Chapter - Thermodynamics

Learning Objectives
To explain the basic terms in thermodynamics
To classify different types of system
To differentiate extensive and intensive properties .

Thermodynamics
The branch of science which deals with study of different forms of
energy and their interconversion is called thermodynamics.

Basic Terms in Thermodynamics

System It refers to that part of universe which is under observation.

Surroundings The remaining portion of universe which is not a part of system but
can interact with the system.

System + surrounding = universe

Boundary The wall (real or imaginary) that separates the system from the
surroundings.
 Example If you are studying the reaction between two substances A and B in
a beaker, the beaker containing the reaction mixture is the system and the room where
the beaker is kept is the surrounding. The wall of the beaker is the boundary.

Types of the System

Open system The system which can exchange energy as well as matter between
the system and the surroundings.
Eg: The presence of reactants in an open beaker
Closed System A system which can exchange energy but not matter between the
system and the surroundings.
Eg: Hot water contained in a closed beaker

Isolated System A system in which there is no exchange of energy or matter between

the system and the surroundings.
Eg: Hot water contained in a thermos flask,

Type of system Exchange of energy Exchange of matter

Open System Yes Yes

Closed System Yes No
Isolated system No No

Depending on the number of particles, systems are of two types:

1. Microscopic system: It is a system containing a few number of particles.
2. Macroscopic system: it is a system contains a large number of particles.
Macroscopic properties
The property which arises from the collective behavior of large no of species is called
macroscopic properties.
The important macroscopic properties are: Temperature (T), Pressure (P), Volume (V),
length (l), breadth (b), height (h), internal energy (U), enthalpy (H), entropy (S), Gibb’s
energy (G) etc.

classifications of macroscopic properties

Intensive property The properties of a system which do not depend on quantity of
matter (the amount or size of matter) present.
Eg; Temperature ,pressure, refractive index ….
Extensive property The property of a system which depends on the quantity of
matter (amount or size of matter) present.
Eg ;volume,mass,enthalpy…

Learning Objectives
To define state variables
To analyse the thermodynamic processes
To explain internal energy

The state of a thermodynamic system.

It refers to the condition of existence of a system, when its measurable or macroscopic

properties have a definite values. The state of a system changes when any one of the
property changes. (Temperature, pressure, volume)
State variables (or) state functions
The thermodynamic properties whose values depend only on the initial and the final
state of the system and independent of the manner (path) by which the state is reached.
Examples: Temperature, pressure, volume, internal energy, enthalpy, entropy, Gibbs
energy etc
Path variables or path functions
The thermodynamic properties whose values depend upon the path followed.
Examples: work and heat.

Thermodynamic processes
A process is the method (path) by which a state change occurs in a system. The
different types of thermodynamic process are:
1. Isothermal process
The process in which temperature of the system remains constant.
For this process ΔT = 0 but Δq ≠ 0
2 Adiabatic process
The process in which there is no transfer of heat between the system and the
surroundings.
Δq= 0 but ΔT ≠ 0
3 Isobaric process
The process in which pressure of the system remains constant.
For such a process ΔP = 0

4 Isochoric process
The process in which volume of the system remains constant.
For such a process ΔV = 0

5 Reversible process The process in which the system and surrounding can be
restored to the initial state from the final state without producing any changes in the
thermodynamic properties of the universe.
6 Irreversible process
The process in which the system and surrounding cannot be restored to the initial state
from the final state is called an irreversible process. All the processes occurring in
nature are irreversible processes
7. Cyclic process
When a system returns to its original state after completing a series of changes, then it
is said that a cycle is completed. This process is known as a cyclic process.
Internal energy (U)
total energy associated within the system under a given condition. The total energy of
all molecules in a system is equal to the sum of their translational energy (Ut),
vibrational energy (Uv), rotational energy (Ur), bond energy (Ub), electronic energy (Ue)
and energy due to molecular interactions (Ui).
U = Ut + Uv + Ur+ Ub + Ue+ Ui

Characteristics of internal energy (U)

1. Absolute value of the internal energy can never be determined only change in internal
energy can be determined. Hence Internal energy (U) is a state function.
ΔU= Uf – Ui
2. The internal energy of a system is an extensive property.
3. In a cyclic process, there is no internal energy change. ΔU(cyclic) = 0

What are the ways by which we can change the internal energy of a system?
 Heat passes into or out of the system.
 Work is done on or by the system.

Heat

It is the form of energy which is exchanged between the system and the surrounding
when they are under different temperatures.

Heat changes and sign conventions (q)

Heat (q) Transfer Sign of q
From the surrounding to the system +
From the system to the surrounding -

Work
Exchange of energy between the system and the surrounding can occur in the form of
work.
Work = force x displacement
Pressure - volume work: work generally considered is the work done in expansion (or
Compression) of a gas. This is known as pressure-volume work, PV work or expansion
work.
work is done : W = - PexΔV

Work done in an adiabatic process and sign convention (w)

Work done (Wad) Sign of w
By the system -
On the system +
Learning Objectives
To understand the first law of thermodynamics and derive its mathematical
expression

To derive the relation between ΔU an ΔH

To identify the significance of ΔU an ΔH

First law of thermodynamics

Energy can neither be created nor destroyed but it can be converted from one form into
another. (Or) The total energy of the universe is constant. It also states that the energy
of an isolated system is constant. (Or) In a physical and chemical process the energy of
the system and surroundings taken together remains constant

Mathematical expression of First Law of Thermodynamics

Consider a system in its initial state having internal energy U1,

if heat equal to q is supplied to the system, work equal to w is done on the system then
the internal energy of the system in the final state U2 is given

U2= U1 + q + w

U2 - U1= q + w

ΔU = q + W

ΔU = change in internal energy.

Substituting the value of w
ΔU = q - Pex ΔV
If a process is carried out at constant volume (∆V = 0),
ΔU = q
ΔU = qv
At constant volume, the heat absorbed/ evolved is equal to change in internal energy ΔU
Free expansion
Expansion of a gas in vacuum (Pex = 0) is called free expansion.
No work is done during free expansion of an ideal gas whether the process is reversible or
irreversible.

Isothermal and free expansion of an ideal gas

For isothermal (T = constant) expansion of an ideal gas into vacuum ; w = 0 since pex = 0. Also,
Joule determined experimentally that q = 0; therefore, ∆U = 0

∆U=q+w

For isothermal irreversible change:

q = - Wirr = Pex ΔV = Pex (Vf –Vi)

From ideal gas equation; PV = nRT

At constant temperature Wrev = - 2.303 nRT log Vf /Vi

For isothermal reversible change: q = - Wrev = 2.303 nRT log Vf /Vi

3.For an Adiabatic change, q = 0 and

ΔU = Wad

Home work
Express the change in internal energy of a system when
(i) No heat is absorbed by the system from the surroundings, but work (w) is done on
the system. What type of wall does the system have ?
(ii) No work is done on the system, but q amount of heat is taken out from the system
and given to the surroundings. What type of wall does the system have?
(iii) w amount of work is done by the system and q amount of heat is supplied to the
system. What type of system would it be?

Enthalpy of a system (H)

The 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
The change in enthalpy ΔH = ΔU + Δ (PV)
At constant pressure,
ΔH = ΔU + PΔV
ΔU = q - PΔV
ΔH = q - PΔV + PΔV
ΔH = qp
At constant pressure, the heat absorbed/ evolved is equal to the change in the
enthalpy ΔH.
∆H is negative for exothermic reactions which evolve heat during the reaction and
∆H is positive for endothermic reactions which absorb heat from the
surroundings.

Significance of ΔH and ΔU
The heat change (q) in a chemical reaction can either be expressed in terms of ΔU or
ΔH.
ΔU is the quantity of heat absorbed/evolved when the reaction takes place at
constant volume.
ΔH is quantity of heat absorbed/evolved when the reaction takes place at
constant pressure.

Relationship between ΔH and ΔU

Consider a reaction A B at constant pressure

Let HA be the enthalpy of reactants and HB the enthalpy of products

Change in enthalpy ΔH = HB - HA
ΔH = ΔU + PΔV at constant pressure.
According to ideal gas equation: PV = nRT
For reactants PVA = nA RT
For products PVB = nB RT
PVB - PVA = nB RT - nA RT
P (VB - VA) = (nB - nA) RT
PΔV = Δng RT
ΔH = ΔU + Δng RT
Δng = no. of moles of gaseous products - no. of moles of gaseous reactants.

In a reaction if all reactants and products are solids ,ΔV= 0 then, ΔH = ΔU

Problem 6.2,3,4 - Page 160

Problem 6.5 Page 161

ENTHALPY CHANGE OF A REACTION – REACTION ENTHALPY (ΔrH)

The enthalpy change accompanying a reaction is called the reaction enthalpy. ΔrH

ΔrH = (sum of enthalpies of products) - (sum of enthalpies of reactants)

The standard enthalpy of reaction (ΔrH 0 )

It is the enthalpy change for a reaction when all the participating substances are in their
standard states. (Pure form & 1 bar )

Standard enthalpy of fusion or molar enthalpy of fusion. (ΔfusH 0 )

The enthalpy change that accompanies the melting of one mole of a solid substance in
standard state.
Standard enthalpy of vaporization or molar enthalpy of vaporization(ΔvapH 0 )
The enthalpy change that accompanies the vaporization of one mole of a liquid at a
constant temperature and under standard pressure (1bar).

Standard enthalpy of sublimation(ΔsubH 0 )

It is the change in enthalpy when one mole of a solid substance sublimes at a constant
temperature and under standard pressure (1bar).

Standard enthalpy of Formation (ΔfH 0 )

The enthalpy change for the formation of one mole of pure compound from its elements
in their most stable states of aggregation.
 By convention, standard enthalpy for formation Δf H 0 , of an element in
reference state, i.e., its most stable state of aggregation is taken as zero.

Standard enthalpy of Combustion (ΔcH 0 )

The enthalpy change when one mole of a compound is completely burnt in excess of
oxygen or air. It is always exothermic in nature.

Standard enthalpy of Atomization (ΔaH 0 )

It is the change in enthalpy when one mole of a substance is converted into its atoms in
gaseous state at a given temperature and 1 bar pressure
 In case of diatomic molecules, like dihydrogen:
H2 (g) →2H (g); ΔaH 0= 435.0 kJ mol–1
the enthalpy of atomization is also the bond dissociation enthalpy.

 In case of elements in solid state, it is equal to the enthalpy of sublimation.

Na(s) → Na (g); ΔaH 0 = 108.4 kJ mol–1

 For elements in liquid state, it is equal to the enthalpy of vaporization.

Hg(l) ⎯→ Hg(g) ΔaH = 61.32 kJ mol–1

dissociation enthalpy(ΔBondH 0 )
The amount of energy required to break one mole of bond of a particular type between
atoms in gaseous state.
ΔrH 0 = Σ bond enthalpies of the reactants – Σ bond enthalpies of the product.

Enthalpy of solution(ΔsoluH 0 )
The enthalpy change when one mole of a substance dissolves in a specified amount of
solvent.
The lattice enthalpy of an ionic compound (ΔLatticeH 0 )
It is the enthalpy change which occurs when one mole of an ionic compound dissociates
into its ions in the gaseous state.
NaCl (s) Na+(g) + Cl-(g)

Hess’s Law of Constant Heat Summation

The enthalpy change of a reaction is the same whether it takes place in one step or in a
series of steps.
Born-Haber Cycle
It is an enthalpy diagram which is used to determine lattice enthalpy of ionic compounds
since they cannot be determined by experiments directly

1. The combustion of one mole of benzene takes place at 298 K and 1 atm. After combustion,
CO2 (g) and H2O (1) are produced and 3267.0 kJ of heat is liberated. Calculate the standard
enthalpy of formation, ∆f H 0 of benzene. Standard enthalpies of formation of CO2 (g) and H
O(l) 2 are –393.5 kJ mol–1 and – 285.83 kJ mol –1 respectively.

Spontaneous / feasible / probable process.

A process that can take place by itself without the help of any external energy under a given set
of conditions. (Or) A spontaneous process is an irreversible process and may only be reversed
by some external agency.
Factors that support spontaneity
1. The tendency of a system to acquire a state of minimum energy.
2. The tendency of a system to acquire maximum randomness.

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 (S)

The entropy is the measure of disorder or randomness in a system.

 The greater the disorder in a system, the greater is the entropy of the system.
 For a given substance, solid state is the state of lowest entropy and gaseous state is the state
of maximum entropy. Entropy decreases in the order: Gases > liquids > solids  Entropy of any
substance increases on heating.
 In a chemical reaction, entropy increases if there is an increase in number of moles of gases
during the reaction and vice-versa.

Characteristics of Entropy

1. Entropy is an extensive property.

2. It is a state function.
3. Total entropy for an isolated system is the sum of the entropy change of system and the
surrounding.
ΔS Total = ΔS universe = ΔS system + ΔS surrounding

Entropy change (∆S)

Entropy change is defined as the heat absorbed reversibly by the system divided by the
temperature at which the heat is absorbed.
 For a reversible process entropy change is given by
The second law of thermodynamics

All spontaneous or natural processes produce an increase in entropy of the universe.

Criteria for spontaneity of a process in terms of entropy

1. If ΔS > 0 (+ ve), the process is spontaneous.
2. If ΔS < 0 (- ve), the process is Non spontaneous.
3. If ΔS = 0, the system is at equilibrium.

Gibbs free energy or Gibbs energy (G)

G is the maximum amount of energy available in a system that can be converted to do useful
work.
G = H – TS
 Gibbs function, G is an extensive property.
 It is a state function.

Gibb’s Helmholtz equation

G = H - TS

ΔG = ΔH – Δ (TS)

At constant temperature ; Δ T = 0

ΔG = ΔH – TΔS

Criteria for spontaneity of a process in terms of Gibb’s Free energy

If Δ G < 0, process is spontaneous - ΔG must be negative.

If Δ G = 0, process is in equilibrium
If Δ G > 0, process is non-spontaneous

Relation between Gibbs energy change ΔrGᵒ and equilibrium constant Kc

 ΔrGᵒ = - RTlnK 
ΔrG 0 = - 2.303 RT log K

Effect of temperature on Spontaneity of Reactions

In deciding the spontaneity of a chemical reaction, the equation Δ G = Δ H –T ΔS takes

into account two factors:
(i) The energy factor ΔH, and
(ii) The Entropy factor ΔS. Based on the signs of Δ H and Δ S there are four possibilities
for Δ G. These possibilities are outlined in table

Given N2 (g) + 3H2 (g) → 2NH3 (g) ; ∆r H 0 = –92.4 kJ mol–1 What is the standard enthalpy
of formation of NH3 gas?
Calculate the standard enthalpy of formation of CH3OH(l) from the following data:

CH3OH (l) + 3 2 O2 (g) → CO2 (g) + 2H2O(l) ; ∆rH 0 = –726 kJ mol–1

C(graphite) + O2 (g) → CO2 (g) ; ∆cH 0 = –393 kJ mol–1

H2 (g) + 1 /2 O2 (g) → H2O(l) ; ∆f H 0 = –286 kJ mol-1