Thermodynamics

Introduction
Thermodynamics provides a description of matter on a macroscopic scale using bulk
properties such as pressure, density, volume, and temperature.
This part of a course introduces the basic concepts employed in thermodynamics including
system, surroundings, intensive and extensive variables, adiabatic and diathermal walls,
equilibrium, temperature, and thermochemistry.
The macroscopic variables such as pressure and temperature are also discussed in terms of
a molecular level model. The usefulness of equations of state, which relate the state variables of
pressure, volume, and temperature, is also discussed for an ideal gas.
What is Thermodynamics?
Thermodynamics is the branch of science that describes the behavior of matter and the
transformation between different forms of energy on a large/macroscopic scale.
Or
Thermodynamics is the branch of science that studied the flow of heat or any other form
of energy into or out of a system as it undergoes a physical or chemical transformation on a
macroscopic scale.
In studying and evaluating the flow of energy into or out of a system, it will be useful to
consider changes in certain properties of the system. These properties include temperature,
pressure, volume and concentration of the system. Measuring the changes in these properties from
the initial state to the final state, can provide information concerning changes in energy and related
quantities such as heat and work.
The Three Empirical Laws
The study of thermodynamics is based on three broad generalizations derived from well-
established experimental results. These generalizations are known as the First, Second and Third
law of thermodynamics. These laws have stood the test of time and are independent of any theory
of the atomic or molecular structure. The discussion of these laws will be the subject of our study
in the two chapters on thermodynamics.
Scope of Thermodynamics
✓ Most of the important laws of Physical Chemistry, including the van’t Hoff law of lowering of
vapour pressure, Phase Rule and the Distribution Law, can be derived from the laws of
thermodynamics.
1
✓ It tells whether a particular physical or chemical change can occur under a given set of
conditions of temperature, pressure and concentration.
✓ It also helps in predicting how far a physical or chemical change can proceed, until the
equilibrium conditions are established.
Limitations of Thermodynamics
➢ Thermodynamics is applicable to macroscopic systems consisting of matter in bulk and not
to microscopic systems of individual atoms or molecules. It ignores the internal structure of
atoms and molecules.
➢ Thermodynamics does not bother about the time factor. That is, it does not tell anything
regarding the rate of a physical change or a chemical reaction. It is concerned only with the
initial and the final states of the system.
Definition of Thermodynamic Terms and Basic Concepts
❖ System: is any part of the matter/universe that is under thermodynamic study which is
separated from the rest of the universe with a boundary surface.
❖ Surrounding: the rest of the matter/universe which might be in a position to exchange energy
and matter with the system under investigation.
❖ Boundary: This is the real or imaginary surface separating the system from the surroundings.

Figure 1: Thermodynamic system

The interface between the system and its surroundings is called the boundary. Boundaries
determine if energy and mass can be transferred between the system and the surroundings and
lead to the distinction between open, closed, and isolated systems. Consider Earth’s oceans as a
system, with the rest of the universe being the surroundings. The system–surroundings boundary
consists of the solid–liquid interface between the continents and the ocean floor and the water–
air interface at the ocean surface. For an open beaker in which the system is the contents, the
boundary surface is just inside the inner wall of the beaker, and it passes across the open top of
the beaker. In this case, energy can be exchanged freely between the system and surroundings

2
through the side and bottom walls, and both matter and energy can be exchanged between the
system and surroundings through the open top boundary. The portion of the boundary formed by
the beaker in the previous example is called a wall. Walls can be rigid or movable and permeable
or nonpermeable. An example of a movable wall is the surface of a balloon. An example of a
selectively permeable wall is the fabric used in raingear, which is permeable to water vapor, but
not liquid water.
Homogeneous and Heterogeneous Systems
When a system is uniform throughout, it is called a Homogeneous System. Examples
are: a pure single solid, liquid or gas, mixtures of gases, and true solution of a solid in a liquid. A
homogeneous system is made of one phase only. A phase is defined as a homogeneous, physically
distinct and mechanically separable portion of a system.
A heterogeneous system is one which consists of two or more phases. In other words, it
is not uniform throughout. Examples of heterogeneous systems are: ice in contact with water, ice
in contact with vapour etc. Here ice, water and vapour constitute separate phases.
Types of Thermodynamic Systems
There are three types of thermodynamic systems depending on the nature of the boundary.
If the boundary is closed or sealed, no matter can pass through it. If the boundary is insulated, no
energy (say heat) can pass through it.
(1) Isolated System: When the boundary is both sealed and insulated, no interaction is possible
with the surroundings. Therefore, an isolated system is one that can transfer neither matter
nor energy to and from its surroundings.
Let us consider a system of 100 ml of water in contact with its vapour in a closed vessel
which is insulated. Since the vessel is sealed, no water vapour (matter) can escape from it. Also,
because the vessel is insulated, no heat (energy) can be exchanged with the surroundings.
A substance, say boiling water, contained in a thermos flask, is another example of an
isolated system.
(2) Closed System: a closed system is one which cannot transfer matter but can transfer
energy in the form of heat, work and radiation to and from its surroundings. Therefore, here
the boundary is sealed but not insulated.

3
 A specific quantity of hot water contained in a sealed tube, is an example of a closed
system. While no water vapour can escape from this system, it can transfer heat through the walls
of the tube to the surroundings.
A gas contained in a cylinder fitted with a piston constitutes a closed system. As the piston
is raised, the gas expands and transfers heat (energy) in the form of work to the surroundings.
(3) Open System: an open system is one which can transfer both energy and matter to and
from its surroundings. Therefore, in such a system the boundary is open and un-insulated.
Hot water contained in a beaker placed on laboratory table is an open system. The water
vapour (matter) and also heat (energy) is transferred to the surroundings through the imaginary
boundary.
Zinc granules reacting with dilute hydrochloric acid to produce hydrogen gas in a beaker,
is another example of open system. Hydrogen gas escapes and the heat of the reaction is
transferred to the surroundings.

Figure 2: Isolated, closed and open systems.

Properties of a System
The bulk/macroscopic properties of a system (volume, pressure, mass, density,
concentration etc.) can be divided into two classes:
(a) Intensive properties

4
(b) Extensive properties
(a) Intensive Properties: is a property which does not depend on the quantity of matter
present in the system.
Some examples of intensive properties are pressure, temperature, density, and
concentration. If the overall temperature of a glass of water (our system) is 20ºC, then any drop
of water in that glass has a temperature of 20ºC. Similarly, if the concentration of salt, NaCl, in
the glass of water is 0.1 mole/litre, then any drop of water from the glass also has a salt
concentration of 0.1 mole/litre.
(b) Extensive Properties: is a property that does depend on the quantity of matter present
in the system.
Some examples of extensive properties are volume, number of moles, enthalpy, entropy,
and Gibbs’ free energy. Some of these properties are unfamiliar to you but these will be defined
and illustrated later.
By definition, the extensive properties are additive while intensive properties are not.
Let us consider the system ‘a glass of water’. If we double the mass of water, the volume is
doubled and so is the number of moles and the internal energy of the system.
State of a System
A thermodynamic system is said to be in a certain state when all its fundamental
properties are fixed.
The fundamental properties which determine the state of a system are pressure (P),
temperature (T), volume (V), mass and composition. Since a change in the magnitude of such
properties alters the state of the system, these are referred to as State variables or State functions
or Thermodynamic parameters. It also stands to reason that a change of system from the initial
state to the final state (2nd state) will be accompanied by change in the state variables.
It is not necessary to state all the properties (state variables) to define a system completely.
For a pure gas, the composition is fixed automatically, as it is cent per cent. The remaining state
variables P, V, T are interrelated in the form of an algebraic relationship called the Equation of
State. Thus, for one mole of a pure gas, the equation of state is:
PV = RT
where R is gas constant. If of the three state variables (P, V, T), P and T are specified, the
value of third (V) is fixed automatically and can be calculated from the equation of state. The

5
variables (P and T) which must be necessarily specified to define the state of a system, are
designated as Independent state variables. The remaining state variable (V) which depends on
the value of P and T, is called Dependent state variable.
An important characteristic of a state variable (or state function) is that when the state of a
system is altered, the change in the variable depends on the initial and final states of the
system. For example, if we heat a sample of water from 0º C to 25º C, the change in temperature
is equal to difference between the initial and final temperatures.
ΔT = Tfinal – Tinitial = 25ºC
The way in which the temperature change is brought about has no effect on the result.
Equilibrium and Non–Equilibrium States
A system in which the state variables have constant values throughout the system is
said to be in a state of thermodynamic equilibrium.
Suppose we have a gas confined in a cylinder that has a frictionless piston. If the piston is
stationary, the state of the gas can be specified by giving the values of pressure and volume. The
system is then in a state of equilibrium.
A system in which the state variables have different values in different parts of the
system is said to be in a non-equilibrium state.
If the gas contained in a cylinder, is compressed very rapidly by moving down the piston,
it passes through states in which pressure and temperature cannot be specified, since these
properties vary throughout the gas. The gas near the piston is compressed and heated and that at
the far end of the cylinder is not. The gas then would be said to be in non-equilibrium state.
The exchange of energy and matter across the boundary between system and surroundings
is central to the important concept of equilibrium. The system and surroundings can be in
equilibrium with respect to one or more of several different system variables such as pressure
(P), temperature (T), and concentration. Thermodynamic equilibrium refers to a condition in
which equilibrium exists with respect to P, T, and concentration.
The Criteria for Equilibrium
❖ The temperature of the system must be uniform and must be the same as the temperature
of the surroundings (thermal equilibrium).

6
❖ The mechanical properties must be uniform throughout the system (mechanical
equilibrium). That is, no mechanical work is done by one part of the system on any other part
of the system.
❖ The chemical composition of the system must be uniform with no net chemical change
(chemical equilibrium).
If the system is heterogeneous, the state variables of each phase remain constant in
each phase.
What conditions are necessary for a system to come to equilibrium with its surroundings?
Equilibrium is established with respect to a given variable only if that variable does not
change with time, and if it has the same value in all parts of the system and surroundings. For
example, the interior of a soap bubble (the system) and the surroundings (the room) are in
equilibrium with respect to P because the movable wall (the bubble) can reach a position where P
on both sides of the wall is the same, and because P has the same value throughout the system and
surroundings. Equilibrium with respect to concentration exists only if transport of all species
across the boundary in both directions is possible. If the boundary is a movable wall that is not
permeable to all species, equilibrium can exist with respect to P, but not with respect to
concentration. Because N2 and O2 cannot diffuse through the (idealized) bubble, the system and
surroundings are in equilibrium with respect to P, but not to concentration.
Equilibrium with respect to temperature is a special case that is discussed next. Two
systems that have the same temperature are in thermal equilibrium. We use the concepts of
temperature and thermal equilibrium to characterize the walls between a system and its
surroundings. Considering two systems with rigid walls as shown in Figure 3. Each system has the
same molar density and is equipped with a pressure gauge.

Figure 3: Two systems with rigid walls at thermal equilibrium.

7
 If we bring the two systems into direct contact, two limiting behaviors are observed. If
neither the pressure gauge changes, as in Figure 4, we refer to the walls as being adiabatic.
Because, the systems are not in thermal equilibrium and, therefore, have different temperatures.
An example of a system surrounded by adiabatic walls is coffee in a Styrofoam cup with a
Styrofoam lid. Experience shows that it is not possible to bring two systems enclosed by adiabatic
walls into thermal equilibrium by bringing them into contact, because adiabatic walls insulate
against the transfer of “heat.” If we push a Styrofoam cup containing hot coffee against one
containing ice water, they will not reach the same temperature.

Figure 4: Two systems in direct contact separated by adiabatic wall.

The second limiting case is shown in Figure 5. In bringing the systems into intimate
contact, both pressures change and reach the same value after some time. We conclude that the
systems have the same temperature, T1 = T2, and say that they are in thermal equilibrium. We refer
to the walls as being diathermal. Two systems in contact separated by diathermal walls reach
thermal equilibrium because diathermal walls conduct heat. Hot coffee stored in a copper cup is
an example of a system surrounded by diathermal walls. Because the walls are diathermal, the
coffee will quickly reach room temperature.

Figure 5: Two systems in contact separated by diathermal walls

8
 Thermodynamic Processes
When a thermodynamic system changes from one state to another, the operation is
called a Process. These processes involve the change of conditions (temperature, pressure and
volume). The various types of thermodynamic processes are:
(1) Isothermal Processes: These are processes in which the temperature remains fixed/constant.
This is often achieved by placing the system in a thermostat (a constant temperature bath).
For an isothermal process dT = 0
(2) Adiabatic Processes: These are processes in which no heat can flow into or out of the system.
Adiabatic conditions can be approached by carrying the process in an insulated container such as
‘thermos’ bottle. High vacuum and highly polished surfaces help to achieve thermal insulation.
For an adiabatic process dq = 0
(3) Isobaric Processes: These are processes which take place at constant pressure. For example,
heating of water to its boiling point and its vaporization take place at the same atmospheric
pressure. These changes are, therefore, designated as isobaric processes and are said to take place
isobarically.
For an isobaric process dp = 0
(4) Isochoric Processes: These are processes in which the volume remains constant. The heating
of a substance in a non-expanding chamber is an example of isochoric process.
For isochoric processes dV = 0

Figure 6: The four basic thermodynamic processes

9
(5) Cyclic Process: When a system in a given state goes through a number of different processes
and finally returns to its initial state, the overall process is called a cycle or cyclic process and is
shown in Figure 7. For a cyclic process dE = 0, dH = 0.

Figure 7: A cyclic process

Reversible and Irreversible Processes
A thermodynamic reverse process is one that takes place infinitesimally slowly and its
direction at any point can be reversed by an infinitesimal change in the state of the system.
In fact, a reversible process is considered to proceed from the initial state to the final state through
an infinite series of infinitesimally small stages. At the initial, final and all intermediate stages, the
system is in equilibrium state. This is so because an infinitesimal change in the state of the system
at each intermediate step is negligible.
When a process goes from the initial to the final state in a single step and cannot be carried
in the reverse order, it is said to be an irreversible process. Here the system is in equilibrium state
in the beginning and at the end, but not at points in between.
Consider a certain quantity of a gas contained in a cylinder having a weightless and
frictionless piston. The expansion of the gas can be carried by two methods illustrated in Figure 8.
Let the pressure applied to the piston be P and this is equal to the internal pressure of the
gas. Since the external and internal pressures are exactly counterbalanced, the piston remains

10
stationary and there is no change in volume of the gas. Now suppose the pressure on the piston is
decreased by an infinitesimal amount dP. Thus, the external pressure on the piston being P – dP,
the piston moves up and the gas will expand by an infinitesimal small amount. The gas will,
therefore, be expanded infinitely slowly i.e., by a thermodynamically reversible process. At all
stages in the expansion of the gas, dP being negligibly small the gas is maintained in a state of
equilibrium throughout. If at any point of the process the pressure is increased by dP, the gas would
contract reversibly as shown in Figure 8a.
On the other hand, the expansion is irreversible (Figure 8b) if the pressure on the piston is
decreased suddenly. It moves upward rapidly in a single operation. The gas is in equilibrium state
in the initial and final stages only. The expansion of the gas, in this case, takes place in an
irreversible manner.

Figure 8: (a) Reversible expansion occurs by decreasing the pressure on the piston by
infinitesimal amounts. (b) Irreversible expansion occurs by sudden decrease of
pressure from P to P', when the gas expands rapidly in a single operation.

11
 Differences Between Reversible and Irreversible Processes
S/No. Reversible Process Irreversible Process
It takes place in infinite number of
1 infinitesimally small steps and it would take It takes place infinite time.
infinite time to occur.
It is imaginary as it assumes the presence
2 It is real and can be performed actually.
of frictionless and weightless piston.

3 It is in equilibrium state at all stages of the It is in equilibrium state only at the initial
operation. and final stages of the operation.
After this type of process has occurred all
4 All changes are reversed when the process is
changes do not return to the initial state by
carried out in reversible direction.
themselves.
5 It is extremely slow. It proceeds at measurable speed
Work done by a irreversible process is
6 Work done by a reversible process is greater
smaller than the corresponding reversible
than the corresponding irreversible process.
process.

Nature of Heat and Work

When a change in the state of a system occurs, energy is transferred to or from the
surroundings. This energy may be transferred as heat or mechanical work.
Sign Convention of Heat
The symbol of heat is q. If the heat flows from the surroundings into the system to raise
the energy of the system, it is taken to be positive, +q. If heat flows from the system into the
surroundings, lowering the energy of the system, it is taken to be negative, –q. We shall refer the
term ‘work’ for mechanical work which is defined as force × distance.

Figure 9: Sign convention for heat flow in a thermodynamic system.

12
 Sign Convention of Work
The symbol of work is w. If work is done on a system by the surroundings and the energy
of the system is thus increased, it is taken to be positive, +w. If work is done by the system on the
surroundings and energy of the system is decreased, it is taken to be negative, –w.
Summary of Sign Conventions
Heat flows into the system, q is +ve Heat flows out of the system, q is –ve
Work is done on the system, w is +ve Work is done by the system, w is –ve

Pressure–Volume Work
In physics, mechanical work is defined as force multiplied by the distance through which
the force acts. In elementary thermodynamics the only type of work generally considered is the
work done in expansion (or compression) of a gas. This is known as pressure-volume work or PV
work or expansion work.
Consider a gas contained in a cylinder fitted with a frictionless piston (Figure 10). The
pressure (force per unit area) of the gas, P, exerts a force on the piston. This can be balanced by
applying an equal but opposite pressure from outside on the piston. Let it be designated as Pext. It
is important to remember that it is the external pressure, Pext. and not the internal pressure
of the gas itself which is used in evaluating work. This is true whether it be expansion or
contraction.
If the gas expands at constant pressure, the piston would move, say through a distance l.
We know that
work = force × distance
or w = f × l .... (1)
Since pressure is force per unit area,
f = Pext × A .... (2)
where A is the cross-section area of the piston. From (1) and (2), we have
w = Pext × A × l
w = Pext × ΔV
where ΔV is the increase in volume of the gas.
Since the system (gas) is doing work on the surroundings (piston), it bears negative sign. Thus,
w = –Pext × ΔV

13
 Proceeding as above the work done in compression of a gas can also be calculated. In that
case the piston will move down and sign of the work will be positive.
w = Pext × ΔV
As already stated, work may be expressed in dynes-centimetres, ergs, or joules. PV work
can as well be expressed as the product of pressure and volume units e.g., in litre or atmospheres.
It may be noted that the work done by a system is not a state function. This is true of the
mechanical work of expansion. We shall show presently that the work is related to the process
carried out rather than to the internal and final states. This will be evident from a consideration of
the reversible expansion and an irreversible process.

Figure 10: Pressure volume work of a system (gas) confined by a frictionless piston.
Example 1:
Calculate the pressure-volume work done when a system containing a gas expands from
1.0 litre to 2.0 litres against a constant external pressure of 10 atmospheres.
Solution:
w = – Pext (V2 – V1)
= – (10 atm) (2 l – 1 l)
= – 10 l atm

14
 Isothermal Reversible Expansion Work of an Ideal Gas
Consider an ideal gas confined in a cylinder with a frictionless piston. Suppose it expands
in a reversible manner from volume V1 to V2 at a constant temperature. The pressure of the gas
is successively reduced from P1 to P2.
The reversible expansion of the gas takes place in a finite number of infinitesimally small
intermediate steps. To start with the external pressure, Pext, is arranged equal to the internal
pressure of the gas, Pgas, and the piston remains stationary. If Pext is decreased by an infinitesimal
amount dP the gas expands reversibly and the piston moves through a distance dl.
Since dP is so small, for all practical purposes,
Pext = Pgas = P
The work done by the gas in one infinitesimal step dw, can be expressed as
dw = P × A × dl
= P × dV
where dV is the increase in volume and A is the cross-sectional area of piston.
The total amount of work done by the isothermal reversible expansion of the ideal gas from
V1 to V2 is, therefore,
𝒗
w = - ∫𝒗 𝟐 𝑷𝒅𝑽
𝟏

By the ideal gas equation

𝐧𝐑𝐓
PV = nRT and P = 𝑽
𝒗 𝐧𝐑𝐓
∴ w = - ∫𝒗 𝟐 𝒅𝑽
𝟏 𝐕

𝒗 𝒅𝑽
w = -nRT ∫𝒗 𝟐 𝐕
𝟏

which integrates to give

𝑽
w = -nRT𝐥𝐧 𝑽𝟐
𝟏

Since
P1V1 = P2V2
V2/V1 = P1/P2
𝑷 𝑷
∴ w = -nRT𝐥𝐧 𝑷𝟏 or w = – 2.303 nRT 𝐥𝐨𝐠 𝑷𝟏
𝟐 𝟐

15
 Isothermal compression work of an ideal gas may be derived similarly and it has exactly
the same value with the sign changed. Here the pressure on the piston, Pext, is increased by dP
which reduces the volume of the gas.
Isothermal Irreversible Expansion Work of an Ideal Gas
Suppose we have an ideal gas contained in a cylinder with a piston. This time the process
of expansion of the gas is performed irreversibly i.e., by instantaneously dropping the external
pressure, Pext, to the final pressure P2. The work done by the system is now against the pressure P2
throughout the whole expansion and is given by the following expression:
𝒗
w = - Pext ∫𝒗 𝟐 𝒅𝑽
𝟏

= P2 (V2 – V1)
= P2 dV
Maximum Work Done in Reversible Expansion
The isothermal expansion of an ideal gas may be carried either by the reversible process
or irreversible process as stated.

Figure 11: (a) The reversible work of expansion; (b) The irreversible work done by the gas
when the external pressure is at once dropped to the final value P2
The reversible expansion is shown in Figure 11 in which the pressure is falling as the
volume increases. The reversible work done by the gas is given by the expression which is
represented by the shaded area in Figure 11 (a).
𝒗
- 𝒘𝒊𝒓𝒓 = ∫𝒗 𝟐 𝑷𝒅𝑽
𝟏

16
 Suppose the expansion is performed irreversibly by suddenly reducing the external
pressure to the final pressure P2. In that case, the irreversible work is shown by the shaded area in
Figure 11 (b).
- 𝒘𝒊𝒓𝒓 = P2 (V2 – V1)
In both the processes, the system's state has changed from A to B but the work done is much
less in the irreversible expansion than in the reversible expansion. Thus, mechanical work is not a
state function as it depends on the path by which the process is performed rather than on the initial
and final states. It is a path function.
It is also important to note that the work done in the reversible expansion of a gas is the
maximum work that can be done by a system (gas) in expansion between the same initial (A) and
final state (B). This is proved as follows:
We know that the work always depends on the external pressure, Pext; the larger the Pext
the more work is done by the gas. But the Pext on the gas cannot be more than the pressure of the
gas, Pgas or a compression will take place. Thus, the largest value Pext can have without a
compression taking place is equal to Pgas. But an expansion that occurs under these conditions is
the reversible expansion. Thus, maximum work is done in the reversible expansion of a gas.
Example 2:
Find the work done when one mole of the gas is expanded reversibly and isothermally from
5 atm to 1 atm at 25ºC.
Solution:
T = 25ºC + 273K = 298K
P1 = 5 atm
P2 = 1 atm
R = 8.314
n = 1 mole
𝑷 𝑷
Using w = -nRT𝐥𝐧 𝑷𝟏 = – 2.303 nRT 𝐥𝐨𝐠 𝑷𝟏
𝟐 𝟐

𝟓
= - 2.303 x 1 x 8.314 x 298 x log 𝟏 = -3988J or = -3.988kJ

Example 3:
One mole of an ideal gas at 25ºC is allowed to expand reversibly at constant temperature
from a volume of 10 litres to 20 litres. Calculate the work done by the gas in joules.

17
Solution:
T = 25ºC + 273K = 298K
V1 = 10L
V2 = 20L
R = 8.314
n = 1 mole
Using
𝑽 𝑽
w = -nRT𝐥𝐧 𝑽𝟐 = – 2.303 nRT 𝐥𝐨𝐠 𝑽𝟐
𝟏 𝟏

𝟐𝟎
= - 2.303 x 1 x 8.314 x 298 x log 𝟏𝟎 = - 1717.5 J or = - 1.7175kJ

Internal Energy
A thermodynamic system containing some quantity of matter has within itself a definite
quantity of energy. This energy includes not only the translation kinetic energy of the molecules
but also other molecular energies such as rotational, vibrational energies. The kinetic and potential
energy of the nuclei and electrons within the individual molecules also contribute to the energy of
the system.
The total of all the possible kinds of energy of a system, is called its Internal Energy
of that system.
The word ‘internal’ is often omitted and the energy of a system always implies internal
energy. The internal energy of a system, like temperature, pressure, volume, etc., is determined by
the state of a system and is independent of the path by which it is obtained. Hence internal energy
of a system is a state function.
For example, we consider the heating of one mole of liquid water from 0º to 100ºC. The
change in energy is 1.8 kcal and is the same regardless of the form in which this energy is
transferred to the water by heating, by performing work, by electrical means or in any other way.
Since the value of internal energy of a system depends on the mass of the matter contained
in a system, it is classed as an extensive property.
The internal energy of a system is represented by the symbol E (Some books use the symbol
U). It is neither possible nor necessary to calculate the absolute value of internal energy of a
system. In thermodynamics we are concerned only with the energy changes when a system changes

18
from one state to another. If Δ E be the difference of energy of the initial state (Ein) and the final
state (Ef), we can write.
∆E = Ef – Ein
∆E is +ve if Ef is greater than Ein and –ve if Ef is less than Ein.
A system may transfer energy to or from the surroundings as heat or as work, or both. The
SI unit for internal energy of a system is the joule (J).
First Law of Thermodynamics
The first law of thermodynamics is, in fact, an application of the broad principle known as
the Law of Conservation of Energy to the thermodynamic system. It states that:
the total energy of an isolated system remains constant though it may change from one form
to another.
When the state of a system is changed from x to y, it undergoes a change in the internal
energy from Ex to Ey. Thus, we can write
ΔE = Ex – Ey
This energy change is brought about by the evolution or absorption of heat and/or by
work being done by the system. Because the total energy of the system must remain constant,
we can write the mathematical statement of the First Law as:
ΔE = q – w ……………………... (1)
where q = the amount of heat supplied to the system, w = work done by the system
Thus, First Law may also be stated as: the net energy change of a closed system is equal
to the heat transferred to the system minus the work done by the system.

Figure 12: Illustration of First Law. Heat adds to internal energy, while work subtracts.

19
 To illustrate the mathematical statement of the First Law, let us consider the system
‘expanding hot gas as shown in Figure 12.
The gas expands against an applied constant pressure by volume ΔV. The total mechanical
work done is given by the relation
w = P × ΔV …………………...... (2)
From (1) and (2), we can restate
ΔE = q – P × ΔV
Other Definitions of First Law of Thermodynamics
(1) Whenever energy of a particular type disappears equivalent amount of another type must be
produced.
(2) Total energy of a system and surrounding remains constant (or conserved)
(3) It is impossible to construct a perpetual motion machine that can produce work without
spending energy on it.
Some Special Forms of the First Law of Thermodynamics
The mathematical statement of the First Law of Thermodynamics is
ΔE = q – w
Form 1: For a cyclic process involving isothermal expansion of an ideal gas
ΔE = o
∴q=w
Form 2: For an isochoric process (no change in volume) there is no work of expansion i.e. w = 0.
Hence: ΔE = qv
Form 3: For an adiabatic process there is no change in heat gained or lost i.e. q = 0.
Hence: ΔE = – w
In other words, the decrease in internal energy is exactly equal to the work done on
the system by surroundings.
Form 4: For an isobaric process there is no change in pressure, i.e. P remains constant. Hence
ΔE = q – w
or ΔE = q – PΔV
Example 4:
Find ΔE, q and w if 2 moles of hydrogen at 3 atm pressure expand isothermally at 50ºC
and reversibly to a pressure of 1 atm.

20
Solution:
Since the operation is isothermal and the gas is ideal
ΔE = 0
From the First Law
ΔE = q – w
∴ q–w=0
when ΔE = 0
or q=w
For a reversible process
𝑷 𝑷
w = –nRT 1n𝑷𝟏 or – 2.303 nRT 𝐥𝐨𝐠 𝑷𝟏
𝟐 𝟐

= – 2 × 1.987 × 323 × 2.303 × log 3

= – 1410 cals
Since q=w
q = – 1410 cals
Example 5:
1g of water at 373 K is converted into steam at the same temperature. The volume of water
becomes 1671 ml on boiling. Calculate the change in the internal energy of the system if the heat
of vaporization is 540 cal/g.
Solution:
As the vaporization takes place against a constant pressure of 1 atmosphere, work done for
an irreversible process, w, is
w = P (V2 – V1)
= nRT
𝟏
= 𝟏𝟖 × 1.987 × 373

= 41 cal/g
Now q = 540 cal/g
Since ΔE = q – w (First Law)
= 540 – 41 (cal/g)
∴ ΔE = 499 cal/g

21
Exercise 1:
A gas contained in a cylinder fitted with a frictionless piston expands against a constant
external pressure of 1 atm from a volume of 5 litres to a volume of 10 litres. In
doing so it absorbs 400 J thermal energy from its surroundings. Determine ΔE for the process.
Exercise 2:
Calculate the maximum work done when pressure on 10 g of hydrogen is reduced from 20
to one atmosphere at a constant temperature of 273 K. The gas behaves ideally. Will there be any
change in internal energy? Also calculate ‘q’.
Enthalpy of a System
In a process carried at constant volume (say in a sealed tube), the heat content of a system
is the same as internal energy (E), as no PV work is done. But in a constant-pressure process, the
system (a gas) also expends energy in doing PV work. Therefore, the total heat content of a
system at constant pressure is equivalent to the internal energy E plus the PV energy. This is
called the Enthalpy (Greek en = in; thalpos = heat) of the system and is represented by the symbol
H. Thus, enthalpy is defined by the equation:
H = E + PV …………………..(1)
Enthalpy – A Function of State
In equation (1), E, P, V are all state functions. Thus H, the value of which depends on the
values of E, P, V must also be a function of state. Hence its value is independent of the path by
which the state of the system is changed.
Change in Enthalpy
Let Δ H be the difference between the enthalpy of a system in the final state (H2) and that
in the initial state (H1),
ΔH = H2 – H1 ………………….... (2)
Substituting the values of H2 and H1, as from (1) and (2), we have
ΔH = (E2 + P2V2) – (E1 + P1V1)
= (E2 – E1) + (P2V2 – P1V1)
= ΔE + ΔPV
If P is constant while the gas is expanding, we can write
ΔH = ΔE + PΔV
or ΔH = ΔE + w (w = work) …………….... (3)

22
According to the First Law,
ΔE = q – w ………………….. (4)
where q = heat transferred
From equations (3) and (4)
ΔH = q when change in state occurs at constant pressure
This relationship is usually written as
ΔH = qp
where subscript p means constant pressure.
Thus, ΔH can be measured by measuring the heat of a process occurring at constant
pressure.
Note:
ΔH = H2 – H1
ΔH is positive if H2 > H1 and the process (reaction) is endothermic. ΔH is negative if
H1 > H2 and the reaction is exothermic.
In case of a chemical reaction carried in the laboratory in an open vessel,
ΔH = Hproducts – Hreactants = qp
The heat of reaction at one atmospheric pressure (1atm) is usually shown along with the
equation. The units of ΔH are kilocalories (kcal) or kilojoules (kJ).
Relation Between ΔH and ΔE
Calorific values of many gaseous fuels are determined in constant volume calorimeters.
These values are, therefore, given by the expression
qv = ΔE
When any fuel is burnt in the open atmosphere, additional energy of expansion, positive or
negative, against the atmosphere is also involved. The value of q thus actually realized, i.e., qp =
ΔH, may be different from the equation
ΔH = ΔE + PΔV ………………..(1)
If gases are involved in a reaction, they account for most of the volume change as the volumes
of solids and liquids are negligibly small in comparison.
Suppose we have n1 moles of gases before reaction, and n2 moles of gases after it.
Assuming ideal gas behaviour, we have
P V2 = n2 RT

23
 P V1 = n1 RT
∴ P (V2 – V1) = (n2 – n1) RT
or PΔV = Δn RT ………………………(2)
Substituting in equation (1) into 2 we have,
ΔH = ΔE + Δn RT
Example 6:
Calculate ΔH for the reaction for the reaction below.
H2F2 (g) ⎯⎯→ H2(g) + F2(g). ΔE = – 14.2 kcal/mole at 25º C
Solution:
Using ΔH = ΔE + Δ n RT
Δ n = n2 – n1
Now n2 = 1 + 1 = 2
n1 = 1
n2 – n1 = 2 – 1 = 1
ΔH = ΔE + 1 × 1.987 × 298/1000
= – 14.2 + 0.592
= – 13.6 kcal/mole
Molar Heat Capacities
By heat capacity of a system we mean the capacity to absorb heat and store energy. As the
system absorbs heat, it goes into the kinetic motion of the atoms and molecules contained in the
system. This increased kinetic energy raises the temperature of the system.
If q calories is the heat absorbed by mass m and the temperature rises from T1 to T2, the
heat capacity (c) is given by the expression:
𝒒
c = 𝒎 ×(𝑻 ……………….(1)
𝟐 − 𝑻𝟏 )

Thus, heat capacity of a system is the heat absorbed by unit mass in raising the temperature
by one degree (K or º C) at a specified temperature.
When mass considered is 1 mole, the expression (1) can be written as:
𝒒 𝒒
c=𝑻 = ∆𝑻………………. (2)
𝟐 − 𝑻𝟏

24
where C is denoted as Molar heat capacity.
The molar heat capacity of a system is defined as the amount of heat required to raise
the temperature of one mole of the substance (system) by 1 K.
Since the heat capacity (C) varies with temperature; its true value will be given as:
𝒅𝒒
c = 𝒅𝑻 ………………. (3)
where dq is a small quantity of heat absorbed by the system, producing a small temperature
rise dT.
Thus, the molar heat capacity may be defined as the ratio of the amount of heat
absorbed to the rise in temperature.
Units of Heat Capacity
The usual units of the molar heat capacity are calories per Kelvin per mole (cal K–1 mol–1),
or joules per Kelvin per mole (J K–1 mol–1), the latter being the SI unit.
Heat is not a state function, neither is heat capacity. It is, therefore, necessary to specify
the process by which the temperature is raised by one degree. The two important types of molar
heat capacities are those: (1) at constant volume; and (2) at constant pressure.
Molar Heat Capacity at Constant Volume
According to the first law of thermodynamics
dq = dE + PdV .....................................(i)
Dividing both sides by dT, we have
𝒅𝒒 𝒅𝑬 + 𝑷𝒅𝑽
= .....................................(ii)
𝒅𝑻 𝒅𝑻

At constant volume dV = 0, the equation reduces to

𝒅𝑬
cv = ( 𝒅𝑻 )v
Thus, the heat capacity at constant volume is defined as the rate of change of internal
energy with temperature at constant volume.
Molar Heat Capacity at Constant Pressure
Equation (ii) above may be written as
𝒅𝑬 𝑷𝒅𝑽
C= + .....................................(iii)
𝒅𝑻 𝒅𝑻

25
Remember that: H = E + PV
Now, differentiating the above equation with respect to T at constant pressure, we have
𝒅𝑯 𝒅𝑬 𝒅𝑽
( 𝒅𝑻 )p = ( 𝒅𝑻 )p + P ( 𝒅𝑻 )p .....................................(iv)
Comparing equation (iv) with (iii) we obtain

𝒅𝑯
Cp = ( )p.....................................(v)
𝒅𝑻
Thus, heat capacity at constant pressure is defined as the rate of change of enthalpy with
temperature at constant pressure as shown in equation (v).
Relation Between Cp and Cv
From the definitions, it is clear that two heat capacities are not equal and Cp is greater than
Cv by a factor which is related to the work done. At a constant pressure part of heat absorbed by
the system is used up in increasing the internal energy of the system and the other for doing work
by the system. While at constant volume the whole of heat absorbed is utilised in increasing the
temperature of the system as there is no work done by the system. Thus, increase in temperature
of the system would be lesser at constant pressure than at constant volume. Thus, Cp is greater
than Cv.
Remember that:
𝒅𝑯
Cp = .....................................(i)
𝒅𝑻
𝒅𝑬
cv = 𝒅𝑻
.....................................(ii)

By definition H = E + PV for 1 mole of an ideal gas or H = E + RT (⸪PV = RT). Now,

differentiating this equation with respect to T at constant pressure, we have
𝒅𝑯 𝒅𝑬
= +R
𝒅𝑻 𝒅𝑻
or

Cp = cv + R
or

Cp - cv = R

26
 Thus, Cp is greater than Cv by a gas constant whose value is 1.987 cal K–1 mol–1 or 8.314 J
K–1 mol–1 in S.I. units.
Calculation of ΔE and ΔH
(A) ΔE: For one mole of an ideal gas, we have
𝒅𝑬
cv = 𝒅𝑻
or dE = Cv × dT
For a finite change, we have
ΔE = E2 – E1 = Cv (T2 – T1)
and for n moles of an ideal gas we get
ΔE = E2 – E1 = n × Cv × (T2 – T1)
(B) ΔH: We know
ΔH = Δ (E + PV)
= ΔE + Δ (PV)
= ΔE + Δ RT [⸪PV = RT]
= ΔE + Δ RT
= Cv (T2 – T1) + R (T2 – T1)
= (Cv + R) (T2 – T1)
= Cp (T2 – T1) [⸪Cp – Cv = R]
and for n moles of an ideal gas we get
ΔH = n × Cp × (T2 – T1)
Example 7:
Calculate the value of ΔE and ΔH on heating 64.0 g of oxygen from 0ºC to 100ºC. Cv and
Cp on an average are 5.0 and 7.0 cal mol–1 degree–1.
Solution:
We know
ΔE = n × Cv × (T2 – T1) ………….…..(i)
and ΔH = n × Cp × (T2 – T1) …………....(ii)
𝟔𝟒
n = 𝟏𝟔
= 4 moles,

T2 = 100ºC = 373K and T1 = 0ºC = 272K

27
 On substitution we get
ΔE = 4 × 5.0 × (373 – 273)
= 4 × 5.0 × 100 = 2000 cals
And ΔH = 4 × 7.0 × (373 – 273)
= 4 × 7.0 × 100 = 2800 cals
Exercise 3:
Calculate the amount of heat necessary to raise 213.5 g of water from 25ºto 100ºC. Molar
heat capacity of water is 18 cal mol–1 K–1.
Exercise 4:
Three moles of an ideal gas (Cv = 5 cal deg–1 mol–1) at 10.0 atm and 0º are converted to
2.0 atm at 50º. Find ΔE and ΔH for the change. R = 2 cal mol–1 deg–1
Exercise 5:
Read on adiabatic expansion of an ideal gas, comparison between isothermal and adiabatic
expansions, work done in adiabatic reversible expansion and make sure you solve some problems.
Thermochemistry
It is noticed that energy in the form of heat (thermal energy) is generally evolved or
absorbed as a result of a chemical change.
Thermochemistry is a branch of physical chemistry which deals with the thermal or
heat changes caused by chemical reactions.
We know that every substance has a definite amount of energy known as the intrinsic
energy or internal energy, E. Its exact value cannot be determined but the change in internal
energy, ΔE, can be accurately measured experimentally.
When the internal energy of reactants (Er) is greater than the internal energy of the products
(Ep), the difference of internal energy, ΔE, is released as heat energy. Such a reaction is called
exothermic reaction.
If the internal energy of the products (Ep) is greater than that of the reactants (Er), heat is
absorbed from the surroundings. Such a reaction is called endothermic reaction. The amount of
heat released or absorbed in a chemical reaction is termed the heat of reaction.
ΔE = Eproducts – Ereactants
or ΔE = Ep – Er
The energy changes in chemical reactions are largely due to the breaking of existing bonds

28
between the atoms and the formation of new bonds. Thus, thermochemistry provides useful
information regarding the bond energies.
Enthalpy of a Reaction
Thermochemical measurements are made either at (a) constant volume or (b) constant
pressure. The magnitudes of changes observed under the two conditions are different.
The change in internal energy (ΔE) is the heat change accompanying a chemical
reaction at constant volume because no external work is performed.
However, at constant pressure not only does the change in internal energy take place but
work is also involved because of expansion or contraction. In the laboratory most of the chemical
reactions are carried out at constant pressure (atmospheric pressure) rather than at constant volume.
In order to study the heat changes for reactions taking place at constant pressure and constant
temperature, chemists have introduced a new term called enthalpy.
The enthalpy of a system is defined as the sum of the internal energy and the product
of its pressure and volume. That is,
H = E + PV
where E is the internal energy, P is the pressure and V is the volume of the system. It is
also called Heat content.
Just like internal energy, enthalpy is also a function of the state and it is not possible to
measure its absolute value. However, a change in enthalpy (ΔH) accompanying a process can be
measured accurately and is given by the expression:
ΔH = Hproducts – Hreactants
= Hp – H r
Thus, if ΔV be the change in volume in case of a reaction at constant temperature and
pressure, the thermal effect observed will be the sum of the change in internal energy (ΔE) and the
work done in expansion or contraction. That is,
ΔΗ = ΔE + P × ΔV
Therefore, while the heat change in a process is equal to its change in internal energy
ΔE at constant volume, it gives at constant pressure the enthalpy changes ΔH. That is,
ΔE = Heat change in a reaction at constant volume
ΔH = Heat change in a reaction at constant pressure

29
 For reactions involving solids and liquids only the change in volume (ΔV) is very small
and the term P × ΔV is negligible. For such reactions ΔH is equal to ΔE. In case of gases, however,
we must specify whether the reaction has taken place at constant volume or at constant pressure
because the value of P × ΔV is appreciable. Most of such reactions are, however, studied at constant
pressure and change in enthalpy (ΔH) is involved.
Exothermic and Endothermic Reactions
Let us consider a general reaction at constant pressure,
A+B→C+D
If HA, HB, HC and HD be the enthalpies of A, B, C and D respectively, the heat of reaction
at constant pressure viz., ΔH is equal to the difference in enthalpies of the products and the reactants
i.e.,
ΔH = Hproducts – Hreactants
ΔH = (HC + HD) – (HA + HB)
The value of ΔH may be either zero, negative or positive. Where ΔH is zero, the enthalpies
of the products and reactants being the same, the heat is evolved or absorbed. In the case of ΔH
being negative, the sum of enthalpies of the products is less than that of the reactants and the
difference in enthalpy is given out in the form of heat.

Figure 13: Enthalpy diagram for exothermic and endothermic reactions.

Such reactions which are accompanied by the evolution of heat energy are called
Exothermic reactions.
When ΔH is positive, the enthalpy or heat content of the reactants and an equivalent of heat
is absorbed by the system from the surroundings (Figure 13).

30
 Such reactions which are accompanied by absorption of heat are called Endothermic
reactions.
Thus, for an exothermic reaction Hp < Hr and ΔH = – ve, for an endothermic reaction Hp >
Hr and ΔH = +ve.
When trying to classify a process as exothermic or endothermic, watch how the
temperature of the surroundings changes. An exothermic process releases heat, and causes the
temperature of the immediate surroundings to rise. An endothermic process absorbs heat and cools
the surroundings.
Examples of Exothermic and Endothermic Processes
S/N Exothermic Process Endothermic Process
1 Making ice cubes Melting ice cubes
2 Formation of snow in clouds Conversion of frost to water vapour
3 Condensation of rain from water vapour Evaporation of water
4 Mixing sodium sulfite and bleach Baking bread
5 Rusting iron Cooking an egg
6 Burning sugar Producing sugar by photosynthesis
7 Mixing water and strong acids Mixing water and ammonium nitrate

Calculation of ΔH from ΔE and ΔE from ΔH

The enthalpy changes of a reaction at constant pressure (ΔH) and internal energy change
(ΔE) are related to each other as
ΔH = ΔE + P × ΔV ........................ (i)
where ΔV is the change in volume due to expansion or contraction when measurement is
done at constant pressure, P. Though heat changes of reactions are usually measured at constant
pressure, it is sometimes necessary to carry out the reaction at constant volume as, for example, in
the measurement of heat of combustion in a bomb calorimeter. The above relationship can be used,
if desired, for the conversion of ΔH into ΔE and vice versa.

Let us consider a reaction

aA + bB → cC +dD
Change in number of moles = No. of moles of products – No. of moles of reactants
= (c + d) – (a + b)
= Δn

31
 Let the volume occupied by one mole of the gas be V. Then, change in volume, ΔV =
change in No. of moles × volume occupied by one mole of the gas.
ΔV = Δn × V
or P × ΔV = P (Δn × V)
P × ΔV = PV × Δn …………………....(ii)
But PV = RT (for one mole of gas)
Putting RT in place of PV in equation (ii) we obtain
PΔV = RT Δn
Substituting the value of PΔV in equation (i) we have
ΔH = ΔE + Δn RT
It may be pointed out that while determining the value of ΔH, only the number of moles of
gaseous reactants and products are taken into consideration. The value of gas constant R is taken
either in calories or joules per degree per mol and is 1.987 cal (approximately 2 calories) or 8.314
joules.
Example 8:
The heat of combustion of ethylene at 17ºC and at constant volume is – 332.19 kcals.
Calculate the heat of combustion at constant pressure considering water to be in liquid state. (R =
2 cal degree–1 mol–1).
Solution:
The chemical equation for the combustion of ethylene is
C2H4(g) + 3O2(g) → 2CO2(g) + 2H2O(l)
1 mole 3 moles 2 moles negligible volume
No. of moles of the products = 2
No. of moles of the reactants = 4
∴ Δn = (2 – 4) = – 2
We know that ΔH = ΔE + Δn RT
Given that ΔE = – 332.19 kcal
T = 273 + 17 = 290 K
R = 2 cals = 2 × 10– 3 kcals
∴ ΔH = – 332.19 + 2 × 10–3 × –2 × 290
= – 333.3 kcal

32
Example 9:
The heat of formation of methane at 298 K at constant pressure is – 17.890 kcal. Calculate
its heat of formation at constant volume. (R = 1.987 cal degree–1 mol–1).
Solution:
The thermochemical equation for the heat of formation of methane at 298 K at constant
pressure is: C(s) + 2H2(g) → CH4(g) ΔH = – 17.890 kcal
No. of moles of gaseous products = 1, No. of moles of the gaseous reactants = 2 and Change
in No. of moles, Δn = 1 – 2 = – 1
Given that ΔH = – 17.890 kcal; T = 25 + 273 = 298 K and R = 1.987cal = 1.987 × 10–3 kcal
Substituting these values in the equation: ΔH = ΔE + Δn × RT
ΔE = – 17.89 + [– 1 × (1.987 × 10–3) × 298]
= – 18.482 kcal
∴ The heat of formation of methane at constant volume is – 18.482 kcal.
Exercise 6:
Read on different types of heat (enthalpy) of reactions, such as;
➢ Heat of Combustion
➢ Heat of Neutralization
➢ Energy Changes During Transitions or Phase Changes
➢ Heat of Fusion
➢ Heat of Vaporization
➢ Heat of Sublimation
➢ Hess’s Law of Constant Heat Summation
➢ Applications of Hess’s Law

33