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# CHAPTER – 12 The law states that “If an amount of

## heat is given to a system, a part of the

THERMODYNAMICS
heat is used to increase the internal
Thermodynamics means heat energy and other part is used to do the
flow. Thermodynamics deals with the external work”
conversion of heat into work and
Q  U  W
work into heat.
 Q  H eat sup plied to the system.
Thermal equilibrium  U  change in int ernal energy
Two systems are said to be in  W  workdone by the system
thermal equilibrium, if their But  W  P  V
temperatures are the same. Then there  Q  U  P V
will not be any heat flow from one
system to another. Thermodynamic state variables

## Internal energy The physical quantities which

characterise a system are known as
It is the sum of all kinetic energies state variables.
and potential energies of the
molecules of the system. Eg: - Pressure, volume, temperature,
mass, density, internal energy, heat
Zeroth Law of thermodynamics capacity, specific heat capacity etc.
This law was formulated by R.H. Thermodynamic state variables are of
Fowler.
two types:
The law states that “two systems
i) Intensive state variables
which are in thermal equilibrium with
They are the state variables which
a third system separately are in do not depend on the size of the
thermal equilibrium with each other.” system.
Eg: - Pressure, temperature, density,
specific heat capacity etc.
ii) Extensive sate variables
They are the state variables which
depend on the size of the system.
Eg: -volume, mass, heat capacity,
internal energy etc.
Note: - Heat and work are not state
variables.
First Law of thermodynamics Thermodynamic Processes
The first law of thermodynamics is a (i) Quasi - static Process
statement of law of conservation of
energy. A quasi-static process is an
infinitely slow process such that the

SAJU K JOHN, M.Sc. Physics, NET, Doctoral Research Fellow at NIT Calicut 1
system remains in thermal and Eg: - The expansion of a gas in a
mechanical equilibrium with the metallic cylinder placed in a large
surroundings throughout the process. reservoir of fixed temperature is an
example of isothermal process.
(ii) Isobaric Process Melting of ice at its normal melting
In an isobaric process, pressure is point, vaporization of a liquid at its
constant throughout the process. normal boiling point etc. are other
If heat is applied, the piston moves up. examples.
A part of heat supplied is used
increase the internal energy and the Work done during an isothermal
other part are used to do the work. process
Q   U   W.
Q  nC P T Suppose a system of gas is
C P  Molar specific heat capacity expanding from an initial volume V1
at cons tan t pressure. to a final volume V2 during an
isothermal process.
(iii) Isochoric Process
The work done for the small change in
In an isochoric process, volume is
volume ‘dV’ is given by
constant throughout the process.
dW  PdV
V  0
 The total workdone,
W  PV  0
V2
 Q  U W  V1
dW
The heat sup plied is completely V2

## used to increase the int ernal energy.

  V1
PdV, ButPV  nRT

Q  nC V T nRT
P
C V  molar specific heat capacity V
nRTV2
at cons tan t volume. W V1 V dV
V2 1
(iv) Isothermal process  nRT  dV
V1 V

##  nRT  log V V2

V
It is a process taking place at
1
constant temperature.
 nRT  log V2  log V1 
Equation for isothermal process
is PV = Constant [Boyle’s law] A
But we have, logA-logB=log
(Here the constant is µRT) B
V 
 W  nRT log  2 
Conditions for isothermal process  V1 
i. The process must be slow
ii. There should be a perfect conducting V 
W  nRT log  2 
wall (diathermic wall) between the  V1 
system and surroundings.

SAJU K JOHN, M.Sc. Physics, NET, Doctoral Research Fellow at NIT Calicut 2
x n 1
During an adiabatic process, no We have,  x n dx 
n 1
heat enters or leaves the system. In an V2
adiabatic process all of the quantities  V   1 
W  k  
P, V and T changes.    1  V1
k V2
Cp   V1  
PV   Constant,  = 1  V1

Cv k
 1
  V21   V11  
or TV  C ons tan t 1 
or P  V 1    Cons tan t 1
  kV21   kV11  
1 
Eg: - Sudden burst of an inflated But k  P1V1   P2 V2 
balloon or a tyre tube, propagation of
1
sound through air. W   P2 V2  .V21   P1V1  .V11  
1  
[During a sudden expansion no intake
1
of heat takes place. So the work for   P2 V2  P1V1 
the expansion is done using the 1 
internal energy of the system. So the but P1 V1  nRT1 and P2 V2  nRT2
internal energy of the system 1
decreases and hence temperature
W   nRT2  nRT1 
1 
decreases. Thus during an adiabatic nR
expansion cooling is produced.]  T2  T1 
1 
nR
Work done during an adiabatic  T1  T2 
process  1
The work done during an adiabatic nR
change of an ideal gas from the state W  T1  T2 
 1
(P1, V1, T1) to the stateP 2,V2, T2) is
given by, Problem1: Three moles of an ideal
V2 gas kept at a constant temperature of
W   dW 300 K are compressed from the
V1
V2 volume of 10 litres to 5 litres.
  PdV Calculate the work done to compress
V1

## We have, PV   k this gas.

Ans:
k
P
V
V2 k
W   dV
V1 V
V2
 k  V  dV
V1

SAJU K JOHN, M.Sc. Physics, NET, Doctoral Research Fellow at NIT Calicut 3
coffee. It is violently shaken.
Considering the coffee as a system

## a) Does the temperature rise?

b) Has heat been added to it?
c) Has internal energy changed?

Ans:

processes.

Ans:

## Problem5: Isothermal, isobaric,

some special thermodynamic
processes. In which of these
processes, the work done is maximum
Problem3: If a gas is compressed to
when the gas expands from V1 to V2 ?
half its volume first rapidly and then
Ans:
slowly, in which case the work done
will be greater?

Ans:

SAJU K JOHN, M.Sc. Physics, NET, Doctoral Research Fellow at NIT Calicut 4
Problem6: A gas expands
adiabatically so that 50 J of work is
obtained. What is the change in
temperature in the above process if
the working substance is a
monoatomic gas? (R=8.314J/molK)

Ans:

Cyclic Process
In a cyclic process, the system
returns to its initial state.
  U  0, for a cyclic process.
Then  Q   W
Heat Engines:

## Heat engine is a device to convert

heat energy in to mechanical energy.

It consist of:
i. A very hot body of large specific heat
capacity called the source.
ii. A working substance. Eg: a
mixture of fuel vapour and air in a
Problem7: A thermodynamic system
petrol or diesel engine or steam in a
performs work without taking heat
steam engine.
from an external source.
iii. An insulating stand
a) Which process is involved in this iv. A cold body of large specific
case? heat capacity called sink.
b) What is the source of energy for
Schematic representation of a heat
this work?
engine is given below.
c) By what factor does the pressure
of the system decrease if the
volume is doubled (γ=1.4).

## Working substance absorbs heat of

amount Q 1 from the source; a part of
the heat is converted into useful work

SAJU K JOHN, M.Sc. Physics, NET, Doctoral Research Fellow at NIT Calicut 5
W and other part Q2 is given to the or W = Q1 - Q2
sink.
The coefficient of performance of a
Efficiency of a heat engine () refrigerator
W Q1  Q 2 Q
   1 2 Q2 Q2
Q1 Q1 Q1  = 
W Q1  Q 2
Q2
  1
Q1 A heat pump is a device to pump heat
into a portion of space (room).
For Q 2  0, =1
i.e., 100% efficiency for heat engine, Coefficient of performance of a heat
which is never possible. pump

## Types of heat engines: Q1 Q1

= 
W Q1 Q2
1. External combustion engine – in
which heat is produced by burning [In a refrigerator, sink is the cooling
fuel outside the cylinder. Eg: chamber. Source is the room in which
steam engine the refrigerator is placed. The work
2. Internal combustion engine – in (W) is the work done by the
such engines heat is produced by compressor by consuming electricity.]
burning fuel inside the cylinder.
Eg. Petrol and diesel engines. [In a heat pump, sink is the
environment outside the room. Source
Refrigerators and heat Pumps: is the room which is to be heated.]
A refrigerator works in the reverse Second Law of Thermodynamics
order of a heat engine.
Kelvin – Planck Statement:
The working substance for both
refrigerator and heat pump is Freon. No process is possible whose sole
result is the absorption of heat from
a reservoir and the complete
conversion of heat into work.

## Explanation: - This statement says

that the complete heat Q1 cannot be
Here the working substance converted into work. Thus the
absorbs heat Q 2 from the sink, some efficiency of a heat engine cannot be
work W is done on the working 100%.
substance by an external agency and Clausius Statement: No process is
the working substance liberates a possible whose sole result is the
large amount of heat Q1 to the source. transfer of heat from a cold
reservoir to a hot reservoir.
Q1 = Q2 + W

SAJU K JOHN, M.Sc. Physics, NET, Doctoral Research Fellow at NIT Calicut 6
Explanation: - This statement says (P2, V2, T1) by absorbing a heat Q1
that the transfer of heat from a cold from the source at T1 K. The work
object to a hot object will not takes done by the gas during this process.
place if no work is supplied. Thus the
coefficient of performance cannot be Step 2  3: Adiabatic expansion
infinite. of the gas from (P2 , V2 , T2 ) to
Reversible and irreversible (P3 ,V3 ,T1 ). Work done bythe gas
processes during this process,
nR
A process is reversible if it can
W23   T1  T2 
be reversed such that both the  1
Step 3  4: Isothermal compression
their initial states, with no other
change anywhere else in the of the gas from (P3 ,V3 ,T2 ) to (P4 ,V4 ,T2 ).
universe. Heat released (Q2 ) by the gas during
Spontaneous processes of nature this compression is equal to the work
are irreversible. The idealised done on the system.
reversible process is a quasi –static V 
process with no dissipative factors W34  nRT2 log  4  = Q2
such as friction, viscosity etc.  V3 
Step 4  1: Adiabatic compression of
Carnot engine the gas from (P4 , V4 , T2 ) to (P1 ,V1 ,T1 ).
A reversible heat engine Work done on the gas
nR
operating between two temperatures is W3 4   T2  T1 
called a Carnot engine. Nicolas Sadi  1
Carnot introduced this ideal heat  The total work done by the gas in
engine whose cycle of operation is one complete cycle,
called Carnot cycle. W = W1 2  W2 3  W3 4  W4 1
 V  nR
W  nRT1 log  2   T1  T2 
 V1    1
 V  nR
 nRT2 log  4    T2  T1 
 V3    1
 V  nR
 nRT1 log  2    T1  T2 
 V1    1
 V  nR
 nRT2 log  3    T1  T2 
 V4    1
V   V3 
The operation of the engine is W  nRT1 log  2   nRT2 log  
 V1   V4 
completed in four stages:

## Step 1→2: Isothermal expansion of

the gas from the state (P1, V1, T1) to

SAJU K JOHN, M.Sc. Physics, NET, Doctoral Research Fellow at NIT Calicut 7
The efficiency () of the carnot engine Problem8: a) Which law of
Q
  1 2
thermodynamics is used to explain the
Q1 working of a heat engine?
V3
nRT2 log ( ) b) What are the sink, source and
V4
 1  (1)
V2 working substance of a domestic
nRT1 log ( )
V1 refrigerator?
Since step 2  3 is an adiabatic process, Ans:
T2 V2 1
 T1V2 1  T2 V3 1  
T1 V3 1
1
T V 
 2  2 
T1  V3 
1
V T
 2  ( 2 )  1  (2)
V3 T1
Similarly step 4  1 is an adiabatic process,
T2 V11
 T2 V4 1  T1V11  
T1 V4  1
1
T V 
 2  1 
T1  V4 
1 Problem9: (a) What is the working
V  T  1 substance of an ideal heat engine?
 1   2   (3)
V4  T1 
From (2) and (3) (b) Calculate the maximum
V1 V2 V V efficiency of a heat engine
 or 3  2  (4)
V4 V3 V4 V1 working between steam point
Substituting (4) in (1) and ice point. Can you design
an engine of 100% efficiency?
T2
  1
T1 Ans:

Carnot’s Theorem: -

## i) Working between two given

temperatures T1 and T2 of the hot
and cold reservoirs respectively,
no engine can have efficiency
more than that of the Carnot
engine.
ii) The efficiency of the Carnot
engine is independent of the nature
of the working substance.

SAJU K JOHN, M.Sc. Physics, NET, Doctoral Research Fellow at NIT Calicut 8
Problem10: An ideal heat engine
utilizes a perfect gas. The source is at
450 K and sink is at 320 K. If the
engine takes 3600J per cycle from the
source, calculate the efficiency of the
engine.

Ans:

## Problem 11: a) Which

thermodynamic process is called an
iso-entropic process?

## b) The efficiency of a Carnot

engine is 1/6. If on reducing the
temperature of the sink by 650C,
its efficiency becomes 1/3, find the
temperature of the sink and source.

SAJU K JOHN, M.Sc. Physics, NET, Doctoral Research Fellow at NIT Calicut 9
Problem12: A Carnot engine working
between 5270C and 1270C has a work
output of 800J per cycle. How much
heat is supplied to the engine from the
source per cycle?

Ans:

SAJU K JOHN, M.Sc. Physics, NET, Doctoral Research Fellow at NIT Calicut 10