4

CHAPTER
4.1 INTRODUCTION
Thermodynamics is a branch of physics that deals with the inter-relations between heat and other forms
of energy. It is based on principles, which has been formulated by generalizing experimental
observations made on a variety of physical systems. It makes no attempt about what is going on at
microscopic (atomic or molecular) level. It is a macroscopic (large-scale) theory of natural phenomena.
Its aim is to establish relationship between directly observed macroscopic quantities viz. pressure,
volume, temperature, concentration, electric field, magnetic field, polarization, magnetization, etc.
which define the state of the system under investigation. As the name itself suggests, it employs both
thermal and mechanical concepts. Its principles are widely used in design of heat engines, nuclear power
stations, rocket propulsion, biological phenomena etc. One of the shortcomings of thermodynamics is
that it gives no picture of the internal mechanism of phenomena.
The kinetic theory, on the other hand, attempts to establish relationships between macroscopic
quantities and microscopic quantities. In this method, the laws of mechanics are applied to the motion
of individual molecule and macroscopic properties (such as heat capacity, expansion coefficient,
viscosity, diffusion, etc.) are deduced.
In statistical mechanics, no attention is paid to individual molecule, instead the assembly of
microscopic particles is treated statistically. This approach of describing behavior of system will be
discussed in a separate chapter.
4.2 THERMODYNAMIC SYSTEM AND SURROUNDINGS
To study the behavior of a substance thermodynamically, we select a finite portion of that substance.
The portion that is set aside (in imagination) on which we pay our attention or on which experimental
observations are made is called system. Everything outside this portion which has direct bearing on
the behavior of the system is called surroundings. The system and the surroundings comprise what we
call universe.
The boundary which separates the system from surroundings is called wall. The wall of the system
may or may not allow it to interact with the surroundings.
A wall, which prevents any exchange of matter and energy between the system and surroundings is
called isolating wall and the system is said to be isolated. Such a system will not be affected by its
surrounding and is not of much importance from thermodynamic point of view.
Zeroth Law of Thermo-
dynamics: Preliminary
Concepts
70 Thermal and Statistical Physics
If the boundary of the system permits exchange of matter and energy, the system is called open
system.
On the other hand, if the exchange of energy and not matter occurs between the system and
surroundings, the system is called closed system.
A wall which prevents thermal interaction is known as adiabatic wall and a system enclosed within
an adiabatic wall is called thermally isolated.
If exchange of heat takes place between the system and surroundings through the boundary wall,
the boundary is called diathermic wall.
4.3 THERMODYNAMIC VARIABLES
There are, in general, two points of view to study the behavior of the system or its interactions with
the surroundings or both: macroscopic point of view and microscopic point of view. The macroscopic
description of system involves the specification of a few fundamental measurable properties of the
system such as volume, pressure, temperature, amount of substance etc., without considering the
internal structure of the system. The macroscopic quantities refer to gross characteristics or large-
scale properties of the system and are called macroscopic thermodynamic coordinates (variables or
parameters). Of the many thermodynamic variables, only a few variables are needed for the
description of the system. In microscopic description of a system assumptions are made about the
structure of matter under investigation. It postulates the existence of molecules, their motion, their
energy states, their interactions etc. Thus a large number of quantities, which refer to small-scale
properties of the system, needed to specify the state of the system. These are called microscopic
coordinates (variables or parameters). These variables cannot be measured in laboratory.
A thermodynamic system is one whose state can be described in terms of thermodynamic variables.
The variables defining the state of a thermodynamic system differ from system to system. For
instance, the state of a gas enclosed in a vessel is described by its pressure, volume, temperature and
mass. The state of a metal bar is described by its length, cross-section, tension, temperature, the state
of a liquid film by its area, surface tension etc. A dielectric and a magnetic system need additional
variables such as polarization and magnetization respectively.
Although it might seem that the macroscopic and microscopic points of view are entirely different and
incompatible, there is nevertheless, a relation between them and when both points of view are applied to
the same system, they lead to the same conclusion. The relation between the two points of view lies in the
fact that the macroscopic properties are really averages over a long period of time of a large number of
microscopic characteristics. For example the macroscopic quantity pressure is the average rate of change of
momentum due to all the molecular collisions made on a unit area of the container of the gas.
4.4 EXTENSIVE AND INTENSIVE VARIABLES
The state variables which are proportional to the mass of the system are called extensive variables. For
instance, volume, internal energy, enthalpy, entropy, etc. are extensive variables. On the other hand,
intensive variables are those which are independent of mass of the system. Temperature, pressure and
density are intensive variables. Intensive variables are invariably denoted by capital letters such as T
and P.
Zeroth Law of Thermodynamics: Preliminary Concepts 71
The value of extensive variable per unit mass is called specific variable. Usually an extensive
variable is denoted by capital letter and its specific value by small letter. The specific value of an
extensive variable is independent of mass and hence is an intensive variable. If a system with mass m
occupies a volume V, then its specific volume is denoted by v and given by
Specific volume, v =
V
m
The ratio of the value of an extensive variable to the number of moles of the system is called molar
specific value. For example, molar specific volume is given by
Molar specific volume, v =
V
n
, n is number of moles.
Writing thermodynamic equations in terms of specific values of extensive variables is convenient
because they become independent of mass of the system.
Table 4.1 Extensive and Intensive Variables
Systems Extensive variables Specific value Intensive variables
(1) Hydrostatic system Volume (V) v Pressure (P),
Energy (U or E) u or e Temperature (T)
Entropy (S) s
Enthalpy (H) h
(2) Stretched wire Length (L) l Tension (F)
(3) Liquid film Area (A) a Surface tension (s)
(4) Electric cell Charge (Q) q E.M.F. (e)
(5) Dielectric slab Polarization (P) p Electric field (E)
(6) Paramagnetic salt Magnetization (M) m Magnetic field (B or H)
4.5 THERMAL EQUILIBRIUM: ZEROTH LAW OF THERMODYNAMICS
A system is said to be in thermal equilibrium if its thermodynamic coordinates remain unchanged.
Consider two gaseous systems which are separated by a wall. If the change in thermodynamic
coordinates of one system has no effect on those of the other system, then the wall separating the two
systems is said to be adiabatic wall. On the other hand, if the changes in thermodynamic coordinates
of one system causes changes in those of the other and the composite system attains a new equilibrium
state, then the wall separating them is called diathermic or diathermal wall. Two systems separated by
a diathermic wall are in equilibrium with each other.
Now consider two systems A and B separated by an adiabatic wall and a third system C separated
from A and B both by a diathermic wall as shown in Fig. 4.1.
In this arrangement, system A and C will be in thermal equilibrium and so will be the systems B
and C. Now if the adiabatic wall between A and B is replaced by a diathermic wall, it is found that A
and B are also in thermal equilibrium. From this fact we come to conclusion that if system A is in
thermal equilibrium with B and B is in thermal equilibrium with C, then A and C will also be in
thermal equilibrium. This result is known as Zeroth law of thermodynamics and is stated as follows.
72 Thermal and Statistical Physics
A B
C
Diathermic wall
Adiabatic wall
Fig. 4.1.
When any two bodies or systems are each separately in thermal equilibrium with a third body, they
are also in thermal equilibrium with each other and there exists a common useful scalar quantity
called temperature which is a property of all thermodynamic systems in equilibrium states such that
the temperature equality is a necessary and sufficient condition for thermal equilibrium.
The above statement can also be stated in a mathematical form. Consider three systems 1, 2 and 3.
Let X and Y be independent variables to describe their states. For the system 3, these variables are X
3
and Y
3
. The condition for system 1 to be in thermal equilibrium with system 3 can be expressed in
functional form as
f
1,3
(X
1
, Y
1
, X
3
, Y
3
) = 0
or X
3
= F
13
(X
1
, Y
1
, Y
3
) ...(4.1)
That is, out of the four variables, only three are independent. Similarly, the condition of
equilibrium of system 2 and 3 can be expressed as
X
3
= F
23
(X
2
, Y
2
, Y
3
) ...(4.2)
Eliminating X
3
from Eqs. (4.1) and (4.2) we have
F
13
(X
1
, Y
1
, Y
3
) F
23
(X
2
, Y
2
, Y
3
) = 0 ...(4.3)
But according to the zeroth law, system 1 and 2 will also be in thermal equilibrium with one
another. This requires that
f
12
(X
1
, Y
1
, X
2
, Y
2
) = 0 ...(4.4)
To satisfy the Eqs. (4.3) and (4.4) simultaneously, the function F
13
and F
23
must be of the form
F
13
= f
1
(X
1
,Y
1
) f (Y
3
) + h (Y
3
)
F
23
= f
2
(X
2
, Y
2
) f (Y
3
) + h (Y
3
)
These imply that Eq. (4.3) should be of the form
f
1
(X
1
, Y
1
) = f
2
(X
2
, Y
2
)
or in general we can write
f
1
(X
1
, Y
1
) = f
2
(X
2
, Y
2
) = f
3
(X
3
, Y
3
)
This equation shows that when two or more systems are in thermal equilibrium, for each system there
exists a single valued function of state variables which has a common numerical value for all of them. The
common value is known as empirical temperature. Thus we may write, in general, for thermal equilibrium
f (X, Y) = q
Zeroth Law of Thermodynamics: Preliminary Concepts 73
This equation is called the equation of state and q is the empirical temperature. Thus temperature
is a physical quantity which describes the thermal state of the system. It gives the feeling of hotness
and coldness of a body. The temperature defined in this way has no objective use and hence cannot be
used in scientific methods. If it is to be used in scientific analysis, it must have objective definition
and should be assigned numerical value. The instruments employed for the measurement of tempera-
ture are called thermometers. The construction of a thermometer involves following methods :
(i) A suitable material and its temperature dependent property is chosen.
(ii) Two fixed states of the material, which can be easily reproduced are selected. In ordinary glass
thermometer, the material used is mercury and its temperature dependent property which is
used is the length of column in glass tube. The fixed states are the ice point and the steam point.
These two states are arbitrarily assigned zero and 100 on Celsius scale and the interval between
0 and 100 is divided into 100 parts. Each part represents 1C.
Many other properties of materials have been used to devise thermometers. Unfortunately, all the
thermometers do not agree in the whole range of their operation. To remove indefiniteness or
inconsistency in their readings, the International Temperature scale was revised in 1968 and triple
point of water (temperature at which the three phases ice, water and vapor coexist) was assigned a
temperature 273.16 K (= 0.01C). This scale of temperature is known as Giaque Scale.
If P
tr
represents the pressure of gas thermometer at triple point of water, P the pressure at unknown
temperature T, then
T = lim .
P
tr
tr
P
P
F
H
G
I
K
J
0
27316 kelvin
The Celsius temperature scale employs a degree of the same magnitude as that of the ideal gas
scale, but its zero point is shifted so that the Celsius temperature of triple point of water is 0.01 degree
Celsius (0.01C). Thus the zero on the Celsius temperature scale is 273.15 on Kelvin or absolute
scale of temperature.
4.6 THERMODYNAMIC EQUILIBRIUM
If the temperature at all points in a system under investigation has the same value, which is equal to
that of the surroundings, the system is said to be in a state of thermal equilibrium. If there exists any
temperature gradient inside an isolated system, after a sufficiently long time, the temperature will
level out and the system will come in thermal equilibrium.
When there is no unbalanced force in the interior of a system and none between a system and its
surroundings, the system is said to be in a state of mechanical equilibrium. It should be borne in mind
that for a system to be in mechanical equilibrium it is not necessary that the pressure at all points be
the same. For instance, a liquid in a vessel has maximum hydrostatic pressure at the bottom and
minimum at the top level, still it may be in mechanical equilibrium.
When a system does not undergo any change in density or chemical composition, it is said to be in
chemical equilibrium.
A system in thermal, mechanical and chemical equilibrium is said to be in the state of thermodynamic
equilibrium. In thermodynamic equilibrium, all the parameters of the system have definite values and
remain unchanged as long as the external conditions of the system remain unchanged. If we choose
any two thermodynamic variables and plot one along x-axis and the other along y-axis, the system in
74 Thermal and Statistical Physics
equilibrium will be represented by a point on the graph. If the state variables of a system undergo
erratic change, it is said to be in non-equilibrium state and this state cannot be represented by a point
on such a graph.
4.7 THERMODYNAMIC PROCESS
If a system initially in non-equilibrium state, left to itself, will pass over to equilibrium state. The
transition of a system from one equilibrium state to another is accompanied by changes in state
variables. The term process is used to describe this transition. A process, in which a system passes
through a continuous sequence of equilibrium states, is called quasi-static process. An infinitely slow
process is a quasi-static process.
4.8 REVERSIBLE AND IRREVERSIBLE PROCESSES
A reversible process is one which when retraced in opposite direction, the system and the surroundings
pass through the same intermediate states as encountered in the forward process, the thermal and
mechanical effects in the reverse process should be equal in magnitude but opposite in sign to those in
the forward process. A reversible process should not produce a permanent change in the system and
its surroundings. The changes produced in the forward process should be completely erased in the
reverse process. A reversible process can be carried out in either direction.
A reversible process is one in which the system and the surroundings both can be restored to their
initial states by reversing the direction of the process.
If a system absorbs heat Q and performs work W in the direct process, then by extracting heat Q
from the system and doing work W on the system, the system should pass through the same
intermediate states in the reversible process. The conditions for a process to be reversible are
(i) There should be no dissipating forces acting within the system.
(ii) The process should be carried out infinitesimally slowly so that the system is at each step in
equilibrium state i.e., the process should be quasi-static.
These conditions are never realized in practice. Hence perfectly reversible processes are only
abstractions. By minimizing the dissipating forces and allowing the system under investigation to go
over from one state to another quasi-statically, a real process may be approximated to a reversible one.
Consider a process in which a body exchanges heat with another body, which we shall call heat
reservoir. Let the heat capacity of the reservoir be infinitely great. This means that addition to or extraction
of finite amount of heat from the reservoir will not cause any change in its temperature. The process of
heat exchange between the body and the reservoir can be reversible only if upon receiving heat and
returning it in the reverse process to the reservoir, the body has the same temperature as that of the
reservoir. Strictly speaking, when receiving heat the temperature of the body must be lower than that of the
reservoir by an infinitely small value (otherwise no heat will flow from the reservoir to the body) and when
giving up heat, the temperature of the body must be higher than that of the reservoir by an infinitely small
value. Consequently, the only reversible process, attended by heat exchange with reservoir whose
temperature remains constant, is an isothermal process at the temperature of the reservoir.
A system in equilibrium state is specified by thermodynamic coordinates. Since in a reversible
process the system is always very near to the equilibrium states, and therefore it can be represented by
a continuous curve on P-V diagram and the analysis of a reversible process is easier.
Zeroth Law of Thermodynamics: Preliminary Concepts 75
A process which does not satisfy the conditions of reversible process is called irreversible process.
Now consider a viscous liquid in contact with a heat bath. By shaking the liquid, work may be done
against the viscous forces. This work appears as heat, which is transferred to the heat bath. If W is the
work done on the liquid and Q is the heat transferred to the heat bath in the direct process, then by
extracting heat Q from the heat bath, we never get the same amount of work W in the reverse process.
(According to second law of thermodynamics, the extraction of heat and its complete conversion into
work is not possible.) In general, the processes, in which dissipative forces like friction, viscosity,
electrical resistance, magnetic hysteresis are involved, are irreversible. All natural processes i.e.,
those which occur spontaneously are irreversible.
A process of heat transfer between two bodies with finite temperature difference is irreversible.
4.9 EQUATION OF STATE
The parameters describing the state of a system are not independent. Instead they are interrelated through
an equation called the equation of state. For a system described by P, V, T, a relation of the type
f (P, V, T) = 0 ...(4.5)
always exists and is called the equation of state. This type of equation cannot be derived from
thermodynamic methods. It is obtained either from experimental observations or from microscopic
considerations.
Ideal and real gases are the two important systems for our study. By ideal gas, we mean a gas in
which the interaction between the molecules is negligibly small and the volume occupied by the
molecules themselves is insignificant in comparison to the volume of the gas. For n moles of ideal gas
the relation between P, V, T and n is
PV = nRT ...(4.6)
In terms of specific volume v = V/n, this equation is written as
Pv = RT ...(4.7)
In real gases, the intermolecular forces and the volume of the molecules are not negligible.
However, at sufficiently high temperature and low pressure, real gases behave like ideal gases.
Deviations from ideal behavior are observed at low temperature and high pressure. In order to explain
the behavior of real gases, J. D. van der Waals modified the ideal gas equation taking intermolecular
forces and finite size of molecules into consideration. His equation of state is
( )
2
2
+
n a
P V nb
V

-


= nRT (for n moles) ...(4.8)
In terms of specific volume v = V/n, this equation is written as
( )
2
+
a
P b

-


v
v
= RT ...(4.9)
where a and b are constants called van der Waals constants.
76 Thermal and Statistical Physics
4.10 COEFFICIENT OF EXPANSION (EXPANSIVITY)
The coefficient of volume expansion b is defined as the fractional change in volume per unit change in
temperature at constant pressure. If a P, V, T system undergoes expansion from volume V to V + DV
due to rise in temperature from T to T + DT at constant pressure P then b is defined as follows.
b =
0
1
lim
T
P
V
V T
D
D


D
or b =
1
P
V
V T

...(4.10)
In terms of molar specific volume v,
b =
v
v
1
P
T

For an ideal gas,

= R
Therefore b =
1 R
P



v
=
1
T
Fig. 4.2. Expansitivity of water
Thus the expansivity of an ideal gas depends only on its temperature. In general, expansivity is a
function of both temperature and pressure. The change in volume of water when it is heated from
0C is shown in the Fig. 4.2. The specific volume of water decreases on heating in the temperature
range from 0 to 4C and increases beyond 4C. Thus expansitivity of water () at 4C is negative.
4.11 COMPRESSIBILITY
The isothermal compressibility of a substance is defined as the fractional change in volume per unit
change in pressure at constant temperature.
k
T
=
1
T
P

-

v
v
...(4.11)
The negative sign indicates that an increase in pressure is accompanied by a decrease in volume.
Zeroth Law of Thermodynamics: Preliminary Concepts 77
If the change in pressure is carried out under adiabatic condition, then the compressibility defined
as above is called adiabatic compressibility.
k
S
=
1
S
P

-

v
v
...(4.12)
where the subscript S indicates that process is adiabatic in which entropy S, remains constant. For an
ideal gas
Pv = RT

T
P
P

+

v
v = 0
Whence
k
T
=
1
P
For a real substance the compressibility is a function of both temperature and pressure. The
reciprocal of compressibility is called bulk modulus E, of the substance.
E
T
=
1
T
k
= and
S
T
P
E

-

v
v
=
S
1
k
=
S
P
-

v
v
4.12 RELATION BETWEEN PARTIAL DERIVATIVES
Let x, y, z be the thermodynamic variables of a system and each one be expressible in terms of the
remaining two. If
z = z (x, y)
then dz =

F
H
G
I
K
J
+

F
H
G
I
K
J
z
x
dx
z
y
dy
y
x
...(4.13)
Similarly, if
x = x (y, z)
then dx =

F
H
G
I
K
J
+

F
H
G
I
K
J
x
y
dy
x
z
dz
z
y
...(4.14)
Substituting the value of dx from (4.14) in (4.13) we obtain
dz =

F
H
G
I
K
J

F
H
G
I
K
J
+

F
H
G
I
K
J
L
N
M
M
O
Q
P
P
+

F
H
G
I
K
J
z
x
x
y
dy
x
z
dz
z
y
dy
y
z
y
x
=

F
H
G
I
K
J

F
H
G
I
K
J
+

F
H
G
I
K
J
L
N
M
M
O
Q
P
P
+

F
H
G
I
K
J

F
H
G
I
K
J
z
x
x
y
z
y
dy
z
x
x
z
dz
y
z x
y y
1 -

F
H
G
I
K
J

F
H
G
I
K
J
L
N
M
M
O
Q
P
P
z
x
x
z
dz
y y
=

F
H
G
I
K
J

F
H
G
I
K
J
+

F
H
G
I
K
J
L
N
M
M
O
Q
P
P
z
x
x
y
z
y
dy
y
z x
...(4.15)
78 Thermal and Statistical Physics
Let us apply Eq. (4.15) to two neighboring equilibrium states. If the two states have the same
y, then dy = 0. Equation (4.15) reduces to
1 -

F
H
G
I
K
J

F
H
G
I
K
J
L
N
M
M
O
Q
P
P
z
x
x
z
y y
= 0
or

F
H
G
I
K
J
z
x
y
=
1

F
H
G
I
K
J
x
z
y
...(4.16)
Similar relations hold for other variables i.e.,

F
H
G
I
K
J
x
y
z
=
1
and
x
z
y
y z
x

=
1

F
H
G
I
K
J
z
y
x
...(4.17)
Let us apply the Eq. (4.15) to two equilibrium states having the same value of z, i.e., dz = 0 then
.
y
z
z x
x y





= -

F
H
G
I
K
J
z
y
x
or . .
x y
z
x y z
y z x





= 1 ...(4.18)
If the variables x, y, z denote pressure P, volume V, and temperature T, respectively then equation
(4.18) takes the form
. .
T P V
P V T
V T P




= 1 ...(4.19)
Notice that P, V, T occur cyclically in Eq. (4.19).
Solved Examples
Example 1. Show that the coefficient of expansion of a van der Waals gas is
b =
R b
RT 2 b
2
3
2
v v
v v
-
- -
a f
a f a
Solution. By definition, b =
1
T
P

v
v
=
1 P
T
P
T

v
v
v
...(1)
van der Waals equation of state is
P =
2
RT a
b
-
- v v
Zeroth Law of Thermodynamics: Preliminary Concepts 79

P
T

v
= and
T
R P
b



- v v
=
( )
2 3
2 RT a
b
- +
-
v
v
Substituting these values in (1) we get
b =
( )
2 3
1
2
R
b
RT a
b



-

-

- +

-

v
v
v
v
=
( )
( )
2
2
3
2
R b
RT a b
-
- -
v v
v v
For ideal gas a = 0, b = 0, then b =
1
T
Example 2. Show that the compressibility of van der Waals gas is
k
=
v v
v v
2
3
RT 2
-
- -
b
a b
a f
a f
2
2
.
Solution. By definition
k
=
1
T
P

v
v
...(1)
For van der Waals gas P =
2
RT a
b
-
- v v
Therefore,
T
P


v
=
( )
2 3
2 RT a
b
- +
-
v
v
=
( )
( )
3
2
3
2 RT a b
b
- + -
-
v v
v v
\
k
=
( )
( )
v v
RTv v
2
2
2
3
2
b
a b
-
- -
For ideal gas a = 0, b = 0,
k
=
1
.
P
Example 3. Find the equation of state of a hypothetical substance whose isothermal compressibility is
given by k =
a
v
and expansivity is given by b =
2bT
v
, where a and b are constants.
Solution. Given that b =
1
T
P

v
v
=
2 1
and
T
bT
P

-

v
v v
=
a
v
That is,
P
T

v
= 2 and
T
bT
P

v
= a
Integration of these equations yield
v = bT
2
+ f (P) and v = aP + f (T)
Combining these equations we have
v bT
2
+ aP = const.
80 Thermal and Statistical Physics
Questions and Problems
1. State Zeroth law of thermodynamics. Explain the following terms:
(i) Thermodynamic variables (parameters)
(ii) Extensive and intensive variables
(iii) Thermodynamic equilibrium
(iv) Thermodynamic process
(v) Reversible and irreversible processes
(vi) Equation of state
(vii) Expansivity and compressibility