Thermodynamics 135

Chapter

14
Thermodynamics
(b) Closed system : It exchange only energy (not
matter) with the surroundings.
(c) Isolated system : It exchange neither energy nor
matter with the surrounding.

Thermodynamics is a branch of science which deals

with exchange of heat energy between bodies and
conversion of the heat energy into mechanical energy
and vice-versa.

Some Definitions
(2) Thermodynamic variables and equation of
(1) Thermodynamic system state : A thermodynamic system can be described by
(i) It is a collection of an extremely large number of specifying its pressure, volume, temperature, internal
atoms or molecules energy and the number of moles. These parameters are
called thermodynamic variables. The relation between
(ii) It is confined with in certain boundaries.
the thermodynamic variables (P, V, T) of the system is
(iii) Anything outside the thermodynamic system to called equation of state.
which energy or matter is exchanged is called its For  moles of an ideal gas, equation of state is PV
surroundings. = RT and for 1 mole of an it ideal gas is PV = RT
Surrounding (3) Thermodynamic equilibrium : In steady state
thermodynamic variables are independent of time and
the system is said to be in the state of thermodynamic
equilibrium. For a system to be in thermodynamic
equilibrium, the following conditions must be fulfilled.
Gas System (i) Mechanical equilibrium : There is no unbalanced
force between the system and its surroundings.
(ii) Thermal equilibrium : There is a uniform
Fig. 14.1 temperature in all parts of the system and is same as
that of surrounding.
(iv) Thermodynamic system may be of three types No heat
Heat
(iii) in or
Chemical Heat in or: There
equilibrium is atransfer
uniform
(a) Open system : It exchange both energy and chemical out out
composition(B)through out the system
Open system and the
(A) Isolated (C) Closed
matter with the surrounding. surrounding.
system system
Fig. 14.2
 136 Thermodynamics
(4) Thermodynamic process : The process of constant pressure is different from that required to
change of state of a system involves change of change the temperature of same gas through same
thermodynamic variables such as pressure P, volume V amount at constant volume.
and temperature T of the system. The process is known
as thermodynamic process. Some important processes (ii) For gases when heat is absorbed and
are temperature changes  Q  CT
(i) Isothermal process : Temperature remain
At constant pressure (Q)P   C P T
constant
(ii) Adiabatic process : No transfer of heat At constant volume (Q)V  C V T
(iii) Isobaric process : Pressure remains constant (2) Internal energy (U) : Internal energy of a
(iv) Isochoric (isovolumic process) : Volume remains system is the energy possessed by the system due to
constant molecular motion and molecular configuration.
(v) Cyclic and non-cyclic process : Incyclic process The energy due to molecular motion is called
Initial and final states are same while in non-cyclic process internal kinetic energy UK and that due to molecular
these states are different. configuration is called internal potential energy UP i.e.
(vi) Reversible and irreversible process : Total internal energy U  U K  U P
(5) Indicator diagram : Whenever the state of a (i) For an ideal gas, as there is no molecular
gas (P, V, T) is changed, we say the gaseous system is
attraction U p  0
undergone a thermodynamic process. The graphical
representation of the change in state of a gas by a i.e. internal energy of an ideal gas is totally kinetic
thermodynamic process is called indicator diagram. 3
Indicator diagram is plotted generally in pressure and and is given by U  UK  RT and change in
volume of gas. 2
3
Zeroth Law of Thermodynamics internal energy U  R T
2
If systems A and B are each in thermal equilibrium
with a third system C, then A and B are in thermal (ii) In case of gases whatever be the process
equilibrium with each other. f
U   RT  C V T
2
Insulating Conductin
g R  R(Tf  Ti )
Syste Syste Syste Syste  T 
m m m m (  1)  1
A B A B
RTf  RTi (P f Vf  Pi Vi )
Syste Syste  
m m  1  1
C Conductin C Insulating
(iii) Change in internal energy does not depend on
g
(A) (B) the path of the process. So it is called a point function
Fig. 14.3 i.e. it depends only on the initial and final states of the
(1) The zeroth law leads to the concept of
system, i.e. U  U f  U i
temperature. All bodies in thermal equilibrium must
have a common property which has the same value for (3) Work (W) : Suppose a gas is confined in a
all of them. This property is called the temperature. cylinder that has a movable piston at one end. If P be
(2) The zeroth law came to light long after the first the pressure of the gas in the cylinder, then force
and seconds laws of thermodynamics had been exerted by the gas on the piston of the cylinder F = PA
discovered and numbered. It is so named because it (A = Area of cross-section of piston)
logically precedes the first and second laws of
Piston
thermodynamics.
Heat, Internal Energy and Work in Thermodynamics
dx
(1) Heat (Q) : It is the energy that is transferred
between a system and its environment because of the
F Gas
temperature difference between them.
(i) Heat is a path dependent quantity e.g. Heat
Fig. 14.4
required to change the temperature of a given gas at a
 Thermodynamics 137
When the piston is pushed outward an infinitesimal
distance dx, the work done by the gas
dW  F .dx  P (A dx)  P dV
(iii) Like heat, work done is also depends upon initial
For a finite change in volume from Vi to Vf
and final state of the system and path adopted for the
Total amount of work done process
Vf
W  Vi
P dV  P (Vf  Vi ) P
A
(i) If we draw indicator diagram, the area bounded 1
P
by PV-graph and volume axis represents the work done A 2 B
A1
P V
P (A) Less area
1 B
P
Work = Area = P(V2 – V1) V 2
A A
A2
B
V1 V2 V
V
Fig. 14.5 (B) More
P area
A 1 < A2  W1 < W2 Fig.
14.10
Work (iv) In cyclic process, work done is equal to the area
P of closed curve. It is positive if the cycle is clockwise
V2
  V1
PdV  P(V2  V1) and it is negative if the cycle is anticlockwise.
P
C
V1 dV V2 V P2
Fig. 14.6
Work = Area of triangle ABC

P A
P B
1 1
  (V2  V1) (P2  P1)
2 V1 V2 V
Fig.
Work = 0
14.11

P
V C
P2
Fig. 14.7
P Work = Area of rectangle ABCD
P2 = AB  AD
P1 A
B = (V2 – V1) (P2 – P1)
Work = Area of the shown
trapezium
P V1 V2 V
1

1 Fig.
V1 V2 V
 (P1  P2)(V2  V1)
2 P 14.12
Fig. 14.8 P2

(ii) From W  PV  P (Vf  Vi ) 

Work = (P2  P1)(V2  V1)
If system expands against some external force then P1 4
Vf  Vi
V1 V2 V
 W = positive Fig.
If system contracts because of external force then 14.13
Vf  Vi First Law of Thermodynamics (FLOT)
 W = negative (1) It is a statement of conservation of energy in
thermodynamical process.
P B P B Negativ
Positiv
e e (2) According to it heat given to a system (Q) is
work
work equal to the sum of increase in its internal energy (U)
A
A
V V
(A) Expansion (B)
Compression
Fig. 14.9
 138 Thermodynamics
and the work done (W) by the system against the
surroundings.
dP dP
Q = U + W Slope =
dV
 0 Slope =
dV
 0

(3) It makes no distinction between work and heat

as according to it the internal energy (and hence
temperature) of a system may be increased either by
adding heat to it or doing work on it or both. (i) In isobaric expansion (Heating)

(4) Q and W are the path functions but U is the Temperature  increases so U is positive
point function.
Volume  increases so W is positive
(5) In the above equation all three quantities Q, U
Heat  flows into the system so Q is positive
and W must be expressed either in Joule or in calorie.
(ii) In isobaric compression (Cooling)
(6) The first law introduces the concept of internal
energy. Temperature  decreases so U is negative

(7) Limitation : First law of thermodynamics does Volume  decreases so W is negative
not indicate the direction of heat transfer. It does not Heat  flows out from the system so Q is negative
tell anything about the conditions, under which heat can
be transformed into work and also it does not indicate (3) Specific heat : Specific heat of gas during
as to why the whole of heat energy cannot be converted
f 
into mechanical work continuously. isobaric process C P    1 R
2 
Table 14.1 : Useful sign convention in thermodynamics
P
Quantit K 0
Sign Condition (4) Bulk modulus of elasticity :  V
y
V
+ When heat is supplied to a system
Q [As P = 0]
– When heat is drawn from the system
+ When work done by the gas (5) Work done in isobaric process
(expansion) Vf Vf
W
– When work done on the gas W 

Vi
P dV  P
 Vi
dV  P[Vf  Vi ]
(compression)
[As P = constant]
+ With temperature rise, internal energy
increases  W  P(Vf  Vi )  R[T f  Ti ]  R T
U
– With temperature fall, internal energy
(6) FLOT in isobaric process : From
decreases
Q  U  W

Isobaric Process R
 U   C V T   T and
(  1)
When a thermodynamic system undergoes a
physical change in such a way that its pressure remains W  R T
constant, then the change is known as isobaric process.
R
(1) Equation of state : In this process V and T  (Q)P   T  R T
(  1)
changes but P remains constant. Hence Charle’s law is
obeyed in this process.   
    R T   CP T
Hence if pressure remains constant V  T     1

V1 V2 (7) Examples of isobaric process : All state

 changes occurs at constant temperature and pressure.
T1 T2
Boiling of water Water Vapours
(2) Indicator diagram : Graph 1 represent isobaric
(i) Water  vapours
expansion, graph 2 represent isobaric compression.
P P
(ii) Temperature  constant
Fig. 14.15
1 2

V V
(A) Expansion (B)
Fig. Compression
 Thermodynamics 139
(iii) Volume  increases (3) Specific heat : Specific heat of gas during
f
(iv) A part of heat supplied is used to change isochoric process C V  R
volume (expansion) against external pressure and 2
remaining part is used to increase it's potential energy (4) Bulk modulus of elasticity :
(kinetic energy remains constant) P P
K  
(v) From FLOT Q = U + W  mL = U + P(Vf –  V 0
Vi) V
Freezing of water (5) Work done in isochoric process

Water Ice W  PV  P[Vf  Vi ] = 0 [As V =

(i) Water  ice
constant]
(ii) Temperature  constant (6) FLOT in isochoric process : From
Q  U  W
(iii) Volume  increases Fig. 14.16
W = 0  (Q)V  U   CV T
(iv) Heat is given by water it self. It is used to do P V  Pi Vi
R
work against external atmospheric pressure and to   T  f f
 1  1
decreases the internal potential energy.
(v) From FLOT Q = U + W  – mL = U + P(Vf – Isothermal Process
Vi) When a thermodynamic system undergoes a
Isochoric or Isometric Process physical change in such a way that its temperature
remains constant, then the change is known as
When a thermodynamic process undergoes a
isothermal changes.
physical change in such a way that its volume remains
constant, then the change is known as isochoric (1) Essential condition for isothermal process
process. (i) The walls of the container must be perfectly
(1) Equation of state : In this process P and T conducting to allow free exchange of heat between the
changes but V = constant. Hence Gay-Lussac’s law is gas and its surrounding.
(ii) The process of compression or expansion should
P1 P2
obeyed in this process i.e. P  T    be so slow so as to provide time for the exchange of
T1 T2 heat.
constant Since these two conditions are not fully realised in
(2) Indicator diagram : Graph 1 and 2 represent practice, therefore, no process is perfectly isothermal.
isometric increase in pressure at volume V1 and (2) Equation of state : In this process, P and V
V2 change but T = constant i.e. change in temperature T
isometric decrease in pressure at volume
= 0.
dP Boyle’s law is obeyed i.e. PV= constant  P1V1 =
respectively and slope of indicator diagram 
dV P2V2
(i) Isometric heating P (3) Example of isothermal process : Melting of
(a) Pressure  increases ice (at 0°C) and boiling of water (at 100°C) are common
1
example of this process.
(b) Temperature  increases
(4) Indicator diagram : According to PV = constant,
(c) Q  positive graph between P and V is a part of rectangular
(d) U  positive V1 V hyperbola. The graphs at different temperature are
(A) parallel to each other are called isotherms.
(ii) Isometric cooling P
P
(a) Pressure  decreases
2 T1<T2< T3
(b) Temperature  decreases
Two isotherms never
(c) Q  negative intersect T3
T2
V2 V T1
(d) U  negative (B) V
Fig. Fig.
14.17 14.18
 140 Thermodynamics
(i) Slope of isothermal curve : By differentiating PV = In this process P, V and T changes but Q = 0.
constant. We get
P (1) Essential conditions for adiabatic process
P dV  V dP  0
(i) There should not be any exchange of heat
 PdV   VdP between the system and its surroundings. All walls of
the container and the piston must be perfectly
dP P insulating.
 Slope = tan   
dV V V
Fig. (ii) The system should be compressed or allowed to
(ii) Area between the isotherm and volume axis 14.19 expand suddenly so that there is no time for the
represents the work done in isothermal process. exchange of heat between the system and its
surroundings.
If volume increases W = + (Area under curve) and
Since, these two conditions are not fully realised in
if volume decreases W = – (Area under curve)
practice, so no process is perfectly adiabatic.
(5) Specific heat : Specific heat of gas during
(2) Some examples of adiabatic process
isothermal change is infinite. As
(i) Sudden compression or expansion of a gas in a
Q Q
C   [As T = 0] container with perfectly non-conducting walls.
mT m 0
(ii) Sudden bursting of the tube of bicycle tyre.
(6) Isothermal elasticity (E ) : For this process PV (iii) Propagation of sound waves in air and other
= constant. gases.
dP Stress (iv) Expansion of steam in the cylinder of steam
 P dV   V dP  P    E engine.
 dV / V Strain
(3) FLOT in adiabatic process : From
 E  P i.e. isothermal elasticity is equal to Q  U  W
pressure
For adiabatic process Q  0  U   W
At N.T.P., E = Atmospheric pressure =
If W = positive then U = negative so temperature
1.01 105 N / m2 decreases i.e. adiabatic expansion produce cooling.
(7) Work done in isothermal process If W = negative then U = positive so temperature
increases i.e. adiabatic compression produce heating.
Vf Vf  RT
W  Vi
P dV   Vi V
dV [As PV = (4) Equation of state : In adiabatic change ideal
gases do not obeys Boyle's law but obeys Poisson's law.
RT]
According to it
V  V  CP
W   RT loge  f   2.303 RT log10 f
 V

 PV = constant; where  
 Vi   i  CV
P   
  2.303 RT log10 Pi
(i) For temperature and volume
or W   RT loge  i 
 Pf   Pf 
    TV – 1
= constant  T1V1 1  T2V2 1 or
(8) FLOT in isothermal process : From
T  V1
Q  U  W
(ii) For temperature and pressure
 U  0 [As T = 0]  Q  W
T  1  1
i.e. heat supplied in an isothermal change is used to = const.  T1 P1  T2 P2 or
do work against external surrounding. P  1
 1 
or if the work is done on the system than equal or
  1
amount of heat energy will be liberated by the system. TP PT
Table 14.2 : Special cases of adiabatic process
Adiabatic Process
When a thermodynamic system undergoes a 1  1
Type of gas P  1 T  1
change in such a way that no exchange of heat takes V P T V
place between System and surroundings, the process is
known as adiabatic process.
 Thermodynamics 141
Monoatomic
1 1 (As PV = K, PfVf = RTf and PiVi = RTi)
 = 5/3 P P  T5 / 2 T (i) W  quantity of gas (either M or )
V5 / 3 V2/ 3
(ii) W  temperature difference (Ti – Tf)
Diatomic 1
1 7/2
 = 7/5 P PT T 1
V7 / 5 V2/5 (iii) W 
 1
  mono   di   tri  Wmono <
Polyatomic 1
1 PT
4
Wdia < Wtri
 = 4/3 P 4/3
T 1/ 3
V V (9) Comparison between isothermal and
adiabatic indicator diagrams : Always remember
(5) Indicator diagram
that adiabatic curves are more steeper than isothermal
(i) Curve obtained on PV graph are called adiabatic curves
curve. (i) Equal expansion : Graph 1 represent isothermal
 P process
process and 2 represent adiabatic
(ii) Slope of adiabatic curve : From PV  constant
Wisothermal > Wadiabatic
By differentiating, we get P
Pisothermal > Padiabatic 1
  1
dP V  PV dV  0 Tisothermal > Tadiabatic 2

(Slope)Isothermal < (Slope)Adiabatic V

Vi Vf
dP PV  1 P
  
     Fig.
dV V V V
14.21adiabatic
Fig. (ii) Compression : Graph 1 represent
14.20 P
process and 2 represent isothermal process
P
 Slope of adiabatic curve tan     WAdiabatic > WIsothermal
V PAdiabatic > PIsothermal 1
(iii) But we also know that slope of isothermal curve TAdiabatic > TIsothermal 2
P V
tan  (Slope)Isothermal < (Slope)Adiabatic Vf Vi
V
Fig.
(Slope)Adi (10) Free expansion : Free expansion 14.22
is adiabatic
Hence (Slope)Adi =   (Slope)Iso or 1
(Slope)Iso process in which no work is performed on or by the
system. Consider two vessels placed in a system which
(6) Specific heat : Specific heat of a gas during is enclosed with thermal insulation (asbestos-covered).
Q 0 One vessel contains a gas and the other is evacuated.
adiabatic change is zero As C   0 When suddenly the stopcock is opened, the gas rushes
mT mT into the evacuated vessel and expands freely.
[As Q = 0]
Stop cock
(7) Adiabatic elasticity (E ) : PV   constant
Gas
Differentiating both sides d PV   PV  1dV  0 Vacuum

dP Stress
P    E  E   P
 dV / V Strain
Insulated
i.e. adiabatic elasticity is  times that of pressure Fig.
W = 0 (Because walls14.23
are rigid)
E CP
Also isothermal elasticity E  P    Q = 0 (Because walls are insulated)
E CV
U = Uf – Ui = 0 (Because Q and W are zero. Thus
i.e. the ratio of two elasticity of gases is equal to the the final and initial energies are equal in free expansion.
ratio of two specific heats.
Cyclic and Non-cyclic Process
(8) Work done in adiabatic process
Vf A cyclic process consists of a series of changes
K

Vf
W
 Vi
P dV 
ViV
dV  which return the system back to its initial state.
In non-cyclic process the series of changes involved
[PiVi  Pf Vf ] R(Ti  Tf ) do not return the system back to its initial state.
W 
(  1) (  1)
 142 Thermodynamics

(1) In case of cyclic process as U f  Ui  can move the piston very slowly to make the process as
close to quasi-static as we wish. Thus, a quasi-static
U  U f  U i  0
process is an idealised process in which all changes take
i.e. change in internal energy for cyclic process is place infinitely slowly.
zero and also U  T  T = 0 i.e. temperature of Reversible and Irreversible Process
system remains constant.
(1) Reversible process : A reversible process is
(2) From FLOT Q  U  W  Q  W one which can be reversed in such a way that all
changes occurring in the direct process are exactly
i.e. heat supplied is equal to the work done by the
repeated in the opposite order and inverse sense and no
system. change is left in any of the bodies taking part in the
(3) For cyclic process P-V graph is a closed curve and process or in the surroundings. For example if heat is
area enclosed by the closed path represents the work absorbed in the direct process, the same amount of
done. heat should be given out in the reverse process, if work
is done on the working substance in the direct process
If the cycle is clockwise work done is positive and if
then the same amount of work should be done by the
the cycle is anticlockwise work done is negative.
working substance in the reverse process. The
P P conditions for reversibility are
A A D
B (i) There must be complete absence of dissipative
Positive Negative forces such as friction, viscosity, electric resistance etc.
work work
(ii) The direct and reverse processes must take
D C B C
place infinitely slowly.
V V (iii) The temperature of the system must not differ
(A) (B)
Fig. appreciably from its surroundings.
14.24 Some examples of reversible process are
(4) Work done in non cyclic process depends upon
the path chosen or the series of changes involved and (a) All isothermal and adiabatic changes are
can be calculated by the area covered between the reversible if they are performed very slowly.
curve and volume axis on PV diagram. (b) When a certain amount of heat is absorbed by
P ice, it melts. If the same amount of heat is removed
P C B A from it, the water formed in the direct process will be
converted into ice.
D
B C (c) An extremely slow extension or contraction of a
spring without setting up oscillations.
A
V (d) When a perfectly elastic ball falls from some
V
WABC= + Shaded area WABCD= – Shaded area height on a perfectly elastic horizontal plane, the ball
(A) (B) rises to the initial height.
Fig. (e) If the resistance of a thermocouple is negligible
14.25 there will be no heat produced due to Joule’s heating
Quasi Static Process effect. In such a case heating or cooling is reversible. At
When we perform a process on a given system, its a junction where a cooling effect is produced due to
state is, in general, changed. Suppose the initial state of Peltier effect when current flows in one direction and
equal heating effect is produced when the current is
the system is described by the values P1, V1, T1 and reversed.
the final state by P2, V2, T2 . If the process is (f) Very slow evaporation or condensation.
performed in such a way that at any instant during the
It should be remembered that the conditions
process, the system is very nearly in thermodynamic
mentioned for a reversible process can never be
equilibrium, the process is called quasi-static. This
realised in practice. Hence, a reversible process is only
means, we can specify the parameters P, V, T uniquely
at any instant during such a process. an ideal concept. In actual process, there is always loss
of heat due to friction, conduction, radiation etc.
Actual processes are not quasi-static. To change the
pressure of a gas, we can move a piston inside the (2) Irreversible process : Any process which is not
enclosure. The gas near the piston is acted upon by reversible exactly is an irreversible process. All natural
processes such as conduction, radiation, radioactive
piston. The pressure of the gas may not be uniform
decay etc. are irreversible. All practical processes such as
everywhere while the piston is moving. However, we
free expansion, Joule-Thomson expansion, electrical

heating of a wire are also irreversible. Some examples of
irreversible processes are given below
(i) When a steel ball is allowed to fall on an inelastic
lead sheet, its kinetic energy changes into heat energy
by friction. The heat energy raises the temperature of
lead sheet. No reverse transformation of heat energy
occurs.
(ii) The sudden and fast stretching of a spring may
produce vibrations in it. Now a part of the energy is
dissipated. This is the case of irreversible process.
(iii) Sudden expansion or contraction and rapid
evaporation or condensation are examples of
irreversible processes.
(iv) Produced by the passage of an electric current
through a resistance is irreversible.
Thermodynamics 143
3  Isothermal (T-constant)
4  Isobaric (In isobaric V  T )
Heat Engine
Heat engine is a device which converts heat into
work continuously through a cyclic process.
The essential parts of a heat engine are
(1) Source : It is a reservoir of heat at high
temperature and infinite thermal capacity. Any amount
of heat can be extracted from it.
(2) Working substance : Steam, petrol etc.
(3) Sink : It is a reservoir of heat at low
temperature and infinite thermal capacity. Any amount
of heat can be given to the sink.

(v) Heat transfer between bodies at different Source (T1)

temperatures is also irreversible. Q1
(vi) Joule-Thomson effect is irreversible because on Heat W = Q 1 – Q2
reversing the flow of gas a similar cooling or heating Engin
e Q2
effect is not observed.
Sink (T2)
Mixed Graphical Representation
Fig.
(1) PV-graphs 14.29
The working substance absorbs heat Q1 from the
1  Isobaric (P-constant) source, does an amount of work W, returns the
1 remaining amount of heat to the sink and comes back
2  Isothermal (Because P  to its original state and there occurs no change in its
V
internal energy.
)P 3 4
2 By repeating the same cycle over and over again,
1
3  Adiabatic (Because P   work is continuously obtained.
V The performance of heat engine is expressed by
1
)
means of “efficiency”  which is defined as the ratio of
4  Isochoric (V-constant) useful work obtained from the engine to the heat
O V
Fig.
(2) PT-graphs supplied to it.
14.26
P 2 3 4 1  Isobaric (P-constant) Workdone W
 
Heatinput Q1
2  Isothermal (T-constant)
1
For cyclic process U = 0 hence from FLOT Q =
3  Adiabatic (Because
W

 1 ) T Q1  Q2 Q
PO  T Fig. So W  Q1  Q2    1 2
14.27 Q1 Q1
4  Isochoric (In isochoric P 
T) A perfect heat engine is one which converts all heat
into work i.e. W  Q1 so that Q2  0 and hence
(3) VT-graphs
  1.
V 3 1  Isochoric (V-constant)
2
4 But practically efficiency of an engine is always less
2  Adiabatic (Because than 1.
1
1
1 ) Refrigerator or Heat Pump
VT
O T
Fig.
14.28
 144 Thermodynamics
A refrigerator or heat pump is basically a heat (2) Relation between coefficient of
engine run in reverse direction. performance and efficiency of refrigerator
It essentially consists of three parts Q2 Q2 / Q1
We know  
(1) Source : At higher temperature T1. Q1  Q2 1  Q2 / Q1
(2) Working substance : It is called refrigerant ….. (i)
liquid ammonia and freon works as a working
Q2 Q2
substance. But the efficiency   1 or  1 
Q1 Q1
(3) Sink : At lower temperature T2.
…..(ii)
Source
(Atmosphere)(T1) 1 
From (i) and (ii) we get,  
Q1 
Heat
Engin
W = Q 1 – Q2 Second Law of Thermodynamics
e Q2 First law of thermodynamics merely explains the
Sink equivalence of work and heat. It does not explain why
(Contents of (T2)
heat flows from bodies at higher temperatures to those
refrigerator)
Fig. at lower temperatures. It cannot tell us why the
14.30 converse is possible. It cannot explain why the
The working substance takes heat Q2 from a sink
(contents of refrigerator) at lower temperature, has a efficiency of a heat engine is always less than unity. It is
net amount of work done W on it by an external agent also unable to explain why cool water on stirring gets
(usually compressor of refrigerator) and gives out a hotter whereas there is no such effect on stirring warm
larger amount of heat Q1 to a hot body at temperature water in a beaker. Second law of thermodynamics
T1 (usually atmosphere). Thus, it transfers heat from a provides answers to these questions. Statement of this
cold to a hot body at the expense of mechanical energy law is as follows
supplied to it by an external agent. The cold body is
(1) Clausius statement : It is impossible for a
thus cooled more and more.
self acting machine to transfer heat from a colder body
The performance of a refrigerator is expressed by to a hotter one without the aid of an external agency.
means of “coefficient of performance”  which is
defined as the ratio of the heat extracted from the cold From Clausius statement it is clear that heat
body to the work needed to transfer it to the hot body. cannot flow from a body at low temperature to one at
higher temperature unless work is done by an external
Heatextracted Q2 Q2
i.e.    agency. This statement is in fair agreement with our
Workdone W Q1  Q2 experiences in different branches of physics. For
example, electrical current cannot flow from a
A perfect refrigerator is one which transfers heat
from cold to hot body without doing work conductor at lower electrostatic potential to that at
higher potential unless an external work is done.
i.e. W = 0 so that Q1  Q2 and hence   
Similarly, a body at a lower gravitational potential level
(1) Carnot refrigerator : For Carnot refrigerator cannot move up to higher level without work done by an
Q1 T1 external agency.

Q2 T2 (2) Kelvin’s statement : It is impossible for a
body or system to perform continuous work by cooling it
Q1  Q2 T1  T2 Q2 T2 to a temperature lower than the temperature of the
  or 
Q2 T2 Q1  Q2 T1  T2 coldest one of its surroundings. A Carnot engine cannot
work if the source and sink are at the same temperature
T2
So coefficient of performance  because work done by the engine will result into cooling
T1  T2 the source and heating the surroundings more and
more.
where T1 = temperature of surrounding, T2 =
temperature of cold body. It is clear that  = 0 when T2 (3) Kelvin-Planck’s statement : It is impossible
=0 to design an engine that extracts heat and fully utilises
i.e. the coefficient of performance will be zero if the into work without producing any other effect.
cold body is at the temperature equal to absolute zero. From this statement it is clear that any amount of
heat can never be converted completely into work. It is
 Thermodynamics 145
essential for an engine to return some amount of heat Work done = Heat absorbed by the system
to the sink. An engine essentially requires a source as V2 V 
well as sink. The efficiency of an engine is always less
than unity because heat cannot be fully converted into
W1  Q1   V1
P dV  RT1 loge  2   Area
 V1 
work. ABGE
(ii) Second stroke (Adiabatic expansion) (curve BC) :
Carnot Engine
The cylinder is then placed on the non conducting
(1) Carnot designed a theoretical engine which is
stand and the gas is allowed to expand adiabatically till
free from all the defects of a practical engine. This
the temperature falls from T1 to T2.
engine cannot be realised in actual practice, however,
this can be taken as a standard against which the V3 R
performance of an actual engine can be judged.
W2   V2
P dV =
(  1)
[T1  T2 ]  Area BCHG

(iii) Third stroke (Isothermal compression) (curve

CD) :
Ideal
gas The cylinder is placed on the sink and the gas is
compressed at constant temperature T2.
Work done = Heat released by the system
Source Insulatin Sink
V4 V4

T1 K g stand T2 K
W3  Q2   P dV   RT2 loge
V3 V3
Fig.
14.31 V3
 RT2 loge  AreaCDFH
It consists of the following parts V4
(i) A cylinder with perfectly non-conducting walls
(iv) Fourth stroke (adiabatic compression) (curve
and a perfectly conducting base containing a perfect
DA) : Finally the cylinder is again placed on non-
gas as working substance and fitted with a non-
conducting stand and the compression is continued so
conducting frictionless piston
that gas returns to its initial stage.
(ii) A source of infinite thermal capacity maintained
V1 R
at constant higher temperature T1. W4    V4
P dV  
 1
(T2  T1)
(iii) A sink of infinite thermal capacity maintained at
constant lower temperature T2. R
 (T1  T2)  AreaADFE
(iv) A perfectly non-conducting stand for the  1
cylinder.
(3) Efficiency of Carnot cycle : The efficiency of
(2) Carnot cycle : As the engine works, the engine is defined as the ratio of work done to the heat
working substance of the engine undergoes a cycle Workdone W
supplied i.e.  
known as Carnot cycle. The Carnot cycle consists of the Heatinput Q1
following four strokes
Net work done during the complete cycle
P
A(P1, Q1 W  W1  W2  (W3 )  (W4 )
V1)
T1  W1  W3  Area ABCD

W = Q1 – Q 2 [As W2  W4 ]


(P4,
W W1  W3 Q1  Q2 W Q
V4)D
Q2
C(P3, T2     1 3  1 2
V3) V Q1 W1 Q1 W1 Q1
E F G H
RT2 loge (V3 / V4 )
Fig.
or   1
14.32
(i) First stroke (Isothermal expansion) (curve AB) : RT1 loge (V2 / V1)
The cylinder containing ideal gas as working Since points B and C lie on same adiabatic curve
substance allowed to expand slowly at this constant
temperature T1.
 146 Thermodynamics
 1 It is associated with the risk No risk of explosion,
 1  1 T V 
 T1V2  T2V3 or 1   3  of explosion, because petrol because only air is
T2  V2  vapour and air is compressed. Hence
…..(i) compressed. So, low compression ratio is kept
compression ratio is kept. large.
Also point D and A lie on the same adiabatic curve
Petrol vapour and air is Spray of diesel is obtained
 1
T1  V4  created with spark plug. through the jet.
 1
 T1V1  T2V4 1 or  
T2  V1  Entropy
…..(ii)
Entropy is a measure of disorder of molecular
V3 V4 V3 V2 motion of a system. Greater is the disorder, greater is
From (i) and (ii),  or   the entropy.
V2 V1 V4 V1
The change in entropy i.e.
V  V  Heatabsorbedby system dQ
loge 3   loge  2  dS  or dS 
 V4   V1  Absolutetemperatu
re T
The relation is called the mathematical form of
T2
So efficiency of Carnot engine   1 Second Law of Thermodynamics.
T1 (1) For solids and liquids
(i) Efficiency of a heat engine depends only on (i) When heat given to a substance changes its state
temperatures of source and sink and is independent of all at constant temperature, then change in entropy
other factors. dQ mL
dS  
(ii) All reversible heat engines working between
T T
same temperatures are equally efficient and no heat where positive sign refers to heat absorption and
engine can be more efficient than Carnot engine (as it is negative sign to heat evolution.
ideal). (ii) When heat given to a substance raises its
temperature from T1 to T2, then change in entropy
(iii) As on Kelvin scale, temperature can never be
negative (as 0 K is defined as the lowest possible dQ T2 dT T 
temperature) and Tl and T2 are finite, efficiency of a
dS   T
  T1
mc
T
 mcloge  2 
 T1 
heat engine is always lesser than unity, i.e., whole of
heat can never be converted into work which is in T 
accordance with second law.  S  2.303mclog10 2  .
 T1 
(4) Carnot theorem : The efficiency of Carnot’s
(2) For a perfect gas : Perfect gas equation for n
heat engine depends only on the temperature of source
moles is PV = nRT
T2 dQ CV dT  P dV
(T1) and temperature of sink (T2), i.e.,   1
T1
. S   T
  T
[As dQ =

dU + dW]
Carnot stated that no heat engine working between
two given temperatures of source and sink can be more  RT
CV dT  dV

efficient than a perfectly reversible engine (Carnot
engine) working between the same two temperatures.
S   T
V

Carnot's reversible engine working between two given T2 dT V2 dV

temperatures is considered to be the most efficient  CV  T1 T
 R  V1 V
[As PV
engine. =  RT]
Table 14.3 : Difference Between Petrol Engine and Diesel T  V 
Engine  S  CV loge 2    R loge  2 
Petrol engine Diesel engine  T1   V1 
Working substance is a Working substance in this In terms of T and P,
mixture of petrol vapour engine is a mixture of diesel T  P 
and air. vapour and air. S  CP loge  2    R loge  2 
Efficiency is smaller Efficiency is larger (~55%).  T1   P1 
(~47%).
It works with a spark plug. It works with an oil plug.
 Thermodynamics 147
and in terms of P and V (mg)
P  V  1
S  CV loge  2   CP loge  2   W  P0V  Kx 2  mgx
 P1   V1  2
 The efficiency of an actual engine is much lesser
than that of an ideal engine. Actually the practical
efficiency of a steam engine is about (8-15)% while
that of a petrol engine is 40%. The efficiency of a
diesel engine is maximum and is about (50-55)%.
 When a thermos bottle is vigorously shaken :  When P and V bear the relation PV x = constant,
Heat transferred to the coffee  Q = 0 where x  1 or  the process is called a polytropic one.
[As thermos flask is insulated from the In this process the molar heat capacity is,
surrounding]
R R R
Work is done on the coffee against viscous force C  CV   
1 x   1 1 x
W = (–)
 Enthalpy : Four quantities called
Internal energy of the coffee increases U = (+)
“thermodynamic potentials” are useful in the
and temperature of the coffee also increases T = chemical thermodynamics of reactions and non-cyclic
(+)
processes. They are internal energy, the enthalpy, the
 Work done without the volume limits Helmoltz free energy and the Gibbs free energy.
Vf Enthalpy is defined by
W  Vi
P dV
H = U + PV
From this equation it seems as if work done can where P and V are the pressure and volume, and U is
be calculated only when P-V equation is known and
internal energy, Enthalpy is somewhat parallel to the
limits Vi and Vf are known to us. But it is not so.
first law of thermodynamics for a constant pressure
We can calculate work done if we know the limits of
system Q = U + PV since in this case Q = H.
temperature.
 Confusion about FLOT

For  moles of an ideal gas if P  with It is typical for chemistry texts to write the first
T
law as
temperature limits T0 and 2T0.
U = Q + W
RT RT 2 It is the same law, of course the thermodynamic
From PV = RT  V  
P  expression of the conservation of energy principle. It
2RT is just that W is defined as the work done on the
dV  dT system instead of work done by the system. In the

context of physics, the common scenario is one of
 adding heat to a volume of gas and using the
Vf 2T0     2RT  expansion of that gas to do work, as in the pushing
W  Vi
P dV   T0
 
T   
 dT  2RT0
down of a piston in an internal combustion engine. In
the context of chemical reactions and process, it may
 Work done with spring : If mass less piston is be more common to deal with situations where work
attached to a spring of force constant K and a mass m is done on the system rather than by it.
is placed over the piston. If the external pressure is
 Possibilities
P0 and due to expansion
P of gas the piston moves up
through a distance x then
Total work done by the gas a
M
W  W1  W2  W3 b x
M
where W1 = Work done against V
external pressure (P 0 ) P If a  Isothermal then b  Must be adiabatic

W2 = Work done against spring But If b  adiabatic then it is not compulsory that
a must be isothermal, it may be adiabatic also.
force (Kx)
W3 = Work done against gravitational force
 148 Thermodynamics

(c) PV1 , Zero (d) PV1, P1V1

8. If the amount of heat given to a system be 35

joules and the amount of work done by the
system be 15 joules, then the change in the
First Law of Thermodynamics (Q = U + W) internal energy of the system is
1. First law of thermnodynamics is given by [CPMT [MP PMT 1989]
1977, 91]
(a) 50 joules (b) 20 joules
(a) dQ  dU  PdV (b) dQ  dU  PdV
(c) 30 joules (d) 50 joules
(c) dQ  (dU  dV) P (d) dQ  PdU  dV
9. A system is given 300 calories of heat and it does
2. The internal energy of an ideal gas depends upon 600 joules of work. How much does the internal
[RPMT 1997; MP PMT 1999; CPMT 2003] energy of the system change in this process

(a) Specific volume (b) Pressure (J = 4.18 joules/cal) [MP PET 1991]

(c) Temperature (d) Density (a) 654 Joule (b) 156.5 Joule

3. In changing the state of thermodynamics from A to (c) – 300 Joule (d) – 528.2 Joule
B state, the heat required is Q and the work done 10. Work done on or by a gas, in general depends
by the system is W. The change in its internal upon the
energy is
(a) Initial state only
[MP PMT 1986; AMU (Med.) 2001]
(b) Final state only
(a) Q + W (b) Q – W
(c) Both initial and final states only
Q W (d) Initial state, final state and the path
(c) Q (d)
2
11. If R = universal gas constant, the amount of heat
4. Heat given to a system is 35 joules and work done needed to raise the temperature of 2 mole of an
by the system is 15 joules. The change in the ideal monoatomic gas from 273K to 373K when no
internal energy of the system will be work is done [MP PET 1990]
[MP PET/PMT 1988]
(a) 100 R (b) 150 R
(a) – 50 J (b) 20 J
(c) 300 R (d) 500 R
(c) 30 J (d) 50 J
5. The temperature of an ideal gas is kept constant 12. Find the change in internal energy of the system
as it expands. The gas does external work. During when a system absorbs 2 kilocalorie of heat and at
this process, the internal energy of the gas the same time does 500 joule of work
[MP PMT 1990] [EAMCET 1984]
(a) Decreases (a) 7900 J (b) 8200 J
(b) Increases (c) 5600 J (d) 6400 J
(c) Remains constant
(d) Depends on the molecular motion
6. The first law of thermodynamics is concerned with
the conservation of [MP PMT 1987; CBSE PMT
1990, 92;
AFMC 1997; CPMT 1999; BHU 1999;
DCE 2000; BCECE 2003]
(a) Momentum (b) Energy
(c) Mass (d) Temperature

7. A thermodynamic system goes from states (i) P1

, V to 2P1 , V (ii) P, V to P, 2V. Then work done in
the two cases is
[MP PMT 1990]

(a) Zero, Zero (b) Zero, PV1