GATE COACHchemical Engineering Thermodynamics Sample Chapter PDF

Revised Study
Material
For
GATE – PSU
Chemical Engineering
Chemical Engineering Thermodynamics
GATE Syllabus
First and Second laws of thermodynamics. First law

application to close and open systems. Second law and
Entropy. Thermodynamic properties of pure substances:
equation of state and departure function, properties of
mixtures: partial molar properties, fugacity, excess
properties and activity coefficients; phase equilibria:
predicting VLE of systems; chemical reaction equilibria. The Gate Coach
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CHEMICAL ENGINEERING THERMODYNAMICS The Gate Coach
TABLE OF CONTENTS
Chapter 1
INTRODUCTION 1
1.1 Introduction 1
1.2 Classification of Thermodynamics System 2
1.2.1 Closed System 2
1.2.2 Open System 2
1.2.3 Isolated System 2
1.3 Basic Terminology 3
1.3.1 Thermodynamic Equilibrium 3
1.3.2 Control Volume 3
1.3.3 Steady State 3
1.3.4 Thermodynamic Process 3
1.3.4.1 Cyclic Process 4
1.3.4.2 Reversible Process 4
1.3.4.3 Irreversible Process 5
1.3.4.4 Adiabatic Process 5
1.3.4.5 Polytropic Process 5
1.3.4.6 Throttling Process 6
1.4 Properties of a System 6
1.4.1 Fundamental Properties 7
1.4.1.1 Volume 7
1.4.1.2 Pressure 7
1.4.1.3 Force 8
1.4.1.4 Velocity 10
1.4.1.5 Temperature 10
1.4.2 Zeroth Law of Thermodynamics 11
1.5 Ideal Gas 14
1.6 Avogadro’s Hypothesis 14
1.7 Energy, Work And Heat 14
1.7.1 Energy 15
1.7.1.1 Potential Energy 15
1.7.1.2 Kinetic Energy 15
1.7.1.3 Specific Internal Energy 16
1.7.1.4 Specific P – V Enrgy 16
1.7.1.5 Specific Enthalpy 17
1.7.2 Work 17
1.7.3 Heat 18
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Chapter 2
LAWS OF THERMODYNAMICS 19
2.1 First Law of Thermodynamics 19
2.2 Internal Energy 21
2.3 Joule’s Law 21
2.4 Second Law of Thermodynamics 22
2.4.1 Kelvin Plank Statement 22
2.4.1.1 Thermal Reservoir 22
2.4.1.2 Heat Engine 22
2.4.1.3 Carnot Cycle 24
2.4.1.4 Efficiency Optimization 26
2.4.2 Clausius Statement 27
2.4.2.1 Refrigerator 27
2.4.2.2 Coefficient of Performance 28
2.4.2.3 Heat Pump 29
2.4.2.4 The Reversed Carnot Cycle 30
2.4.3 Equivalence of Two Statements 31
2.4.4 Clausius Inequalities 32
2.5 Entropy 34
2.6 Thermodynamic Processes 35
2.6.1 Adiabatic Process 35
2.6.1.1 PVT Relationship 35
2.6.1.2 PV diagram 36
2.6.1.3 TS diagram 36
2.6.1.4 Change in Internal Energy 36
2.6.1.5 Change in Entropy 37
2.6.1.6 Work done 37
2.6.1.7 Heat Transferred 37
2.6.2 Constant Temperature Process 37
2.6.3 Constant Pressure Process 40
2.6.4 Constant Volume Process 42
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2.6.5 Polytropic Process 44
2.7 Adiabatic Expansion 46
2.7.1 Closed System 46
2.7.2 Open System 46
2.8 Throttling Process 47
2.8.1 PV Diagram 48
2.8.2 TS Diagram 48
2.8.3 Change in Entropy 48
2.9 Thermodynamic Relations 49
2.9.1 Maxwell’s Equation 49
2.9.2 Clapeyron Equation 50
Chapter 3
PURE SUBSTANCE 54
3.1 Pure Substance 54
3.2 Critical Point 55
3.3 Saturated Liquid And Saturated Vapor States 56
3.4 Saturated Liquid – Vapor Mixture 57
3.5 Super-Heated Vapor 57
3.6 Compressed Liquid 58
3.7 Compressibility Factor 59
3.8 Van Der Waals Equation of State 59
Chapter 4
SOLUTION THERMODYNAMICS 60
4.1 Fugacity 60
4.1.1 Fugacity Coefficient 61
4.1.2 Effect of Temperature And Pressure on Fugacity 61
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4.1.3 Calculation of Fugacity of Pure Gases 62

4.1.3.1 Using Compressibility Factor 62
4.1.3.2 Using Residual Volume 62
4.1.3.3 Using Enthalpy And Entropy Data 62
4.1.4 Fugacity of Liquids And Solids 63
4.2 Activity 64
4.2.1 Effect of Temperature And Pressure on Activity 64
4.3 Partial Molar Properties 64
4.3.1 Partial Properties of Solution 65
4.4 Chemical Potential 67
4.4.1 Effect of Temperature And Pressure on Chemical Potential 68
4.5 Fugacity in Solutions 69
4.5.1 Fugacity in Gaseous Solution 69
4.6 Lewis – Randall Model 70
4.7 Ideal Solution 70
4.8 Raoult’s Law 70
4.9 Henry Law 71
4.10 Activity in Solutions 71
4.11 Activity Coefficient 72
4.11.1 Effect of Temperature And Pressure on Activity Coefficient 72
4.12 Gibbs Duhem Equation 73
4.13 Excess Properties 74
4.14 Activity Coefficient Equation 74
Chapter 5
CHEMICAL REACTION EQUILIBRIUM 76
5.1 Chemical Reaction Equilibrium 76
5.2 Ideal Gas Reactions 79
5.3 Ideal Solution Reactions 80
5.4 Temperature And Pressure Dependence of Keq 81
Chapter 6
MCQS LEVEL 1 87
Chapter 7
MCQS LEVEL 2 110
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Chapter 8
UNSOLVED QUESTIONS 139
Chapter 9
QUESTIONS (2004 TO 2015) 146
2004 146
2005 148
2006 150
2007 152
2008 156
2009 158
2010 160
2011 161
2012 162
2013 164
2014 166
2015 167
Chapter 10
GATE SOLUTIONS 170
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CHAPTER • LAWS OF THERMODYNAMICS

2
2.1 FIRST LAW OF THERMODYNAMICS
“In a closed system undergoing any thermodynamic cycle, cyclic integral of heat and
cyclic interval of work are proportional to each other when expressed in their own units
and are equal to each other when expressed in the consistent (same) units”
 Q   W
kcal kJ
Verification:
 W   Q
kJ kcal
 W  J.  Q
kJ kJ
Where,
J = constant of proportionality
4.1868 kJ
and J= (Joule’s mechanical equivalent of heat)
kcal
 W   Q
kJ kJ
Explanation:
 W   Q (both are in same units)
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  W     W     Q  A    Q B ..........(1)
2 1 2 1
For cycle 1  A  2  B  1  A B
1 2 1 2
1  W A  2  W C  1  Q A  2  Q C ..........(2)
2 1 2 1
For cycle 1  A  2  C  1 
Subtracting equation (2) from (1), we get:
  W     W     Q B    Q C
1 1 1 1
2 B 2 C 2 2
2  Q C  2  W C  2  Q B  2  W B
1 1 1 1

  Q  W     Q  W B
1 1
 C
2 2
i.e.  Q  W  does not depend on path
Since,  Q  W  is independent of path and not a path function
Hence,  Q  W  is a point function.
Thus,  Q  W  is a thermodynamic property.
  Q  W  will be a form of energy and should be a

perfect differential as every thermodynamic property is a
perfect differential.
Therefore,
Q  W  dU  internal energy
For a cyclic process,
1 2  1Q2 1 W2  U 2  U1
23  2Q3  2 W3  U3  U 2
34 3Q4 3 W4  U 4  U3
4 1 4 Q1  4 W1  U1  U 4
Adding all equations, we get
  1Q2  2 Q3  3 Q4  4 Q1    1W2  2 W3  3 W4  4 W1   0
  Q   W  0
  dU cycle  0
2.2 INTERNAL ENERGY
The part of heat energy which does not converted into work, just stored into the system
is called increase in internal energy of the system.
This is called the law of conservation of energy.
Conclusively, first law of thermodynamics says that “Heat and Work are mutually inter-
convertible.”
Limitation:
First law of thermodynamics only gives information that heat and work can be convert
into each other and vice versa but it does not tell us about how much heat and work get
converted into each other.
2.3 JOULE’S LAW
It state that,
“The change in specific internal energy is always proportional to change in

temperature.”
du  dT
 du  k.dT
Where,
k = constant of proportionality (which is equivalent to specific heat of gas

at constant volume)
 du  Cv .dT
Hence, change in internal energy,
 U2  U1  mCv T2  T1 
2.4 SECOND LAW OF THERMODYNAMICS
The observations which generally restricted on processes beyond that imposed by the
first law.
The second law is equally well expressed in two statements that describe these
restrictions:
(i) Kelvin Planck Statement

(ii) Clausius Statement
2.4.1 KELVIN – PLANCK STATEMENT
This statement is simply related to the work. And it state that
“It is impossible to construct a device that operates in a thermodynamic cycle and

produces no effect other than net amount of positive work having heat exchange with a
single thermal reservoir.”
2.4.1.1 THERMAL RESERVOIR
Thermal reservoir is a body from which we can take / give any amount of heat without
affecting its temperature. (i.e. its temperature remains
constant)
Thermal reservoir has infinite heat capacity.
2.4.1.2 HEAT ENGINE
It is the device that operates in a thermodynamic cycle

and produces net amount of positive work having heat
exchange with at least two thermal reservoirs.
Energy balance:
Energy in = Energy out
 QH = Wnet + QL
Wnet  QH  QL
From first law of thermodynamics,
 Q   W
  QH   0   QL   0   Q
 WT  WP  Wnet   W
 QH  QL   Wnet
Thermal efficiency of heat engine
Output Net work done

 
Input Heat supplied
Wnet QH  QL
 
QH QH
QL
   1
QH
  100% is impossible
 QL  0 does not possible
Example 2.1 Calculate U and H in kJ for 1 kmol water, as it is vaporized at the

constant temperature of 373 K and constant pressure of 101.3 kPa. The specific volumes
of liquid and vapor at these conditions are 1.04  103 and 1.675 m3 / kmol respectively;
1030 kJ of heat is added to water for this change.
Solution: The expansion work done by the system during vaporization is
W  P V  101.3  103 1.675  0.00104   10 3  169.57 kJ

Q  1.03  103 kJ
U  Q  W  860.43 kJ
H  U    PV 
For constant pressure process, this becomes
H  U  P V  1.03  103 kJ
2.4.1.3 CARNOT CYCLE
Probably the best known reversible cycle is the Carnot cycle, first pro-posed in 1824 by
French engineer Sadi Carnot. The theoretical heat engine
that operates on the Carnot cycle is called the Carnot
heat engine. The Carnot cycle is composed of four
reversible processes—two isothermal and two
adiabatic—and it can be executed either in a closed or a
steady-flow system.
Consider a closed system that consists of a gas contained

in an adiabatic piston–cylinder device, as shown in figure.
The insulation of the cylinder head is such that it may be
removed to bring the cylinder into contact with reservoirs
to provide heat transfer. The four reversible processes
that make up the Carnot cycle are as follows:
Reversible Isothermal Expansion (process 1-2, TH =

constant). Initially (state 1), the temperature of the gas is
TH and the cylinder head is in close contact with a source
at temperature TH. The gas is allowed to expand slowly,
doing work on the surroundings. As the gas expands, the
temperature of the gas tends to decrease. But as soon as
the temperature drops by an infinitesimal amount dT,
some heat is transferred from the reservoir into the gas,
raising the gas temperature to TH. Thus, the gas
temperature is kept constant at TH. Since the temperature difference between the gas
and the reservoir never exceeds a differential amount dT, this is a reversible heat transfer
process. It continues until the piston reaches position 2. The amount of total heat
transferred to the gas during this process is QH.
Reversible Adiabatic Expansion (process 2-3, temperature drops from TH to TL). At

state 2, the reservoir that was in contact with the cylinder head is removed and replaced
by insulation so that the system becomes adiabatic. The gas continues to expand slowly,
doing work on the surroundings until its temperature drops from TH to TL (state 3). The
piston is assumed to be frictionless and the process to be quasi-equilibrium, so the
process is reversible as well as adiabatic.
Reversible Isothermal Compression (process 3-4, TL = constant). At state 3, the

insulation at the cylinder head is removed, and the cylinder is brought into contact with
a sink at temperature TL. Now the piston is pushed inward by an external force, doing
work on the gas. As the gas is compressed, its temperature tends to rise. But as soon as
it rises by an infinitesimal amount dT, heat is transferred
from the gas to the sink, causing the gas temperature to
drop to TL. Thus, the gas temperature remains constant
at TL. Since the temperature difference between the gas
and the sink never exceeds a differential amount dT, this
is a reversible heat transfer process. It continues until
the piston reaches state 4. The amount of heat rejected
from the gas during this process is QL.
Reversible Adiabatic Compression (process 4-1, temperature rises from TL to TH). State
4 is such that when the low-temperature reservoir is removed, the insulation is put back
on the cylinder head, and the gas is compressed in a reversible manner, the gas returns
to its initial state (state 1). The temperature rises from TL to TH during this reversible
adiabatic compression process, which completes the cycle.
The P – V diagram of this cycle is shown in figure given below. Remembering that on a
P – V diagram the area under the process curve represents the boundary work for quasi-
equilibrium (internally reversible) processes, we see that the area under curve 1-2-3 is
the work done by the gas during the expansion part of the cycle, and the area under
curve 3-4-1 is the work done on the gas during the compression part of the cycle. The
area enclosed by the path of the cycle (area 1-2-3-4-1) is the difference between these
two and represents the net work done during the cycle.
2.4.1.4 EFFICIENCY OPTIMIZATION
The efficiency of a heat engine is given by
TL
  1
TH
We can maximize the efficiency by decreasing TL or by increasing TH, let check which one
is more efficient way to optimize the efficiency of a heat engine.
TL  T TL
Let, 1  1  and 2  1 
TH TH  T
Where, T = temperature difference
 T  T   TL 
 1  2   1  L   1 
 TH   TH  T 
TL T  T
 1  2   L
TH  T TH
TLTH  THTL  TL T  TH T  T 2
 1  2 
TH  T  .TH
 1  2 
TH  TL  T  T 2  ve
TH  T  .TH
thus, 1  2  0
 1  2
Hence, decreasing TL to maximize the efficiency is better choice.
2.4.2 CLAUSIUS STATEMENT
This statement is simply related to the heat. And it state that
“It is impossible to construct a device that operates in a thermodynamic cycle and

produces no effect other than transfer of heat from a body at low temperature to a
body at high temperature.”
2.4.2.1 REFRIGERATOR
The devices used to transfer heat from a low-temperature medium to a high-

temperature called refrigerators.
Refrigerators, like heat engines, are cyclic devices. The working fluid used in the
refrigeration cycle is called a refrigerant. The most frequently used refrigeration cycle is
the vapor-compression refrigeration cycle, which involves four main components: a
compressor, a condenser, an expansion
valve, and an evaporator, as shown in figure.
The refrigerant enters the compressor as a

vapor and is compressed to the condenser
pressure. It leaves the compressor at a
relatively high temperature and cools down
and condenses as it flows through the coils
of the condenser by rejecting heat to the
surrounding medium. It then enters a
capillary tube where its pressure and
temperature drop drastically due to the
throttling effect. The low-temperature
refrigerant then enters the evaporator,
where it evaporates by absorbing heat from the refrigerated space. The cycle is
completed as the refrigerant leaves the evaporator and reenters the compressor.
A refrigerator is shown schematically in figure given below. Here QL is the magnitude of

the heat removed from the refrigerated space at temperature TL, QH is the magnitude of
the heat rejected to the warm environment at temperature TH, and Wnet, in is the net
work input to the refrigerator. As discussed before, QL and QH represent magnitudes and
thus are positive quantities.
2.4.2.2 COEFFICIENT OF PERFORMANCE
The efficiency of a refrigerator is expressed in terms of the coefficient of performance

(COP), denoted by COPR. The objective of a refrigerator is
to remove heat (QL) from the refrigerated space. To
accomplish this objective, it requires a work input of
Wnet,in .
Then the COP of a refrigerator can be expressed as
Desired output
COPR 
Required input
QL
COPR 
Wnet ,in
This relation can also be expressed in rate form by replacing QL by QL and Wnet,in by Wnet ,in
.
The conservation of energy principle for a cyclic device requires that
Wnet ,in  QH  QL (kJ)
Then the COP relation becomes
QL 1
COPR  
QH  QL QH QL  1
Notice that the value of COPR can be greater than unity. That is, the amount of heat
removed from the refrigerated space can be greater than the amount of work input. This
is in contrast to the thermal efficiency, which can never be greater than 1. In fact, one
reason for expressing the efficiency of a refrigerator by another term—the coefficient of

performance—is the desire to avoid the oddity of having efficiencies greater than unity.
2.4.2.3 HEAT PUMP
Another device that transfers heat from a low-temperature medium to a high-

temperature one is the heat pump, shown schematically in figure given below.
Refrigerators and heat pumps operate on the same cycle but differ in their objectives.
The objective of a refrigerator is to maintain the refrigerated space at a low temperature
by removing heat from it. Discharging this heat to a higher-temperature medium is
merely a necessary part of the operation, not the purpose.
The objective of a heat pump, however, is to maintain a
heated space at a high temperature. This is accomplished
by absorbing heat from a low-temperature source, such as
well water or cold outside air in winter, and supplying this
heat to the high-temperature medium such as a house
figure showing below.
The measure of performance of a heat pump is also

expressed in terms of the coefficient of performance
COPHP, defined as
Desired output QH
COPHP  
Required input Wnet ,in
Which also can expressed as
QH 1
COPHP  
QH  QL 1  QL QH
A comparison of COP of Refrigerator and Heat pump gives
COPHP  COPR  1
For the fixed values of QL and QH. This relation implies that the coefficient of
performance of a heat pump is always greater than unity since COPR is a positive
quantity. That is, a heat pump will function, at worst, as a resistance heater, supplying as
much energy to the house as it consumes. In reality, however, part of Q H is lost to the
outside air through piping and other devices, and COPHP may drop below unity when
the outside air temperature is too low. When this happens, the system usually switches
to a resistance heating mode. Most heat pumps in operation today have a seasonally
aver-aged COP of 2 to 3.
2.4.2.4 THE REVERSED CARNOT CYCLE
The Carnot heat-engine cycle just described is a totally reversible cycle. Therefore, all the
processes that comprise it can be reversed, in which case it becomes the Carnot
refrigeration cycle. This time, the cycle remains exactly the same, except that the
directions of any heat and work interactions are reversed: Heat in the amount of Q L is
absorbed from the low-temperature reservoir, heat in the amount of QH is rejected to a
high-temperature reservoir, and a work input of Wnet, in is required to accomplish all
this. The P-V diagram of the reversed Carnot cycle is the same as the one given for the
Carnot cycle, except that the directions of the processes are reversed, as shown in figure
shown below.
 No engine can be more efficient than a reversible Carnot

engine, operating between the two give temperature
limits.
2.4.3 EQUIVALENCE OF TWO STATEMENTS
The Kelvin–Planck and the Clausius statements are equivalent in their consequences,
and either statement can be used as the expression of the second law of
thermodynamics. Any device that violates the Kelvin–Planck statement also violates the
Clausius statement, and vice versa. This can be demonstrated as follows.
Consider the heat-engine-

refrigerator combination
shown in figure, operating
between the same two
reservoirs. The heat engine
is assumed to have, in
violation of the Kelvin–
Planck statement, a thermal
efficiency of 100 percent,
and therefore it converts all
the heat QH it receives to
work W. This work is now
supplied to a refrigerator
that removes heat in the
amount of QL from the low-
temperature reservoir and rejects heat in the amount of QL + QH to the high-
temperature reservoir. During this process, the high-temperature reservoir receives a net
amount of heat QL (the difference between QL + QH and QH). Thus, the combination of
these two devices can be viewed as a refrigerator, as shown in figure (a), that transfers
heat in an amount of QL from a cooler body to a warmer one without requiring any
input from outside. This is clearly a violation of the Clausius statement. Therefore, a
violation of the Kelvin–Planck statement results in the violation of the Clausius
statement.
It can also be shown in a similar manner that a violation of the Clausius statement leads
to the violation of the Kelvin–Planck statement. Therefore, the Clausius and the Kelvin–
Planck statements are two equivalent expressions of the second law of thermodynamics.
2.4.4 CLAUSIUS INEQUALITIES
The work done is given as
 W   Q
1 H   Q
We know that
Q T

 QH TH
TH
  QH  . Q
T
 T 
   W1    H . Q   Q 
 T 
   W2    Q
For a composite system,
 W net    W1    W2
 T 
   Wnet    H . Q    Q     Q
 T 
TH
  W net  T . Q
But this work cannot be positive as by Kelvin – Planck Statement.
 W net 0
TH
 T . Q  0
TH is a constant and positive term,

Q
  T
0
Hence,
Q
when  T
 0  System is Actual  Irreversible System
Q
when  T
 0  System is Ideal  Reversible System
Q
when  T
 0  Impossible
These is called Clausius Inequalities.
2.5 ENTROPY
 Q 
For   T 
Re v
0
For reversible cycle, 1 – A – 2 – B – 1
2  Q  1  Q 
 1  T   2  T   0 ................( i )
 A  B
For reversible cycle, 1 – A – 2 – C – 1
2  Q  1  Q 
 1  T   2  T   0 ................( ii )
 A  C
Subtracting equation (ii) from (i), we get
1  Q  1  Q 
      0
2
 T B 2  T C
1  Q  1  Q 
   T
2 
B
 
2 
 T C
Q
Thus, = Independent of path and not a path function
T
Q
Therefore, would be a point function and a thermodynamic property.
T
Since, all thermodynamic properties are perfect differential
Q
 would be a exact differential, and known as Entropy (S or Φ).
T
Q
i.e. dS 
T
“Entropy is a thermodynamic property that increases when heat is supplied and

decreases when heat is rejected and remains constant if there is no heat transfer”
 Q  T .dS
 Entropy is independent of temperature.

 Entropy is subjected to the disorder (or order) of the molecules in the system.
as dS   disorder of molecules 
as dS   disorder of molecules 
Disorder of molecules  random motion of molecules.
2.6 THERMODYNAMIC PROCESSES
2.6.1 ADIABATIC PROCESS
A process during which there is no heat transfer is called an adiabatic process. The word
adiabatic comes from the Greek word adiabatos, which means not to be passed. There
are two ways a process can be adiabatic:
 If the system is well insulated so that only a negligible amount of heat can pass
through the boundary.
 The system is extremely fast, so there is practically no time available for heat transfer.
2.6.1.1 PVT RELATIONSHIP
The following P-V-T relationships can be derived for a compressible fluid undergoing an
adiabatic process:
 1  1 
 T2   V1  P 
    2
 T1   V2   P1 
Where  is the coefficient of adiabatic compression or expansion. For an ideal gas, it can
be shown that:   Cp Cv
If the adiabatic process is reversible, then from the definition of entropy, the process
becomes an isentropic processor the entropy of the system does not change during a
reversible adiabatic process. Hence all reversible, adiabatic processes are isentropic
processes, however, the converse is not true, i.e., all isentropic processes need not be
reversible, adiabatic processes.
2.6.1.2 PV DIAGRAM
For an ideal gas, the pressure – volume diagram is given by
2.6.1.3 TS DIAGRAM
For an ideal gas, the temperature – entropy diagram is given as
2.6.1.4 CHANGE IN INTERNAL ENERGY
The change in internal energy for an ideal gas, for a process 1 – 2 is given by
U2  U1  mCv T2  T1 
2.6.1.5 CHANGE IN ENTROPY
The change in entropy is given by
q 0
ds   0
T T
 s2  s1  0
 s  constant
This process is also known as isentropic process or reversible adiabatic process or

friction less adiabatic process.
If the entropy changes in the process then it is known as irreversible adiabatic process or
adiabatic with friction process.
2.6.1.6 WORK DONE
Work done for a process 1 – 2 is given by the
1 1  P2V2
PV
W2 
1
 1
2.6.1.7 HEAT TRANSFERRED
For an adiabatic process, there is no heat transfer to or from the system.
Q2  0
1
2.6.2 CONSTANT TEMPERATURE PROCESS (ISOTHERMAL PROCESS)
According to Boyle’s law, when a gas is compressed or expanded at constant

temperature, the pressure will vary inversely with the volume. Since the gas does work
as it expands, if the temperature is to remain constant, energy to do the work must be
supplied from an external source. When a gas is compressed, work is done on the gas
and if the gas is not cooled during the process the internal energy of the gas will
increase by an amount equal to the work of compression.
The fundamental requirement of the process to be isothermal is as follows:
 It should be extremely slow process, i.e. infinitely slow so that there is no storage of
energy in the system.
The following P-V-T relationships can be derived for a ideal fluid undergoing an
isothermal process:
 V1   P2 
     & T1  T2
 V2   P1 
2.6.2.2 PV DIAGRAM
For an ideal gas, the pressure – volume diagram is given as
2.6.2.3 TS DIAGRAM
The change in internal energy for an ideal gas,
For a process 1 – 2 is given by
U2  U1  mCv T2  T1  T1  T2
 U2  U1  0
v2 P
s2  s1  R ln  R ln 1
v1 P2
2.6.2.6 WORK DONE
V2 V
W2  PV
1 1 1 ln  P2V2 ln 2
V1 V1
P1 V
W2  mRT1 ln
1  P2V2 ln 2
P2 V1
V2
1Q2  PV
1 1 ln
V1
2.6.3 CONSTANT PRESSURE PROCESS (ISOBARIC PROCESS)
For the temperature of a gas is increased by the addition of heat while the gas is
followed to expand so that its pressure is kept constant, the volume of the gas will
increase in accordance with Charles law. Since the volume of the gas increases during
the process, work is done by the gas at the same time that its internal energy also
changes.
The following P-V-T relationships can be derived for an ideal gas undergoing isobaric
process:
 1  1 
 T2   V1  P 
    2
 T1   V2   P1 
2.6.3.2 PV DIAGRAM
2.6.3.3 TS DIAGRAM
U2  U1  mCv T2  T1 
T2
s2  s1  Cp ln
T1
v2
s2  s1  Cp ln
v1
2.6.3.6 WORK DONE
W2  P V2  V1 
1
1Q2  mCp T2  T1 
2.6.4 CONSTANT VOLUME PROCESS (ISOCHORIC PROCESS)
Any process for which the volume of the system remains constant either there is any
change in the state of the system. Since the volume of the gas increases during the
process, work is done by the gas at the same time that its internal energy also changes.
The following P-V-T relationships can be derived for an ideal gas undergoing a isochoric
process:
 T2   P2 
     & V1  V2
 T1   P1 
2.6.4.2 PV DIAGRAM
2.6.4.3 TS DIAGRAM
U2  U1  mCv T2  T1 
T2
s2  s1  Cp ln
T1
2.6.4.6 WORK DONE
1W2  P V2  V1  V2  V1 

 1W2  0
For an isochoric process, the heat transfer is given by
Q2  mCv T2  T1 
1
2.6.5 POLYTROPIC PROCESS
During actual expansion and compression processes of gases, pressure and volume are
often related by PVn = C, where n and C are constants. A process of this kind is called a
polytropic process. Below we develop a general expression for the work done during a
polytropic process.
The following P-V-T relationships can be derived for a ideal gas undergoing an
polytropic process:
n 1  n 1n 
 T2   V1  P 
    2 .
 T1   V2   P1 
2.6.5.2 PV DIAGRAM
2.6.5.3 TS DIAGRAM
U2  U1  mCv T2  T1 
n  T
s2  s1  Cv ln 2
n 1 T1
2.6.5.6 WORK DONE
1 1  P2V2
PV
W2 
n 1
1
Q2 
  n  mR T1  T2 
(n  1)(  1)
1
2.7 ADIABATIC EXPANSION
The work done for the expansion process adiabatically for an open and closed system is
given as:
2.7.1 CLOSED SYSTEM
We know that
PV   k
1 1  P2V2
PV
And work done is given by W2 
1
 1
2.7.2 OPEN SYSTEM
We know that
PV   k

And work done is given by W2  PV
1 1  P2V2 
1
 1
The expressions of work done required for open and closed system can be relate as
follows:
 1W2 open
system
  .  1W2 closed
system
2.8 THROTTLING PROCESS
A throttling process occurs when a fluid flowing through a passage suddenly encounters
a restriction in the passage. The restriction could be due to the presence of an almost
completely closed valve or due to sudden and large reduction in flow area etc. The
result of this restriction is a sudden drop in the pressure of the fluid as it is forced to
flow through the restriction. This is a highly irreversible process and is used to reduce
the pressure and temperature of the refrigerant in a refrigeration system. Since generally
throttling occurs in a small area, it may be
considered as an adiabatic process (as area available
for heat transfer is negligibly small) also since no
external work is done, we can write the 1st law of
thermodynamics for this process as:
Q W  0
V12 V2
h1   h2  2
2 2
where V1 and V2 are the inlet and exit velocities of the fluid respectively. The areas of
inlet and outlet of a throttling device are designed in such a way that velocities at inlet
and outlet become almost equal.
Then the above equation becomes
h1  h2
Thus throttling process is an isenthalpic process.
Though throttling is an expansion process, it is fundamentally different from expansion

taking place in a turbine. The expansion of a fluid in a turbine yields useful work output,
and can approach a reversible process (e.g. isentropic process), whereas expansion by
throttling is highly irreversible. Depending upon the throttling conditions and the nature
of the fluid, the exit temperature may be greater than or equal to or less than the inlet
temperature.
2.8.1 PV DIAGRAM
For an ideal gas, the Pressure – Volume diagram is given as
2.8.2 TS DIAGRAM
For an ideal gas, the Temperature – Entropy diagram is given as
2.8.3 CHANGE IN ENTROPY
The entropy change for an ideal gas, for a process 1 – 2 is given as
P1
s2  s1  R ln
P2
2.9 THERMODYNAMIC RELATIONS
There are many relations which relates the thermodynamic relations. Some of them are
as follows:
2.9.1 MAXWELL’S EQUATION
The equations that relate the partial derivatives of properties P, v, T, and s of a simple
compressible system to each other are called the Maxwell relations. They are obtained
from the four Gibbs equations by exploiting the exactness of the differentials of
thermodynamic properties.
Two of the Gibbs relations were expressed as
du  Tds  Pdv
dh  Tds  Pdv
The other two Gibbs relations are based on two new combination properties—the
Helmholtz function a and the Gibbs function g, defined as
a  u  Ts
g  h  Ts
Differentiating, we get
da  du  dTs  sdT
dg  dh  dTs  sdT
Simplifying the above relations by, we obtain the other two Gibbs relations for simple
compressible systems:
da  sdT  Pdv
dg  sdT  vdP
A careful examination of the four Gibbs relations reveals that they are of the form
dz  Mdx  Ndy
with
 M   N 
   
 y  x  x  y
since u, h, a, and g are properties and thus have exact differentials. Applying above
equations to each of them, we obtain
 T   P 
 v     s 
 s  v
 T   v 
 P    s 
 s  P
 s   P 
 v    T 
 T  v
 s   v 
 P    T 
 T  P
These are called the Maxwell relations. They are extremely valuable in thermodynamics
because they provide a means of determining the change in entropy, which cannot be
measured directly, by simply measuring the changes in properties P, v, and T. Note that
the Maxwell relations given above are limited to simple compressible systems.
2.9.2 CLAPEYRON EQUATION
The Clapeyron equation is applicable to any phase-change process that occurs at

constant temperature and pressure. It can be expressed in a general form as
 P  h12
 T   Tv
 sat 12
Example 2.2 When valve is open the atmospheric air at 27 0C and 1 atm pass into
vacuum chamber and flow until its pressure become 1 atm. The new temperature of air
would be?
Solution: The energy balance equation on chamber
m1h1 1 Q2  m ' u ' 1 Ws 2  m2h2  m " u "
Where
m1 is input air, m’ is the initially present air,
m” is the finally present air, m2 is the output air
 m1h1  m " u "

 h1  u " ( m1  m " )
We know that
h  u  Pv  CvT  RT and u  CvT

h  Cv  R T  CpT  u "  CvT "
 h1  CpT1
Hence,
CpT1  CvT "

Cp
T "  .T1
Cv
 T "   .T1
 T "  1.4  300
 T "  420K
Example 2.3 Ten kg water at 375 K is mixed adiabatically with 30 kg water at 275 K.
What is the change in entropy? Assume that the specific heat of water is 4.2 kJ / kg and
is independent of temperature.
Solution: Let T be the final temperature attained by the system. Then the heat
balance gives
10  375 – T   30 T – 275 
 T  300K
Let S1 be the change in the entropy of the hot water and let S1 be that of cold water.
Then
300
S1  10  4.2  ln  9.37 kJ/K
375
300
S2  30  4.2  ln  10.96 kJ/K
275
The total entropy change is
S  S1  S2  1.59 kJ/K
Example 2.4 A steel casing at temperature 725K and weighing 35 kg is quenched in 150
kg oil at 275 K. if there are no heat losses, determine the change in entropy. The specific
heat (Cp) of steel is 0.88 kJ / kg.K and that of oil is 2.5 kJ / kg.K. and evaluate the loss in
capacity for doing work when the steel casting in
Solution: Let T be the final temperature attained by the system. Then the heat
balance gives
35(0.88)(725  T )  150(2.5)(T  275)
Where T is the final temperature attained by the system. Solving this, we get, T =
309.15K. let S1 be the change in entropy of the casting and let S2 be that of oil. Then,
309.15
S1  35  0.88  ln  26.25 kJ/K
725
309.15
S2  150  2.5  ln  43.90 kJ/K
275
The total entropy change of the casting and oil together is
S  S1  S2  17.65 kJ/K
The loss in capacity for doing work is
T0 S  275  17.65  4853.75 kJ/K
Example 2.5 A vapor compression refrigeration system with ammonia as the working
fluid is to open between 266 K and 300 K. Determine the following:
(a) COP, given that the enthalpy of saturated vapor at 266 K = 656 kJ/kg and
enthalpy of superheated vapor leaving the compressor = 724 kJ/kg, enthalpy of
saturated liquid at 300K = 144 kJ / kg.
(b) COP, if a temperature approach of 5 K I necessary in the evaporator and
condenser, and the efficiency of the compressor is 75%. Enthalpy of saturated
vapor at 261 K = 652 kJ / kg and the enthalpy of super heated vapor entering the
condenser = 758 kJ / kg, enthalpy of saturated liquid at 305 K = 159 kJ / kg.
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Revised Study

Chemical Engineering Thermodynamics

First and Second laws of thermodynamics. First law

4.1.3 Calculation of Fugacity of Pure Gases 62

CHAPTER • LAWS OF THERMODYNAMICS

2.1 FIRST LAW OF THERMODYNAMICS

 W   Q (both are in same units)

i.e.  Q  W  does not depend on path

Since,  Q  W  is independent of path and not a path function

Hence,  Q  W  is a point function.

Thus,  Q  W  is a thermodynamic property.

  Q  W  will be a form of energy and should be a

For a cyclic process,

2.2 INTERNAL ENERGY

This is called the law of conservation of energy.

2.3 JOULE’S LAW

“The change in specific internal energy is always proportional to change in

k = constant of proportionality (which is equivalent to specific heat of gas

Hence, change in internal energy,

2.4 SECOND LAW OF THERMODYNAMICS

(i) Kelvin Planck Statement

2.4.1 KELVIN – PLANCK STATEMENT

This statement is simply related to the work. And it state that

“It is impossible to construct a device that operates in a thermodynamic cycle and

2.4.1.1 THERMAL RESERVOIR

Thermal reservoir has infinite heat capacity.

2.4.1.2 HEAT ENGINE

It is the device that operates in a thermodynamic cycle

Energy in = Energy out

From first law of thermodynamics,

Thermal efficiency of heat engine

Output Net work done

Example 2.1 Calculate U and H in kJ for 1 kmol water, as it is vaporized at the

Solution: The expansion work done by the system during vaporization is

W  P V  101.3  103 1.675  0.00104   10 3  169.57 kJ

For constant pressure process, this becomes

2.4.1.3 CARNOT CYCLE

Consider a closed system that consists of a gas contained

Reversible Isothermal Expansion (process 1-2, TH =

Reversible Adiabatic Expansion (process 2-3, temperature drops from TH to TL). At

Reversible Isothermal Compression (process 3-4, TL = constant). At state 3, the

2.4.1.4 EFFICIENCY OPTIMIZATION

The efficiency of a heat engine is given by

Where, T = temperature difference

Hence, decreasing TL to maximize the efficiency is better choice.

2.4.2 CLAUSIUS STATEMENT

This statement is simply related to the heat. And it state that

“It is impossible to construct a device that operates in a thermodynamic cycle and

The devices used to transfer heat from a low-temperature medium to a high-

The refrigerant enters the compressor as a

A refrigerator is shown schematically in figure given below. Here QL is the magnitude of

2.4.2.2 COEFFICIENT OF PERFORMANCE

The efficiency of a refrigerator is expressed in terms of the coefficient of performance

Then the COP of a refrigerator can be expressed as

The conservation of energy principle for a cyclic device requires that

Wnet ,in  QH  QL (kJ)

Then the COP relation becomes

reason for expressing the efficiency of a refrigerator by another term—the coefficient of

2.4.2.3 HEAT PUMP

Another device that transfers heat from a low-temperature medium to a high-

The measure of performance of a heat pump is also

A comparison of COP of Refrigerator and Heat pump gives

2.4.2.4 THE REVERSED CARNOT CYCLE