CH 211: Chemical Thermodynamics

Thermodynamics

The branch of science dealing with the relations between energy, heat, and work and
accompanying changes in the nature and behavior of various substances around us is called
thermodynamics. The word thermodynamics stems from the Greek words therme (heat) and
dynamics (force). The formal study of thermodynamics began in the early nineteenth century
through consideration of the motive power of heat: the capacity of hot bodies to produce
work. Today the scope is larger, dealing generally with energy and with relationships among
the properties of matter. 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.

MACROSCOPIC AND MICROSCOPIC VIEWS OF THERMODYNAMICS

Systems can be studied from a macroscopic or a microscopic point of view. The macroscopic
approach to thermodynamics is concerned with the gross or overall behavior. This is
sometimes called classical thermodynamics. No model of the structure of matter at the
molecular, atomic, and subatomic levels is directly used in classical thermodynamics.
Although the behavior of systems is affected by molecular structure, classical
thermodynamics allows important aspects of system behavior to be evaluated from
observations of the overall system.

The microscopic approach to thermodynamics, known as statistical thermodynamics, is

concerned directly with the structure of matter. The objective of statistical thermodynamics is
to characterize by statistical means the average behavior of the particles making up a system
of interest and relate this information to the observed macroscopic behavior of the system.
For applications involving lasers, plasmas, high-speed gas flows, chemical kinetics, very low
temperatures (cryogenics), and others, the methods of statistical thermodynamics are
essential.

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CHEMICAL THERMODYNAMICS:

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.

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.

In practice, the primary objective of chemical thermodynamics is to establish a criterion for

determining the feasibility or spontaneity of a given physical or chemical transformation.
Once the spontaneous direction of a natural process is determined, we may wish to know
how far the process will proceed before reaching equilibrium. Thermodynamic methods
provide the mathematical relations required to estimate such quantities.

Although the main objective of chemical thermodynamics is the analysis of spontaneity and
equilibrium, the methods also are applicable to many other problems. For example, the study
of phase equilibria, in ideal and nonideal systems, is basic to the intelligent use of the
techniques of extraction, distillation, and crystallization; to metallurgical operations; to the
development of new materials; and to the understanding of the species of minerals found in
geological systems. Similarly, the energy changes that accompany a physical or chemical
transformation, in the form of either heat or work, are of great interest, whether the
transformation is the combustion of a fuel, the fission of a uranium nucleus, or the transport

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of a metabolite against a concentration gradient. Thermodynamic concepts and methods
provide a powerful approach to the understanding of such problems.

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 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.

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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.

Or

The system is whatever we want to study. It may be as simple as a free body or as complex
as an entire chemical refinery.

A thermodynamic system

A thermodynamic system is a device or combination of devices containing a quantity of

matter that is being studied.

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.

Or

Everything external to the system is considered to be part of the system’s surroundings.

Boundary: The space that separates the system and the surroundings is called the boundary.
The system and surroundings interact across the boundary. The boundary may be real or even
imaginary Boundary.

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.

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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

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(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
(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.

PROPERTY, STATE, AND PROCESS

A property is a macroscopic characteristic of a system such as mass, volume, energy,

pressure, and temperature to which a numerical value can be assigned at a given time without
knowledge of the previous behavior (history) of the system.

state

The word state refers to the condition of a system as described by its properties.

Process

When any of the properties of a system change, the state changes and the system is said to
have undergone a process. A process is a transformation from one state to another.

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However, if a system exhibits the same values of its properties at two different times, it is in
the same state at these times. A system is said to be at steady state if none of its properties
changes with time.

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.

List of extensive and intensive properties

Extensive properties Intensive properties

Volume, mass, amount (mole), energy, Molar volume, density, molar mass,
enthalpy, entropy, free energy, heat capacity molarity, mole fraction, molality, specific
heat capacity

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),

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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.

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

(1) Density is an intensive property

(2) Molarity is an intensive property

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)
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

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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).

VOLUME IS A STATE PROPERTY– demonstration by calculation

Ex: Consider a given amount of an ideal gas in its initial state T I = 300 K, PI = 1 bar, VI = 20
dm3. Let us suppose that the state variables of the gas are changed to a final state T 2 = 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.

Solution

Method 1. The gas is heated and allowed to expand simultaneously from the initial state T 1 =
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

Thus change of volume = ∆V (1) = V2 – V1 = 50 dm 3 – 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:

∆V (2 a) = (40 – 20) dm 3 = 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

∆V (2 b) = (50 dm3 – 40 dm3) = 10 dm3

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Net change of volume in step 2 =∆V (2 ) = ∆V (2a) + ∆V (2b) = (20 dm 3 + 10 dm3) = 30
dm3

Method 3.

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

∆V (3a) =(25 dm3– 20 dm3) = 5 dm3

Step (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:

∆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)

Types of process

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).

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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

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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

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.

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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).

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).

ENERGY

Energy is the capacity to do work. The total energy of a particle is the sum of its kinetic and
potential energies. The kinetic energy of a particle is the energy it possesses as a result of its
motion. The potential energy of a particle is the energy it possesses as a result of its position.

For a body of mass m travelling at a speed v

The potential energy, equation or more commonly V, of a body is the energy it possesses as a
result of its position. For a particle of mass m at an altitude h close to the surface of the Earth,
the gravitational potential energy is

Where g is the acceleration of free fall (g=9.81 m s−2). The total energy of a particle is the
sum of its kinetic and potential energies

E = E K + EP

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 THE LAWS OF THERMODYNAMICS

ZEROTH LAW OF THERMODYNAMICS (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, 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

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.

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)

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 q = Heat absorbed by the system
w = Work done on the system (it includes all possible types of work)
“The energy of an isolated system is constant

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
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

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

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

∆U = q when w = 0

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This relation tells that change in internal energy is equal to the heat exchanged between the
system and the surroundings.

2. 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

It implies that if work is done on the system its internal energy will increase.

3. 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

Internal energy (U)

In thermodynamics, the total energy of a system is called its internal energy, U. The internal
energy is the total kinetic and potential energy of the molecules in the system. We denote by
ΔU the change in internal energy when a system changes from an initial state i with internal
energy Ui to a final state f of internal energy Uf:

ΔU=Uf −Ui

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 (U t),
vibrational energy (Uv), rotational energy (Ur), bond energy (Ub), electronic energy (Ue),
energy due to molecular interactions (V T) and the relativistic energy. Thus:

U = Ut + U v + Ur + Ub + Ue + V T

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.

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Characteristics of internal energy ™

Internal energy of a system is an extensive property and state property. The change in
internal energy of a fixed amount the system is expressed as:

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

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

Calorimetry - Measurement of ∆U

We can measure energy changes associated with chemical or physical processes by an

experimental technique called calorimetry. For chemical reactions, heat absorbed at constant
volume, is measured in a bomb calorimeter (Fig).

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Here, a steel vessel is (the bomb) is immersed in a water bath. The whole device is called
calorimeter. The steel vessel is immersed in water bath to ensure that no heat is lost to the
surroundings. A combustible substance is burnt in pure dioxgen supplied in the steel bomb.
Heat evolved during the reaction is transferred to the water around the bomb and its
temperature is monitored. Since the bomb calorimeter is sealed, its volume does not change
i.e., the energy changes associated with reactions are measured at constant volume.

Under these conditions, no work is as the reaction is carried out at constant volume in the
bomb calorimeter. Even for reactions involving gases, there is no work done as ΔV = 0.
Temperature change of the calorimeter produced by the completed reaction is then converted
to qV, by using the known heat capacity of the calorimeter with the help of the following
equation

q = c × m × ΔT

where q = heat; m = mass of the water; c = heat capacity of water; ΔT = change of

temperature

Example: A 1.000 g sample of octane (C8H18) is burned in a bomb calorimeter containing

1200 grams of water at an initial temperature of 25.00 0C. After the reaction, the final
temperature of the water is 33.20C. The heat capacity of the calorimeter (also known as the
“calorimeter constant”) is 837 J/0C. The specific heat of water is 4.184 J/g 0C. Calculate the
heat of combustion of octane in kJ/mol. If one mole of octane is burned, what is the heat of
combustion in kJ/mol?

Solution: Since this is a combustion reaction, heat flows from the system to the
surroundings- thus, it is exothermic. The heat released by the reaction will be absorbed by
two things: (a) the water in the calorimeter and (b) the calorimeter itself.

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b. Calculate the heat absorbed by the calorimeter (qcal) the temperature change of the
calorimeter is the same as the temperature change for water. In this step, however, we must
use the heat capacity of the calorimeter, which is already known. When using heat capacity,
the mass of the calorimeter is not required for the calculation. (It’s already incorporated into
the heat capacity).

The TOTAL heat absorbed by the water and the calorimeter is the sum of (a) and (b):
41.2 + 6.86 = + 48.1 kJ.
The amount of heat released by the reaction is equal to the amount of heat absorbed by the
water and the calorimeter. We just need to change the sign. So,

Since 1.000 gram of octane was burned, the heat of combustion for octane is equal to – 48.1
kJ/gram.

c. 1 mol of octane weighs 114 grams, so (-48.1 kJ/g)(114 g/mol) = – 5483 kJ/mol.

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CONCEPT OF WORK IN THERMODYNAMICS:

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

w = –F × ∆x
where ∆x is the path length over which action is taken and F is force.
Units of Work: Our definition of work involves the product of unit force (one newton)
acting through a unit distance (one meter). This unit for work in SI units is called the joule
(J). 1J=1Nm

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 × A ×∆x
= –P × ∆V (Here P = F/A = Force per unit area = pressure)

Sign of work:
► w is positive = work done on the system (System gaining energy)
► w is negative = work done by the system (System loss energy)

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 by the system. That is, in the
process the energy of the system would decrease.

(a)The general expression for work

Now consider the arrangement shown in Fig , in which one wall of a system is a massless,
frictionless, rigid, perfectly fitting piston of area A.

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When the system expands through a distance dz against an external pressure p ex, it follows
that the work done is dw = −pexAdz.
Therefore, the work done when the system expands by dV against a pressure p ex is

To obtain the total work done when the volume changes from an initial value V i to a final
value Vf we integrate this expression between the initial and final volumes:

(b) Free expansion

Free expansion is expansion against zero opposing force. It occurs when p ex = 0. According
to this equation,

Therefore
dw = 0 for each stage of the expansion.
That is, no work is done when a system expands freely. Expansion of this kind occurs when a
gas expands into a vacuum.

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(c) Expansion against constant pressure
Now suppose that the external pressure is constant throughout the expansion.

by taking the constant pex outside the integral:

Therefore, if we write the change in volume as ΔV = Vf −Vi,

(d) Reversible expansion

To achieve reversible expansion we set pex equal to pat each stage of the expansion. When
we set pex= p, in the following equation

The total work of reversible expansion from an initial volume V i to a final volume Vf is
therefore

(e) Isothermal reversible expansion

Consider the isothermal, reversible expansion of a perfect gas. The expansion is made
isothermal by keeping the system in thermal contact with its surroundings (which may be a
constant-temperature bath). We know that p = nRT/V, with V the volume at that stage of the
expansion. The temperature T is constant in an isothermal expansion, so it may be taken
outside the integral. It follows that the work of reversible isothermal expansion of a perfect
gas from Vi toVf at a temperature T is

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 22

(f) Adiabatic Expansion
Consider the adiabatic expansion of a perfect gas. No heat is gained or lost by the gas, dq = 0,
so the process is adiabatic (Isolated steam)
The First law of thermodynamics
dU = dq + dw
dU = dw = -pexdV
If the system expands adiabatically, dV is positive and dU is negative. If the expansion is
opposed by an external pressure, work is done on the surroundings and the temperature drops
as internal energy is converted to work.
U2 V2

 dU    Pex dV
U1 V1

For ideal gas, the internal energy is a function of temperature is C V

dU
CV   dU  CV dT
dT

dU  U 2  U1  w
w  CV (T2  T1 )
w  CV dT

PdV  C V dT
nRT
 dV  CV dT
V
This is a differential equation that can be solved to give T as a function of V if the
dependence of CV on T and V is known
C V dT nR
 dV
T V

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 23

Integrate the above equation, the initial state denoted by V1 and T1 to the final stae V2 and T
T  V 
CV ln  2    nR ln  2 
 T1   V1 
T  nR  V2 
ln  2    ln  
 T1  C V  V1 
nR /CV
 T2   V1 
  
 T1   V2 
nR /CV
V 
T  T1  1 
 V2 

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 24

Problems

Problem 1. 3000 J of heat is added to a system and 2500 J of work is done by the system.
What is the change in internal energy of the system?
Known :
Heat (Q) = +3000 Joule
Work (W) = +2500 Joule
Wanted: the change in internal energy of the system
Solution :
The equation of the first law of thermodynamics
ΔU = Q-W
ΔU = 3000-2500
ΔU = 500 Joule
Internal energy increases by 500 Joule.
Problem 2. 2000 J of heat is added to a system and 2500 J of work is done on the system.
What is the change in internal energy of the system?
Known :
Heat (Q) = +2000 Joule
Work (W) = -2500 Joule
Wanted: The change in internal energy of the system
Solution :
ΔU = Q-W
ΔU = 2000-(-2500)
ΔU = 2000+2500
ΔU = 4500 Joule
Internal energy increases by 4500 Joule.
Problem 3. 2000 J of heat leaves the system and 2500 J of work is done on the system.
What is the change in internal energy of the system?
Known :
Heat (Q) = -2000 Joule
Work (W) = -3000 Joule

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 25

Wanted: The change in internal energy of the system
Solution :
ΔU = Q-W
ΔU = -2000-(-3000)
ΔU = -2000+3000
ΔU = 1000 Joule
Internal energy increases by 4500 Joule.
Problem 4. Compute the internal energy change and temperature change for the two
processes involving 1 mole of an ideal monatomic gas. (a) 1500 J of heat are added to the
gas and the gas does no work and no work is done on the gas (b) 1500 J of work are done
on the gas and the gas does no work and no heat is added or taken away from the gas

Solution

Problem 5. A system is taken from state a to state c by two paths adc and abc as shown in
the figure. The internal energy at a is Ua = 10 J. Along the path adc the amount of heat
absorbed dQ1 = 50 J and the work done dW1 = 20 J whereas along the path abc the heat
absorbed dQ2 = 36 J. The amount of work done along the path abc is

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 26

Problem 6. Calculate the work done whaen 1 mole of gas expands from 5 dm 3 to 10 dm3
against a constant pressure of 2 atm.

Solution:

W = PΔV
Converting the data in the example to SI units
W = 2×1.013×105(10×10-3-10×5-3)Pa m3
W = 1013J
Problem 7. Calculate the work done when 50 g of iron reacts with hydrochloric acid to
produce FeC12(aq) and hydrogen in (a) a closed vessel of fixed volume, (b) an open beaker at
25°C.

Solution:

(a) the volume cannot change, so no expansion work is done and w=0.

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 27

(b) the gas drives back the atmosphere and therefore w = − p exΔV.

We can neglect the initial volume because the final volume (after the production of gas) is so
much larger and ΔV = Vf − Vi ≈ Vf = nRT/pex, where n is the amount of H2 produced.
Therefore,

Because the reaction is Fe(s) + 2 HCl(aq) → FeC12(aq) + H2(g), we know that 1 mol H2is
generated when 1 mol Fe is consumed, and n can be taken as the amount of Fe atoms that
react. Because the molar mass of Fe is 55.85 g mol −1, it follows that

Problem 8. Calculate the work done on a closed system consisting of 50.0 g of argon,
assumed ideal gas when it expands isothermally and reversibly from a volume of 5.0 L to a
volume of 10.0 L at temperature of 298.15K.

Solution:

V 
w   nRT ln  2 
 V1 
V 
w  2.303nRT ln  2 
 V1 
 1mol  1 1  10.0L 
w  2.303(50.0g)   (8.3145JK )mol (298.15) log  
 39.938g   5.0L 
w  4.953.7J

Problem 9. A system consisting of 2.0 mol of argon gas expands adiabatically and reversibly
from a volume of 5.0 L and a temperature of 373.15K to a volume of 20.0 L. Find the final
temperature (Assume argon to be ideal gas with CV = 3nR/2).

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 28

Solution:

nR /CV
V 
T2  T1  1 
 V2 
nR
 5.0L  3nR / 2
T2  373.15K  
 20.0L 
2
 5.0L  3
T2  373.15K  
 20.0L 
T2  148K

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 29

 ENTHALPY

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. The enthalpy is a Greek
word which means heat in (en = in, thalpos = heat). Enthalpy is a measure of heat in the
system.

Definition of enthalpy (H)

The enthalpy (H) is defined by

H = U + PV

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

It is equal to the internal energy of the system plus the product of pressure and volume.

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 T 1, P1, V1 to T2, P2, V2
the enthalpy of a given amount (fixed n) of the system is changed from H 1 to H2.

The change in enthalpy is represented as:

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

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 30

Sign conventions of ∆H

●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 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)

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 31

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 = q v
(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.

Heat capacity

The quantity of heat required to rise 10C in the temperature of a substance is called its heat
capacity. It is denoted by symbol C and defined by.

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.

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 32

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 C m. Thus,

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.

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

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

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

and CV = n× CV,m

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 33

 (2) Heat capacity at constant pressure

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

Molar heat capacity at constant pressure = CP,m = CP/n and CP = n× CP, m

Derivation of the relation between CP and CV
Definition of enthalpy H = U + PV
Differentiation of above equation with respect to T an constant P gives

Heat capacity at constant pressure is defined by

For an ideal gas

where, CV = Heat capacity at constant volume

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

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

C p = CV + nR
C p – CV = nR

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 34

The variation of enthalpy with temperature
The enthalpy of a substance increases as its temperature is raised. The relation between the
increase in enthalpy and the increase in temperature depends on the conditions (for example,
constant pressure or constant volume). The most important condition is constant pressure,
and the slope of the tangent to a plot of enthalpy against temperature at constant pressure is
called the heat capacity at constant pressure, Cp, at a given temperature

For infinitesimal changes of temperature

The variation of heat capacity with temperature can sometimes be ignored if the temperature
range is small; this approximation is highly accurate for a monatomic perfect gas (for
instance, one of the noble gases at low pressure).

The empirical parameters a, b, and c are independent of temperature (Table ) and are found
by fitting this expression to experimental data.

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 35

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 36
 Thermo chemistry

The branch of chemistry dealing with the measurement and calculation of energy changes
(∆U) and enthalpy changes (∆H) of various types of physical transformations and chemical
reactions is called thermochemistry. 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 experimental conditions the heat of a reaction is classified as follows.

►When the reaction is performed at constant volume the accompanying energy change (∆U)
is called heat of reaction at constant 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 of reaction at constant 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 chemical reactions (∆rH)

(a) Enthalpy of formation (∆fH)
(b) Enthalpy of combustion (∆cH)
(c) Enthalpy of neutralization (∆nH)
(d) Bond enthalpy ∆H( A –B)

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 37

(2) Enthalpy changes in physical transformation (∆trssH)

(a) Enthalpy of vaporization (∆vapH)

(b)Enthalpy of fusion (∆fusH)

(c) Enthalpy of sublimation (∆subH)

(d) Enthalpy of solution (∆solH)

(a) Enthalpy changes in chemical 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.

Enthalpy of reaction is denoted by ∆rH and expressed in the units of kJ mol–1. It is also called
as the heat of reaction at constant pressure.

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

(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

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 38

i) Standard state

The enthalpy change depends on temperature, pressure and the physical states of the
reactants and products.

The standard state of a substance at a specified temperature is its pure form at 1 bar.

For example, the standard state of liquid ethanol is pure liquid at 298 K and 1 bar; the
standard state of solid iron is pure at 500 K and 1 bar.

ii) 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.

Note: The values of standard enthalpy of formation of substances are given in any
thermochemistry text books

iii) Standard enthalpy of formation of an element

The standard enthalpy of formation of an element is taken as zero. That is, ∆ fHυ(element) =
0, because of an element cannot be synthesized or decomposed by chemical or physical
methods.

iv) 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:

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 39

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

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

(b) 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 CO 2 and two moles of H2O are formed
and 890 kJ heat is liberated.

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

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 40

(c) 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.

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 41

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

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

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

(d) 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.
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 kJ/mol 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 kJmol–1
The enthalpy of dissociation of one mole of H–H bonds is 436 kJ mol –1

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 42

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
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) → 2O(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– Cl(g) → H(g) + Cl(g) ∆H (H–Cl) = 432 kJ mol –1

Enthalpy of bond dissociation in polyatomic molecules

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.

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 43

Examples: Use the following bond dissociation enthalpies to compute the C–H bond
enthalpy in methane (CH4)

On adding equations (i), (ii), (iii) and (iv) and canceling the common terms on the two sides,
we get

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

Calculation of enthalpy of reactions from bond enthalpy data

The enthalpy of a reaction is given by the relation

∆rH Θ = 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

Solution. The given reaction

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 44

 C3H8(g) + 5O2 (g) → 3CO2(g) + 4H2O(g)
may be represented in terms of breaking of bonds in reactants and formation of bonds in
products as follows:

The enthalpy of reaction (∆rHΘ)

∆rHΘ = 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 C 3H8 and five
O = O bond in O2.
Therefore,

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 45

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
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

Method 1. A calculated quantity of carbon (graphite) is burnt directly in the presence of
oxygen to form carbon dioxide

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

On adding equations (ii) and (iii) along with the ∆Hθ values we get

On cancelling the common species on both the sides of the above equation we have

Since the chemical equations (i) and (iv) are the same, their enthalpy changes are also the
same. Thus

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.

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 46

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
Finding a correct path is different for each Hess's Law problem and may require some trial
and error. A good place to start is to find one of the reactants or products where there is only
one mole in the reaction.
►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 H 2O is
given by the reaction

Now, according to the Hess’s law, the enthalpy of decomposition of H 2O is represented by

►When an equation is multiplied by a number, the enthalpy change is also multiplied by the
same number. For example

►When equations are added, the enthalpy changes are also added accordingly with proper
signs. For example

On adding equations (a) and (b) we get

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 47

 According to the Hess’s law the enthalpy of reaction (c) is given by

Example: Apply Hess’s law to calculate the enthalpy change (∆rHθ) of the following
reaction

Given data

Solution:
Operations: On multiplying equation (ii) by 2 and reversing equation (iii) we get

On adding equations (i), (iv) and (v) along with corresponding ∆ rHυ values, we get equation
(vi)

On canceling the common terms on the two sides of equation (vi), we get equation (vii)

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

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 48

Example: Use the following combustion data to calculate the enthalpy change for the
hydrogenation of ethene as represented by the reaction C 2H4 (g) + H2 (g) —→ C2H6(g)
Combustion data:

Solution: Our aim is to calculate ∆Hυ for the reaction

Operations: Subtract equation (ii) from the sum of equations (i) and (iii) to get

On canceling the common terms on the two sides of the above equation we get

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 49

 Hess’s Law Practice Problems

1. Given the following equations and Ho values, determine the heat of reaction (kJ) at 298
K for the reaction:

B2H6(g) + 6 Cl2(g) 2 BCl3(g) + 6 HCl(g)

BCl3(g) + 3 H2O(l) H3BO3(g) + 3 HCl(g) Ho/kJ = -112.5

112.5
B2H6(g) + 6 H2O(l) 2 H3BO3(s) + 6 H2(g) Ho/kJ = -493.4
493.4
o
1/2 H2(g) + 1/2 Cl2(g) HCl(g) H /kJ = -92.3
92.3

2. Given the following equations and Ho values, determine the heat of reaction (kJ) at 298
K for the reaction:

2 OF2(g) + 2 S(s) SO2(g) + SF4(g)

OF2(g) + H2O(l) O2(g) + 2 HF(g) Ho/kJ = -276.6

SF4(g) + 2 H2O(l) 4 HF(g) + SO2(g) Ho/kJ = -827.5
827.5
o
S(s) + O2(g) SO2(g) H /kJ = -296.9
296.9

3. Determine Ho/kJ for the following reaction using the listed enthalpies of reaction:

N2H4(l) + 2 H2O2(g) N2(g) + 4 H2O(l)

N2H4(l) + O2(g) N2(g) + 2 H2O(l) Ho/kJ = -622.3 kJ

H2(g) + 1/2 O2(g) H2O(l) Ho/kJ = -285.8
285.8 kJ
o
H2(g) + O2(g) H2O2(l) H /kJ = -187.8 kJ

4. Calculate the value of Ho/kJ for the following reaction using the listed thermochemical
equations:

P4O10(g) + 6 PCl5(g) 10 Cl3PO(g)

1/4 P4(s) + 3/2 Cl2(g) PCl3(g) Ho/kJ = -306.4

o
P4(s) + 5 O2(g) P4O10(g) H /kJ = -2967.3
PCl3(g) + Cl2(g) PCl5(g) Ho/kJ = -84.2
PCl3(g) + 1/2 O2(g) Cl3PO(g) Ho/kJ = -285.7

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 50

5. Given the following equations
quations and Ho values, determine the heat of reaction (kJ) at 298
K for the reaction:

2 SO2(g) + 2 P(s) + 5 Cl2(g) 2 SOCl2(l) + 2 POCl3(l)

SOCl2(l) + H2O(l) SO2(g) + 2 HCl(g) Ho/kJ = +10.3

PCl3(l) + 1/2 O2(g) POCl3(l) Ho/kJ = -325.7
o
P(s) + 3/2 Cl2(g) PCl3(l) H /kJ = -306.7
4 HCl(g) + O2(g) 2 Cl2(g) + 2 H2O(l) Ho/kJ = -202.6

6. Calculate the heat of combustion (kJ) of propane, C 3H8 using the listed standard enthapy
of reaction data:

C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(g)

3 C(s) + 4 H2(g) C3H8(g) Ho/kJ = -103.8

C(s) + O2(g) CO2(g) Ho/kJ = -393.5
H2(g) + 1/2 O2(g) H2O(g) Ho/kJ = -241.8

7. Given the following equations and Ho values given below, determine the heat of
reaction at 298 K for the reaction:

2 N2(g) + 5 O2(g) 2 N2O5(g)

2 H2(g) + O2(g) 2 H2O(l) Ho/kJ = -571.6

N2O5(g) + H2O(l) 2 HNO3(l) Ho/kJ = -73.7
N2(g) + 3 O2(g) + H2(g) 2 HNO3(l) Ho/kJ = -348.2

8. Given the following equations and Ho values, determine the heat of reaction at 298 K
for the reaction:

C(s) + 2 H2(g) CH4(g)

C(s) + O2(g) CO2(g) Ho/kJ = -393.5

H2(g) + 1/2 O2(g) H2O(l) Ho/kJ = -285.8
CO2(g) + 2 H2O(l) CH4(g) + 2 O2(g) Ho/kJ = +890.3

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 51

9. 2-Methylpropan-1-ol can also be converted to produce diesel and jet fuel. The first step in
the process is the production of 2-methylpropene.

Using the data below, calculate the enthalpy change, in kJ mol-1, for the production of 2-
methylpropene from 2-methylpropan-1-ol.

Answers for the problems

1. Answer: -1376 kJ
2. Answer: -319.5 kJ
3. Answer: -818.3 kJ
4. Answer: -610.1 kJ
5. Answer: -1041.6 kJ
6. Answer: -2043.9
7. Answer: 22.6 kJ
8. Answer: -252.9 kJ
9. Answer: + 76 kJ

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 52

Enthalpy of physical transformation
(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

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 100oC will absorb 2.26 kilojoules of heat to be converted into 1 g of water
vapour at 100oC. 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.

Latent of fusion of ice is 334 Jg–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

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 53

Example, the enthalpy of sublimation of naphthalene is computed as follows.
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)

Solution:
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

Relation between ∆rH and ∆rU

In a chemical reaction involving gases

For a general reaction involving gases

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 54

For the reaction N2 (g) + 3 H2 (g) → 2 NH3 (g)

Example: For a reaction CH4 (g) + 2O2 (g) → CO2(g) + 2H2O(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.

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 55

Example. The enthalpy change (∆rH) for the reaction N2(g)+3 H2(g) → 2NH3(g) is
– 92.38 kJ mol−1 at 298 K. Calculate the value of ∆rU at 298 K.

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.

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 56

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 57
Hess’s Law Practice Problems

1. Given the following equations and Ho values, determine the heat of reaction (kJ) at 298
K for the reaction:

B2H6(g) + 6 Cl2(g) 2 BCl3(g) + 6 HCl(g)

BCl3(g) + 3 H2O(l) H3BO3(g) + 3 HCl(g) Ho/kJ = -112.5

112.5
B2H6(g) + 6 H2O(l) 2 H3BO3(s) + 6 H2(g) Ho/kJ = -493.4
493.4
o
1/2 H2(g) + 1/2 Cl2(g) HCl(g) H /kJ = -92.3
92.3

2. Given the following equations and Ho values, determine the heat of reaction (kJ) at 298
29
K for the reaction:

2 OF2(g) + 2 S(s) SO2(g) + SF4(g)

OF2(g) + H2O(l) O2(g) + 2 HF(g) Ho/kJ = -276.6

276.6
SF4(g) + 2 H2O(l) 4 HF(g) + SO2(g) Ho/kJ = -827.5
827.5
S(s) + O2(g) SO2(g) Ho/kJ = -296.9
296.9

3. Determine Ho/kJ for the follow

following
ing reaction using the listed enthalpies of reaction:

N2H4(l) + 2 H2O2(g) N2(g) + 4 H2O(l)

N2H4(l) + O2(g) N2(g) + 2 H2O(l) Ho/kJ = -622.3 kJ

H2(g) + 1/2 O2(g) H2O(l) Ho/kJ = -285.8 kJ
H2(g) + O2(g) H2O2(l) Ho/kJ = -187.8 kJ

4. Calculate the
he value of Ho/kJ for the following reaction using the listed thermochemical
equations:

P4O10(g) + 6 PCl5(g) 10 Cl3PO(g)

1/4 P4(s) + 3/2 Cl2(g) PCl3(g) Ho/kJ = -306.4

P4(s) + 5 O2(g) P4O10(g) Ho/kJ = -2967.3
PCl3(g) + Cl2(g) PCl5(g) Ho/kJ = -84.2
PCl3(g) + 1/2 O2(g) Cl3PO(g) Ho/kJ = -285.7

5. Given the following equations and Ho values, determine the heat of reaction (kJ) at 298
K for the reaction:

2 SO2(g) + 2 P(s) + 5 Cl2(g) 2 SOCl2(l) + 2 POCl3(l)

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 58

SOCl2(l) + H2O(l) SO2(g) + 2 HCl(g) Ho/kJ = +10.3
PCl3(l) + 1/2 O2(g) POCl3(l) Ho/kJ = -325.7
P(s) + 3/2 Cl2(g) PCl3(l) Ho/kJ = -306.7
4 HCl(g) + O2(g) 2 Cl2(g) + 2 H2O(l) Ho/kJ = -202.6

6. Calculate the heat of combustion (kJ) of propane, C 3H8 using the listed standard
standar enthapy
of reaction data:

C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(g)

3 C(s) + 4 H2(g) C3H8(g) Ho/kJ = -103.8

C(s) + O2(g) CO2(g) Ho/kJ = -393.5
H2(g) + 1/2 O2(g) H2O(g) Ho/kJ = -241.8

7. Given the following equations and Ho values given below, determine

etermine the heat of
reaction at 298 K for the reaction:

2 N2(g) + 5 O2(g) 2 N2O5(g)

2 H2(g) + O2(g) 2 H2O(l) Ho/kJ = -571.6

N2O5(g) + H2O(l) 2 HNO3(l) Ho/kJ = -73.7
N2(g) + 3 O2(g) + H2(g) 2 HNO3(l) Ho/kJ = -348.2

8. Given the following equa

equations and Ho values, determine the heat of reaction at 298 K
for the reaction:

C(s) + 2 H2(g) CH4(g)

C(s) + O2(g) CO2(g) Ho/kJ = -393.5

H2(g) + 1/2 O2(g) H2O(l) Ho/kJ = -285.8
CO2(g) + 2 H2O(l) CH4(g) + 2 O2(g) Ho/kJ = +890.3

9. 2-Methylpropan-1-ol ol can also be converted to produce diesel and jet fuel. The first step in
the process is the production of 22-methylpropene.

Using the data below, calculate the enthalpy change, in kJ mol

mol-1,
1, for the production of 2-
2
methylpropene from 2-methylpropan
methylpropan-1-ol.

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 59

Answers for assignment

1. Answer: -1376 kJ
2. Answer: -319.5 kJ
3. Answer: -818.3 kJ
4. Answer: -610.1 kJ
5. Answer: -1041.6 kJ
6. Answer: -2043.9
7. Answer: 22.6 kJ
8. Answer: -252.9 kJ
9. Answer: + 76 kJ

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 60

 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.

The second law of thermodynamics is a statement about which processes occur and which do
not. i.e the recognition of two classes of process, spontaneous and non-spontaneous, is
summarized by the Second Law of thermodynamics. There are many ways to state the
second law; here is one:

Heat can flow spontaneously from a hot object to a cold object; it will not flow
spontaneously from a cold object to a hot object.

This law may be expressed in a variety of equivalent ways.

Second Law in Kelvin words: No process is possible in which the sole result is the
absorption of heat from a reservoir and its complete conversion into work.

Second Law in Clausius words: No process is possible whose sole result is the transfer of
heat from a body of lower temperature to a body of higher temperature.

Entropy (S)

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 61

The Second Law of thermodynamics, may also be expressed in terms of another state
function, the entropy (S). The Second Law uses the entropy to identify the spontaneous
changes among those permissible changes.

The Second Law of thermodynamics can be expressed in terms of the entropy:

The entropy of an isolated system increases in the course of a spontaneous change: ΔS tot > 0

Where Stot is the total entropy of the system and its surroundings.

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. This term was introduced by Clausius. He denoted
entropy by the symbol S in the honour of Sadi Carnot (S from Sadi).

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 thermodynamic definition of entropy

The thermodynamic definition of entropy is based on the expression

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 62

Where qrev is the heat supplied reversibly. For a measurable change between two states intial
(i) and final (f ) this expression integrates to

That is, to calculate the difference in entropy between any two states of a system

Statistical definition of entropy

For any system, the entropy is given by the Boltzmann equation:

where w is the number of possible configurations of the system and k B is Boltzmann’s

constant.

This definition allows the entropy to be understood as a measure of the disorder in a

system.

Greater the randomness larger is the value of entropy. Lower is randomness smaller is the
value of entropy.

Relation between energy and entropy

The change of internal energy is given by the first law of thermodynamics as

The change of entropy is given by the second law of thermodynamics as

On substituting the expression for dq from equation (ii) in to equation (i), we get

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 63

Equations (iii) and (iv) represent the combined form of first and second laws of
thermodynamics.

Entropy changes accompanying specific processes

(A) Entropy change for isothermal reversible expansion of an ideal gas
The thermodynamic definition of entropy is

Where qrev is the heat supplied reversibly. For a measurable change between two states i and
f this expression integrates to

we know that

It follows that

V2 V
S2  S1  S  nR ln  2.303nR log 2
V1 V1

(B) 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

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 64

volume VA + VB. Therefore, the mixing process can be assumed that gas A expands from its
initial volume VA to a final volume of V A + VB.
The entropy change of gas A at constant temperature is given by

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

The total entropy change is equal to the sum of the entropy changes of gas A and gas B on
mixing.

(F) 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 .
(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.

∆vapS = Entropy in the final state – Entropy in the initial state

= Entropy of vapour phase – Entropy of the liquid phase
= S (vapour) – S (liquid)
∆vapH = Enthalpy of vaporization of the liquid = Heat of vaporization of the liquid

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 65

 Tb = Boiling point (in Kelvin) of the liquid
(B) Entropy of fusion ∆fusS
The 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.

∆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

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.

For an irreversible process (spontaneous process) when only P-V work is considered

In an isolated system energy and volume are constant that is, dU = 0 and dV= 0, therefore,

In a reversible processes ( equilibrium)

In an isolated system energy and volume are constant that is, dU = 0 and dV= 0, therefore,

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 66

The combined result is written as (dS)U, V >= 0
For finite changes (∆S)U, V >= 0
Thus in an isolated system at constant energy and constant volume the entropy is maximum
at equilibrium

Power Cycles
Most power producing devices operate on cycles. To make simple thermodynamics analysis
possible, we use the concept of ideal cycle. Ideal cycles are internally reversible, thus, the
thermal efficiency of an ideal cycle, in general, is less than that of a totally reversible cycle
operating between the same temperature limits, i.e., Carnot cycle.
CARNOT CYCLES
Sadi Carnot was a French physicist who proposed an “ideal” cycle for a heat engine in 1824.
Carnot proposed that a cycle comprised of completely (internally and externally) reversible
processes would give the maximum amount of net work for a given heat input, since the
work done by a system in a reversible (ideal) process is always greater than that in an
irreversible (real) process.
Consider the thermodynamic path shown below:

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 67

This closed thermodynamic path or cycle is called the Carnot cycle. In the ABC portion of
the cycle, the system expands, so it does work. In the CDA portion of the path, the system is
compressed, so work is done on it. The net work, which is the sum of contributions from
paths ABC and path CDA, is the net work done by the system, so it must be negative:

(1)
Note that the net work performed by the engine is just the area of enclosed by the by four
paths in the P-V plane.
Since, for a closed path, the change in energy is 0, the net work done by the gas must be
equal the negative of the heat absorbed by the system:

(2)
THE CARNOT HEAT ENGINE CYCLE CONSISTS OF FOUR REVERSIBLE PROCESSES IN A SEQUENCE:
1. Path AB: Reversible isothermal expansion (Th).

(3)
2. Path BC: Reversible adiabatic expansion

(3)
3. Path CD: Reversible isothermal compression (T i).

(4)
4. Path DA: Reversible adiabatic compression

(5)
The net work done on the system is

(6)
Recall, however, that in an adiabatic expansion, the temperatures T 1 and T2 are related to the
volumes V1 and V2 by
Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 68
 (7)
which can be applied to the paths BC and DA, the adiabatic expansion and compression parts
of the cycle. Thus, for the path BC,

(8)
from which it follows that

(9)
and the net work done on the system is

(10)
From equation (2)

Therefore

the negative ratio of these, which gives the efficiency, is

Thus, for an engine operating reversibly between a high temperature Th and a low
temperature Tl , the maximum efficiency of such a machine is 1 − (T l/Th).

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.

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 69

For the process
Gas → Liquid
∆S = 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
∆S = S(final) – S(initial) = S(solid) – S(liquid) = –ve

Comparison: The increasing order of entropy S(Gas) >> S (Liquid) > S(Solid) suggests that
the value of ∆S(Gas → Liquid) is more negative as compared to the value of ∆S(Liquid →
Solid)
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

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.

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 70

Problem 1: Calculate the change in entropy 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 C P, m = 25 JK–1
mol–1
Solution: For isobaric heating of an ideal gas

Problem 2. 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

Problem 3. 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

and entropy change in this phase transformation is equal to the entropy of fusion of ice.

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 71

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 72
 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.

The second law of thermodynamics is a statement about which processes occur and which do
not. i.e the recognition of two classes of process, spontaneous and non-spontaneous, is
summarized by the Second Law of thermodynamics. There are many ways to state the
second law; here is one:

Heat can flow spontaneously from a hot object to a cold object; it will not flow
spontaneously from a cold object to a hot object.

This law may be expressed in a variety of equivalent ways.

Second Law in Kelvin words: No process is possible in which the sole result is the
absorption of heat from a reservoir and its complete conversion into work.

Second Law in Clausius words: No process is possible whose sole result is the transfer of
heat from a body of lower temperature to a body of higher temperature.

Entropy (S)

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 73

The Second Law of thermodynamics, may also be expressed in terms of another state
function, the entropy (S). The Second Law uses the entropy to identify the spontaneous
changes among those permissible changes.

The Second Law of thermodynamics can be expressed in terms of the entropy:

The entropy of an isolated system increases in the course of a spontaneous change: ΔS tot > 0

Where Stot is the total entropy of the system and its surroundings.

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. This term was introduced by Clausius. He denoted
entropy by the symbol S in the honour of Sadi Carnot (S from Sadi).

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 thermodynamic definition of entropy

The thermodynamic definition of entropy is based on the expression

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 74

Where qrev is the heat supplied reversibly. For a measurable change between two states intial
(i) and final (f ) this expression integrates to

That is, to calculate the difference in entropy between any two states of a system

Statistical definition of entropy

For any system, the entropy is given by the Boltzmann equation:

where w is the number of possible configurations of the system and k B is Boltzmann’s

constant.

This definition allows the entropy to be understood as a measure of the disorder in a

system.

Greater the randomness larger is the value of entropy. Lower is randomness smaller is the
value of entropy.

Relation between energy and entropy

The change of internal energy is given by the first law of thermodynamics as

The change of entropy is given by the second law of thermodynamics as

On substituting the expression for dq from equation (ii) in to equation (i), we get

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 75

Equations (iii) and (iv) represent the combined form of first and second laws of
thermodynamics.

Entropy changes accompanying specific processes

(A) Entropy change for isothermal reversible expansion of an ideal gas
The thermodynamic definition of entropy is

Where qrev is the heat supplied reversibly. For a measurable change between two states i and
f this expression integrates to

we know that

It follows that

V2 V
S2  S1  S  nR ln  2.303nR log 2
V1 V1

(B) 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

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 76

volume VA + VB. Therefore, the mixing process can be assumed that gas A expands from its
initial volume VA to a final volume of V A + VB.
The entropy change of gas A at constant temperature is given by

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

The total entropy change is equal to the sum of the entropy changes of gas A and gas B on
mixing.

(F) 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 .
(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.

∆vapS = Entropy in the final state – Entropy in the initial state

= Entropy of vapour phase – Entropy of the liquid phase
= S (vapour) – S (liquid)
∆vapH = Enthalpy of vaporization of the liquid = Heat of vaporization of the liquid

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 77

 Tb = Boiling point (in Kelvin) of the liquid
(B) Entropy of fusion ∆fusS
The 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.

∆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

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.

For an irreversible process (spontaneous process) when only P-V work is considered

In an isolated system energy and volume are constant that is, dU = 0 and dV= 0, therefore,

In a reversible processes ( equilibrium)

In an isolated system energy and volume are constant that is, dU = 0 and dV= 0, therefore,

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 78

The combined result is written as (dS)U, V >= 0
For finite changes (∆S)U, V >= 0
Thus in an isolated system at constant energy and constant volume the entropy is maximum
at equilibrium

Power Cycles
Most power producing devices operate on cycles. To make simple thermodynamics analysis
possible, we use the concept of ideal cycle. Ideal cycles are internally reversible, thus, the
thermal efficiency of an ideal cycle, in general, is less than that of a totally reversible cycle
operating between the same temperature limits, i.e., Carnot cycle.
CARNOT CYCLES
Sadi Carnot was a French physicist who proposed an “ideal” cycle for a heat engine in 1824.
Carnot proposed that a cycle comprised of completely (internally and externally) reversible
processes would give the maximum amount of net work for a given heat input, since the
work done by a system in a reversible (ideal) process is always greater than that in an
irreversible (real) process.
Consider the thermodynamic path shown below:

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 79

This closed thermodynamic path or cycle is called the Carnot cycle. In the ABC portion of
the cycle, the system expands, so it does work. In the CDA portion of the path, the system is
compressed, so work is done on it. The net work, which is the sum of contributions from
paths ABC and path CDA, is the net work done by the system, so it must be negative:

(1)
Note that the net work performed by the engine is just the area of enclosed by the by four
paths in the P-V plane.
Since, for a closed path, the change in energy is 0, the net work done by the gas must be
equal the negative of the heat absorbed by the system:

(2)
THE CARNOT HEAT ENGINE CYCLE CONSISTS OF FOUR REVERSIBLE PROCESSES IN A SEQUENCE:
1. Path AB: Reversible isothermal expansion (Th).

(3)
2. Path BC: Reversible adiabatic expansion

(3)
3. Path CD: Reversible isothermal compression (T i).

(4)
4. Path DA: Reversible adiabatic compression

(5)
The net work done on the system is

(6)
Recall, however, that in an adiabatic expansion, the temperatures T 1 and T2 are related to the
volumes V1 and V2 by
Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 80
 (7)
which can be applied to the paths BC and DA, the adiabatic expansion and compression parts
of the cycle. Thus, for the path BC,

(8)
from which it follows that

(9)
and the net work done on the system is

(10)
From equation (2)

Therefore

the negative ratio of these, which gives the efficiency, is

Thus, for an engine operating reversibly between a high temperature Th and a low
temperature Tl , the maximum efficiency of such a machine is 1 − (T l/Th).

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.

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 81

For the process
Gas → Liquid
∆S = 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
∆S = S(final) – S(initial) = S(solid) – S(liquid) = –ve

Comparison: The increasing order of entropy S(Gas) >> S (Liquid) > S(Solid) suggests that
the value of ∆S(Gas → Liquid) is more negative as compared to the value of ∆S(Liquid →
Solid)
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

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.

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 82

Problem 1: Calculate the change in entropy 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 C P, m = 25 JK–1
mol–1
Solution: For isobaric heating of an ideal gas

Problem 2. 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

Problem 3. 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

and entropy change in this phase transformation is equal to the entropy of fusion of ice.

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 83

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 84
 Free Energy and chemical equilibria

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 or change of enthalpy 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. 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 automatically incorporate
the internal energy, enthalpy and entropy changes of the system.

Two thermodynamic functions namely Gibbs energy (G) and Helmholtz energy (A) are
introduced which fulfill the above requirements.

Gibbs energy

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 which automatically accounts for
the enthalpy and entropy of the system. 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

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 85

Gibbs energy change and useful work
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)
The definitions of thermodynamic functions of G and H
G = H – TS (1)
H = U + PV (2)
Equation (1) substituted in equation (2)
G = U +PV – TS (3)
If the changes are made in the system so that its properties are also changed
ΔG = ΔU + PΔV – TΔS (4)
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 (5)
On substituting the expression for ∆U from equation (5) into equation (4), we get
∆G = T∆S + w + P∆V –T∆S
= w + P∆V (P∆V is mechanical)
Therefore, ∆G = 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).

Free energy change and spontaneous processes

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

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 86

If there is increase in the free energy, the process is non spontaneous
∆G)T, P > 0
These criteria may be summarized as follows
(i) ∆G is negative Spontneous process
(ii) ∆G is positive Nonspontneous process
(iii) ∆G is zero Equilibrium state

Variation of Gibbs energy (G) with temperature and pressure

G = H – TS and H = U + PV
G = U + PV –TS (1)
For small changes
dG = dU + PdV +VdP – TdS – SdT (2)
From combined form of first and second laws thermodynamics, we have
TdS = dU + PdV (3)
From equations (2) and (3),
dG = TdS +VdP – TdS – SdT
= VdP – S dT (4)
This expression, which shows that a change in G is proportional to a change in p or T,
suggests that G may be best regarded as a function of p and T.
At constant Temperature

At constant pressure

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 87

Calculation of ∆G for isothermal pressure change of an ideal gas

dG= VdP – S dT
In an isothermal process, T is constant and dT = 0, therefore, equation is written as

A finite change in G is calculated by integrating equation (i) for the change of state from
initial state 1 to final state 2

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 ( liquids and 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

(b) For an ideal gas

The volume of an ideal gas is given by V= nRT/P. Therefore, equation (i) is rewritten

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 88

From above equation 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 H. L. F. 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.

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

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which can be obtained from a system. It is because of this relation that A is called work
function.

Helmholtz energy change and spontaneous processes

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
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
(∆A)T, V > 0 nonspontaneous
These criteria may be summarized as follows
(i) ∆A is negative Spontneous process
(ii) ∆A is positive Nonspontneous process
(iii) ∆A is zero Equilibrium state

Variation of Helmholtz energy (A) with volume and temperature

From combined form of first and second laws thermodynamics, we have

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

(i) When T is constant, dT = 0, therefore,

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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,

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

A finite change in A is calculated by integrating equation (i) for the change of state from
initial state 1 to final state 2

For an an ideal gas we have PV = nRT and P= nRT/V. Therefore, equation (ii) is rewritten as

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

From equations (i) and (ii) we get

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 91

For a finite change in the state of the system

At constant temperature, P2V2 = P1V1 for an ideal gas

Therefore, for an ideal gas at constant temperature

In terms of change of pressure and volume for an ideal gas at constant temperature

VARIATION OF G AND A WITH T (Gibbs Helmholtz equation)

Variation of free energy functions with T is called Gibbs Helmholtz equation. Such variation
is studied for G and A separately.

The change of Gibbs energy is given by

At constant pressure, dP = 0 and thus

G = H + TS

This equation is called Gibbs Helmholtz equation

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 92

Second form of Gibbs Helmholz equation:
From Gibbs Helmholz equation

For finite changes in H and G Gibbs Helmholtz equation is written as

On dividing both sides of above equation by T 2, we get

Now right hand side of above equation is the differential of – ∆G/T with respect to T.
Therefore

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

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 maintain in the laboratory. Therefore, the use of ∆A or ∆G is preferred over ∆S as
a driving force to predict the direction of a process

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

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.

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.
(ii) Maxwell relations are useful to derive other important thermodynamic relations in
a simple way.

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 94

 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

On dividing equation (i) by dV at constant temperature we gave

But Maxwell relation states that

From equations (iii) and (iv) we get

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.

(c) Thermodynamic equation of state in terms of change in enthalpy

Entropy change and enthalpy change are related by

On dividing equation (i) by dP at constant temperature we gave

But Maxwell relation states that

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 95

 From equations (iii) and (iv) we get

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 (∆ rG0)

The standard free energy of a reaction is calculated by the following methods
(i) Using the relation

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

(b) The value of ∆rSυ is calculated by the use of standard entropy (Sυ) values of the reactants
and products as

(ii) Using the relation

Where ∆rGυ = standard free energy of formation.

(a) For compounds the values ∆rGυ 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
∆rGυ (element) = 0
(c) Entropy of an element is not zero at temperatures higher than 0 K; S υ (element) ≠0

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 96

Problems in Free energy
Problem.1. Calculate ∆rGυ at 25oC for the reaction 2NH3 (g) → N2(g) + 3H2(g) using the
following data

Solution

For the reaction

Step 1 : calculation of ∆rHυ

Step 2 : calculation of ∆rSυ

Therefore

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 97

Problem.2. 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.

Solution

Problem.3. Using the ∆f Gυ values calculate ∆rGυ for the following reactions and state the
spontaneous and nonspontaneous reactions by given data

Solution

∆rGυ is negative, therefore the given reaction is spontaneous.

∆rGυ is positive, therefore the given reaction is nonspontaneous.

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 98

∆rGυ is negative, therefore the given reaction is spontaneous.

Problem.4. Use the following ∆rG values at 1073 K to calculate the change in Gibbs energy
for the reaction 2ZnS(s) + 3O2(g) → 2ZnO(s) + 2 SO2(g) and show that the roasting of zinc
sulphide in to zinc oxide is a spontaneous process.

Solution

The reaction

2ZnS(s) + 3O2(g) → 2ZnO(s) + 2 SO2(g) (iv)

Operations: Equation (i) + equation (ii) − equation (iii) = Equation (iv)

On cancelling the common terms and rearranging the above equation we get

The value of is negative. Therefore, roasting of zinc sulphide is spontaneous.

Problem.5. For the reaction Ag2O(s) → 2Ag (s) +1/2O2(g), ∆rHυ = 30.56 kJ mol−1 and ∆rSυ
= 6.6 JK−1 mol−1 at 1 bar. Calculate the temperature at which ∆rGυ will be zero. What will be

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 99

the direction of the reaction at this temperature and above and below this temperature and
why?

Solution

So

(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

Problem.6. 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

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 100

Thermodynamic treatment of solutions
The partial pressure, which is the contribution of one component to the total pressure, is used
to discuss the properties of mixtures of gases already known. For a more general description
of the thermodynamics of mixtures we need to introduce other analogous ‘partial’ properties.

(a) Partial molar volume

The partial molar volume of a substance A in a mixture is the change in volume per mole of
A added to a large volume of the mixture.

The partial molar volumes of the components of a mixture vary with composition because the
environment of each type of molecule changes as the composition changes from pure A to
pure B. It is this changing molecular environment, and the consequential modification of the
forces acting between molecules, that results in the variation of the thermodynamic
properties of a mixture as its composition is changed.

The partial molar volume, VJ, of a substance J at some general composition is defined
formally as follows:

where the subscript n′ signifies that the amounts of all other substances present are constant.
The definition in equation (1) implies that, when the composition of the mixture is changed
by the addition of dnA of A and dnB of B, then the total volume of the mixture changes by

Provided the relative composition is held constant as the amounts of A and B are increased,
we can obtain the final volume by integration:

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 101

(b) Partial molar Gibbs energies

For a substance in a mixture, the chemical potential is defined as the partial molar Gibbs

energy:
The total Gibbs energy of a binary mixture is

Where μA and μB are the chemical potentials at the composition of the mixture. The chemical
potentials depend on composition (and the pressure and temperature), the Gibbs energy of a
mixture may change when these variables change, and, for a system of components A, B,
etc., the equation
dG = Vdp − SdT becomes

This expression is the fundamental equation of chemical thermodynamics.

At constant pressure and temperature, equation (3) simplifies to

We know that under the same conditions dG = dwmax. Therefore, at constant temperature and
pressure

That is, additional (non-expansion) work can arise from the changing composition of a
system. For instance, in an electrochemical cell, the chemical reaction is arranged to take
place in two distinct sites (at the two electrodes). The electrical work the cell performs can be
traced to its changing composition as products are formed from reactants.

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 102

The Gibbs–Duhem equation

The total Gibbs energy of a binary mixture is given by

The chemical potentials depend on the composition, when the compositions are changed
infinitesimally we might expect G of a binary system to change by

but, by the fundamental equation

Subtracting, the two equations yield and at constant temperature and pressure

This equation is a special case of the Gibbs–Duhem equation:

In a binary mixture, if one partial molar quantity increases, then the other must decrease, with
the two changes related by

The chemical potentials of liquids

(a) Ideal solutions
In solution the pure substance (solvent) chemical potential can be write
A  0A  RT ln pA (1)
Where
A = the chemical potential of pure substance A

0A = the chemical potential of standard stae substance A

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If another substance, a solute, is also present in the liquid, the chemical potential of A in the
liquid is changed to μA and its vapour pressure is changed to pA. The vapour and solvent are
still in equilibrium, so we can write

 A  0A  RT ln p A (2)
From equation (1) , we can write

 0A  A  RT ln pA (3)

Equation (3) substituted in equation (2)

A  A  RT ln pA  RT ln pA
A  A  (RT ln p A  RT ln pA ) (4)
pA
A  A  RT ln
pA
In a series of experiments on mixtures of closely related liquids (such as benzene and
methylbenzene), the French chemist François Raoult found that the ratio of the partial vapour
pressure of each component to its vapour pressure as a pure liquid, pA / pA , is approximately
equal to the mole fraction of A in the liquid mixture. That is, he established what we now call
Raoult’s law:
pA
 xA
pA (5)

pA  x A p A

For an ideal solution, it follows from equations (4) and (5)

 A  A  RT ln x A (6)

This important equation can be used as the definition of an ideal solution, i.e an ideal
solutions the solute, as well as the solvent, obeys Raoult’s law.
(b) Ideal-dilute solutions
The English chemist William Henry found experimentally that, for real solutions at low
concentrations, although the vapour pressure of the solute is proportional to its mole fraction,
the constant of proportionality is not the vapour pressure of the pure substance.
Henry’s law is:

pB  x BK B

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 104

Where xB is the mole fraction of the solute and
KB is an empirical constant (with the dimensions of pressure)
KB value is chosen so that the plot of the vapour pressure of B against its mole fraction is
tangent to the experimental curve at x B =0.
Mixtures for which the solute obeys Henry’s law and the solvent obeys Raoult’s law are
called ideal-dilute solutions.
The Gibbs energy of mixing liquids
(a) Ideal solutions The Gibbs energy of mixing of two liquids to form an ideal solution is
calculated in exactly the same way as for two gases. The total Gibbs energy before liquids
are mixed is

When they are mixed, the individual chemical potentials are given by equations the total
Gibbs energy is

The Gibbs energy of mixing, the difference of these two quantities, is

G f  G i  n A A  RT ln x A   n B B  RT ln x B   n A A  n BB

G f  G i  n A A  n A RT ln x A  n BB  n B RT ln x B  n A A  n BB
G f  G i  n A RT ln x A  n B RT ln x B
nA
 x A  n A  nx A
n
G f  G i  nx A RT ln x A  nx B RT ln x B

 mix G  nRT x A ln x A  x B ln x B 

The entropy of mixing

ΔmixG = ΔmixH - TΔmixS
the ideal enthalpy of mixing (ΔmixH) is zero, therefore
ΔmixG = - TΔmixS
ΔmixS = - ΔmixG/T
 mixS   nR x A ln x A  x B ln x B 

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 105

Phase equilibria and their thermodynamic criterion
A phase is a form of matter that is uniform throughout in chemical composition and physical
state. The thermodynamic analysis of phases is based on the fact that, at equilibrium, the
chemical potential of a substance is the same throughout a sample.

Two phases at equilibrium as a function of pressure and temperature

The equations that describe equilibrium conditions between two phases of the same
substance are derivable from the two laws of thermodynamics with the aid of the functions.

Let us represent the equilibrium in a closed system at any given temperature and pressure by
the equation

Phase A = Phase B

As the system is at equilibrium at constant temperature and pressure, any infinitesimal

transfer of matter between Phase A and Phase B occurs with a change of zero in the Gibbs
function and in the Planck function. That is,

in which GmA and GmB are the molar Gibbs functions of A and B, YmA and YmB are the
respective Planck functions, and dnA and dnB are the infinitesimal changes in the number of
moles of A and B.

As the system is closed, dnB = -dnA and

As Equation (2) holds for any infinitesimal transfer dnA whatsoever, the quantities in
parentheses must equal zero and

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 106

If the temperature and pressure are changed by amounts dT and dP such that the system
reaches a new state of equilibrium, then the molar Gibbs functions of A and B change by
amounts of dGA and dGB such that

From equation (3)

Similarly,

Clapeyron Equation

Where VmA and VmB are the molar volumes of A and B and SmA and SmB are the molar
entropies

At equilibrium

(2)

which can be rearranged to give

(3)

(4)

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 107

From above Equation , we conclude that T and P are functions of each other at equilibrium.
For an isothermal, reversible (that is, equilibrium) condition at constant pressure, from
Equation

(5)
Therefore, Equation (4) can be converted to

which is generally known as the Clapeyron equation.

The Clapeyron equation is applicable to equilibrium between any two phases of one
component at the same temperature and pressure, and it describes the functional relationship
between the equilibrium pressure and the equilibrium temperature.

Phase transitions

A phase transition, the spontaneous conversion of one phase into another phase, occurs at a
characteristic temperature for a given pressure. Thus, at 1 atm, ice is the stable phase of water
below 0°C, but above 0°C liquid water is more stable. This difference indicates that below
0°C the Gibbs energy decreases as liquid water changes into ice and that above 0°C the
Gibbs energy decreases as ice changes into liquid water.

The transition temperature, Ttrs, is the temperature at which the two phases are in equilibrium
and the Gibbs energy of the system is minimized at the prevailing pressure.

Thermodynamic criterion for Phase Equilibrium

The thermodynamic criterion for phase equilibrium is simple. It is based upon the chemical
potentials of the components in a system. For simplicity, consider a system with only one
component. For the overall system to be in equilibrium, the chemical potential of the
compound in each phase present must be the same. Otherwise, there will be some mass
migration from one phase to another, decreasing the total chemical potential of the phase
from which material is being removed, and increasing the total chemical potential of the

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 108

phase into which the material is being deposited. So for each pair of phases present (α and β)
the following must be true:
µα = µ β
The Gibbs phase rule describes the number of compositional and phase variables that can be
varied freely for a system at equilibrium. For each phase present in a system, the mole
fraction of all but one component can be varied independently. However, the relationship

places a constraint on the last mole fraction. As such, there are C–1 compositional degrees of
freedom for each phase present, where C is the number of components in the mixture.
Similarly, all but one of the chemical potentials of each phase present must be equal, leaving
only one that can be varied independently, leading to P–1 thermodynamic constraints placed
on each component. Finally, there are two state variables that can be varied (such as pressure
and temperature), adding two additional degrees of freedom to the system. The net number of
degrees of freedom is determined by adding all of the degrees of freedom and subtracting the
number of thermodynamic constraints.

Gibbs phase rule may be stated as follows: "In a heterogeneous system in equilibrium, the
number of degrees of freedom plus the number of phases is equal to the number of
components plus two".
Mathematically,

F+P=C+2 or

F=C–P+2

where F = number of degrees of freedom

C = number of components
P = number of phases
2 = additional variables of temperature and pressure besides the concentration variables.

Prof. Nambury Surendra BaBu, Associate Professor, UDOM Page 109