BASIC

THERMODYNAMICS
(Theory + Objective + Conventional)

[For GATE, UPSC-ESE, State Public Service Commission,

Recruitment tests by Public Sector Undertakings]
By
Mr. Praveen Kulkarni

KULKARNI’S ACADEMY PUBLICATION

16-11-1/1/2, 5th floor, Above Bantia Furnitures, Near Super Bazar Bus Stop,

Malakpet, Hyderabad, Telangana 500036

Phone: +91-9000770927, E-mail: kamehyderabad@gmail.com

Website: www.kulkarniacademy.com
KULKARNI’S ACADEMY PUBLICATION
16-11-1/1/2, 5th floor, Above Bantia Furnitures, Near Super Bazar Bus Stop,

Malakpet, Hyderabad, Telangana 500036

Phone: +91-9000770927, 7893190907

E-mail: kamehyderabad@gmail.com

Website: www.kulkarniacademy.com

 ALL RIGHTS STRICTLY RESERVED

Copyright 2020, by KULKARNI ACADEMY OF MECHANICAL ENGINEERING. No part of this book may be reproduced, or
distributed in any form or by any means, electronic, mechanical, photocopying or otherwise or stored in a database or retrieval
system without the prior information of KAME Publication, Hyderabad. Violates are liable to be legally prosecuted.

First Edition: 2020

Price: ₹350/-

Typesetting by: Kulkarni’s Academy Publication, Hyderabad

ACKNOWLEDGEMENTS

I owe special thanks to two individuals who have influenced my thinking during the
preparation of this book- Pushpendra Jangid and Hrishikesh Kulkarni
I appreciate the help of Pushpendra Jangid, the backbone of this book who prepared
solutions in a simplified manner with neat explanations. I remain indebted to Hrishikesh
Kulkarni for editing the material.

Praveen Kulkarni Director,

Kulkarni’s Academy - Hyderabad
PREFACE TO THE FIRST EDITION

This book is designed for mechanical engineering students who are interested in
appearing for GATE, ESE and other PSU’s. The main emphasis is placed on the precise
and logical presentation of basic concepts and principles, which are essential for
better understanding of the subject. Since, this is an introductory book, care has
been taken to present questions in a gradual manner to instil confidence in the
minds of the students. Due effort has been made to keep fundamentals and
principles at a very simple level. Looking forward for constructive criticism and
suggestions, if any.

Praveen Kulkarni
ABOUT THE DIRECTOR

Praveen Kulkarni did his B.E. and subsequently M.E. (Production Engineering) from
Osmania University, Hyderabad. He has qualified GATE, IES (ESE) and other state
service examinations. He secured all India 39th and 14th rank in ESE 1999 and 2001
respectively. After joining Engineering Services in IOFS (Indian Ordnance Factory
Services) and MES (Military Engineer Services), quit due to his passion for teaching.
Mr. Praveen Kulkarni is regarded as one of the best teachers in India due to his
simplification of subjects. A great Motivator, student friendly and a humble person.
He is the recipient of National Merit scholarship (NMS) and Telugu Vignana
Paritoshakam (TVP). He handles Thermodynamics, Fluid Mechanics, RAC, Heat
Transfer, IC Engines, Power Plant, Turbo machinery, Strength of Materials and
Machine Design with equal ease.
 To
My beloved students
Past and Present
 Table of Contents

Sr. Chapter Pages

1. Basic Concepts 1 to 6

2. Zeroth law of thermodynamics 7 to 10

3. Energy Interactions (Heat and Work) 11 to 47

4. Second Law of Thermodynamics 48 to 64

5. Entropy 65 to 87

6. Available Energy, Availability & Irreversibility 88 to 95

7. Properties of Pure Substances 96 to 114

8. Thermodynamics Relations 115 to 118

9. Mixture of gases 119 to 126

1.1 Thermodynamics Note :
Boundary can be rigid (fixed), it can be flexible
It is the science of energy transfer and its effects
(movable), it can be real or imaginary.
on properties of system.
Energy transfer may be heat or work or both heat
and work.
The main aim of thermodynamics study is to
convert disorganized form of energy (heat) into
organized form of energy (work) in an efficient
manner.
● Applications of Thermodynamics:
Refrigeration, air-conditioning, steam power
plant, I.C. engines etc.
1.2 Basic concepts
1.3 Types of system
System: It is a region in space upon which the
study is focused or concentrated, Type of Mass Energy Example
System Transfer Transfer
Surroundings: Anything external to the system,
Water in
where the effect of system is felt, is known as sealed
surrounding. container,
Universe = System + Surrounding Closed piston
cylinder
without
valve
Turbine,
compressor,
Open
pump,
boiler
Universe,
hot tea in
Isolated well
Boundary: The separation between system and insulated
surroundings is known as boundary. flask
Basic Thermodynamics 2 Kulkarni’s Academy
Note:
● Control mass system: In a closed system, as
there is no mass transfer- the system mass
remains constant and hence it is also known
as control mass system.
● Control Volume system: It is the volume
enclosing or surrounding the device which
we wish to analyze, across the control
volume both mass transfer and energy
transfer can take place.
● A pure substance can exist in a single phase or
1.4 Microscopic and macroscopic approach more than one phase.
of Thermodynamics ● Dry air is a pure substance but moist air (liquid
air) is not a pure substance that is, in moist air
In microscopic approach- the behavior of
water vapour can be condensed and separated.
individual molecules is taken into consideration,
this approach is also statistical thermodynamics. ● A pure substance can be mixture of gases also.
This approach is useful at low densities (at higher Ex. Gaseous air, which is a mixture of oxygen,
altitudes). nitrogen and other inert gases.
In macroscopic approach individual molecular 1.6 Property of a system
behavior is not taken into consideration, that is Any Measurable characteristic is a property.
average behavior of molecules is taken into
Ex. Pressure, temperature, volume, density etc.
consideration. This approach is also known as
classical thermodynamics. ● Properties are of two types-

Note: In our course we follow classical (1) Intensive

thermodynamics. (2) Extensive
● Thermodynamic Equilibrium: A system is said ● Intensive properties are independent of size or
to be in thermodynamic equilibrium if it is in- mass of the system.

(1) Thermal equilibrium (Equality of Ex. Pressure, temperature, density, viscosity,

temperature).
(2) Mechanical equilibrium
pressure/forces).
(3) Chemical equilibrium (Equality of chemical
potential).
1.5 Pure substances
thermal conductivity, velocity.
● Extensive properties are dependent on size or
(Equality of
mass of the system.
Ex. Volume, Mass, All forms of energy (K.E,
P.E, Internal Energy), momentum.

A substance is said to be pure substance, if it is

(1) Homogeneous in chemical composition.
(2) Homogeneous in chemical aggregation
(bonding).
Kulkarni’s Academy 3 Basic Concepts

● Note: ● Most of the practical processes are irreversible

(1) Ratio of two extensive properties is an
intensive property.
(2) All specific properties (Extensive properties
divided by mass) are intensive properties.
Ex. specific volume, specific enthalpy,
specific internal energy, specific entropy.
● Important Points with respect to properties:
(1) Properties are point functions or state
functions.
(2) Properties are independent of past history i.e.
they are independent of path.
(3) Properties are exact differentials.
dVa = dVb = 5 m3
processes. Reversible process are discussed-
(i) To simplify the analysis.
(ii) They are efficient process.
● Quasi-static process: A process which is carried
out very slowly with a small difference in
properties is known as a Quasi-static process.
● Note: Though all reversible processes are quasi-
static process, but the converse is not true i.e., all
quasi-static processes need not to be reversible.
● Friction Less Quasi-Static Process is a
Reversible Process.
1.8 Gibbs phase rule

According to Gibbs Phase Rule

PF C2

Where,

P  No. of phases

F  Minimum number of independent intensive

variable required to fix the state or degree of
freedom
(4) Properties are macroscopic characteristic of a
system. C  No. of component

● State of a system: The condition of a system is

known as state of a system.
1.7 Process

Any change of state is a process.

● Reversible and Irreversible process: A process
is said to be a reversible process if when reversed,
follows the same path without leaving any effect
on system and surrounding.
A process which is not a reversible process is an
irreversible process. Friction is one of the reasons
which makes the process irreversible. ● At triple point the degree of freedom is zero.
Basic Thermodynamics 4 Kulkarni’s Academy
1.9 Thermodynamic Cycle
P Practice Questions
A system is said to have undergone a cycle, if the
initial and final state of the system is same. 1.1 A Control volume is
(A) An isolated system
● Minimum number of processes required for a
(B) A closed system but heat and work can
cycle are Two.
cross the boundary
● The cyclic integral of any property is zero i.e. (C) A specific amount of mass in space
the change in property for a cycle is zero. (D) A fixed region in space where mass, heat
and work can cross the boundary of that
region
1.2 For a pure substance at its triple point, the
number of degree of freedom is
(A) 0 (B) 1
(C) 2 (D) 3
1.3 In which system, boundaries allow only
energy transfer
(A) Isolated system (B) Closed system
1.10 Concept of continuum (C) Open system (D) None
Continuum means continuous, in continuum 1.4 Which property remains unchanged when the
concept is assumed to be distributed uniformly system is partitioned into number of parts
and continuously. For applying the concept of (A) Intensive
continuum- (B) Extensive
(1) There should be large no. of molecules. (C) Both intensive and extensive
(D) Neither intensive nor extensive
(2) Mean free path must be small i.e. mean free
1.5 What are the properties of thermodynamic
path (distance between molecules) must be
system, whose value for the entire system is
less than system dimension.
equal to the sum of their value for individual
(3) Continuum concept is a macroscopic parts of the system?
approach. (A) Thermodynamic properties
(B) Extensive properties
(C) Intensive properties
(D) None of the above
1.6 Which of the following statements regarding
thermodynamic properties are correct?
P. They are exact differentials
Q. They are point functions
R. Does not depend on past history of the
system
S. Depends on past history of the system
(A) Q and S (B) Q only
(C) P, Q and R (D) P and S
Kulkarni’s Academy
1.7 Which of the following statements regarding
the concept of continuum are correct?
P. Large number of molecules enable
meaningful statistical averaging and
assignment of property values
Q. Mean free path of the molecules is order
of magnitude higher than system
dimensions
R. Behavior of individual molecules is
disregarded
5 Basic Concepts
(A) Both A and R are individually true and
R is the correct explanation of A
(B) Both A and R are individually true but R
is not the correct explanation of A
(C) A is true but R is false
(D) A is false but R is true
1.12 Given P = Pressure, T = Temperature; V =
Specific volume. Which one of following can
be considered as a property of system?

 pdv
S. Mean free path of the molecules (A)
approaches the order of magnitude of the
system dimensions (B)  vdp
(A) P and R (B) Q and R
 dT pdv 
(C) R and S (D) P and S (C)   T 
V 

1.8 Which of the properties listed below are
intensive properties?  dT vdp 
P. Weight Q. Temperature
(D)   T 
T 

R. Volume S. Density
1.13 Identify the group containing the appropriate
(A) Q and S (B) P and R match of items in List I and List II
(C) P and Q (D) R and S
List-I
1.9 A system is said to be consisting of a pure
substance when P. A jet engine in flight
(A) It is homogeneous is composition Q. Water being heated in a sealed container
(B) It is homogeneous and invariable in R. Internal energy
chemical composition and aggregation
S. Specific entropy
(C) It has only one phase
(D) It has more than one phase List-II
1.10 Which of the following are pure substances? 1. Closed system
P. Gaseous air 2. Control system
Q. A mixture of gaseous air and liquid 3. Intensive Property
water
4. Extensive Property
R. A mixture of liquid water and water
vapour (A) P-1, Q-2, R-3, S-4
S. A mixture of gaseous air and oil] (B) P-2, Q-1, R-3, S-4
1.11 Assertion (A) : Air is a pure substance but a (C) P-2, Q-1, R-4, S-3
mixture of air and liquid air in a cylinder is
(D) P-1, Q-2, R-4, S-3
not a pure susbstance.
Reason (R) : Air is homogeneous in 1.14 In the fig. showing a schematic of a vapour
compression refrigeration system, the system
composition but a mixture of air and liquid
(s) and control volume (s) are as
air is heterogeneous.
Basic Thermodynamics 6 Kulkarni’s Academy
1.3 (B)
1.4 (A)
1.5 (B)
1.6 (C)
1.7 (A)
1.8 (A)
(A) Compressor and condenser are control
1.9 (B)
volumes; and expansion valve and
evaporator are systems 1.10 (P&R)
(B) Expansion valve and evaporator are 1.11 (A)
control volumes; and compressor and
condensor are systems 1.12 (D)
(C) Compressor, condenser, expansion PV  RT
valve and evaporator are control V R

volumes; and overall boundary is a T P
system  dz  Mdx  Ndy
(D) Overall boundary is a control volume;  dT VdP  
z       M   N 
and compressor, condenser, expansion  T T    
  Y    
 X  X Y
valve and evaporator are systems
dT VdP
A Answer Key
dz  
T T
1 V
1.1 D 1.2 A 1.3 B dz  (dT )  (dP)
T T
1.4 A 1.5 B 1.6 C
1
1.7 A 1.8 A 1.9 B M x T
T
1.10 P&R 1.11 A 1.12 D V
N yP
1.13 C 1.14 C T
 PV  mRT
 M     1  
E Explanation        0  V mR
 Y  X  P  T  T  T  P
1.1 (D)
 N     V 
1.2 (A)     
 X Y  T  T  P
By using Gibb’s phase rule     mR  
PF C2      0
 T  P   P
At triple point P  3
So it is a property
C 1
Hence, the correct option is (D).
3  F  1 2
F 0 1.13 (C)
Hence, the correct option is (A). 1.14 (C)
NOTES
2.1 Zeroth Law of Thermodynamics

Zeroth law was developed by Fowler in 1931.

This law was developed after 1st and 2nd law of
thermodynamics.
Statement: When the body A is in thermal
equilibrium with body B, and body B is in
P R
thermal equilibrium with body C separately, then 
Q S
A and C are in thermal equilibrium.
Significance of Zeroth law of
Thermodynamics:
Without bringing two bodies into direct contact
with the help of zeroth law it can be establish
whether they are in thermal equilibrium or not. (2) Thermocouple:
Thermocouples are based on seeback effect.
According to seeback effect when two
dissimilar metals are joined to form a
junction, and if these two junctions are
maintained at different temperature then
2.2 Thermometric Principle electromotive force (emf) or voltage is
In this principle, the property which is changing generated-with the help of voltage
with temperature is calculated first and with the temperature is calculated.
help of this property, temperature is calculated. In thermocouple voltage or emf plays the
The property which helps in calculating the role of thermometric property.
temperature is known as thermometric property.

2.3 Types of thermometer

(1) Resistance thermometer [Thermistors] :

Thermistors are based on Wheatstone bridge
principle. In resistance thermometers,
Resistance is thermometric property.
Basic Thermodynamics 8 Kulkarni’s Academy
Note : Platinum-Rhodium thermocouple is ● The single fixed-point reference temperature
used is triple point of water. [273.16 k]
capable of measuring highest temperature.
PV  mRT
(3) Constant volume gas thermometer:
V  constant
These thermometers are based on ideal gas
TP
laws, and in this thermometer- Pressure is
thermometric property. T  CP … (i)

PV  mRT (Volume = constant, mass = At triple point

constant, R = constant) Tt p  CPt p
Hence, T  F ( P) . Tt p
C … (ii)
(4) Constant pressure gas thermometer: Pt p
These thermometers are based on ideal gas
Tt p
laws, and in this thermometer-Volume is T P {Tt p  273.16 k}
thermometric properties. Pt p

PV  mRT (Pressure= constant, mass= If P  constant

constant, R= constant)
V 
Hence, T  F (V ) . T  273.16  
 Vt 
 p 
2.4 Temperature Scales
 P 
Temperature scales are arbitrary i.e. randomly T  273.16  
 Pt 
taken.  p 
In Celsius or centigrade scale ice point is taken
Note :
as 00 C and steam point is taken as 1000 C .
● Ideal gas thermometer is independent of material
of construction.
● Kelvin which is designated by K (not 0 K , degree
symbol was officially dropped from kelvin in
1967).
● Using non-conventional refrigeration techniques,
scientists have approached absolute zero kelvin
[0.000000002 K in 1989]
● Rankine scale :
K 0 C  273.15
T ( R )  T ( 0 F)  459.67
● The triple point of water is taken as 0.010 C
[273.16 K]. T ( R)  1.8T ( K )
● Ideal gas temperature scale and kelvin ● Absolute gas temperature scale is not a
temperature scale are same and hence in ideal thermodynamic temperature scale, since it
gas equation PV  mRT , Temperature T cannot be used at very low temperature (due to
should be in kelvin. condensation) and at very high temperature (due
to dissociation and ionization).
● The S.I. unit of Temperature is Kelvin.
Kulkarni’s Academy 9 Zeroth Law of Thermodynamics
(C) 5 kg of wet steam at 100ºC is mixed with
P Practice Questions
40 kg of dry and saturated steam at
2.1 Which law of thermodynamics deals with the 100ºC
concept of temperature
(D) 10 cc of water at 20ºC are mixed with 10
(A) Zeroth law (B) First law cc of sulphuric acid at 20ºC
(C) Second law (D) Third law 2.6 Match List-I (type of thermometer) with
2.2 A new linear temperature scale, denoted by List-II (Thermometric property) and select
0
S , has been developed, where the freezing the correct answer
point of water is 2000 S and the boiling point List-I
is 4000 S . On this scale, 5000 S corresponds, P. Mercury in Glass
in degree Celsius, to Q. Thermocouple
(A) 100ºC (B) 125ºC R. Thermistor
(C) 150ºC (D) 300ºC S. Constant volume gas thermometer
2.3 A single fixed point temperature scale is List-II
based on :
1. Pressure
(A) Ice point
2. Electrical Resistance
(B) Steam point
3. Volume
(C) Triple point of water 4. Voltage
(D) Critical point of water (A) P-1, Q-4, R-2, S-3
2.4 The thermometric property, x, of a (B) P-3, Q-2, R-4, S-1
thermometer varies with temperature, t,
(C) P-1, Q-2, R-4, S-3
according to the relation t  ax2  b , where t
is in ºC, x is in cm, and a & b are constants. (D) P-3, Q-4, R-2, S-1
At ice point (0ºC) and steam point (100ºC), 2.7 Assertion (A) : The temperature of a system
the values of x and 5 cm and 20 cm, given by a mercury thermometer and an
respectively. When this thermometer is electric resistance thermometer would not be
brought in contact with a heated body, the exactly the same except at their common
value of x is recorded as 15 cm. The fixed points.
temperature of the heated body in ºC is Reason (R) : The empirical temperature
(A) 83.3 (B) 73.3 scales are dependent on the nature of the
(C) 63.3 (D) 53.3 thermometric substance used.

2.5 For which of the following situations, Zeroth (A) Both A and R are individually true and
law of thermodynamics will not be valid? R is the correct explanation of A

(A) 50 cc of water at 25ºC are mixed with (B) Both A and R are individually true but R
150 cc of water at 25ºC is not the correct explanation of A

(B) 500 cc of milk at 15ºC are mixed 100 cc (C) A is true but R is false
of water at 15ºC (D) A is false but R is true
Basic Thermodynamics 10 Kulkarni’s Academy
2.8 Which one of the following correctly defines 2.3 (C)
1K, as per the internationally accepted
definition of temperature scales 2.4 (D)
(A) 1/100th of the difference between normal
boiling point and normal freezing point Given Data :
(B) 1/273.15th of the normal freezing point x ( 0 C)  5 cm
of water
(C) 100 times the difference between triple x(1000 C)  20 cm
point of water and the normal freezing t  ax2  b
point of water
0  a(25)  b
(D) 1/273.16th of the triple point of water
2.9 Which thermometer is independent of 25a  b  0 … (i)
material of construction? 100  a(400)  b
(A) Mercury Thermometer
(B) Alcohol Thermometer 400a  b  100 … (ii)
(C) Ideal gas Thermometer From equation (i) and (ii)
(D) Resistance Thermometer a  0.266, b  6.67
A Answer Key When, x  15 cm , then temperature of the
2.1 A 2.2 C 2.3 C heated body

2.4 D 2.5 D 2.6 D t  0.266(15) 2  (6.67)

2.7 A 2.8 D 2.9 C t  53.180 C

E Explanation
2.5 (D)

When water is mixed with sulphuric acid due

2.1 (A)
to chemical reaction, the temperature is not
2.2 (C) same, therefore it is not in thermal equilibrium.
0
S  a(0 C )  b Hence, the correct option is (D).
00 C  2000S 2.6 (D)
1000 C  4000S
200  a (0 C)  b 2.7 (A)
b  200
2.8 (D)
400  a(100)  200
a2 2.9 (C)
Then the equation is
0
S  2(0 C )  200 Ideal gas thermometer independent on material
of construction.
On this scale 5000 S corresponds to –
500  2( 0 C)  200 Hence, the correct option is (C).
C  150
0

Hence, the correct option is (C).

NOTES
3.1 Work
Work is said to be done by the system- if the
sole effect on things external to the system, can
be equated to raising of weights (weight may
not be actually raised, but the effect can be
equated to raising of weights).

3.2 Generalized equation for closed system

work:

Work transfer occurs only when it crosses

the boundary. Therefore, work transfer is
boundary phenomenon.
● Convention of work transfer: Force
Pressure 
Work done by the system is taken as Area
positive and work done on the system is
F  PA
taken as negative.
Work = Force  Displacement
Work  PA  dx
Work  PdV
This work is known as closed system work or
non-flow work or displacement work.
Basic Thermodynamics 12 Kulkarni’s Academy
● Work on P-V diagram W   PdV

V  constant
dV  0
W 0

Area  PdV
Work  PdV
Work = Area
Area under the curve when projected on volume Constant volume closed system work is equal
axis gives non flow or closed system work. to zero.
Conditions for applying the equation ● Special Case of Constant Volume Process
W  PdV
In this case, weights are lowered and hence
1. System must be a closed system. work is done on the system-therefore paddle
2. Work should and cross the boundary. wheel work is negative.
3. Process must be reversible process.

Wa ≠ Wb
 Though the end points are same for path a Though dV  0[PdV  0] -Work is not zero.
and b-work transfer is not same because
Because W  PdV is valid only for a reversible
area’s are different for paths a and b-
process, whereas paddle wheel work is
therefore work transfer is a path function, it
associated with irreversibilities.
is not a property it is inexact differential
(2) Constant Pressure / isobaric / isopiestic
( d W or W ) .
process:
3.3Closed system work transfer in various
Process
(1) Constant volume/Isochoric/Isometric process:
Ex.
(i) Fluid in a rigid container when heated or
cooled.
(ii) Piston cylinder arrangements with stops.
Kulkarni’s Academy 13 Energy Interactions (Heat & Work)
Free body diagram of piston C
P
V

Patm A  Wpiston  Pgas A

Wpiston
Pgas  Patm 
AC Equation for rect. Hyperbola
So, Pgas  C 1 1  PV
PV 2 2 C
V2 V2

W  PdV W  PdV
V1
V1

W  P [V2  V1 ]
V2
C
W  V dV
W  P [V final  Vinitial ] V1
V2
dV
W C
V1
V
V2
W  C ln
V1
V2
W  PV
1 1 ln
V1
V2
W  mRT1 ln
V1
(3) Constant temperature / isothermal process :
Ex. ● When an ideal gas undergoes isothermal
process, it is represented by a rectangular
hyperbola on P-V diagram.
(4) Adiabatic Process: A process in which
there is no heat transfer from the system or
to the system is an adiabatic process.
● For on adiabatic process, it can be derived as
PV   C where  is known as adiabatic
index and it is greater than 1.
Removing weight and simultaneously adding V2
heat for an ideal gas is an example of isothermal W  PdV
process i.e. in isothermal process though the V1


temperature is constant, there is heat transfer. Adiabatic process: PV  C
For Ideal gas (T = constant)
P  CV 
PV  mRT V2

PV  mRT  C W   CV  dV
PV  C V1
Basic Thermodynamics 14 Kulkarni’s Academy
C 3.3 Representation of various processes on
W V2 1  V1  1 
  1 P-V diagram

1 General equation is
W CV  

2 V2  CV1 V1 
  1 PV k  constant
2 2  PV
PV
W 1 1 Process K-value
  1
Constant pressure 0
1 1  PV
PV
W 2 2
(Valid for Closed Isothermal process 1
 1
Polytropic process n
system, Reversible process, Adiabatic
process, Ideal gas). Adiabatic process 

Note : Constant volume 

An adiabatic system need not be isolated

system, because in an isolated system there is no
(1) PC (2) T  const.
energy interaction (no heat transfer and no work PV k  C PV  mRT
transfer). Where as in an adiabatic system
though there is no heat interaction, there can be PV 0  C PV  C
work interaction, PC PV '  C
K 1
(5) Polytropic Process
A process in which pressure and volume (3) PV n  C (4) PV   C
follows the relationship PV  C is known PV k  C PV k  C
n

as a polytropic process, where n is known as

k n K 
polytropic index.
Generally, 1  n   (5) PV k  C
Ex. ( PV k )1/ k  C1/ k
(1) Gas in a balloon when heated
P1/ kV  C1/ k if k  
Volume = constant

(2) Piston-cylinder arrangement with spring

when heated.
● In polytropic process there is both heat
transfer and work transfer, whereas in
adiabatic process there is only work transfer.
1 1  PV
PV
Wpolytropic  2 2
(Valid for Closed
n 1
system, Reversible process, Polytropic
process)
Kulkarni’s Academy 15 Energy Interactions (Heat & Work)
Adiabatic slope
  1
Isothermal slope
Adiabatic slope > Isothermal slope

3.4 Relationship between slope of

isothermal and adiabatic curve on P-V
diagram 3.5 Ideal gas equations for various
processes:
Slope of Isothermal Curve on P-V diagram:
For an ideal gas (i) Constant Volume Process :
T = Constant
PV  mRT
PV  C
PdV  VdP  0
dP P

dV V
P V  constant
Isothermal slope on P-V diagram is 
V PV  mRT
Slope of adiabatic curve on P-V diagram: P T
P2 T2
PV   C 
P1 T1
P( V 1dV )  V  dP  0
(ii) Constant Pressure Process :
V
PdV  V  dP
V
dP P
 
dV V
P
Adiabatic slope on P-V diagram is  
V
P P = Constant
Adiabatic slope  
V PV  mRT
 P V T
Adiabatic slope     
 V V2 T2

Adiabatic slope   [Isothermal slope] V1 T1
Basic Thermodynamics 16 Kulkarni’s Academy
(iii)Isothermal process : (5) Polytropic process :
 
 
 PV n
 PV n

 n 1 
1 1 2 2
n 1 
TV 1 1  T V
2 2  Valid for an ideal gas
 n 1 
 T2  P2  n 
   
 T1  P1  
T  Constant undergoing polytropic process
PV  mRT n 1
n
PV  C T1  P1  n
P V 
  ; 1  2 
1 1  PV
PV 2 2
T2  P2  P2  V1 
(iv) Adiabatic process : n 1 n 1
T1  V2     m
PV   C    1   
T2  V1   2   v
 
1 1  PV
PV … (i) n 1
T1  1 
2 2

PV  mRT  
T2  2 
mRT
P Example 1
V
 mRT   A spherical balloon of 1 m diameter
 V  C contains a gas at 150 kPa the gas inside the
 V 
balloon is heated until the pressure reaches
C
TV 1  450 kPa during the process of heating
mR
pressure of a gas proportional to D 3 of the
TV 1  C
1 balloon find the work by the gas.
TV
1 1  T2V21
1/ 1 Sol. Assumption:
V1  T2 
  … (ii) 1. Given system can be treated as closed
V2  T1 
system.
From equation (i) and (ii), 2. The process can be treated as reversible
1/  1/ 1
 P2  T  process.
   2 
 P1   T1 
1
1
 P2  
T V 
   2  1 
 P1  T1  V2 
 
 
 PV 
 PV 

 1 
1 1 2 2
1 
TV 1 1  T V
2 2  Valid for an ideal gas
 1 
 T2  P2    P  D3
   
 T1  P1   P  kD3
undergoing adiabatic process
Kulkarni’s Academy 17 Energy Interactions (Heat & Work)
P1 P Sol.
3
 23
D1 D2
150 450
 3
13 D2
D2  1.442 m
P1 150
k   150
D13 13
W   PdV   kD3dV
3 Ax  V1  V1  2V1  V1  V1
4 D
V    0.05
3 2 x  0.2 m
0.25
D3
V
6

dV  [3D 2 dD]
6
D 2
dV  dD
2
D2
 2 P1 A  Patm A  W
W  kD
3
D dD
2 W
D1
P1  Patm   200
D2 A
k   D6 

2  6  D
1

150  
W [1.4426  16 ]
12
W  313.79 kJ
Note: +ve work means work done by the
system P2 A  Patm A  W  kx
Example 2
W kx
A piston cylinder assembly contains P2  Patm  
A A
0.05 m3 of a gas initially at 200 KPa, at this
150  0.2
state linear spring which has a spring P2  200   320 kPa
constant of 150 kN/m is touching the piston 0.25
but exerting no force on it. Heat is added to
the gas causing the piston to rise and to
compress the spring until the volume inside
the cylinder doubles if cross sectional area
of the piston is 0.25 m2 , find-
(1) Final pressure of gas in cylinder
(2) Work done by the gas
Basic Thermodynamics 18 Kulkarni’s Academy
Area of trapezium 1-2  constant pressure
1 Sum of parallel side)  2-3  constant volume
 
2 (difference between them)
1
  (320  200)  0.05
2
W  13 kJ
Example 3
A piston cylinder arrangement shown in
figure initially contains air at 150 kPa and
PV  mRT
4000C. The setup is allowed to cool to V2 T2

ambient temperature of 200C. V1 T1
(1) is the piston resting on stop in the final L T
state, _________ what is the final  2 2
L1 T1
pressure in the cylinder.
1 T
(2) what is the specific work done by air   2
2 673
during the process.
T2  336.5 K  63.50C
When the piston is about to touch stops the
temperature of the gas is 63.50C [state 2]
once it touches stops it further looses heat to
reach a final temperature of 200C. [state-3]

Sol. Let us assume there are no stops with this

assumption let us calculate the final height
of the gas if this final height is more than 1
m then it will not touch stops and if the
height is less than 1 m it will touch stops.
So, process is constant pressure
W  W12  W23
V T
V2 T2 W23  0 [constant volume]

V1 T1 W12  P (V2  V1 )
A  L2 T2 W12  PV2  PV1
 – 
A  L1 T1 W12  P2 V2  PV
1 1 {because ideal gas
L 293
 2   mRT2  mRT1
1  1 673
W12
L2  0.87 m  Specific work
m
L2  1 m
 R(T2  T1 )  0.287[63.5  400]
as L2  1 m the piston test on stop.
  96.5 kJ/kg
Kulkarni’s Academy 19 Energy Interactions (Heat & Work)
2-3 constant volume
PV  mRT
P2 T2

P3 T3
P2 336.5 150
  
P3 293 P3
150  293 P1  250 kPa
P3   130.6 kPa
336.5
V1  400 liter  400 103 m3
Final pressure is 130.6 kPa
150 130.6  19.4 kPa pressure is taken by P2  Patm  101.325 kPa
stop. 1
P
Example 4 V
A rigid tank of 400 liter volume is connected 1 1  PV
PV 2 2

to a large vertical cylinder B and is fitted a P1 101.325

leak proof piston of negligible mass.
Initially the piston is at the bottom of the
cylinder, friction between piston and
cylinder can be neglected the top surface of
the piston is open to atmosphere
[ Patm  101.325 kPa] tank A contains argon
gas at 250 kPa and 300C. The valve is
opened and argon gas enters the cylinder to
raise the piston during this process the
pressure and volume of argon are inversely
proportional finally the piston comes to rest,
treating Ar gas as a system. Find the
magnitude and direction of work transfer.
Sol. When the valve is opened high pressure Ar
gas pushes the piston up until inside and
outside pressures are same as the outside
atmospheric pressure is constant the final
pressure of Argon when it reaches
equilibrium will be atmospheric pressure.
V2  V1   400 103
P2 250
V2  0.987 m3
As the piston is mass less than the work
done by Argon is equal to work done in
displacing atmosphere air therefore
W  Patm (V2  V1 )
 101.325(0.986  0.4)
W  59.47 kJ
This work is done by the system that is
argon gas.
Example 5
A closed cylinder of 0.25 m diameter fitted
with a light friction less piston the piston is
retain in position by stops in the cylinder
wall and the volume on one side of the
piston contains air at a pressure of
750 kN/m2 the volume on the other side of
the piston is evacuated. Spring is mounted in
this evacuated space to give a force of 120 N
in this position the stops are removed and
the piston travel along the cylinder until it
comes to rest after a stroke of 1.2 m. The
spring force increases linearly to a final
volume of 5 kN. Calculate work done by
compressed air ON the piston.
Basic Thermodynamics 20 Kulkarni’s Academy
Sol. Example 6
An ideal gas is undergoing a process in
which T  V 2/5 . Calculate work done by
the gas from state 1 to state 2.
State-1
P1  104 kPa
V1  4 m3
As the piston is mass less work done in V2  2 m3
raising the piston is zero. When stops are
removed compressed air (system), Sol. TV 2/5  C
compresses spring therefore work done by
TV n1  C
air is equal to work done in compressing the
2
spring. n  1  1.4
5
F1 120
P1    2446.61 N/m 2 1.4
A1  P2  V1 
(0.25) 2  
4 P1  V2 
 2.45 kPa P2  104 (2)1.4  26390.158 kPa
F2 5 kN
P2    102 kPa 104  4  26390.158  2
A2  (0.25) 2 W  31950 kJ
4 0.4
Negative means work done on the system.
3.6 Heat
The energy interaction due to temperature
difference is known as heat interaction.

1
W  ( P1  P2 )(V2  V1 )
2
Q  t
1  
 (2.45  102)  (0.25)2 1.2 
2 4  Q  mt
V2  V1  A  L Q  mct
W  3.07 kJ Where c is proportionality constant and it is
 known as specific heat.
 (0.25)2 1.2
4 Unit of specific heat is kJ/kg 0 C or kJ/kg-K
Kulkarni’s Academy 21 Energy Interactions (Heat & Work)
● Physical meaning of specific heat: ● Convention of Heat Transfer:
It is the amount of heat required to raise the Heat supply to the system is taken as
temperature of unit mass of substance to unit positive and heat rejection from the system
degree temperature difference. is taken as negative.
Physically specific heat represents heat
absorbing capacity. Greater the specific
heat, greater is the heat absorbing capacity.
The specific heat of air is 1.005 kJ/kgK and
that of water is 4.187 kJ/kgK that is as the
specific heat of water is more it absorbs 3.7 First law of thermodynamics
more heat compare to air. (conservation of energy)

Statement:
For a closed system undergoing a cycle net heat
transfer [Q] is equal to net-work transfer
[W ]
Q  W
This equation is valid only for a reversible and
irreversible cycle, it not applicable for a process.
● Consequences of First law of
thermodynamics
QP  QV (1) Heat transfer is a path function:
(mcT ) P  (mcT )V
CP  CV
CP
 1
CV
 1
Specific heat at constant pressure (C P ) is
Q1a2  Q2b1  W1a2  W2b1
greater than specific heat at constant volume
Q1a2  Q2 c1  W1a2  W2 c1
(CV ) because C P includes internal energy and ______________________
external work whereas CV includes internal Q2b1  Q2c1  W2b1  W2c1
energy only.
● Specific heat of liquid and solids:
In case of solids and liquids C P and CV are
almost same because the expansion of solid
W2b1  W2c1
and liquids is negligible and hence work
transfer is zero. W2b1  W2 c1  0
𝐶𝑃 ≃ 𝐶𝑉 = 𝐶 Q2b1  Q2c1  0
CP  CV  Gas
Q2b1  Q2c1
Basic Thermodynamics 22
Though the end points are same for path ‘b’ and
‘c’ heat transfer is not same therefore heat
transfer is not a property it is a path function and
it is inexact differential.
● Important Points with respect to heat and
work
(a) Both are not properties.
(b) Both are inexact differentials.
(c) Both are path function.
(d) Both are boundary phenomenon.
(e) Both are energies in transit i.e. it appears
only during a process once the process is
over it loses their meaning.
Note : It is used to wrong word heat and work,
the correct terms are heat transfer and work
transfer.
(2) Energy is a property :
Q2b1  Q2c1  W2b1  W2c1
Q2b1  W2b1  Q2c1  W2c1
(Q  W )2b1  (Q  W )2c1
(Q  W ) is same for path b and c.
Though paths are different Q  W ) is same
for path ‘b’ and ‘c’. Therefore [Q  W ] must
be a property and this property is known as
energy.
(Q  W )2b1  (Q  W )2c1  dE
Kulkarni’s Academy
This is the First law of thermodynamic equation
for a closed system undergoing any process
when kinetic and potential energy changes are
neglected.
Internal Energy (U) :
All forms of energy associated with molecule is
known as internal energy. It is an extensive
property.
Specific Internal Energy (u) :
Internal energy per unit mass is known as
specific internal energy. It is an intensive
property and generally it is expressed in kJ/kg.
(3) Energy of an isolated system is always
constant
0  dE  0
dE  0
E2  E1  0
E2  E1  Constant

(Q  W )2b1  dE (4) Perpetual motion machine of first kind

Q  dE  W (PMM-1) is impossible:
This is the First law of thermodynamic equation
There can be no machine which produces work
for any (reversible or irreversible) process.
continuously without absorbing any heat. If
The equation Q  dE  PdV is valid for a
such a machine is developed then it would
closed system undergoing reversible process violate first law for a cycle.
only because W  PdV is applicable only for
a closed system undergoing reversible process.
Energy:
E  KE  PE  U
dE  d ( KE)  d ( PE)  dU
KE and PE changes are negligible
E  dU
Q  dE  W
Q  dU  W
Kulkarni’s Academy 23 Energy Interactions (Heat & Work)
3.8 Heat transfer for various process Ideal gas U  F (T )
(1) Constant Volume Process: T = constant, U = constant, dU  0
Q  dU  W Q  0  W
V  C, W  0 Q  W
Qv  dU When an ideal gas undergoes an isothermal
In a constant volume process, heat transfer is process heat transfer is equal to work transfer.
equal to change in internal energy. (4) Adiabatic process :
Q  0 i.e. there is no heat transfer in adiabatic
Enthalpy (H) : In thermodynamic the term
U  PV appears frequently and for convenience process.
this term is taken as enthalpy. Example 7
It is an extensive property. Generally, it is To show that CP  CV  R for an ideal gas.
expressed in kJ. Sol. H  U  PV
H  U  PV dH  dU  d (PV )
This equation H  U  PV is valid for any For ideal gas
process, any system and for any working fluid. 𝑑𝑈 = 𝑚𝐶𝑣 𝑑𝑇
(2) Constant Pressure Process : 𝑑𝐻 = 𝑚𝐶𝑃 𝑑𝑇
𝑃𝑉 = 𝑚𝑅𝑇
Q  dU  W
mCP dT  mCV dT  d (mRT )
Q  dU  PdV mCP dT  mCV dT  mRdT
Q  dU  d (PV ) CP  CV  R
QP  d (U  PV ) CP  CV  R

QP  dH H  U  PV CP

CV
Heat transfer in constant pressure closed system
CP  CV
process is equal to change in enthalpy.
CP  CV  R
Note : The equation dU  mCv dT is valid for
CV  CV  R
an ideal gas undergoing any process. The
R
equation dU  mCv dT is valid for real gases CV 
 1
only under constant volume condition.
R
CP 
The equation dH  mC p dT is valid for an ideal  1
gas undergoing any process. The equation For air
dH  mC p dT is valid for real gases only under CP  1.005 kJ/kgK
constant pressure condition. CV  0.718 kJ/kgK

(3) Isothermal process : R  0.287 kJ/kgK

Q  dU  W   1.4 (for air)
Basic Thermodynamics 24 Kulkarni’s Academy
(5) Polytropic process:  n    
Qpoly  m   Cv  dT
Q  dU  W  n  1  
Ideal gas  Polytropic process
n   
  C poly   Cv
 n  1 
PV  PV
dU  mCv dT W  1 1 2 2 n
n 1 C poly    Cv
 n 1 
PV  PV
Qpoly  mCv dT  1 1 2 2
n 1 For example:
mR(T2  T1 ) ( PV  PV ) 1 n  
Qpoly   11 2 2
 1 (n  1) n  1.2,   1.4
2 2  PV
PV PV  PV
Qpoly  1 1
 11 2 2  ve 
 1 n 1 C poly     ve  ve
 ve 
 1 1 
Qpoly  PV
1 1  PV
2 2     n
 (n  1) (   1)  Qpoly    (W ) poly
  1 
 (   1)  (n  1) 
Qpoly  PV
1 1  PV
2 2    1.4  1.2 
 (n  1)(   1)  Qpoly    (W ) poly
 1.4  1 
2 2   n
1 1  PV
PV
Qpoly 
(n  1)    1 
1
Qpoly  (W ) poly
2
  n
Qpoly    (W ) poly Wpoly  2  (Q) poly
  1 
Conditions: Let us-
1. Closed system Qpoly  30
2. Reversible process
Wpoly  2  30  60
3. Ideal gas
4. Polytropic process
Polytropic Specific Heat [C poly ]
   n   PV
1 1  PV
2 2
Qpoly     
  1   n 1 
   n   mRT1  mRT2 
Qpoly    
  1   n 1
For 1  n   C poly is negative i.e. during this
   n  mR
Qpoly   (T1  T2 ) process though heat is supplied there is a
  1  n 1 reduction in temperature. This is because
dT  T2  T1 compared to heat supplied the work transfer is

dT  T1  T2 more and this extra work transfer comes from
the internal energy of the system. As there is
  n  R
Qpoly    mCv (dT ) Cv  decrease in internal energy therefore there is a
 n 1    1
decrease in temperature.
Kulkarni’s Academy 25 Energy Interactions (Heat & Work)

Example 8 Example 9
To prove PV   C for adiabatic process. PV   C is valid for
Sol. Q  dU  W (A) Any adiabatic
(B) Irreversible adiabatic
Q  dU  PdV (C) Reversible adiabatic
Ideal gas undergoing adiabatic process (D) None of these
  Ans. (C)
dU  mCv dT Q  0 Sol. Equation PV   C is valid for an ideal gas
undergoing reversible adiabatic process
0  mCv dT  PdV only.
mCv dT   PdV … (i) Note:
1
(1) While deriving TV  T2V21 and
H  U  PV
1 1
1

dH  dU  PdV  VdP T2  P2  
  we have used PV   C ,
T1  P1 
dH  Q  VdP Q  dU  PdV
therefore all these three equations must be
Ideal gas undergoing adiabatic process used only when an ideal gas undergoes
  reversible adiabatic process.
dH  mC p dT Q  0 (2) Equation PV   C is valid for both open
and closed system.
mC p dT  0  VdP Example 10
A gas in confined to a cylinder by a spring-
mC p dT  VdP … (ii)
loaded frictionless piston so that the pressure
Equation (ii) is divided by equation (i) in the fluid is a linear function of volume i.e.
dP V P  a  bV . The internal energy of a gas is
 given by u  34  3.15PV where U is in kJ,
P dV
P in kPa and V in m 3 . If the gas changed
dV dP
  from initial state of
V P
P1  170 kPa, V1  0.03 m to a final state of
3

dP dV
 0 P2  400 kPa, V2  0.06 m3 . Find the
P V
magnitude and direction of heat and work
ln P   ln V  ln C transfer.
ln PV   ln C Sol.

PV   C
Valid for:
1. Ideal gas
2. Adiabatic process
3. Reversible process
Basic Thermodynamics 26 Kulkarni’s Academy
Work done = Area under trapezium
1
  (400  170) (0.06  0.03)
2
W  8.55 kJ
As work is positive therefore work is done by
the system
Q  dU  W
dU  U 2  U1
U 2  34  3.15 PV
2 2 Free expansion of an ideal gas :
U1  34  3.15 PV
1 1
U f  Ui
__________________________
dU  U 2  U1  3.15[ PV Ideal gas U  F (T )
2 2  PV
1 1]

dU  3.15[400  0.06  170  0.03] Tf  Ti

 59.53 kJ
Q  dU  W
 59.53  8.55  68.03 kJ
As heat is positive therefore heat is supply to the
system.
3.9 Free Expansion
The expansion of a gas against vacuum (zero
resistance) is known as free expansion. Though in free expansion of an ideal gas
Free expansion work = 0 Ti  Tf it does not mean the process is
For work transfer there should be external isothermal. For an isothermal process all point
resistance in free expansion as there is no should pass through same temperature but
external resistance therefore work transfer is during free expansion initially during expansion
zero. temperature decreases and finally when
Q  dU  W molecules coming contact with walls of the
0  dU  0 container due to friction heat is generated and
dU  0 temperature increases. Though Ti  Tf as the
U f  Ui  0 temperature is not constant throughout therefore
U f  Ui it is not an isothermal process.
In free expansion though work is equal to zero,
but PdV  0 . This is because W  PdV is valid
only for a closed System undergoing reversible
process but free expansion is an irreversible
process.
Free expansion for an ideal gas
U f  Ui
𝑻𝒇 = 𝑻𝒊
] Not for real gas
𝑯𝒇 = 𝑯𝒊
Kulkarni’s Academy 27 Energy Interactions (Heat & Work)
H  U  PV F  PA
For ideal gas Work = Force  Distance
U  F (T ) Flow work  P  dA  x
PV  mRT Flow work  PdV
H  F (T )  mRT Flow work PdV
  PV
H  (T ) . Mass dm
If ‘m’ mass enters control volume
Note: For an ideal gas internal energy and enthalpy
both are functions of temperature only. Total flow work  Pvm
Flow work  PV
̄)
3.10 Universal Gas Constant (𝑹 If the fluid enters at (1) then the entry flow work
is  PV
1 1 , if the fluid leaves at (2) then the exit
𝑚 Mass
No. of moles(𝑛) = = flow work is  PV
𝑀 Molecular mass or weight 2 2.

m 3.12 Steady Flow Energy Equation (SFEE)

n
M
A Flow is said to be steady flow when fluid
m  nM properties do not change with respect to time for
PV  mRT achieving steady flow condition mass entering
PV  nMRT the control volume must be equal the mass
MR  R (Universal gas constant) leaving the control volume. Similarly, energy
entering the control volume must be equal to
R
R energy leaving the control volume.
M
PV  nRT
PV  mRT
R  8.314 kJ/k-mol-K
R  8.314 J/mol.K
3.11 Flow Work
The work transfer causing the fluid element either
to enter or to leave the control volume is known as
flow work.

W  Wentry flow  WControl volume  WExit flow

W   PV
1 1  WCV  PV
2 2

Eentering  Eleaving

1
mC12  mgz1  U1  Q
2
1
 mC22  mgz2  U 2  W
2
Basic Thermodynamics 28 Kulkarni’s Academy
1
mC12  mgz1  U1  Q
2
1
 mC22  mgz2  U 2  PV
1 1  Wcv  PV
2 2
2
1
mC12  mgz1  U1  PV
1 1 Q
2 C12 C22
1 h1   gz1  q  h2   gz2  Wcv
 mC22  mgz2  U 2  PV 2 2  Wcv
2 2
2
C12 C2
1 h1   h2  2
H1  mC12  mgz1  Q 2 2
2
C1  C2
1
 H 2  mC22  mgz2  Wcv
2 C22
h1  h2 
2
C12 C22
h1   gz1  q  h2   gz2  Wcv (2) Turbine
2 2
Assumptions:
This equation is known as SFEE and this can
1. Steady flow
be applied for reversible or irreversible
2. P.E. changes are neglected
process. This equation is first law of
thermodynamics equation for open system 3. K.E. changes are neglected
under steady flow conditions. 4. Turbine is perfectly insulated
Examples of Steady flow devices
● Nozzle
● Diffuser
● Turbine
C12 C22
● Compressor h1   gz1  q  h2   gz2  Wcv
2 2
● Boiler
h1  h2  Wcv
● Throttling device
Wcv  h1  h2
● Condenser etc.
Wturbine  h1  h2
Applications of Steady Flow Energy
Equations: In turbine work is developed at the expanse of
enthalpy i.e. as the fluid flows to turbine
(1) Nozzle: Nozzle is a device which is used for
enthalpy decreases and this decrease in enthalpy
increasing velocity at the expense of
is converted into work.
pressure. Nozzles are used in jet engines
impulse turbines etc. (3) Compressor : Assumptions same as incase
of turbine.
Diffuser is a device which is used for increasing
Wturbine  h1  h2
pressure at the expender of velocity.
In nozzles and diffusers there is no work Wturbine  h2  h1
transfer i.e. Wcv  0 . Wcompressor  h2  h1
Kulkarni’s Academy 29 Energy Interactions (Heat & Work)
Example: Example 10
To derive W  VdP
Sol. Assumptions :
(1) Steady flow
(2) K.E. Changes neglected
(3) P.E. changes neglected
Note : In compressors enthalpy increases (4) Reversible process
because of work input.
(4) Throttling Device:
Examples:
1. Flow through a partially open valve,
2. A flow through a very small opening.
C12 C2
3. Flow through a porous plug. h1   gz1  q  h2  2  gz2  W
2 2
Characteristics of Throttling:
h1  q  h2  W
(1) No heat transfer (Generally the size of the
q  h2  h1  W
throttling device is so small and the time
q  dh  W
spend by the fluid in the device is very small
TdS  dh  W
and hence there is no time available for heat
TdS  dh  VdP
transfer therefore heat transfer is zero.) W  VdP
(2) No work transfer (though there is a 3.13 Unsteady Flow (Transient)
pressure drop in throttling, due to friction When fluid properties change with respect to
work is lost) time then the flow is unsteady.
Throttling occur in the direction of pressure Examples:
drop. Filling the tank
Emptying (discharging) the tank
 Let mi and me be the masses entering and
leaving the control volume.
Let m1 and m2 be masses in the control volume
under initial and final conditions.

(3) It is an irreversible process

(4) It is an isenthalpic process
C12 C22
h1   gz1  q  h2   gz2  Wcv
2 2 1-Control volume condition initially
2 2
C C 2-Control volume condition finally
h1  1
 h2  2

2 2 i - inlet condition
h1  h2 e - exit condition
Basic Thermodynamics 30 Kulkarni’s Academy
Example: Assumption 2
If hi and he do not change with respect to time
 dU  dmi dm
   hi  Q  he e  W
 dt cv dt dt
 dU 
(1) Conservation of mass    hi mi  Q  he me  W … (ii)
 dt cv
 dm  dmi dme
    Conventional Questions:
 dt cv dt dt
m  kg Example 12
m  kg/s An insulated storage tank is initially
 dm  evacuated and is connected to a supply pipe
   mi  me line carrying a fluid at a specific internal
 dt cv
energy ui and specific enthalpy hi the valve
mi  Mass entering per unit time
is opened and the fluid flow into the tank
me  Mass leaving per unit time
from supply pipe line and reaches the
II. Conservation of energy – pressure same as that of supply pipe line.
 dE  dEi dEe Show that the final specific internal energy
   
 dt CV dt dt of the fluid in a tank is equal to hi and
Ci2 C2 hence deduce if the fluid is an ideal gas the
hi   gzi  q  he  e  gze  W final temperature T2 of the gas in the tank is
2 2
Energy at inlet  times supply line temperature.
1  dm 
Ei  mi hi  mi ci2  mi gzi  Q
2 Sol.    mi  me
 dt cv
Energy at exit
As no mass is leaving in control volume i.e.
1 me  0
Ee  me he  mece2  me gze  W
2
 dE  d  1  d
   mi hi  mi ci  mi gzi  Q  
2

 dt cv dt  2  dt
 1 
 me he  2 me ce  me gze  W 
2

E  KE  PE  U
dE  d ( KE)  d ( PE)  dU
dE  dU
{if kinetic and potential energy changes are
neglected}
Assumption 1
Neglect KE and PE changes
 dU  d d  dm 
    mi hi  Q    me he  W     mi
 dt cv
… (i)
 dt cv dt dt
Kulkarni’s Academy 31 Energy Interactions (Heat & Work)

 dU   dm 
   hi mi  Q  he me  W    mi  me
 dt cv  dt cv
 dU   dm 
   hi mi … (ii)    mi … (i)
 dt cv  dt cv
Substitute (i) in (ii),
 dU   dm 
   hi  
 dt cv  dt cv
Integrating
(dU ) cv  hi (dm) cv
(U 2  U1 )  hi (m2  m1 )
m2U 2  m1U1  hi (m2  m1 )  dU 
   hi mi  Q  h2 me  W … (ii)
m2U 2  hi m2  dt cv
U 2  hi  dU   dm 
   hi  
If the fluid is an ideal gas  dt cv  dt cv
CvT2  C pTi (dU ) cv  hi (dm) cv
Cp (U 2  U1 )  hi (m2  m1 )
T2  Ti
Cv  m2U 2  mU 1 1  hi ( m2  m1 )

T2  Ti PV
m1  1
Example 13 RT1
An insulated pressure cylinder of volume V C
 m2  CV T2  m1CV T1  P Ti (m2  m1 )
contains air at a pressure P1 temperature T1 CV
it is to filled by supply air pipeline PV
m2  i
maintained at a pressure Pi temperature Ti RT2
show that the final temperature of air T2 in PV PV  PV PV 
the cylinder after it has been charged to a  i
 T2  1  T1   Ti  i  1 
RT2 RT1  RT2 RT1 
pressure Pi is given by
 PV PV 
Ti  PV  PV   Ti  i  1 
T2  i 1
 T2 T1 
P  T 
1  1  i  1 P P
Pi  T1   Pi  P1   Ti  i  1 
Sol.  T2 T1 
P T P
 Pi  P1   Ti  i  i 1
T2 T1
P T P
  Ti  i  Pi  P 1 i 1
T2 T1
Pi  P  T 
 Ti   Pi 1  1  i  1 
T2  Pi  T1 
Ti
T2 
 Pi  Ti  
1    1 
 P1  T 1 
Basic Thermodynamics 32 Kulkarni’s Academy
Example 14  dm 
   mi … (i)
A large vessel contains steam at a pressure  dt C .V .
of 20 bar and a temperature of 3500C Energy equation
[h  3137 kJ/kg ] this large vessel is
 dU 
connected to a steam turbine to a valve    hi mi  a  he me  WCV
 dt C .V .
followed by a small initially evacuated tank
with a volume of 0.8 m3 during emergency  dU 
   mi hi  WCV … (ii)
power requirement the valve is opened and  dt C .V .
tank fills with steam until the pressure is 20 Substitute (i) into (ii)
0
bar and temperature is 400 C  dU   dm 
(v  0.1512 m /kg, u  2945.2 kJ/kg] assume
3     hi  WCV
 dt C .V .  dt CV
the filling process takes place adiabatically {Integrating
and changes in kinetic and potential energy
 (dU )C .V  (dm)CV hi  WCV
are negligible. By drawing control volume
work developed by the turbine.  U 2  U1  (m2  m1 ) hi  WC .V .
Sol. Assumption : m2u2  m1u1  (m2  m1 ) hi  WC .V .
1. Turbine and small tank taken as control {C.V. is evacuated so m1  0
volume.
m2U 2  m2hi  WCV
2. K.E. and P.E. changes are neglected.
3. The enthalpy of the fluid entering the WCV  m2 hi  m2U 2
control volume does not vary with time. WCV  5.29(3137  2945.2)
4. The process is treated as adiabatic.
W  1014.6 kJ

 dm 
(1)    mi  me
 dt C .V .
As no mass laves CV
me  0
Kulkarni’s Academy 33 Energy Interactions (Heat & Work)

P 3.4 An ideal gas at pressure P0 and temperature

Practice Questions
T0 undergoes a reversible isothermal
3.1 A closed system undergoes a process from
one state to another state. Match Group I compression and attains a pressure P1 .The
and with Group Ii given below. characteristic gas constant is R. Net heat
Group I Group II transferred during this process is
P. Path function 1. Work (A) Zero
Q. Point function 2. Heat (B) RT0 ln ( P1 / P0 )
3. Specific enthalpy
(C)  RT0 ln ( P1 / P0 )
4. Specific entropy
(A) P-1, 4; Q-2, 3 (D) RT0 ln ( P1 / P0 ) / P0
(B) P-1, 2; Q-3, 4 3.5 A paddle wheel that is turned by a motor
(C) P-1, 3; Q-2, 4 stirs a liquid in a rigid insulated vessel.
(D) P-2, 4; Q-1, 3 Consider the liquid together with the
3.2 Match the items in Group I for their container as the system. Which one of the
correctness with the corresponding following statements is true?
appropriate terms given in Groups II and II
(A) Heat is transferred to the system
Group - I
P. Pressure . (B) Work is done on the system.
Q. Heat (C) Work is done by the system
Group – II (D) The process is reversible
1. Path Dependent quantity 3.6 An adiabatic system can exchange energy
2. Path independent quantity (A) Only in the form of work with its
Group III surroundings
X. Intensive property
(B) Either in the form of work or heat with
Y. Extensive property
its surroundings
(A) P, 1, X (B) P, 2, X
(C) Q, 1, X (D) Q, 2, Y (C) In the form of heat with its
3.3 The work done by one mole of a Vander surroundings
Waals fluid undergoing reversible (D) Both in the form of work and heat with
isothermal expansion from initial volume to its surroundings
final volume is 3.7 For the reversible adiabatic expansion of an
V  ideal gas from the initial conditions P1 , T1 . To
(A) RT ln  f 
 Vi  the final conditions P2 , T2 , which ONE of the

V b  following relations is valid? (  c p / cv )

(B) RT ln  f 
 Vi  b  

 P  T   P   T  1
 Vf  b   1 1  (A)  1    2  (B)  1    1 
(C) RT ln    a     P2   T1   P2   T2 
 i
V  b   V f Vi  1
 P  T   P  T  
 Vf  b   1 1  (C)  1    1  (D)  1    1 
(D) RT ln    a     P2   T2   P2   T2 
 Vi  b   V f Vi 
Basic Thermodynamics 34 Kulkarni’s Academy
3.8 A system is capable of exchanging energy (A) Q  0 W  0 (B) Q  0; W  0
with its surroundings in the form of n (C) Q  0; W  0 (D) Q  0; W  0
reversible work modes. The number of 3.11 Match Group I with Group II
independent variables that completely Group I
specify that state of the system is P. Work done
(A) n  2 (B) n  1 Q. Thermal equilibrium
(C) n (D) n  1 R. Internal energy
3.9 On a P-V diagram of an ideal gas, suppose a S. No work and heat
reversible adiabatic line intersects a
Group II
reversible isothermal line at point A. Then at
point A, the slope of the reversible adiabatic (1) Point function (2) Path function
 P  (3) Isolated system
line   and the slope of the reversible (4) Equality of temperature interaction
 V  S
(A) P – 2, Q – 4, R – 1, S - 3
 P 
isothermal line   are related as (B) P – 2, Q – 3, R – 4, S – 2
 V T
(C) P – 4, Q – 2, R –3, S – 1
 P   P  (D) P – 3, Q – 1, R – 2, S – 4
(A)    
 V  S  V T 3.12 A frictionless piston – cylinder device

 P   P   contains a gas initially at 0.8 MPa and 0.015
(B)      
 V  S  V T  m 3 . It expands quasi – statically at constant
 P   P  temperature to a final volume of 0.030 m3 .
(C)     
 V  S  V T The work output (in kJ) during this process
 P  1  P  will be
(D)      (A) 8.32 (B) 12.00
 V  S   V T
(C) 554.67 (D) 8320.00
C
Where,   P 3.13 An electric heater is put insider an insulated
CV
chamber containing a gas. Considering the
3.10 A mixture of ice and water is contained in a system boundaries A and B as Shown in the
piston – cylinder arrangement as shown in figure, we have
figure. Flame is applied to the base of the
cylinder and the piston is allowed to move
as the ice melts. The heat Q and the work W
for the system (ice + water) are:

(A) Heat transfer across A and B

(B) Heat transfer across A, work transfer
across B
(C) Work transfer across A, work transfer
across B
(D) Work transfer across A, heat transfer
across B
Kulkarni’s Academy 35 Energy Interactions (Heat & Work)
3.14 A person starts a 60 W table fan in a (A) In both (a) and (b) net workdone is + 12
insulated room of volume 86.4 m3. The units
person expects to cool the room from 320C (B) In (b) net workdone is more since in (a)
(pressure = 100 kPa) and allows the fan to no work is produced by the constant
rotate for 4 hours. volume process
If the specific heat at constant volume of the (C) Magnitudes of network produced in
room air is 0.718 kJ/kg K and characteristic both (a) and (b) are 12 units but their
gas constant is 0.287 kJ/kg K , after 4 hours, signs are opposite
the person will find that the room is (D) Magnitudes of network produced in
(A) Hotter by approximately 120C both (a) and (b) are different
(B) Cooler by approximately 100C
3.18 A ideal gas (  1.67) at a pressure of 2 bar
(C) At the same temperature
expands to twice its volume quasi- statically
(D) Hotter by approximately 80C
by a polytropic process pV n  constant.
3.15 Air is compressed via a quasi – static
Maximum work (among the four options
process in a piston cylinder assembly. The
given) is done by the gas when
initial temperature and pressure of the air are
270C and 0.1 MPa., respectively and it (A) n  1.67 (B) n  1
occupies a volume of 1103 m3 . The (C) n  1.2 (D) n  1.3
compression process follows the law 3.19 The net work output for the cycle 1-2-3-4-5-
pv1.3  cons tan t and the final pressure is 2 6-1 shown in figure is
MPa. The work done on air during the
compression in J, is
(A) 1106 (B) 431.6
(C) 332.0 (D) 99.6
3.16 In respect of a closed system, when an ideal
gas undergoes a reversible isothermal
process, the
(A) Heat transfer is zero
(B) Change in internal energy is equal to
work transfer
(A) 200kJ (B) 1200kJ
(C) Work transfer is zero
(D) Heat transfer is equal to work transfer (C) 0kJ (D) 1000kJ
3.17 Consider the cycles given below and state 3.20 Air enters an adiabatic compressor at 300K
which one of the following statements is
.The exit temperature for a pressure ratio of
true
3, assuming air to be an ideal gas
(  C p / Cv  7 / 5) and the process to be
reversible, is
(A) 300(32/7 ) (B) 300 (33/5 )
(C) 300(33/7 ) (D) 300(35/7 )
Basic Thermodynamics 36 Kulkarni’s Academy
3.21 Match items from groups I,II, III IV and V 3.24 Specific heat at constant pressure (C p ) of
Group I Group II Group III Group IV Group helium is 5.19kJ/kg.K and its molecular
V
weight is 4kg/Kmol . The specific heat at
When added Differential Function
constant volume of helium, in kJ/kg.K is
Phenomenon to the system, is
E Heat G Positive I Exact K Path M (A) 1.11 (B) 2.11
Transient
(C) 3.11 (D) 4.11
F Work H Negative J Inexact L Point N
Boundary 3.25 An ideal gas expands isothermally from a
(A) F-G-J-K-M, E-G-I-K-N volume V1 to V2 and then compressed
(B) E-G-I-K-M, F-H-I-K-N adiabatically to the original volume V1 .
(C) F-H-J-L-N, E-H-I-L-M Initial pressure is P1 and final pressure is P3 .
(D) E-G-J-K-N, F-H-J-K-M The total work done is W. Then
3.22 One kilogram of a perfect as at 150 C and
(A) P3  P1;W  0 (B) P3  P1;W  0
100kPa is heated to 450 C by (i) a constant
pressure process and (ii) a constant volume (C) P3  P1;W  0 (D) P3  P1;W  0
p of the gas  1.042kJ/kg.K and 3.26 A cyclic process ABC is shown on a V-T
P  0.2968kJ/kg.K . Heat added in the diagram. The same cycle on P-v diagram
constant pressure ( Q p ) and constant volume will be represented as
( Qv ) pressure are
(A) QP  31.26 kJ, Qv  22.35kJ
(B) QP  22.35kJ, Qv  31.26 kJ
(C) QP  31.26 kJ, Qv  31.26 kJ
(D) QP  22.35kJ, Qv  0 kJ
3.23 Match List I with List II and select the
correct answer
List I
P. Work done in a polytropic process.
Q. Work done in steady flow process zero
R. Heat transfer in a reversible adiabatic
(A)
process
S. Work done in an isentropic process
List II
1.   vdp 2. Zero

1 1  p2V2
pV p1V1  p2V2
3. 4.
 1 n 1
(A) P-4, Q-1, R-3, S-2
(B)
(B) P-1, Q-4, R-2, S-3
(C) P-4, Q-1, R-2, S-3
(D) P-1, Q-2, R-3, S-4
Kulkarni’s Academy 37 Energy Interactions (Heat & Work)
3.30 Match List I (Process) with List II (Index n
in) and select the correct answer.
List I
P. Adiabatic
(C) Q. Isothermal
R. Constant pressure
S. Constant volume
(A) P – 2, Q – 3, R – 5, S – 4
(B) P – 2, Q – 3, R – 5, S – 1
(C) P – 3, Q – 2, R – 1, S – 5
(D) P – 2, Q – 5, R – 1, S – 3
(D)
3.31 The contents of a well – insulated tank are
heated by a resistor of 23 ohm in which 10
A current is flowing. Consider the tank
3.27 If  Pdv and   Vdp for thermodynamic along with its contents as a thermodynamic
system of an ideal gas on valuation give the system. The work done by the system and
same quantity during a process, then the heat transfer to the system is positive. The
process undergone by the system is rates of heat (Q), work (W) and change in
(A) Isenthalpic (B) Isentropic internal energy during the process in kW are
(C) Isobaric (D) Isothermal (A) Q  0,W  2.3, U  2.3
3.28 A battery is used to light a bulb, run a fan (B) Q  2.3,W  0, U  2.3
and heat an electric iron in case of a power (C) Q  2.3,W  0, U  2.3
failure. If each of the as above system has
(D) Q  0,W  2.3, U  2.3
100 W rating and is run for 15 minutes, what
are the work done (W) and heat transferred 3.32 Assertion (A) : C p for a gas is always greater
(Q) by the battery? than Cv
(A) W  90kJand Q  90 kJ Reason (R): C p includes work of expansion
(B) W  180kJand Q  0 in addition to storage of internal energy
(C) W  270kJand Q  0 (A) Both A and R are individually true and
(D) W  90kJand Q  180 kJ R is the correct explanation of A
(B) Both A and R are individually true but
 P
3.29 A gas expands from P1 To P2  P2 1  ; if the R is not correct explanation of A
 10 
(C) A is true but R is False
process of expansion is isothermal, the
(D) A is false but R is true
volume at the end of expansion is 0.55 m3 if
3.33 Assertion (A): Though heat is added during
the process of expansion is adiabatic, the
a polytrophic expansion process for which
volume at the end of expansion will be close
  n  1, the temperature of the gas
to
decreases during the process
(A) 0.45 m3 (B) 0.55 m3
Reason (R): The work done by the system
(C) 0.65 m3 (D) 0.75 m 3 exceeds the heat added to the system
Basic Thermodynamics 38 Kulkarni’s Academy
(A) Both A and R are individually true and 3.37 The net work interaction for the cycle in kJ
R is the correct explanation of A is
(B) Both A and R are individually true but (A) 126 (B) 194
R is not correct explanation of A (C) 486 (D) –486
(C) A is true but R is False
Common data for Questions 38 and 39
(D) A is false but R is true
A certain balloon maintains an internal gas
Common data for Questions 34 and 35
pressure of P0  100 kPa until the volume
5
An ideal with molar heat capacity C p R reaches V0  20m3 . Beyond a volume of
2
(where R = 8.314 J/mol. K) is compressed 20 m3 , the internal pressure varies as
adiabatically from 1 bar and 300 k to P  P0  2(V  V0 )2 , where P is in kPa and V
pressure P2 in a closed system. The final is in m 3 . Initially, the balloon contains
temperature after compression is 50% helium gas at 200 C , 100 kPa, with a 15 m 3
3.34 The work required for compression (in volume. The balloon is then heated until the
kJ/mol) is volume becomes 25 m3 and the pressure is
(A) 3.74 (B) 6.24 150 kPa. Assume ideal gas behavior for
(C) 7.48 (D) 12.48 helium.
3.35 The final pressure P2 (in bar) is
3.38 The final temperature of the balloon in
3/4 5/4
(A) 2 (B) 2 degrees Kelvin is
3/2
(C) 2 (D) 25/2 (A) 656 (B) 842
Common data for Questions 36 and 37 (C) 912 (D) 733
A system undergoes three quasi-static 3.39 The work done by the balloon for the entire
processes sequentially as indicated in the process in kJ is
figure. 1-2 is an isobaric process, 2-3 is a (A) 1256 (B) 1414
polytropic process with (C) 1083 (D) 1512
Common data for Questions 40 and 41
An insulated vertical cylinder encloses 0.1
kg of argon (Ar) with the help of a
frictionless non-conducting piston as shown
in the figure. The mass of the piston is 5 kg
and it initially rests on the bottom of the
cylinder. The rests on the bottom of the
n = 1.4 and 3-1 is a process in which pV = cylinder. The cylinder is connected to a
constant. The following data may be made nitrogen ( N 2 ) tank at 100 bar through a
use of p1  p2  4bar, p3  1bar andV1  1m3 pipeline fitted with a valve. The valve is
3
3.36 Volume of the system at state point 2 in m opened and nitrogen is slowly admitted into
is the cylinder. During this operation , the
(A) 1.741 (B) 6.96 piston is lifted through a height of 10 cm by
(C) 2.173 (D) 1.486 the nitrogen gas.
Kulkarni’s Academy 39 Energy Interactions (Heat & Work)
The initial pressure and temperature of Contains air (R = 287 J/kg-K, and
argon gas are 100 kPa and 300 K Cv  718 J/kg-K ) of mass 4 kg Both piston
respectively. The final temperature of argon and paddle wheel can be considered as
is 320 K. Fir argon C p  520J/kgK and insulated and massless. Temperature and
Cv  312 J/kgK pressure of air inside the cylinder are 300 K
and kPa respectively. Ambient pressure is
100 kPa.
3.42 If the piston is locked in the fixed position
and the paddle wheel delivers 75kJ of work
final air temperature is
(A) 300 K (B) 318.7 K
(C) 320.6 K (D) 326.1 K
3.43 If the piston is free to slide without any
friction when the paddle wheel delivers 75
kJ of work, final temperature of air in the
cylinder is
(A) 305.2 K (B) 309.3 K
3.40 The work done by argon in kJ during the (C) 312.6 K (D) 318.7 K
process is
(A) 10 (B) 1.041
(C) –0.6208 (D) –1.041
3.41 The work done by nitrogen in kJ during the
process is
(A) 1.046 (B) 0.626
(C) –1.046 (D) –10

Common data for Questions 42 and 43

An insulated piston-cylinder assembly
having a paddle wheel, as shown in the
adjacent figure,
Basic Thermodynamics 40 Kulkarni’s Academy
V
A Answer Key  1
F

W  RT  ln(V  b) V  a  
VF
i
 V Vi
3.1 B 3.2 B 3.3 D
V  b   1 1
3.4 C 3.5 B 3.6 A W  RT  F a  
3.7 B 3.8 D 3.9 C  Vi  b  VF Vi 
3.10 C 3.11 A 3.12 A Hence, the correct options is (D).

3.13 D 3.14 A 3.15 C 3.4 (C)

3.16 D 3.17 C 3.18 B When ideal gas undergoing isothermal
3.19 C 3.20 A 3.21 D process.
3.22 A 3.23 C 3.24 C P1
Q  W   RT0 ln
3.25 C 3.26 D 3.27 D P0
3.28 C 3.29 A 3.30 B Hence, the correct options is (C).
3.31 A 3.32 A 3.33 A 3.5 (B)
3.34 C 3.35 D 3.36 C
3.6 (A)
3.37 A 3.38 D 3.39 C
3.40 C 3.41 B 3.42 D 3.7 (B)
3.43 D 3.8 (D)
Case: 1
E Explanation

3.1 (B)

3.2 (B)

3.3 (D) Fig. (i)

n 1
 a 
 P  [V  b]  RT
V 2  Means only one work mode : Raising piston
Variable required  P, dV  2
a RT
P 2  Case: 2
V (V  b)

RT a
P  2
(V  b) V
VF
W   PdV
Vi

VF  RT a 
   2  dV Fig.(ii)
Vi
V b V 
Work mode (n  2) 
Kulkarni’s Academy 41 Energy Interactions (Heat & Work)
1. Raising piston. 3.13 (D)
2. Compress the spring.
3.14 (A)
Variable required  P, dV , Spring constant
(K )  3
From above analysis we can conclude that if
number of reversible work modes is n, then
number of independent variables that
completely specify the state of the system is
n  1.
Hence, the correct options is (D).
3.9 (C)
Given :
3.10 (C)
V  86.4 m3
ti  320C

P  100 kPa
t  4 hours
W  60 kJ/s  4  3600  864 kJ
(Work done on the system)
From FLOT :

As heat is supplied to the system. [Q  0] Q  dU  W

Ice melt  Volume is decreasing (piston W  dU
goes down)
864  mCV dT
So, work done on the system (W  0).
864
Hence, the correct options is (C).  dT 
mCV
3.11 (A)
864
dT  {PV  mRT
3.12 (A)  PV 
   CV
 RT 
V2
W  PV
1 1 ln
V1 864
dT   0.718
 100  86.4 
 0.030 
 8000  0.015  ln     CV
  0.287  305 
 0.015 
W  8.317 kJ dT  12.10C or 12.1 K
Hence, the correct options is (A). Hence, the correct options is (A).
Basic Thermodynamics 42 Kulkarni’s Academy
3.15 (C) 3.18 (B)

PV
1 1
1.3
 PV 1.3
2 2

1
 P 1.3 V
  1  2 V2  2V1
 P2  V1
• Area under the curve when projected on
 V2  9.98 105 m3
volume axis gives non-flow or closed
1 1  PV
PV system work.
W 2 2
n 1
• In isothermal process maximum work is
100 103  2000  9.98 105
 done by the gas.
1.3  1
W  0.332 kJ or  332 J 3.19 (C)
Note: Negative sign indicates compression
Net-work  Area enclosed the cycle on P-V
work or work done on the system.
diagram.
Hence, the correct options is (C).
1 1
3.16 (D)   (100 1)   (100 1)  0 kJ
2 2
In isothermal process
Hence, the correct options is (C).
Q  W
Hence, the correct options is (D). 3.20 (A)

3.17 (C) 1

T2  P2  

Cycle-(a)  
T1  P1 
W  Positive (because clockwise in nature)
1 T2  300(3)2/7
W   3  8  12 units
2 Hence, the correct options is (A).
Cycle-(b)
W Negative (because cycle 3.21 (D)
counterclockwise in nature)
E-G-J-K-N
1
W   4  6  12 units F-H-J-K-M
2
Hence, the correct options is (C). Hence, the correct options is (D).
Kulkarni’s Academy 43 Energy Interactions (Heat & Work)

3.22 (A) P3  P1

m  1 kg In adiabatic process compression work is

more because area under the curve represent
T1  150 C  288 K work transfer. Whereas in isothermal
P1  100 kPa process expansion work is less. So, Net-
work is negative (W<0).
T1  450C  318 K
Hence, the correct options is (C).
CP  1.042 kJ/kg-K
3.26 (D)
CV  CP  R  1.042  0.2968
 0.7452 kJ/kg-K
QP  dH  mCP dT
 11.042  30  31.26 kJ
QV  dU  mCV dT
 11.7452  30  22.35 kJ
Hence, the correct options is (A).
3.23 (C)
PV  mRT
3.24 (C)  mR 
V  T
CP  5.19 kJ/kgK  P 
Compare above equation with line equation
M  4 kg/K-mol
y = mx + C
R 8.314
R   2.0785 kJ/kg K mR
M 4  Slope – Constant  P  Constant
P
CP  CV  R
AB  P  C
CV  CP  R  5.19  2.0785 BC  V  C
 3.11 kJ/kgK CA  T  C
Hence, the correct options is (C).
3.25 (C)

In BC process volume is constant.

PV  mRT
 P T 
Hence, the correct options is (D).
Basic Thermodynamics 44 Kulkarni’s Academy
3.27 (D) 3.29 (A)

Isothermal process

PV  C V2 a  0.55

PdV  VdP  0 3.30 (B)

PdV  VdP 3.31 (A)

R  23 Ω
 PdV

   VdP

Closed System
Work
Open System
Work I  10 A

Note: When an ideal gas undergoes

isothermal process open system and closed
system works are same because isothermal
process is represented by rectangular
hyperbola which is symmetric about x and y-
axis.
Q  0 {In isolated system heat transfer is
Hence, the correct options is (D). zero.

3.28 (C) W  I 2R
W  2300 W
W  2.3 kW
Negative sign indicates work done on the
system.
Q  dU  W
W  3100  300 W dU  W
dU  2.3 kW
J
W  300 15  60
s Hence, the correct options is (A).

W  270 kJ 3.32 (A)

Hence, the correct options is (C). 3.33 (A)

Kulkarni’s Academy 45 Energy Interactions (Heat & Work)
5
3.34 (C) 3
1 2
600  P2  5
  3
1 1  PV
3
PV 300  1  5
Work (W )  2 2
 1 3
nRT1  nRT2 P2  (2)5/ 2
W
 1 Hence, the correct options is (D).

 W
nR
(T1  T2 ) 3.36 (D)
 1
Given data :
1 8.314 P1  P2  4 bar
 (300  600)
5
1 P3  1 bar
3
W  3.74 kJ/mol V1  1 m3
Work required for compression Process 3-1 ( PV  C)
3.74 3 3  PV
PV
Wcomp.   7.48 kJ/mol 4 4

0.5 1 V3  4  1
Hence, the correct options is (C).
V3  4 m3
3.35 (D) Process 2-3 ( PV 1.4  C )
5
CP  R PV 1.4
2 2  PV
3 3
1.4

2
 4 V21.4  1 (4)1.4
R  8.314 kJ/k-mol K
 V2  1.4859 m3
P1  1 bar T1  300 K
Hence, the correct options is (D).
P2  ? T2  600 K
3.37 (A)
mech  50% WNet  W12  W23  W31
1
T2  P2  
  2 2  PV
PV V1
T1  P1   P(V2  V1 )  3 3
 PV
3 3 ln
 1 V3
CP  CV  R 400 1.4859  100  4
 400(1.4859  1) 
5R 1.4  1
 CV  R 1
2  100  4  ln  
3R 4
CV 
2  194.36  485.9  554.51
CP 5 WNet  125.74 126 kJ

CV 3 Hence, the correct options is (A).
Basic Thermodynamics 46 Kulkarni’s Academy
3.38 (D) 3.40 (C)

As Argon cylinder is insulated and the

piston is non-conducting. Ar gas undergoes
adiabatic process.

Mass is same in both case

PV
From ideal gas equation M 
RT
PV PV
1 1
 2 2
RT1 RT2

T2  732.5  733 K

Hence, the correct options is (D).

CP  520 J/kgK
3.39 (C)
CV  312 J/kgK

1 1  PV
PV mR (T1  T2 )
Warg on  2 2

 1  1
0.1 0.208(300  320)

1.667  1

Warg on  0.6208 kJ

Hence, the correct options is (C).

W  W12  W23
3.41 (B)
W12  P (V2  V1 )

 100(20 15) WN2  Wraising piston  Wcompressing Ar

W12  500 kJ
mgh
  0.6208
2 1000
100(25  20)  (25  20)3  (20  20)3 
3
5  9.81 0.1
 500  83.33   0.6208
1000
W23  583.33 kJ
WN2  0.626 kJ
W  500  583.33  1083.33 kJ
Hence, the correct options is (C). Hence, the correct options is (B).
Kulkarni’s Academy 47 Energy Interactions (Heat & Work)

3.42 (D) 3.43 (D)

42 and 43 solution Common data 75  H 2  H1
Concept : If piston is free to move:
75  mCP (dT )
75  4 1.005  (T2  300)
T2  318.7 K
Hence, the correct options is (D).

Q  dU  W
W  W paddle  W piston


W  Wpaddle  P (V2  V1 )
P1  P2  P
Q  0 (Insulated)
0  U 2  U1  Wpaddle  PV
2 2  PV
1 1

0  (U 2  PV
2 2 )  (U1  PV
1 1 )  Wpaddle

P1  P2  P
Wpaddle  H 2  H1
If piston is fixed

Q  dU  W
0  U 2  U1  Wpaddle  Wpiston
Wpaddle  U 2  U1
75  U 2  U1
75  mCV (T2  T1 )
75  4  0.718(T2  300)
T2  326.11 K
Hence, the correct options is (D).
NOTES
4.1 Need of Slot 4.3 Statements of Second Law of
Thermodynamics:
First law of thermodynamics simply says that
(1) Kelvin-Plank Statement: (Valid only for a
energy is conserved, it does not give any
cycle)
direction for a particular process to know
It is impossible to develop device operating
whether the process is possible or not i.e. to know
on a cycle which produces work continuously
the direction SLOT must be applied if the
while exchanging heat with a single
direction is known then first law is must be
reservoir.
applied and hence second law is known as
directional law.
It is found from experiment complete conversion
of law grade energy (heat) into high grade energy
(work) is impossible in a cycle.

Note : The complete conversion of heat into

work may be possible in a process i.e., when an
ideal gas undergoes isothermal process heat Output

transfer and work transfer are same i.e. in such a Input
process complete heat is converted into work. Useful work (W)
th 
Work is known as organized form of energy or Heat input (Q)
high grade energy, whereas heat is known as W Q
PMM II    1 or 100%
disorganized form of energy or low grade energy. Q Q
Note : The efficiency of PMM-II is 100 % as
4.2 Thermal Energy Reservoirs [TER]
PMM-II is impossible, therefore 100 %
1. Source: It is a reservoir which is capable of efficiency of an engine is impossible according
supplying heat without any temperature to second law of thermodynamics.
change.
Heat Engine: Heat engine is a device [operating
2. Sink: It is a reservoir which absorbs heat
on a cycle] which converts part of heat into work
without undergoing any temperature change.
and rejects remaining to sink or surroundings.
Note : Thermal energy reservoir (source and Heat engine is a power producing or work
sink) are closed system with only heat transfer. developing device.
Basic Thermodynamics 49 Kulkarni’s Academy

W
th 
Q1 Desired Effect
COP 
Q1  W  Q2 Energy Input

W  Q1  Q2 or W  QS  QR (COP) R 
Q2
W
Q1  Q2 Q
th   1 2
Q1 Q1 W  Q2  Q1
QR
th  1  W  Q1  Q2
QS
(Valid for both Reversible and irreversible cycles) Q2
(COP) R 
(2) Clausius Statement: Q1  Q2
It is impossible to develop a device operating (Valid for both reversible and irreversible cycles)
on a cycle and which transfers heat from
lower temperature to higher temperature 4.5 Heat Pump
without any external input. Heat Pump: Heat pump is a device which
maintains higher temperature compare to
surroundings as higher temperature is to maintain
continuously heat pump operates on a cycle.

4.4 Refrigerator
Refrigerator : It is a device which maintain
lower temperature compare to surroundings.
As lower temperatures are maintain continuously
refrigerant or should operate on a cycle.
Kulkarni’s Academy 50 Second Law of Thermodynamics
Desired effect (2) Violation of Kelvin-Plank Statement
(COP) HP 
Energy input

Q1
(COP) HP 
W

W  Q1  Q2

Q1
(COP) HP  From both cases we can conclude that the two
Q1  Q2
statements are parallel statements and both are
(Valid for both reversible and irreversible cycles) known as statements of Second Law of
Thermodynamics.
Note : Heat engine, refrigerator and heat pump 1 1
HE  
operate on a cycle. (COP) HP 1  (COP) R

Relationship between COP of a heat pump Note : A process which satisfies first law of
and COP of a refrigerator operating between thermodynamics need not be practically possible.
same temperature limits:
4.6 Carnot Cycle (Reversible Cycle)
Q1
(COP) HP  A cycle is said to be a reversible cycle when all
Q1  Q2 process in a cycle are reversible.
1-2– Reversible isothermal heat addition
Q2
(COP) R  (expansion)
Q1  Q2
2-3 – Reversible adiabatic expansion
Q1 Q2 3-4– Reversible isothermal heat rejection
(COP) HP  (COP) R  
Q1  Q2 Q1  Q2 (compression)
4-1 – Reversible adiabatic compression
(COP) HP  1  (COP) R

Equivalence of Kelvin Plank and Clausius

Statement:

(1) Violation of Clausius Statement:

Carnot cycle consists of two isothermal

Similarly, it can be proved that violation of
kelvin-plank statement leads to violation of
Clausius statement.
processes and two adiabatic processes.
Isothermal process is a slow process and
adiabatic process is a fast process and hence these
two combinations are difficult to achiever in
practice.
Basic Thermodynamics
Moreover as each process is a reversible process
and as reversible process is a Quasi-static
process- it should occur slowly therefore the
complete cycle runs very slowly. Because of
these results Carnot cycle is not a practical cycle
but this cycle is used for comparing other
practical cycles.
Carnot’s Theorem:
(1) For different engines operating between
same temperature limits, no engine can
have for efficiency greater than Carnot or
reversible cycle efficiency.
51 Kulkarni’s Academy
This is the violation of K-P statement hence our
assumption is wrong, therefore irreversible cycle
efficiency can never be greater than reversible
cycle efficiency- operating between same
temperature limits.
Important point’s w.r.t reversible cycle
(1) All reversible engines operating between
same temperature limit have same efficiency.
(2) Efficiency of a reversible cycle is
independent of working fluid.
(3) Reversible cycle efficiency depends only on
temperature limits.

4.7 Thermodynamic Temperature Scale

Let us assume that the efficiency or irreversible

engine ( E1 ) is greater than the reversible engine
( E2 ) .

1  2

W1 W2

Q1 Q1

W1  W2

As E2 is a reversible engine let us reverse the

engine.

Q2
1  F1 (T1 , T2 )
Q1

Q2
 1  F1 (T1 , T2 )
Q1
Q1 1

Q2 1  F1 (T1 , T2 )
Kulkarni’s Academy 52 Second Law of Thermodynamics
Q1 4.7 Efficiency of a Reversible Engine
 1 (T1 , T2 )
Q2

Similarly,

Q2 Q
 2 (T2 , T3 ) and 1  3 (T1 , T3 )
Q3 Q3

Q2
  1 - For any cycle
Q1
Q1 T1
If reversible 
Q2 T2
T2
rev  1 
T1
Reversible engine has maximum efficiency.
Q
1  1  R COP of a reversible refrigerator:
QS

Q2
1  1 
Q1

E1 is a reversible engine

1  F1 (T1 , T2 )

Q1
And,  3 (T1 , T3 ) Q2
Q3 (COP) R 
Q1  Q2
Q1 Q1 / Q3 If refrigerator is reversible

Q2 Q2 / Q3
Q1 T1

Q1 3 (T1 , T3 ) Q2 T2

Q2 2 (T2 , T3 ) Q1 Q2
 K
T1 T2
Q1 (T1 )

Q2 (T2 ) Q1  kT1 and Q2  kT2
kT1
Q1 T1
 (COPrev ) R 
Q2 T2 kT1  kT2
T1 TL
This equation is valid only for a reversible (COPrev ) R  
T1  T2 TH  TL
cycle, here temperatures are in kelvin.
Basic Thermodynamics 53 Kulkarni’s Academy
TH Case 2 : Irreversible cycle :
Note : COP of a reversible heat pump 
TH  TL

 / COP  / COP
Device Reversible Irreversible/
reversible
Engine 1-TL /TH QR
1
QS
Refrigerator TL Q2
TH  TL Q1  Q2
Q1 Q2
Heat pump TH Q1 For reversible 
T1 T2
TH  TL Q1  Q2
rev  irrev
4.8 Clausius Inequality W1 W2

𝛿𝑄 𝛿𝑄 Q1 Q1
The cyclic integral of (∮ ) is less than or
𝑇 𝑇
equal to zero. W1  W2
𝛿𝑄
∮ 𝑇
≤0 So, Q2irrev  Q2
𝛿𝑄
∮ < 0 ⇒ Irreversible cycle ∮𝑖𝑟𝑟𝑒𝑣
𝛿𝑄
=
𝑄1
−
𝑄2𝑖𝑟𝑟𝑒𝑣
𝑇
𝑇 𝑇1 𝑇2
𝛿𝑄
∮ = 0 ⇒ Reversible cycle
𝑇 𝛿𝑄 𝑄2 𝑄2𝑖𝑟𝑟𝑒𝑣  Q1 Q2 
Case 1 : Reversible cycle ∮ 𝑇
= 𝑇2
− 𝑇2   
 T1 T2 
𝛿𝑄 𝑄2 −𝑄2𝑖𝑟𝑟𝑒𝑣
∮𝑖𝑟𝑟𝑒𝑣 =
𝑇 𝑇2

𝛿𝑄
∮𝑖𝑟𝑟𝑒𝑣 <0 Since Q2,irrev > Q2
𝑇

Note :
Significance of Clausius Inequality: With the
help of Clausius inequality the nature of the cycle
𝛿𝑄 𝑄1 −𝑄2
∮rev = +( ) can be establish i.e. whether the cycle is
𝑇 𝑇1 𝑇2
reversible or irreversible can be establish with the
For reversible help of Clausius inequality.
Q1 T1
 ∮
𝛿𝑄
= 0 = Reversible cycle
Q2 T2 𝑇
𝛿𝑄
Q1 Q2 ∮ < 0 = Irreversible cycle
 𝑇
T1 T2
𝛿𝑄
𝛿𝑄 ∮ > 0 = Impossible cycle
𝑇
∮rev =0
𝑇
Kulkarni’s Academy 54 Second Law of Thermodynamics
Q.1 To show that it is impossible to reach Sol.
absolute zero (0 K) according to second law
of thermodynamics.

𝜹𝑸 𝟏𝟎𝟎𝟎 −𝟐𝟎𝟎
∮ = +( )
𝑻 𝟏𝟎𝟎𝟎 𝟔𝟎𝟎
Q1 Q2  0.67

T1 T2
𝜹𝑸
∮ >𝟎
Q 𝑻
Q2  1  T2
T1 If engine has to be reversible
Let us assume that T2  0 K Q1 Q2

T1 T2
Q2  0
1000 Q2

1000 600
Q2  600 kJ

Q1 Q2

T1 T2

Violation of K-P statement 300 180


Conventional Questions: 700 T2

T2  420 K
Example 1
TL
State Clausius inequality and explain its rev  1 
significance. An inventor has claim that he TH
has develop an engine which receives 1000 T2 420
kJ of heat at the temperature of 1000 K and A  1   1  0.4 or 40 %
T1 700
rejects 200 kJ of heat at a temperature of 600
K delivering the remaining input has work  A  40%
check whether the claim is possible using
T2 280
above theorem. In case if this engine has to B  1   1  0.33 or 33 %
be reversible determine the amount of heat T1 420
rejected. B  33%
Basic Thermodynamics 55 Kulkarni’s Academy

Example 2  w 
0   A  B 1  A 
Two engines A and B are connected in series  Q1 
0   A  B 1   A 
show that the overall efficiency of combined
engine is given by
0   A  B   AB
o   A  B   AB
Sol.

Total net work output

overall 
Total energy input
WA  WB
o 
Q1

WA
A 
Q1

WB
B 
Q2

WA  WB WA WB
o   
Q1 Q1 Q1

1
 A  [B  Q2 ]
Q1

1
o   A  [B (Q1  WA )]
Q1
Kulkarni’s Academy
P Practice Questions
4.1 Which one of the following statements is
TRUE?
(A) Heat can be fully converted into work
(B) Work cannot be fully converted into heat
(C) The efficiency of a heat engine increases
as the temperature of the heat source is
increased while keeping the temperature
of the heat sink fixed
(D) A cyclic process can be devised whose
sole effect is to transfer heat from a
lower temperature to a higher
temperature.
4.2 Which of the following statement(s) are in
violation of the second law of
thermodynamics:
P. It is impossible to construct a cyclically
operating device which absorbs heat
from a single thermal reservoir and
produces an equivalent amount of work.
Q. It is possible to construct a device that
absorbs heat from a low temperature
body and rejects it to a high temperature
body without any external work.
R. a reversible engine has a higher
efficiency than an irreversible engine
that operates between the same two
thermal reservoirs at constant
temperatures.
(A) P only (B) Q only
(C) P and Q only (D) Q and R only
4.3 A heat pump, which operates in a cycle,
extracts heat energy from the cold reservoir
and supplies the same amount of energy to
the hot reservoir. Which of the following
statements holds for this process?
(A) This process violates both the first and
the second law
56 Second Law of Thermodynamics
(B) This process violates the first law but not
the second law
(C) This process violates the second law but
not the first law
(D) The process does not violate both first
and second law
4.4 Which of the following statements does not
represent the second law of thermodynamics?
(A) Perpetual motion machine of the first
kind is not possible
(B) A 100% efficient machine to convert
heat to work operating between
attainable temperatures is not possible.
(C) A machine to transfer heat from a lower
to a higher temperature without external
work input is not possible
(D) The entropy of the system in an adiabatic
enclosure can never decrease.
4.5 According to second law of thermodynamics
(A) Efficiency of a steam power plant is
always less than unity
(B) Efficiency of a steam turbine is always
less than unity
(C) COP of heat pump is always less than
unity
(D) COP of a refrigerator is always greater
than unity
4.6 In a thermodynamic cycle consisting of four
processes, the heat and work are as follows:
Q : + 30, - 10, – 20, + 5
W : + 3, + 10, – 8,0
The thermal efficiency of the cycle will be
(A) Zero (B) 7.15 %
(C) 14.33 % (D) 28.6 %
Basic Thermodynamics
4.7 Consider a refrigerator and a heat pump
working on the reversed Carnot cycle
between the same temperature limits. Which
of the following is correct.
(A) COP of refrigerator = COP of heat pump
(B) COP of refrigerator = COP of heat pump
+1
(C) COP of refrigerator = COP of heat pump
–1
(D) COP of refrigerator = inverse COP of
heat pump
4.8 An industrial heat pump operates between the
temperatures of 27°C and –13°C. The rates of
heat addition and heat rejection are 750 W
and 1000 W, respectively. The COP for the
heat pump is
(A) 7.5 (B) 6.5
(C) 4.0 (D) 3.0
4.9 An inventor claims to have constructed a
device that rejects 100 kJ of heat to a single
heat reservoir while absorbing 100 kJ of work
during a single cycle of the device. This
device violates:
(A) The first law of thermodynamics
(B) The second law of thermodynamics
(C) Both the first law and Second laws of
thermodynamics
(D) Neither the first law nor Second law of
thermodynamics
4.10 An irreversible heat engine extracts heat from
a high temperature source at a rate of 100 kW
and rejects heat to a sink at a rate of 50 kW.
The entire work output of the heat engine is
used to drive a reversible heat pump
operating between a set of independent
isothermal hear reservoirs at 17 0C and 75 0C
. The rate (in kW) at which the heat pump
delivers heat to its high temperature sink is
(A) 50 (B) 250
(C) 300 (D) 360
57 Kulkarni’s Academy
4.11 A solar collector receiving solar radiation at
the rate of 0.6 kW/m 2 transforms it to the
internal energy of a fluid at an overall
efficiency of 50 %. The fluid heated to 350 K
is used to run a heat engine which rejects heat
at 313 K. If the heat engine is to deliver 2.5
kW power, then minimum area of the solar
collector required would be
(A) 8.33 m2 (B) 16.66 m2
(C) 39.68 m2 (D) 79.36 m2
4.12 Efficiency of a Carnot engine can be
increased by
(A) Increasing the sink temperature while
keeping the source temperature constant
(B) Decreasing the sink temperature while
keeping the source temperature constant
(C) Decreasing the source temperature while
keeping the sink temperature constant
(D) Does not depend on source and sink
temperatures
4.13 A cyclic device operates between three
thermal reservoirs, as shown in the
figure.
Heat is transferred to/form the cyclic device.
It is assumed that heat transfer between each
thermal reservoir and the cyclic device takes
place across negligible temperature
difference. Interactions between the cyclic
device and the respective thermal reservoirs
that are shown in the figure are all in the form
of heat transfer
The cyclic device can be
(A) A reversible heat engine
Kulkarni’s Academy 58 Second Law of Thermodynamics
(B) A reversible heat pump or a reversible 4.18 A heat engine undergoes a cyclic process
refrigerator receiving 10,000 kJ from a reservoir at 1000
(C) An irreversible heat engine K and 8000 kJ from another reservoir at 800
K, while rejecting heat to a third reservoir at
(D) An irreversible heat pump or an
300 K. If the heat engine is assumed to be
irreversible refrigerator.
internally reversible, then the network output
4.14 A heat engine operates at 75% of the in kJ is
maximum possible efficiency. The ratio of (A) 17000 (B) 12000
the heat source temperature (in K) to the heat (C) 5000 (D) 3600
sink temperature (in K) is 5/3. The fraction of 4.19 Two reversible engines E1 and E2 reject heat
the heat supplied that is converted to work is to a common reservoir at a temperature T.
(A) 0.2 (B) 0.3 The engine E1 receives heat from a reservoir
(C) 0.4 (D) 0.6 at temperature T1 and delivers work W1.
The engine E2 receives same amount of heat
4.15 According to Clausius statement of the
from a reservoir at temperature T2 and
second law of Thermodynamics, the
delivers work W2. If the temperature T2 is
coefficient of performance of a refrigerator is
less than T1, then
never
(A) W1 = W2 = 0 (B) W1 > W2
(A) Infinity (C) W1 < W2 (D) W1 = W2
(B) Greater than unity 4.20 A Carnot engine operates between the
temperature limits of 1000 K and 900 K. A
(C) Unity
second Carnot engine operates between the
(D) Less than unity temperature limits of 500 K and 450 K. Both
4.16 For two cycles coupled in series, the topping the engines produce the same amount of
cycle has an efficiency of 30% and the work. Which one of the following statements
bottoming cycle has an efficiency of 20%. is true regarding the efficiency  and the
The overall combine cycle efficiency is heat rejected OR (Subscripts 1 and 2 are used
(A) 50% (B) 44 % to denote the respective engines)?
(A) 1  2 and QR1  QR2
(C) 38% (D) 55%
(B) 1  2 and QR1  QR2
4.17 A heat transformer is a device that transfers a
part of the heat, supplied to it at an (C) 1  2 and QR1  QR2
intermediate temperature, to a high (D) 1  2 and QR1  QR2
temperature reservoir while rejecting the
4.21 A Carnot heat engine is operated between
remaining part to a low temperature heat
two temperature T1 and T2 ( T1  T2 and T in
sink. In such a heat transformer, 100 kJ of
heat is supplied at 350K. The maximum Kelvin). The efficient of the engine can be
amount of heat in kJ that can be transferred to increased by
400K, when the rest is rejected to a heat sink (A) Decreasing T2 and keeping T1 constant
at 300K. (B) Decreasing both T1 and T2
(A) 12.50 (B) 14.29 (C) Increasing both T1 and T2
(C) 33.33 (D) 57.14 (D) None of these
Basic Thermodynamics 59 Kulkarni’s Academy
4.22 For a closed system with internal Common Data Questions 26 - 27
irreversibilities undergoing a cyclic process,
A reversible heat engine receives heat inputs
the cyclic integral of (dQ/T) is
at 300 kJ and 200 kJ from two thermal
(A) Less than or equal to zero reservoirs at 1000 K and 800 K, respectively.
(B) Greater than or equal to zero
The engine rejects heat Q to a reservoir at 300
(C) Greater than zero K.
(D) Less than zero 4.26 The value of Q is
4.23 A heat engine E1 operates between an (A) 65 kJ (B) 165 kJ
0
infinite reservoir at 800 C and a body B. The (C) 100 kJ (D) 265 kJ
temperature of the body B remains constant 4.27 The work delivered by the engine is
0
550 C . Heat transferred to the engine E1 is (A) 35 kJ (B) 135 kJ
900 kJ and the work output is 200 kJ. Another (C) 235 kJ (D) 335 kJ
engine E2 operates between the body B and Common Data Questions 28 - 29
0
the atmosphere at 27 C . Heat rejected to the A Carnot heat engine is used to drive a Carnot
atmosphere is 350 kJ. The thermal efficiency heat pump. The arrangement, along with the
of the engine E2 is pertinent temperatures, is indicated in Figure.
(A) 0.39 (B) 0.5
(C) 0.61 (D) 0.635
4.24 Assertion (A) : Two engines A and B work
on the Carnot cycle. Engine A uses air as the
working substance and B uses steam as the
working substance. Both engines are having
same efficiency.
Reason (R) : Carnot cycle efficiency is
4.28 Q3 in kJ is
independent of working substance.
(A) 1000 (B) 500
4.25 300 kJ/sec of heat is supplied at a constant
(C) 3000 (D) 2500
fixed temperature of 2900 C to a heat engine.
The heat rejection takes place at 8.50 C . Then 4.29 The COP of the heat pump is
match the following. (A) 4 (B) 6
Results Obtained Cycle (C) 0.4 (D) 2
P. 215 kJ/sec are rejected 1. Reversible Common Data Questions 30 - 31
Q. 150 kJ/sec are rejected 2. Irreversible Two reversible heat engines work between
R. 75 kJ/sec are rejected 3. Impossible three thermal reservoirs at temperatures
T1 , T2 and T3 respectively. Engine E1
(A) P – 1, Q – 2, R – 3
receives heat from the reservoir at
(B) P – 2, Q – 1, R – 3
temperature T1 and rejects heat to the
(C) P – 3, Q – 2, R – 1
reservoir at temperature T2 engine E2
(D) P – 1, Q – 3, R – 2
Kulkarni’s Academy 60 Second Law of Thermodynamics
receives heat from the reservoir at A Answer Key
temperature T2 and rejects heat to the
4.1 C 4.2 B 4.3 C
reservoir at temperature T3 . Assume that the
4.4 A 4.5 A 4.6 C
heat rejected by engine E1 is equal to the heat
4.7 C 4.8 C 4.9 D
input to engine E2 . All temperatures are in
4.10 C 4.11 D 4.12 B
Kelvin.
4.13 A 4.14 B 4.15 A
4.30 If the efficiencies of engines E1 and E2 are
4.16 B 4.17 D 4.18 B
same, the reservoir temperature T2 can be 4.19 B 4.20 D 4.21 A
expressed as 4.22 D 4.23 B 4.24 A
(A) T2  TT
1 3 4.25 b 4.26 B 4.27 D
4.28 C 4.29 B 4.30 A
(B) T2  (T1  T3 ) / 2
4.31 B
(C) T2  (T1  T3 ) / 2
E Explanation
(D) T2  2TT
1 3

4.31 If the work delivered by engines E1 and E2 4.1 (C)

are same, the reservoir temperature T2 can be
4.2 (B)
expressed as

(A) T2  TT
1 3
4.3 (C)

(B) T2  (T1  T3 ) / 2 4.4 (A)

(C) T2  (T1  T3 ) / 2
4.5 (A)
(D) T2  2TT
1 3
4.6 (C)

Network output
Efficiency 
Heat supplied

(3  10  8) 5
   14.28%
(30  5) 35

Hence, the correct option is (C).

4.7 (C)

(COP) R  (COP) HP  1

Hence, the correct option is (C).

Basic Thermodynamics 61 Kulkarni’s Academy

4.8 (C)

For minimum area   max  rev.

TL W
Q1 rev.  1  
(C.O.P) H .P  TH Q1
Q1  Q2
313 2.5
1000  1 
= 4 350 0.3A
1000  750
 Amin  A  78.8 m2
Hence, the correct option is (C).
Hence, the correct option is (D).
4.9 (D) 4.12 (B)
4.10 (C) 4.13 (A)

Q1  ?
Q 100 50 60
TH Q  T
 
1000 500 300

COP   1
TH  TL Win 1 1 1
   =0
348 Q1 10 10 5
  Work developing and reversible heat engine.
58 50
Hence, the correct option is (A).
Q1  50  6  300 kW
4.14 (B)
Hence, the correct option is (C).
TH 5

4.11 (D) TL 3
TL 3
max  1   1   0.4
TH 5
W
actual  0.4  0.75  0.3 
Q1
W  0.3Q1
If A is area of collector then Q1  3A kW Hence, the correct option is (B).
Kulkarni’s Academy 62 Second Law of Thermodynamics
4.15 (A) 4.18 (B)
Refrigerating effect
COP 
work input
For Refrigerator Win  0
So, COP  
Hence, the correct option is (A).
4.16 (B)
 A  0.3 Q
B  0.2
For reversible cycle  T 0
10,000 8000 Q3
0   A  B   AB   0
1000 800 300
 0.3  0.2  0.06 Q
 0.44 or 44%  10  10  3
300
Hence, the correct option is (B). Q3  6000 kJ
4.17 (D) 10,000  8000  WNet  Q3
 18,000  6000  WNet
 WNet  12,000 kJ
4.19 (B)

Q1  Q2  Q3
Q
100  Q2  Q3 … (i)  T
0 Given
T2  T1
rev

100 Q2 Q
  3 0 T T
350 400 300 1  1  ; 2  1 
T1 T2
100 Q2 100  Q2
   0 as T2  T1
350 400 300
100 Q2 100  Q2 So, 1  2
  
350 400 300 W1 W2
 
100 300Q2  40000  400Q2 Q1 Q1

350 400  300 As heat supplied ( Q1 ) is same for both
 Q2  57.14 kJ
engines. So, W1  W2 .
Hence, the correct option is (D).
Hence, the correct option is (B).
Basic Thermodynamics 63 Kulkarni’s Academy

4.20 (D) 4.24 (A)

4.25 (B)

1  2  0.1
W W
 281.5
QS1 QS2 rev.  1   0.5  50%
563
 QS1  QS2 (1) 215 kJ/s are rejected
So, QR1  QR2 85
1   0.28 (irreversible)
Hence, the correct option is (D). 300
4.21 (A) (2) 150 kJ/s are rejected
150
4.22 (D) 2   0.5 (reversible)
300
4.23 (B) Hence, the correct option is (B).
4.26 (B)

Q 300 200 Q3
   
T 1000 800 300
0

Q3  165 kJ
Hence, the correct option is (B).
Q2  900  200 4.27 (D)
Q2  700 kJ 300  200  Q3  W
W2
2  300  200  165  W
Q2
W  335 kJ
350
  0.5  50% Hence, the correct option is (D).
700
Hence, the correct option is (B). 4.28 (C)
Kulkarni’s Academy 64 Second Law of Thermodynamics
4.29 (B) 4.31 (B)
If, W1  W2
then Q1  Q2  Q2  Q3
We know that for rev. engine
Q1 Q2 Q3
  K
T1 T2 T3
Q1  KT1; Q2  KT2 ; Q3  KT3
250  KT1  KT2  KT2  KT3
  1
500 KT1  KT3
 0.5  KT2 
2
W  500 kJ T T
TH 300 T2  1 3
C.O.P   6 2
TH  TL 50 Hence, the correct option is (B).
Q3
(COP) HP 
Win
Q3  6  500  3000 kJ
Hence, the correct option is (B).
4.30 (A)

1  2
T2 T
 1  1 3
T1 T2
T2 T3
 
T1 T2
 T2  TT
1 3

Hence, the correct option is (A).

NOTES
  Q   Q 
5.1 Entropy      dS
 T  rev b  T  rev c
Case 1 : Reversible cycle
 Q 
   dS
 T  rev

 Q 
dS   
 T  rev b

 Q 
Though paths b and c are different but   is
 T  rev
𝜹𝑸 same.
∮rev =𝟎
𝑻
1-a-2-b-1 – reversible cycle  Q 
For path b and c, therefore   must be a
 T  rev
 Q   Q 
    0 … (i) property and this property is known as entropy.
 T 1a 2  T  2b1
Case 2 : Irreversible cycle
1-a-2-c-1 – reversible cycle
 Q   Q 
    0 … (ii)
 T 1a 2  T  2 c1
Equation (i) – (ii),
 Q   Q 
    0
 T  2b1  T  2 c1

1-a-2-b-1 – reversible cycle

𝛿𝑄
∮rev =0
𝑇

 Q   Q   Q   Q 
        0
 T  2b1  T  2 c1  T 1a 2  T  2b1

 Q   Q   Q   Q 
         … (i)
 T  rev b  T  rev c  T 1a 2  T  2b1
Basic Thermodyanamics 66 Kulkarni’s Academy
1-a-2-c-1 – irreversible cycle As long as the end points are same entropy
𝛿𝑄 change will be same irrespective of the process
∮irrev <0
𝑇
i.e. reversible or irreversible.
 Q   Q 
    0 … (ii)
 T 1a 2  T  2 c1
From (i) and (ii),
 Q   Q 
    0
 T 2b1  T  2 c1

 Q   Q 
   
 T  2 c1  T  2b1
In order to calculate entropy, change for
 Q   Q 
    irreversible process it must be replace by a
 T irrev  T rev reversible process between same end points.
 Q   Q 
   dS or dS    Entropy change of a System in a reversible
 T irrev  T irrev
process:
We know that, For Reversible- Case 1: Reversible heat supply
 Q  Q
dS    dS 
 T  rev T
For Irreversible- dS  positive, dS  0
 Q  S 2  S1  0
dS   
 T irrev S2  S1  S 
 Q  * In a reversible process when heat is supplied,
Therefore, dS   
 T  the system entropy increases.

NOTE : Case 2: Reversible heat rejection

dSrev  S2  S1 Q
dS 
T
dSirrev  S 2  S1
dS  Negative or dS  0
dSrev  dSirrev
S 2  S1  0

S2  S1  S 
* In a reversible process when heat is rejected,
the system entropy decreases.
Case 3: Reversible Adiabatic process
Q
dS  (Reversible)
T
Q  0 (Adiabatic)
Kulkarni’s Academy 67 Entropy
dS  0  All adiabatic processes are not isentropic, if
S 2  S1  0 the adiabatic process is isentropic then it must
S 2  S1 Or S = constant – Isentropic be reversible, if the adiabatic process is
irreversible then the system entropy
* A reversible adiabatic process is always
increases. Therefore, in adiabatic process
isentropic process.
system entropy can never decrease.
In a reversible process system entropy can
5.2 Physical Meaning of Entropy
increase, can decrease or can remains same
depending on heat transfer. Entropy is a measure of randomness or
Entropy Change in Irreversible Process for a disorderness of molecule, greater the
system disorderness- greater is the entropy, lesser is the
 Q  efficiency.
dS    ● Entropy Change of Universe:
 T irrev
 Q 
dS     (S )gen
 T irrev

(dS )univ  dSsys  dSsurr

Q
Irreversible + Non-adiabatic dS 
T
 Q 
dS     (S )gen (dS )univ 
0
 T irrev T
dS  3  3 { Assume (dS ) univ 0
dS  0
According to second law of thermodynamics, all
Though a reversible adiabatic process is always
those processes are possible for which the change
isentropic and isentropic process need not be
in entropy of universe is greater than or equal to
reversible adiabatic.
zero i.e., according to second law of
thermodynamics universe entropy can never
decrease and this is known as the Principal of
increase of entropy.
System entropy can increase or decrease,
similarly surrounding entropy can increase or
decrease, but the universe entropy can never
decrease.
Ssolids  Sliquids  Sgases
dS univ  0  process is irreversible
dS univ  0  process is reversible
dSuniv  0  process is impossible
Basic Thermodyanamics 68 Kulkarni’s Academy
5.3 Entropy Generation Q
dS   Sgen
T
0
dSuniv   Sgen
T
Sgen  dSuniv
Sgen  dSsys  dSsurr
 dQ 
dS     (S )gen T-S Diagram :
 T irrev

 Q 
dS    0
 T rev

 Q 
dSa     Sgen, a
 T irrev, a

 Q 
dSb     Sgen, b
 T irrev, b
‘a’ is more irreversible than ‘b’ Area under the curve  TdS
Sgen, a  Sgen, b Q
For reversible process dS 
T
Q  TdS
Q  Area under the curve
Area under the curve when projected on entropy
axis gives reversible heat transfer.
5.4 Representation of Carnot cycle on T-S
diagram:

Though entropy is a property, entropy generation

is not a property. Because entropy generation
depends on extend of irreversibilities, greater the
irreversibility greater is the entropy generation.
1-2 – Reversible isothermal heat addition
(expansion)
2-3 – Reversible adiabatic expansion
3-4 – Reversible isothermal heat rejection
4-1 – Reversible adiabatic compression
Kulkarni’s Academy 69 Entropy

Carnot cycle is represented by a rectangle on T-

S diagram.
TdS  dU  PdV
Note: A cycle which is clockwise on P-V diagram is
V  Const. dV  0
also clockwise on T-S diagram.
𝑻𝒅𝑺 = 𝒅𝑼
5.5 Combined 1st and 2nd Law of
𝑻𝒅𝒔 = 𝑪𝒗 𝒅𝑻 {𝒅𝑢 = 𝑪𝒗 𝒅𝑻}
Thermodynamics:
𝒅𝑻 𝑻
From First law of thermodynamics = 𝑪 {Slope of constant volume process
𝒅𝒔 𝒗
Q  dU  PdV * This equation is valid for both ideal and real
Second law of thermodynamics gas because 𝑑𝑢 = 𝐶𝑣 𝑑𝑇 is valid for ideal and
Q real gases under constant volume conditions.
dS  TdS  dH  VdP
T
Q  TdS P  constant, dP  0

TdS  dU  PdV TdS  dH

This equation is applicable for any process i.e. 𝑇𝑑𝑠 = 𝑑ℎ

reversible or irreversible because this equation 𝑇𝑑𝑠 = 𝐶𝑝 𝑑𝑇 {dh  C p dT }
connects various properties and this equation can 𝑑𝑇 𝑇
= 𝐶 {Slope of constant pressure
be used for any working fluid. 𝑑𝑠 𝑝

We know that * This equation is valid for both ideal and real
H  U  PV gas because 𝑑ℎ = 𝐶𝑝 𝑑𝑇 is valid for ideal and
dH  dU  PdV  VdP real gases under constant pressure conditions.
dH  Q  VdP  FLOT
Q
dS   Q  TdS  SLOT
T
dH  TdS  VdP
TdS  dH  VdP
This equation is application for any process i.e.
reversible or irreversible and for any working
fluid.
Representation of constant volume and * As C p  Cv slope of constant volume curved
constant pressure process on T-S diagram for
is greater than slope of constant pressure
an ideal gas:
curve on T-S diagram.
Basic Thermodyanamics 70 Kulkarni’s Academy
5.6 Entropy Change for an Ideal Gas Sol.
𝑇2 𝑉2
From 1st TdS equation 𝑠2 − 𝑠1 = 𝐶𝑣 𝑙𝑛 + 𝑅 𝑙𝑛
𝑇1 𝑉1
TdS  dU  PdV 𝑇2
𝑠2 − 𝑠1 = 𝐶𝑣 𝑙𝑛 𝑇 + (𝐶𝑝 − 𝐶𝑣 ) 𝑙𝑛 𝑉2
𝑉
1 1
dU P 𝑉2 𝑇2 /𝑇1
dS   dV 𝑠2 − 𝑠1 = 𝐶𝑝 𝑙𝑛 𝑉 + 𝐶𝑣 𝑙𝑛 [𝑉 /𝑉 ]
T T 1 2 1

R  C p  Cv

1 1  mRT1
PV
dT mR
dS  mCv  dV 2 2  mRT2
PV
T V PV PV
S2 T2 V2
1 1
 2 2
dT dV
 dS   mC   mR T1 T2
v
S1 T1
T V1 V T2V1 P2

T2 V TV P1
S2  S1  mCv ln  mR ln 2
1 2

T1 V1 𝑉 𝑃
𝑠2 − 𝑠1 = 𝐶𝑝 𝑙𝑛 𝑉2 + 𝐶𝑣 𝑙𝑛 𝑃2
1 1
𝑇 𝑉
𝑠2 − 𝑠1 = 𝐶𝑣 𝑙𝑛 𝑇2 + 𝑅 𝑙𝑛 𝑉2 5.7 Entropy change for solids and liquids
1 1

This equation is valid only for ideal gas (Both open TdS  dU  PdV
and close system) Solid and Liquids are generally incompressible.
From 2nd TdS equation So, dV = 0
TdS  dH  VdP TdS  dU
dH V dU  mCdT
dS   dP TdS  mCdT
T T
Sf Tf
dT
 dS 
Si
 mC
Ti
T
Tf
dT dP S f  Si  mC ln
dS  mC p  mR Ti
T P
S2 T2 P
5.8 Entropy change for Reservoir
dT 2 dP
S dS  T mC p T  P mR P
1 1 1

T2 P
S2  S1  mC p ln  mR ln 2
T1 P1
𝑇 𝑃
𝑠2 − 𝑠1 = 𝐶𝑝 𝑙𝑛 𝑇2 − 𝑅 𝑙𝑛 𝑃2
1 1

This equation is valid only for ideal gas (both

open and close system)
Example 1
Show that for an ideal gas
𝑉 𝑃
𝑠2 − 𝑠1 = 𝐶𝑝 𝑙𝑛 𝑉2 + 𝐶𝑣 𝑙𝑛 𝑃2
1 1
Note : At equilibrium the entropy is maximum
Kulkarni’s Academy 71 Entropy
(S )gen  Internal irreversibility (II)
dSsys  EI  II
dS surr  EI
In adiabatic process, Q  0, EI  0
dSsurr  0 and dSsys  0
 Q 
dS     (S )gen dSsys  II
 T 
dSuniv  dSsys  dSsurr
Where dS  Entropy change
 Q  dSuniv  dSsys
   Entropy transfer
 T  dSsys  S gen
(S )gen  Entropy generation or entropy In an adiabatic process as there is no external
production interaction in the form of heat transfer, therefore
In an adiabatic process, as there is no heat entropy change of surrounding is equal to zero.
transfer entropy transfer is zero. Therefore, in an 5.9 Entropy change In Open System
adiabatic process, entropy change is equal to
entropy generation.
 In a reversible process as there is no entropy
generation, therefore entropy change is equal
to entropy transfer.
 In a reversible adiabatic process, entropy
Q
transfer and entropy generation both are zero. dS   S gen
T
Therefore, entropy change is zero, hence a
 dS  Q
    S gen  mi Si  me Se
reversible adiabatic process is always -
isentropic.  dt cv T
For both steady & unsteady flow
But in steady flow
 dS 
 0
 dt 
Q
0  (S gen )  mi si  me se
T

Q
me se  mi si   (S gen )
T
 Q  Q
dS     (S )gen dS   (S gen )
 T  T
 Q  In case of steady flow open and close system
   External interaction (EI)
 T  equations are same.
Basic Thermodyanamics
Example 2
Air is flowing steady in an insulated pipe, the
pressure and temperature at two section 1 and
2 are given in the table establish the direction
of flow of air in pipe treating air as an ideal
gas.
Sol.
72 Kulkarni’s Academy
Example 3
Steam enters the turbine with a pressure of 30
bar, 4000 C[h  3230.9 kJ/kg] exit a velocity
of 160 m/s saturated vapour at
1000 C[h  2676.1 kJ/kg] exit with a velocity
of 100 m/s at a steady state, turbine develops
a work of 540 kJ/kg, heat transfer between
turbine and surrounding occur at an average
temperature of 350 K. Determine the entropy
produced (gentropy generated) with in the
turbine per kg of steam, neglect P.E. changes,
take inlet entropy.
Sol. S1  6.932 kJ/kgK and S 2  7.361 kJ/kgK
Q
dS   S gen
T

Let us assume the flow from 1 to 1

dSuniv  0

dSsys  dSsurr  0

As the pipe is insulated dS surr  0

T2 P C12 gz C2 gz
dS sys  dSair  C p ln  R ln 2 h1   1  q  h2  2  2
T1 P1 2000 1000 2000 1000
1602 1002
286 100 3230.9   q  2676.1   540
dSsys  1.005  ln  0.287  ln 2000 2000
323 130
h1  3230.9 kJ/kg, h2  2676.1 kJ/kg
dSsys  0.04697 kJ/kgK
C1  160 m/s, C2  100 m/s
dSuniv  0.04697  0 S1  6.932 kJ/kgK, S 2  7.361 kJ/kgK

dSuniv  0.04697 kJ/kgK q  22.6 kJ/kg

Q
dSuniv  0 S2  S1   S gen
T
22.6
With our assumption of flow from 1 to 2, the 7.361  6.932    (S ) gen
entropy change of universe is less than zero 350
(Which is impossible according to Second law of (S ) gen  0.4935 kJ/kgK
thermodynamics). Therefore, flow is not from 1 As the entropy generation is positive, process is
to 2, but it is from 2 to 1. irreversible.
Kulkarni’s Academy 73 Entropy
5.5 Irreversibility in a thermodynamic process is
P Practice Questions
caused by:
5.1 The relation ds = dQ/T, where ‘S’ represent P. Heat transfer across a finite temperature
entropy, ‘Q’ represents heat and ‘T’ difference
represents temperature (absolute), holds good
Q. Frictional effects
in which one of the following processes?
R. Unrestrained expansion
(A) Reversible process only
S. Mixing of two dissimilar pure
(B) Irreversible process only substances
(C) Both reversible and irreversible (A) P only
processes (B) P and Q only
(D) All real processes (C) P, Q and S only
5.2 A system is changed from a single initial (D) P, Q, R, S
equilibrium state to the same final 5.6 For any process at all, the second law requires
equilibrium state by two different processes, that the entropy change of the system is
one reversible and the other irreversible.
(A) Positive or zero
Which of the following is true, where S
refers to the system? (B) Zero
(C) Negative or zero
(A) sirr  Srev
(D) Positive or zero or negative, but does not
(B) sirr  Srev say which
(C) sirr  Srev 5.7 The equation S  R ln( p1 / p2 ) determines
the change in entropy of an ideal gas for a
(D) No decision is possible with respect to
reversible process which is
(A), (B) or (C)
(A) Adiabatic
5.3 Process ‘A’ is irreversible and adiabatic.
Process ‘B’ is reversible and adiabatic. The (B) Isothermal
entropy change in process ‘A’ and process (C) Isobaric
'B', respectively, are (D) All of the above
(A) Zero and positive 5.8 For a system undergoing an irreversible
(B) Zero and negative process

(C) Negative and zero (A)  Tds  Q (B)  Tds  2Q

(D) Positive and zero (C)  Tds  Q (D)  Tds  Q
5.4 The equation T dS= dU + P dV is applicable
5.9 If a system undergoes an irreversible
(A) Only to reversible process adiabatic process, then (symbols have usual
(B) Only to ideal gases meanings)
dQ
T
(C) Only to reversible processes in ideal  0 and S  0
(A)
gases
(D) To all processes and all working dQ
substances
(B) T  0 and S  0
Basic Thermodyanamics 74 Kulkarni’s Academy
dQ 5.13 The given figure shows a thermodynamic
(C) T  0 and S  0
cyclic on T-S diagram. All the processes are
dQ straight lines. The efficiency of the cycle is
(D) T  0 and S  0 given by
5.10 A reversible engine (modified Carnot
engine) as shown in the figure receives 100
kJ of heat at 500 K and another 40 kJ at 400
K. Heat is rejected at 300 K.

(A) (0.5Th  Tc ) / Th (B) 0.5(Th  Tc ) / Th

(C) (Th  Tc ) / 0.5Th (D) (Th  0.5Tc ) / Th
5.14 An insulated rigid container having 1 m3
The work output is equal to
volume has two compartments having equal
(A) 140 kJ (B) 90 kJ
volume separated by a thin membrane. Half
(C) 60 kJ (D) 50 kJ
of the container is filled with helium (
5.11 Heat flows between two reservoirs having
R  20.8 kJ/kg-K, C p  5.19 kJ/kg-K and
temperatures 1000 K and 500 K,
respectively. If the entropy change of the cold Cv  3.11 kJ/kg-K ), while the remaining half
reservoir is 10 kJ/K, then what is the entropy is empty. Suddenly the membrane ruptures
change for the hot reservoir? and helium fills the whole volume of the
(A) – 10 kJ/K (B) – 5 kJ/K container. Temperature and pressure of
(C) 5 kJ/K (D) 10 kJ/K helium before rupture are 5000 C and 0.1
5.12 A certain amount of fluid at temperature T1 is MPa respectively. The change in the entropy
of helium is
mixed with an equal amount of the same fluid
at temperature T2 in an insulated container (A) 0.019 kJ/K (B) 0.045 kJ/K
with total fluid as the system, consider the (C) 0.112 kJ/K (D) 0.675 kJ/K
following statements 5.15 A system of 100 kg mass undergoes a process
1. Energy of the system is conserved in which its specific entropy increases from
2. Entropy of the system is conserved 0.3 kJ/kg-K to 0.4 kJ/kg-K. At the same time,
the entropy of the surrounding decreases
3. Entropy of the system increases
from 80kJ/K to 75 kJ/K. The process is
4. Entropy of the system decreases
(A) Reversible and isothermal
Choose the correct answer using the codes
given below: (B) Irreversible
(A) 1 and 2 (B) 1 and 3 (C) Reversible
(C) 1 and 4 (D) 1 only (D) Impossible
Kulkarni’s Academy 75 Entropy
5.16 A solid metallic block weighing 5 kg has an 5.20 An ideal gas undergoes a cyclic process as
initial temperature of 5000 C , 40 kg of water shown in P-V diagram below
initially at 250 C is contained in a perfectly
insulated tank. The metallic block is brought
into contact with water. Both of them come
to equilibrium. Specific heat of block
material is 0.4 kJ/kg-K. Ignoring the effect of
expansion and contraction and also the heat
capacity of tank, the total entropy change in
kJ/kg-K is
(A) 1.87 (B) 0.0
(C) 1.26 (D) 3.91
The same cycle, represented in T-S diagram
5.17 Atmospheric air ( R  287 J/kg-K,   1.4) at is
1 bar and 250 C is compressed adiabatically
to 2 bar and 1050 C . Which of the following
statements is correct?
(A) The process is possible but irreversible (A)
(B) The process is possible and reversible
(C) The process is impossible
(D) The process is possible and it is
isentropic
5.18 Which one of the following is the correct (B)
statement? Two reversible adiabatics will
(A) Intersect at absolute zero temperature
(B) Never intersect
(C) Become orthogonal at absolute zero
temperature (C)
(D) Become parallel at absolute zero
temperature

5.19 Ninety kilograms of ice at 00 C are

completely melted. Find the entropy change,
in kJ/k,
(A) 0 (B) 45 (D)

(C) 85 (D) 105

Basic Thermodyanamics 76 Kulkarni’s Academy
5.21 Consider the following statements Which representation shows correctly the
When a perfect gas enclosed in a cylinder above processes on the temperature-entropy
piston device executes a reversible adiabatic co-ordinates?
expansion process,
1. Its entropy will increase
2. Its entropy change will be zero
(A)
3. The entropy change of the surroundings
will be zero. Of these statements
(A) 1 and 3 are correct
(B) 2 alone is correct
(C) 2 and 3 are correct
(D) 1 alone is correct
5.22 One kilomole of an ideal gas is throttled from (B)
an initial pressure of 0.5 MPa to 0.1 MPa. The
initial temperature is 300K. The entropy
change of the universe is
(A) 13.38 kJ/K (B) 401.3 kJ/K
(C) 0.0446 kJ/K (D) – 0.0446 kJ/K
5.23 Consider the following two processes;
I. A heat source at 1200 K loses 2500 kJ of (C)
heat to a sink at 800 K
II. A heat source at 800 K loses 2000 kJ of
heat to a sink at 500 K
Which of the following statements is true?
(A) Process I is more irreversible than
process II
(D)
(B) Process II is more irreversible than
process I
(C) Irreversibility associated in both the
processes are equal 5.25 An ideal gas undergoes a thermodynamic
(D) Both the processes are reversible cycle which when represented on T – s
5.24 Two polytropic processes undergone by a diagram is a circle with maximum and
perfect gas are shown below in the pressure minimum temperatures of 600 K and 300 K.
volume co-ordinates. What is its efficiency?
(A) 61.5 % (B) 41.5 %
(C) 51.5 % (D) 31.5 %
5.26 Increase in entropy represents
(A) Increase in available energy
(B) Increase in temperature
(C) Decrease in pressure
(D) Degradation of energy
Kulkarni’s Academy 77 Entropy

5.27 A liquid of mass m at temperature T1 is mixed
with an equal amount of the same liquid at
temperature T2 . The specific heat of the
liquid is c. The total entropy change due to
the mixing process is
5.31 A heat engine operates between two thermal
reservoirs, one at 1000 C and another at 200 C
. 373 J of energy is removed from the hot
reservoir. The change in entropy of the hot
reservoir in J/K is

T2 T1  T2 (A) 1.27 (B) 1.0

(A) 2mc ln (B) 2mc ln
T1 2 TT (C) 1.0 (D) 1.27
1 2

5.32 The specific heat C p is given by

T 2 TT1 2
(C) 2mc ln 1 (D) 2mc ln
T2 T1  T2  v   T 
(A) T   (B) T  
5.28 A rigid insulated tank is divided into two  T  p  S  p
compartment contains 1 kmol of O 2 and the  S   T 
(C) T   (D) T  
other compartment contains 4 kmol of N 2 .  T  p  v  p
Both gases are initially at 300 K and 200 kPa 5.33 Match curves in Diagram I with curves in
pressure. Now the partition is removed, the Diagram II
two gases are allowed to mix. Assuming both
gases are ideal, the total entropy change in
kJ/K of the gases is
(A) 0 (B) 20.8
(C) 0.718 (D) 2.502
5.29 Consider an isentropic process undergone by
an incompressible liquid. The change (A) P - 3,Q - 2,R - 4,S - 5
temperature experienced by the liquid is
(B) P - 2,Q - 3,R - 4,S - 5
T  T2  T1 . Which one of the following is
(C) P - 2,Q - 3,R - 4,S -1
correct
(D) P - 1,Q - 4,R - 2,S – 3
(A) T  0
5.34 Assertion (A) : An adiabatic process is
(B) T  0
always a constant entropy process
(C) T  0
Reason (R) : In an adiabatic process there is
(D) T depends on the liquid under
no heat transfer
consideration
(A) Both A and R are individually true and
5.30 At constant temperature, pressure of an
R is the correct explanation of A
incompressible fluid is changed from 400
KPa to 4MPa. Which of the following set of (B) Both A and R are individually true but R
thermodynamic properties remain unchanged is not the correct explanation of A
during the process: (u is specific internal (C) A is true but R is false
energy, v is specific volume, h is specific (D) A is false but R is true
enthalpy and s is specific entropy) 5.35 Assertion (A) : The constant pressure lines
(A) u, v, h (B) u, s, h are steeper than the constant volume lines for
(C) u, v, s (D) v, s, h a perfect gas on the T - S plane
Basic Thermodyanamics 78 Kulkarni’s Academy
Reason (R) : The specific heat at constant Characteristic gas constant,
pressure is more than the specific heat at R  0.287 kJ/kgK .
constant volume for a perfect gas.
Enthalpy, h  C pT
(A) Both A and R are individually true and
R is the correct explanation of A Internal energy, u  CvT

(B) Both A and R are individually true but R 5.38 If the air has to flow from station P to station
is not the correct explanation of A Q, the maximum possible value of pressure
in kPa at station Q is close to
(C) A is true but R is false
(A) 50 (B) 87
(D) A is false but R is true
(C) 128 (D) 150
Common Data Questions 5.36 and 5.37 5.39 If the pressure at station Q is 50 kPa, the
Nitrogen gas (molecular weight 28) is change in entropy ( SQ  S P ) in kJ/kgK is
enclosed in a cylinder by a piston, at the (A) 0.155
initial condition of 2 bar, 298K and 1 m3. In (B) 0
a particular process, the gas slowly expands (C) 0.160
under isothermal condition, until the volume (D) 0.355
becomes 2 m3. Heat exchange occurs with
the atmosphere at 298K. During this process. Common Data Questions 5.40 and 5.41

5.36 The work interaction for the Nitrogen gas is Air at an initial temperature and volume of

(A) 200 kJ (B) 138.6 kJ 300 K and 0.002 m3 is contained in a piston-

cylinder a assembly as shown in the figure.
(C) 2 kJ (D) – 200 kJ
Heat is added to the air and it expands slowly
5.37 The entropy change for the Universe during
to occupy a final volume of 0.003 m3 . Area
the process in kJ/K is
of the piston is 0.02 m3 and the spring
(A) 0.4652 (B) 0.0067
constant k is 10 kN/m. The atmosphere
(C) 0 (D) – 0.6711
pressure may be assumed to be 100 kPa.

Common Data Questions 5.38 and 5.39

In an experimental set up, air flows between
two stations P and Q adiabatically. The
direction of flow depends on the pressure and
temperature conditions maintained at P and
Q. The conditions at station P are 150 kPa
and 350 K. The temperature at station Q is
300 K. The following are the properties and 5.40 The final pressure of air in kPa is
relations pertaining to air (A) 25 (B) 125
Specific heat at constant pressure, (C) 102.5 (D) 112.5
C p  1.005 kJ/kgK ; 5.41 The specific entropy change of air from the
initial to the final state in kJ/kg K is
Specific heat at constant volume,
(A) 0.631 (B) – 0.631
Cv  0.718 kJ/kgK ;
(C) 0.409 (D) 0.567
Kulkarni’s Academy 79 Entropy

Common Data Questions 5.42 and 5.43 5.44 The above cycle is represented on T-s plane
By
Two identical bodies of equal mass m and
specific heat at constant pressure initially at
temperature T1 and T2 (T1  T2 in K) are
used as reservoirs for a heat engine operating
in infinitesimal reversible cycles. The bodies
may be treated as pure substances which (A)
operate at constant pressure. If the engine
interacts with the reservoirs until they attain
the same final temperature T f .

5.42 The final temperature is equal to

(A) (T1  T2 ) / 2

(B TT
1 2
(B)

(C) T1  T2

(D) (T1  T2 )2 / TT
1 2

5.43 The work obtained is

 
2
(A) mc p T1  T2

(B) mc pT1 (C)

(C) mc pT2

(D) mc p TT
1 2

Common Data Questions 5.44 and 5.45

A thermodynamic cycle with an ideal gas as

working fluid is shown below.
(D)

5.45 If the specific heats of the working fluid are

constant and the value of specific heat ratio is
1.4, the thermal efficiency (%) of the cycle is
(A) 21 (B) 40.9
(C) 42.6 (D) 59.7
Basic Thermodyanamics 80 Kulkarni’s Academy
A Answer Key 5.4 (D)

5.1 A 5.2 A 5.3 D 5.5 (D)

5.4 D 5.5 D 5.6 D
5.6 (D)
5.7 B 5.8 C 5.9 A
5.10 D 5.11 B 5.12 B 5.7 (B)
5.13 B 5.14 B 5.15 B For isothermal process T1  T2
5.16 C 5.17 A 5.18 B
T2 P
5.19 D 5.20 B 5.21 C S  C p ln  R ln 2
T1 P1
5.22 A 5.23 B 5.24 B
5.25 B 5.26 D 5.27 B T1  T2
5.28 B 5.29 A 5.30 C P2 P
S   R ln   R ln  1 
5.31 C 5.32 C 5.33 B P1  P2 
5.34 D 5.35 D 5.36 B Hence, the correct option is (B).
5.37 C 5.38 B 5.39 C
5.8 (C)
5.40 B 5.41 D 5.42 B
5.43 A 5.44 C 5.45 A irreversible process
Q
ds 
E Explanation T
5.1 (A) Tds  Q

5.2 (A)  Tds  Q

Hence, the correct option is (C).
5.9 (A)
 Q 
ds     (s) gen
 T 
Process is irreversible and adiabatic
ds  ve ds  0
𝛿𝑄
Hence, the correct option is (A). ∫ = 0, 𝛥𝑠 > 0
𝑇
5.3 (D) Hence, the correct option is (A).
Q 5.10 (D)
ds   (s) gen
T
irreversible adiabatic process (𝛿𝑠𝑔𝑒𝑛 >
0, 𝛿𝑄 = 0)
ds  ve
For reversible adiabatic process
(sgen  0, Q  0)
ds  0
Hence, the correct option is (D).
Kulkarni’s Academy 81 Entropy

5.13 (B)

𝛿𝑄
 ∮𝑟𝑒𝑣. =0
𝑇
100 40 Q3
   0 WNet
500 400 300 
Qs
Q3  90 kJ
 Q  W (FLOT)
 140  Q3  W
For a cycle
W  140  90  50 kJ
Q
Hence, the correct option is (D). 
Qs
5.11 (B) 1
 Q  W  closed area = 2 (𝑇ℎ − 𝑇𝑐 )𝛥𝑠
𝑄𝑠 = 𝑇ℎ ⋅ 𝛥𝑠
1
(𝑇ℎ −𝑇𝑐 )𝛥𝑠
𝜂=2 𝑇ℎ ⋅𝛥𝑠
Q
dscold  𝜂=
0.5(𝑇ℎ −𝑇𝑐 )
T 𝑇ℎ
Q Hence, the correct option is (B).
 10 
500 5.14 (B)
Q  5000 kJ
Q 5000
dsHot    5 kJ/K
T 1000
Hence, the correct option is (B).
5.12 (B)

P1  0.1 MPa
Entropy is a non-conserved property
Q T1  5000C = 773 K
ds   (s) gen
T R  2.08 kJ/kgK
For adiabatic process heat transfer is zero. Cv  3.11 kJ/kgK
ds  sgen   ve
C p  5.19 kJ/kg K
ds  ve
In free expansion of ideal gas
s2  s1  (Entropy increases)
U1  U 2 T1  T2 H1  H 2
Hence, the correct option is (B).
Basic Thermodyanamics 82 Kulkarni’s Academy
T2 V Ti  298 K
dsHe  Cv ln  R ln 2
T1 V1 𝐶𝑤 = 4.187 kJ/kg𝐾
1 1  mRT1
PV 𝑑𝑠 = 𝑑𝑠𝑚𝑏 + 𝑑𝑠𝑤
PV 00  0.5 𝑑𝑠 = (𝑚𝐶 𝑙𝑛 𝑇𝐹)
𝑇 𝑇
+ (𝑚𝐶 𝑙𝑛 𝑇𝐹)
m 1 1

RT1 2.08  773 𝑖 𝑚𝑏 𝑖 𝑤
Heat lost by metallic block  Heat gain by water
=0.031 kg
𝑚𝑚𝑏 𝐶𝑚𝑏 (𝑇𝑖 − 𝑇𝐹 )𝑚𝑏 = 𝑚𝑤 𝐶𝑤 (𝑇𝐹 − 𝑇𝑖 )𝑤
dsHe  0.031 2.08ln 2  0.045 kJ/K
5  0.4  (773  TF )  40  4.186  (TF  298)
Hence, the correct option is (B).
TF  303.6 K
5.15 (B)
303.6  303.6 
ds  5  0.4  ln  40  4.187  ln  
773  298 
ds  1.248 kJ/K
Hence, the correct option is (C).
m  100 kg
Si  0.3 kJ/kg K 5.17 (A)

S F  0.4 kJ/kg K P1  1 bar

Si  30 kJ/K T1  250C  298 K
S F  40 kJ/K P2  2 bar
dssys  40  30  10 kJ/kg K T2  378 K
dssurr  75  80  5 kJ/kg K For adiabatic process dssurr  0
dsuniv  0 T2 P
dsuniv  dssys  CP ln  R ln 2
 dssys  dssurr  10  5 T1 P1
dssurr  5 kJ/K  378  2
 1.005ln    0.287  
dsuniv  0  298  1
The process is irreversible.  0.04 kJ/kgK
Hence, the correct option is (B). dsuniv  0 Process is possible and
5.16 (C) irreversible.
Hence, the correct option is (A).
5.18 (B)

Metallic block
mmb  5 kg
Timb  5000C  773 K
Cmb  0.4 kJ/kg K
Mass of water 𝑚𝑤 = 40 kg
Kulkarni’s Academy 83 Entropy
Note: Two reversible adiabatic will never  0.1 
dssys  8.314  ln  
intersect because reversible adiabatic is an  0.5 
isentropic process and there two same  13.38 kJ/K
entropy lines cannot intersect if intersect it
violate kelvin-plank statement. dsuniv  13.38 kJ/K
Hence, the correct option is (B). Hence, the correct option is (C).
5.19 (D) 5.22 (A)
5.20 (B) Statement-I

Hence, the correct option is (B).

5.21 (C)
2500 2500
n  1 mole dsuniv  
1200 800
h1  h2
dsuniv  sgen  1.041
𝑃1 = 0.5 MPa
Statement-II
𝑃2 = 0.1 MPa
Ti  300 K
During Throttling
h1  h2
For ideal gas h  CPT
CPT1  CPT2
T1  T2
sgen  dsuniv
In throttling
Q0 2000 2000
ds  
800 400
dssurr  0
dsuniv  sgen  1.5
𝑤=0
h1  h2 (ds )univ.2  ( ds )univ.1 ,

And process is irreversible, so So process 2 is more irreversible than process 1.

dsuniv  dssys  dssurr Hence, the correct option is (A).
{for adiabatic process dssurr. = 0 5.23 (B)
T2 P 5.24 (B)
dssys  C p ln  R ln 2
T1 P1
Basic Thermodyanamics 84 Kulkarni’s Academy
2
5.25 (B) T
ds  mC ln 3
TT
1 2

T3
ds  2mC ln
TT
1 2

Heat lost by I  Heat gain by II

mC (T1  T3 )  mC (T3  T2 )
𝑇1 +𝑇2
𝑇3 = = 𝐴𝑟𝑖𝑡ℎ𝑚𝑒𝑡𝑖𝑐 𝑚𝑒𝑎𝑛 (𝐴𝑀)
2

𝜂=
Net work √𝑇1 𝑇2 = 𝐺𝑒𝑜𝑚𝑒𝑡𝑟𝑖𝑐 𝑚𝑒𝑎𝑛 (𝐺𝑀)
𝑄𝑠
 T T 
 ds  2mC ln  1 2 
  Q  W  (300)2  70685.83 kJ
4  2 TT
1 2 

AM
dssys  2mC ln
GM
AM  GM
dssurr  0
dsuniv  dssys  dssurr ds
univ  sgen
AM
𝜋
𝑄𝑠 = (300 × 450) + 8 × 3002 dsuniv  dssys  2mC ln
GM
W  As AM is greater than GM, entropy
  41.5%
Qs change of universe is greater than
Hence, the correct option is (B). therefore mixing is an irreversible
process
5.26 (D)
Hence, the correct option is (B).
5.27 (B)
5.28 (B)
5.29 (A)
In isentropic process 𝐸𝑛𝑡𝑟𝑜𝑝𝑦(𝑆) =
𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 , 𝑑𝑆 = 0
Incompressible mean volume is constant so
dV  0
𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉
𝑇𝑑𝑆 = 𝑑𝑈
𝑇𝑑𝑆 = 𝑚𝑐𝑑𝑇
(𝑑𝑆 = 0)
0  mcdT
Tet us assume T1  T2
dT  0
ds  dsI  dsII Hence, the correct option is (A).
T3 T 5.30 (C)
 ds  mC ln  mC ln 3
T1 T2
Given data :
Kulkarni’s Academy 85 Entropy
T  C, Incompressible 𝜕𝑠
 𝑇( ) −𝑇( ) = 𝑅
𝜕𝑠
𝜕𝑇 𝑃 𝜕𝑇 𝑣
P1  400 kPa
Hence, the correct option is (C).
P2  4 MPa  4 10 kPa 3
5.33 (B)
For incompressible fluid
V C 5.34 (D)
dV  0 5.35 (D)
Tds  dU  pdV  0
5.36 (B)
Tds  dU
dU  mCdT dU  0 Tds  0 H  U  PV Given data :
T C U C ds  0 As U is Isothermal expansion
dT  0 S C constant,
volume is
constant but
Pressure is
changing.
So, H is not
constant. Difference in temperature is negligible and
process is very slow so,
Hence, the correct option is (C). it is considered as a reversible.
5.31 (C) dsuniv  0
P1  2 bar  200 kPa
T1  298 kPa
V1  1 m3 V2  2 m3

ds  
Q1
 1 J/K T C
T1 Tatm  298 K
Hence, the correct option is (C). V2
W  PV
1 1 ln  200 1 ln 2  138.6 kJ
5.32 (C) V1
dsuniv  dssys  dssurr .
138.6
dssurr   0.465 kJ/K
298
T V
dssys  CV ln 2  R ln 2
T1 V1
𝑇𝑑𝑠 = 𝑑ℎ − 𝑣𝑑𝑃 |𝑃 = 𝐶 T1  T2
Tds  CP dT V2
𝑑𝑠 dssys  R ln  0.296  ln 2
𝐶𝑃 = 𝑇 (𝑑𝑇) V1
𝑃
𝑑𝑠  0.2058 kJ/kgK
𝐶𝑉 = 𝑇 (𝑑𝑇)
𝑉
Basic Thermodyanamics 86 Kulkarni’s Academy
 R 8.314  5.40 (B)
 R  m  28 
 
5.41 (D)
PV1 1  mRT ,

PV 200 1 5.42 (B)

m 1 1
  2.267 kg
RT1 0.296  298
dssys  0.2058  2.267  0.465 kJ/K
dsuniv  0.465  0.465  0
𝐴𝑠 Process is reversible
𝑠𝑜, 𝑑𝑠𝑢𝑛𝑖𝑣 = 0
Hence, the correct option is (B).
5.37 (C)
5.38 (B)
dsuniv  0 dsuniv  0
Maximum pressure is possible when it is
reversible. (reversible)
1
TQ P   dssys  dssurr  0
 Q 
TP  PP  System is undergoing a cycle entropy is a property
1.41
ssys  0
 300   PQ  0.4
   
 350   150 
 PQ  87.4 kPa
Hence, the correct option is (B).
5.39 (C)

ds  0 cycle
dssurr  0

 dsI  dsII  0

TF T
TP  350 K PP  150 kPa mC ln  mC ln F  ln1
T1 T2
TQ  300 K PQ  50 kPa
 TF2 
T P
ds  CP ln 2  R ln 2
mC ln   ln1  TF2  TT
1 2

T1 P1  TT1 2

300 50 TF  TT
1.005  ln  0.287  ln  0.16 kJ/kgK 1 2
350 150
Hence, the correct option is (C). Hence, the correct option is (B).
Kulkarni’s Academy 87 Entropy

5.43 (A) T 
T2  1  1
W  Q1  Q2 mCP (T1  T2 )  T2 
  1  1
mCV (T3  T2 ) T 
Q1  mC (T1  TF ) T2  3  1
 T2 
Q2  mC (TF  T2 )
T 
W  mC [T1  TF  TF  T2 ]   1  1
  1  2 
T
 W  mC [T1  T2  2TF ] TF  TT  T3 
 T  1
1 2

 2 
W  mC T1  T2  2 TT 
1 2
Process 1-2 PC
 
2
W  mC T1  T2 V T
Hence, the correct option is (A). V1 V2

T1 T2
5.44 (C)
 
3 3  PV
PV 1 1

 400 11.4  100 V1

1.4
 400 
V1   
 100 

P3  V1 
1-2  P  C  
P1  V3 
2-3  V  C
Y
3-1  rev. adiabatic P 
V1  V3  3 
1-2  ( P  C)  P1 
𝑃𝑉 = 𝑚𝑅𝑇 V1  2.69 m3
V T
V1 T1 2.69
2-3  V  C  
V2 T2 1
𝑃𝑉 = 𝑚𝑅𝑇
P T Process 2-3 V C
Hence, the correct option is (C). P T
5.45 (A) P2 T2 T3 4
 ,  4
P3 T3 T2 1
QR
  1
QS 1.4[2.69  1]
  1
[4  1]
QR  mCP (T2  T1 )
  21.04%
QR  mCP (T2  T1 )
Hence, the correct option is (A).
QR  mCP (T1  T2 )
QS  mCV (T3  T2 )
NOTES
  T 
6.1 Available Energy (AE): (Exergy) Wmax (possible)  AE  Q1 1  0 
 T1 
The maximum possible work that can be
obtained in a cycle is known as available energy. This maximum possible work is known as
available energy.
 T 
AE  Q1 1  0 
 T1 

W

Q1
Wmax
max 
Q1
T2
max  rev  1 
T1
Wmax T
 1 2
Q1 T1
Heat supply Q1  T1S
 T 
Wmax  Q1 1  2  Heat rejection Q2  T0 S
 T1 
Q1  AE  Q2
This work can be further increased if temperature
of heat rejection (T2 ) is minimum. Minimum heat rejection = Unavailable energy
The lowest possible temperature of heat rejection (UAE)
is that of surroundings (T0 ) . Q1  AE  UAE

Work will be maximum when T2  T0 T0 S  Minimum heat rejection  UAE

Basic Thermodyanamics 89 Kulkarni’s Academy
6.2 Unavailable Energy (UAE) : Initial UAE  T0 S
The minimum heat rejection is known as Final UAE  T0 S '
unavailable energy i.e. area below atmospheric Q1  T2 S '
temperature (T0 ) represents unavailable energy  in UAE  T0S ' T0S
on T-S diagram.  T0 [S ' S ]
Q Q 
 T0  1  1 
 T2 T1 
 Q1 
Q1  T2S ' S '  T 
 2 
 
Q  T S S  Q1 
 1 1 T1 
T  T 
 in UAE  Q1T0  1 2 
 TT
1 2 

Example:
Loss of AE (increase in UAE) due to heat transfer:

* According to First Law of Thermodynamics,

thermal energy at higher temperature and the
same amount of thermal energy at lower
temperature have same meaning, therefore
First law of thermodynamics is known as
Quantitative law.
According to Second Law of
Thermodynamics, thermal energy at higher
temperature has greater significance when
compare to equal amount of thermal energy
at lower temperature because thermal energy
at higher temperature can produce more work
and hence Second Law of Thermodynamics
is known as Qualitative law.
Note: Thermal energy at higher temperature
must be preserve and hence steam turbines are
Q1  T1S insulated.
Kulkarni’s Academy 90 Available Energy, Availability & Irreversibility
6.3 Availability Qsurr  T0 dS surr … (iii)
The maximum work useful that can be obtained Qsys  dU sys  Wsys
in a process when the system comes in
equilibrium with atmospheric conditions Wsys  Qsys  dU sys

Note : Wsys  Qsurr  dU sys [From eq. (ii)]

Wsys  T0dSsurr  dU sys [From eq. (iii)]

Wsys  T0dSsys  dU sys [From eq. (i)]

Wmax  T0 ( S 2  S1 )  (U 2  U1 )

Wmax  (U1  U 2 )  T0 ( S1  S 2 )

In closed system as the expands against

For calculating availability, the reference state is
atmospheric conditions.
6.4 Maximum Work in a Closed System
atmospheric condition out of the maximum some
work is used for displacing atmospheric air. This
work cannot be utilized therefore maximum
useful work is equal to maximum work minus
atmospheric work.

dSuniv  0

dSuniv  0 (Reversible process)

dSsys  dSsurr  0

dSsys  dSsurr … (i)

Qsys  Qsurr … (ii)

Wmax.useful  Wmax  Watm

(U1  U 2 )  T0 ( S1  S 2 )  P0 (V2  V1 )

Wmax useful  (U1  T0 S1  PV

0 1 )  (U 2  T0 S 2  PV
0 2)
1 2

Q Wmax useful  1  2
dS 
T
  U  T0 S  PV
Q
0

dS surr  surr
T0 Availability function for a closed system.
Basic Thermodyanamics 91 Kulkarni’s Academy
6.5 Maximum Work in Open System
P Practice Questions
2 2
C C
h1   gz1  q  h2 
1
 gz2  W 2
6.1 The reference state for availability
2 2 computation is
K.E and P.E. changes are neglected
(A) Practical ambient conditions
h1  Q  h2  W (B) 0K, 1 bar
q  dh  W (C) 0K, 0 bar
Wmax  (h1  h2 )  T0 ( S1  S 2 ) (D) Triple point of water
(h1  T0 S1 ) (h2  T0 S2 ) 6.2 The difference in availability of a system
Wmax    Wmax useful between two states is
1 2
(A) The work done by the system
Wmax useful  1  2
(B) The heat input to the system
Change in availability or decrease in availability (C) The maximum possible work output
  h  T0 S from the prescribed change of states
Valid only when neglect KE and PE (D) None of the above
Availability function for open system 6.3 A large furnace can supply heat at a
temperature of 1200 K at a steady rate of
Irreversibility (I): 3200 kW. The ambient temperature is 27°C.
I  Wmax  Wact The availability of this energy is
(A) 0 kW (B) 800 kW
I  T0 (dS ) sys  (dS ) surr 
(C) 1200 kW (D) 2400 kW
I  T0 (dS )univ 6.4 For a steady flow process from state 1 to 2,
I  T0 (dS )univ enthalpy changes from h1  400 kJ/kg to

Valid for open and closed sys h2  100 kJ/kg and entropy changes from
dSuniv  S gen s1  1.1kJ/kg to s2  0.7 kJ/kg-K . The
surrounding environmental temperature is
I  T0gen
300 K. The change in availability of the
According to Guoy-stodola theorem system is.
irreversibility is directly proportional to entropy (A) 420 kJ/kg (B) 300 kJ/kg
generation.
(C) 180 kJ/kg (D) 90 kJ/kg
Note : 6.5 A heat reservoir at 900 K is brought into
 Irreversibility is never negative. contact with the ambient at 300 K for a short
 Gibbs function (𝐺) = 𝐻 − 𝑇𝑆 time. During this period 9000 kJ of heat is
Difference in Gibbs in gives maximum work for lost by the heat reservoir. The total loss in
open system availability due to this process is.
(A) 18000 kJ
 Helmholtz function ( F )  U  TS
(B) 9000 kJ
Difference in Helmholtz in gives maximum work
(C) 6000 kJ
for closed system.
(D) None of the above
Kulkarni’s Academy 92
6.6 The maximum work that can be obtained
from a closed system exchanging heat with
only the ambient during a process in which
the initial and final temperatures of the
system are equal to the temperature of the
ambient, is equal to the decrease in its
(A) Helmholtz energy
(B) Internal energy
(C) Gibbs energy
(D) Enthalpy
6.7 An engine reversibly receives 1200 J of heat
at 900 K. After rejecting heat to the ambient
at 300 K, it develops 600 J of work. The
irreversibility in joules is equal to
(A) 600 (B) 400
(C) 200 (D) Zero
6.8 A solid aluminium sphere 0.1 metres in
diameter and initially at 200ºC, is allowed to
cool to the ambient temperature of 25ºC. The
irreversibility of this process in kJ is (for
aluminium, density = 2700 kg/m3. Specific
heat 0.9 kJ/kg.K)
(A) 47.5
(B) 32.6
(C) 24.8
(D) 16.4
6.9 Air at state 1 at 5 and 1000 K having 0.01 kg
mass is expanded in a reciprocating cylinder
to state 2 at a pressure of 1 bar and
temperature of 600 K. Atmospheric
temperature and pressure are 300 K and 1 bar,
respectively. Decrease in availability of air
during the process in kJ is
( s1  836 J/kg.K, s2  787J/kg.K)
(A) 2.42 (B) 1.57
(C) 1.28 (D) 2.87
Available Energy, Availability & Irreversibility
6.10 Availability per unit mass associated with air
( R  297 J/kg.K, C p  1005J/kg.K &   1.4)
flowing from a reservoir at 10 atm and 25ºC
when atmosphere is at 1 atm and 25ºC is
(Neglect changes in the potential and the
kinetic energies)
(A) 98.4 kJ/kg (B) 196.6 kJ/kg
(C) 492.3 kJ/kg (D) 689.14 kJ/kg
6.11 In a certain steady flow process, vapour
enters a heat exchanger at 527ºC and is
condensed at the same temperature by
transferring heat at the rate of 1 kW to water
at 227ºC. The water, in turn, vaporizes at
227ºC. The atmospheric temperature is 27ºC
and the pressure is 0.1 MPa. The rate of loss
of available energy in Watts is
(A) 67.7 (B) 375
(C) 600 (D) 225
6.12 The pressure, temperature and velocity of air
flowing in a pipe are 5 bar, 500 K and 50 m/s,
respectively. The specific heats of air at
constant pressure and at constant volume are
1.005 kJ/kgK and 0.718 kJ/kgK, respectively.
Neglect potential energy. If the pressure and
temperature of the surroundings are 1 bar and
300 K, respectively, the available energy in
kJ/kg of the air stream is
(A) 170 (B) 187
(C) 191 (D) 213
6.13 A steel billet of 2000 kg mass is to be cooled
from 1250K to 450K. The heat released
during this process is to be used as a source
of energy. The ambient temperature is 303 K
and specific heat of steel is 0.5 kJ/kg K. The
available energy of this billet is
(A) 490.44 MJ (B) 30.95 MJ
(C) 10.35 MJ (D) 0.10 MJ
Basic Thermodyanamics 93 Kulkarni’s Academy

A Answer Key 6.4 (C)

Given data :
6.1 A 6.2 C 6.3 D
h1  400 kJ/kg
6.4 C 6.5 C 6.6 A
h2  100 kJ/kg
6.7 C 6.8 A 6.9 B
S1  1.1 kJ/kg-K
6.10 B 6.11 D 6.12 B
S 2  0.7 kJ/kg-K
6.13 A
T0  300 K
E Explanation Change in availability  1  2

6.1 (A)  (h1  h2 )  T0 ( S1  S 2 )

 (400 100)  300(1.1  0.7)
6.2 (C)  300 120  180 kJ/kg
Hence, the correct option is (C).
6.3 (D)
6.5 (C)
1200 k
Given data :
3200 kW
T1  900 K
T2  T0  300 K
Wmax  AE
Q1  9000 kJ
Q1T0 (T1  T2 )
Loss of A.E. 
300 k
T1T2
Q1T0 (T1  T0 )
T 
T1T0
Q1 (T1  T0 )

1200 k T1
9000  (900  300)
AE   6000 kJ
600
300 k
Hence, the correct option is (C).
UAE 6.6 (A)
S
6.7 (C)
 T 
Wmax  AE  Q1 1  0  900 k
 T1 
1200 J
 300 
 3200 1  
 1200  600 J

 2400 kW 600 J

Hence, the correct option is (D). 300 k

Kulkarni’s Academy 94 Available Energy, Availability & Irreversibility
According to Guoy-Stodola theorem,  298 
 1.41370  0.9  ln  
irreversibility  473 
I  T0 (dS )univ  0.58782 kJ/K
(dS )univ  (dS )sys  (dS )surr mcdT
(dS ) surr 
T
(dS ) sys  0 1.41371 0.9  (200  25)

Because system works on a cycle and for a 298
cycle change in properties is equal to zero.  0.747178 kJ/K
(dS )univ  (dS ) surr I  T0 (dSsys  dSsurr )

1200 600 2  298(0.58782  0.747178)

  
900 300 3  47.47 kJ/K
I  T0 (dS )univ
Hence, the correct option is (A).
6.9 (B)
2
 300   200 Joule Given data :
3
State : 1 State : 2
Hence, the correct option is (C).
P1  5 bar P2  1 bar
6.8 (A)
T1  1000 K T2  600 K
Given data :
S1  836 J/kg-K S2  787 J/kg-K
d  0.1
T0  300 K, P0  1 bar
4
Volume (V )  r 3 m  0.01 kg
3
3 1 1  mRT1
PV
4  0.1 
   mRT1 0.01 0.287 1000
3  2  V1  
P1 500
 0.5235 104 m3
 5.74 103 m3
  2700 kg/m3
2 2  mRT2
PV
Mass  V  1.41371 kg
mRT2 0.01 0.287  600
V2  
T1  200 C  473 K
0
P2 100
 0.01722 m3
Aluminium
Sys. (Wmax )useful  1  2
sphere
(T1 )  (U1  U 2 )  T0 ( S1  S 2 )  P0 (V2  V1 )
 mCv (T1  T2 )  T0 ( S1  S 2 )  P0 (V2  V1 )
Q
 0.01 0.718(400)  300  0.01
T2  298 k Surr.  (0.836  0.787)
I  T0 (dSsys  dSsurr )  100  (0.01722  5.74 103 )

T2 (Wmax ) useful  1.577 kJ

(dS ) sys  mc ln
T1 Hence, the correct option is (B).
Basic Thermodyanamics 95 Kulkarni’s Academy

6.10 (B) At dead state C0  0

Given data : 1(i)

P1  10 atm , T0  250 C  298 K , P0  1 atm

1

Dead
0( f ) state
Dead state C12  C02
0 1  0  h1  h0  T0 (S1  S0 ) 
At dead state availability (0 )  0 2000
1  0  (h1  h0 )  T0 ( S1  S0 ) C2
1  CP (T1  T0 )  T0 (S1  S0 )  1
2000
0  0
1  1.005  (500  300)
1  CP (T1  T0 )  T0 ( S1  S0 )
 T P  502
{h  CPT }  T0 CP ln 0  R ln 0  
 T1 P1  2000
As T1  T0  1.005  200  300
So, 1  T0 ( S1  S0 )  300 1
1.005ln  0.287 ln 
 T P  500 5
 T0 CP ln 0  R ln 0 
 T1 P1  502

 1 2000
1  298  0.287  ln 
 10  1  186.809 187 kJ/kg
1  196.6 kJ/kg Hence, the correct option is (B).
Hence, the correct option is (B).
6.13 (A)
6.11 (D)
Given data :
Given data : m  2000 kg, T1  1250 K, T2  450 K
T1  5270 C  800 K , Q1  1000 W T0  303 K, C  0.5 kJ/kg-K
T2  227 C , T0  27 C
0 0
 T 
Q T (T  T ) AE  Q1 1  0 
Loss in AE  1 0 1 2  T1 
TT
1 2 (Used when temperature is not changing)
1000  300(800  500) Available energy when temperature is
  225 Watt
800  500 changing given by
Hence, the correct option is (D). T
 T 
2

  mc 1  0  dT
6.12 (B) T1  T 
Given data : 450 450
dT
P1  5 bar , T1  500 K , C  50 m/s 
1250
 mcdT  
1250
mcT0
T
CP  1.005 kJ/kg-K  2000  0.5  (450  1250)
CV  0.718 kJ/kg-K 450  490.4 MJ
 2000  0.5  303  ln
Potential energy changes are neglected 1250
P0  1 bar , T0  300 K Hence, the correct option is (A).
NOTES
  ℎ = 𝑢 + 𝑃𝑣 (For Liquid Specific volume
7.1 Properties of Pure Substances
(v) is less)
Explanation:
Hence,𝑃𝑣 = 0
For phase change of Water at
200 C  Steam at 2000C h U
C pT  CvT  CT

C p  Cv (Only for Liquids)

 Specific volume (𝑣) is larger

So, 𝑃𝑣 ≠ 0
C p  Cv For gas
Experiment –I Experiment -II
Critical point: It is the point at which saturated
Steps during phase change:
liquid and saturated vapour curve meet. At this
i. Water at 200 C (1) to Water at 1000 C (2)
point it is difficult to distinguish between liquid
( Liquid to Liquid) and vapour.
ii. Water at 1000 C (2) to Steam at 1000 C (3)
(Liquid to vapour) Similarly, we can plot a graph between T and S
iii. Steam at 1000 C (3) to Steam at 2000 C (4), as follows-
(Vapour to Vapour). Corresponding T-S
diagram as follows.

(1) Subcooled or Undercooled or compressed

liquid region
Basic Thermodynamics 97 Kulkarni’s Academy

It is region in which the actual temperature is less

than saturation temperature corresponding to that
pressure.
Degree of sub-cooling  Tsat  Tact
7.2 Sensible Heat (SH)
The heat transfer associated with temperature
difference is known as sensible heat.
SH  mCT
Latent heat (LH): The heat transfer is associated
with phase change is known as latent heat.

This region is also known as compressed liquid

region because Pact is greater than Psat
corresponding to that temperature.
(2) Superheated Region: It is a region is which
actual temperature is greater than saturation
corresponding to that pressure.
Degree of superheat  Tact  Tsat

At lower pressure less molecular activity so more

latent heat is required and vice versa.
(3) Wet Region: It is the region in which both
With increase in pressure, Latent heat of vaporization
liquid and vapour exists in equilibrium.
decreases. At critical point, Latent heat of
When the point is in wet region it will exists
vaporization is zero.
at saturation temperature.
Kulkarni’s Academy 98 Properties of Pure Substances
7.3 Dryness fraction (Quality of mixture) [x] m m
v  L vL  v vL
It is the ratio of mass of vapour to the total mass m m
mv mL
of mixture. v vv  vL
mV mv  mL mv  mL
x
mV  mL v  xvV  (1  x )vL
At critical we can’t distinguish liquid and vapour, mL
(Since 1  x  )
so can’t calculate x at critical point. mV  mL
v  xvv  vL  xvL
v  vL  x (vV  vL )
v  vF  x(vg  vF )
Similarly
H = Hg + Hf = hf +x (hg – hf)
S = Sg + Sf = sf +x (sg – sf)
U = Ug + Uf = uf +x (ug – uf)
 Throttling calorimeter used to measure Example 1
dryness fraction of pure substance. When to treat super-heated vapour as an ideal
 All constant dryness fraction lines converse gas?
at critical point.
Sol. Superheated vapour can be treated as an ideal
7.4 Specific properties of mixture:
gas at low pressures. In vapour compression
Specific Volume of Mixture: refrigeration system pressures are low and
V  VL  VV  VF  Vg hence superheated vapour can be treated as
V an ideal gas.
v
m Enthalpy of various points:
V  mv (1) When the point is on saturated vapour
m  mV  mL curve:
mv  mL vL  mV vV
mLvL  mV vV
v
m

hi  hg
hg  h f  LH
LH  hg  h f
Basic Thermodynamics 99 Kulkarni’s Academy
Case: 2 when the point is in wet region S1  S f  S
S g  S f  S
LH
Sg  S f 
Tsat
Q
dS 
T
LH
Sg  S f 
Tsat
LH hg  h f
dS  
Tsat Tsat
h1  h f  x(hg  h f )
Phase change is a reversible process during phase
h1  h f  x( LH ) change complete system us at same temperature
Case 3: When the point is in superheated and same pressure.
region (2) When the point is in wet region:

h1  hg  h
S1  S f  x(S g  S f )
h1  hg  C p (T )
 LH 
h1  hg  C pvapour (T1  Tsat ) S1  S f  x  
 Tsat 
Entropy at various points:
(3) When the point is in superheated region:
(1) When the point is on saturated vapour
curve:
Kulkarni’s Academy 100 Properties of Pure Substances
1 is in superheated region at low pressure vapour In superheated region constant pressure line
can be treated as ideal gas so we used ideal gas diverge, because slope of constant pressure line
equation for entropy change in this region. = temperature. As the temperature increases - the
S1  S g  S slope also increases and during phase change as
temperature is constant- slope is constant and
Tf Pf therefore on Mollier diagram constant pressure
S  C p ln  R ln
Ti Pi liens are straight lines in wet region.
T P-V diagram:
S  C p ln 1
Tsat
T1
S1  S g  CPv ln
Tsat
Mollier Diagram: h-s diagram is known as
Mollier diagram.

For liquid change in pressure v is less.

For vapour change in pressure v is large
That why curve like this
Solid  Liquid  Melting
Liquid  Solid  Freezing
Liquid  Vapour  Vaporization
dh
Slope on h-s curve represented by Vapour  Liquid  Condensation
ds
Solid  Vapour  Sublimation
TdS  dh  VdP
General Substances Water
P  C, dP  0
Solid  liquid  Ice  water =
TdS  dh expands contracts
dh Liquid  solid  Water  ice =
T
ds contracts expands

P-T Diagram:

dh
 Tkelvin
ds
T in kelvin can never be negative
Basic Thermodynamics
( P1, Tsat1 ), ( P2 , Tsat2 ), ( P3 , Tsat3 )
101 Kulkarni’s Academy
properties can be changed i.e. intensive
properties are fixed at triple point. Therefore,
triple point is a unique state.
 On P-V diagram triple point is a line and on P-T
diagram triple point is a point.
 On U-V diagram triple point is a triangle.

7.4 General Substances

 For water the slope of fusion curve on P-T
diagram is negative.
 Representation of all the three phases on P-V
diagram.

Triple Point Data for Water:

Reference State in Standard Steam Tables:

The internal energy (U) and entropy (S) of
saturated liquid at triple point temperature
(0.010 C) is arbitrary taken as zero.

PF C2
3  F  1 2
F 0
Where F  Minimum no. of independent
intensive variable required to fix the state = 0
U  0, S  0
According to Gibb’s phase rule to D.O.F. at triple
point is zero, i.e. the minimum no. of independent
intensive variable required to fix the state at triple
point is zero i.e. at triple point np intensive
Kulkarni’s Academy 102 Properties of Pure Substances
7.5 Two systems A and B, processing the same
P Practice Questions
internal energy, contain saturated liquid -
7.1 At its critical point, any substance will vapour mixture of water at 1 MPa, The
(A) Exist in all the three phases maximum value of the ratio of their masses is
(B) Change directly from solid to vapour (u f  761.7 kJ/kg, ug  2583.6 kJ/kg)
(C) Lose phase distinction between liquid
and vapour (A) 1.4 (B) 2.4
(D) Behaves as an ideal gas (C) 3.4 (D) 4.4
7.2 Consider the following properties of vapour 7.6 A pressure cooker contains saturated water
1. Pressure vapour mixture at 1000 C with volume of
2. Temperature vapour being eight times that of the volume
3. Dryness friction of liquid. The specific volume saturated
4. Specific volume liquid and saturated vapour at 1000 C are,
Which of these two properties alone are not V f  _______ 3 /kg
sufficient to specify the condition of a
vapour? and Vg  1.6729 m3 /kg, 1000C respectively.
(A) 1 and 2 (B) 1 and 3 The quality of the mixture is
(C) 2 and 3 (D) 3 and 4
(A) 0.005 (B) 0.125
7.3 In a steam turbine, superheated steam at state
(C) 0.889 (D) 0.995
1 is made to expand isentropically from
pressure P1 to a dry saturated condition at 7.7 A rigid vessel contains saturated liquid-
vapour mixture of water at 10 MPa. On being
pressure P2 . If the expansion occurs
heated, the mixture reaches the critical point.
irreversibly between these two pressures,
then the final condition of steam at state 2 The initial quality of the mixture is
will be. approximately. Given: Critical specific
(A) Saturated liquid volume, Vw  0.00317 m3 /kg
(B) Superheated steam
(C) Wet steam
(D) Dry saturated vapour. (A) 1% (B) 5%
7.4 The reference state adopted in the standard (C) 10% (D) 15%
steam tables assigns the following numerical
7.8 A substance expands on freezing only if
values to the thermodynamic properties.
(A) The slope of the sublimation line on
(A) h = 0 and s = 0 for liquid water at 00 C
pressure-temperature chart is negative
and 1 bar
(B) h = 0 and s = 0 for liquid water at its (B) The slope of the sublimation line on
triple point pressure-temperature chart is positive
(C) u = 0 and s = 0 for liquid water at 00 C (C) The slope of the fusion line on pressure
and 1 bar temperature chart is negative
(D) u = 0 and s = 0 for liquid water at its (D) The slope of the fusion line on pressure
triple point temperature chart is positive
Basic Thermodynamics
7.9 The entropy of saturated water at a pressure
of 1 bar is given in the table. The saturation
temperature corresponding to this pressure is
99.630 C . The entropy of dry saturated steam
at the same pressure in kJ/kg-K is 99.630 C
(A) 130.26 (B) 7.362
(C) 23.96 (D) 3.561
7.10 A Saturated liquid vapour mixture of
refrigerant has a density of 36.12 kg/m3 at
300 C . If the densities of saturated liquid
and saturated vapour at 300 C are
1377 kg/m 3 and 7.379 kg/m3 , respectively,
the quality of the mixture is
(A) 0.98 (B) 0.2
(C) 0.02 (D) 0.80
7.11 A frictionless piston cylinder arrangement is
loaded with outside atmospheric pressure, P0
and piston mass to a pressure of 200 kPa as
shown below. It contains water at a dryness
fraction of 0.4, and occupies a volume of
1 m3 , It is then cooled slowly by rejecting
heat to the surroundings which is at 300 C . In
the final state, the temperature of water is
same as that of surroundings.
The specific internal energy and specific
0
enthalpy of liquid water at 30 C and 200 kPa
are both equal to 125.77 kJ/kg. The heat
transfer from the water to the surroundings in
kJ is
103 Kulkarni’s Academy
(A) 1260 (B) 3150
(C) 3350 (D) 3550
7.12 A rigid closed vessel of volume 20 m3
contains dry saturated steam at 1 MPa. The
vessel loses heat to the surroundings and as a
result, the pressure reduces to 0.1 MPa. The
surrounding temperature and pressure are
270 C and 0.1 MPa. The heat lost by the
vessel to the surroundings in MJ is
(A) 1.9 (B) 2.1
(C) 198.3 (D) 216.3
7.13 In the Mollier diagram for steam, dryness
fraction lines converge at
(A) Triple point
(B) Critical point
(C) Saturation point
(D) None of these
7.14 A rigid spherical vessel contains 1 kg of wet
steam of quality x at pressure P1 . This is
shown by point A on the T-v diagram. Heat
is transferred to the vessel to form
superheated steam at pressure P2 and
temperature T2 as shown by point B. Specific
enthalpy and specific internal energy
corresponding to the saturated water and
saturated vapour at pressure P1 and P2 as well
as at points A and B are given by
Heat transferred to the steam is
Kulkarni’s Academy 104 Properties of Pure Substances
7.16 Consider the phase diagram of a certain
substance as shown in figure. Match List I
(Process) with List II (Curves/lines) and
select the correct answer using the codes
given below the lists.

(A) hB  hA (B) hB  h f1
(C) u B  u A (D) uB  u f1
7.15 Which PV diagram for steam illustrates
correctly the isothermal process undergone
by wet steam till it becomes superheated?
List I List II
P. Vaporisation 1. EF
Q. Fusion 2. EG

(A) R. Sublimation 3. ED
(A) P-1, Q-3, R-2 (B) P-1, Q-2, R-3
(C) P-3, Q-2, R-1 (C) P-3, Q-1, R-2
7.17 The given diagram shows the throttling
process for a pure substance. The ordinate
and abscissa are respectively.

(B)

(A) Pressure and volume

(B) Enthalpy and entropy
(C) (C) Temperature and entropy
(D) Pressure and enthalpy
7.18 Superheated Steam enters adiabatic turbine
steadily at 4500 C and 4 MPa and leaves at
50 kPa. The minimum possible dryness
fraction of steam at turbine exit is
approximately
(D) (A) 85% (B) 90%
(C) 95% (D) 97%
Basic Thermodynamics 105 Kulkarni’s Academy
Take at 4 MPa and The tank is now slowly heated. The liquid
4500 C, S  6.9362 kJ/kg-K level inside the tank

At (A) Will rise

50 kPa  s f  1.091 kJ/kg-K, (B) Will fall
sg  7.5939 kJ/kg-K
(C) Will remain constant
7.19 Saturated liquid water at 0.4 MPa and 1000
kg/hr of steam at 0.4 MPa and 3000 C enter (D) May rise or fall depending on the
steadily into an insulated mixing chamber. At amount of heat transferred.
0.4 MPa, the enthalpy of saturated liquid and 7.22 When wet steam flows through a throttle
saturated vapour are 604.73 and 2738.53 valve and remains wet at exit.
kJ/kg respectively; also, the enthalpy of
superheated steam at 3000 C is 3066.75 kJ/ (A) Its temperature and quality increases
kg. The quality of the water-vapour mixture (B) Its temperature decreases but quality
exiting the chamber is 0.9. The mass flow rate increases
of saturated liquid water in kg/hr is
(A) 182 (B) 282 (C) Its temperature increases but quality
decreases
(C) 382 (D) 1000
7.20 Match items Group I with those in Group II (D) Its temperature and quality decreases
Group I
7.23 Which of the statements regarding pure
P. Critical point substances are correct.
Q. Dry saturated vapour
P. At a pressure below triple point pressure
R. Superheated vapour
pure substances can not exist in liquid
Group II state
1. Quality = 1.0
Q. At a pressure below triple point pressure
2. v f  vg
substance when heated transforms from
3. T  Tsat solid to liquid
4. T  Tsat R. At a pressure below triple point pressure
(A) P-1, Q-2, R-3 substance when heated transforms from
solid to vapour
(B) P-1, Q-3, R-2
(C) P-2, Q-1, R-3 (A) P and R (B) Q and R
(D) P-2, Q-1, R-4
(C) Only P (D) Only Q
7.21 Water has a critical specific volume of
0.003155 m3 /kg . A closed and rigid steel 7.24 A steam turbine operates with a superheated
steam flowing at 1 kgs 1 . This steam is
tank of volume of 0.025 m3 /kg contains a
mixture of water and steam at 0.1 MPa. The supplied at 41 bar and 5000 C , and discharges
mass of the mixture is 10 kg. at 1.01325 bar and 1000 C .
Kulkarni’s Academy 106 Properties of Pure Substances
7.27 Assertion (A): For a mixture of solid, liquid
and vapour phases of a pure substance in
equilibrium, the number of independent
intrinsic properties needed is equal to one.
Reason (R) : The three phases can coexist
only at one particular pressure
(A) Both A and R are individually true and
R is the correct explanation of A
(B) Both A and R are individually true but R
is not the correct explanation of A
(C) A is true but R is false
(D) A is false but R is true
7.28 Assertion (A): When solid CO2 (dry ice) is
The maximum power output (in kW) will be exposed to the atmosphere, it gets
(A) 644.0 (B) 767.9 transformed directly into vapour absorbing
(C) 871.3 (D) 3024.8 the latent heat of sublimation from the
7.25 For a pure substance at 50ºC and 10 bar; only surroundings.
the following saturation properties are Reason (R) : The triple point of CO2 is at
available about 5 atmospheric pressure and at 216 K
(A) Both A and R are individually true and
R is the correct explanation of A
(B) Both A and R are individually true but R
is not the correct explanation of A
The entropy of the substance at 500 C and 10 (C) A is true but R is false
bar is approximately:
(D) A is false but R is true
(A) 7.3313 kJ/kg-K
Linked Data Questions 29 and 30
(B) 2.1386kJ/kg-K
(C) 0.7037kJ/kg-K The following table of properties was printed
(D) 1.4214kJ/kg-K out for saturated liquid and saturated vapour
of ammonia. The title for only the first two
7.26 Assertion (A): In mollier chart for steam, the
columns are available. All that we know that
constant pressure lines are straight lines in
the other columns (columns 3 to 8) contain
wet region.
data on specific properties, namely, internal
Reason (R) : The slope of constant pressure
energy (kJ/kg), enthalpy (kJ/kg) and entropy
lines in wet region is equal to T.
(kJ/kg-K)
(A) Both A and R are individually true and
R is the correct explanation of A
(B) Both A and R are individually true but R
is not the correct explanation of A 7.29 Specific enthalpy data are in columns
(C) A is true but R is false (A) 3 and 7 (B) 3 and 8
(D) A is false but R is true (C) 5 and 7 (D) 5 and 8
Basic Thermodynamics 107 Kulkarni’s Academy

7.30 When saturated liquid at 400 C is throttled to Pressure Saturation v f (m3 /kg) vg (m3 /kg)
200 C , the quality at the exit will be (kPa) temp.

(A) 0.189 (B) 0.212 Tsat (0 C)

(C) 0.231 (D) 0.78 100 100 0.001 0.1
Common Data Questions 31 to 33 200 200 0.0015 0.002

In the figure shown, the system is a pure

7.31 At the end of the process, which one of the
substance kept in a piston-cylinder
following situations will be true?
arrangement. The system is initially a two-
phase mixture containing 1 kg of liquid and (A) Superheated vapour will be left in the
0.03 kg of vapour at a pressure of 100 kPa. system
Initially, the piston rests on a set of stops, as (B) No vapour will be left in the system
shown in the figure.
(C) A liquid + vapour mixture will be left in
the system
(D) The mixture will exist at a dry saturate
vapour state
7.32 The work done by the system during the
process is
(A) 0.1 kJ (B) 0.2 kJ
(C) 0.3 kJ (D) 0.4 kJ
7.33 The net entropy generation (considering the
A pressure of 200 kPa is required to exactly
system and the thermal reservoir together)
balance the weight of the piston and the
during the process is closest to
outside atmospheric pressure. Heat transfer
takes place into the system until its volume (A) 7.5 J/K (B) 7.7 J/K
increases by 50%. (C) 8.5 J/K (D) 10 J/K
Heat transfer to the system occurs in such a
manner that the piston, when allowed to
move, does so in a very slow (quasi-static /
quasi equilibrium) process. The thermal
reservoir from which heat is transferred to the
system has a temperature of 4000 C . Average
temperature of the system boundary can be
taken as 1750 C . The heat transfer to the
system is 1 kJ, during which its entropy
increases by 10 J/K. Specific volume of
liquid v f and vapour vg phases, as well as
values of saturation temperatures, are given
in the table below.
Kulkarni’s Academy 108 Properties of Pure Substances
A Answer Key 7.5 (C)

7.1 C 7.2 A 7.3 B U A  U B (Given)

7.4 D 7.5 C 7.6 A

7.7 C 7.8 C 7.9 B
7.10 B 7.11 D 7.12 C
7.13 B 7.14 C 7.15 C
7.16 C 7.17 D 7.18 B
7.19 B 7.20 C 7.21 A
7.22 B 7.23 A 7.24 C
U
7.25 C 7.26 A 7.27 D u
m
7.28 A 7.29 B 7.30 B U  mu
7.31 A 7.32 D 7.33 C  mAU A  mBU B
mA uB uF  xB (u g  u f )
E Explanation  
mB u A uF  xA (u g  u f )

7.1 (C)  mA  uF  xB (u g  u f )
  
 mB max uF  xA (u g  u f )
7.2 (A)
U g and U f can’t be change because pressure
7.3 (B) is fixed. So, for maximum value of
mA xB (max)  1

mB xA (min)  0
uF  1(ug  u f )

uF  0
 mA  u g 2583.6 kJ/kg
     3.4
 mB max u f 761.7 kJ/kg
Hence, the correct option is (C).
Because turbines are insulated, (i.e.
adiabatic) 7.6 (A)

In adiabatic process entropy increases or vF  0.001051 m3 /kg

entropy remains constant but entropy can vg  1.6729 m3 /kg
never decrease.
vg  8v f
Hence, the correct option is (B).
V V
7.4 (D) v m
m v
Basic Thermodynamics 109 Kulkarni’s Academy
mV 1 1 7.8 (C)
x  
mV  mL 1  mL VF
mV v 7.9 (B)
1 F
Vg
vg
1
Or
m
1 f
mg
1

V v
1 F g
vFVg Tsat  372.63 K
1 LH
 s g  sF 
VF 1.6729
1 Tsat
0.001051 8VF
(hg  hF )
1 s g  sF 
 Tsat
1.6729
1
8  0.001051 (2675.5  417.5)
 1.3025 
1 372.63

1.6729 =7.362 kJ/kgK
1
0.008408 Hence, the correct option is (B).
1
  0.005 7.10 (B)
199.965
Hence, the correct option is (A).
7.7 (C)

F  1377 kg/m3 ,  g  7.379 kg/m3

1

v(Specific Vol.)
v1  v2  vCr  0.00317
 v  vF  x (vg  vF )
v1  vF  xvFg
1 1  1 1 
0.00317  0.001452  x    x  
 F   
(0.01802  0.001452)  g F 

(0.00317  0.001452) 1 1  1 1 
x   x  
(0.01802  0.001452) 36.12 1377  7.379 1377 
x  0.1036  10.3%  x  0.2
Hence, the correct option is (C). Hence, the correct option is (B).
Kulkarni’s Academy 110 Properties of Pure Substances
7.11 (D) 7.12 (C)

Fig. (1) Fig. (2)

QP C  dh

 h2  h1 QV  du  u2  u1
u1  ug at 1 MPa  2583.6 kJ/kg
h1  hF  xhFg
v1  vg at 1 MPa
 504.7  0.4(2706.70  504.7) v2  v1  0.1944 m3 /kg

 1385.5 kJ/kg v2  vF  x (vg  vF )

0.1944  0.001043  x
QPC  h2  h1  125.77  1385.5
(1.694  0.001043)
 1259.7 kJ/kg
x  0.114
V  u2  417.4  x (2506.1  417.3)
v
m u2  655.5 kJ/kg

V Q  u2  u1  655.5  2583.6
m  1928.1 kJ/kg
v
V 20
v1  vF  xVFg m   102.88 kg
v 0.1944
 0.001061  0.4(0.8857  0.001061) Q  1928.1102.88
 198364.197 kJ
v1  0.355 m3 /kg  198.364 MJ
1 Hence, the correct option is (C).
m  2.82 kg
0.355 7.13 (B)

kJ
QP C  1259.7  2.89  kg
kg

  3550 kJ

(Here negative sign represents heat

rejection).
Hence, the correct option is (D).
Basic Thermodynamics 111 Kulkarni’s Academy

7.14 (C) T  3000C

hg  3066.75 kJ/kg
7.15 (C)
hg  h f  xhFg
7.16 (C)
 604.73  0.9(2738.58  604.73)
7.17 (D)
h3  2525.15 kJ/kg
7.18 (B)
By using steady flow energy equation
KE  0, P.E  0
Q 0 (Assumptions)
Then
m1h1  m2 h2  m3h3

m1 (604.73)  1000(3066.75)
 (m1  1000)(2525.15)
For minimum x, process must be isentropic m1  282 kg/hr
S1  S 2
Hence, the correct option is (B).
S1  6.9362
7.20 (C)
S1  S 2  6.9362
7.21 (A)
S2  SF  xSFg
6.9362  1.091  x (7.5939 1.091)
x  0.899  90%
Hence, the correct option is (B).
7.19 (B)
ms  1000 kg/hr

vcr  0.003155

V  0.025 m3
P  0.1 MPa
m  10 kg
0.025
Properties of steam given: vact   0.0025 m3 /kg
10
h2  1000 kg/hr
Then, the liquid level will rise.
P  0.4 MPa Hence, the correct option is (A).
Kulkarni’s Academy 112 Properties of Pure Substances
7.22 (B) Discharge Pressure and temperature =
1.01325 bar, T  1000C
When wet steam flows through a throttle
valve and remains wet at exit - P?

For maximum power output process must be

T1  T2 reversible.
  m (h1  h2 )
Temperature  dryness fraction (x) 
During throttling m 1 kg/s h1  3443.9 kJ/kg
Q 0 S1  S 2
dS Surr  0  s1  s2  sF  x (sg  sF )
dSuniv  0  7.0785  1.3069  x (7.3554 1.3069)
dSSys  dSSurr  0 x  0.954
dSSys  0 h2  hF  xhFg

s2  S1  419.1  0.954(2676  419.1)

Hence, the correct option is (B). h2  2572.09 kJ/kg

7.23 (A) P  1(3443.9  2572.09)

P  871.71 kW
Hence, the correct option is (C).
7.25 (C)

Below triple point there is no liquid only solid

and vapor phase are present.
Hence, the correct option is (A).
7.24 (C)
Given data :
m  1 kg/s S1  S F at 500C
P  41 bar  0.7031 Nearest option is (C).
T  100 C 0
Hence, the correct option is (C).
Basic Thermodynamics 113 Kulkarni’s Academy

7.26 (A)

During throttling h1  h2
h2  hF  xhFg
dh
T
dS  371.43  89.05  x (1418  89.05)
Hence, the correct option is (A). x  0.212
7.27 (D) Hence, the correct option is (B).
7.31 (A)
7.28 (A)
Initial dryness fraction
0.03
( x1 )   0.02913
1  0.03
Initially the system is at 100 kPa
Initial specific volume
(v1 )  v f  x1 (vg  v f )

v f and vg are at 100 kPa

Triple point pressure for CO 2
v1  0.001  x1 (0.1  0.001)
Ptp  5 bar
v1  3.884 103 m3 /kg
But solid CO 2 exposed at 1 atm.
Initial total volume  mv1  V1
Hence, the correct option is (A).
 1.03 3.88 103
7.29 (B)
V1  0.004 m3
7.30 (B)
Final volume  V2  1.5V1  1.5  0.004

V2  0.006 m3
Final pressure of the system  P2  200 kPa

At 200 kPa, vg  0.002  2 103 m3 /kg

As the actual final specific weight, v2  vg at

200 kPa steam is in super-heated state
Hence, the correct option is (A).
Kulkarni’s Academy 114 Properties of Pure Substances
7.32 (D)
Work done  P (V2  V1 )
When the system reaches 200 kPa, then the
rise of piston will take place
W  200(0.006  0.004)  0.4 kJ
Hence, the correct option is (D).
7.33 (C)
Given data : dSsys  10 J/K

dQ
dS   S gen
T
If system and reservoir are taken as a system,
it will be universe
0
dSuniv   S gen
T
dSuniv  Sgen
Since Q  0 for universe
dSsys  dSsurr  S gen
1000
dS  surr  J/K
673
 1000 
10     S gen
 673 
S gen  8.51 J/K
Note : If the generation is to be calculated
only for system
dQ
dSsys   S gen
T
000
10   S gen
(273  175)
S gen  7.767 J/K
Hence, the correct option is (C).
NOTES
 (3) G  H  TS
8.1 Thermodynamics Relations
dG  dH  TdS  SdT
Th.1 The equation ds  mdz  ndy is an exact {TdS  dH  VdP
differential equation if, dH  TdS  VdP}
 M   N  dG  VdP  SdT
     V   S 
 y  x  x  y      … (iii)
 T  P  P T
Th.2 f  ( x, y, z)
(4) F  U  TS
 x   y   z  dF  dU  TdS  SdT
      1 {TdS  dU  PdV
 y  f  z  f  x  f
 PdV  dU  TdS}
Th.3 z  f ( x, y)
dF  PdV  SdT
 x   y   z   P   S 
       1     
 y  z  z  x  x  y  T V  V T
8.2 Maxwell’s Equations  P   S 
    ….(iv)
(1) TdS  dU  PdV  T V  V T
𝝏𝑻 𝝏𝑷 𝝏𝑽 𝝏𝑺
dU  TdS  PdV (𝟏) ( ) = ( )
𝝏𝑽 𝝏𝑺
𝑺 𝑽
(𝟐) (𝝏𝑻) = − (𝝏𝑷)
𝑷 𝑻
dz  Mdx  Ndy 𝝏𝑻
(𝟑) ( ) = ( )
𝝏𝑽 𝝏𝑷 𝝏𝑺
(𝟒) (𝝏𝑻) = (𝝏𝑽)
𝝏𝑷 𝝏𝑺
𝑺 𝑷 𝑽 𝑻
M  T , x  S , N  P, y  V
8.3 Physical Meaning of Enthalpy
 M   N 
    It is the microscopic form of energy of a flowing
 y  x  x  y
fluid.
 T   P  Note: Internal energy is also microscopic form of
    … (i)
 V  S  S V energy but it is for stationary fluid.
(2) TdS  dH  VdP
dH  TdS  VdP
 T   V 
    … (ii)
 P  S  S  P
Basic Thermodynamics 116 Kulkarni’s Academy
 The microscopic form of energy of a flowing   P  
fluid is greater than the microscopic form of dU  Cv dT  T    P  dV
  T v 
energy of a stationary fluid.
Case 1 : Constant volume process (any gas)
 Difference in the microscopic form of energy
V C
of flowing fluid and that of stationary fluid is
dV  0
equal to flow work [PV]
𝑑𝑢 = 𝐶𝑣 𝒅𝑻 - Valid for any gas undergoing
U  PV  U  PV
constant volume process
8.4 TdS Equations:
𝑑𝑢 = 𝐶𝑣 𝒅𝑻 is valid for any gas undergoing
1st TdS equation
constant volume process.
S  F (T , V )
Case 2 : Ideal gas
 S   S  mR P
dS    dT    dV PV  mRT  
 T V  V T V T
Multiply T both side, mR
P T
 S   S  V
TdS  T   dT  T   dV
 T V  V T  P  mR P
   
 T  T  T V V T
  
 S  P C p  P   P 
T   P or T   P0
 S   S   T V  T V
Cp  T   Cv  T  
 T  P  T V  The equation 𝑑𝑢 = 𝐶𝑣 𝑑𝑇 is valid for real gas
sonly under constant volume process/
 P 
TdS  Cv dT  T   dV conditions.
 T v  𝑑𝑢 = 𝐶𝑣 𝑑𝑇 is valid for ideal gas undergoing
T
Or TdS  Cv dT  dV any process.
K Equating two TdS equations we have
This equation is valid for any gas.  P 
2nd TdS Equation TdS  Cv dT  T   dV
 T v
S  F (T , P)
 V 
 S   S   C p dT  T   dP
dS    dT    dP  T  p
 T  P  P T
 P   V 
 S   S  T  dV  T   dP  (CP  CV )dT
TdS  T   dT  T   dP  T V  T  P
 T  P  P T
T  P  T  V 
 V  dT    dV    dP
TdS  CP dT  T   dP CP  CV  T V CP  CV  T  P
 T  P
… (i)
This equation is valid for any gas.
T  F ( P, V )
8.5 Energy Equation
 T   T 
dT      dV … (ii)
TdS  dU  PdV  P dP  V  P
dU  TdS  PdV Comparing (i) and (ii) we have –
 P  T  V   T 
dU  Cv dT  T   dV  PdV    
 T v CP  CV  T  P  P V
Kulkarni’s Academy 117 Thermodynamics Relations

 V   P   1  2 2
CP  CV  T     … (iii) CP  CV  T    V 
 T  P  T V  KTV 
T  F ( P, V ) TV 2
CP  CV 
 P   V   T  KT
       1
 V T  T  P  P V 8.8 Joule Thomson Coefficient (𝝁):

 P   P   V  It shows variation of temperature w.r.t. pressure

       … (iv)
 T V  V T  T  P under isenthalpic or under throttling condition.

 V  
2  T 
 P   
CP  CV  T    T    P  h
 V T  P 
TdS  dh  VdP
CP  CV  Negative
dh  TdS  VdP
CP  CV
 V 
TdS  CP dT  T   dP
At T  0 K for gas CP  CV  0  T  P
CP  CV   V  
dh  CP dT  T    V  dP
Note:   T  P 
 C P and CV are equal at absolute zero Case (1): Any gas undergoing constant
pressure process
temperature [0 K].
dh  C P dT
8.6 Coefficient of Volume Expansivity(𝜷):
This equation is valid for any gas undergoing
This shows variation of volume with respect to
constant pressure process.
temperature under constant pressure condition.
Case (2) : Ideal gas undergoing any process
1  V 
   PV  mRT
V  T  P
mR
8.7 Isothermal Compressibility (𝑲𝑻 ) V T
P
This shows variation of volume w.r.t. pressure  V  mR V
   
under constant temperature / isothermal  T  P P T
conditions.
 V 
1  V  T  V  0
KT      T  P
V  P T
dh  C P dT
We know that
This equation is valid for ideal undergoing any
 P   V 
2

CP  CV  T  process
  
 V T  T  P   V  
dh  CP dT  T    V  dP
 P  1  V    T  P 
   and    V
 V T KT V  T  P Throttling (h  C, dh  0)
Basic Thermodynamics 118 Kulkarni’s Academy
  V  
0  CP dT  T    V  dP
  T  P 

  V  
CP dT  T    V  dP
  T  P 

  V  
T  T   V 
dT   P 

dP CP

 T  1   V  
   T  V 
 P hc CP   T  P 
Slope of isenthalpic curve on T-P diagram
1   V    T 
 T  T   V 
CP   P    
 P  h
8.9 Clausius-Clapeyron-Equation
  V  
For an ideal gas T   V   0
  T  P 
  0 - For an ideal gas
Note: For an ideal gas   0 i.e., when an ideal
gas undergoes throttling T remains constant

 T 
   P   S 
 P  h    
 T V  V T
h  U  PV During phase change P and T are independent of
h  F (T ) volume
dP S g  S f

dT Vg  V f
LH
Sg  S f 
Tsat
dP LH

dT T (Vg  V f )
Volume of liquid is very small as compared
volume of vapour
dP LH

dT Tvg
dP P( LH )

dT RT 2
RT
( PV  mRT PV  RT V )
P1, h1, T1 P2, h2, T2 P
NOTES
 (3) Mixture is homogeneous.
9.1 Mixture of Gases
(4) Mixture is non- reactive.
(1) Number of moles (n): n  n1  n2  n3  ....
It is the ratio of moss of the gas to its molecular
mass. i.e., Pv  nRT …. (i)
mass (m) PV  n1 RT
Number of Moles  1

molecular weight (M)

PV
2  n2 RT
m
n
M
𝑃1 𝑉 + 𝑃2 𝑉+. . . . = 𝑛1 𝑅𝑇 + 𝑛2 𝑅𝑇+. . ..
(2) Mole Fraction (𝒙)
It is the ratio of no. of moles of a gas to the total ( P1  P2  P3  ....)V  (n1  n2  n3  ....) R T
number of moles. …. (i)
n1 ( P1  P2  P3  ....)V   n R T … (ii)
x1 
n1  n2  n3  n4 ... From equation i and ii
x1 
n1 P  P1  P2  P3  ....
n
This equation is known as Dalton’s law of partial
R4 m4, M 4, n4
P, V , T pressure.
PV
1  n1 RT
n3, M 3, m3
R1 m1, M1, n1 PV   n RT

PV n RT P  n1
R2 m2, M 2, n2
1
 1  1  x1   x1
𝑛
PV  n RT P  n
𝑥2 = 𝛴𝑛2
P1  x1 P
Similarly, P2  x2 P
x1  x2  x3  x4 .....  1
3. Equivalent Molecular weight of mixture
Assumptions- (𝑴𝒆) : -
(1) Individual gas can be treated as an ideal gas. m
(2) Mixture can be treated as on ideal gas. n
M
Basic Thermodynamics 120 Kulkarni’s Academy
m  nM Similarly, from enthalpy  h  h1  h2  h3
m1  n1m1 , m2  n2 M 2  mC pe T  m1C p1  ....
 m   n.Me m1C p1  m2C p2 ....
C pe 
 n m
x 
 m  m1  m2  m3  ....  n
C pe  Cve  Re


C pe
𝛴𝑚. 𝑀𝑒 = 𝑛1 𝑀1 + 𝑛2 𝑀2 +. . . .. e 
Cve
n n
Me  1 M1  2 M 2  .....
n n Example 1
A mixture of ideal gases consist of 5 kg of
Me  x1M 1  x2 M 2  x3 M 3  ....
𝑁21 & 6𝑘𝑔 of CO 2 , at a pressure of 4 bar and
4. Equivalent Gas constant (Re) :-
temperature of 270C . Find-
PV  m1 R1T
1 (A) Mole fraction of each constituent.
PV
2  m2 R2T (B) Equivalent molecular weight of mixture.
(C) Equivalent gas constant
n1, M1, m1
(D) Partial pressures.
R1
(E) The volume & density of mixture
(D) C p & Cv of mixture
P1
If this mixture is heated at constant volume to
V .T .
600 C . Find change in internal energy,
P1  P2  P3  ......V  (m1 R1  m2 R2  ...) T enthalpy & entropy of the mixture. Take
 PV  (m1 R1  m2 R2  ....)T CO2  1.286  N2  1.4

 m Re T  (m1 R1  m2 R2  ....) T Sol. Given data :

m1R1  m2 R2  ... N 2 [1] CO 2 [2]

Re 
m m1  5 kg m2  6 kg

Re 
R M 1  28 M 2  44
Me
1  1.4
5. Specific heat of Mixture:
 2  1.286
U  mCve T
[a]
U1  m1 Cv1T
n1
x1 
U 2  m2 Cv2 T n1  n2
 U  U1  U 2  .... n2
x2 
n1  n2
 mCve T  m1Cv1T  m2Cv2 T  ....
x1  x2  1
m1Cv1  m2CV2  ....
Cve  m 5
m n1  
M 28
Kulkarni’s Academy 121 Thermodynamics Relations
6 8.314
n2  R1   0.296 kJ/kg K
44 28
5 / 28 R 8.314
x1   0.567 R2    0.188 kJ/kg K
5 6
 M2 44
28 44
1R1 1.4  0.296
x2  1  0.567  0.433 CP1  
1  1 1.4  1
x1  0.567
CP1  1.036 kJ/kgK
x2  0.433
 2 R2 1.286  0.188
[b] CP2  
2 1 1.286  1
Me  x1M 1  x2 M 2  0.845 kJ/kg K
 0.567  28  0.433 44 CV1  1.036  0.296 = 0.74 kJ/kgK
 34.92 kg/mol
R 0.188
[c] CV2    0.657 kJ/kg K
 2  1 1.286
R 8.314
Re    0.238 kJ/kg.K m1CP1  m2CP2
Me 34.92 CPe 
[d] m1  m2
P1  x1P P2  x2 P P  4 bar 5 1.036  6  0.845
  0.931 kJ/kg K
P1  0.567  4
11
T1  300 K
P1  2.268 bar (For N 2 )
m  11 kg T2  333 K
P2  0.433  4 Re  0.238
CP e  0.931
P2  1.732 bar (For CO 2 ) Cve  0.693 kg/kmol
[e] Me  34.92
PV  mRT
400 V  11 0.238  300 C pe  Cve  Re
Cve  C pe  Re
5  6  11 kg = m
P  4 bar  0.931  0.238  0.693 kJ/kgK
T  300 K 𝑑𝑈 = 𝑚𝐶𝑣𝑐 𝑑𝑇 = 11 × 0.693 × (333 −
300)
V  1.9635 m 3
  251.559 kJ
m
  𝒅𝐻 = 𝒎𝑪𝒑𝒄 𝒅𝑻 = 𝟏𝟏 × 𝟎. 𝟗𝟑𝟏 × 𝟑𝟑 =
v
𝟑𝟑𝟕. 𝟗𝟓𝟑kJ
11
    5.6 kg/m3 𝑇
𝑠2 − 𝑠1 = 𝐶𝑣 𝑙𝑛 𝑇2 + 𝑅 𝑙𝑛 𝑉2
𝑉
1.9635 1 1
333
[f] 𝑠2 − 𝑠1 = 0.693 × 𝑙𝑛 300 ⇒ 0.0732kJ/kg𝐾
R
R1  Total entropy
M1 𝑆2 − 𝑆1 = 0.07232 × 11 = 0.7955kJ/𝐾
Basic Thermodynamics 122 Kulkarni’s Academy
Example 2  T2 
V2
T1
A piston cylinder arrangement contains air V1
ideal gas mixture of 1 kg  T2  440.646 K
N 2 [ M  28 kg/kmol],   1.4] & 2 kg
m1CP1  m2CP2
Argon [M  40 kg/kmol,   1.667] at CPe 
m1  m2
100 kPa , 300 K the gas expands at constant
1R1 1.4×0.296 𝐾𝐽
pressure until the volume increase by 1 m 3 . { CP1  = 0.4 = 1.036 𝑘𝑔−𝑘
 1
Then calculate-
 2 R2 1.667×0.2078 𝐾𝐽
(A) The initial volume of mixture. CP2  = 0.667 = 0.519 𝑘𝑔−𝑘
(B) Heat added 2 1

Sol. 11.036  2  0.519


3
CPe  0.6915 kJ/kg K
PV  m ReT
1 kg N2
R 𝑑𝐻 = 3 × 0.6915 × (440.646 − 300)
R1 
2 kg Ar M1 𝑑𝐻 = 291.79kJ
R
R2  Example 3
M2
Vessels A & B both containing O2 are
m 1
n1    0.035 connected by a valve before mixing the
M 28
properties are given in the table
2
n2   0.05
40
n1
x1   0.4117
n1  n2
x2  0.588
Me  0.4117  28  0.588  40  35.04 Valve is opened and both contents mix with
–each other the temperature after mixing is
R
Re   0.237 kJ/kg K 270 C , Calculate the final equilibrium
35.0476
pressure & the amount of heat transfer
(a) PV   m ReT
[   1.4 ]
100 V  (3)  0.237  300
Sol.
3  0.231 300
V  2.133 m3
100 A B AB

V2  1  V1  3.133 m3
O2 O2 O2

(b) Heat added at constant Pressure.

𝑄𝑝 = 𝑑𝐻 = 𝑚𝐶𝑝 (𝑇2 − 𝑇1 ) mA  n M
V2 T2
  0.5  32  16 kg
V1 T1
PAVA  mA RTA
Kulkarni’s Academy 123 Thermodynamics Relations

R 8.314 Sol. O2  1
R   0.259 kJ/kg K
M 32 N2  2

VA  16  0.259 
323
 0.8923 m3 m1  1 kg, P  1 bar  100 kPa
1500
m2  3.5 kg, T1  270 C  300 K
PBVB  mB RT
m1 1
(a) n1    0.03125
2.5  0.259  293 M1 32
VB   0.3161 m3
600 m2 3.5
n2    0.125
V  VA  VB  1.2084 m3 M 2 28
n1 0.03125
𝑃𝑒 𝑉 = 𝛴𝑚. 𝑅𝑇 x1    0.2
n1  n2 0.03125  0.125
18.5  0.259  300
Pe  x1  x2  1
1.2084
 1189.45 kPa  11.89 bar x2  1  x1  0.8
n2
Amount of heat transfer: x2   0.8
n1  n2
𝑑𝑈 = 𝑚𝐶𝑣 𝑑𝑇
(b) M e  x1M 1  x2 M 2
𝑅 0.259
 𝐶𝑣𝑒 = = =0.6475 kJ/kg-k
𝛾−1 0.4 M e  0.2  32  0.8  28
 𝑑𝑄 = 𝑑𝑈 + 𝛿𝑤 (Work transfer = 0) M e  28.8
𝑑𝑄 = 𝑑𝑈 = 𝑈𝐹 − 𝑈𝑖 (c) P1  x1P
 m f CV TF  [mACvTA  mBCvTB ] P1  0.2 100  20 kPa
P2  x2 P
16  0.6475  323  
18.5  0.6475  300   
 2.5  0.6475  293  P2  0.8 100  80 kPa

 226.9 kJ m1R1  m2 R2
(d) Re 
m1  m2
Example 4
R 8.314
A gas mixture contains 1 kg O2 and 3.5 kg R1    0.2598125, m1  1 kg
M1 32
N 2 . The pressure and temperature of the
R 8.314
mixture are 1 bar and 270 C . Determine R2    0.29692857
M2 28
(a) Mole fraction of each constituent
m2  3.5 kg
(b) Molecular weight of the mixture
(c) Partial pressure of constituents 1 0.2598125  3.5  0.29692857
Re 
(d) Gas constant 1  3.5
(e) Mixture volume Re  0.28868 kJ/kgK
(f) Mixture density (e) P  100 kPa, T  300 K
M O2  32, M N2  28
R  0.28868, m  4.5 kg
Basic Thermodynamics 124 Kulkarni’s Academy
PV  mRT M e  35.6

mRT 4.5  0.28868  300 Mass analysis  Gravimetric

V 
P 100
Vol analysis
V  3.89718 m 3
O2  0.3 32  0.3  32  9.6
m 4.5 CO2  0.4 44  0.4  44  17.6
(f)     1.15468 kg/m3
V 3.89718 N 2  0.3 28  0.3  28  8.4
____
Example 5 35.6
____
A gaseous mixture has the following volume
analysis,
O2  30 %, CO2  40 %, N 2  30 % .
m
Determine n
M
(i) Analysis on mass basis
(ii) Partial pressure of each component m  nM
(iii)Molecular weight of mixture if the total
9.6
pressure is 100 kPa and temperature is O2  100  27 %
35.6
320 C
Volume analysis  Molar analysis 17.6
Sol. CO2  100  49.4%
35.6
(1) O2  0.3  x1
8.4
N2  100  23.6%
P  100 kPa 35.6

(2) CO2  0.4  x2 Example 6

A cubical tank of 1 m side contains a mixture
T  320 C  305 K of 1.8 kg of N 2 and 2.8 kg of an unknown
(3) N 2  0.3  x3 gas. The mixture pressure and temperature
are 290 kPa and 340 K. Determine the
(ii) PO2  P1  x1P  0.3 100  30 kPa molecular weight and gas const of unknown
gas.
PCO2  P2  x2 P  0.4 100  40 kPa
Sol.
PN2  P3  x3 P  0.3 100  30 kPa

(iii) M e  x1M 1  x2 M 2  x3 M 3

M1  32, M 2  CO2  12  32  44
M 3  28

M e  0.3  32  0.4  44  0.3  28

Kulkarni’s Academy 125 Thermodynamics Relations

Volume  111 m3 Example 7

V  1 m3 A gas mixture consists of 1 kg of O2 and 2 kg

N 2  (1) of N 2 at 1.5 bar and 200 C . Calculate the Cv

and C p of mixture. Also find the change in
m1  1.8 kg, P  290 kPa
internal energy enthalpy and entropy of the
Unknown  (2) mixture when it is heated under const volume
m2  2.8 kg, T  340 K to a temperature of 1000 C . Take
Cv for O2  0.653 kJ/kgK for
m  m1  m2
N 2  0.741 kJ/kgK
 1.8  2.8 C p for O2  0.917 kJ/kgK for
m  4.6 kg N 2  1.038 kJ/kgK
PV  mRT Sol. O2  (1)
For mixture PV  mReT
m1  1 kg, P  1.5 bar  150 kPa
PV 290 1
Re  
mT 4.6  340 N 2  (2)

Re  0.185421 kJ/kgK m2  2 kg, T1  200 C  293 K

R T2  373 K
R
M
m1CP1  m2CP2
R CPe 
Me   Universal gas constant m1  m2
Re
Cv1  0.653 kJ/kgK
8.314
Me   44.838 Cv2  0.741 kJ/kgK
0.185421
C p1  0.917 kJ/kgK
m R  m2 R2
Re  1 1 C p2  1.038 kJ/kgK
m1  m2

R 8.314 1 0.917  2 1.038

R1    0.296928 CPe 
M1 28 1 2
1.8  0.296928  2.8  R2 CPe  0.99766 kJ/kgK
Re 
1.8  2.8
m1Cv1  m2Cv2
R2  0.113737 kJ/kgK Cve 
m1  m2
R
R2  1 0.653  2  0.741
M2 
1 2
R 8.314
M2    73.09 Cve  0.71166 kJ/kgK
R2 0.113737
Basic Thermodynamics 126 Kulkarni’s Academy
m  1  2  3, T1  293 K, T2  373 T1  300 K, CVHe  3.14 kJ/kgK
Cv  0.7116, C p  0.99766
T2  600 K, CPN  1.038 kJ/kgK
dU  mCv dT
2

CVN  0.741 kJ/kgK

dH  mC p dT 2

dU  3 0.7116  (373  293) m1  1 kg, m2  2.5 kg

 170.784 kJ m1CP1  m2CP2

CP2 
dH  3 0.99766  (373  293) m1  m2

dH  239.43 kJ 1 5.233  2.5 1.038

CP2 
T2 V 1  2.5
S  Cv ln  R ln 2
T1 V1 CP2  2.236 kJ/kgK
V2
V2  V1  1 m1CV1  m2CV2
V1 CVe 
m1  m2
ln1  0 1 3.14  2.5  0.741

T2 1  2.5
S  Cv ln
T1 CVe  1.426 kJ/kgK
373
 0.7116ln
293
S  0.171784 kJ/kgK
S  m  0.171784 kJ/K
 0.51535 kJ/K
Example 8
A gas mixture at 1 bar, 270 C consists of 1 kg
of He and 2.5 kg of N 2 . If the mixture is
compressed isentropic ally in cylinder until
600 K. Find
(i) The final pressure of mixture
(ii) The initial and final partial pressure
(iii)Change in internal energy
(iv) Change in enthalpy
(v) Work required for compression
Sol. He  (1)

P1  1 bar, CPHe  5.233 kJ/kgK

N 2  (2)
NOTES