UNIT: 5 THERMODYNAMICS

Not for sale. For Students of GMHSS, 2024

SECTION A: SOME BASIC TERMS AND CONCEPTS

SYSTEM AND SURROUNDINGS:

System: A specified part of the universe which is under observation is called the
system. A homogenous system consists of one phase while a heterogeneous system
consists of two or more phases.
Surroundings: The remaining portion of the universe which is not a part of the
system is called the surroundings.
The system and the surroundings together constitute the universe.
System + Surroundings = Universe

Types of Systems: Systems may be classified into three types:-

(i) Open system: A system which can exchange matter as well as energy with the
surroundings is called an open system.
(ii) Closed system: A system which can exchange energy but not matter with its
surroundings is called a closed system.
(iii) Isolated system: A system which can neither exchange matter nor energy with
the surroundings is called an isolated system.

Surroundings Surroundings Surroundings

Energy
Energy
Matter

Matter & Matter & Matter &

Energy Energy Energy

System System System

OPen System Closed System Isolated System

Exchanges matter Exchanges energy No Exchange of matter
and energy and energy
Different types of system

Macroscopic Properties of the system: The properties of the system which arise
from the bulk behavior of matter are called macroscopic properties. The common
examples of macroscopic properties are pressure, volume, temperature, surface
tension, viscosity, density, refractive index etc.
Macroscopic properties can be divided into two types:-

(i) Extensive properties: The properties of the system whose value depends upon
the amount or size of substance present in the system are called extensive
properties. For example, For example, mass, volume, surface area, internal
energy, enthalpy, entropy, free energy, heat capacity etc.

(ii) Intensive properties: The properties of the system whose value is independent
of the amount or size of substance present in the system are called intensive
properties. For example, For example, temperature, pressure, viscosity, vapour
pressure, refractive index, specific heat, surface tension etc.

State of a System and State Variables: The state of a system means the condition of
existence of the system when its macroscopic properties have definite values. If any of
the macroscopic properties of the system changes, the state of the system also
change.
The measurable properties required to describe the state of the system are
called state variables. For example, temperature, pressure, volume, composition
etc. are the state variables.
A state function is a property of the system whose value depends only upon
the state of the system and is independent of the path or manner by which the state is
reached. Some common state functions are pressure, volume, temperature, internal
energy, enthalpy, entropy etc.

Types of Processes: Some common types of processes are:-

(i) Isothermal process: A process in which the temperature of the system remains
constant. In such a system heat is either supplied to the system or removed from
it.
(ii) Adiabatic process: A process in which the system does not exchange heat with the
surroundings i.e., no heat leaves or enters the system. In such a process,
temperature of the system always changes. The systems in which such processes
occur are thermally insulated from the surroundings.
(iii) Isobaric process: A process in which the pressure of the system remains constant.
(iv) Isochoric process: A process in which the volume of the system remains constant.
(v) Reversible process: A process in which the direction may be reversed at any stage
by merely a small change in a variable like temperature, pressure etc.
(vi) Irreversible process: A process which is not reversible is called an irreversible
process.
(vii) Cyclic process: A process in which the system undergoes a series of changes and
ultimately returns to its original state is called a cyclic process.
 PRESSURE – VOLUME WORK:
pex
Force
Pressure =
Area
or, Force = Pressure  Area Cross
sectional
Therefore, force on the piston area A pex dl
𝑓 = 𝑝ex. A dV = A.dl
If 𝑤 is the work done on the
System by movement of the
vi vf
Piston, then,
Work, 𝑤 = force × distance
(a) Initial state (b) Final state
= 𝑝ex . A. 𝑑𝑙
Pressure - Volume work
= 𝑝ex . (−∆V)
= − 𝑝∆V
If Vi is the initial volume and Vf is the final volume of the gas, therefore,
(i) If the gas expands, Vf > Vi and work is done by the system, then 𝒘 is negative
(ii) If the gas contracts, Vf < Vi and work is done on the system, then 𝒘 is positive

SECTION B: FIRST LAW OF THERMODYNAMICS

The first law of thermodynamics states that energy can neither be created nor
destroyed although it can be converted from one form into another.
Mathematical expression for first law of thermodynamics: Let us consider a system
whose internal energy is U1. If the system absorbs 𝑞 amount of heat, the internal
energy increases and becomes U1 + 𝑞.
If 𝑤 is work done on the system, then its internal energy further increases and
becomes U2. Thus,
U2 = U2  q  w
U 2  U1 = q  w
U = q  w
If work done by the system and work is taken as negative (−𝑤), the above
relationship becomes
U = q  (  w) = q  w In general
𝒘 and 𝒒 are positive if energy (as
Sign Conventions for Heat and Work work and heat) enters the system
Heat absorbed by the system = 𝒒 positive
and 𝑤 and 𝑞 are negative if
Heat evolved by the system = 𝒒 negative
energy (as work and heat) leaves
Work done on the system = 𝒘 positive
the system
Work done on the system = 𝒘 negative
Enthalpy and Enthalpy Change: Enthalpy of a system may be defined as the sum of
the internal energy and the product of its pressure and volume. It is denoted by the
symbol H and is given by
H = U + pV
Where, U is the internal energy, 𝑝 is the pressure and V is the volume of the
system. Enthalpy is also called heat content. Since H depends upon three state
functions U, 𝑝 and V, it is also a state function.
Similarly, the change in enthalpy may be represented as:
H = U + (pV)
H = U + pV + Vp
At constant pressure and temperature,
H = U + pV
Thus, the change in enthalpy of a reaction (∆H) is equal to the heat absorbed or
evolved during a reaction at constant temperature and pressure.
Significance of ∆U and ∆H and First Law of Thermodynamics:
According to first law of thermodynamics,
U = q  w
If work is done by the system, then, the pressure-volume work, 𝑤 = −𝑝∆V
U = q  pV
or, q = U + pV
If the process is carried out at constant volume, 𝑖. 𝑒, ∆V = 0, then the product 𝑝∆V is
also zero. Thus,
qv = U
Thus, the change in internal energy (∆U) is equal to heat absorbed or evolved at
constant volume and constant temperature.
And the change in enthalpy (∆H) may be defined as
H = U + pV
Now, U = q  w
If the work is done by the system, the pressure-volume work, 𝑤 = −𝑝∆V
U = q  pV
Therefore, the change in enthalpy (∆H) may become
H = q  pV + pV
H = q p (at constant pressure)
Thus, the enthalpy change (∆H) is a measure of heat change (evolved or absorbed)
taking place during a process at constant pressure.

𝒒 (at constant volume) = ∆U

𝒒 (at constant pressure) = ∆H
Relationship between ∆H and ∆U:
Consider a reaction
A B
The enthalpy change is given as:
H = U + pV ...... (i)
where, ∆U is the change in internal energy and ∆V is the change in volume of the
system.
According to ideal gas equation,
pV = nRT
For reactants,
pVA = nA RT (at constant T and p) ..... (ii)
For products,
pVB = nBRT (at constant T and p) ..... (iii )
Now, subtracting eq. (𝑖𝑖) from eq. (𝑖𝑖𝑖), we get,
p  VB  VA  = nBRT  nA RT
=  nB  nA  RT
or, pV = ng RT
where ∆𝑛g is the change in the number of gaseous moles of products and gaseous
moles of reactants. Thus, equation (𝑖) becomes
H = U + ng RT
Exothermic and Endothermic reactions:
1. Exothermic reactions: The chemical reactions which proceed with the evolution of
heat energy are called exothermic reactions.
In general, exothermic reactions may be represented as:
A+B C + D + 𝑞 (heat)
In exothermic reactions, the enthalpy of the products will be less than the
enthalpy of the reactants.

Reactants
Hr
Enthalpy

ΔH = Hp - Hr
= - ve (Hp < Hr )

Hp
Products

Reaction path
Enthalpy change during an
exothermic reaction
2. Endothermic reactions: The chemical reactions which proceed with the absorption
of heat energy are called endothermic reactions.
In general, endothermic reactions may be represented as:
A+B C + D - 𝑞 (heat)
In endothermic reactions, the enthalpy of the products will be more than the
enthalpy of the reactants due to the absorption of heat.

Products
Hp
Enthalpy

ΔH = Hp - Hr
= + ve (Hp > Hr)

Hr
Reactants

Reaction path
Enthalpy change during an
endothermic reaction

Therefore, it may be concluded that

For exothermic reactions, ΔH or ΔU = -ve

For endothermic reactions, ΔH or ΔU = +ve

Heat capacity and Specific heat:

Heat capacity is defined as the amount of heat required to raise the temperature of
the system by one degree. Heat capacity is denoted by C
Heat absorbed
Heat capactiy =
Rise in temperature
q
C=
T

Specific heat is defined as the heat required to raise the temperature of 1 gram of a
substance by one degree (1K or 1°C) is called specific heat.

Heat absorbed
Specific heat =
Rise in temperature  Mass of sample in gram
 Relationship between Cp and Cv:
The relationship between heat capacity at constant pressure (C p) and heat capacity
at constant volume (Cv) can be derived as:
At constant volume, heat absorbed
𝑞 v = Cv ΔT = ΔU ……. (i)
At constant pressure, heat absorbed
𝑞 p = Cp ΔT = ΔH ……. (ii)
and, the enthalpy change is given by
ΔH = ΔU + pΔV
From an ideal gas equation, 𝑝v = 𝑛RT
For one mole of an ideal gas,
pΔV = Δ(RT)
Since, R is the universal gas constant i.e. it cannot be changed, therefore
pΔV = RΔT
Thus, ΔH = ΔU + RΔT ……. (iii)
Now, substituting the values of ΔH and ΔU in the above equation, therefore,
Cp ΔT = Cv ΔT + RΔT
or, Cp = Cv + R
Cp - Cv = R for 1 mole of an ideal gas

Similarly, for 𝑛 moles of an ideal gas

Cp - Cv = 𝑛R

ENTHALPY CHANGES OF CHEMICAL REACTIONS:

1. Enthalpy of reaction: The enthalpy change (amount of heat evolved or absorbed) in
a reaction when the number of moles of reactants react completely to give the
products as given by the balanced chemical equation. It is denoted by ΔrH
For example, during the reaction of one mole of methane and two moles of oxygen,
890.3kJ of heat is evolved and the enthalpy change of reaction is ΔH = - 890.3kJ
CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g) ΔrH = - 890.3kJ

2. Enthalpy of formation: The enthalpy change when 1 mole of a substance is formed

from its elements in their most stable forms is called enthalpy of formation. It is
generally denoted by ΔfH.
For example, the formation of carbon dioxide and methane may be expressed as:
C (s) + O2 (g) CO2 (g) ΔfH = - 393.5kJ
3. Enthalpy of combustion: The enthalpy change when 1 mole of a substance is
completely burn in excess of oxygen or air is called enthalpy of combustion. It is
denoted by ΔcH
For example, the combustion of methane evolves 890.3kJ amount of heat. The
enthalpy of combustion is always negative because combustion reactions are
always exothermic and heat is evolved during combustion.
CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g) ΔcH = - 890.3kJ

Calorific value: The amount of heat produced in calories (or joules) when 1 gram of
a substance (food or fuel) is completely burnt. The calorific value is usually
expressed in kcal per gram or kilojoules per gram (1 kcal = 4.184 kJ).
For example, when methane burns 890.3kJ mol-1 of energy is liberated as:
CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g) ΔcH = - 890.3kJ

Hess’s Law of constant heat summation: Hess’s Law states that the enthalpy
change (heat evolved or absorbed) in a particular reaction is the same whether the
reaction takes place in one step or in a number of steps.
Hess’s Law can be illustrated by the following diagram:

PATH I
A B
ΔH

PATH II
ΔH1 ΔH2
C

Therefore, according to Hess's Law

ΔH = ΔH1 + ΔH2

This means that the amount of heat evolved or absorbed in a chemical

reaction depends only upon the enthalpy of initial reactants and the final products
irrespective of the path or the manner by which the change has taken place. Therefore,
the enthalpy change for the reaction, whether the reaction follows path I or path II is:
ΔH = ΔH1 + ΔH2. Thus, we can say that enthalpy is a state function.

The main applications of Hess’s Law are:-

(i) Determination of enthalpy of formation of substances which cannot be measured
experimentally.
(ii) Determination of enthalpy of transition
(iii) Calculation of enthalpy of hydration
(iv) Predicting enthalpies of various reactions.
4. Enthalpy of solution: The enthalpy change when 1 mole of a substance dissolves in
a specified amount of solvent at a constant temperature and pressure is called as
enthalpy of solution.
For example, the enthalpy change for dissolving 1 mole of HCl in 1 mole of water
can be represented as:
HCl (g) + 10 H2O (l) HCl.10H2O (l) ΔH = - 69.01kJ mol-1

5. Enthalpy of neutralization: The enthalpy of neutralization is defined as the

enthalpy change when 1 mole of H+ (aq) from an acid are completely neutralized by
a base or 1 mole of OH-(aq) from a base are completely neutralized by an acid.
The neutralization of HCl with NaOH can be represented by the following equation
HCl (aq) + NaOH (aq) NaCl (aq) + H2O (l) ΔH = - 57.1kJ

6. Enthalpy of phase transitions: The enthalpy change in the three states of matter
are:-
(a) Enthalpy of fusion: The enthalpy change when 1 mole of a solid substance is
converted into its liquid state at its melting point is called enthalpy of fusion. It is
denoted as ΔfusH. When the process is carried out at constant temperature and
under standard pressure (1 bar), it is called standard enthalpy of fusion and is
denoted as ΔfusH°
For example, when 1 mole of ice melts at 0°C, the heat absorbed is 6.0 kJ
H2O (s) H2O (l) ΔfusH° = 6.0 kJ mol-1

(b) Enthalpy of vaporisation: The enthalpy change when 1 mole of a liquid is

converted into gaseous state at its boiling point is called enthalpy of vaporisation.
For example, the heat change when 1 mole of water (liquid) coverts into vapour
(gas) at 100°C is 40.6kJ and is represented as:
H2O (l) H2O (g) ΔvapH° = 40.6 kJ mol-1

(c) Enthalpy of sublimation: The enthalpy change when 1 mole of a solid substance
is directly converted into its gaseous state below its melting point is called
enthalpy of sublimation.
For example, when 1 mole of solid iodine sublimes, the heat change is 62.4kJ and is
represented as:
I2 (s) I2 (g) ΔsubH° = 62.4 kJ mol-1
The enthalpy of sublimation is related to enthalpy of fusion and enthalpy of
vaporization as:
ΔsubH° = ΔfusH° + ΔvapH°
7. Enthalpy of atomization: Enthalpy of atomization may be defined as the enthalpy
change in breaking 1 mole of bonds completely into atoms in the gaseous state. It is
represented by ΔaH°
For example, the breaking of H-H bonds in H2 into H atoms is represented as:
H2 (g) H (g) + H (g) ΔaH° = 435 kJ mol-1

8. Bond dissociation enthalpy: The amount of energy required to break 1 mole of

bonds of a particular type between the atoms in the gaseous state is called bond
dissociation enthalpy.
For example, the bond dissociation energy for O2 molecule is
O2 (g) O (g) + O (g) ΔO-OH° = 428 kJ mol-1

LIMITATIONS OF FIRST LAW OF THERMODYNAMICS: The main limitations of the first

law of thermodynamics are discussed as follows:-
1. The first law of thermodynamics does not determine the feasibility or spontaneity
of a process.
2. The first law does not indicate the direction of the flow of heat. It does not explain
whether the heat can flow from a cold end to a hot end or not.
3. It does not tell anything about the conditions under which heat can be transformed
into work.
4. The first law does not indicate as to why the whole of the heat energy cannot be
converted into mechanical work continuously.

SPONTANEOUS AND NON-SPONTANEOUS PROCESS:

Spontaneous process: A process which can take place by itself under the given set of
conditions once it has been initiated if necessary is said to be a spontaneous process.
Non-spontaneous process: The processes which are forbidden and are made to take
place only by supplying energy continuously from outside the system are called non-
spontaneous process.
ENTROPY: Entropy may be defined as the property of a system which measures the
degree of disorder or randomness in the system.
Characteristics of entropy:
1. Entropy is an extensive property. Its value depends upon the amount of the
substance present in the system.
2. Entropy of a system is a state function. The change in entropy in going from one
state to another is independent of the path.
3. The change in entropy (ΔS) at equilibrium is zero.
4. The total entropy change is equal to sum of the entropy change of the system and
entropy change of the surroundings i.e., ΔS = ΔS sys + ΔSsurr
5. In reversible process, ΔSuniverse = 0 and in a irreversible process, ΔSuniverse > 0
 SECTION C: SECOND LAW OF THERMODYNAMICS

The second law of thermodynamics states that the entropy of the universe always
increases in the course of every spontaneous (natural) change.

ENTROPY CHANGES DURING PHASE TRANSITION:

The change of matter form one state (solid, liquid or gas) to another is called phase
transition.
(1) Entropy of fusion: Entropy of fusion may be defined as the entropy change when
1 mole of the solid substance changes into liquid form at its melting point.
For example, when ice melts as:
 fus H
H2O (s) H2O (l) Swater  Sice   fusS =
Tf

(2) Entropy of vaporisation: The entropy change when 1 mole of liquid changes
into vapours at its boiling point is called entropy of vaporisation.
For example, when water boils at 100°C as:
 vap H
H2O (l) H2O (g) Svapour  Swater   vapS =
T

(3) Entropy of sublimation: The entropy change when 1 mole of a solid substance is
directly converted into its gaseous state below its melting point is called entropy
of sublimation.
The entropy of sublimation at a particular temperature is
 sub H
 subS =
T
Where, ΔsubH° is the standard enthalpy of sublimation at the temperature T.

GIBBS ENERGY:
Gibbs energy of a system is defined as the maximum amount of energy
available to a system during a process that can be converted into useful work.
In other words, it is s thermodynamic quantity which is a measure of
capacity of a system to do useful work. It is denoted by symbol G and is given by
G = H – TS
Where, H is the enthalpy of the system, S is its entropy and T is the absolute
temperature. Gibbs energy is also called as Gibbs function. It is an extensive
property and is also a state function.
GIBBS ENERGY CHANGE:
Q. Write Gibbs Helmholtz equation. How is it helpful for predicting the feasibility of a
process?
Ans: The Gibbs energy change (or Gibbs Helmholtz equation) may be written as:
ΔG = ΔH – TΔS
Where, ΔH is the enthalpy change, ΔS is the entropy change and T is the
absolute temperature.
Gibbs Helmholtz equation is very useful for predicting the spontaneity of a
process. There are three conditions:-
(i) If ΔG is negative, the process is spontaneous.
(ii) If ΔG is zero, the process is in equilibrium state. There is no net reaction in either
direction.
(iii) If ΔG is positive, the process does not occur in the forward direction. It may,
however, go in the reverse direction.

Q. What are the conditions for spontaneity of a process or ΔG to be negative?

Ans: To be a spontaneous process in the forward direction, ΔG must be negative.
ΔG would be negative only under the following conditions:-
(i) Both energy and the entropy factors are favourable and may have any magnitude
i.e., ΔH is negative and TΔS is positive.
(ii) When energy factor favours the change (ΔH = -ve) but entropy factor opposes
the change (TΔS = -ve), then, the magnitude of ΔH should be more than that of
TΔS. i.e, ΔH (-ve) > TΔS (-ve)
(iii) When energy factor is not favouring the change (ΔH = +ve) but entropy factor
favours the change (TΔS = +ve), then, the magnitude of TΔS should be more than
ΔH. i.e, TΔS (+ve) > ΔH (+ve)

EFFECT OF TEMPERATURE ON FEASIBILITY OF A PROCESS:

Q. Briefly explain the effects of temperature on the feasibility of a process for
exothermic and endothermic reactions.
Ans: To be a spontaneous process in the forward direction, ΔG must be negative.
The effect of temperature is different for exothermic and endothermic reactions as
discussed below:-
(i) Exothermic reactions: For exothermic reactions, ΔH is always negative and
therefore, it is favourable. But, TΔS can have either positive or negative value.
(a) If TΔS is positive i.e., favourable, then ΔG can have only negative value and
the process is spontaneous at all temperatures.
(b) If TΔS is negative i.e., unfavourable, then ΔG will be negative only if ΔH > TΔS.
This fact will be more predominant at lower temperature. Therefore,
exothermic reactions are favoured by decreasing temperature.
 (ii) Endothermic reactions: For exothermic reactions, ΔH is always positive and
therefore, it is unfavourable. But, TΔS can have either positive or negative value.
(a) If TΔS is negative i.e., unfavourable, then ΔG will be positive and the
process is non-spontaneous at all temperatures.
(b) If TΔS is positive i.e., favourable, then ΔG will be negative only if TΔS > ΔH.
This fact will be more predominant at higher temperature. Therefore,
endothermic reactions are favoured by increasing temperature.

GIBBS ENERGY CHANGE AND EQUILIBRIUM CONSTANT:

Consider a general reaction:
A + B C + D

The Gibbs energy of the reaction, ΔG is related to the reaction mixture and the
standard Gibbs energy, ΔG° as:
ΔG = ΔG° + RT 𝑙𝑛 Q
Where, ΔG is the Gibbs energy change, ΔG° is the standard Gibbs energy
change, Q is the reaction quotient and R is the gas constant equal to 8.314JK -1 mol-1
At equilibrium, Q = K, called equilibrium constant and ΔG° = 0 because the
reaction mixture has no tendency to change in either direction. Therefore, the
above equation becomes:
0 = ΔG° + RT 𝑙𝑛 K
ΔG° = − RT 𝑙𝑛 K
or, ΔG° = − 2.303 RT log K
Thus, we can say that,
ΔG° = ΔH° – TΔS° = − RT 𝑙𝑛 K
This means that the equilibrium constant is related to ΔH° and ΔS°
For strongly endothermic reactions, ΔH° may be large and positive. In such
case, value of K will be much smaller than 1.
For exothermic reactions, ΔH° is large and negative. In such case, value of K
will be larger than 1.

Q. Is the entropy of the universe constant?

Ans: No, entropy of the universe increases everyday.

Q. What is the value of change in entropy at equilibrium?

Ans: At equilibrium, ΔS = 0

Q. Which quantity out of ΔG or ΔG° will be zero at equilibrium?

Ans: ΔG will be zero. ΔG° will be zero for K = 1 because ΔG° = − RT 𝑙𝑛 K. ΔG° will
be non-zero for other values of K.
Q. If standard free energy change for a reaction is found to be zero, what is its
equilibrium constant?
Ans: ΔG° = − 2.303 RT log K = 0
log K = 0, K = 1

SECTION D: THIRD LAW OF THERMODYNAMICS

According to third law of thermodynamics, at absolute zero the entropy of a perfectly

crystalline substance is taken as zero.
The third law of thermodynamics helps to calculate the absolute entropies of pure
substances at different temperatures.

Q. What is entropy of substance taken as zero at absolute zero of temperature?

Ans: At absolute zero of temperature, there is complete orderly molecular
arrangement in the crystalline substance. Therefore, there is no randomness at 0 K
and entropy is taken to be zero.