SYLLABUS (IPU)I SEM

APPLIED PHYSICS-I
Unit I
Introduction to Thermodynamics: Fundamental Ideas of Thermodynamics, The Continuum
Model, The Concept of a “System’”, “State”, “Equilibrium”, “Process’”. Equations of state,
Heat, Zeroth Law of Thermodynamics, Work, first and second laws of thermodynamics, entropy

Unit II
Waves and Oscillations: Wave motion, simple harmonic motion, wave equation, superposition
principle. Introduction to Electromagnetic Theory: Maxwell’s equations. work done by the
electromagnetic field, Poynting’s theorem, Momentum, Angular momentum in electromagnetic
fields, Electromagnetic waves: the wave equation, plane electromagnetic waves, energy carried
by electromagnetic waves
Unit III
Interference: Interference by division of wave front (Young's double slit experiment, Fresnel's
biprism), interference by division of amplitude (thin films, Newton's rings, Michelson's
interferometer), Coherence and coherent sources

Diffraction: Fraunhofer and Fresnel diffraction; Fraunhofer diffraction for Single slit, double slit,
and N-slit (diffraction grating), Fraunhofer diffraction from a circular aperture, resolving power
and dispersive power of a grating, Rayleigh criterion, resolving power of optical instruments

Polarization: Introduction to polarization, Brewster’s law, Malu's law, Nicol prism, double
refraction, quarter-wave and half-wave plates, optical activity, specific rotation, Laurent half
shade polarimeter.

Unit IV
Theory of relativity: The Michelson-Morley Experiment and the speed of light; Absolute and
Inertial frames of reference, Galilean transformations, the postulates of the special theory of
relativity, Lorentz transformations, time dilation, length contraction, velocity addition, mass
energy equivalence. Invariance of Maxwell’s equations under Lorentz Transformation.

Introduction to Laser Physics: Introduction, coherence, Einstein A and B coefficients, population

inversion, basic principle and operation of a laser, the He-Ne laser and the Ruby laser

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 Unit I - THERMODYNAMICS
Syllabus:
Introduction to Thermodynamics: Fundamental Ideas of thermodynamics; the Continuum
Model; The concept of state, equilibrium, process; equation of state; heat, zeroth law of
thermodynamics; work; first and second law of thermodynamics; entropy.

Fundamental Ideas of Thermodynamics

Thermodynamics is the branch of physical sciences that deals with the concept of
heat and temperature and inter-conversion of heat and other forms of energy. It
mainly deals with transformation of heat into mechanical work and vice versa.
Thermodynamics is the science of energy transfer and its effect on the physical
properties of substances. It is applied to design and analysis of various energy
conversion systems and also known as engineering thermodynamics.
Thermodynamics has basically only a few fundamental laws and principles applied
to a wide range of problems. The application of thermodynamic laws and
principles are found in all fields of energy, technology, notably in steam and
nuclear power plants, internal combustion engines, gas turbines, air conditioning,
refrigeration, gas dynamics, jet propulsion, compressors, chemical process plants
and direct energy conversion devices.
CONCEPT OF CONTINUUM
In macroscopic approach of thermodynamics the substance is considered to be
continuous whereas every matter actually comprises of large number of molecules.
Disregarding the behavior of individual molecules matter is treated as continuous.
For facilitating the analysis this concept of continuum is used in which the
substance is treated free from any kind of discontinuity. As this is an assumed state
of continuum in substance the order of analysis / scale of analysis become
important. Thus incase the scale of analysis is large enough, and the discontinuities
are of the order of intermolecular spacing or mean free path then due to relative
order of discontinuity being negligible it may be treated as continuous. For this the
scale of analysis of density is defined. This is explained like this. Also see the
graph for defining range of density.

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Let us consider a certain amount of fluid in a container. We know the density
of the fluid is constant. Let us consider a small volume of the liquid of mass dm
and volume dv. So density of this small amount is ρ = Δm/Δv. Let us reduce
the volume or shrink the volume to Δv0 . Δv0 may be so small, as it contain
relatively few molecules which may also keep on moving in and out of the
considered very small volume; as molecules of any fluid are in continuous
motion. So below this small volume the density of the fluid is changing
continuously as mass is fluctuating. For such a situation, the definite value of
density cannot be given. So density can be considered as constant till Δv 0
bellow this value density is fluctuating.
Δ𝑚
ρ= lim
Δv→Δv0 Δ𝑣
Hence the scale of analysis should be within this limit so that the matter can
be considered as continuous. Macroscopically the scale of density should be in
this range.

Thermodynamic System
A thermodynamic system is defined as a quantity of matter or a region in space
upon which attention is concentrated in the analysis of a problem. It is a collection
of a large number of particles having a certain value of pressure, volume and
temperature.
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For study, these systems are to be clearly defined using a real or hypothetical
boundary. Everything outside this boundary is called surroundings or environment.
The system and surrounding together comprise a universe.
𝑆𝑦𝑠𝑡𝑒𝑚 + 𝑆𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 = 𝑈𝑛𝑖𝑣𝑒𝑟𝑠𝑒
There are three types of systems: Closed; Open; Isolated.

Closed Open Isolated

Surrounding Energy Out Surrounding
Energy
Out
System Mass In System
System

Energy In
Energy in Mass
Out
 No Mass Transfer  Mass and Energy  No Mass or energy
 Only Energy Transfer transfer transfer

In closed system there is no In open system energy and In isolated system there is
mass transfer, only energy mass interaction takes place neither mass nor energy
interaction takes place across across the boundary of the interaction occurs across the
the boundary. system. boundary.
 Ex: boiling water in a  Ex: Automobile engine  Ex: Thermosflasks
closed pan

Thermodynamic Properties: -
Any thermodynamic system is characterized by thermodynamic properties.
These are macroscopic in nature. Properties are the coordinates that describe state
of the system. Ex: Pressure, Temperature, Volume, Viscosity, Modulus of
Elasticity etc.
There are two types of properties:
 Intensive property: These are independent of the mass of the system. They
have the same value for any part of the system. Ex: Pressure, temperature
etc.

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  Extensive property: These are dependent on the mass of the system and do
not have the same value for every part of the system. Ex: Volume, Energy,
Enthalpy, etc.
Extensive properties when estimated on unit mass basis result in intensive
property known as specific (property) Ex: specific heat, specific volume etc.
Thermodynamic State: -
When the properties of a system are quantitatively defined then it refers to the state
of a system.
Every system has certain properties by which its physical condition may be
described. [Pressure (P), Volume (V), Temperature (T)]. These are all macroscopic
in nature. When all the properties of a system have a definite value, the system is
said to exist at a definite state. Properties are the coordinates to describe the state
of a system. Pressure, Volume, Temperature (P, V, T) are single valued functions
of the state of the system are also called state functions or state variable.
Any operation in which one or more properties of a system changes is called a
change of state.
The succession of states passed through during a change of state is called the path
of change of state. When the path is completely specified the change of state is
called a process. Ex: a constant temperature process.
Thermodynamic cycle is defined as a series of state changes such that the final
state is identical with the initial state.
Thermodynamic Equilibrium
A system is said to be in a state of thermodynamic equilibrium when no change in
any macroscopic property is observed, i.e. it’s thermodynamic variables
(properties) remain constant.
A system is said to be in a thermodynamic equilibrium if conditions of the three
equilibriums are satisfied.
i. Mechanical Equilibrium: in the absence of any unbalanced force within the
system itself and also between the system and the surrounding, the system is
said to be in a state of mechanical equilibrium

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 ii. Chemical Equilibrium: If there is no chemical reaction or transfer of matter
from one point to another such as diffusion, the system is said to exist in a
state of chemical equilibrium.
iii. Thermal Equilibrium: When a system existing in mechanical and chemical
equilibrium is separated from its surroundings by a diathermic wall and if
there is no spontaneous change in any property of the system; the system is
said to exist in a state of thermal equilibrium.

Zeroth Law of Thermodynamics

Two systems (A) and (B) are in thermal equilibrium with a third system (C), then
the two systems (A and B) are in thermal equilibrium with each other.

C Adiabatic Wall

A B

Diathermic Wall
Let A, B and C are 3 systems
A and B are separated by adiabatic wall.
A, C and B, C are separated by diathermic wall.
After long time we can observe that the state coordinates of A, B, C remain
constant.
Therefore, systems A and C; and the systems B and C are in thermal equilibrium.
Hence A and B are also in thermal equilibrium.
Let PA, VA are pressure and volume of system A.
Let PB, VB are pressure and volume of system B.
Let PC, VC are pressure and volume of system C.
If A and C are in thermal equilibrium

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 𝛷1 (𝑃𝐴, 𝑉𝐴) = 𝛷3 (𝑃𝐶, 𝑉𝐶)
If B and C are in thermal equilibrium
𝛷2 (𝑃𝐵, 𝑉𝐵) = 𝛷3 (𝑃𝐶, 𝑉𝐶)
Then;
𝛷1 (𝑃𝐴, 𝑉𝐴) = 𝛷2 (𝑃𝐵, 𝑉𝐵) = 𝛷3 (𝑃𝐶, 𝑉𝐶) = 𝑇
Thus for every system there exist a function of it’s state variables such that the
numerical value of the function is same for all systems in thermal equilibrium with
each other. This value is called temperature.
Temperature may be defined as a function of state of a system such that it takes the
same value for all systems in thermal equilibrium with one another.
For any system;
𝛷(𝑃, 𝑉) = 𝑇
This is called the equation of state.
Equation of State
An equation of state is a relation between the thermodynamic coordinates of a
system. Actually it is relation between temperature, volume and pressure of the
thermodynamic system.
Ex: Let a fixed mass (m) of gas is kept in a container of fixed volume and at
temperature of surrounding. The gas has a constant pressure which can be
determined with the nature of gas.
The pressure of the gas cannot be changed without varying the volume or the
temperature of gas. Similarly, if the pressure and volume of gas have arbitrarily
chosen values, the temperature is fixed. We can say if thermodynamic variables (P,
V, T and m) of a system are dependent variables. Hence there must be one relation
between these thermodynamic variables of a system which makes one of them
independent.
This can be expressed as;
𝛷(𝑃, 𝑉, 𝑇, 𝑚) = 0
In mass independent form;

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 𝛷(𝑃, 𝑣, 𝑇) = 0 (1)
Here, 𝑣 = 𝑉/𝑚 = 𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑟 𝑚𝑜𝑙𝑎𝑟 𝑣𝑜𝑙𝑢𝑚𝑒
Equation (1) is called equation of state of a gas. For an ideal gas the equation of
state takes the form;
𝑃𝑣 = 𝑅𝑇 (2)
R = Universal Gas Constant
For real gases the equation of state is known are Vander Waal’s equation, which is
of the form;
𝑎
(𝑃 + ) (𝑣 − 𝑏) = 𝑅𝑇 (3)
𝑣2

Here a and b are constants dependent on the nature of the gas.

Thermodynamic Process
Thermodynamic state of a system changes due to the energy and mass interactions.
The mode in which the change of state of a system takes place is termed as
process.
In other words if a system undergoes a transition from one equilibrium state (P 1 V1
T1) to another state (P2 V2 T2), it is said to undergo a thermodynamic process.
Reversible Process: Thermodynamic system that is capable of restoring its original
state by reversing the factors responsible for occurrence of the process is called
reversible process. Here the state changes during the forward direction of
occurrence of a process are exactly similar to the states passed through by the
system during the reversed direction of the process. Such reversibility can be
realized only if the system maintains its thermodynamic equilibrium throughout
the occurrence of the process. Hence it can also be known as equilibrium process.
Irreversible Process: Thermodynamic system which forbids system from retracing
the same path upon reversal of the factors causing the state change. They do not
maintain equilibrium during the occurrence of the process. Hence it is also known
as non-equilibrium process.
An equation of state exists for every thermodynamic system. It expresses the
individual characteristics of the system as distinct from other systems.
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An equation of state is valid only for states of thermodynamic equilibrium. For
non-equilibrium states no equation of state exists as these states cannot be defined
in terms of thermodynamic coordinates referring to system as a whole.

Quasistatic Process
When a system is in thermodynamic equilibrium and the surroundings are kept
unchanged, there will be no motion and also no work will be done.
On the other hand if the sum of the external forces is altered, resulting in a finite
unbalanced force acting on the system, the conditions for mechanical equilibrium
will not be satisfied any longer.
a. Due to unbalanced forces within the system, turbulence waves etc. may be
set up. The system as a whole may possess an accelerated motion.
b. Due to turbulence, acceleration etc. the temperature distribution within the
system may not be uniform. There may also be a finite temperature
difference between the system and the surroundings.
c. Due to the presence of unbalanced forces and difference in temperature,
chemical reaction may take place.
Hence a finite unbalanced force may cause the system to pass through non-
equilibrium states.
Let us consider a system initially in an equilibrium state. Let an unbalanced force
arise for some reason (say a change taking place in the surroundings). Due to this
one or more property of the system change. The succession of states through which
the system passes is called a process. A process takes place when a thermo
dynamical equilibrium does not exist. To describe the states of a system we can
assume that the unbalanced force is infinitely small so that at any stage in the
process, the changes in the thermodynamic coordinates are infinitely small. This
ensures that the system is always close to some equilibrium state.
Here the system is assumed to pass through a succession of quasi equilibrium
states. Such a process is called quasi-static process.
A quasi-static process is defined as the process in which the deviation from
thermodynamic equilibrium is infinitely small and all the states through which a
system passes during a quasistatic process can be considered as equilibrium
states.
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In actual practice, many processes closely approach a quasistatic process and may
be treated as such with no significant error. Consider the expansion of a gas in a
closed cylinder fitted with a piston. Initially, weights are on the piston and pressure
of the gas inside the cylinder is higher than the atmospheric pressure. If the weights
are small and are taken up slowly, one-by-one, the process can be considered
quasistatic.
If all the weights are removed at once, expansion takes place suddenly and it will
be a non-equilibrium process. The system will not be in equilibrium anytime in this
process.
A quasistatic process is an ideal concept that’s applicable to all thermodynamic
systems. The conditions for such a process can never be satisfied sufficiently in
practice.
Types of thermodynamic Processes
(1) Isothermal Process—An isothermal process is one in which temperature
of the body maintained constant. The process can be realized by
enclosing the system (a gas) in a container fitted with a piston. The
container is kept in good thermal contact with a heat reservoir so that the
temperature of the system is maintained constant.
(2) Adiabatic Process—In adiabatic process no exchange of heat between the
system and surrounding takes place. Here the system is perfectly
insulated from the surroundings. All along the process there is a change
in temperature.
(3) Isobaric Process—In an isobaric process the pressure is maintained
constant. This can be realized in practice by enclosing the system (an
ideal gas) in a cylinder fitted with movable piston and keeping the system
in good thermal contact with a heat reservoir.
(4) Isochoric process -In isochoric process volume of the substance will
remain constant.
HEAT
Heat is a form of energy which can be transferred from one body to another. It can
also transfer to other forms of energy and vice versa. When two systems at
different temperatures are brought into contact the final temperature attained by the
two systems is intermediate temperature of both the systems. It is due to transfer of
something from the system at higher temperature to the one at lower temperature,

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resulting in a change of state of both. The quantity which is transferred is called
heat. When a system changes from state 1 to state 2 will depend on the
intermediate stages through which the system passes (i.e., it’s path) hence it is a
path function.
(Q-1)Can heat be given to a substance without rising temperature ?
Ans- When a condensed system like ice is put in contact with the flame, the heat
from flame will flow into ice due to temperature difference. But the temperature of
ice does not rise. Instead the ice changes to liquid(water) at constant temperature.
Thus the addition of heat without rise in temperature is possible.
WORK
In thermodynamics, work is a specific type of interaction between a system and its
surroundings. As a system interacts with the surroundings, changes occur in the
system which are described by the changes in it’s thermodynamic coordinates.
Work in a Volume Change:

GAS

Let us consider a cylinder having insulating walls and fitted with a movable
frictionless piston. A gas is confined within the cylinder and exerts pressure on the
piston. The piston is kept in equilibrium by placing some weights such as lead
shots on its top. If some of the lead shots are removed gradually, the gas expands
slowly and the system rises upwards. If one slowly adds weights the piston goes
slowly downward and the gas undergoes compression. So mechanical work is
associated with the expansion or compression of a gas in a piston cylinder device.
The side figure shows that the piston attains a new equilibrium position when it’s
raised through an infinitesimal distance dy.

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Let P = Pressure of Gas;
A = Area of piston;
F = P.A
The work done by the gas on the piston is:
𝑑𝑊 = 𝐹. 𝑑𝑦 = 𝑃. 𝐴. 𝑑𝑦 = 𝑃. 𝑑𝑉; where 𝑑𝑉 = 𝐴. 𝑑𝑦 is the infinitesimal
change in the volume of the gas.
𝑑𝑊 = 𝑃. 𝑑𝑉
Let Vi = the initial volume;
Vf = the final volume (after work is done)
Then work done by gas;
𝑉
𝑊 = ∫𝑉 𝑓 𝑃. 𝑑𝑉
𝑖

By knowing the equation of state of the system P can be expressed as a function of

V and the integral is evaluated.
Let us see the P-V diagram of a quasistatic process. The initial state of the gas is
represented by A (Pi Vi); and the final state is represented by B (Pf Vf). The work
done 𝑑𝑊 in a small volume change 𝑑𝑉 is represented graphically by the area 𝑃𝑑𝑉
in a narrow vertical strip of width 𝑑𝑉 and height P.
Work done from A to B is
𝑉
𝑊𝐴𝐵 = ∫𝑉 𝑓 𝑃. 𝑑𝑉 = 𝑎𝑟𝑒𝑎 𝑢𝑛𝑑𝑒𝑟 𝑐𝑢𝑟𝑣𝑒 𝐴𝐵
𝑖

Work is Path Dependent:

A gas can follow several different paths as it expands from initial state (i) to final
state (f).
Each path will have different area under it. Since this area represents the
magnitude of work, work done will be different for different processes.

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Work Done During a Cyclic Process:
Let us consider a cyclic process during which the system goes from A to B via path
A-B-C and returns from C to A via path C-D-A.
C-B-A path represents expansion process.
C-D-A path represents compression process.
Work done during expansion is equal to area under A-C-B.
Work done during compression is equal to area under B-D-A.
Work done during cyclic process ACBDA is:
Area ABCEF – Area BDAFE = Area ACBDA

𝑊𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 = ∮ 𝑃𝑑𝑉 = 𝐴𝑟𝑒𝑎 𝐴𝐶𝐵𝐷𝐴

1. Work Done During Isothermal Process:

Consider a system of n moles of gas which is confined within a cylinder fitted with
a movable piston and is in contact with a heat reservoir at a temperature T. The
ideal gas equation for isothermal process is:
𝑃𝑉 = 𝑛𝑅𝑇 − (1)

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 𝑛𝑅𝑇
𝑃= − (2)
𝑉

Let V1 is initial volume of gas; V2 is final volume of gas

In side figure the area of the shaded strip represents the work done for a small
change in volume dV.
When volume changes from V1 to V2
𝑉
𝑊𝑜𝑟𝑘 𝐷𝑜𝑛𝑒 = ∫𝑉 2 𝑃𝑑𝑉 = 𝐴𝑟𝑒𝑎 𝐴𝐵𝑏𝑎
1

𝑉 𝑛𝑅𝑇 𝑉 𝑉2
= ∫𝑉 2 𝑑𝑉 = 𝑛𝑅𝑇 [log 𝑉]𝑉21 = 𝑛𝑅𝑇 log 𝑒
1 𝑉 𝑉1

𝑃1𝑉1 = 𝑃2𝑉2
𝑃1
Or 𝑊 = 𝑛𝑅𝑇(2.3026) log10
𝑃2

2. Work Done During Isobaric Process:

During an isobaric process, the system (Ideal Gas) undergoes a transition from
initial state (P, V1, T1) to final state (P, V2, T2)
Here the pressure remains constant.
The work done in this process is:
𝑓 𝑉
𝑊 = ∫𝑖 𝑃𝑑𝑉 = 𝑃 ∫𝑉 2 𝑑𝑉 = 𝑃 (𝑉2 − 𝑉1 )
1

𝑊 = 𝑃(𝑉2 − 𝑉1 )
Since 𝑃𝑉1 = 𝑛𝑅𝑇1; 𝑃𝑉2 = 𝑛𝑅𝑇2 so 𝑊 = 𝑛𝑅(𝑇2 − 𝑇1)
3. Work Done During Isochoric Process:
During isochoric process volume of the system is maintained constant. Hence, the
change in volume 𝑑𝑉 = 0

∴W=0

4. Work Done During Adiabatic Process:

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Let us consider a gas enclosed in an adiabatic container, fitted with a movable
piston. During adiabatic expansion, the gas volume changes from V 1 to V2.
Work done is given by:
𝑉
𝑊 = ∫𝑉 2 𝑃𝑑𝑉 = 𝐴𝑟𝑒𝑎 𝐴𝐵𝑏𝑎
1

During an adiabatic process, the equation for gas is

𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = 𝐾
𝐶𝑝
Where γ = ratio of specific heats =
𝐶𝑉
𝐾
𝑃=
𝑉𝛾
𝑉 𝐾 𝐾 1 1
So 𝑊 = ∫𝑉 2 𝛾 𝑑𝑉 = [ − ]
𝑉
1 1−𝛾 𝑉 𝛾−1 2 𝑉1 𝛾−1

Also, we have: 𝑃1𝑉1 𝛾 = 𝑃2 𝑉2 𝛾 = 𝐾

1 𝐾 𝐾 1 𝑃2 𝑉2 𝛾 𝑃1 𝑉1 𝛾 1
𝑊= [ 𝛾−1 − 𝛾−1 ] = [ 𝛾−1 − 𝛾−1 ]= [𝑃2 𝑉2 − 𝑃1𝑉1 ]
1−𝛾 𝑉2 𝑉1 1−𝛾 𝑉2 𝑉1 1−𝛾

Let T1 is the temperature of system at A and T2 is temperature at B, then

𝑃1𝑉1 = 𝑅𝑇1 and 𝑃2𝑉2 = 𝑅𝑇2
1
So 𝑊 = [𝑅𝑇2 − 𝑅𝑇1]
1−𝛾

Here heat transferred is zero because the system is thermally insulated from the
surroundings. The decrease in internal energy of the system (due to fall in
temperature) is equal to the work done by the system and vice-versa.
Internal Energy
The molecules of a system have kinetic energy due to their motion and potential
energy due to their mutual interaction. The adiabatic work done on the system may
increase the kinetic energy and potential energy of the system.
According to molecular theory, internal energy of a system is the total energy of all
of the molecules in the system except for macroscopic kinetic energy (kinetic
energy associated with the motion of the system as a whole). And the external
potential energy (energy due to external interactions). The internal energy includes
the following types of energies:

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 a. Translational and rotational kinetic energy of molecules due to their
individual random motion
b. Vibrational energy of molecules and of atoms within molecules due to
vibrations about their equilibrium positions.
c. Potential energy due to interaction between the atoms and molecules of the
system.
d. Kinetic and potential energy associated with the binding of electrons to
nuclei to form atoms and the binding of protons and neutrons to form nuclei.
In other words, the internal energy of a system is the sum of the kinetic, potential,
chemical, nuclear, electric and all other forms possessed by the atoms and
molecules of the system.
The internal energy of a thermodynamic system is the energy contained within it. It
is the energy necessary to create or prepare the system in any given internal state.
It does not include kinetic energy of motion of the system as a whole nor the
potential energy of the system as a whole due to external force fields, including the
energy of displacement of the surroundings of the system.
Internal energy of a real gas- The molecules of a real gas are in random motion and
due to this they possess energy known as kinetic energy. They exert force of
attraction on each other, due to which they possess potential energy. For a real gas
internal energy is K.E. +P.E.
For an ideal gas, the molecules are infinitely small and there is no force of
attraction between them. The internal energy of the gas is totally kinetic depending
only on temperature. They donot possess potential energy.
For a monoatomic ideal gas, the internal energy is the total kinetic energy of the
3𝑘𝑇
gas molecules and is given by .
2
3
The internal energy of a monoatomic ideal gas system is 𝑈 = 𝑁𝑘𝑇, where N is
2
the number of monoatomic gas molecules comprising the gas.
Internal Energy U is an extensive property of a system.
Internal energy represents the energy of a gas due to molecular agitation as well
as due to the forces of molecular attraction.
If a closed system is caused to change from an initial state to a final state by
adiabatic means only then the work done on the system is the same for all adiabatic

16
paths connecting the two states. This implies adiabatic work is path independent. It
depends only on the initial and the final equilibrium states. So there must exist a
state function whose difference between the two equilibrium states (final and
initial) is equal to the adiabatic work. This state function is the internal energy of
the system U.
During state change of a system the internal energy may change from initial value
Ui to final value Uf.
First Law of Thermodynamics
When a certain quantity of heat is supplied to a system the whole of the heat
energy may not be converted into work. Part of the heat maybe used in doing
external work and rest of the heat might be used in increasing the internal energy
of the molecules.
Let 𝑑𝑄 = 𝑄𝑢𝑎𝑛𝑡𝑖𝑡𝑦 𝑜𝑓 ℎ𝑒𝑎𝑡 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑 𝑡𝑜 𝑎 𝑠𝑦𝑠𝑡𝑒𝑚
𝑑𝑊 = 𝑡ℎ𝑒 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑒𝑥𝑡𝑒𝑟𝑛𝑎𝑙 𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 𝑏𝑦 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚
𝑑𝑈 = 𝑡ℎ𝑒 𝑖𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑖𝑛𝑡𝑒𝑟𝑛𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠
Mathematically,
𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊
This is mathematical statement of First Law of Thermodynamics.
It states that the amount of heat given to a system is equal to the sum of increase in
internal energy of the system and the external work done.
OR
It states that during a thermodynamic process the change in internal energy of a
system is equal to the difference between the heat added to the system and the
external work done by the system.
𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊
The first law of thermodynamics is regarded as the law of conservation of energy
as applied to mechanical and heat energy.
The first law of thermodynamics is the application of the conservation of energy
principle to heat and thermodynamic processes:

17
The change of internal energy of the system
𝑑𝑄 = Δ𝑈 + Δ𝑊
Consequences of First Law When Applied to Different Processes
i. Isolated System:
When a system is isolated from the surroundings there is no heat exchange and no
work is done. In this case; dQ = 0, dW = 0
Hence, dU = 0 ⇒ U = constant
i.e. there is no change in internal energy of the system.
The internal energy of an isolated system is constant.
ii. Isothermal Process:
In an Isothermal process, temperature of the system remains constant. Hence,
internal energy of the system will remain constant. Hence change in internal
energy of a system during isothermal process is 0. i.e. ΔU = 0
⇒ 𝑑𝑄 = 𝑑𝑊
This implies that during isothermal process work done by the system is equal to the
amount of heat absorbed from the surroundings.
iii. Isochoric Process:
In an isochoric process the volume V of the system is constant. Hence change in
volume dV = 0. Hence work done is equal to 0.
∴ 𝑑𝑄 = 𝑑𝑈
𝑑𝑈 = 𝑈𝑓𝑖𝑛𝑎𝑙 – 𝑈𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 𝑈𝑓 – 𝑈𝑖
If heat is added to the system then Q is +ve and 𝑈𝑓 – 𝑈𝑖 > 0
𝑈𝑓 – 𝑈𝑖 > 0 ⇒ 𝑈𝑓 > 𝑈𝑖
Heat added to a system at constant volume increases its internal energy hence its
temperature.
In other words if heat is rejected by a system at constant volume then its internal
energy decreases.

18
iv. Adiabatic Process:
In an adiabatic process there is no exchange of heat between the system and its
surroundings. i.e. Q = 0.
Hence, ∆𝑈 = −∆𝑊
When W is positive, work is done by the system, then ΔU is negative; i.e. there is
decrease in internal energy of the system. Hence there is decrease in temperature of
the system.
When W is negative, work is done on the working substance or system then
internal energy of the system increases and ΔU is positive. And the temperature of
the system increases.
Hence adiabatic process is accompanied by a change in temperature.
The equation of state for adiabatic process is PV   K , where K is a constant.

Cyclic Process:
A cyclic process is one in which the initial and the final states of the system are the
same. Hence there is no change in internal energy of the system.
i.e., ΔU = 0
∴ 𝑑𝑄 = 𝑑𝑊
During a cyclic process, work done by the system is equal to heat input.
Slopes of Isothermal and adiabatic process
(i) Isothermal Process:
For an isothermal process, temperature T is constant. The equation for
isothermal process is PV =Constant. Differentiating both sides we get
PdV + VdP = 0
Or PdV = VdP
Or PV  K
Or PdV  VdP  0
Or PdV  VdP

19
 dP P
Or  -----------(1)
dV V

(ii) Adiabatic Process:

For an Adiabatic process, temperature T is constant.
The equation of state for adiabatic process is PV   K , where K is a constant.
Differentiating both sides we get
Or PV   K
Or PV  1dV  V dP  0
Or V dP  -PV  1dV

dP PV  1 P
Or  
  -----------(2)
dV V V

Comparing equation(1) and (2) we can see that slope of isothermal is smaller
than that of adiabatic curve. Slope of adiabatic curve is γ times the slope of an
isothermal curve (as γ > 1).

Limitations of First Law of Thermodynamics

 First Law of Thermodynamics does not differentiate between heat and work
and assures full convertibility of one into other whereas full conversion of
work into heat and vice versa are not possible.
 First law of thermodynamics does not explain the direction of a process.
Such as theoretically it shall permit even heat transfer from low temperature
body to high temperature body which is practically not feasible. Spontaneity
of the process is not taken care of by the first law of thermodynamics.
Heat Reservoir
A body with a relatively large thermal capacity that can supply or absorb finite
amount of heat without undergoing any change of temperature is called a thermal
energy reservoir or heat reservoir.
Large bodies like rivers, oceans, our atmosphere, and the industrial furnaces are
examples of heat reservoirs; as dumping of heat to them does not cause appreciable
change in temperature.

20
Heat reservoirs can be of two types depended upon nature of heat interaction, i.e.,
heat rejection or heat absorption.
Source: A heat reservoir at high constant temperature is called a source. Any
amount of heat extracted from the source will not affect the temperature of the
source.
Sink: A heat reservoir at lower constant temperature is called a sink. Any amount
of heat given to the sink will not affect temperature of the sink.
Heat Engine
Heat engine is a device which is used to convert heat into work continuously. It has
three essential parts:
1) Source (or hot body): for supply of heat at high temperature.
2) Sink (or cold body): for the rejection of heat at lower temperature
3) The working substance which absorbs heat from the source.
The working substance takes heat from the source, converts a part of it into work
and the rest is given to the sink. This process is known as a cycle; as the working
substance returns to its original state.
Thus heat engine may precisely be defined as a device operating in cycle between
high temperature source and low temperature sink producing work.
The side figure shows a schematic diagram of a heat engine. The working
substance absorbs a quantity of heat Q1 from the source, performs work W on the
sounding and rejects heat Q2 to the cold reservoir (sink) in one complete cycle. The
effectiveness of heat engine into work is measured by a quantity called thermal
efficiency.

Efficiency: The efficiency of a heat engine is the ratio of the work done per cycle
to the heat absorbed per cycle.
Let

21
 𝑄1 = ℎ𝑒𝑎𝑡 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 𝑏𝑦 𝑡ℎ𝑒 𝑤𝑜𝑟𝑘𝑖𝑛𝑔 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑓𝑟𝑜𝑚 𝑡ℎ𝑒 𝑠𝑜𝑢𝑟𝑐𝑒
𝑄2 = ℎ𝑒𝑎𝑡 𝑟𝑒𝑗𝑒𝑐𝑡𝑒𝑑 𝑖𝑛𝑡𝑜 𝑡ℎ𝑒 𝑠𝑘𝑖𝑛 𝑎𝑓𝑡𝑒𝑟 𝑊 𝑎𝑚𝑜𝑢𝑛𝑡 𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒
Then 𝑊 = 𝑄1 − 𝑄2
𝑊 𝑄1 −𝑄2 𝑄2
𝐸𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 𝜂 = = =1−
𝑄1 𝑄1 𝑄1

𝑄2
𝜂= 1−
𝑄1
η = 1 or 100% when Q2 = 0; i.e. heat given to the sink must be zero and all heat is
converted into useful work and no heat is rejected, which is not possible in
practice. Thus the engine cannot convert all heat into work without any sink.
Again, when Q2 = Q1, η = 0; i.e. no work is done.
The Refrigerator:
A refrigerator is a device which is operating in a cycle that extracts heat from a
body at lower temperature and transfers it to a body at higher temperature. During
the process some amount of work is done on the system by some external agent.
Hence refrigerator is a heat engine running backward.
The side figure shows that the working substance which is called the refrigerant
extracts Q2 heat from cold reservoir, work W is done on it by some external agent
and it rejects heat Q1 to the hot reservoir at temperature T1. In the home
refrigerator, the cold chamber in which food is stored is called cold reservoir. The
room in which the unit housed is the hot reservoir. The electric motor which drives
the unit does work on the system.

22
Coefficient of Performance (COP k): It is defined as the ratio of heat extracted at
lower temperature to the work input to the refrigerator.
ℎ𝑒𝑎𝑡 𝑖𝑛𝑝𝑢𝑡 𝑄2
𝑘= =| |
𝑤𝑜𝑟𝑘 𝑖𝑛𝑝𝑢𝑡 𝑊
The net heat absorbed by the system, 𝑄 = 𝑄2 − 𝑄1
Since the process is cyclic ΔU = 0
From first law of thermodynamics, Q = W
Hot Reservoir
−𝑊 = 𝑄 = 𝑄2 − 𝑄1
OR
𝑊 = 𝑄1 − 𝑄2
Refriger
𝑄2 𝑄2 ator
𝑘= =
𝑊 𝑄1 − 𝑄2
𝑄2 𝑄1 1 1
1+𝑘 =1+ = = 𝑄1 −𝑄2 =
𝑄1 −𝑄2 𝑄1 −𝑄2 𝜂
𝑄1
Cold Reservoir
1
𝜂=
1+𝑘
Where η is thermal efficiency of refrigerator; it is always less than one.

Carnot Engine and Carnot Cycle

23
Carnot’s engine is developed by Sadi Carnot is an ideal engine which should be
free from all types of imperfections, of an actual engine and 100% efficient. This
can never be realized in practice. However the performance of practical engines is
judged by taking the Carnot engine as standard. The engine consists of the
following parts:
 The working substance is contained in a cylinder with perfectly non
conducting walls, non-conducting friction less piston and conducting
bottom.
 A hot body of infinitely large heat capacity at a constant temperature T1.
This is called source.
 A hot body of infinitely large heat capacity at a temperature T2( T2 <T1).
This is called sink.
 A perfectly insulating stand.
The cylinder may be placed on any of the three bodies and can be moved from one
to other without doing any work.

24
CARNOT’ CYCLE
The Carnot’s engine utilizes a reversible cycle known as Carnot cycle. A Carnot
cycle is a reversible cycle with two isothermals bound by two adiabatics.
Step-1: Isothermal expansion from state A to B.
Let at point A the working substance is in its initial state at which pressure is P1
and volume is V1. Now the cylinder is placed on the source. Due to this the piston
moves slowly in upward direction as the gas expands. During this isothermal
expansion, temperature of gas falls, but due to contact with the source a certain
amount of heat Q1 is taken from source to maintain temperature at T1. The final
state (P2, V2) of the gas is shown by a point B in the PV indicator diagram. The
work done during this isothermal expansion is WAB (positive).
In this process the amount of work done `by the gas is (ΔU = 0, ∴ Q = W)
𝑉 𝑉 𝑅𝑇1 𝑉
𝑄1 = 𝑊1 = ∫𝑉 2 𝑃𝑑𝑉 = ∫𝑉 2 𝑑𝑉 = 𝑅𝑇1 ln 2 -------------(1)
1 1 𝑉 𝑉1

Step -2: Adiabatic expansion from state B to C

Next the cylinder is placed on the insulating stand and is thermally insulated. The
gas is allowed to expand adiabatically till it reaches the state (P 3, V3, T2). This is
shown by the curve BC.
𝑉 𝑅(𝑇1 −𝑇2 )
Work done 𝑊2 = ∫𝑉 3 𝑃𝑑𝑉 = = 𝐴𝑟𝑒𝑎 𝐵𝐶𝑐𝑏----------(2)
2 𝛾−1

Step 3: Isothermal compression from state C to D

25
Now the cylinder is removed from the stand and placed on the sink. In this position
the piston moved in the downward direction, the gas is compressed to a point D
where the pressure and volume become P4, V4. In this process the work done is

𝑉 𝑉 𝑅𝑇2 𝑉4
𝑄2 = 𝑊3 = ∫𝑉 4 𝑃𝑑𝑉 = ∫𝑉 4 𝑑𝑉 = 𝑅𝑇2 ln = 𝐴𝑟𝑒𝑎 𝐷𝐶𝑐𝑑------(3)
3 3 𝑉 𝑉3

Step -4: Adiabatic compression from state D to A

Finally the cylinder is placed on the insulating stand again and the piston is further
lowered such that the gas is allowed to undergo adiabatic compression. The heat
generated in this process will increase the temperature the gas. When the pressure
and volume corresponds to the point A (P1, V1) the compression is stopped. The
temperature of gas is T1.
𝑉 𝑅(𝑇1 −𝑇2 )
Work done 𝑊4 = − ∫𝑉 1 𝑃𝑑𝑉 = − = 𝐴𝑟𝑒𝑎 𝐴𝐷𝑑 -----(4)
4 𝛾−1

Comparing eqn (1) and (2) W2 =-W4 ------(5)

The net work done by the engine is
W= W1+W2 +W3+W4 = W1+W3
𝑉2 𝑉
𝑊 = 𝑅𝑇1 ln − 𝑅𝑇2 ln 3 -------------(6)
𝑉1 𝑉4

The points A and D are on all the same adiabatics, so

PV   K => P1V1  P4V4

But PV = nRT
nRT1 nRT2
 P1  Also P4 
V1 V4
nRT1V1 nRT2V4
 P1V1  Also P4V4 
V1 V4
 P1V1  P4V4
nRT1V1 nRT 2V4
 =
V1 V4
T1 T
 1
 12 -
V1 V4

26
 1
T V 1  V 
 1  11   1  ------------(7)
T2 V4  V4 
 Similarly the points B and C are on all the same adiabatics, so

1
T1 V21  V2 
Hence  1    --------------(8)
T2 V3  V3 

From Eqns (7) and (8), we have

1 1
 V1  V 
    2 
 V4   V3 

V1 V2
 
V4 V3
V1 V4
 
V2 V3
V2 V3
  -----------(9)
V1 V4
Using Eqn (9) in (6)

𝑉2 𝑉3
𝑊 = 𝑅𝑇1 ln − 𝑅𝑇2 ln
𝑉1 𝑉4

𝑉2 𝑉2 𝑉2
𝑊 = 𝑅𝑇1 ln − 𝑅𝑇2 ln = 𝑅 ln (𝑇1 − 𝑇2)
𝑉1 𝑉1 𝑉1
So
𝑉2
𝑊 = 𝑄1 − 𝑄2 = 𝑅 ln (𝑇1 − 𝑇2)-----------------(9)
𝑉1

Efficiency η is ratio of useful output and input

R T1  T2  ln
V2


W Q1  Q2
 
V1

T1  T2   1  T2
Q1 Q1 V2 T1 T1
RT1 ln
V1

Q2 T
  1 1 2
Q1 T1

27
This is the required expression for the efficiency of heat engine working between
temperatures T1 and T2. It does not depend on the working substance. There is no
dissipation of heat from working substance to the environment. However in real
engines some energy is always dissipated. Hence efficiency of any real heat engine
is always less than efficiency of Carnot engine.
Carnot’s Theorem
All the reversible engines working between the same temperature limits have the
same efficiency. No engine can be more efficient than a Carnot engine operating
between the same two temperatures. Consider two reversible engines A and B
working between the temperatures T1 and T2. A and B are coupled. The engine A
works as a heat engine and B works as a refrigerator. The engine A absorbs an
amount of heat Q1 from the source at temperature T1. It does external work W and
transfers it to B. The heat rejected to the sink is Q2 at temperature T2. The engine B
absorbs heat Q2’ from the sink at temperature T2 and W amount work is done on
the working substance. The heat given to the source at temperature T 1 is Q1’.
Suppose engine A is more efficient than engine B.
W Q1  Q2
Efficiency of engine A is   
Q1 Q1

W Q '1  Q ' 2
Efficiency of engine B is 1'  
Q '1 Q '1

As engine A is more efficient than engine B, η >η’ => Q 1’ >Q1

Also W = Q1 - Q2 = Q’1-Q’2
 Q2’ > Q2
Thus for two engines A and B working as a coupled system (Q’2 –Q2) is the
quantity of heat taken from the sink at temperature T2 and (Q’1 –Q1) is the
quantity of heat given to the source at T1.
It means that heat flows from the sink at low temperature T 2 to the source at
higher temperature T1 i.e heat flows from a body at low temperature to a body
at higher temperature. But no external work has been done on the system. This
is contrary to the second law of thermodynamics. Thus η cannot be greater
than η’.

28
 Hence two reversible engines working between the same two temperature limits
have the same efficiency irrespective of the nature of the working substance.
In actual engine there is always loss of energy due to friction, conduction and
radiation etc. Hence it’s efficiency is always lower than that of Carnot engine.

E- Heat Engine and R –Refrigerator

THE SECOND LAW OF THERMODYNAMICS

The first law of thermodynamics is a form of the law of conservation of energy
applied to thermodynamic processes. But this law does not impose any restriction
on the feasibility of a process. Many processes are forbidden inspite of satisfying
1st law of thermodynamics. Carnot engine shows that it is not possible to construct
29
a heat engine which extracts heat from a reservoir and converts it completely into
work, without rejecting anything to sink. This process cannot occur even if does
not violate the first law of thermodynamics. So physical process can take place if it
satisfies some more conditions, in addition to first law of thermodynamics. This is
second law of thermodynamics which if formulated in different ways which are
logically equivalent.
KELVIN PLANK STATEMENT
It is impossible to construct a heat engine operating in a cycle to convert the
absorbed heat completely into work.
A heat engine works between a hot reservoir at temperature T 1 and a cold reservoir
at temperature T2. In each cycle of operation it receives heat Q1from hot reservoir
converts a part of it into work and rest amount is transferred to a cold reservoir
sink. After one cycle of operation the system returns to its initial state. There is no
net change in internal energy of the system. i.e. ΔU=(Q1-Q2) – W = 0
Or W = Q1-Q2
This is in accordance with 1st law of thermodynamics. (100% efficient)
W Q1  Q2
The thermal efficiency of heat engine is   
Q1 Q1

According to second law W can never be equal to Q1.

Hence η can never be 1 or 100%. And Q2 can never be equal to zero.
This implies, the heat engine must exchange heat with a low temperature
reservoir(sink) as well as a high temperature heat reservoir(source) to keep
operating. Hence Kelvin Planck statement can also be expressed as no heat
engine can be 100% efficient.
CLAUSIUS STATEMENT
Heat cannot flow spontaneously from a body at lower temperature to a body at
higher temperature.
Or
Heat cannot flow from a cold body to a hot body without any external agent.
Let us consider the working of a refrigerator.

30
In each cycle of operation external work W is done on the system and the system
absorbs heat Q2 from a cold reservoir (Inside refrigerator) and deposits a larger
amount of heat in the hot reservoir(surrounding).
The coefficient of performance(COP)of a refrigerator is
Q2 Q2
K =K  
W Q1  Q2

The coefficient performance of the refrigerator becomes very large

when W=0 or Q1 = Q2.
That is the heat extracted from a cold reservoir is transferred completely into a hot
reservoir without being any work done on the system. This is practically
impossible. Thus second law of thermodynamics prohibits spontaneous flow of
heat from a body at low temperature to other at high temperature.
EQUIVQLLENCE OF KELVIN PLANCK AND CLAUSIUS STATEMENTS
The Kelvin Planck and Clausius statements of 2nd law of thermodynamis are
logically equivalent. We prove the equivalence by showing that the violation of
one statement implies the violation of other and vice versa.
(a) Consider an engine A which violated Kelvin Planck statement as shown
in Figure. This engine extracts heat Q1 from the hot reservoir at
temperature T1 and converts it completely into work W = Q1. Let the
engine A be coupled to a refrigerator B which extracts heat Q 2 from a
cold reservoir at temperature T2 and delivers heat (Q1+ Q2) to the hot
reservoir at temperature T1. This coupled system transfers a net amount
of heat Q2 from cold reservoir to the hot reservoir without any external
aid. This violates Clausius statement.
(b) Consider a refrigerator C which violates Clausius statement as shown in
Fig. It transfers heat Q2 from a cold reservoir without any external aid.
This refrigerator is coupled to a heat reservoir without any external aid.
This refrigerator is coupled to a heat engine D which extracts heat Q 1
from hot reservoir, rejects heat Q2 to cold reservoir and performs work.
W= Q1- Q2.
From the above argument we conclude that the Clausius and Kelvin
Plank statement of 2nd law of thermodynamics are equivalent, as violation
of one leads to violation of other.

31
32
Thermodynamic Scale of Temperature
A temperature scale which is independent of the properties of any particular
substance is known as absolute scale of temperature.According to Carnot’s
theorem the efficiency of a reversible engine is independent of the working
substance and depends only on the two temperatures between which it isworking.
Using this concept Lord Kelvin defined a temperature scale which does not depend
on the properties of any particular substance. This is the Kelvins absolute
temperature scale or the thermodynamic scale of temperature.

 1  2  f T1 , T2         (1)
W Q
Mathematically  
Q1 Q1

 F T1 , T2         ( 2)
Q1 1
Or we can write 
Q2 1  f T1 , T2 

This shows that Q2/Q1 is a function of T1 and T2.

These temperatures T1 and T2 are measured on an arbitrary scale.
ENTROPY
Entropy is a measure of the molecular disorder, or randomness, of a system. Its
introduction by the German physicist Rudolf Clausius in 1850 is a highlight of
19th-century physics. Entropy S is a state function. It is an extensive property of a
thermodynamic system.
By the Clausius definition, if an amount of heat Q flows into a large heat reservoir
at temperature T then the entropy increase is ΔS = Q/T.

33
Assume that there are two heat reservoirs R1 and R2 at temperatures T1 and T2. If an
amount of heat Q flows from R1 to R2, then the net entropy change for the two
reservoirs is

1 1
dS  Q  
 T1 T2 

which is positive provided that T1 > T2. Thus, the observation that heat never flows
spontaneously from cold to hot is equivalent to requiring the net entropy change to
be positive for a spontaneous flow of heat. If T1 = T2, then the reservoirs are
in equilibrium, no heat flows and ΔS = 0.

Suppose a heat engine absorbs heat Q1 from R1 and exhausts heat Q2 to R2 for each
complete cycle. The work done per cycle is W = Q1 – Q2, and the net entropy change is

Q2 Q1
dS  
T2 T1

To make W as large as possible, Q2 should be as small as possible relative to Q1.

However, Q2 cannot be zero, because this would make ΔS negative and so violate the
second law. The smallest possible value of Q2 corresponds to the condition ΔS = 0,
Q2 Q1
yielding 
T2 T1

A process for which ΔS = 0 is reversible.

Change of entropy in a reversible Process is zero.

The change in entropy of a substance in passing from state 1 to 2

Let us consider a system goes from state 1 to 2 through two different paths A and
B as shown in figure. The net change in entropy for the whole cycle is zero.
dQ
ds   0
T
i.e

There could be many different reversible paths between state a and state b.

34
Starting from point a one can reach point b along many reversible paths
connecting a and b.

Let us consider two reversible paths acb and bdc. These two paths constitute a
reversible cyclic process. Eqn (3) can be written as sum of two integrals for paths
R1 and R2.
b a
dQ dQ
a T  b T  0
R1 R2

b a b
dQ dQ dQ
a T  b T  a T
R1 R2 R2

Since R1 and R2 are two arbitrary paths connecting the initial equilibrium state to
final state b, the above expression indicates that
dQ
ds  
T

is independent of reversible paths connecting the points a and b.

b
dQ
 dS  S a  Sb   T
Ra -------------------(8)

The entropy change of the system between the states a and b is independent of the
path connecting points a and b.

Entropy S depends on properties of states a and b.

ENTROPY CHANGE IN REVERSIBLE PROCESSES

(1)Adiabatic process

During an adiabatic process there is no exchange of heat between the system and
surrounding i.e. dQ = 0. So dQ/T= 0

So S = Constant----------( 9)

35
The entropy of a system remains constant during an adiabatic process. Change in
entropy is zero. Hence adiabatic processes are isentropic.

(2) Isothermal Process

During a reversible isothermal process the temperature T of the thermodynamic

system remains constant. Change in entropy dS can be written as
dQ 1 Q
dS     dQ 
T T T

Q
dS  0
T
-----------(10)

If Q is positive, dS is a positive quantity, i.e. entropy of the system increases.

If Q is negaitive, dS is a negative quantity, i.e. entropy of the system decreases.

(3)Isobaric Process

During isobaric process pressure P remains constant.

The dQ =CP dT

Where CP is the heat capacity at constant pressure. Eqn (8) can be written as
b b b
 CP ln T a  CP ln b
dQ C dT dT T
 dS  ( Sa  Sb ) P    P  CP 
b

T T T Ta
a a a -----------------(11)

(4)Isochoric Process

During isochoric process volume V of the system remains constant and dQ=CVdT.

Change in entropy in irreversible Process

The efficiency ηi of an irreversible engine is less than efficiency η of a reversible

process.

ηi < η

For irreversible process

36
 Q2 T
1 1 2
Q1 T1

Q2 T2

Q1 T1

Q2 Q1

T2 T1

Q2 Q1
dS   0
T2 T1

Thus dS >0.
Thus in an irreversible process entropy of whole system always increases.

Example-Entropy of a system.

Let us consider 1 gm of ice at temperature T1 changes into steam at

temperature T2. Let L1 and L2 are latent heat of ice and steam respectively.
The change in entropy is given by dS = dQ/T
(i) When ice at temperature T1 changes into water at temperature T1 then
the change in entropyis L1/T1.
(ii) When water at temperature T1 changes into watet at temperature T2
the change in entropy is
T2 T T
dQ 2 1 * CV * dT 2
dT T
dS  T T T T
  T T  C[log T ]T12  C log T12
T
C
1 1 1

Where C is the specific heat of water.

(iii) When water at temperature T2 changes into vapour at temperature T2,
the the change in entropy is L2/T2
Therfore the total change in entropy is
L T L
dS  1  C log 2  2
T1 T1 T2

Entropy change of the Universe For A reversible Process

37
A system is a finite region of the universe which is chosen for thermodynamic
consideration. The region surrounding the system is, that is the reminder of
Universe is called the surroundings. The entropy change of the universe for the
due to a Process is equal to the sum of the entropy changes of the system and
surroundings.
Suppose during a reversible process the amount of heat dQ enters a system from
the surroundings at temperature T. Then the change in entropy of the system is
dQ
dS Sys 
T

The change in entropy of the surrounding is

dQ
dS surrounding 
T

The change in entropy of the Universe is

ds universe =dS system + dS surrounding

dQ dQ
dSUniverse   0
T T

dSUniverse  0

The change in entropy of the Universe is zero for a reversible process.

TEMPERATURE ENTROPY DIAGRAM (TS- DIAGRAM)

Unlike PV diagrams TS diagrams are also describing various thermodynamic

processes. Suppose the equilibrium state A of a system is characterized by entropy
S1 and temperature T1. It undergoes a change along path AB to another equibrium
state B( T2, S2).

38
From second law of thermodynamics an infinitesimal heat exchange at temperature
T is dQ = TdS

So the total heat exchange by the system as it goes from state A to B is

S2

Q   TdS  AreaABCD
S

Thus the total heat exchanged by the system during a thermodynamic change is
equal to the area enclosed by the TS curve and the S axis
TS Diagrams for some thermodynamic processes

(1) Isothermal Process:- Temperature remains constant during an isothermal

process.So TS curve for this process is parallel to x axis. If the constant
temperature is T and the entropy changes from S1 to S2 the heat
exchange is
Q = T(S2- S1)
(2) Adiabatic Process
An adiabatic process does not cause any heat exchange,
hence dQ =TdS =0 Or dS = 0.
Hence change in entropy is zero. The adiabatic processes are isoentropic
and are represented by straight lines parallel to T axis.

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 TS Diagram for a Carnot Cycle

A Carnot cycle consists of two isothermals and two adiabatic transformations.

Since the TS diagram for an isothermal process is a straight line parallel to S
axis and that for an adiabatic process is is a straight line is parallel to T axis, TS
diagram for a Carnot cycle is a rectangle.

40
TUTORIAL THERMODYNAMICS

1. Calculate the change in internal energy when 0.004 Kg of air is heated from
00C to 20C, the specific heat of air at constant volume being 0.172kilo
Cal/Kg 0C.
Solution:- From 1st law of thermodynamics dQ = dU + dW
Since air is heated at constant volume, dV =0
So dW = PdV =0
The heat taken by air is dQ = m CV dT
Given m = 0.004, dT =20C, CV= 0.172
dU = dQ = m CV dT = 0.004 X 2X2 = 1.376x 10 -3 Kcal
2. One CC of water becomes 1671 cc of steam when boiled at a pressure of one
atmosphere. The heat of vapourisation at this temperature is 540 cal/gm.
Compute the external work done and the increase in internal energy.
Solution:
Here P = 1 atm = 76 x 13.6 x 981 = 1.013 x 106 dyne/cm2= 1.013 x 105 N/m2
Here V1 =1 , V2 = 1671
Change in volume is dV = 1671 – 1 = 1670
The external work done is dW = PdV = 1.013 x 106 x1670 = 1693 x 106
= 169.3 x 107 ergs =169.3 Joule
= 169.3/4.2 =40.3 Cal
Given dQ = 540 Cal
Change internal energy.= 540 Cal - 40.3 Cal = 499.7 Cal
3. Calculate the work done when a gram molecule of a gas expands
isothermally at 270C to double its original volume(R= 8.3 Jouledegree-1mole-
1
).
Solution: Since the gas expands isothermally, the work done is

41
 𝑉2
𝑊 = 𝑅𝑇 (2.3026) log10
𝑉1
Here T = 270C = 27 + 273 =300K
V1 =V, V2 = 2V , so V2/V1 = 2
R= 8.3
𝑉
𝑊 = 𝑅𝑇(2.3026) log10 2 = 2.303 x 8.3 x 300 log 2 = 1725.8 Joule.
𝑉1

42