Subject Chemistry

Paper No and Title 10, Physical Chemistry- III (Classical Thermodynamics,

Non-Equilibrium Thermodynamics, Surface chemistry, Fast
kinetics)
Module No and Title 2, Zeroth and first law of thermodynamics

Module Tag CHE_P10_M2

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 2: Zeroth and first law of thermodynamics
 TABLE OF CONTENTS
1. Learning Outcomes
2. Introduction
3. Zeroth law of thermodynamics
4. First law of thermodynamics
5. Internal energy, U
6. Internal energy and the first law
7. The Euler reciprocal relation
8. Internal energy and heat
9. Summary

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 2: Zeroth and first law of thermodynamics
 1. Learning Outcomes

After studying this module you shall be able to:

 Know about the zeroth law of thermodynamics
 Learn about first law of thermodynamics
 Differentiate between exact and inexact differential
 Learn about Euler reciprocal relations

2. Introduction

Classical thermodynamics is that branch of science which deals with the macroscopic properties of
matter. Thermodynamics is exact mathematical science that describes the relationships of heat and
mechanical energy. This classical thermodynamics is based upon three general laws.
 The first law of the conservation of energy which represents the connection between heat
and mechanical work.
dE = dq + dw
 The second law deals with the entropy change in the system and the manner in which
energy change takes place divided by the absolute temperature T.
dS= dqrev/T
 The third law deals with the absolute value of entropy. The entropy at absolute zero (0 K)
is zero for any pure crystalline substance.
S° = (0 K) = 0

3. Zeroth law of thermodynamics

Although zeroth law of thermodynamics was formulated after first law of thermodynamics but
was of primary importance thus called Zeroth law.
This law states that if two systems are in thermal equilibrium with a third system then they are in thermal
equilibrium with each other i.e. if body A is in equilibrium with body C and body B is also in equilibrium
with body C, then both the bodies are in equilibrium with each other. In other words if systems A and
B are placed in contact with each other, then no exchange of heat will take place.
The use of thermometer is based on this principle. The thermometer behaves as the body C in
above statement. Thus, in comparing the temperature of two systems A and B thermometer is allowed
to come in equilibrium with the body A and then in equilibrium with body B by placing in contact with
each other. Thus the readings of thermometer give comparative ideas of degree of hotness of the two
bodies A and B. Because of small size of thermometer, an insignificant amount of energy exchange
takes place during measurement of the temperature.
CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical
Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 2: Zeroth and first law of thermodynamics
 Change in property of fluid with degree of hotness helps in the measurement of temperature by
thermometer. This property in a mercury thermometer involves change in length of the mercury column
and in an air thermometer it involves change in volume (v) and pressure (P) of air enclosed within.
Thus if the systems are in thermal equilibrium with each other, then they must have the same
value of property called temperature.

4. First law of thermodynamics

The first law of thermodynamics deals with the relation between the change in the energy with
work and heat. This law is also known as the law of conservation of energy. It states that energy can
neither be created nor destroyed but can be transformed from one form to another. Therefore, if energy
in one form disappear then equal amount of energy must appear in any other form. This law therefore
states that it is impossible to construct a perpetual motion machine i.e. machine which can produce
energy without expenditure of energy.
Before moving to first law in detail we should learn first about the internal energy.

5. Internal energy, U

A definite amount of energy which is present in every substance that depends upon its chemical
nature as well as upon its temperature, pressure and volume. This energy is known as internal energy.
Since the chemical nature includes such indeterminant factors as the translational, rotational and
vibrational movements of the molecules, the manner in which the molecules are put together, the nature
of the individual atoms, the arrangement and number of electrons, the energy possessed by the nucleus
etc. therefore, exact magnitude of the energy is not known. But the internal energy of a substance or a
system is a definite quantity and it is a function only of the state (i.e., chemical nature, composition,
temperature, pressure and volume) of the system at the given moment, irrespective of the manner in
which that state has been reached.

6. Internal energy and the First law

Let us consider a system which is subjected to change of pressure and volume. Initial state can
be represented by A and the final state by B (Fig. 1). U A and U B are respective energies associated
with the system in the states A and B respectively and they are definite quantities. Then, the change in
internal energy i.e. U will also be definite quantity.

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 2: Zeroth and first law of thermodynamics
 Fig. 1- Change of internal energy

The change in internal energy will be given by U  UB  UA

The change in internal energy does not depend on the path or the manner in which the
change is brought about. If it is not definite quantity, it would again be possible to construct a
perpetual motion machine which violates the first law of thermodynamics.
For example, let the system changes from state A to state B by path I and change of
energy is equal to U . Now consider the same change of state which is brought by different
path, say, path II, and the change of energy is U . Suppose U  U . Now coupling these
two processes:

A 
 B (by path I) and

B 
 A (by path II),
as shown in Fig. 1. By coupling these two processes, the system would return to its
initial state. At this time extra energy equal to U  U would become available. Repetition
of this cycle again and again leads to generation of energy continuously therefore possibility
of perpetual motion machine which contradicts first law. Hence, U  U . Thus, the energy
change accompanying a process is a function only of the initial and the final states of the system
and does not depend on the path or the manner by which the change is brought about.
Energy changes in relation to work and heat changes. Let us suppose U A be the
energy of a system in state A and U B be the energy in state B and system is undergoing change
from state A state B. Let system absorbs heat q from the surroundings and also performs some

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 2: Zeroth and first law of thermodynamics
 work (mechanical or electrical) equal to w. We already know that the absorption of heat by the
system raises the energy of the system while the work done by the system lowers the energy of
the system as expenditure of energy is utter requirement for performing some work. Hence, the
change of internal energy U will be given by

ΔU = UB - U A = q - w ….(1)

In general, if in a given process, the quantity of heat transferred from the surroundings
to the system is q and the work done in the process is w, then the change in internal energy U
, is given by

ΔU = q + w ….(2)
The above equation is the mathematical statement of the First law of thermodynamics.
If work is done by the surroundings on the system (as during the compression of a gas),
w is taken as positive so that U  q  w (Eq 2). If however, work is done by the system on
the surroundings (as during the expansion of a gas), w is taken as negative so that U  q  w
When the process involves infinitesimal change, then change in internal energy will be
given by
dU = dq + dw ...(3)
where dq and dw do not represent exact differentials i.e. dq  q 2  q1 . This is due to
the fact that the heat of the initial state and heat of the final state has no meaning. dq represents
a small amount of heat absorbed by the system. Similarly dw is the small amount of work done
on the system during the change.
When only mechanical work i.e. work of expansion or compression is done then
dw   pdV . Therefore equation (3) becomes

dU = dq - pdV ...(4)

State functions, exact and inexact differentials:

The state function is a property of a thermodynamic system which has a definite value
for a particular state of the system. It does not depend on the manner in which the state is
reached. The change in the state function associated with the change in the state of the system
depends only on the initial and the final states of the system and not on the path by which the
change is done. Since, pressure, temperature, volume and energy depend on the initial and final
states, therefore are state function while work is not a state function since the work done in a

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 2: Zeroth and first law of thermodynamics
 given change of state depends upon the manner in which the change is brought about. In the
first law equation (U  q  w) , U is a definite quantity and if w is not a state function then
q also is not a state function. Mathematically, we can say that while the differential of energy,
dU is an exact differential, the differentials of heat and work, viz. dq and dw respectively, are
inexact differentials. Exact differentials can be integrated between the appropriate limits. But
this cannot be done in the case of inexact differentials. Therefore,

U2
U1
dU = U 2 - U1 Exact differential …. (5)

w2

q2
But q1
dq  q 2 - q1 and
w1
dw  w 2 - w1 Inexact differential …. (6)

7. Internal energy and Heat

When work done is zero and no phase transformation occurs in system then the heat transfer
between the system and its surroundings results in the change in temperature of the system. This results
in the change in volume and pressure of the system. The conditions can be maintained in such a way
that either the volume or the pressure is kept constant. Heat exchange is also accompanied by the change
in energy of the system. This change in energy will be different for the two conditions, that is when
volume is kept constant and when the pressure is kept constant.
Heat exchange at constant volume
From first law of thermodynamics

U = q + w
= q - PV

q = E – W
= E + PV
If volume is constant and V = 0 (work of expansion is zero)

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 2: Zeroth and first law of thermodynamics
 If volume of system remains constant, then V  0 . Hence, PV is also zero. Then heat
exchanged q can be written as q v . Therefore,

ΔU = q v ...(7)

This implies that, at constant volume, the change in internal energy of a system becomes equal
to heat exchange between the system and its surroundings. As internal energy is a state function,
therefore, heat exchange at constant volume will also be a state function.
Heat exchange at constant pressure will be discussed in next module.

8. The Euler Reciprocal relation

Consider a state function z which is function of two independent variables x and y of the system
i.e. z = f(x, y). Since z is a state function, hence differential of z is an exact differential. The exact
differential can be written as

dz = (∂z / ∂x)y dx + (∂z / ∂y)x dy

= M(x, y)dx + N(x, y)dy ….(8)

where M(x, y) = ( z / x)y and N(x, y) = (z / y)x
Taking mixed second derivatives, we have

(M / y)x =  2z / y x and (∂N / ∂x )y = ∂ 2 z / ∂y ∂x

Since ∂ 2z / ∂y∂x = ∂ 2z / ∂x∂y

Hence (∂M / ∂y)x = (∂N / ∂x)y ….(9)

Eq. (8) is called the Euler reciprocal (or reciprocity) relation. This is applicable to state functions
only.
Since z is a state function, then finite change, z when the system passes from initial state
A to final state B is given by z  z B  z A . Also,
 dz  0 where cyclic integral  means that

the system is in the same state at the end of its path as it was at the beginning, i.e. it has traversed a
closed path. Thus dz is an exact differential.
Question. Two mol of an ideal gas are held by a piston under 10 atm pressure and at 273 K. The pressure
is suddenly released to 0.4 atm and the gas is allowed to expand isothermally. Calculate w, q, E and
H for the process?
CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical
Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 2: Zeroth and first law of thermodynamics
 Solution: Since pressure is released suddenly, the expansion must be irreversible. The final pressure
and external pressure become equal.

n = 2 mol,
P1 = 10 atm,
P2 = 0.4 atm
T1  T2 = 273 K

Since, ideal gas expands isothermally, T = 0 and hence E = 0.

From the first law,

E = q + w = 0
q = -w = + 4358 J

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 2: Zeroth and first law of thermodynamics
 9. Summary

 The generalized laws of thermodynamics are

o Zeroth law of thermodynamics states that if two systems are in thermal equilibrium
with a third system then they are in thermal equilibrium with each other
o The first law of the conservation of energy which represents the connection between
heat and mechanical work.
o The second law deals with the entropy change in the system and the manner in which
energy change takes place.
o The third law deals with the absolute value of entropy.
 A definite amount of energy which is present in every substance that depends upon its chemical
nature as well as upon its temperature, pressure and volume. This energy is known as internal
energy
 The mathematical statement of the First law of thermodynamics.
U  q  w
where U is change in internal energy, q is the amount of heat exchange between the
system and the surroundings and w is the amount of work done.
 At constant volume, the change in internal energy of a system becomes equal to heat exchange
between the system and its surroundings i.e.
U  q v

CHEMISTRY Paper No. 10: Physical Chemistry- III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface chemistry, Fast kinetics)
Module No. 2: Zeroth and first law of thermodynamics