INTRODUCTION TO THERMODYNAMICs 15

110 INTERNAL ENERGY

energy possessed by a body or a system by virtue of its
molecules is called internal energy or intrinsic
molecules arrangement and molecular
otion of
thermodynamic state of the system.energy microscopic energy. This or
ergy is associated with
For perfect
only on the temperature of the system as it is assumed that gases, internal energy
ends
depe the molecular forces of
and repulsion are absent. For non-permanent
a t t r a c t i o n

gas, vapour or liquid, the internal energY

strongly
tepends on temperature and weakly on pressure.
For all gases U= u(T,P)
For ideal gases u= U(T)
The main characteristics of internal energy are:
Internal energy is associated with the thermodynamic state of the system. Therefore, it
is a point function and a thermodynamic
property.
Internal energy depends upon the mass of the system, hence it is extensive property.
(i) As per Joule's law
dV = mCy dT

u-u =m| CyaT=mC,(T2 -T) .(1.30)

(du
For ideal gas
CyT
(iv) When a system undergoes a thermodynamic process or change of state both heat and
and is
work transfer take place. The net energy transfer is stored within the system
called stored energy
80-8W=8E or 2-W-2E2E2 -E1
The total energy of the system
E= P.E. + K.E. + U 1.31)
no change of P.E. and
also
non-flow process, when there is
For a closed system or
or out of the system,
there is no kinetic energy present.
there is no flow of mass into
.(1.32)
-2-W2 =U2 -u the net heat transfer is
a thermodynamic cycle,
(v) When a closed system undergoes
equal to net work transfer
29-2W or 60-f8w
of work transfer
of heat transfer is equal to cyclic integral
The cyclic integral ..(1.33)
du=0
(vi) For an isolated system
=0
-2 0 , W2 .(1.34)
 PHYSICS -

I
16 ENGINEERING

THERMODYNAMICS
1.11 FIRST LAW OF

is conserved.
Heat is a form of energy and energy
in the modern world, Wo
similar to any thinking person y
Theidea behind the first law is
which heating, and we know that.the
we use for
oil etc.,
we pay for. Heat is said t
for energy, in the form of electricity,
gas,
to the amount
of energy that
amount of heat that we get,
is proportional is the w o r k d o n e by a mechanic
work on the system.
The simplest example
be generated by doing systems this appears
In simple thermodynamic
force the work is force times the displacement. unit area) and displacement beino
with the force being identified as the pressure (force
per
of a surface area times that area). Another
identified as the change in volume (displacement
involves electricity: the force is then
identified as the emt (electromotive force
example of work
and the displacement as the charge transferred (electric current x time). Other torce-displacement
pairs that will appear in this course include surface tension and surtace areas, and the chemical

potential and chemical concentration.

The first law of thermodynamics is the statement of the principle of conservation of energy. In
very general terms, it asserts that the net flow of energy across the boundary of a system is equal to the
change in energy of the system. For the purpose of thermodynamics it is sufficient to consider only
two types of energy flow across a boundary. One of these consists of workdone on or by the system
and other is flow of heat either
by conduction or by radiation.
Considerquantity dQ of heat supplied to a system. This heat energy is, in general, spent in
threeways:
() Partially, it is spent in raising the
temperature of the body, which is equivalent of
increasing its internal kinetic energy.
(i) A part of it is spent in doing internal work
against molecular attractions which is
equivalent of increasing the internal potential
energy of the
(ii) The remaining heat energy is system.
i.e., in
spent in expanding the system against external pressure
doing external work.
If dU,
and du, are
respectively the
energy and dW is the external
change in internal kinetic
workdone, then since, "emergy can energy and internal potential
only converted from one form to another", we have neither be created nor
destroyed but
dQ= du +du, +dW
But dU, + dU, dU .(1.35)
= =
increase in total intermal
energy of the system.
Hence dQ= dU+dW
Here all quantities are measured
in same units .(1.36)
(Joule, calories or
Equation (1.36) represents the
stated as, differential form of first law of kilocalories).
thermodynamics. This may be
"n all
transformations the heat energy supplied must be balanced
workdone plus the increase in internal by the external
energy.
 INTRODUCTION TO THERMODYNAMICS 17
The first law of
thermodynamics thus establishes an exact relationship between heat and
Work.
he
Th statement
of this law involves the
assumption that the internal energy is a function of
stem (here the term state
of the syste implies state of
has a definite energy in a definite state. It is thermodynamic equilibrium). In fact the
state

the

SYSt obvious that the change in energy

u) depends only the end (initial and
on
final) states and not at all on the process by
u he system is taken from one state to the other. The entire structure of the
which science of
is consister with this
t h e r m o d y n a

assumption.
Erom Eq. (1.36), we can make following conclusions

As Uis a state function, in a

cyclic process dlu=0
dQ-fdu+faw =faw .(1.37)
Therefore, the total work obtained is same as the net heat supplied and no excess
work is produced.
(i) In a isothermal process, there will be no change in internal energy as at constant
temperature, internal energy is constant i.e., dl =0.
So dQ=dW.
This means that all the heat supplied to the system is spent to external work.
(in) In an adiabatic process, there will be no exchange of heat between the body and the
surroundings i.e., dQ=0, so dW= -du
It means that in an isolated system, work is done by the system at the expense ot its
own material energy.

1.11.1 Corollaries of the First Law of Thermodynamics

universe is constant
(a) Internal energy of the
From the first law of thermodynamics, we have dU =dQ-dW.The system absorb dQ heat to

internal energy increases by dlu. We

perform dW amount of work and at the same time
an amount dQ and a work dW is
now consider that the surroundings, where heat has lost is by
done on it.
is then written as
The change of energy of the surroundings
AU' = dW-AQ

AU' = -Au
(1.38)
Or U+U' =Constant
and the surroundings takern together
neretore, net change in internal energy of the system
would be zero.

Impossibility of the constant motion of the first kind then called it is constant
without supply of any heat(dQ=0),
Can be done continuously then the
returns to its initial state,
mo i St Kind. When after a series of changes the system
hane in internal energy will be zero, 1.e.
change
 ENGINEERING PHYSICS - I
18

dll-0

Hence dO-fdw ..(1.39

substance receives heat while at otho..
In a complete cycle, at one stage the working
dQthen is positive and if heat is rejected, dQ is negati. es it
rejects heat. If heat is absorbed, bo the
workdone o n the system is taken as
workdone by the system is taken as positive and the
So from Eq. (1.39), it can be concluded that if after
a number of changes the working s ve
returns to its initial state, then total absorbed heat and total work are same. For that reason bstance
in cyclic process dQ=0, then dW =0. Hence perpetual motion of first kind is impossible when

1.11.2 Applications of First Law of Thermodynamics

The applications of the first law of thermodynamics to some special processes are as followe
s:

(a) Isothermal Process (Isothermal Change)

When a change in pressure and volume of a substance takes place but the
temperature remains constant, the change (process) is said to be isothermal

When gas is compressed suddenly some heat is produced but if the compression is slow and
the heat produced is removed at once, so that the temperature remains constant, the change is
isothermal.
Similarly when a gas is allowed to expand suddenly work is done by the gas and some heat is
absorbed. If heat is continuously supplied from outside so that the temperature remains constant
the change is isothermal.
Thus, in an isothermal change the temperature is kept constant by adding heat or taking it
away from the substance. As there is no change in temperature, there will be no change in internal
energy.
du =0
According to the first law of thermodynamics

dQ=du+dW
dQ= dW ..(1.40)
In anisothermal process (or process or transformation).
Heat added (or subtracted) External workdone
=
by (or on) the gas.
For a perfect gas an isothermal is
change represented by Boyle's law, given by equation
PV =constant. (1.41)
(b) Adiabatic Change (Process)
When a change in pressure and volume of a substance taken place but no heat is
allowed to enter or leave it, the change (process) is said to be adiabatic.
In an adiabatic change the temperature does not remain constant and no heat from outside is
supplied to the system or taken away from it.
 INTRODUCTION TO THERMODYNAMICS 19
It Jes not mean that the heat of the system remains constant. When a gas is allowed to
it does external work and the energy for this purpose is drawn from the heat energy of the
exhe heat energy of the gas, theretore, decreases. When the gas is compressed, work is done on
gas
it and the energy gained.appears as heat energy. The heat energy of the gas, therefore, increases
ag an adiabatic process no heat enters or leaves the gas i.e., dQ =0.

According to the first law of thermodynamics

dQ=du+dW
0 dU + dW

du = dW
or
In an adiabatic process,
Increase (or decrease) in internal energy = External workdone on (or by) the gas.

Adiabatic Equation of State

Consider one gm molecule a perfect gas contained in a perfectly non-conducting cylinder
fitted with a non-conducting piston as shown in Fig. 1.13. Let the pressure, volume and
that the
gas is compressed adiabatically,
so
temperature be P, V and T respectively. Suppose a

piston moves inward through a distance dx.

LLIIIILILIIIIIIIA
Gas
F PA

IIITIZIIITI*IÍITTZIIDZA
dx

adiabatic equation of state.

Fig. 1.13 Nlustration for

total force applied is Px A and

If A is the area of cross-section of the piston, then
Force x Distance
by the piston
=
Workdone
= Px Axdx
1.42)
or
dW PdV
causes a rise of
due to compression
The heat generated heat at constant
as
aV gives the change in volume. molecular specific
Cy is gram
C,dT, where
Perature dT and is given by
volume.
AcCording to first law of thermodynamics .(1.43)
dlU+ dW = dll+ Pdv
dQ=
For adiabatic change dQ =0
dU+ PdV =0
 20 ENGINEERING PHYSICS - I

du
Now
Cydt
dU=CydT .(1.44)
Now putting dQ=0 and du = Cy dT in Eq. (1.43), we have

Cy dT+ PdV =
0

The equation of state for one mole of perfect gas is

PV RT (1.45)
Differentiating Eq. (1.45), we have
PdV+VáP = RáT

PdV+VapP (1.46)
R
Substituting the value of dT from Eq. (1.46) is Eq. (1.44), we get

C Pdv+Vap
R aPdV =0
or Cy PdV+Cy VdP+ RPdV = 0
.(1.47)
But Cp-Cy = R or Cy +R=Cp

where Cp gram molecular specific heat at constant pressure

Here (Cy + R)PdV +Cy VdP=0

or
Cp PdV+C, VdP=0
.(148)

Dividing Eq. (1.48) by Cy PV and

where y =
ratio of specific heats at constant pressure and constant volume.
Now we have dP
dV
p ..(1.49)
Integrating Eq. (149), we have
y log, V + log, P= constant
or log, PVY = constant

or PV = Constant = K

or PV = K
(1.50)
Equation (1.50) is the equation of state for an adiabatic change (process) in terms of
thermodynamic variables Pand V.
 INTRODUCTION TO THERMODYNAMICS 21
n ather words if P,V, are the initial and P,, V, the final pressure and volume of the gas in
adiabatic change, then

PV-P,V (1.51)
c ) isobaric p r o c e s s

A thermodynamic process, which takes place at constant pressure is called isobaric process
Acording to the first law of thermodynamics

dQ= dU+dW

In an isobaric process, pressure remains constant, so the

am.ount of heat supplied partly used in doing external work
15

due to increase in temperature. If pressure remains constant at

Pand increase in volume dv, the extermal workdone dW = PdV.

The shape of curve on P-V diagram for one isobaric

prcess is a straight line parallel to the volume (V) axis for a
aonstant value of pressure (P) as shown in Fig. 1.14.
Fig. 1.14 Isobaric process.
Isochoric process
A thermodynamic process in which volume of the system remains constant is known as an
isochoric process.
According to first law of thermodynamics

dQ=dU+áW
Since the volume remains constant, dV =0, the workdone
aW= PdV=0
dQ= du .(1.52)
Thus, whole of the heat supplied to the system is used to
ncrease its internal energy only. Hence the condition that
Whole of the heat supplied to the system should be used to
ncrease its internal energy only is that the process should be Fig. 1.15 Isochoric process.
1Sochoric i.e., takes place at constant volume.
The shape of the curve on a P-V diagram for an isochoric process is straight line parallel to the
Pressure (P) axis for a constant value of V as shown in Fig. 1.15.

Exam 1.4 One gram of water (1 cn? ) becomes 1671 cn' of steam when boiled at a constant pressure of
emple
I atm
(1.0 Pa). The heat vapourization at this pressure is L, =2.256x l0° |/kg, compute (a) the
10" of
AOTe by the water when it vapourizes and (b) its increase in internal energy.

Sofution. Given V, =1 cm =10 m3, V, = 1671 cm' = 1.671 x 10m",

P=1.013 x 10 Pa, and IL, =2.256 x 10° J/kg.m = 10kg =1g

 ENGINEERING PHYSICS I
22
dW= PdV = P(V2 - V,)
169 J.
(a) The w o r k d o n e
(1671x 10
-1x 10 ) =

= (1.013x 10*)x

Increase in internal energy

(b)
the water to vapourizee
Heat added to
=10x (2.256x 10°)
= 2256 J
dQ= ml,
Now from first law
of thermodynamics
dW
dQ= dU +
du = d-dW
or
= 2256 - 169 = 2087 J.

1.12 LIMITATIONS OF FIRST LAW OF THERMODYNAMICSS

law of conservation
of energy and
We have seen that first law of thermodynamics
is simply a
has following limitations:
i.e., the first law of thermodynamics
(1) The law considers all forms of energy equivalent far as the account of
is necessary condition so
is law of energy equivalence. This law
concerned with the possibility
of transformation of one kind of
energy balance is
energy to another.
direction of energy transformation.
(i) The first law does not consider the
consider the grade of the energy or energy
(iii) The first law of thermodynamics does not
reservoirs. It assumes all energy reservoirs are identical.

1.13 REVERSIBLE AND IRREVERSIBLE PROCESSES

1.13.1 Reversible Processes
Consider a gas is enclosed in a cylinder fitted with a frictionless piston, perfectly insulated
from its surroundings so that no heat can leave or enter into it. Some removable weights are placed
on top ofthe piston and P,V,T are pressure, volume and temperature respectively of the gas in a
cylinder at the initial state.
The weights are now removed by very small amount at a time so that the piston moves outward
very slowly. The gas is now expanded adiabatically and pressure and volume of the gas adjust
themselves so that the system is always in thermodynamic
equilibrium.In other words, the adiabatic
expansion of the gas is quasi-static. The process of removing of weights in small steps is continued
so that
P, V2,12 are pressure, volume and temperature respectively of the gas at the final state.
The weights are now replaced again in very small amount at a time
so that the piston moves
inwards very slowly. In other words the adiabatic
compression of the gas is also quasi-static. The
process of replacing the weights in small steps in continued till the gas reaches the initial state with
PV,T, as pressure, volume and
temperature respectively. During this process of
compression the gas would pass through exactly the same intermediate steps through adiabatic
which it
passed during the adiabatic expansion ie., all the intermediate states are retraced in the
opposite
direction. Such a process is known as a reversible process.
 INTRODUCTION TO THERMODYNAMICS 23
He areversible process is that which can be retraced in
through exactly the same condition as it does opposite
substance passes thr
in the
direction, so that the
working

process. direct
te
n ather words it means that in a step where heat is absorbed
out in
reverse process and vice versa. Similarly, in a step whereinwork
the direct process, it is
is done by the
given
ct process
an equal amount of work is done working
s u b s t a n c e

on the working substance in the

reverse process.

Conditions of Reversible Process

113.2
Thereare following conditions for reversible
process
The substance undergoing reversible change must not lose heat
a

convection radiation or in
or by conduction,
overcoming friction. No heat must at all be converted
into magnetic or electrical energy. Hence for
reversibility
dissipative effects such as friction, electrical resistance, magneticcomplete absence of
hysteresis etc., is a
must.

( The change in the pressure and volume of the working substance must take place at
an infinitely show rate, so that when the
substance is receiving heat its temperature
differs from the hotter body by only an infinitesimal amount and when it is losing
heat the temperature again differs by an infinitesimal amount from the colder
body.
Thus all reversible processes must take place infinitely slowly.

These conditions are never strictly realized in practice because no mechanical process is
frictionless and no insulator or conductor is perfect. Thus rigorous reversibility is an ideal conception
wohile irreversibility is the rule. However, the conditions necessary for reversibility can be fulfilled
approximately and such processes may be regarded as reversible within the limits of experimental
errors
1.13.3 Examples of Reversible Processes
There are following examples of reversible processes:
() If all isothermal and adiabatic changes are performed slowly, then they arereversible.
Hence, it is assumed that there is no friction to be overcome as workdone
in
is slow,
overcoming friction is wasted in such cases. Since the process very
no energy
is wasted in producing oscillations and eddy current and no heat is lost by
conditions if heat is supplied to a
conduction, convection and radiation. Under these
and does some external work. If
given mass of a gas at constant pressure, expands
it
the same amount of work is done on the gas
in compressing it, the same quantity of

heat will be given out.

there will be no heat produced due to
(7) If the resistance of thermocouple is neglected reversible. At a
Peltier heating or cooling is
Joule's heating effect. In such a case
flows in one
due to Peltier effect when current
Junction where a cooling effect results
the current is reversed.
is produced when
lrection, an equal heating effect be
by it. The water so formed
can
absorbed
lce melts when a certain amount of heat is
4 amount of heat is removed from it.
converted into ice if the same

reversible process.
D) Electrolysis process is an example of
 24 ENGINEERING PHYSICSI

1.13.4 Irreversible Process

are
r e m o v e d quickly, the gas will undergo
o n the piston
the weights it will not
If in any experiment, not be equilibrium state i.e.,
intermediate states will
s o that the for these states. Similarly, when
sudden expansion volume and temperature
values of pressure,
possible define the
to the gas will undergo
sudden compression and the value of
pressure,

the weights a r e replaced quickly, intermediate state will again

be not defined. Thus during the
for the through
volume and temperature to reproduce the intermediate states
sudden compression
it will not be possible
process of Such a process is known a s irreversible process.
sudden expansion.
which the svstem passed during so that the
is that uvhich
cannot be retraced in the opposite direction
irreersihle proces
Heee a n
same intermediale states through
which it passes during the
does not pass through the
wrkTmgsubstancr
diret prcess
Processes
1.13.5 Examples of Irreversible
similar
()Joule-Kelvin effect is irreversible
because on reversing the flow of gas, a

conduction and
cooling or heating effect is not observed. Similarly diffusion,
radiation are also irreversible.
of
irreversible. It is because in reversing the direction
() Workdone against friction is
motion again work has to be done against friction.
It is
(zi) Heat produced by the passage of a current through a resistance is irreversible.
because even when current is reversed the same effect is observed.
(17) Rusting of iron is an example of irreversible process.

114 HEAT-ENGINE AND THERMAL EFFICIENCY

We know that mechanical work can be converted into heat and

heat into mechanical work.

The conversion of heat into work has found various applications

in modern civilization. We have
heat engines, where the same
considered here the physical principle governing the operation of
property is applied.

A device, which converts heat into work is called a

heat engine. Out of various types the most
internal combustion engines, jet engines etc. The schematic
important are reciprocating steam engines,
a heat engine is shown in Fig. 1.16. The
essential sections of a heat engine
energy flow diagram for
are the following
(i) Source/Heat Reservoir. A hot body, at a fixed high
temperature T from which the heat engine
can
Source(T)
draw heat, is known as source.

(ii) Sink/cold Reservoir. A cold body, at afixed

temperature 7,, to which any amount of heat can be
rejected, is called sink.
(iii) Working Substance. The material, which on being
supplied with heat, performs mechanical work, is
called the working substance. In internal-combustion 7Sink
engines, such as those used in automobiles, the
Fig. 1.16 Schematic energy-flow
working substance is mixture of air and fuel; in
diagram for a heat engine.
steam turbine it is water.
 INTRODUCTION TO THERMODYNAMICS 25
two types of heat engines:
Thereare
The external combustion engine where combustion of fuel
Steam engine is an example of it. take place outside the sink.

The internal combustion engine where combustion of fuel takes

Petrol engine, diesel engine etc., are the examples. place inside the sink.
tengine, the working substance takes in heat from the
gives out the rest to the sink and returns to its initial source converts a part of the
external

state. This series of

ucle. This is shown in Fig. 1.16. The work can be operation
const
cycle again.
continuously obtained by performin8
same
the
The energy transfor ormation of heat engine is shown in
ad by the circle. The amount of heat
Fig. 1.16. The engine itselt
elf is
Q supplied to the engine by hot reservoir (source)is
repional
proportion
to the width ot the incoming
"pipeline" at the top of the diagram. The width of
outgoing pipeline .at the bottom is
proportional to the magnitude |Q, | of the heat rejected in the
The branch line to the right represents the portion of the heat supplied that the
engine
exhaust.

mechanical work, W,
onverts to
When an engine repeats the same cycle again and again, Q and Q, represent the quantities of
st absorbed and rejected by the engine during one
cycle; Q, is positive and Q, is negative.
The net heat Q absorbed per cycle is

Q-0,+2 -1Q,-1 .1.53)

The useful output of engine is the net workdone W by the working substance.

From the first law, W=Q=Q + =1l-1 .(1.54)

ldeally, we would like to convert all the heat Q into work; in that case we would have Q, =w
and Q, -0. Experience shows thatthis is impossible ; there is always some heat wasted, and Qis
never zero. We define the thermal efficiency of an engine, denoted by n, as the quotient
W
.(1.55)
,
The thermal efficiency (n) represents the fraction of Q, that is converted to work or in other
words, we can say that efficiency of an engine is ratio of net workdone by the working substance
and heat absorbed by the engine. To put it another way, n is what you get divided by what you pay
for. This is always less than unity. In terms of the heat flow diagram of Fig. 1.16, the most efficient
engine is one for which the branch pipeline representing the heat thrown always is as narrow as
possible.
When we substitute the two expressions for
NOTE
given by Eq. (1.54) into Eq. (1.56), we get the
n is a quotient of two energy quantities, thus
tollowing equivalent expression for n is a pure number, without units of course,
we must always express W,Q, and Q, in the
W same unit.
.1.56)
.
 FNGINEFRING PHYSICS I
32
Soution. Given m-10 kg, 1.-34 10°Jkg ",T, 37°C310 K,T, =0° C=273 K
ideal Carnot's cycle
Since we know that, for an

T2
y1

Here ,-ml -10 3.4x 10-3.4 10"

310
-3.4x10"; 3.86 10°J
Then
213
Therefore, workdone by the refrigerator
W - - , - (3.6-3.4) 10" =0.46 10" =4.6 10J
Now coefficient of performance

3.4 3.4x10 347.4.

W 4.6x 10 4.6

1.17 SECOND LAW OF THERMODYNAMICs

The first law of thermodynamics establishes an exact relation
between heat and work
follows directly from this law, that it is
impossible to get work from
any machine without givingi
an
equivalent amount of energy in any form. In other words, this law is merely the
of the law of conservation of generalizatio
energy including heat energy and states that the energy the
remains constant. of univere
The first law of
thermodynamics tells us that heat and mechanical work both a
interconvertible. This does not tell us the limitation and
condition for this conversion ie., how
much heat is converted into work and
whether the transformation itself can take
direction of energy
transformation). The law place or not (the
into work, is called the second law
the specifying
condition of transformation of heat
of thermodynamics.
1.17.1 Kelvin's Statement of Second Law of
It is
impossible to get a continuous supply of wvork by
Thermodynamics
the coldest of its cooling a body to a temperature lower than nu
surroundings.
Or
A
transformation, whose only final result is to
temperature throughout is impossible. transform
at the same into work the extracted from a s0ure

1.17.2 Clausius Statement of

Second Law of
1s
npo551ble Jor a self acting machine, unaided
Thermodynamics hody
to another at a higher by anu external agency to transfer heat ro
temperature.
Or
If is inpOSsIDle Jor any
cyclic machine to produce no other effect than
one body to another al a
higher to convey neut
temperature.
 INTRODUCTION TO THERMODYNAMICS 33
Rath statements of second law are equivalent. Violation of one automatically leads to
.ian of the other. They impart a direction for making the energy transformation. Let us take
up,
a r the sake of illustration, the following examples of isolated system.
Freeexpansion. The free expansion of an ideal gas from a region of high pressure to
a region ot low pressure takes place spontaneously until the pressure becomes
unitorm
Heat conduction. The passage of heat from
a
region of high temperature to a region
of low temperature takes place spontaneously until the temperature becomes
uniform.

(in) Diffusion. The diffusion of a solute from a region of high concentration toa region of
low concentration takes place spontaneously until concentration becomes uniform.
Thus we can conclude that every system, if left to itself (isolated), changes spontaneously at
slow or rapid rate in such a way as to approach a definite final state of equilibrium. In such
processes, according to first law of thermodynamics, the total energy of the system involved
rem.ains constant betore and atter the change. The important point to note in these processes is the
direction i.e., from high pressure to low pressure, from high temperature to low temperature.
There is thus a direction which allows a system to come to equilibrium. However, if we imagine
that after acquiring equilibrium, the process is reversed then obviously the system, at its own,
will not move away from the state of equilibrium unless aided by some external agency. For

example, two bodies at the same temperature, being in a state of thermal equilibrium will itself not
create temperature difference between them provided one of them is not heated by some extermal
sources.
This principle which determines the direction for the process' to take place is second lawe of
been attained
thermodynamics. For first law it does not matter how the equilibrium state has
remains the same. Therefore,
because of before and after equilibrium state, energy of the system
another thermo
second law of thermodynamics cannot be derived from first law. It requires
is known
dynamical parameter for the description and mathematical formulation. This parameter
as entropy.

1.17.3 Entropy and Second Law of Thermodynamics

ditferent value for
variable which has a
As said above, we require such a thermodynamical
the initial and final states of an isolated system when the process
has taken place even though the
We know that entropy is a variable. It is
a
internal energy for the two states remains the same.
manner in which
not affected in any way by the
a
aeuite function of the thermal state of a body and is
particular state is reached.
state A to another
state Bis given by
entropy passing from
ne in one
change
.(1.61)

from state A to
rejected at a tenmperature T is going
the quantity of heat absorbed or
ostate B,1S
we also note that :
 ENGINEERING PHYSICS I Substance
Working
of
38 lndependent efficiency of
a

Scale is
on
the
basis of the
source
a nd
d esinksibjg
but
T h e r m o d y n a m i c

been
derived of the
scale has rature is als
1.19.3 temperature
temperah.
on
the scale of
The
thermodynamic

depends only thermodynamic

which
Hence the
Carnot's
heat engine, substance.
substance.

of the working
independent
properties
of the working
of the
independent

vary but in
adiak.
1.20 ENTROPY of the system
does not baig
temperature the surroundings and
isothermal process, and
We know that
in between the body
done on the e ass and
no exchange
of heat takes place the work is
adiabatically,
process,
If gas is compressed if the gas expand
temperature changes. increases. On
the other hand,
of the gas adiabatic process
temperature, and internal energy decreases. Thus in
internal energy of gas the
adiabatically, temperature
and
remains constant,
rather they increase or decreas
nor the temperature
neither the internal energy
simultaneously.
second law of thermodynamics, which led to believe
Clausius concept was applied for the
remains constant, a heat in an adiabatic proces. This
that as in isothermal process temperature
adiabatic process is known as entropy of the
property of the gas which remains constant during
substance. Hence entropy is a physical quantity which remains constant in an adiabatic process.

The concept ofentropy can be best understood from P-V indicator diagram (Fig. 1.24) at the
temperatures T1,T2 and T3
Let E, and E, are two adiabatics, which intersect the isothermal at the points(A,, A,)(B, B)
and (C, C2). This is shown in Fig. 1.24.

We consider the Carnot

cycle A, A, B, B,.If the working substance passes from state A, to state
A along isothermal A^ 4z, it absorbs Q, amount of heat at temperature and when it
B to B, it rejects heat Q at temperature T, T, passes from
According to Carnot's theorem, we then have
-2 T-T
T
T T .1.83)
If weconsider Carnot's
A A2 - T
isothermals and the adiabatics, wecycle bounded by other B B,
We may write this may get similar results. T2
C2
-T
T .(1.84) Volume ()

= Constant Fig. 1.24 P-V indicator diagram

T2 T ..(1.85)
 INTRODUCTION TO THERMODYNAMICS 39

Thus, when going from one adiabatic to another if Qunits of heat are absorbed or rejected,
then
constant (5) ..(1.86)
The constant S is the change of entropy between two states of the working substance as
represented by the two adiabatics.
If the two adiabatics are very close so that heat absorbed or given out by the working
substance is small and equal to dQ, then small change in entropy is given by

dS aQ
(1.87)
T
Thus the change in entropy is passing from an adiabatic A to another adiabatic B

..(1.88)

Under adiabatic process dO 0,as during adiabatic process no heat is absorbed or given out

by the working substance. Thus in an adiabatic process change in entropy becomes zero, ie,
entropy remains constant in an adiabatic process. For this reason, the adiabatic curves are called
isentropic curves.
When there is any gain or loss of heat by a body, the entropy of the body alters. If such gain or
dS where T the
lossof heat takes place reversibly, change of entropy of a body is given by
= is
T
absolute temperature of the body. The entropy of a body alters from one adiabatic to another and
in such transition, the change is independent of the path followed by the substance.

1.20.1 Physical Significance of Entropy

The role of entropy is highly significant in thermodynamics. Like pressure, volume,

temperature etc. the entropy of a body isphysical quantity. Its value depends only on the
a real
o n its initial and final states
perfect state of the body. Change in entropy of a body depends
to the final state. This
whatever be the way followed by the body in going from the initial state
means entropy is afunction of state. It is a single valued
function which means that it allows only one
value for a particular state and thus it is a perfect differential.

1.20.2 Second Law of Thermodynamics in Terms of Entropy

In terms of entropy the second law of thermodynamics may be stated in following way
of
in such a way that the sum of entropy
Every physical or chemical process in nature occurs
of a reversible process, the sum of
all bodies taking part in process increases. In the limiting case

entropies remains constant.

1.20.3 Entropy Change of Heat and Work Reservoirs

and the finite transters of heat into or
A heat reservoir issystem of infinite source of energy
a

out of the reservoir does not affect its temperature.

 ENGINEERING PHYSICS I
t e m p e r a t u r e
T,
decreases in
in entropy of he
entr

at
40 heat
reservoir

from a
drawn

If dQ is the
heat

by d (1.89
reservoir
is given
(45)heat reservoir T

dQ
..(1
T
(AS)heat reservor
reservoir.

from the heat it follows

Total heat
abstracted
zero i.e., dQ =0,
where - transfers are
since the heat
reservoirs,

In case of work
..(1.91)
(ds)work reservoir T

(T-S) Diogram two properties of,

1.20.4
Temperature-Entropy because any
various processes
to represent and these properties
We have used
P-V diagrams
define the state of the system
single phase
could the workdone durine
existing in a abscissa represent
pure
substance
The area under the curve PdV on information.
measurable. additional
are easily thus provides on
of a closed system, T is taken in absolute
T-Sdiagram where
reversible process
any on
could also be represented
Similarly, the processes
units.
has the following advantages:
diagram
This
vertical line on T-S diagram, since
A reversible adiabatic process
will be represented by a
) a reversible
the remains constant. Process (a-b) represents
entropy during process
shown in Fig. 1.25.
adiabatic expansion process as
a horizontal line on T-S diagram,
since
(i) A reversible isothermal process is represented by
an isothermal
constant. The process (c-d) represents
temperature during the process
1.25.
heating process as shown in Fig.
(ii) A compression process on T-S diagram
following same law of processis Isothermal d
Reversible
-

represented by curve
(1>2) in Fig. 1.25.
adiabatic
dQ
dS
T
.(1.92)

It follows that dQ= TdS

or 2 |T4S ...(1.93) TdS

Therefore, the area under the process

ds -
Curve on T-S diagram represents the heat
transfer during a reversible process as
shown in Fig. 1.25. Fig. 1.25 T-S diagram.
 INTRODUCTION TO THERMODYNAMICS 41
Heat transfer
.(1.94)
2 TdS =Area(1 -2- f-)
(iv) According to first law of thermodynamics for a cyclic process
...(1.95)
dQ-dW
It follows that the area enclosed by the loop representing a reversible cycle either on
P-V diagram represents either the net heat transfer
or net work during
T-S diagram or

a cycle.
dotted lines P-V and T-S
on
() Irreversible processes are usually represented by
diagrams. However, area under the curve on T-S diagram
representing the heat
transfer will be greater than that of heat transfer during a reversible process.

For example, consider reversible irreversible

adiabatic processes represented on T-S
diagram by process (1>2) and
curves

(12') respectively. The entropy of an

irreversible process shown in Fig. 1.26 is
greater; we say its irreversibility.

(vi) In quite number of it is convenient to

cases (As)jrreversible
represent the processes and cycle on T-S
diagram. To illustrate this fact we shall take
the case of Carnot's cycle. Fig. 1.26 Reversible and
ireversible processes.

1.21 THIRD LAW OF THERMODYNAMICS (NERNST'S LAW)

The entropy of a system approaches a constant value as the temperature
approaches absolute zero.

The third law is relatively easy to understand from a statistical point of view in which entropy
is associated with disorder. As absolute zero is approached, all thermal motions cease, and any
an ordered state in which the particle do not move. Hence, the entropy of
a
system must approach
system is defined only for an arbitrary constant, and only changes in entropy have physical
significance. The changes in entropy become negligibly small as absolute zero is approached.
The third law of thermodynamics states that "The entropy of all homogeneous crystalline
substances in a state of equilibrium is zero at absolute zero of temperature".

Mathematically, Lt S=0 (1.96)

T0
It implies that the entropy ceases, it is the function of state at absolute zero. However, many
substances like alloys, all amorphous solids, chemical compounds like Co, Ni etc., the entropy does
not tend to zero as T->0 but takes a finite value of entropy at absolute zero.
The third law provides an absolute base from which the entropy of each substance can be
measured. Third law of thermodynamics is helpful in explaining the behaviour of solids at very
low temperatures and is analysing the chemical phase equilibrium.