond enthalpy and bond energy

Bond enthalpy and bond energy of a chemical bond A&B are related by

∆Hθ A&B) = ∆Uθ (A&B) + P ∆V

If the bonded species A—B and its fragments A and B are assumed to obey ideal gas
equation, then P ∆V = ∆∆ng RT. Therefore,

∆Hθ (A&B) = ∆Uθ (A&B) + ∆ng RT

or, ∆Uθ (A&B) = ∆Hθ (A–B) & ∆ng RT

The dissociation of bond A&B is represented by

A&B (g) ⎯
⎯→ A(g) + B(g)

Therefore, ∆ng = 1 + 1 –1 = 1. Thus,

∆Uθ (A&B) = ∆Hθ (A&B) & RT

--3
• At 0 K, RT = 8.314 × 10 kJ mol &1× 0 K = 0. Therefore,

∆Uθ (A&B) = ∆Hθ (A&B)

• At 298 K,
--3 --1 --1 --1
RT = 8.314 x 10 kJ mol × 298 K = 2.4775 kJ mol = 2.5 kJ mol .

Therefore, ∆Uθ (A&B) = ∆Hθ (A&B) &2.5 kJ mol --1

.

For example, for H & H bond in H2, ∆Hθ (H&H) = 436 kJ mol --1. Therefore,

∆Uθ (H&H) = 436 kJ mol --1 – 2.5 kJ mol --1

.= 433.5 kJ mol --1

From the above example it is clear that in general the values of ∆Hθ (A&B) and ∆Uθ
(A&B) differ only slightly. Therefore, for all practical purposes the two terms are used
interchangeably.

Enthalpy of atomization

The enthalpy change in converting one mole of a substance into its constituent atoms
in gaseous states is called the enthalpy of atomization or heat of atomization of that
substance.

89
(1) Enthalpy of atomization of a diatomic molecule. The enthalpy of atomization of a
diatomic molecule is equal to its enthalpy of dissociation ∆dH Thus:

H2 (g) ⎯
⎯→ 2 H (g) ∆aH (H2) = 436 kJ mol–1

O2 (g) ⎯
⎯→ 2 O (g) ∆aH (O2) = 498 kJ mol–1

(2) Enthalpy of atomization of a polyatomic

molecule

The enthalpy of atomization of a polyatomic molecule of a compound is equal to the

enthalpy change to breaking all the covalent bonds so that gaseous constituent atoms are
produced. The enthalpy of atomization of CH4 is 1664 kJ mol–1. which is equal to the
enthalpy change associated with the breaking of the four C–H bonds per mole of CH4
molecules.

CH4 (g) ⎯
⎯→ C(g) + 4 H(g) ∆aH (CH4) = 1664 kJ mol–1

(3) The enthalpy of atomization of a solid element is equal to its heat of sublimation.

C (graphite, solid) ⎯
⎯→ C (gas) ∆aH = 716.67 kJ mol–1 = ∆subH(C)

(A) Calculation of C–H bond energy from thermochemical data

The simplest molecule involving only C–H bonds is methane (CH4) Therefore, the
bond energy of C–H bond is calculated from the thermochemical data (enthalpy of
atomization) of methane.

CH4 (g) ⎯
⎯→ C (g) + 4 H(g) ….(A)

∆ a H (CH 4 )
∆H(C–H) =
4

But the enthalpy of atomization of methane is equal to the enthalpy of reaction (A)

∆aH (CH4) = ∆rH (A)

Now, ∆rH (A) = ∆fH (C, g) + 4 ∆fH (H) – ∆fH (CH4)

= 716. 7 kJ mol–1 + 4× 218 kJ mol–1 – (–74.8 kJ mol–1)

= 1663.5 kJ mol–1 = ∆aH (CH4)

∆ a H (CH 4 )
Therefore, ∆H(C–H) =
4

1663.5 kJ mol −1
=
4

= 415.87 kJ ml–1

90
The actual value of ∆H(C–H) is 414 kJ mol–1

(B) Calculation of C–C bond energy from thermochemical data

The simplest molecule involving C – C bond (along with 6 C–H bonds) is ethane (C2H6)
Therefore, the value of enthalpy of C– C bond is calculated from the thermochemical data
(enthalpy of atomization) of ethane and C–H bond enthalpy (= 414 kJ mol–1).

H3C – CH3 (g) . ⎯

⎯→ 2 C (g) + 6 H(g) .(B)

But ∆aH (C2H6) = ∆rH (B)

Now enthalpy of reaction (B) is the enthalpy of atomization of ethane which is the energy
needed to break one mole C–C bonds and six moles C–H bonds in one mole of ethane. Thus

∆aH (C2H6) = ∆rH (B) = ∆H(C–C) + 6 ∆H(C–H)

Therefore, ∆H(C–C) = ∆rH (B) – 6 ∆H(C–H)

Now ∆rH (B) = 2 ∆fH (C, g) + 6 ∆fH (H) – ∆fH (C2H6, g)

= 2×716.7 kJ mol–1 + 6× 218 kJ mol–1 – (–85.6 kJ mol–1)

= 2827 kJ mol–1

Therefore, ∆H(C–C) = ∆rH (B) – 6 ∆H(C–H)

= 2827 kJ mol–1 – 6×214 kJ mol–1

= 2827 kJ mol–1 – 2484 kJ mol–1 = 343 kJ mol–1

(C) Calculation of C=C bond energy from thermochemical data

The simplest molecule involving C = C bond along with 4 C–H bonds is ethene (C2H4)
Therefore, enthalpy of C = C bond is calculated from the thermochemical data (enthalpy of
atomization) of ethene and C–H bond enthalpy.

H2C = CH2 (g) ⎯

⎯→ 2 C (g) + 4 H(g) ….(C)

The enthalpy of reaction (C) is the enthalpy of atomization of ethene which is the energy
needed to break one mole C = C bonds and four moles C–H bonds in one mole of ethene.
Thus

∆aH (C2H4) = ∆rH (C) = ∆H (C = C) + 4 ∆H (C–H)

Therefore, ∆H(C = C) = ∆rH (C) – 4∆ H(C–H)

Now, ∆rH (C) = 2 ∆fH (C, g) + 4 ∆fH (H) – ∆fH (C2H4, g)

= 2×716.7 kJ mol–1 + 4× 218 kJ mol–1 – (+52.3 kJ mol–1)

= 2253 kJ mol–1

91
Therefore, ∆H(C=C) = ∆rH (C) – 4 ∆H(C–H)

= 2827 kJ mol–1 – 4 ×414 kJ mol–1

=597 kJ mol–1

The actual value of ∆H(C=C) is 611 kJ mol–1

(D) Calculation of C ≡C bond energy from thermo chemical data

The simplest molecule involving C ≡ C bond (along with 2 C–H bonds) is ethyne (C2H2)
Therefore, enthalpy of C≡C bond is calculated from the thermochemical data (enthalpy of
atomization) of ethyne and C–H bond enthalpy

H – C ≡ C – H (g) ⎯
⎯→ 2 C (g) + 2 H(g) (D)

The enthalpy of reaction (D) is the enthalpy of atomization of ethyne which is the energy
needed to break one mole C≡C bonds and two moles C–H bonds in one mole of ethyne.
Thus

∆aH (C2H2) = ∆rH (D) = ∆H(C≡C) + 2 ∆H(C–H)

Therefore, ∆H(C≡C) = ∆rH (D) – 2∆H(C–H)

Now, ∆rH (D) = 2 ∆fH (C, g) + 2 ∆fH (H) – ∆fH (C2H2, g)

= 2×716.67 kJ mol–1 + 2× 218 kJ mol–1 – (+226.7 kJ mol–1)

= 1642.7 kJ mol–1

Therefore, ∆H(C ≡ C) = ∆rH (D) – 2 ∆H(C–H)

= 1642.7 kJ mol–1 – 2×414 kJ mol–1

= 814.7 kJ mol–1

The actual value of ∆H(C ≡ C) is 837 kJ mol–1

92
 Table 2. Single bond enthalpy data ( ∆H Θ ) expressed in kJ mol --1

A −B H C N O F Si P S Cl Br I

H 436 569 339 431 368 297

C 414 347 293 351 439 289 264 259 330 276 238

N 389 201 272 209 201 243

O 464 138 184 205

F 159

Si 293 289 368 540 176 213 226 360 289 213

P 318 264 351 490 213 230 331 272 213

S 259 327 213 251 213

Cl 205 255 243

Br 197 218 192

I 201 209 180 151

Method to find the enthalpy of a bond from the table

• In the table the values of bond enthalpy are given for the bonds which are written as A –
B, for example as

C – C, N – H, O – H, H – Cl, S – F

• Select the first atom (A) of the desired bond from the vertical column and the second
atom (B) of the bond from the horizontal row.

• The value on the right side of the first atom and below the second atom is the bond
enthalpy of the desired bond.

Illustration of the method: To find the bond enthalpy of the S – F bond, select S from the
vertical column and F from the horizontal row. The value on the right of S and below F is the
bond enthalpy of S – F bond. Thus,

∆Hθ (S – F) = 327 kJ mol --1

Table 3. Bond enthalpy data ( ∆H Θ ) expressed in kJ mol --1 for double and triple bonds

Bond C=C C=O C=N N=N O=O C≡C C≡O N≡N C≡N

∆H Θ 611 741 615 418 498 837 1070 946 891

93
Note: The bond energy of a bond is assumed to be the same irrespective of the type of the
molecule in which this bond is present. For example, the bond energy of a C – H bond is
assumed to be the same whether it is present in a hydrocarbon or carboxylic acid or alcohol
or aldehyde etc.

CALCULATION OF ENTHALPY OF REACTIONS FROM BOND ENTHALPY

DATA

. The enthalpy of a reaction is given by the relation

Θ
∆
 rH = ΣBond enthalpy of reactants– ΣBond enthalpy of products

Example: Use the bond enthalpy data to calculate the enthalpy change for the
combustion of n-propane (C3H8) represented by the reaction

C3H8(g) + 5 O2 (g) ⎯
⎯→ 3 CO2(g) + 4 H2O(g)

Bond C −C C −H O −H C=O
O=O

∆H Θ (bond)/ kJ mol -1 347 414 464 741

498

Solution. The given reaction C3H8(g) + 5 O2 (g) ⎯ ⎯→ 3 CO2(g) + 4 H2O(g) may be

represented in terms of breaking of bonds in reactants and formation of bonds in products as
follows:

CH3 — CH2 — CH3 + 5 O = O ⎯

⎯→ 3 O = C = O + 4 H–O–H

The enthalpy of reaction (∆r H Θ) and bond enthalpies of reactant and product are related by

∆r H Θ = Σ Bond enthalpy of reactants − Σ Bond enthalpy of products

The given reaction involves breaking of three C–C bonds, eight C–H bond in C3H8 and five
O = O bond in O2. Therefore,

Σ Bond enthalpy of reactants =3 ∆H Θ (C−C ) + 8 ∆H Θ (C−H) + 5 ∆H Θ (O = O)

= 3 × 347 kJ mol −1 + 8 × 414 kJ mol −1 + 5 × 498 kJ mol −1

= 6843 kJ mol −1

The given reaction involves formation of six C=O bonds in CO2, four O–H bonds in H2O.
Therefore,

Σ Bond enthalpy of products = 6 ∆H Θ (C = O) + 8 ∆H Θ (O – H)

= 6 × 741 kJ mol −1 +8 ×464 kJ mol −1

= 8158 kJ mol −1

94
Therefore, ∆r H Θ = Σ Bond enthalpy of reactants − Σ Bond enthalpy of products

 = 6843 kJ mol −1 – 8158 kJ mol −1

= –1315 kJ mol −1

Enthalpy of physical transformation

The process by which a substance is changed from one physical state into its another
physical state is called physical transformation or phase transformation. Here we shall
discuss the processes of vaporization, fusion and sublimation and the related enthalpy
changes.

(A) Enthalpy of vaporization

The quantity of heat absorbed for complete conversion of one mole of a liquid in to vapour at
its boiling point is called its enthalpy of vaporization. It is denoted by ∆vapH. The enthalpy of
vaporization is called the heat of vaporization also..

The enthalpy of vaporization per mole of water at 373 K is 40.70 kJ

H2O(l) ⎯
⎯→ H2O(v) ∆vapH = 40.70 kJ mol–1

Latent heat of vaporization:The heat absorbed to convert one gram liquid into vapour is
called latent heat of vaporization. The latent heat of vaporization of water is 2.26 kJ per
gram at 100 oC. This means that 1 g of liquid water at 100 oC will absorb 2.26 kilojoules of
heat to be converted into 1 g of water vapour at 100 oC. Since no change of temperature is
involved the absorbed heat is stored in water molecules in vapour state. That is why this is
called latent heat.

(B) Enthalpy of fusion

The quantity of heat absorbed for complete conversion of one mole of solid into liquid.at
its melting point is called its enthalpy of fusion. The enthalpy of fusion is denoted by ∆fusH
It is called heat of fusion also. The enthalpy of fusion of water is 6.01 kJ mol–1 at 273 K and 1
atm.

H2O(s) ⎯
⎯→ H2O(l) ∆fusH = 6.01 kJ mol–1

Latent of fusion of ice is 334 J g–1

(C) Enthalpy of sublimation

The quantity of heat absorbed for complete conversion of one mole of solid directly into
vapour is called enthalpy of sublimation or heat of sublimation. The enthalpy of sublimation
of a substance is denoted by ∆subH

According to Hess’s law of constant heat summation, the enthalpy of sublimation is equal to
the sum of the enthalpy of fusion and the enthalpy of vaporization of the same substance (all
the quantities refer to same temperature)

∆subH = ∆fusH + ∆vapH

95
For example, the enthalpy of sublimation of naphthalene is computed as follows.

Aim : Naphthalene(s) ⎯
⎯→ Naphthalene (v) ∆subH = ? (to be calculated

Data given

Naphthalene(s) ⎯
⎯→ Naphthalene(l) ∆fusH = 22.4 kJ mol–1 (i)

Naphthalene(l) ⎯
⎯→ Naphthalene(v) ∆vapH = 48.5 kJ mol–1 (ii)

On adding equations (i) and (ii) we get

Naphthalene(s) + Naphthalene(l) ⎯
⎯→ Naphthalene(l) + Naphthalene(v)

On canceling the common terms on the two sides of the above equation, we have

NaphthaIene(s) ⎯
⎯→ Naphthalene (v) (iii)

and ∆H(iii) = ∆H(i) + ∆H(i)

or, ∆subH = ∆fusH + ∆vapH

= 22.4 kJ mol–1 + 48.5 kJ mol–1

=70.9 kJ mol–1

Temperature dependence of reaction enthalpy (Kirchhoff’s equation)

Statement Variation of reaction enthalpy (∆rH, heat of reaction) with temperature is called
Kirchhoff’s equation. It is stated as follows

⎛ ∂∆ r H ⎞
⎜ ⎟ =∆ C
⎜ ∂T ⎟ r P
⎝ ⎠P

d∆rH = ∆rCp dT at constant pressure

Where

∆rH = reaction enthalpy ( heat of reaction at constant pressure)

and ∆rCp = reaction heat capacity at constant pressure

= Σ Cp(products) – ΣCp (reactants)

Similarly, for the heat of reaction at constant volume the Kirchhoff’s equation is given by

d ∆rU = ∆rCV dT at constant volume

Relevance of Kirchhoff’s equation Standard enthalpy of reaction (heat of reaction at 298

K and at 1 bar) is calculated using the standard enthalpy of formation data of reactants and
products given in the International tables. But when it is required to find the enthalpy of

96
reaction at other temperatures then we use Kichhoff’s equation.

Derivation of Kirchhoff’s equation

Let us consider a familiar reaction of synthesis of ammonia from nitrogen and hydrogen as
represented by chemical equation

N2(g) + 3 H2 (g) ⎯
⎯→ 2 NH3(g)

The standard enthalpy of this reaction is given by

∆rHυ = 2×H Θm (NH3) – [H Θm (N2) + 3 ×H Θm ( H2)

On differentiating the above equation with respect to T at constant P, we get

⎛ ∂∆ H Θ ⎞ ⎛ Θ ⎞ ⎡⎛ Θ ⎞ ⎛ Θ ⎞ ⎤
⎜ r ⎟ = 2 ⎜ ∂H m ( NH 3 ) ⎟ − ⎢⎜ ∂H m ( N 2 ) ⎟ + 3 ⎜ ∂H m (H 2 ) ⎟ ⎥
⎜ ∂T ⎟ ⎜ ∂T ⎟ ⎢⎜ ∂T ⎟ ⎜ ∂T ⎟ ⎥
⎝ ⎠P ⎝ ⎠ P ⎣⎝ ⎠P ⎝ ⎠P ⎦

By definition

⎛ ∂H Θ ⎞
⎜ m ⎟ = C Θ = Standard molar heat capacity at constant pressure
⎜ ∂T ⎟ p, m
⎝ ⎠P

⎛ ∂∆ H Θ ⎞
Therefore, ⎜ r ⎟ = 2 C Θ (NH3) – [ C Θ (N2) + 3 C Θ (H2)]
p, m
⎜ ∂T ⎟ p, m p, m
⎝ ⎠P

= Σ C pΘ (products) – Σ C pΘ (reactants)

= ∆r C pΘ

Or, d ∆rHυ = ∆r C pΘ dT

It is differential form of Kirchhoff’s equation

Integarated form of Kirchhoff’s equation

Case I. When heat capacity is independent of temperature, ∆r C pΘ is constant and integration

of Kirchhoff’s equation gives
2 2

∫1 d∆ r H Θ = ∆r C pΘ ∫1 dT

Or, ∆rHυ (at T2) – ∆rHυ (at T1) = ∆r C pΘ (T2 – T1)

Or, ∆rHυ (at T2) = ∆rHυ (at T1) + ∆r C pΘ (T2 – T1)

97
 It is integrated form of Kirchhoff’s equation. From this equation the value of enthalpy
of reaction at any temperature T2 can be calculated provided its value at a temperature T1 is
known and the molar heat capacities of reactants and products are also known

Similarly, the Kirchhoff’s equation for heat of reaction at constant volume is given by

∆rUυ (at T2) = ∆rUυ (at T1) + ∆r C vΘ (T2 – T1)..

Kirchhoff’s equation for any general reaction

aA +bB ⎯
⎯→ c C + d D

is given by

∆rHυ (at T2) = ∆rHυ (at T1) + ∆r C pΘ (T2 – T1)

where,

∆r C pΘ = Σ C pΘ (products) – Σ C pΘ (reactants)

= [c C p,Θ m (C) + d C p,Θ m (D)] – [a C p,Θ m (A) + b C p,Θ m (B)]

Case II. When molar heat capacity depends on temperature as

Θ
C p, m = α + β T + γ T2

the heat capacity of reaction is given by

∆r C p,Θ m = ∆α + ∆β T + ∆γ T2

where

∆α = [cα + d α ] –[a α + bα]

∆ β  = [c β +d β ] –[a β + b β ]

∆ γ = [c γ +d γ ] –[a γ + b γ ]

On ignoring integrating Kirchhoff’s equation we shall get

2 2

∫1 d∆ r H Θ = ∫1 ∆r C pΘ dT

2 2 2

= ∫1 ∆ α dT + ∫1 ∆ β TdT + ∫1 ∆ γ T2dT

98
 1 1
∆rHυ (at T2) – ∆rHυ (at T1) = ∆ α (T2 – T1) + ∆β  T22 – T12 + ∆γ  T23 – T13 
2 3

1 1
Or, ∆rHυ (at T2) = ∆rHυ (at T1) + ∆α (T2 – T1) + ∆β  T22 – T12 + ∆γ  T23 – T13 
2 3
This equation is used to calculate accurate value of reaction enthalpy at any temperature T2
when the value at a temperature T1 and the values of heat capacities of reactants are known

Example: The enthalpy of decomposition of gaseous water at 298 K and 1 bar is 241.75
kJ mol–1. Calculate its value at 348 K. The molar heat capacity values in JK–1 mol–1
are: C p,Θ m (H2O) = 33.56, C p,Θ m (O2) = 29.12, C p,Θ m (H2) = 28.82.

Solution. Kirchhoff’s equation ∆rHυ (at T2) = ∆rHυ (at T1) + ∆r C pΘ (T2 – T1) is used to
perform the calculation

For the decomposition of water H2O (g) ⎯

⎯→ H2 (g) + ½ O2 (g)

∆rHυ (298 K) = 241.75 kJ mol–1

∆r C pΘ = C p,Θ m (H2) + ½ C p,Θ m (O2) – C p,Θ m (H2O)

= 28.82 JK–1 mol–1 + ½ (29.12 JK–1 mol–1 ) – 33.56 JK–1 mol–1

= 9.83 JK–1 mol–1 = 9.83 × 10–3 k JK–1 mol–1

Therefore, ∆rHυ (348 K) = ∆rHυ (298 K) + ∆r C pΘ (T2 – T1)

= 241.75 kJ mol–1 + 9.83 × 10–3 kJK–1 mol–1 ( 348 K – 248 K)

= 242.24 kJ mol–1

99
CONFIDENCE BUILDING QUESTIONS ON THERMOCHEMISTRY

(A) Complete the following statements using a correct word/term from the list:

[exothermic, ∆ H, endothermic, ∆ U, negative, positive, element, bond enthalpy, enthalpy of

fusion, sublimation, liberated, zero, ∆ νg RT, diatomic, Kirchhoff’s, exothermic]

1. Heat of reaction at constant pressure is equal to ----------------

2. Heat of reaction at constant volume is equal to the change of ----------------

3. Heat is liberated in an …………. thermic process

4. In an exothermic reaction the value of ∆ H is ----------------

5. The standard enthalpy of formation of ……………. is zero.

6. The average of bond dissociation enthalpies of a bond in different chemical species is

called its …………

7. In a combustion reaction heat is …………..

8. Cooling in the surroundings is observed in an ………….thermic process

9. Enthalpy of sublimation = enthalpy of vaporization + --------

10. In an endothermic process ∆ H is ---------------

11. ∆ H is negative in an -------------------- process.

12. The standard enthalpy of formation of an element is ------------

13. In -------------- molecules the bond dissociation enthalpy is equal to bond enthalpy.

14. The enthalpy change for the process C (graphite) ⎯⎯→ C (gas) is called the enthalpy of --
-----------

15. The difference of ∆ H and. ∆ U in a chemical reaction is equal to ---------------

16. The expression d ∆rHυ = ∆r C pΘ dT is the differential form of ------------- equation

(B) Short answer questions:

1. Define the following

(a) Enthalpy of sublimation

(b) Enthalpy of combustion

(c) Standard enthalpy of formation of a compound

(d) Enthalpy of neutralization

100
(e) Enthalpy of atomization

2. What is the basic difference between the heat of formation and heat of reaction?

3. Enthalpy of formation is enthalpy of reaction but every enthalpy of reaction need

represent enthalpy of formation. Illustrate with suitable examples.

4. Give a very brief description of exothermic and endothermic reactions.

5. State the Hess’s law of constant heat summation.

6. Write a relation between the reaction enthalpy ( ∆ rH) and the standard enthalpies of
formation of reactants and products for N2 (g) + 3H2 (g) ⎯
⎯→ 2NH3 (g)

7. Write a relation between the change in enthalpy ( ∆ rH) and the change in internal energy
( ∆ rU) for the reaction N2 (g) + 3H2 (g) ⎯
⎯→ 2NH3 (g)

8. Derive the relation between qp and qv in a chemical reaction involving gaseous species.

9. How are the bond dissociation enthalpies and bond enthalpy of C–H bond in methane
(CH4) are related?

10. An exothermic reaction is allowed to occur very rapidly in air. Will the temperature of
air increase or decrease?

11. An endothermic reaction is allowed to occur very rapidly in air. Will the temperature of
air increase or decrease?

12. Evaporation of acetone causes cooling effect in the surroundings. Is this process
endothermic or exothermic?

13. Illustrate the following with suitable examples :

(i) Exothermic process

(ii) Endothermic process

(iii) Standard state of a gas

(iv) Thermochemical equation

(v) Hess’s law of constant heat summation

(vi) Enthalpy of hydrogenation

14. Write the relationship showing the variations of enthalpy of reaction with temperature

(C) Numerical problems

1. Calculate the enthalpy of combustion of glucose from the following data :

(i) C (graphite) + O2 (g) ⎯⎯→ CO2(g) ∆ rH = – 393.5 kJ mol–1

101
 –1
(ii) H2(g) + 0.5 O2 (g) ⎯⎯→ H2O (l) ∆ rH = – 286 kJ mol

(iii) 6 C (graphite) + 6 H2(g) + 3 O2(g) ⎯⎯→ C6H12O6 (s) ∆ rH = –1260 kJ

–1
mol

[Ans. Application of Hess’s law gives ∆ cH = –2817 kJ mol–1]

2. Calculate the enthalpy change of the reaction C2H2 (g) + H2 (g) ⎯⎯→ C2H4 (g)at 298 K
when the enthalpy of combustion data are ∆ cH (H2, g) = –286 kJ mol–1, ∆ cH (C2H2 , g) = –
1300 kJ mol–1, ∆ cH (C2H4, g) = – 1411 kJ mol–1 [Ans: – 175 kJ mol–1]

3. The standard enthalpy of formation of CH4 (g), CO2(g) and H2O (g) are –74.8, – 393.5 and
– 241.6 kJ mol–1 respectively. Calculate the enthalpy change on burning 1 m3 of methane
measured under standard conditions. [Ans.
–1
∆ rH = – 35799.1 kJ mol ]

4.. Calculate the enthalpy of formation of ethane when its enthalpy of combustion is – 1560
kJ mol–1 and –1
∆ fH (CO2) = –393.5 kJ mol and ∆ fH (H2O) = –285.8 kJ mol
–1

[Ans: ∆ fH (C2H6) = – 84.4 kJ mol–1 ]

5. What is the difference between ∆ rH and ∆ rU at 298 K for the reaction

2 C6H6(l) + 15 O2 (g) ⎯⎯→ 12 CO2 (g) + 6H2O (l)

[Ans. – 7.43 kJ mol–1]

6. Using the given data calculate the C–H bond energy in CH4 :

Species : CH4 (g) C (g) H (g)

–1
∆ fH /kJ mol : – 74.8 716.7 218

[Ans. 415.87 kJ mol–1]

⎯→ HCl (g) at 293 K is – 91.2 kJ mol–1

7.. If the enthalpy of the reaction H2 (g) + Cl2 (g) ⎯
what will be its value at 313 K. The molar heat capacities at constant pressure of H2 (g), Cl2
(g) and HCl (g) are 29.3, 34.7 and 28.9 JK-1 mol–1 respectively. [Application of Kirchhoff’s
equation gives ∆rH (313 K) = – 91.324 kJ mol–1]

8. The enthalpy of reaction N2 + 3 H2 ⎯⎯→ 2 NH3 at 27 0C was found to be – 91.94 kJ mol–

1
. What will be its value at 50 C. The molar heat capacities at constant pressure and at 27 oC
o

for N2, H2 and NH3 are 28.45, 28.32 and 37.07 J K–1 mol–1 respectively.

[Ans: Application of Kirchhoff’s equation gives ∆rH (313 K) = – 92.843 kJ mol–1]

9. The enthalpy of neutralization of CH3COOH with NaOH is –51.63 kJ mol–1 Calculate the
enthalpy of ionization of CH3COOH. Assume that the enthalpy of neutralization of HCl with
NaOH is –57.35 kJ mol–1.

102
 [Ans: For CH3COOH(aq) ' H+ (aq) + CH3COO– (aq), ∆rH = 5.72 kJ
mol–1]

10. Calculate the enthalpy change for the polymerization of ethyne to benzene at 298 K as
represented by the reaction. 3 C2H2 (g) ⎯
⎯→ C6 H6(l) when

C6H6 (l) + 7.5 O2 ⎯

⎯→ 3H2O (l) + 6CO2 (g) ∆cH Θ = –3267.70 kJ mol–1

C2H2 (g) + 2.5 O2(g) ⎯

⎯→ 2CO2 (g) + H2O(l) ∆cH Θ = –1299.55 kJ mol–1

[Ans: Application of Hess’s law gives ∆ r H Θ = –630.95 kJ mol–1]

11. Calculate the standard enthalpy of formation of methane using the following data:

(i) CH4(g) + 2O2(g) →CO2(g) + 2H2O(l) ∆c H Θ = -890.35 kJ mol–1

(ii) H2(g) + ½O2 → 2H2O(l) ∆c H Θ = -285.84 kJ mol–1

(iii) C(graphite) +O2(g) → CO2(g) ∆c H Θ = -393.50 kJ mol–1

[Ans: Application of Hess’s law gives ∆ f H Θ (CH4) = 74.83 kJ mol–1]

12. Find an expression for the variation of heat capacity of a reaction with temperature if the
D
variation of its enthalpy change with temperature is expressed by ∆rH Θ = A – BT –CT2 – ,
T
where A, B, C, D are constants.

∂∆ HΘ ⎞
[Ans: ∆r C pΘ = ⎛⎜ r
D
⎟ = – B – 2 CT + 2 ]
⎝ ∂T ⎠P T

13. The standard enthalpy of combustion of hydrogen, cyclohexene (C6H10) and cyclohexane
(C6H12) are – 241, – 3800 and – 3920 kJ mol–1 respectively at 298 K. Calculate the enthalpy
of hydrogenation of cyclohexene in to cyclohexane. [Ans. –121 kJ mol–1]

103
SECOND LAW OF THERMODYNAMICS

Limitations of the first law of thermodynamics and Need of the second law

The first law of thermodynamics enables us to compute the energy changes (∆U) and
enthalpy changes (∆H) for different types of chemical reactions and physical transformations.
But this law is not capable of predicting the direction of a process. From the first law of
thermodynamics we cannot get the answers of the following type of questions:

• Why do changes take place in a particular direction?

• How and why the systems are aware to proceed only in the particular direction?

• What are the driving forces which lead the process in a given direction?

Therefore, to answer such questions we need a second law of thermodynamics. This law
introduces the concept of entropy and the methods of evaluating entropy changes which in
turn act as driving force for spontaneous processes in isolated systems..

Different statements of the second law of thermodynamics

The second law of thermodynamics has been stated in different ways. But each statement is
related to human experiences and is in agreement with experimental observations.

1. Heat cannot spontaneously pass from a colder to a warmer body. – R.J.E. Clausius

2. Every system left to itself changes rapidly or slowly in such a way to approach definite
final state of rest. No system of its own will change away from the state of equilibrium
except through the influence of external agencies –G. N. Lewis

3. Entropy is time’s arrow. –A. Edington

4. The state of maximum entropy is the most stable state for an isolated system. –Enrico
Fermi

5. In an irreversible process the total entropy of all bodies concerned is increased. –G.N.
Lewis

6. The entropy function of a system of bodies tends to increase in all possible processes
occurring in nature, if we include in the system all such bodies which are affected by the
changes. – M.N. Saha

7. There exists a characteristic thermodynamic property called entropy. The difference in

entropies of the system in states 1 and 2 is given by

dq rev
S2 – S1 = ∫ over a reversible path
T

dq irr
S2 – S1 > ∫ over an irreversible path
T

104
The entropy is property of state only. Its value for an isolated system never decreases. – R.
E. Gibson

Concept of entropy

Entropy is a Greek word which stands for trope meaning change; a prefix 'en' is written to
identify it as a thermodynamic property which belongs to the family of energy and enthalpy.
This term was introduced by Clausius. He denoted entropy by the symbol S in the honour of
Sadi Carnot (S from Sadi).

We know that energy is defined as the capacity of a system to do work. But entropy of
a system is considered as an index of exhaustion of its capacity to do work. Thus entropy is a
measure of unavailable portion of energy. On this basis entropy has been used to represent
randomness. Greater is the randomness larger is the value of entropy. More regular is the
molecular arrangement lower is the value of entropy. Thus, the entropy of a substance in
gaseous state is greater than in the liquid state and that is greater than in its solid state. That
is,

S (gas) > S (liquid) > S (solid)

Characteristics of entropy

1. Entropy is an extensive property. Its value depends upon the amount of the substances
present in the system.

2. Entropy of a system is a state function. It depends only on the state variables (T, P, V, n).
Thus, the change of entropy is given by ∆S = S (final) – S (initial)

3. Entropy change of system (∆S system) does not depend on the path followed by the change,
but the entropy change of the surroundings (∆Ssurronnd1ngs) depends upon the path.

4. The total entropy change of an isolated system is equal to the sum of the entropy change
of system and the entropy change of the surroundings.

∆S total = ∆Ssystem + ∆Ssurroundings

The total entropy change of an isolated system is also called the entropy change of the
universe (∆Suniverse)

5. In a reversible process ∆Ssystem = – ∆Surroundings

6. In an irreversible process ∆.S total > 0. This implies that in spontaneous changes there is
increase of entropy of universe.

Entropy is the ratio of heat and temperature. Since heat is expressed as joule (J) and
temperature is expressed in kelvin (K), therefore, the entropy and change in entropy is
expressed as Joules per kelvin ≡J K–1

Notes

105
(i) If the amount of the substance is one mole, then entropy and its changes are expressed
as joules per kelvin per mole (J K–1 mol–1).

(ii) Calories per kelvin = cal K–1 is the non-SI unit of entropy.

dq rev
Background of using dS = as definition of entropy change of the system
T

Historically the above relation was introduced by Clausius via Carnot cycle. . But in
the present discussion we shall give another logical basis of introducing the definition of
entropy in view of the Euler’s reciprocity relations for exact differential of state function.
First we shall prove that dqrev is inexact differential and then show that dqrev divided by T
i.e., dqrev /T is an exact differential

Proof I: dqrev is inexact differential

For a reversible process the first law of thermodynamics is written as

dqrev = dU + P dV when only P-V work is considered

For an ideal gas P = n RT /V and for a monotomic gas U = 1.5 n RT (from kinetic theory of
gases) and thus

dU = 1.5 R dT

nRT
Therefore, dqrev = 1.5 n R dT + dV (i)
V

= M dT + N dV in the form of total differential

nRT
Where, M = 1.5 n R and N =
V

On differentiating M with respect to V at constant T and N with respect to T at constant V, we

get

⎛ ∂M ⎞ ∂
⎜ ⎟ = (1.5 n R )T = 0
⎝ ∂V ⎠ T ∂V

⎛ ∂N ⎞ ∂ ⎛ nRT ⎞ nR
and ⎜ ⎟ = ⎜ ⎟ =
⎝ ∂T ⎠ V ∂T ⎝ V ⎠ V V

It is seen that

⎛ ∂M ⎞ ⎛ ∂N ⎞
⎜ ⎟ ≠ ⎜ ⎟
⎝ ∂V ⎠ T ⎝ ∂T ⎠ V

and thus Euler’s reciprocity relation is not valid. Therefore, dqrev is inexact differential and
qrev is a path dependent quantity

Proof II: dqrev /T is exact differential Let us divide both sides of equation (i) by T to get

106
 dq rev nR
=1.5 n R dT + dV
T V

= M dT + N dV

nR
Where, M = 1.5 n R and N =
V

On differentiating M with respect to V at constant T and N with respect to T at constant V, we

get

⎛ ∂M ⎞ ∂
⎜ ⎟ = (1.5 n R )T = 0
⎝ ∂V ⎠ T ∂V

⎛ ∂N ⎞ ∂ ⎛ nR ⎞
and ⎜ ⎟ = ⎜ ⎟ =0
⎝ ∂T ⎠ V ∂T ⎝ V ⎠ V

It is seen that

⎛ ∂M ⎞ ∂N
⎜ ⎟ = 0 = ⎛⎜ ⎞⎟
⎝ ∂V ⎠ T ⎝ ∂T ⎠ V

and Euler’s reciprocity relation is valid. Therefore, dqrev /T is an exact differential

Logical discussion: dqrev /T is an exact differential. Therefore, it should represent a total

differential of a state function. This state function is represented by S and thus dS = dqrev /T

.Notes

(i) We have presented the discussion for an ideal gas but the same is applicable for
reversible process involving any type of system.

(ii) dqrev is an inexact differential and q is path dependent quantity but when it is
multiplied by 1/T, then dqrev/T represents a term dS which is an exact differential.
Therefore, 1/T is called the integrating factor.

Statement: dqirr /T is inexact differential therefore, dS ≠ dqirr /T.

Proof: For an irreversible process the first law of thermodynamics is written as

dqirr = dU + P dV

For an ideal monotomic gas dU = CV dT = 1.5 n R dT and in irreversible process P = Pext

=constant

Therefore, dqirr = 1.5 n R dT + Pext dV (i)

Let us divide both sides of equation (i) by T to get

dqirr nR Pext
= 1.5 dT + dV
T T T

107
 = M dT + N dV

nR Pext
Where, M = 1.5 and N =
T T

On differentiating M with respect to V at constant T and N with respect to T at constant V, we

get

⎛ ∂M ⎞ ∂ nR
⎜ ⎟ = ( )T = 0
⎝ ∂V ⎠ T ∂V T

⎛ ∂N ⎞ ∂ ⎛ Pext ⎞ P
and ⎜ ⎟ = ⎜ ⎟ = – ext
⎝ ∂T ⎠ V ∂T ⎜ T ⎟ T2
⎝ ⎠V

It is seen that

⎛ ∂M ⎞ ⎛ ∂N ⎞
⎜ ⎟ ≠ ⎜ ⎟
⎝ ∂V ⎠ T ⎝ ∂T ⎠ V

That is, Euler’s reciprocity relation is not valid. Therefore dqirr /T is an inexaxt differential.
Hece, dS ≠ qirr /T

Entropy as a state function – a detailed discussion

Entropy (S) is a state function if dS is an exact differential and dS is an exact differential if it

obeys Euler’s reciprocity relation. To prove it let us start with the first law of
thermodynamics applied to an ideal gas undergoing a reversible change

dU = dqrev – PdV

dqrev = dU + PdV (i)

Now, energy is a function of temperature and volume, U = U(T, V) and its total differential is
given by

∂U ∂U
dU = ⎛⎜ ⎞⎟ dT + ⎛⎜ ⎞⎟ dV
⎝ ∂T ⎠ V ⎝ ∂V ⎠ T

∂U
= CV dT + ⎛⎜ ⎞⎟ dV (ii)
⎝ ∂V ⎠ T

∂U ⎞
where, CV = ⎛⎜ ⎟ = Heat capacity at constant volume
⎝ ∂T ⎠ T

From equations (i) and (ii), we get

∂U
dqrev = CV dT + ⎛⎜ ⎞⎟ dV + PdV (iii)
⎝ ∂V ⎠ T

For an ideal gas

108
 (∂U/∂V)T = 0 ,Joule’s law

and P = nRT/V

nRT
Therefore, dqrev = CV dT + dV
V

dq rev CV nR
Or, = dT + dV
T T V

dq rev
By definition = dS
T

Therefore, small change in entropy (dS) is given by the relation

CV nR
dS = dT + dV (iv)
T V

From equation (iv) it is clear that change in entropy (dS) depends on changes in T and V .
Thus entropy is a function of T and V and S = S(T, V)

Total differential of S is given by

∂S ∂S
dS = ⎛⎜ ⎞⎟ dT + ⎛⎜ ⎞⎟ dV (v)
⎝ ∂T ⎠ V ⎝ ∂V ⎠ T

On comparing the coefficients of dT in equations (iv) and (v), we get

⎛ ∂S ⎞ CV
⎜ ⎟ = (vi)
⎝ ∂T ⎠V T

On differentiating equation (vi) with respect to V at constant T, we get

∂2S ∂ ⎛C ⎞
= ⎜⎜ V ⎟
⎟ =0 (vii)
∂V∂T ∂V ⎝ T ⎠T

On comparing the coefficients of dV in equations (iv) and (v), we get

⎛ ∂S ⎞ nR
⎜ ⎟ = (viii)
⎝ ∂V ⎠ T V

On differentiating the equation (viii) with respect to T at constant V, we get

∂2S ∂ ⎛ nR ⎞
= ⎜ ⎟ =0 (ix)
∂T∂V ∂T ⎝ V ⎠V

From equation (vii) and (ix), it is observed that

∂2S ∂2S
=0=
∂V∂T ∂T∂V

109
That is, dS obeys Euler’s reciprocity relation. Therefore, dS is an exact differential and S is a
state function

Logical proof that entropy (S) is a state function

For an ideal gas under reversible condition

dq rev
= dS = CV d ln T + n R d ln V
T

Integration of the above equation for a change from initial state 1 to final state 2 gives
2 2 2

∫1 dS = CV ∫1 d ln T +nR ∫1 d ln V
T2 V2
= CV ln + n R ln
T1 V1

Discussion: The right hand side of the above equation depends on the state variables (T1, V1,
T2 V2) of the system. Therefore, the left hand side should also depend on the state variables.
That is, left hand side should describe the change in a state property. Now left hand side
represents the change of entropy. Therefore, we conclude that entropy is a state property and
change of entropy is given by
2 2
dq rev
∫ T
= ∫ dS = S2 (T2, V2) – S1(T1, V1)
1 1

T2 V2
and ∆S = CV ln + n R ln
T1 V1

Relaation between energy and entropy

The change of internal energy is given by the first law of thermodynamics as

dU = dq – PdV (i)

The change of entropy is given by the second law of thermodynamics as

dq rev
= dS
T

Or, dqrev = TdS (ii)

On substituting the expression for dq from equation (ii) in to equation (i), we get

dU = TdS – PdV (iii)

Or, TdS = dU + PdV (iv)

110
Equations (iii) and (iv) represent the combined form of first and second laws of
thermodynamics.

Applications of the combined form of first and second laws of thermodynamics

(Optional)

The relation TdS = dU + PdV is useful to derive various other thermodynamic relations.

(A) Thermodynamic equation of state

A relation between the change in a thermodynamic property ( say U) and state variables
(PVT) s called thermodynamic equation of state.

The combined form of first and second laws of thermodynamics states that

TdS = dU + PdV

1 1
Or, dS = dU + PdV (i)
T T

Energy of a given amount of a system is a function of temperature and volume,U = U(T, V),
and its total differential is given by

∂U ∂U
dU = ⎛⎜ ⎞⎟ dT + ⎛⎜ ⎞⎟ dV (ii)
⎝ ∂T ⎠ V ⎝ ∂V ⎠ T

1 ⎛ ∂U ⎞ 1 ⎡⎛ ∂U ⎞ ⎤
Therefore, dS = ⎜ ⎟ dT + ⎢⎜ ⎟ + P ⎥ dV (iii)
T ⎝ ∂T ⎠ V T ⎣⎝ ∂V ⎠ T ⎦

From equation (iii) it is seen that entropy is a function of T and V and S = S(T, V) The total
differential of S is given by

∂S ∂S
dS = ⎛⎜ ⎞⎟ dT + ⎛⎜ ⎞⎟ dV (iv)
⎝ ∂T ⎠ V ⎝ ∂V ⎠ T

On comparing the coefficients of dT in equations (iii) and (iv), we get

⎛ ∂S ⎞ 1 ⎛ ∂U ⎞
⎜ ⎟ = ⎜ ⎟ (v)
⎝ ∂T ⎠V T ⎝ ∂T ⎠ V

On differentiating equation (iv) with respect to V at constant T, we get

∂2S 1 ∂ 2U
= (vi)
∂V∂T T ∂V∂T

On comparing the coefficients of dV in equations (iii) and (vi), we get

⎛ ∂S ⎞ 1 ⎡⎛ ∂U ⎞ ⎤
⎜ ⎟ = ⎢⎜ ⎟ + P⎥ (vii)
⎝ ∂V ⎠ T T ⎣⎝ ∂V ⎠ T ⎦

On differentiating equation (vii) with respect to T at constant V, we get

111
 ∂2S ∂ ⎡ 1 ⎧⎛ ∂U ⎞ ⎫⎤
= ⎢ ⎨⎜ ⎟ + P ⎬⎥
∂T∂V ∂T ⎣⎢ T ⎩⎝ ∂V ⎠ T ⎭⎥⎦ V

1 ⎛ ∂U ⎞ 1 ∂ 2U 1 ∂P
– 2 + ⎛⎜ ⎞⎟
P
=– ⎜ ⎟ + (viii)
2
T ⎝ ∂V ⎠T T ∂T ∂V T T ⎝ ∂T ⎠ V

Now S is a state function , therefore, Euler’s reciprocity relation must be valid and

∂2S ∂2S
=
∂V∂T ∂T∂V

In view of the above condition equations (vi) and (viii) give

1 ∂ 2U 1 ∂U 1 ∂ 2U 1 ∂P
= – 2 ⎛⎜ ⎞⎟ + – 2 + ⎛⎜ ⎞⎟
P
(ix)
T ∂V∂T T ⎝ ∂V ⎠ T T ∂T∂V T T ⎝ ∂T ⎠ V

Now U is a state function , therefore, Euler’s reciprocity relation must be valid and

∂ 2U ∂ 2U
=
∂V∂T ∂T∂V

In view of the above equality condition, equation (ix) gives

1 ⎛ ∂U ⎞ P 1 ⎛ ∂P ⎞
– ⎜ ⎟ – 2 + ⎜ ⎟ =0
2
T ⎝ ∂V ⎠T T T ⎝ ∂T ⎠ V

⎛ ∂U ⎞ ∂P
Or, ⎜ ⎟ = T ⎛⎜ ⎞⎟ – P (x)
⎝ ∂V ⎠T ⎝ ∂T ⎠ V

Equation (x) is called thermodynamic equation of state. It provides an expression for the
internal pressure (∂U/∂V)T in terms of state variable of a system. This equation is valid for
both the ideal and nonideal systems.

(B) Internal pressure of an ideal gas

Internal pressure is given by thermodynamic equation of state

⎛ ∂U ⎞ ∂P
⎜ ⎟ = T ⎛⎜ ⎞⎟ – P (i)
⎝ ∂V ⎠ T ⎝ ∂T ⎠ V

For an ideal gas PV = nRT and P = nRT/V, therefore,

⎛ ∂P ⎞ nR P
⎜ ⎟ = = (ii)
⎝ ∂T ⎠V V T

From equations (i) and (ii), we get

⎛ ∂U ⎞ P
⎜ ⎟ = T –P=0
⎝ ∂V ⎠ T T

112
Comclusions

1. The internal pressure (∂U/∂V)T of an ideal gas is zero.

2. The relation (∂U/∂V)T = 0 is a thermodynamic definition of ideal gas

3. The relation (∂U/∂V)T = 0 gives a thermodynamic proof of Joule’s law

(C) Internal pressure of a nonideal gas ( a gas obeying van der Waals equation)

Internal pressure is given by thermodynamic equation of state

⎛ ∂U ⎞ ∂P
⎜ ⎟ = T ⎛⎜ ⎞⎟ – P (i)
⎝ ∂V ⎠T ⎝ ∂T ⎠ V

van der Waals equation of state is written as

nRT an 2
P= – 2 (ii)
V − nb V

⎛ ∂P ⎞ nR
Now, ⎜ ⎟ = (iii)
⎝ ∂T ⎠ V V − nb

From equations (i), (ii) and (iii), we have

⎛ ∂U ⎞ nRT nRT an 2
⎜ ⎟ = – + 2
⎝ ∂V ⎠ T V − nb V − nb V

⎛ ∂U ⎞ an 2
Or, ⎜ ⎟ = 2
⎝ ∂V ⎠ T V

This relation reveals that internal pressure of a gas is large when the value of the van der
Waals constant a is large i.e., when the molecular force of attraction is strong.

Relation between enthalpy and entropy

Enthaly is defined by H = U + PV and

dH = dU + PdV + VdP (i)

From the combined form of first and second laws of thermodynamics we have

TdS = dU + PdV (ii)

From equations (i) and (ii), we have

dH = TdS + VdP (iii)

Or, TdS = dH – VdP (iv))

Equations (iii) and (iv) represent a combined form of the first and second laws of

113
thermdynamics in terms of enthalpy and entropy changes.

(A) Thermodynamic equation of state in terms of enthalpy change (Optional)

A relation between the change in a thermodynamic property (say H) and state variables (PVT)
s called thermodynamic equation of state.

The combined form of first and second laws of thermodynamics in terms of enthalpy states
that

TdS = dH – VdP

1 1
Or, dS = dH – VdP (i)
T T

Enthalpy of a given amount of a system is a function of temperature and pressure, H = H(T,

P), and its total differential is given by

∂H ∂H
dH = ⎛⎜ ⎞⎟ dT + ⎛⎜ ⎞⎟ dP (ii)
⎝ ∂T ⎠ P ⎝ ∂P ⎠ T

1 ⎛ ∂H ⎞ 1 ⎡⎛ ∂H ⎞ ⎤
Therefore, dS = ⎜ ⎟ dT + ⎢⎜ ⎟ − V ⎥ dP (iii)
T ⎝ ∂T ⎠P T ⎣⎝ ∂P ⎠ T ⎦

From equation (iii) it is seen that entropy is a function of T and P and S = S(T, P) and its total
differential of S is given by

∂S ∂S
dS = ⎛⎜ ⎞⎟ dT + ⎛⎜ ⎞⎟ dP (iv)
⎝ ∂T ⎠ P ⎝ ∂P ⎠ T

On comparing the coefficients of dT in equations (iii) and (iv), we get

⎛ ∂S ⎞ 1 ⎛ ∂H ⎞
⎜ ⎟ = ⎜ ⎟ (v)
⎝ ∂T ⎠ P T ⎝ ∂T ⎠ P

On differentiating equation (v) with respect to P at constant T, we get

∂2S 1 ∂2H
= (vi)
∂P∂T T ∂P∂T

On comparing the coefficients of dP in equations (iii) and (iv), we get

⎛ ∂S ⎞ 1 ⎡⎛ ∂H ⎞ ⎤
⎜ ⎟ = ⎢⎜ ⎟ −V ⎥ (vii)
⎝ ∂P ⎠ T T ⎣⎝ ∂P ⎠ T ⎦

On differentiating equation (vii) with respect to T at constant P, we get

∂2S ∂ ⎡1 ⎧⎛ ∂H ⎞ ⎫⎤
= ⎢ ⎨⎜ ⎟ − V ⎬⎥
∂T∂P ∂T ⎢⎣ T ⎩⎝ ∂P ⎠T ⎭⎥⎦ V

114
 1 ⎛ ∂H ⎞ 1 ∂2H 1 ∂V
+ 2 – ⎛⎜ ⎞⎟
V
=– ⎜ ⎟ + (viii)
2
T ⎝ ∂P ⎠T T ∂T∂P T T ⎝ ∂T ⎠ P

Now S is a state function , therefore, Euler’s reciprocity relation must be valid and

∂2S ∂2S
=
∂P∂T ∂T∂P

In view of the above condition equations (vi) and (viii) give

1 ∂2H 1 ∂H 1 ∂2H 1 ⎛ ∂V ⎞
= – 2 ⎛⎜ ⎞⎟ +
V
+ 2 – ⎜ ⎟ (ix)
T ∂P∂T T ⎝ ∂P ⎠ T T ∂T∂P T T ⎝ ∂T ⎠ P

Now H is a state function , therefore, Euler’s reciprocity relation must be valid and

∂2H ∂2H
=
∂P∂T ∂T∂P

In view of the above equality condition, equation (ix) gives

1 ⎛ ∂H ⎞ V 1 ⎛ ∂V ⎞
– ⎜ ⎟ + 2 – ⎜ ⎟ =0
2
T ⎝ ∂P ⎠T T T ⎝ ∂T ⎠ P

⎛ ∂H ⎞ ∂V
Or, ⎜ ⎟ = V – T ⎛⎜ ⎞
⎟ (x)
⎝ ∂P ⎠T ⎝ ∂T ⎠P

Equation (x) is called thermodynamic equation of state in terms of enthalpy change with
change of pressure at constant temperature.

Calculation of (∂H/∂P)T for an ideal gas

For an ideal gas PV = nRT and PV = nRT/P. Therefore,

⎛ ∂V ⎞ nR V
⎜ ⎟ = =
⎝ ∂T ⎠P P T

⎛ ∂H ⎞ ∂V
V – T ⎛⎜ ⎞ V
⎜ ⎟ = ⎟ = V–T =0
⎝ ∂P ⎠T ⎝ ∂T ⎠P T

Entropy as a function of T and V

From the combined form of first and second laws of thermodynamics we know that

TdS = dU + PdV

1 1
Or, dS = dU + PdV (i)
T T

But U is a state function and thus

115
 ∂U ∂U
dU = ⎛⎜ ⎞⎟ dT + ⎛⎜ ⎞⎟ dV
⎝ ∂T ⎠ V ⎝ ∂V ⎠ T

∂U
= CV dT + ⎛⎜ ⎞⎟ dV (ii)
⎝ ∂V ⎠ T

⎛ ∂U ⎞
where, CV = ⎜ ⎟ = Heat capacity at constant volume
⎝ ∂T ⎠ V

From equations (i) and (ii), we get

CV 1 ⎡⎛ ∂U ⎞ ⎤
dS = dT + ⎢⎜ ⎟ + P ⎥ dV (iii)
T T ⎣⎝ ∂V ⎠ T ⎦

For an ideal gas (∂U/∂V)T = 0 and P/T = nRT/V. Therefore,

CV nR
dS = dT + dV (iv)
T V

From equation (iv) it is seen that entropy is a function of T and V and

S = S(T, V)

The total differential of S is given by

∂S ∂S
dS = ⎛⎜ ⎞⎟ dT + ⎛⎜ ⎞⎟ dV (v)
⎝ ∂T ⎠ V ⎝ ∂V ⎠ T

Evaluation of partial derivatives of S for an ideal gas

(i) On comparing the coefficients of dT in equations (iv) and (v) we get

⎛ ∂S ⎞ CV
⎜ ⎟ = (vi)
⎝ ∂T ⎠ V T

⎛ ∂S ⎞
⎜ ⎟ = Partial derivative of S with T at constant V
⎝ ∂T ⎠ V

= Rate of change of entropy with temperature at constant volume

Conclusion: In equation (vi), CV /T is positive. Therefore, (∂S/∂T)V is also positive. Thus it

is concluded that the entropy of the system increases with increase of temperature at constant
volume and decreases with decrease of temperature.

(ii) On comparing the coefficients of dV in equations (iv) and (v), we get

⎛ ∂S ⎞ nR P
⎜ ⎟ = = (vii)
⎝ ∂V ⎠ T V T

116
 ⎛ ∂S ⎞
⎜ ⎟ = Partial derivative of S with V at constant T
⎝ ∂V ⎠T

= Rate of change of entropy with volume at constant temperature

Conclusion: In equation (vii), P/T is positive. Therefore, (∂S/∂V)T is also positive. Thus it is
concluded that the entropy of the system increases with increase of volume at constant
temperature and decreases with decrease of volume.

Entropy as a function of T and P

The combined form of first and second laws of thermodynamics in terms of enthalpy states
that

TdS = dH – VdP

1 1
Or, dS = dH – VdP (i)
T T

Enthalpy of a given amount of a system is a function of temperature and pressure, H = H(T,

P), and its total differential is given by

∂H ∂H
dH = ⎛⎜ ⎞⎟ dT + ⎛⎜ ⎞⎟ dP
⎝ ∂T ⎠ P ⎝ ∂P ⎠ T

∂H
= CP dT + ⎛⎜ ⎞⎟ dP (ii)
⎝ ∂P ⎠ T

⎛ ∂H ⎞
where, ⎜ ⎟ = CP = Heat capacity at constant pressure
⎝ ∂T ⎠ P

CP 1 ⎡⎛ ∂H ⎞ ⎤
Therefore, dS = dT + ⎢⎜ ⎟ − V ⎥ dP (iii)
T T ⎣⎝ ∂P ⎠T ⎦

For an ideal gas (∂H/∂P)T = 0 and V/T = nR/P. Therefore,

CP V
Therefore, dS = dT – dP (iv)
T T

From equation (iii) it is seen that entropy is a function of T and P and S = S(T, P) and its total
differential of S is given by

∂S ∂S
dS = ⎛⎜ ⎞⎟ dT + ⎛⎜ ⎞⎟ dP (v)
⎝ ∂T ⎠ P ⎝ ∂P ⎠ T

Evaluation of partial derivatives of S for an ideal gas

(i) On comparing the coefficients of dT in equations (iv) and (v) we get

⎛ ∂S ⎞ CP
⎜ ⎟ = (vi)
⎝ ∂T ⎠ P T

117
 ⎛ ∂S ⎞
⎜ ⎟ = Partial derivative of S with T at constant P
⎝ ∂T ⎠ P

= Rate of change of entropy with temperature at constant pressure

Conclusion: In equation (vi), CP/T is positive. Therefore, (∂S/∂T)P is also positive. Thus it is
concluded that at constant pressure the entropy of the system increases with increase of
temperature and decreases with decrease of temperature

(ii) On comparing the coefficients of dP in equations (iv) and (v) we get

⎛ ∂S ⎞ V
⎜ ⎟ = – (vi)
⎝ ∂P ⎠ T T

⎛ ∂S ⎞
⎜ ⎟ = Partial derivative of S with P at constant T
⎝ ∂P ⎠ T

= Rate of change of entropy with pressure at constant temperature

Conclusion: In equation (vi), V/T is positive. Therefore, right hand side is negative. Thus left
hand side should also be negative and hence (∂S/∂P)T is negative.. It is therefore, concluded
that at constant temperature the entropy of the system decreases with increase of pressure and
increases with decrease of pressure.

Entropy changes for change of states of an ideal gas

The combined form of first and second laws of thermodynamics is useful to calculate the
entropy changes under different conditions. Here we shall describe the calculations of ∆S for
an ideal gas for two types of processes.

(i) When T and V are changed

(ii) When T and P are changed

(A) Entropy change for isochoric reversible temperature change of an ideal gas

The variation of entropy with temperature and volume for an ideal gas is given by

CV nR
dS = dT + dV (i)
T V

In an isochoric process, volume is constant and dV = 0, therefore,

CV
dS = dT = CV d ln T (ii)
T

For the change of state from initial state 1 to final state 2, the entropy change is obtained on
integrating equation (iii) [assuming that CV is independent of temperature]

118
 2 2

∫1 dS = CV ∫1 d ln T
T2
Or, S2 – S1 = CV ln
T1

Thus, for an isochoric process the change of entropy with change of temperature of an ideal
gas is given by

T2 T2
∆S (isochoric) = CV ln = nCV, m × 2.303 log
T1 T1

Conclusions

ƒ Entropy of an ideal gas increases when it is heated at constant volume because T2>T1 and
log. T2/ T1 is positive.

ƒ Entropy of an ideal gas decreases when it is cooled at constant volume because

T2Therefore,T1 and log. T2/ T1 is negative

(B) Entropy change for isothermal reversible volume change of an ideal gas

In an isothermal process the temperature is constant and dT = 0. Therefore,

nR
dS = dV = nR d lnV
V

For the change of state from initial state 1 to final state 2, the entropy change is obtained on
integrating the above equation
2 2

∫1 dS =nR ∫1 d ln V
V2 V2
Or, S2 – S1 = ∆S (isothermal) = n R ln n R×2.303 log
V1 V1

Conclusions

ƒ Entropy of an ideal gas increases when it is allowed to expand at constant temperature

because V2>V1 and

log. V2/ V1 is positive

ƒ Entropy of an ideal gas decreases when it is compressed at constant temperature. because

V2<V1 and log. V2/ V1 is negative (C) Entropy change when both the temperature and volume
of an ideal gas are changed simultaneously

The variation of entropy with temperature and volume for an ideal gasis given by

119
 dS = CV d lnT + nR d lnV

For the change of state from initial state 1 to final state 2, the entropy change is obtained on
integrating the above equation
2 2 2

∫1 dS = CV ∫1 d ln T +nR ∫1 d ln V
T2 V2
Or, S2 – S1 = CV ln + n R ln
T1 V1

T2 V2
∆S = nCV, m × 2.303 log + nR × 2.303 log
T1 V1

(D) Entropy change for isobaric reversible temperature change of an ideal gas

The variation of entropy with temperature and pressure is given by

CP 1 ⎡⎛ ∂H ⎞ ⎤
dS = dT + ⎢⎜ ⎟ − V ⎥ dP (i)
T T ⎣⎝ ∂P ⎠ T ⎦

For an ideal gas (∂H/∂P)T = 0 and V/T = nR /P. Therefore,

CP nR
dS = dT – dP (ii)
T P

In an isobaric process, pressure is constant and dP = 0, therefore,

CP
dS = dT = CP d ln T (iii)
T

For the change of state from initial state 1 to final state 2, the entropy change is obtained on
integrating equation (iii) [assuming that CP is independent of temperature]
2 2

∫1 dS = CP ∫1 d ln T
T2
Or, S2 – S1 = CP ln
T1

Thus, for an isobaric process the change of entropy with change of temperature of an ideal
gas is given by

T2 T2
∆S (isobaric) = CP ln = nCP, m × 2.303 log
T1 T1

120
Conclusions

ƒ Entropy of an ideal gas increases when it is heated at constant pressure because T2>T1 and
log. T2/ T1 is positive.

ƒ Entropy of an ideal gas decreases when it is cooled at constant pressure because

T2Therefore,T1 and log. T2/ T1 is negative

Example: Calculate the change inentropy when 2 moles of an ideal gas are heated from
300 K to 600 K at a constant pressure under reversible condition. It is given that CP, m =
25 JK–1 mol–1

Solution: For isobaric heating of an ideal gas

T2
∆S (isobaric) = n CP, m × 2.303 log
T1

Data given: n = 2 mol, CP, m = 25 JK–1 mol–1 , T1= 300 K, T2 = 600 K

T2/ T1 = 600 K/ 300 K = 2

log T2/ T1 = log 2 = 0.301

Therefore, ∆S (isobaric) = 2 mol × 25 JK–1 mol–1×2.303 × 0.301

=34.6 JK–1

(E) Entropy change for isothermal reversible pressure change of an ideal gas

The variation of entropy with temperature and pressure for an ideal is given by

CP nR
dS = dT – dP
T P

In an isothermal process, temperature is constant and dT = 0, therefore,

nR
dS = – dP = –nR d lnP
P

For the change of state from initial state 1 to final state 2, the entropy change is obtained on
integrating the above equation
2 2

∫1 dS = – nR ∫1 d ln P
P2
Or, S2 – S1 = – nR ln
P1

Thus, for an isobaric process the change of entropy with change of temperature of an ideal
gas is given by

121
 P2 P1 P1
∆S (isothermal) = – nR ln = nR ln = nR × 2.303 log
P1 P2 P2

Conclusions

ƒ Entropy of an ideal gas increases when it is allowed to expand at constant temperature

because P1 >P2 and P1/ P2 >1 thus log P1/ P2 > 0 (positive).

ƒ Entropy of anideal gas decreases when it is compressed at constant temperature

because P1/ P2 <1 thus log P1/ p2 < 0 (negative).

(F) Entropy change when temperature and pressure of an ideal gas are changed
simultaneously

The variation of entropy with temperature and pressure for an ideal is given by

dS = CP d ln T – nR d ln P

For the change of state from initial state 1 to final state 2, the entropy change is obtained on
integrating the above equation
2 2 2

∫1 dS = CP ∫1 d ln T –nR ∫1 d ln P
T2 P2
Or, S2 – S1 = CP ln – n R ln
T1 P1

T2 P1
= nCP, m × 2.303 log + nR × 2.303 log
T1 P2

(G) Entropy change for an ideal gas under reversible -adiabatic conditions

In adiabatic reversible process there is no entropy change that is, ∆S = 0. This is proved as
follows.

For simultaneous change of temperature and volume the entropy is of an ideal gas
(system) is given by

T2 V2
∆S = CV ln + nR log (i)
T1 V1

For an ideal gas undergoing adiabatic reversible change the temperature and volume are
related by
CV / nR
⎛ T2 ⎞ V1
⎜ ⎟ =
⎜T ⎟ T2
⎝ 1 ⎠

CV T2 V1
Therefore, ln = ln
nR T1 V2

122
 T2 V1 V2
Or, CV ln = nR ln = – nR ln (ii)
T1 V2 V1

On replacing the first term of the right hand side of equation (i) by the right hand side term of
equation (ii), we find that

V2 V2
∆S = – nR ln + nR ln =0
V1 V1

Discussion

Zero entropy change (∆S = 0) for an adiabatic reversible change of state of an ideal gas
suggests that

(i) During adiabatic reversible expansion the increase of entropy due to increase of
volume is exactly balanced by the decrease of entropy due to lowering of temperature.

(ii) During adiabatic reversible compression the decrease of entropy due to decrease of
volume is exactly balanced by the increase of entropy due to increase of temperature.

Entropy changes involved in the Carnot cycle

The Carnot cycle involves alternating isothermal and adiabatic expansion and
alternating isothermal and adiabatic compression respectively. For a gas the steps of the
changes of temperature and entropy are shown as T–S indicator diagram in Fig. 12.

Fig. 12. Indicator diagram of Carnot cycle in terms

of temperature (T) and entropy (S).

The isothermal reversible expansion is represented by the horizontal line AB which

tells that T is constant and S increases whereas the isothermal reversible compression is
represented by horizontal line CD which tells that entropy decreases during compression. The
reversible adiabatic expansion is represented by vertical line BC which tells that temperature
decreases but entropy remains constant, whereas adiabatic compression is represented by

123
vertical line DA which tells that temperature increases but entropy remains constant (as qrev=
0).

q2
∆S (1) = = nR × 2.303 log (V2/V1)
T2
isothermal reversible expansion

q rev 0
∆S (2) = = =0 adiabatic reversible expansion
T T

q1
∆S (3) = – = nR × 2.303 log (V4/V3)
T1
isothermal reversible compression

q rev 0
∆S (4) = = =0 adiabatic reversible compression
T T

For the entire cycle the entropy change is given by

∆S (cycle) = ∆S (1) + ∆S (2) + ∆S (3) + ∆S (4)

= nR × 2.303 log (V2/V1) + 0 + nR × 2.303 log (V4/V3) + 0

V4 V2
But log = – log
V3 V1

Therefore, ∆S (cycle) = nR × 2.303 log (V2/V1) – nR × 2.303 log (V2/V1) = 0

Conclusions:

(1) Entropy increases during isothermal reversible expansion but decreases during isothermal
compression in Carnot cycle.

(2) The increase of entropy for isothermal reversible expansion is equal and opposite to the
decrease in entropy for isothermal reversible compression in Carnot cycle.

(3) The total entropy change in Carnot cycle is zero.

Important deduction: For Carnot cycle we have shown that

q2 q1
∆S(cycle) = +0– +0=0
T2 T1

q2 q1
That is, =
T2 T1

q1 T1
Or, =
q2 T2

Efficiency of Carnot cycle is defined as

124
 q1 T1
η= 1 – =1– (i)
q2 T2

In this expression T1 and T2 are the absolute temperatures defined on thermodynamic scale.
Now, it is observed that the expression (i) is the same as that derived in the previous part
where T1 and T2 were the absolute temperatures defined in terms of ideal gas temperatures.
From this similarity it is concluded that the temperatures on the two scales are proportional
to each other.

Entropy of isothermal mixing of ideal gases

Let us consider two ideal gases A and B kept in two separate compartments separated by a
very thin partition of a container and maintained at constant temperature. Further suppose that
nA and nB are the amounts and VA and VB are the initial volumes of gases A and B
respectively. When the thin partition is removed, both the gases mix and occupy a final total
volume VA + VB. Therefore, the mixing process can be assumed that gas A expands from its
initial volume VA to a final volume of VA + VB..

The entropy change of gas A at constant temperature is given by

VA + V B
∆S (A) = nA R × 2.303 log
VA

Similarly, gas B expands from its initial volume VB to a final volume of VA + VB. The entropy
change of gas B at constant temperature is given by

VA + V B
∆S (B) = nB R × 2.303 log
VB

The total entropy change is equal to the sum of the entropy changes of gas A and gas B on
mixing.

∆S (mixing) = ∆S (A) +∆S (B)

⎛ VA + VB ⎞ ⎛ VA + VB ⎞
= nA R × 2.303 log ⎜⎜ ⎟
⎟
+ nB R × 2.303 log ⎜⎜ ⎟
⎟
⎝ VA ⎠ ⎝ VB ⎠

⎛ V ⎞
Now, ⎜⎜ A ⎟ = xA = Mole fraction of gas A
⎟
V
⎝ A + VB⎠

⎛ V ⎞
and ⎜ B ⎟ = xB = Mole fraction of gas B
⎜V +V ⎟
⎝ A B⎠

⎛ 1 ⎞ ⎛ 1 ⎞
Therefore, ∆S (mixing) = nA R × 2.303 log ⎜⎜ ⎟⎟ + nB R × 2.303 log ⎜⎜ ⎟⎟
x ⎝ A ⎠ x ⎝ B ⎠

= – R × 2.303 [nA log xA + nB log xB]

Discussion

125
(i) xA< 1 and thus log xA is negative, similarly log xB is also negative. Therefore, each
term within bracket of right side of the above equation is negative and thus entire right
side is positive. Hence entropy of mixing the gases is positive and mixing process is
spontaneous.

(ii) For more than two gases ( say k gases) the entropy of mixing is given by

∆S (mixing) = – R × 2.303 Σnk log xk, where k represents different type of gases A, B, C,
D etc.

Entropy changes in phase transformations

The change of entropy accompanying the transformation of one mole of a substance from one
physical state into another physical state at its transition temperature is called entropy of a
phase transformation or entropy of transition. It is denoted by ∆transS .

The phase transformation may involve change from liquid to vapour (L V) or solid to
liquid (S L) or in general from αphase to -phase (α  ) Accordingly, we can define
different types.of entropy of transitions. Since, transformation from one phase into another
phase at the transition temperature of a substance is a reversible process, the entropy change
can be calculated as

q transition
∆transS =
Ttransition

For a process at constant pressure qp = ∆H, therefore,

∆ trans H
∆transS =
Ttransi

Important note: In the above equation if any two quantitie are known the third can be
calculated. Thus

∆ trans H ∆ trans S
(i) ∆transS = (ii) Ttrans = (iii) ∆transH = Ttrans × ∆transS
Ttrans ∆ trans S

(A) Entropy of vaporization ∆vapS

The change of entropy accompanying the conversion of one mole of a liquid into vapour at its
boiling point is called entropy of vaporization. It is denoted by ∆vapS. It is equal to enthalpy
of vaporization divided by the boiling point

∆ vap H
∆vapS =
Tb

∆vapS = Entropy in the final state – Entropy in the initial state

= Entropy of vapour phase – Entropy of the liquid phase

= S (vapour) – S (liquid)

126
∆vapH = Enthalpy of vaporization of the liquid = Heat of vaporization of the liquid

Tb = Boiling point (in Kelvin) of the liquid

Example. Calculate the entropy change when one mole of liquid water is converted into
vapour at 100 oC. The enthalpy of vaporization is 40.850 kJ mol–1

Solution. The phase transformation is represented by

H2O(l) H2O(v)

Data given:

∆vapH = 40.850 kJ mol–1 = 40850 J mol–1

Boiling point = Tb = 100 + 273 = 373 K

∆ vap H
Therefore, ∆vapS =
Tb

40850 J mol -1
= = 109.5 J K–1 mol–1
373K

Remarks. Here it is observed that:

∆vapS = Entropy of vapour phase – Entropy of the liquid phase = 109.5 J K–1 mol–1

Therefore, Entropy of vapour phase = Entropy of liquid phase + 109.5 J K–1 mol–1

This observation is in line with the fact that in the vapour phase there is more randomness as
compared to the liquid phase.

Exercise 1. Calculate the entropy of vaporization of a liquid if ∆vapH.= 42400 J mol–1and Tb =

351.4 K

(∆vapS. = 42400 J mo1–1 / 351.4 K = 120.66 J K–1 mol–1)

Exercise 2. Calculate the entropy of vaporization of a liquid which boils at 110.6 °C when
∆vapH. is 35.2 kJ mol –1 (∆vapS = 35200 J mol–1 / 383.6 K = 91.76 J K–1 mol–1)

Trouton’s rule. For nonpolar liquids Trouton observed that entropy of vaporization is
between 80 to 90 JK–1 mol–1 . Therfore, he suggested that entropy of vaporization of such
liquids may be approximately taken equal to 85 JK–1 mol–1 which is called Trouton’s rule.

According to Trouton’s rule

∆ vap H
(i) = 85 JK–1 mol–1
Tb

(ii) ∆vapH. =Tb × 85 JK–1 mol–1

127
 ∆ vap H
(iii) Tb =
85 kJ mol -1

Molar entropy of vaporization of liquids at their normal boiling points

Liquid Benzene Cyclohexane Methane Methanol Ethanol Water

∆vapS/ JK–1 mol–1 87 85 83 104 110 109

Remarks. Trouton’s rule is not obeyed by the liquids (such as ethanol C2H5OH and water
H2O) involving dipole – dipole interaction and hydrogen bonding

(B) Entropy of fusion ∆fusS

Tbe change of entropy accompanying the conversion of 1 mole of a solid into liquid at its
melting point is called entropy of fusion. It is denoted by ∆fusS and calculated as follows.

∆ fus H
∆fusS =
Tm

∆fusS = Entropy of liquid phase – Entropy of solid phase

= S (liquid) – S (solid)

∆fusH = Enthalpy of fusion of the solid

Tm = Melting point (in kelvin) of solid

Example. Calculate the entropy of fusion of ice if its enthalpy of fusion is 6.01 kJ mol–1 at
its melting point of 273 K.

Solution. The phase transformation is represented by

H2O (s) H2O (l)

and entropy change in this phase transformation is equal to the entropy of fusion of ice.

Data given:

∆fusH = 6.01 kJ mol–1 = 6010 J mol–1

Tm = 273 K

∆ fus H
Therefore, ∆fusS = = 22 J K–1 mol–1
Tm

Remarks. The entropy of fusion is positive. This suggests that the entropy of liquid water is
greater than that of ice. Thus

Entropy of water = Entropy of ice + 22 J K–1 mol–1

128
Relation between entropy and randomness in terms of entropy change

Entropy is a measure of randomness. Greater is randomness in a system, larger is its

entropy. Let us illustrate it for fusion and vaporization processes.

ƒ For the the process H2O (s) H2O (l )

∆fusS = S (liquid) – S (solid) = 22 J K–1 mol–11

Or, S (liquid) = S (solid) + 22 J K–1 mol–1

Thus the entropy of liquid water is greater than the entropy of ice by 22 J K–1 mol–1. But there
is more randomness in liquid water than in ice. Therefore, entropy is a measure of
randomness.

ƒ For the process H2O(l) H2O(v)

∆vapS = S (vapour) – S (liquid) = + 109.5 J K–1 mol–1Therefore,

S (vapour) = S (liquid) + 109.5 J K–1 mol–1

The entropy of water vapour is greater.than the entropy of liquid water by 109.5 J K–1 mol–1.
But, there is more randomness in vapour phase than in liquid phase. Therefore entropy is a
measure of randomness.

The data:

S (vapour) = S (liquid) + 109.5 J K–1 mol–1

and S (liquid) = S (solid) + 22 J K–1 mol–1

suggest that the difference in the randomness between water vapour and liquid water is much
larger (equivalent to 109.5 J K–1 mol–1) as compared to the difference in the randomness
between water (liquid) and ice (solid) which is equivalet to only 22 J K–1 mol–1.This
discussion confirms the correlation

S (vapour) >> S(liquid) > S (solid)

Example. Justify that a decrease in entropy is observed as a gas condenses into liquid.
Compare it with decrease of entropy when a liquid sample is converted into solid.

Solution. For the process Gas ⎯⎯→ Liquid (a)

∆S (a) = S(final) – S(initial) =S(liquid) –S(gas) = –ve

Justification. There is more randomness in a gas as compared to its liquid form. Therefore,
entropy of a gas is greater than its liquid state. Thus ∆S is negative, that is, entropy decreases
when a gas condenses.

For the process Liquid ⎯⎯→ Solid (b)

∆S(b) = S(final) – S(initial) = S(solid) – S(liquid) = –ve

129
Comparison. The increasing order of entropy S(Gas) >> S (Liquid) > S(Solid) suggests that
the value of ∆S(a) is more negative as compared to the value of ∆S(b)

Example. Predict with justification the entropy change for each one of the following
processes.

(a) Dissolution of iodine in a solvent

(b) HCl is added to AgNO3 solution and precipitate of AgCl is obtained

(c) A partition is removed to allow two gases to mix

Solution. The entropy change is given by the relation

∆S = S(final) — S(initial)

(a) For the process I2(s) ⎯⎯→ I2(solution)

∆S = S (I2, solution) — S (I2, solid) = +ve

Justification. There is more randomness hence more entropy in the dissolved state as
compared to the solid state of iodine. Thus dissolution of iodine in a solvent is accompanied
by an increase in entropy.

(b) For the process HCl (aq) + AgNO3(aq) ⎯⎯→ AgCl (s) + HNO3(aq)

∆S = S(final) — S(initial) = − ve

Justification. The entropy on the product side is lower because of the presence of a solid and
a solution as compared to the reactants where both the reactants are solution

(c)For the process Gas A | Gas B ⎯⎯→ Mixture of A+B.

∆S = S(final) — S(initial) = + ve

Justification. In the mixture each gas has to move in a larger volume and thus there is more
randomness and larger entropy as compared to that in isolated gases before mixing

Example. Predict the sign of the entropy change for each of the following :

(a) Hg (l) ⎯⎯→ Hg (g) (b) AgNO3(s) ⎯⎯→ AgNO3(aq)

(c) I2(g) ⎯⎯→ I2 (s) (d) C(graphite) ⎯⎯→ C (diamond)

Solution. Entropy change is positive when there is more randomness and hence large entropy
in the final state as compared to the initial state. Thus

(a) For the process Hg (l) ⎯⎯→ Hg (g),

∆S = S(final) – S(initial) = S(Hg, gas) – S(Hg, liqiid) = + ve

130
Reason. The entropy of gaseous mercury is greater than that of the liquid mercury

(b) For the process AgNO3(s) ⎯⎯→ AgNO3(aq)

∆S = S(final) – S(initial) = S(AgNO3, aq) – S(AgNO3, s) = + ve

Reason. The entropy of AgNO3 in solution is greater than that of a solid AgNO3.

(c) For the process I2(g) ⎯⎯→ I2(s)

∆S = S(final) – S(initial) = S(I2, s) – S(I2, g) = − ve

Reason. The entropy of I2 in solid state is lower than that of I2(gas).

(d) For the process C(graphite) ⎯⎯→ C(diamond)

∆S = S(final) – S(initial) = S(Diamond) – S(graphite) = − ve

Reason. There is less randomness and hence the entropy of diamond is lower than that of
graphite in which there is more randomness

Clausius inequality statement

Clausius stated that in an isolated system the entropy change is greater than zero
under irreversible condition but under reversible condition it is equal to zero. In terms of
symbolic notations the Clausius inequality is stated as follows

∆Sirreversible > 0

and ∆Sreversible = 0

Or, ∆S ≥ 0

Justification of Clausius inequality (Nonevaluative)

For reversible and irreversible processes the first law of thermodynamics is stated as

∆Uirr = qirr + wirr (i)

and ∆Urev = qrev + wrev (ii)

We know that internal energy is a state function and dU is exact differential. Therefore,
change in internal energy is the same whether a process occurs under reversible or
irreversible condition. Thus

∆Urev = ∆Uirr (iii)

From equations (iii), (ii) and (i). we get

qrev + wrev = qirr + wirr

Or, qrev – qirr = – wrev + wirr

131
 = – wrev– (– wirr)

= wrev (by) – wirr (by) (iv)

The work done by the system under reversible condition is greater than that under irreversible
condition. That is,

wrev (by) > wirr (by)

Or, wrev (by) – wirr (by) > 0 (v)

From equations (iv) and (v). we get

qrev – qirr > 0

Or, qrev > qirr (vi)

On dividing both side of equation (vi) by T, we get

q rev q irr
>
T T

But from the second law of thermodynamics

q rev
∆S = (vii)
T

q irr
Therefore, ∆S > (viii)
T

But first law of thermodynamics states that

q = ∆U – w

∆U − wrev
Therefore, ∆S = (ix)
T

∆U − wirr
and ∆S > (x)
T

In an isolated system, there is no exchange of heat, energy and work between the system and
surroundings. Therefore,

q = 0, ∆U = 0 and w = 0 in isolated system

On introducing these conditions in to equations (ix) and (x), we get

∆Srev = 0

∆Sirr > 0

Or, ∆S (isolated) >= 0

132
where > refers to irreversible change and = refers to reversible change.

For infinitesimal change the Clausius inequality is given by

dS (isolated) >=0

Comments: From the relation ∆S (isolated) >=0 it appears that entropy is not a state function
because it is different for reversible and irreversible processes. But we know that entropy is a
state function. Thus there appears to be contradiction. This contradiction was explained by
Clausius that an isolated system includes both the system under investigation and the
surroundings in its immediate vicinity. Therefore, the entropy change of an isolated system is
equal to the entropy changes of the system and surroundings.

∆S (isolated) = ∆S (system) + ∆S (surroundings)

Calculation of Entropy Changes of systems and surroundings

While calculating the entropy change, we must take into account the entropy changes in the
system and surroundings. The combination of system and surroundings constitutes an
isolated system. The total entropy change of an isolated system is called the entropy change
of the universe

∆Stotal = ∆Ssystem + ∆Ssurroundings = ∆Suniverse

Nature of surroundings. The surroundings are considered to be any one of the following:

(a) Heat reserviour which can exchange heat with the system i.e., which can either add heat
to the system or extract heat from the system

qsystem = – q surroundings

(b) Mechanical device which can accept work from the system or which can do work on the
system.

wsystem = – w surroundings

Entropy change of system (∆Ssystem)

The entropy change of the system can be calculated from the mathematica1 statement of the
second law of thermodynamics

q rev
∆S system=
T

The methods of calculation of entropy changes for an ideal gas under different conditions
have already been described. For irreversible processes the entropy change of the system is
the same as that for reversible process
reversible irreversible
∆S system = ∆Ssystem

But it is not equal to the heat exchanged between the system and surroundings divided by
temperature. That is,

133
 irreversible
∆Ssystem ≠ qirr/T

Entropy change of the surroundings (∆Ssurroundings)

The entropy change of the surroundings is calculated as

qsurroundings
∆Ssurroundings =
T

For surroundings, this relation is valid whether the change is reversible or irreversible.

Now the heats exchanged between the system and the surroundings are related by

qsurroundings = – qsystem

qsurroundings qsystem
Therefore, ∆Ssurrounding: = =–
T T

reversible irreversible
But ∆Sssurroundi ngs ≠ ∆Sssurroundings

Comments

(i) In a reversible process

reversible
q rev
∆S system = = – ∆Ssurroundings
T

reversible
Therefore, ∆Stotal reversible
= ∆S system reversible
+ ∆S ssurroundi ngs = 0

(ii) In an irreversible process

∆Ssystem ≠ ∆Ssurroundings

Example: Mention the methods to calculate the entropy change for the following
process?

H2O (l, 298 K, 1 bar ) ⎯

⎯→ H2O (v, 398 K, 0.8 bar)

Solution: The given process involves phase change, change of temperature and change of
pressure for which a single formula cannot be used. Therefore, we shall split the given
process in to several steps for which entropy changes an be determined. Thus

(i) Liquid water is heated at constant pressure from 298 K to 373 K (the boiling point of
water)
Heat
H2O (l, 298 K, 1 bar) ⎯⎯⎯→ H2O (l, 373 K, 1 bar)

134
 373 K
∆S(i) = CP, m (l) × 2.303 log
298 K

(ii) Liquid water is allowed to vaporize under isothermal and isobaric conditions at 373 K
Vaporize
H2O (l, 373 K, 1 bar) ⎯⎯ ⎯⎯→ H2O (v, 373 K, 1 bar)

∆ vap H
∆S(ii) = ∆vapS =
373 K

(iii) Water vapour is heated at constant pressure from 373 K to 398 K

H2O (v, 373 K, 1 bar) ⎯Heat

⎯⎯→ H2O (v, 398 K, 1bar)

398 K
∆S(iii) = CP, m(v) × 2.303 log
373 K

(iv) Water vapour is allowed to expand isothermally at 398 K from 1 bar to 0.8 bar

H2O (v, 398 K, 1 bar) ⎯Expansion

⎯ ⎯⎯→ H2O (v, 398 K, 0.8 bar)

1 bar
∆S(iv) = R × 2.303 log
0.8 bar

On adding equations of steps (i) to (iv) and canceling the common terms on the two sides, we
shall get

H2O (l, 298 K, 1 bar ) ⎯

⎯→ H2O (v, 398 K, 0.8 bar)

and ∆S (system) = ∆S(i) + ∆S(ii) + ∆S(iii) + ∆S(iv)

373 K ∆ vap H
= CP, m(l) × 2.303 log +
298 K 373 K

398 K 1 bar
+ CP, m(v) × 2.303 log + R × 2.303 log
373 K 0.8 bar

On substituting the values of various quantities the entropy change can be calculated

Entropy as criteria of spontaneity and equilibrium

A process is said to be spontaneous if it has a tendency to occur. All natural processes are
spontaneous. It is an experimental observation that in a spontaneous process total entropy
increases as the change progresses. When a state of equilibrium is attained the entropy
becomes maximum. At any other stage the entropy is lower than its equilibrium value. These
statements may be proved starting with the combined form of the first and second laws of
thermodynamics.

ƒ For an irreversible process (spontaneous process) when only P-V work is considered

135
 dU + PdV
dS >
T

In an isolated system energy and volume are constant that is, dU = 0 and dV= 0, therefore,

(dS)U, V > 0

ƒ In a reversible processes ( equilibrium)

dU + PdV
dS =
T

In an isolated system energy and volume are constant that is, dU = 0 and dV= 0, therefore,

(dS)U, V = 0

ƒ The combined result is written as (dS)U, V >= 0

ƒ For finite changes (∆S)U, V >= 0

Thus in an isolated system at constant energy and constant volume the entropy is maximum at
equilibrium

Discussion: Why the entropy should be maximum at equilibrium? This can be explained like
this. Equilibrium is the state when the progress of the change has stopped, that is, the system
has exhausted to undergo further change in the desired direction. Now any property which
increases as the change progresses must attain its limiting value when the system has
exhausted to undergo further change. It is a common experience that the limiting value of an
increasing property is its highest or maximum value. Hence entropy is maximum at
equilibrium

Spontaneity and equilibrium in terms of internal energy

Combined form of first and second laws of thermodynamics states that for an irreversible
process

T dS > dU + PdVirr

Or, dU < TdS – PdVirr

At constant entropy dS = 0 and at constant volume dV= 0. Therefore,

(dU)S, V < 0 for spontaneous change

For a reversible change

dU = TdS – PdVrev

At constant entropy dS = 0 and at constant volume dV= 0. Therefore,

(dU)S, V = 0 at equilibrium

For finite changes (∆U)S, V ≤ 0

136
Conclusion: The result (∆U)S, V ≤ 0 implies that for a spontaneous process at constant
entropy and constant volume the internal energy decreases and attains a minimum value at
equilibrium.

Spontaneity and equilibrium in terms of enthalpy

Combined form of first and second laws of thermodynamics in terms of enthalpy change
states that for an irreversible process

T dS > dH – VdP

Or, dH < TdS + VdP

At constant entropy dS = 0 and at constant pressure dP = 0. Therefore,

(dH)S, P < 0 for spontaneous change

For a reversible change

dH = TdS + VdP

At constant entropy dS = 0 and at constant pressure dP= 0. Therefore,

(dH)S, P = 0 at equilibrium

For finite changes (∆H)S, P ≤ 0

Conclusion: The result (∆H)S, P ≤ 0 implies that for a spontaneous process at constant entropy
and constant pressure the enthalpy decreases and attains a minimum value at equilibrium.

A critical comment: In the chemistry laboratories the experiments are seldom carried at
constant entropy and constant volume or at constant entropy and constant pressure.
Therefore, decrease of internal energy or decrease of enthalpy is not a suitable criterion of
spontaneity of a process. Then what next? Refer to free energy functions.

137
THIRD LAW OF THERMODYNAMICS

The first law of thermodynamics provides methods of calculation of the energy changes (∆U)
and enthalpy changes (∆H). On the other hand, the second law of thermodynamics helps in
the calculation of entropy changes (∆S). But this law as such cannot be used to calculate the
absolute value of entropy. Therefore, we need a new law of thermodynamics which can guide
us to evaluate the absolute value of entropy of different type of substances. This new law is
called the Third law of thermodynamics which is also called Nernst heat theorem in a
limited perspective.

Nernst heat theorem

In 1906 Nernst stated the heat theorem that in the vicinity of absolute zero all processes
should take place without any change in entropy and heat capacity. In terms of symbolic
notations Nernst heat theorem may be stated as

Lim ∆S → 0 and Lim ∆CP → 0

T→0 T→0

In 1913 Plank extended heat theorem in the form of third law of thermodynamics

Statement of the third law of thermodynamics

Every substance has a finite positive entropy but at 0 K (absolute zero) the
entropy may become zero and does so become in case of a perfectly crystalline substance

This statement also implies that

At absolute zero the entropy of a perfect crystal is zero

That is, when T = 0 K then S = 0

Molecular basis of third law of thermodynamics

We know that entropy is a measure of randomness. Greater the randomness larger is the value
of entropy. Lower is radomness smaller is the value of entropy. If the randomness is reduced
to zero the entropy is also reduced to zero. This implies that when there is perfect order in the
system its entropy is zero. It is in tune with the third law of thermodynamics which states that
at absolute zero the entropy of a perfect crystal is zero. This is true because at absolute zero
of temperature there is complete order in a perfect crystal and no chaos hence entropy is zero.
The correlation between entropy and molecular arrangement is given by Boltzmann equation

S = k ln W (i)

Here, S = Entropy

Gas constant R
k = Boltzmann constant = =
Avogadro constant NA

W = Number of ways of molecular arrangements

138
 From equation (i) it is clear that larger is the value of W higher is entropy (S). At
absolute zero (0 K ≡ 273.16 oC) all types of motions cease. Therefore, molecules (atoms and
ions) can arrange themselves in one way only. That is, W = 1 and there is perfect order.
Therefore,

S = k ln W = k ln 1 = k × 0 = 0

Thus entropy is zero at absolute zero. At temperatures higher that 0 K, the molecules can
have different types of motions and they arrange themselves in more than one ways. That is,
W > 0 and therefore, ln W > 0 and hence S is positive.

Concept of residual entropy

There are certain substances which have positive entropy even at absolute zero. The value of
entropy possessed by a substance at 0 K is called its residual entropy.

Origin of residual entropy: The residual entropy arises because the molecules can arrange
themselves in more that one ways. For example, in case of carbon monoxide (CO) the
molecules can have the following type of arrangements even at 0 K.

CO CO CO CO

Or, CO CO OC CO

This suggests that each CO molecule can have two orientations. Thus W = 2 for each
molecule.

Calculation of residual entropy: In a system containing one Avogadro number of molecules

(one mole) the entropy is given by

S = NA × k ×2.303 log W = R×2.303 log W

Now, R = 8.314 J K—1 mol–1. Therefore, when W = 2 we shall have

S = 8.314 J K—1 mol–1 × 2.303 log 2

= 5.7 J K–1 mol–1

The experimental value of residual entropy is lower 5.7 J K–1 mol–1

Remarks: Substances such as CO, N2O, H2O, H2 have residual entropy. Therefore, in the
reactions where one or more of such substances are involved the entropy change is finite even
at absolute zero. This type of observation is called as exception to the third law or limitation
of third law.

Evaluation of absolute entropy

The absolute entropy of a system can be evaluated using the relations derived from the
second law of thermodynamics and then applying the third law. From the second law of
thermodynamics we know that the entropy

change of a system is related to its heat capacity at constant pressure by

139
 Calculation of absolute entropy from heat capacity by evaluation
TK
C
of ∫ P dT
0K T

CP
dS = dT (i)
T

On integration equation (i) between the limits T = T1, S = S1 and T = T2, S = S2 , we get
S2 T2
CP
∫ dS =∫ dT
S1 T1 T

T2
C
S2 – S1 = ∫ P dT
T1 T

T2
C
Or, S2 = S1 + ∫ P dT (ii)
T1 T

On introducing the third law of thermodynamics that

when T1 = 0 K, S1 = 0

and when T2 = T K, S2 = So(T) = Absolute entropy at temperature T

equation (ii) gives

TK
o C
S (T) = ∫ P dT (iii)
0K T

The value of absolute entropy So(T) can be evaluated provided the integral on right side of
equation (iii) is known.

Note: Absolute entropy So(T) is also called third law entropy, because it is calculated by
assuming the validity of the third law of thermodynamics that at T = 0 K, So(T) = 0.

The value of above integral is evaluated by the method of extrapolation. In this method the
heat capacities of the substance are measured at different temperatures. The experiment is
carried up to a lower temperature of 10 K (because the measurements can not be made right
up to 0 K). These experimental values of CP/T are plotted against the corresponding
temperatures.(T). The curve thus obtained is extended up to T = 0 K. The area under the curve
from T = 0 to T = T (the temperature of interest) gives the value of integral and thus the value
of absolute entropy So(T) is evaluated.

Note: The heat capacity from 0 K to 10 K may also be estimated by Debye equation

3 4
CV = 3R[ πr (T / θ) 3 ] = a(T/ θ )
4

140
It is assumed that for a solid CV = CP at and near 0 K

Method of calculation of absolute entropy of a gaseous substance A at 298 K which also

exists in α and β physical modifications in solid state

The method of calculation of absolute entropy may be considered to involve the calculation
of entropy change for the following process

A(s, 0 K, 1 atm) ⎯⎯→ A(g, 298 K, 1 atm) (I)

∆S (I) = So (A, g, 298 K, 1 atm) – So (A, s, 0 K, 1 atm)

But So (A, s, 0 K, 1 atm) = 0 .. third law

Therefore, ∆S (I) = So (A, g, 298 K, 1 atm) = Absolute entropy of A

To calculate the value of ∆S (I) and thus So (A, g, 298 K, 1 atm) let us assume that the main
process (I) takes place in to the following steps.

(1) Heating solid A from T= 0 K to T= Tt (transition temperature)

(2) Transition from α to β at T= Tt

(3) Heating of β from T = Tt to T= Tm (melting point)

(4) Melting of solid A ( ) at T= Tm

(5) Heating of liquid A from T = Tm to T= Tb (boiling point)

(6) Evaporation of liquid A at T= Tb

(7) Heating of gas A from T= Tb to T = 298 K

The entropy is a state function and change in entropy is the same whether the change is
carried in a single step as indicated by (I) or in several steps as indicated by steps (1) to (7).
Thus
(I) (7)
A(s, 0 K, 1 atm) ⎯⎯→ A(g, 298 K, 1 atm) ←⎯⎯ A(g, Tb )

↓ (1) ↑ ( 6)

A(α, Tt ) ⎯⎯→
(2) (3)
A( , Tt ) ⎯⎯→ (4)
A( , Tm ) ⎯⎯→ (5)
A(l, Tm ) ⎯⎯→ A(l, Tb )

∆So(I) = So = ∆So (1) + ∆So (2) + ∆So (3)

+ ∆So (4) + ∆So (5) + ∆So (6) + ∆So (7)

Tt Tm
C P (α ) ∆t H C P (β) ∆ fus H
= ∫
0
T
dT +
Tt
+ ∫
Tt
T
dT +
Tm

141
 Step Sυ /JK–1 mol–1

Tb 298 K
C P (l ) ∆ vap H C P (g )
+ ∫
Tm
T
dT +
Tb
+ ∫
Tb
T
dT

The calculation of absolute entropy (Sυ) of nitrogen gas at 298 K and 1 atm is summarized
below and the values for other substances are given in table 4.

Steps of evaluation of Sυ of nitrogen

35.61 K
C P (α )
(1) Heating solid N2 from T= 0 K to T= 35.61 K ∫
0
T
dT = 27.2

∆t H 228.9
(2) Transition from α to β at 35.61 K = = 6.4
Tt 35.61

T
m
C P (β)
 Heating β from 35.61 K to 63.14 K ∫
Tt
T
dT = 23.4

∆ fus H 720.9
(4) Melting at Tm = 63.14 K = = 11.4
Tm 63.14

Tb
CP (l )
(5) Heating liquid N2 from Tm to Tb
T
∫ T
dT =12.4
m

∆ vap H 5535
(6) Evaporation of liquid N2 at Tb = = 71.6
Tb 77.32

298 K
C P (g )
(7) Heating N2 gas from Tb to 298 K ∫
Tb
T
dT = 39.2

(I) N2(s, 0 K, 1 atm) ⎯⎯→ N(g, 298 K, 1 atm) 191.6

142
 Substance S Θ / JK–1 mol–1 Substance S Θ / JK–1 mol–1

H2 (g) 130.6 S (rhombic) 31.9

He (g) 126.0 NO2 (g) 240.5

N2 (g) 191.5 N2O (g) 304.3

O2 (g) 205.0 NaCl (s) 72.4

Halogens KCI (s) 82.7

F2 (g) 203.3 CaCO3 (s) 92.9

CI2 (g) 223.0 Al2O3 (s) 51.0

Br2 (l) 152.3 AgCl (s) 96.1

I2(s) 116.7
Allotropes of carbon

Hydrogen halides C (graphite) 5.7

HF (g) 173.7 C (diamond) 2.4

HCI (g) 186.7 Hydrocarbons

HBr (g) 198.5 CH4 (g) 186.2

HI (g) 206.3 C2H6 (g) 229.5

Common
C3H8 (g) 270.9
substances

CO(g) 197.9 C4H10 (g) 310.8

CO2(g) 213.6 C2H4 (g) 219.0

H2O (g) 188.7 C2H2 (g) 201.0

Compounds
H2S (g) 205.6
with OH group

NH3 (g) 192.5 HOH (l) 69.9

SO2 (g) 248.5 CH3OH (l) 126.8

SO3 (g) 256.2 C2H5OH (l) 160.7

143
 Discussion of absolute entropies

The values of absolute entropy of substances reveal the following interesting facts:

(1) The entropy of graphite (5.7 J K–1 mol–1) is greater than that of diamond (2.4 J K–1 mol–1).
This is in tune with the fact that diamond has a compact structure than graphite. That is, there
is less randomness in the lattice of diamond as compared to that in graphite.

(2) The absolute entropies of halogens (Cl2 = 223 JK–1 mol–1, Br2 = 152 JK–1 mol–1, I2 = 117
JK–1 mol–1) confirm the trend S(gas) > S(l) > S(s) which suggests that there is more
randomness in gas as compared to liquid and solid

(3) The entropy hence randomness increases with increasing molar mass in a family of
compounds. This is clear from the trends in the Sυ values of alkanes.

Alkane CH4 C2H6 C3H8 C4H10

Sυ/ JK–1 mol–1 186.2 229.5 270.9 310.8

(4) The entropy of hydrogen (130.6 JK–1 mol–1) is greater than the entropy of helium (126
JK–1 mol–1) though the molar mass of He is twice the molar mass of H2. This suggests that in
H2 (a diatomic molecule) the entropy arises due to translational, rotational and vibrational
motions of the H–H system, while in He (a monotomic molecule) there is only translational
motion

Need of a new thermodynamic property

The change of internal energy or change of enthalpy or the change of entropy of the system
alone cannot be used as a criterion to decide the direction of a process because of the
following reasons.

(i) The use of change of the internal energy [(∆U)S, V ≤ 0] or change of enthalpy [(∆H)S, P ≤ 0]
requires the condition of constant entropy which is not easy to maintain.

(ii) The use of total entropy change (∆Suniverse ≥ 0) requires the calculation of entropy changes
for both the system and surroundings. Here again one may not like to bother directly
about the surroundings while concentrating on the investigation of the system.

In view of the above limitations of the use of the changes in U, H and S separately, we need
new thermodynamic function or functions of the system which should satisfy the following
requirements:

(i) The new function must be able to predict the direction of the process

(ii) It should automatically incorporate the internal energy / enthalpy and entropy changes of
the system.

(iii) If required the changes in new function of the system should also account for the changes
of entropies of both the system and surroundings.

Two thermodynamic functions namely Gibbs energy (G) and Helmholtz energy (A)
are introduced which fulfill the above requirements. The change in Gibbs energy (∆G) serves

144
as driving force at constant temperature and constant pressure while Helmholtz energy (∆A)
acts as driving force at constant temperature and constant volume.

Comments:

(i) The function G is called Gibbs free energy or free energy or Gibbs energy.

(ii) The function A is called Helmholtz free energy or work function or Helmholtz
energy

(iii) The use of the last name of each function is the IUPAC recommendation.

Gibbs energy

Gibbs energy is an important thermodynamic property which automatically accounts for the
enthalpy and entropy of the system. It was introduced by American physicist J.W. Gibbs and
is therefore, called Gibbs energy function denoted by symbol G in the honour of the scientist.
Gibbs energy function is defined by

G = H – TS

where H = Enthalpy of the system

S = Entropy of the system

T = Temperature on kelvin scale

Characteristics of Gibbs energy (G)

1. Gibbs energy is an extensive property. Its value depends on the amount of the system.

2. Gibbs energy of a system is a state property. For a known amount of the system it depends
only on the state

variables (T, P, V). If the state variables are changed the Gibbs energy is also changed.

3. The change in Gibbs energy (∆G) does not depend on the path by which the final state of
the system is reached.

4. The change in Gibbs energy of the system is related to the entropy change of the universe
as

∆Gsystem= – [T∆Ssystem +T∆Ssurroundings] = – T∆Stotal = – T∆Suniverse

5. For a spontaneous process there is decrease in Gibbs energy and ∆Gsystem < 0

6. In an isothermal reversible process the decrease in Gibbs energy is equal to the net useful
work that can be obtained from the system.

Gibbs energy change and useful work

By useful work we mean the total possible work minus the mechanical work involved in a
system.

145
 w (useful) = w (total) – w (mechanical)

= w (net)

At constant T and P in a reversible process the free energy change (∆G) and w (net) are
related by

∆G = w (net)

Derivation of the equation ∆G = w (net)

We shall start with the definitions of thermodynamic functions of G and H then derive the
relation between ∆G and w(net)

G = H – TS Definition of free energy G

H = U + PV Definition of enthalpy H

Therefore, G = U + PV – TS

If the changes are made in the system so that its properties are also changed, we shall have

∆G = ∆(U + PV –TS)

= ∆U + ∆(PV) –∆ (TS)

= ∆U + P∆V + V∆P – T∆S –S ∆T

For isothermal process ∆T = 0 and for isobaric process ∆P = 0. Therefore, under isothermal
and isobaric conditions

∆G = ∆U + P∆V – T∆S .(i)

From the first law of thermodynamics, we have

∆U =.q + w

Second law of thermodynamics gives

T ∆S = qrev

For a reversible change the combined form of the two laws is written as

∆U = q + w = T∆S + w (ii)

On substituting the expression for ∆U from equation (ii) into equation (i), we get

∆G = T∆S + w + P∆V –T∆S

= w + P∆V

The mechanical work (involving pressure - volume work) is defined as

146
 w (mechanical) = – P∆V

Therefore, ∆G = w – w (mechanical) = w (nonmechanicaI)

= w (net) = w (useful)

This relation is valid for isothermal isobaric reversible process. In reversible process
the work obtained from the system is maximum therefore useful work is also written as w
(max)

Interpretation of the relation ∆G = w (net)

In an isothermal isobaric reversible process:

1. The increase in free energy of the system is equal to the work done on the system over
and above the mechanical work.

2. The decrease in free energy of the system is equal to the net work that can be
obtained from the system

Application of the relation ∆G = w (net)

In electrochemical processes, the network that can be obtained from the system is equal to the
electrical work.

w (net) = w (electrical)

In a galvanic cell

w (electrical) = – nFE = w (net)

where n = moles of electrons involved in a redox reaction

F = faraday constant = 96500 C mol–1

E = potential difference (emf of reversible cell)

Therefore, ∆G = w (net ) = w (electrical) = – nFE

(i) The electrical work can be used for different purposes. That is why w(net) is called useful
work and ∆G is called free energy change or available energy.

(ii) The relation ∆G = -nFE implies that decrease of free energy in a chemical reaction is the
cause of cell potential and such reactions are source of electricity.

Relation between ∆G system and ∆S universe

At constant pressure and constant temperature the change of free energy of the system is
related to the enthalpy change (∆H) and entropy change (∆S) by

∆G system = ∆H system – T ∆S system (i)

147
 At constant pressure the heat exchanged between the system and surroundings is
equal to the enthalpy change of the system.

q system = ∆Hsystem at constant pressure

But heat exchanged between the system and surroundings are related by

qsurroundings = – qsystem = – ∆Hsystem

Therefore, entropy change of surroundings is given by

q surroundings q ssystem ∆H ssystem

.∆Ssurroundings = =– =–
T T T

Or, ∆Hsystem = –T ∆S surroundings (ii)

Substituting equation (ii) into equation (i), we get

∆G system = –T ∆S surroundings – T∆Ssystem

= –[T ∆S surroundings + T ∆Ssystem] (iii)

But ∆S surroundings + ∆Ssystem = ∆Suniverse (iv)

Therefore, from equations (iii) and (iv), we get

∆G system = – T∆Suniverse

Or, – ∆G system = T∆Suniverse

Conclusion: The decrease in the free energy of the system is equal to increase in the entropy
of the universe multiplied by the kelvin temperature.

Free energy change and spontaneous processes

We have already discussed that for a spontaneous process the total entropy change
(∆Suniverse) must be positive. Therefore, in view of the relation ∆G system = – T∆Suniverse, the free
energy change of the system must be negative. That is, at constant temperature and constant
pressure the free energy of the system must decrease in a spontaneous process and

(∆G)T, P < 0 .for a spontaneous process

A decreasing quantity must attain its minimum value at equilibrium after which there is no
net change, therefore.

(∆G)T, P = 0 at equilibrium

If there is increase in the free energy, the process is nonspontaneous (forbidden)

(∆G)T, P > 0 nonspontaneous

These criteria may be summarized as follows

148
 (i) ∆G is negative Spontneous process

(ii) ∆G is posive Nonspontneous process

(iii) ∆G is zero Equilibrium state

Criteria of spontaneous process in terms of ∆H and T ∆S

A change is spontaneous only when ∆G is negative. Therefore, it is essential to learn

the roles of ∆H and

T ∆S in the relation ∆G = ∆H – T∆.S and decide the direction of the change under different
situations.

(1) When ∆H is negative and ∆S is positive

From the relation ∆G = ∆H – T∆.S, it is clear that under the given situation ∆G is
negative and therefore, the change is spontaneous. In other words, we may state that an
exothermic reaction with positive entropy change is always spontaneous.

(2) When ∆H is positive and ∆S is negative

From the relation ∆G = ∆H – T∆.S, it is clear that under the given situation ∆G is
positive and therefore, the change is nonspontaneous (forbidden) in the desired direction. In
other words, we may state that an endothermic reaction with negative entropy change is never
spontaneous However, it may be spontaneous in the opposite direction

(3) When both ∆H and ∆S are positive

At lower temperature T∆S will be small therefore, ∆H will predominate. Thus ∆G =

∆H – T∆S will be positive and the change will be nonspontaneous. But at higher temperature
T∆S will be larger than ∆H. Therefore, ∆G = ∆H – T∆.S will be negative and the change will
be spontaneous. In other words, we may state that an endothermic reaction with positive
entropy change is spontaneous at high temperature but nonspontaneous at lower temperature.

(4) When both ∆H and ∆S are negative

At lower temperature T∆S will be small therefore, ∆H will predominate. Thus ∆G =

∆H – T∆S will be negative and the change will be spontaneous. But at higher temperature
T∆S will predominate ∆H. Therefore, ∆G = ∆H – T∆.S will be positive and the change will
be nonspontaneous. In other words, we may state that an exothermic reaction with negative
entropy change is spontaneous at lower temperature but nonspontaneous at higher
temperature.

Summary of the direction of the change in terms of ∆H and T∆S

S. No. Sign of ∆H Sign of ∆S Sign of ∆G Nature of the change

(1) – (exothermic) positive Always negative Spontaneous

(2) + (endothermic) negative Always positive

Nonspontaneous

149
 Important deductions from equation dG= VdP – S dT

(3) + (endothermic) positive Positve at lower T Nonspontaneous

Negative at higher T Spontaneous

(4) – (exothermic) negative Negative at lower T Spontaneous

Positive at higher T Nonspontaneous

Example. An exothermic reaction is sometimes thermodynamically not spontaneous.

Give reason

Soluion. An exothermic reaction is sometimes thermodynamically not spontaneous under the

conditions when the entropy change ∆S is large negative and temperature T is very high

Reason. Under the above conditions T∆S is large postive and therefore, ∆G = ∆H – T∆S is
positive

Variation of Gibbs energy (G) with temperature and pressure

G = H – TS and H = U + PV

Therefore, G = U + PV –TS (i)

For small changes

dG = dU + PdV +VdP – TdS – SdT (ii)

From combined form of first and second laws thermodynamics, we have

TdS = dU + PdV (iii)

From equations (ii) and (ii), we get

dG = TdS +VdP – TdS – SdT

= VdP – S dT (iv)

From equation (vi) it is observed that Gibbs function depends on pressure and temperature
that is, G =G(P, T). Its total differential is written as

∂G ⎞ ∂G
dG = ⎛⎜ ⎟ dP + ⎛⎜ ⎞⎟ dT (v)
⎝ ∂P ⎠ T ⎝ ∂T ⎠ P

(i) When T is constant, dT = 0, therefore,

⎛ ∂G ⎞
⎜ ⎟ =V
⎝ ∂P ⎠ T

150
Volume is positive and thus right hand side of the above equation is positive. Therefore,
( ∂G / ∂P )T is also positive. This means that at constant temperature, Gibbs energy increases
with increase of pressure and decreases with decrease of pressure.

(ii) When P is constant, dP = 0, therefore,

⎛ ∂G ⎞
⎜ ⎟ = –S
⎝ ∂T ⎠ P

Entropy (S) is positive and thus right hand side of the above equation is negative. Therefore,
( ∂G / ∂T )P is also negative. This means that at constant pressure, Gibbs energy decreases with
increase of temperature and increases with decrease of temperature.

Note: The entropy depends on the nature of the three states matter as given by

S(gas) > S(liquid) > S(solid)

Therefore, with increase of temperature there is more decrease in Gibbs energy of a gas than
that of a liquid and there is more decrease in G of a liquid than that of a solid

Calculation of ∆G for isothermal pressure change of an ideal gas

In an isothermal process, T is constant and dT = 0, therefore, equation dG= VdP – S

dT is written as

dG = VdP (i)

A finite change in G is calculated by integrating equation (i) for the change of state from
initial state 1 to final state 2
2 2
∫1 ∫
dG = VdP
1
(ii)

Equation (ii) is applicable for all the three states of matter. But right hand side of this
equation has different values for different substances. Therefore, variation of G is also
different for different type of substances.

(a) For condensed states of matter namely liquids ad solids

The volume of a liquid or solid is almost independent of pressure at constant temperature.

Therefore, it can be taken outside the integration sign of equation (ii). Thus
2 2
∫ dG
1
= V ∫ dP
1

Or, G2 – G1 = V(P2 – P1)

Or, ∆G = V∆P

(b) For an ideal gas

The volume of an ideal gas is given by V= nRT/P. Therefore, equation (ii) is rewritten

151
as
2 2 dP 2
∫ dG
1
= nRT ∫
1 P ∫
= nRT d ln P
1

P2
Or, G2 – G1 = ∆G = nRT ln (iii)
P1

From equation (iii) it is clear that ∆G is negative for isothermal expansion of an ideal gas
(Gibbs energy decreases as the gas expands) while it is positive for isothermal compression
(Gibbs energy increases as the gas is compressed).

Helmholtz energy

Helmholtz energy function (A) was introduced by German physicist Hermann Ludwig
Ferdinand von Helmholtz and is defined by

A = U – TS

where U is internal energy, T is Kelvin temperature and S is entropy. The symbol A is the first
letter of the German word Arbeit which means work. Therefore, Helmholtz energy (A) is also
called work function.

Helmholtz energy as work function

Definition: A = U – TS (i)

For infinitesimally small change

dA = dU – TdS – SdT (ii)

From the combined form of first and second laws of thermodynamics we have

dU = dq + dw =TdS + dwrev (iii)

From equations (ii) and (iii) we get

dA = TdS + dwrev – TdS – SdT

= dwrev – SdT (iv)

For isothermal process, T is constant and dT = 0, therefore, equation (iv) reduces to

(dA)T = dwrev

For finite changes

(∆A)T = wrev

Or, – (∆A)T = - wrev= wrev(by)

The work done by a system under isothermal reversible condition is the maximum work
Therefore, decrease in Helmholtz energy is equal to the isothermal reversible maximum work

152
which can be obtained from a system It is because of this relation that A is called work
function.

Relation between ∆A system and ∆S universe

At constant volume and constant temperature the change of Helmholtz energy of the system
is related to the internal energy change (∆U) and entropy change (∆S) by

∆A system = ∆U system – T ∆S system (i)

At constant volume the heat exchanged between the system and surroundings is equal
to the internal energy change of the system.

q system = ∆Usystem at constant volume

But heat gained by the system is equal to heat lost by the surroundings and vice versa. That
is,

qsurroundings = – qsystem = – ∆Usystem

Entropy change of surroundings is given by

q surroundings q ssystem ∆U ssystem

∆Ssurroundings = =– =–
T T T

Or, ∆Usystem = –T ∆S surroundings (ii)

Substituting equation (ii) into equation (i), we get

∆A system = –T ∆S surroundings – T∆Ssystem

= –[T ∆S surroundings + T ∆Ssystem] (iii)

But ∆S surroundings + ∆Ssystem = ∆Suniverse (iv)

From equations (iii) and (iv), we get

∆A system = – T∆Suniverse

Or, – ∆A system = T∆Suniverse

Conclusion: The decrease in the Helmholtz energy of the system is equal to increase in the
entropy of the universe multiplied by the kelvin temperature.

Helmholtz energy change and spontaneous processes

We have already discussed that for a spontaneous process the total entropy change (∆Suniverse)
must be positive. Therefore, in view of the relation ∆A system = – T∆Suniverse , the Helmholtz
energy change of the system must be negative. That is, at constant temperature and constant
volume in a spontaneous process the Helmholtz energy of the system must decrease and

(∆A)T, V < 0 for a spontaneous process

153
 A decreasing quantity must attain its minimum value at equilibrium after which there is no
change, therefore,

(∆A)T, V = 0 at equilibrium

If there is increase in the Helmholtz energy, the process is nonspontaneous (forbidden)

(∆A)T, V > 0 nonspontaneous

These criteria may be summarized as follows

(i) ∆A is negative Spontneous process

(ii) ∆A is posive Nonspontneous process

(iii) ∆A is zero Equilibrium state

Summary of the direction of the change at constant T and V in terms of ∆U and

T∆S

S. No. Sign of ∆U Sign of ∆S Sign of ∆A Nature of the change

(1) – (exothermic) positive Always negative Spontaneous

(2) + (endothermic) negative Always positive

Nonspontaneous

(3) + (endothermic) positive Positve at lower T Nonspontaneous

Negative at higher T Spontaneous

(4) – (exothermic) negative Negative at lower T Spontaneous

Positive at higher T Nonspontaneous

ADVANTAGES OF USING ∆A AND ∆G OVER ∆S

(i) Use of entropy change to predict the nature of a process requires the knowledge of the
entropy changes for both the system and surroundings. But the change of Helmholtz energy
or change of Gibbs energy of the system alone is sufficient to predict the direction of a
process.

(ii) While using the entropy change it is required that energy and volume are constant (∆S)U,
V. >0. But it is not very convenient to maintain a constant energy condition in the laboratory.
On the other hand, while using free energy change ∆A or ∆G only the state variables (T, V, or
T, P) are to be kept constant, which are easy to maintain in the laboratory. Therefore, the use
of ∆As or ∆G is preferred over ∆S as a driving force to predict the direction of a process

Advantages of using ∆G over ∆A

When ∆G is used to predict the direction of a process it is required to maintain

154
constant temperature and constant pressure as (∆G)T, P < 0 for a spontaneous process.. On the
Important deductions from equation dA= – PdV – S dT

other hand, if ∆A is used to decide the direction of a process the temperature and volume are
to be kept constant as (∆A)T, V < 0 for spontaneous process. Since in the chemistry laboratory
usually the experiments are performed at constant temperature and constant pressure,
therefore, the use of ∆G as driving force is preferred over the use of ∆A which requires the
condition of constant T and constant V.

Variation of Helmholtz energy (A) with volume and temperature

A = U – TS (i)

dA = dU – TdS – SdT (ii)

From combined form of first and second laws thermodynamics, we have

dU = TdS –PdV (iii)

From equations (ii) and (iii), we get

dA = TdS –PdV – TdS – SdT

= –PdV – S dT (iv)

From equation (iv) it is observed that A = A(V, T) and its total differential is written as

∂A ⎞ ⎛ ∂A ⎞
dA = ⎛⎜ ⎟ dV + ⎜ ⎟ dT (v)
⎝ ∂V ⎠ T ⎝ ∂T ⎠ V

(i) When T is constant, dT = 0, therefore,

⎛ ∂A ⎞
⎜ ⎟ = –P
⎝ ∂V ⎠ T

Pressure (P) is positive and thus right hand side of the above equation is negative. Therefore,
( ∂A / ∂V )T is also negative. This means that at constant temperature, Helmholtz energy
decreases with increase of volume and increases with decrease of volume

(ii) When V is constant, dV = 0, therefore,

⎛ ∂A ⎞
⎜ ⎟ = –S
⎝ ∂T ⎠ V

Entropy (S) is positive and thus right and side of the above equation is negative. Therefore,
( ∂A / ∂T )V is also negative. This means that at constant volume, Helmholtz energy decreases
with increase of temperature and increases with decrease of temperature.

Calculation of ∆A for isothermal volume change of an ideal gas

For isothermal process

155
 dA = –PdV (i)

A finite change in A is calculated by integrating equation (i) for the change of state from
initial state 1 to final state 2
2 2
∫ dA = – ∫ PdV
1 1
(ii)

For an an ideal gas we have PV = nRT and P= nRT/V. Therefore, equation (ii) is rewritten as
2 2 dV 2
∫ 1
dA = –nRT ∫1 V ∫
= – nRT d ln V
1

V2
Or, A2 – A1 = ∆A = – nRT ln (iii)
V

From equation (iii) it is clear that ∆A is negative for isothermal expansion of an ideal gas
(Gibbs energy decreases as the gas expands) while it is positive for isothermal compression
(Gibbs energy increases as the gas is compressed).

Relation between G and A

G = H –TS =U + PV –TS (i)

A = U – TS (ii)

From equations (i) and (ii) we get

G = A+ PV

Or, G – A = PV

For a finite change in the state of the system

∆G – ∆A = ∆(PV) = P2V2 – P1V1

At constant temperature, P2V2 = P1V1 for an ideal gas

Therefore, ∆G - ∆A = 0

and ∆G = ∆A for an ideal gas at constant temperature

In terms of change of pressure and volume

P2 V2
nRT ln = – nRT ln for an ideal gas at constant temperature
P1 V

VARIATION OF G AND A WITH T

Variation of free energy functions with T is called Gibbs Helmholtz equation. Such variation
is studied for G and A separately.

156
(1) Variation of G with T at constant P

The change of Gibbs energy is given by

dG = VdP – S dT (i)

At constant pressure, dP = 0 and thus

⎛ ∂G ⎞
⎜ ⎟ =–S (ii)
⎝ ∂T ⎠ P

From equations (ii) and (i) we get

∂G
G = H + T ⎛⎜ ⎞⎟
⎝ ∂T ⎠ P

∂G ⎞
Or, H = G – T ⎛⎜ ⎟ (iii)
⎝ ∂T ⎠ P

Equation (iii) is called Gibbs Helmholtz

Second form of Gibbs Helmholz equation: For finite changes in H and G Gibbs Helmholtz
equation is written as

∂∆G ⎞
∆H = ∆G – T ⎛⎜ ⎟ (iv)
⎝ ∂T ⎠ P

On dividing both sides of equation (iv) by T 2, we get

∆H ∆G − T∂ (∆G / ∂T ) P
= (v)
T 2
T2

Now right hand side of equation (v) is the differential of – ∆G/T with respect to T. Therefore,

∆H ∂ (∆G / T ) ⎞
= – ⎛⎜ ⎟
T2 ⎝ ∂T ⎠P

⎛ ∂ ( ∆G / T ) ⎞ ∆H
Or, ⎜ ⎟ =– 2 (vi)
⎝ ∂T ⎠P T

Third form of Gibbs Helmholtz equation: We know that dT = – T2 d(1/T).How?

d ⎛⎜ ⎞⎟ = – 2 dT
1 1
⎝T ⎠P T

dT = – T2 d ⎛⎜ ⎞⎟
1
Or,
⎝T ⎠P

Therefore, equation (xi) is rewritten as

157
 ⎛ ∂ (∆G / T ) ⎞
⎜⎜ ⎟⎟ = ∆H
⎝ ∂ (1 / T ) ⎠ P

Integrated form of Gibbs Helmholtz equation: Equation (ix) is written as

∆G ⎞ ∆H
∫ d ⎛⎜ ⎟= – ∫ dT + I
⎝ T ⎠ T2

If we suppose that ∆H is independent of temperature, then integration of the above equation

gives

∆G ∆H
= +I
T T

Here , I is the integration constant and its value can be evaluated if the values of ∆G and ∆H
are known

Gibbs Helmholtz equation for work function (A)

Starting with the definition of Helmholtz energy (A) we can derive the following equations.

∂A
A – T ⎛⎜ ⎞⎟ = U (i)
⎝ ∂T ⎠ V

⎛ ∂ (∆A / T ) ⎞ ∆U
⎜ ⎟ =– 2 (ii)
⎝ ∂T ⎠V T

⎛ ∂ ( ∆A / T ) ⎞
⎜⎜ ⎟⎟ = ∆U (iii)
⎝ ∂ (1 / T ) ⎠ V

∆A ∆U
= + Integration constant (iv)
T T

MASTER EQUATIONS OF THERMODYNAMICS

Thermodynamics is an exact science. It is very systematic and interesting. Therefore,

to become a master of the subject one needs to remember the following fundamental
thermodynamic relations

dU =dq – PdV (i)

dq = TdS (ii)

H = U + PV (iii)

A = U – TS (iv)

G = H + TS (v)

158
 Using these equations any other desired relation can be derived keeping in mind the
fact that U, H, S, A and G etc., are state functions and obey Euler’s reciprocity relation.

Maxwell relations

There are four main Maxwell relations which provide the expressions for partial derivatives
and thus the rate of change of one thermodynamic property with another.

⎛ ∂T ⎞ ⎛ ∂P ⎞
(i) ⎜ ⎟ = –⎜ ⎟
⎝ ∂V ⎠S ⎝ ∂S ⎠ V

⎛ ∂T ⎞ ⎛ ∂V ⎞
(ii) ⎜ ⎟ = ⎜ ⎟
⎝ ∂P ⎠ S ⎝ ∂S ⎠ P

⎛ ∂S ⎞ ⎛ ∂P ⎞
(iii) ⎜ ⎟ = ⎜ ⎟
⎝ ∂V ⎠ T ⎝ ∂T ⎠ V

⎛ ∂S ⎞ ⎛ ∂V ⎞
(iv) ⎜ ⎟ =– ⎜ ⎟
∂P
⎝ ⎠T ⎝ ∂T ⎠ P

∂T ⎞ ⎛ ∂P ⎞
(1) Derivation of Maxwell relation ⎛⎜ ⎟ = –⎜ ⎟
⎝ ∂V ⎠S ⎝ ∂S ⎠ V

We shall start with the combined form of first and second laws of thermodynamics and give
the most convenient and accurate method of derivation of Maxwell relation.

dU =TdS – PdV (i)

Remembering that for a state function ( )

d = M dx + N dy (ii)

and Euler’s reciprocity relation states that

⎛ ∂M ⎞ ⎛ ∂N ⎞
⎜⎜ ⎟⎟ = ⎜ ⎟ (iii)
⎝ ∂y ⎠ x ⎝ ∂x ⎠ y

Now, U is a state function and dU is exact differential. Therefore, in view of equations (iii)
and (i) we can state that differential of T with respect to V at constant S is equal to the
differential of –P with respect to S at constant T. That is,

⎛ ∂T ⎞ ⎛ ∂P ⎞
⎜ ⎟ = –⎜ ⎟ … Maxwell relation
⎝ ∂V ⎠ S ⎝ ∂S ⎠ V

∂T ⎞ ⎛ ∂V ⎞
(2) Derivation of Maxwell relation ⎛⎜ ⎟ = ⎜ ⎟
⎝ ∂P ⎠S ⎝ ∂S ⎠ P

The combined form of first and second laws of thermodynamics in terms of enthalpy change
is given by

159
 dH =TdS + VdP

Now, H is a state function and dH is exact differential. Therefore, in view of Euler’s

reciprocity relation it can be stated that differential of T with respect to P at constant S is
equal to the differential of V with respect to S at constant T. That is,

⎛ ∂T ⎞ ⎛ ∂V ⎞
⎜ ⎟ = ⎜ ⎟ Maxwell relation
⎝ ∂P ⎠ S ⎝ ∂S ⎠ P

∂S ⎞ ⎛ ∂P ⎞
(3) Derivation of Maxwell relation ⎛⎜ ⎟ = ⎜ ⎟
⎝ ∂V ⎠ T ⎝ ∂T ⎠ V

The change in Helmholtz energy is given by

dA = –SdT – PdV

Now, A is a state function and dA is exact differential. Therefore, in view of Euler’s

reciprocity relation it can be stated that differential of –S with respect to V at constant T is
equal to the differential of –P with respect to T at constant V. That is,

⎛ ∂S ⎞ ⎛ ∂P ⎞
⎜ ⎟ = ⎜ ⎟ Maxwell relation
⎝ ∂V ⎠ T ⎝ ∂T ⎠ V

∂S ⎞ ⎛ ∂V ⎞
(4) Derivation of Maxwell relation ⎛⎜ ⎟ =– ⎜ ⎟
∂P
⎝ ⎠T ⎝ ∂T ⎠ P

The change in Gibbs energy is given by

dG = –SdT + VdP

Now, G is a state function and dG is exact differential. Therefore, in view of Euler’s

reciprocity relation it can be stated that differential of –S with respect to P at constant T is
equal to the differential of V with respect to T at constant P. That is,

⎛ ∂S ⎞ ⎛ ∂V ⎞
⎜ ⎟ =– ⎜ ⎟ Maxwell relation
∂P
⎝ ⎠T ⎝ ∂T ⎠ P

Significance of Maxwell relations

(i) Maxwell relations provide us methods of evaluation of even those properties which are
otherwise very difficult to measure directly in the laboratory. For example

(a) Variation of entropy with volume at constant temperature cannot be studied directly by
experimental method.

Reason: We do not have an apparatus called entropymeter as we have barometer for pressure
or. thermometer for temperature

160
 ∂S ⎞ ⎛ ∂P ⎞
Remedy: Maxwell relation ⎛⎜ ⎟ = ⎜ ⎟ provides a method to estimate the value of
⎝ ∂V ⎠ T ⎝ ∂T ⎠ V
⎛ ∂S ⎞ ⎛ ∂P ⎞
⎜ ⎟ in terms of the change of pressure with temperature at constant volume ⎜ ⎟ which is
⎝ ∂V ⎠ T ⎝ ∂T ⎠ V
also equal to the ratio of coefficient of thermal expnsion and isothermal compressibity
coefficient (α )

(b) Variation of entropy with pressure at constant temperature cannot be studied directly by
experimental method.

∂S ∂V
But Maxwell relation ⎛⎜ ⎞⎟ = – ⎛⎜ ⎞⎟ provides a method to estimate the value of
⎝ ∂P ⎠ T ⎝ ∂T ⎠ P
⎛ ∂S ⎞ ⎛ ∂V ⎞
⎜ ⎟ in terms of ⎜ ⎟ = – αV
∂P
⎝ ⎠T ⎝ ∂T ⎠ P

(ii) Maxwell relations are useful to derive other important thermodynamic relations in a
simple way. For example,

(a) Thermodynamic equation of state in terms of change in internal energy

Combined form of first and second laws of thermodynamics states that

TdS = dU +PdV (i)

On dividing equation (i) by dV at constant temperature we gave

∂S ⎞ ⎛ ∂U ⎞
T ⎛⎜ ⎟ = ⎜ ⎟ +P (ii)
⎝ ∂V ⎠ T ⎝ ∂V ⎠ T

⎛ ∂U ⎞ ⎛ ∂S ⎞
Or, ⎜ ⎟ = T ⎜ ⎟ –P (iii)
⎝ ∂V ⎠T ⎝ ∂V ⎠ T

But Maxwell relation states that

⎛ ∂S ⎞ ⎛ ∂P ⎞
⎜ ⎟ = ⎜ ⎟ (iv)
⎝ ∂V ⎠ T ⎝ ∂T ⎠ V

From equations (iii) and (iv) we get

⎛ ∂U ⎞ ⎛ ∂P ⎞
⎜ ⎟ =T ⎜ ⎟ –P (v)
⎝ ∂V ⎠ T ⎝ ∂T ⎠ V

Equation (v) is called thermodynamic equation of state. It provides a method to study

the variation of internal energy with volume at constant temperature in terms of PVT data for
any substance.

(b) Thermodynamic equation of state in terms of change in enthalpy

Entropy change and enthalpy change are related by

161
 TdS = dH – VdP (i)

On dividing equation (i) by dP at constant temperature we gave

∂S ⎞ ⎛ ∂H ⎞
T ⎛⎜ ⎟ = ⎜ ⎟ –V (ii)
⎝ ∂P ⎠ T ⎝ ∂P ⎠ T

⎛ ∂H ⎞ ⎛ ∂S ⎞
Or, ⎜ ⎟ = T ⎜ ⎟ +V (iii)
⎝ ∂P ⎠ T ⎝ ∂P ⎠ T

But Maxwell relation states that

⎛ ∂S ⎞ ⎛ ∂V ⎞
⎜ ⎟ = –⎜ ⎟ (iv)
⎝ ∂P ⎠ T ⎝ ∂T ⎠ P

From equations (iii) and (iv) we get

⎛ ∂H ⎞ ⎛ ∂V ⎞
⎜ ⎟ = V –T ⎜ ⎟ (v)
⎝ ∂P ⎠ T ⎝ ∂T ⎠ P

Equation (v) provides a method to study the variation of enthalpy with pressure at
constant temperature in terms of PVT data for any substance.

Calculation of standard reaction free energy (∆rGυ)

The standard free energy of a reaction is calculated by the following methods.

(i) Using the relation ∆rGυ = ∆rHυ – T∆rSυ

where

∆rHυ = standard reaction enthalpy.

and ∆rSυ = standard reaction etropy

(a).The value of ∆rHυ is estimated calorimetrically or by the use of standard enthalpy of

formation values of the reactants and products as

∆rHυ = Σν P ∆fHυ (products) – Σν R ∆fHυ (reactants)

(b) The value of ∆rSυ is calculated by the use of standard entropy (Sυ) values of the reactants
and products as

∆rSυ = Σν P Sυ (products) – Σν R Sυ (reactants)

Here ν P = stoichiometric coefficient of the product

and ν R = stoichiometric coefficient of the reactant

(ii) Using the relation ∆rGυ = Σν P ∆fGυ (products) – Σν R ∆fGυ (reactants)

162
Where ∆fGυ = standard free energy of formation.

(a) For compounds the values ∆fGυ are taken from the table of thermodynamic properties.

(b) The standard free energy of formation of an element is assumed to be zero by

convention

∆fGυ (element) = 0

(c) Entropy of an element is not zero at temperatures higher than 0 K

Sυ (element) ≠ 0

Example: Calculate ∆rGυ at 25 oC for the reaction 2NH3 (g) ⎯⎯→ N2(g) + 3 H2(g)

using the following data

Substance NH3 N2 H2

∆fHυ/ kJ mol–1 – 46 – –

Sυ/ J K–1 mol–1 193 192 131

Solution. Formula used ∆rGυ = ∆rHυ – T∆rSυ

For the reaction 2NH3 (g) ⎯⎯→ N2(g) + 3 H2(g)

∆rHυ = Σν P ∆fHυ (products) – Σν R ∆fHυ (reactants)

= ∆fHυ (N2, g) + 3∆fHυ (H2, g) – 2∆fHυ (NH3, g)

Since ∆fHυ (element) = 0, therefore ∆fHυ (N2, g) = 0 and ∆fHυ (H2, g) = 0

Therefore, ∆rHυ = 0 + 3×0 – 2× (– 46 kJ mol–1

= 92 kJ mol–1

∆rSυ = Σν P Sυ (products) – Σν R Sυ (reactants)

= Sυ (N2, g) +3 Sυ (H2, g) – 2 Sυ (NH3, g)

= 192 J K–1 mol–1 + 3×131 J K–1 mol–1 – 2× 193 J K–1 mol–1

= 199 J K–1 mol–1 = 0.199 kJ K–1 mol–1

Therefore, ∆rGυ = ∆rHυ – T∆rSυ

= 92 kJ mol–1 – 298 K× 0.199 kJ K–1 mol–1 = 32.698 kJ mol–1

163
Example. Calculate the change of entropy at 298 K for the formation of urea from
ammonia and carbon dioxide as per equation 2NH3(g) + CO2(g) → NH2CONH2(aq) +
H2O(l) using the following data.

Substance NH3 CO2 H2O NH2CONH2

Sυ / JK−1 mol−1 192.3 213.7 69.8 174.0

Solution. For the reaction 2NH3(g) + CO2(g) → NH2CONH2(aq) + H2O(l)

∆rSυ = [Sυ(NH2CONH2) +Sυ(H2O) — [2 Sυ(NH3+ Sυ (CO2)]

=174.0 + 69.8] JK−1 — [2×192.3 + 213.7]

= 243.8 JK−1 — 598.3 JK−1 mol−1 = − 354.5 JK−1 mol−1

Example. Using the ∆f Gυ values calculate ∆r Gυ for the following reactions and state the
spontaneous and nonspontaneous reactions.

(a) Ca (s) + Cl2 (g) → CaCl2 (s)

(b) HgO (s) → Hg (1) + 1/2 O2 (g)

(c) NH3 (g) + 2 O2 (g) → HNO3 (1) + H2O (1)

Data given:

Compound CaCl2 HgO NH3 HNO3 H2O

∆f Gυ /kJ mol−1 −748.1 − 58.54 − 16.45 − 80.71 − 237.13

Solution.

(a) For the reaction Ca (s) + Cl2 (g) → CaCl2 (s)

∆r Gυ = ∆f Gυ (CaCl2, s) — [∆f Gυ (Ca,s) +∆f Gυ (Cl2, g)

= −748.1kJ mol−1 − [0 +0] = −748.1kJ mol−1

∆r Gυ is negative, therefore the given reaction is spontaneous.

(b) For the reaction HgO (s) → Hg (1) + 1/2 O2 (g)

∆r Gυ = [∆f Gυ (Hg, l) + 1/2 ∆f Gυ (O2, g) ] — ∆f Gυ (HgO, s)

=[0 + 0] — [− 58.54 kJ mol−1] = 58.54 kJ mol−1

∆r Gυ is positive, therefore the given reaction is nonspontaneous.

(c) For the reaction NH3 (g) + 2 O2 (g) → HNO3 (1) + H2O (1)

∆r Gυ = [∆f Gυ (HNO3, l) + ∆f Gυ (H2O.l) ] — [∆f Gυ (NH3, g)+ 2 ∆f Gυ (O2, g) ]

164
 = [− 80.71 − 237.13] kJ mol−1 —[− 16.45 + 2×0] kJ mol−1

= − 301.39 kJ mol−1

∆r Gυ is negative, therefore the given reaction is spontaneous.

Example. Calculate Gibbs energy change (∆r Gυ) for the reaction CaCO3 (s) →CaO (s)
+ CO2 (g) at 1273 K and at 1 bar using the following data

Substance CaCO3 (s) CaO (s) CO2 (g)

∆f Hυ/ kJ mol−1 −1207 −633.2 −393.5

Sυ/ JK−1 mol−1 92.9 39.75 213.74

Is this reaction spontaneous at this temperature and pressure ?

Solution. For the reaction CaCO3 (s) →CaO (s) + CO2 (g) first we shall calculate the values
of ∆r Hυ and ∆r Sυ then the value of ∆r Gυ

Calculation of ∆r Hυ

∆r Hυ = [ ∆f Hυ (CO2) + ∆f Hυ (CaO) ] — ∆f Hυ (CaCO3)]

= [−393.5 +(− 633.2)] kJ mol−1 — (−1207 kJ mol−1)

= −1026.7 kJ mol−1 + 1207 kJ mol−1 = +180.3 kJ mol−1

Calculation of ∆r Sυ

∆r Sυ = [ Sυ (CO2) + Sυ (CaO) ] — Sυ (CaCO3)]

= [213.74 +39.75] JK−1 mol−1 —92.9 JK−1 mol−1

= 253.49 JK−1 mol−1 — 92.9 JK−1 mol−1 = 160.59 JK−1 mol−1

Calculation of ∆r Gυ

∆r Gυ = ∆r Hυ — T×∆r Sυ

= 180.3 kJ mol−1 — 1273 K × 160.59 JK−1 mol−1

=180.3 kJ mol−1 — 204.4 = − 24.1 kJ mol−1

The negative value of ∆r Gυ suggests that the given reaction is spontaneous

Example. Use the following ∆rG values at 1073 K to calculate the change in Gibbs
energy and show that the roasting of zinc sulphide in to zinc oxide is a spontaneous
process

(i) S2(s) + 2 O2(g) ⎯⎯→ 2 SO2(g) ∆rG(i) = − 544 kJ mol-1

165
 (ii) 2 Zn(s) + O2(g) ⎯⎯→ 2 ZnO(s) ∆rG(ii) = − 480 kJ mol-1

(iii) 2 Zn(s) + S2(g) ⎯⎯→ 2 ZnS(s) ∆rG (iii) = − 293 kJ mol-1

Solution. Roasting of zinc sulphide in to zinc oxide is spontaneous if ∆rG is negative for
reaction (A) 2 ZnS(s) + 3 O2(g) ⎯⎯→ 2 ZnO(s) + 2 SO2(g) (A)

Operations: Equation (i) + equation (ii) − equation (iii) = Equation (A)

That is,

S2(s) + 2 O2(g) +2 Zn(s) + O2(g) − [2 Zn(s) + S2(g)] ⎯⎯→ 2 SO2(g)+ 2 ZnO(s) −2

ZnS(s)

On cancelling the common terms and rearranging the above equation we get

2 ZnS(s) + 3 O2(g) → 2 ZnO(s) + 2 SO2(g)

Therefore, ∆rG(A) = ∆rG(i) + ∆rG(ii) − ∆rG(iii) = −544 − 480 + 293 = − 731 kJ mol-1

The value of is negative. Therefore, roasting of zinc sulphide is spontaneous.

Example. For the reaction Ag2O(s) ⎯⎯→ 2Ag (s) +1/2 O2(g), ∆r Hυ = 30.56 kJ mol−1 and
∆r Sυ = 6.6 JK−1 mol−1 at 1 bar. Calculate the temperature at which ∆r Gυ will be zero.
What will be the direction of the reaction at this temperature and above and below this
temperature and why?

Solution. When ∆r Gυ = ∆r Hυ — T×∆r Sυ = 0

T×∆r Sυ = ∆r Hυ
∆r H Θ 30.56 kJ mol -1
=
or, T= ∆rS Θ 0.0066 kJ mol -1 = 4630 K

(i) The reaction will be at equilibrium when T = 4630 K

(ii) The reaction will proceed in the forward direction when T > 4630 K

(iii) The reaction will proceed in the reverse direction when T < 4630 K

Example. The standard free energy change for a reaction is − 212.3 kJ mol−1 . If the
standard enthalpy change is − 216.7 kJ mol−1, calculate the standard entropy change
for the reaction at 298 K.

Solution. From the relation ∆r Gυ = ∆r Hυ — T×∆r Sυ we have

∆r H Θ − ∆rGΘ
∆r Sυ =
T

− 216.7 kJ mol -1 − (−212.3 kJ mol -1

=
298 K

166
 = − 0.01476 kJ K−1 mol−1 = −14.76 J K−1 mol−1

Example. Calculate the standard Gibbs energy change ∆rGυ for the reaction CaCO3 (s)
+ 2H+ (aq) → Ca2+ (aq) + H2O (l) + CO2 (g) at 298 K using standard Gibbs energy of
formation:

Data given:

Species CO2 (g) H2O(l) CaCO3 (s) Ca2+ (aq)

∆f Gυ/kJ mol−1 −394.36 −237.13 −1128.8 −553.58

Solution. For the reaction CaCO3 (s) + 2H+ (aq) → Ca2+ (aq) + H2O (l) + CO2 (g)

∆rGυ = [[∆f Gυ (Ca2+) +∆f Gυ (CO2) + ∆f Gυ (H2O)] — [∆f Gυ (CaCO3) + 2∆f Gυ (H+)]

= [−553.58 − 394.36 −237.13] kJ mol−1— [ −1128.8 +2×0] kJ mol−1

= — 1185.07 kJ mol−1 + 1128.8 kJ mol−1 = − 56.27 kJ mol−1

Example. Calculate the standard Gibbs free energy change (∆rGυ)for the formation of
propane at 298 K 3 C(graphite) +4H2 (g) → C3H8(g) using the following data:

Data given:

Substance C3H8(g) C(graphite) H2 (g)

∆f Hυ/kJ mol−1 −103.8 0 0

Sυ /JK−1 mol−1 270.2 5.70 130.7

Solution. For the reaction 3 C(graphite) + 4 H2 (g) → C3H8(g) fisrt we shall calculate ∆rHυ
and ∆rSυ then ∆r Gυ

Calculation of ∆rHυ

∆rHυ = ∆f Hυ (C3H8, g) — [3∆f Hυ (C, graphite)) + 4∆f Hυ (H2, g)]

= − 103.8 kJ mol−1 — 3×0 +4×0] = − 103.8 kJ mol−1

Calculation of ∆rSυ

∆rSυ = Sυ (C3H8, g) — [3Sυ (C, graphite)) +4 Sυ (H2, g)]

= 270.2 JK−1 mol−1 — [ 3×5.70 +4×130.7] JK−1 mol−1

= − 269.7 JK−1 mol−1 = − 269.7 ×10−3 kJ K−1 mol−1

Calculation of ∆rGυ

∆r Gυ = ∆r Hυ —T ∆r Sυ

167
= − 103.8 kJ mol−1 — 298 K×(− 269.7×10−3 kJ K−1 mol−1)

= − 103.8 kJ mol−1 + 80.37 kJ mol−1 = − 23.43 kJ mol−1

168
CONFIDENCE BUILDING QUESTIONS ON ENTROPY AND GIBBS ENERGY

(A) Complete the following statements using a correct word/term from the list:

[decrease, lower, more, greater, increase, perfectly crystalline, positive, entropy, ∆ Suniverse, H
+ TS, ∆ G, negative, lower, third, zero, lower, JK–1

1. Higher randomness of a molecular system means ---------------- entropy.

2. For a spontaneous change the Gibbs energy must --------------

3. Entropy of 1 mole of ice is ----------------- than that of steam.

4. Net work done on the system would --------------- its free energy.

5. In a spontaneous process ∆ Suniverse is ----------------- than zero.

6. The Gibbs energy is expressed by the equation G =

7. The entropy of a -------------- substance is zero at 0 K.

8. For a spontaneous change ----------------- is greater than zero.

9. In an isothermal isobaric reversible process ------------ is equal to w( net).

10.For the process Normal egg ⎯⎯→ Hard boiled egg the sign of ∆ S is ---------------

11. When ∆ H is negative and ∆ S is positive then ∆ G is ------------------

12.The ------------- is a measure of randomness of the molecular system.

13.The entropy of diamond is ------------------ than the entropy of graphite.

14. The entropy of a substance is expressed in the units of -------------

15 The -------------- law of thermodynamics provides a method to evaluate the absolute

entropy of a substance.

16.The entropy of helium is ------------- than the entropy of dihydrogen

17. For an ideal gas the entropy change in an adiabatic reversible process is ----------------

(B) Give a very brief answer of the following questions

1. Write a limitation of the first law of thermodynamics.

2. Write the symbol of entropy.

3. Mention the condition when the thermodynamic relation dS = dq/T is applicable.

4. State the third law of thermodynamics.

5. Write the meaning of each term and symbol of the equation G = H – TS

169
 6. Write a relation between the free energy change and net work done.

7. Mention the conditions under which the relation ∆ G = w (net) is valid.

8. Write a relation between Gibbs energy (G) and Helmholtz energy (A).

9. Write the condition or conditions when ∆ G = ∆ A

10. Write the signs of ∆ H and ∆ S when a reaction is always spontaneous.

11. Write the signs of ∆ H and ∆ S when a reaction is never spontaneous.

12. Give an example of a reaction driven by entropy change.

13. Give an example of a reaction driven by enthalpy change.

14. Deduce the sign of ∆ G when ∆ H is positive and ∆ S is negative.

15. Derive the relation ( ∂ G/ ∂ T)P = –S.

16. Prove that ( ∂ G/ ∂ P)T = V

17. Using equation dG = –SdT + VdP derive Maxwell equation.

∂U ∂U ∂P
18. Calculate the value of ⎛⎜ ⎞⎟ for ideal gas when ⎛⎜ ⎞⎟ =T ⎛⎜ ⎞⎟ – P
⎝ ∂V ⎠ T ⎝ ∂V ⎠ T ⎝ ∂T ⎠ V

19. Prove that the internal pressure is zero for an ideal gas.

20. Write the thermodynamic relation which you will use to derive Maxwell
∂T ⎞ ⎛ ∂P ⎞
equation ⎛⎜ ⎟ = –⎜ ⎟
⎝ ∂V ⎠S ⎝ ∂S ⎠ V

21. Derive the following equations:

⎛ ∂T ⎞ ⎛ ∂V ⎞ ∂S ∂P ∂S ∂V
(i) ⎜ ⎟ = ⎜ ⎟ (ii) ⎛⎜ ⎞⎟ = ⎛⎜ ⎞⎟ (iii) ⎛⎜ ⎞⎟ = – ⎛⎜ ⎞⎟
⎝ ∂P ⎠S ⎝ ∂S ⎠ P ⎝ ∂V ⎠ T ⎝ ∂T ⎠ V ⎝ ∂P ⎠ T ⎝ ∂T ⎠ P

(C) Slect True and False Statements

1. The free energy is defined by G = H –TS.

2. The total energy of the universe is constant and its entropy is increasing.

3. The entropy of the universe is constant and its energy (U) is decreasing.

4. For spontaneous process free energy decreases.

5. The entropy change in an adiabatic reversible process is zero.

6. The standard entropy of an element is zero.

170
7. In a spontaneous reaction there is always an increase in the entropy of the system.

8. Entropy is a measure of randomness in a molecular system.

9. ∆G = wnet is valid under all conditions.

Answers

True statements: 1, 2, 4, 5, 8 False statements: 3, 6, 7, 9

(D) Numerical Questions

1. Calculate the standard Gibbs energy change ∆rGυ for the reaction SiH4 (g) + 2O2 (g) →
SiO2 (s) + 2H2O (g) at 298 K using standard Gibbs energy of formation:

Data given:

Species SiH4 (g) SiO2(s) H2O(g)

∆f Gυ/kJ mol−1 52.3 − 805 −228.6

[Ans: ∆rGυ = − 1314.5 kJ mol−1]

2. For the reaction MgO(s) + C(s) → Mg(s) + CO(g) it is given that ∆Hυ= +491.18 kJ mol−1
and ∆Sυ =197.17 JK−1 mol−1. Find out whether it is possible to reduce MgO using carbon at
298 K. If not, at what temperature it becomes spontaneous

[Ans: Nonspontaneous at 298 K because ∆rGυ =+433.148 kJ mol−1, but spontaneous when T
> 2491 K]

3. Error! Bookmark not defined.Calculate the standard Gibbs energy change for the
reaction CH3OH (1) + 3/2O2 (g) → CO2(g) + 2H2O (1) that can be converted into electrical
work in a fuel cell. What is the efficiency of conversion of Gibbs energy into useful work if
standard enthalpy of combustion for methanol is −726 kJ mol−1? Data give:

Compound CH3OH (l) CO2 (g) H2O (l)

∆f Gυ / kJ mol−1 − 166.27 − 394.36 − 237.13

[∆r Gυ = − 702.35 kJ mol−1 , Efficiency = ∆r Gυ /∆r Hυ = = 0.9674 = 96.7%

4. Predict whether the reaction 2NO (g) + O2 (g) → 2NO2 (g) is spontaneous or not. It is
given that ∆f Gυ (NO) = 86.55 kJ mol−1 and ∆fGυ (NO2) =51.31 kJ mol−1

[Ans: ∆r Gυ= − 70.48 kJ mol−1. A negative value of ∆rGυ suggests that the given reaction
is spontaneous]

5. Calculate the standard Gibbs energy change ∆rGυ for the formation of methane at 298 K
using the following data:

Data given:

171
Substance CH4 C(graphite) H2 (g)

∆f Hυ/kJ mol−1 −74.81 0 0

Sυ /JK−1 mol−1 186.3 5.70 130.7

[Ans: ∆r Hυ = − 74.81 kJ mol−1, ∆rSυ = = − 80.8 ×10−3 kJ K−1 mol−1, ∆r Gυ = − 50.7 kJ

mol−1]

6. Two moles of an ideal gas is compressed isothermally at 300 K from 2.0×105 Pa to

P2
4.0×105 Pa Calculate the Gibbs energy change for this process. [ Ans: ∆G = 2.303nRT log =
P1
3458.3 J]

7. One mole of ideal gas is allowed to expand isothermally at 300 K into an evacuated vessel
so that its pressure drops from 1.01 × 106 Pa to 1.01× 105 Pa. Calculate the values of w,q,
∆U, ∆H, ∆S. ∆A, anf ∆G for the process.

[Ans: w =0, q=0, ∆U=0, ∆H= 0, ∆A =∆G = –5744 J, ∆Ssystem = 19.15 J ]

8. The enthalpy of vaporization of a liquid is 30.76 kJ mol–1. What is the boiling point of the
liquid if it obeys Trouton’s rule. [Ans: Tb = ∆vapH/85 JK–1 mol–1 =30760 J mol–1 / 85 JK–1
mol–1 = 361.88 K]

9. The enthalpy of vaporistaion of liquid diethyl ether (C2H5 −O −C2H5) is 26.0 kJ mol−1 at
its boiling point of 35.0 °C. Calculate ∆Sυ for conversion of liquid to vapour

[Ans; ∆vap S = 84.4 J K−1 mol−1]

10. Calculate the entropy change when 0.02 mole of an ideal gas (CV, m = 12.6 JK–1 mol–1) is
heated from 298 K to 373 K so that its volume is also doubled.

T2 V
[Ans: ∆S = nCV, m×2.303 log + nR×2.303 log 2 =0.175 JK-1
T1 V1

172