Thermodynamics

THERMODYNAMICS - CH
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THERMODYNAMICS - CH
THERMODYNAMICS
CONTENTS
1 INTRODUCTION 6
1.1 Introduction
1.2 Classification of Thermodynamics System
1.2.1 Closed System
1.2.2 Open System
1.2.3 Isolated System
1.3 Basic Terminology
1.3.1 Thermodynamic Equilibrium
1.3.2 Control Volume
1.3.3 Steady State
1.3.4 Thermodynamic Process
1.3.4.1 Cyclic Process
1.3.4.2 Reversible Process
1.3.4.3 Irreversible Process
1.3.4.4 Adiabatic Process
1.3.4.5 Polytropic Process
1.3.4.6 Throttling Process
1.4 Properties of a System
1.4.1 Fundamental Properties
1.4.1.1 Volume
1.4.1.2 Pressure
1.4.1.3 Force
1.4.1.4 Velocity
1.4.1.5 Temperature
1.4.2 Zeroth Law of Thermodynamics
1.5 Ideal Gas
1.6 Avogadro‘s Hypothesis
1.7 Energy, Work And Heat
1.7.1 Energy
1.7.1.1 Potential Energy
1.7.1.2 Kinetic Energy
1.7.1.3 Specific Internal Energy
1.7.1.4 Specific P – V Enrgy
1.7.1.5 Specific Enthalpy
1.7.2 Work
1.7.3 Heat
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2 LAWS OF THERMODYNAMICS 41
2.1 First Law of Thermodynamics
2.2 Internal Energy
2.3 Joule‘s Law
2.4 Second Law of Thermodynamics
2.4.1 Kelvin Plank Statement
2.4.1.1 Thermal Reservoir
2.4.1.2 Heat Engine
2.4.1.3 Carnot Cycle
2.4.1.4 Efficiency Optimization
2.4.2 Clausius Statement
2.4.2.1 Refrigerator
2.4.2.2 Coefficient of Performance
2.4.2.3 Heat Pump
2.4.2.4The Reversed Carnot Cycle
2.4.3 Equivalence of Two Statements
2.4.4Clausius Inequalities
2.5 Entropy
2.6 Thermodynamic Processes
2.6.1 Adiabatic Process
2.6.1.1 PVT Relationship
2.6.1.2 PV diagram
2.6.1.3 TS diagram
2.6.1.4 Change in Internal Energy
2.6.1.5Change in Entropy
2.6.1.6Work done
2.6.1.7Heat Transferred
2.6.2 Constant Temperature Process
2.6.2.2 PV diagram
2.6.2.3 TS diagram
2.6.2.5 Change in Entropy
2.6.2.6 Work done
2.6.2.7 Heat Transferred
2.6.3 Constant Pressure Process
2.6.3.2 PV diagram
2.6.3.3 TS diagram
2.6.3.6 Work done
2.6.4 Constant Volume Process
2.6.4.2 PV diagram
2.6.4.3 TS diagram
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2.6.4.6 Work done
2.6.5 Polytropic Process
2.6.5.2 PV diagram
2.6.5.3 TS diagram
2.6.5.6 Work done
2.7 Adiabatic Expansion
2.7.1 Closed System
2.7.2 Open System
2.8 Throttling Process
2.8.1 PV Diagram
2.8.2 TS Diagram
2.8.3 Change in Entropy
2.9Thermodynamic Relations
2.9.1 Maxwell‘s Equation
2.9.2 Clapeyron Equation
3 PURE SUBSTANCE 81
3.1 Pure Substance
3.2 Critical Point
3.3 Saturated Liquid And Saturated Vapor States
3.4 Saturated Liquid – Vapor Mixture
3.5 Super Heated Vapor
3.6 Compressed Liquid
3.7 Compressibility Factor
3.8 Van Der Waals Equation of State
4 THERMODYNAMIC EQUATIONS 104

4.1 Maxwell‘s Equation
4.2 TDs Equation
4.3 Heat Capacity Relationships
4.4 Clausius Clapeyron Equation
4.5 Internal Energy Change for an Ideal gas
4.6 The Joule Thomson Coefficient
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5 SOLUTION THERMODYNAMICS 117

5.1 Fugacity
5.1.1 Fugacity Coefficient
5.1.2 Effect of Temperature And Pressure on Fugacity
5.1.3 Calculation of Fugacity of Pure Gases
5.1.3.1 Using Compressibility Factor
5.1.3.2 Using Residual Volume
5.1.3.3 Using Enthalpy And Entropy Data
5.1.4 Fugacity of Liquids And Solids
5.2 Activity
5.2.1 Effect of Temperature And Pressure on Activity
5.3 Partial Molar Properties
5.3.1 Partial Properties of Solution
5.4 Chemical Potential
5.4.1 Effect of Temperature And Pressure on Chemical Potential
5.5 Fugacity in Solutions
5.5.1 Fugacity in Gaseous Solution
5.6 Lewis – Randall Model
5.7 Ideal Solution
5.8 Raoult‘s Law
5.9 Henry Law
5.10 Activity in Solutions
5.11 Activity Coefficient
5.11.1 Effect of Temperature And Pressure on Activity Coefficient
5.12 Gibbs Duhem Equation
5.13 Excess Properties
5.14 Activity Coefficient Equation
6 CHEMICAL REACTION EQUILIBRIUM 135

6.1 Chemical Reaction Equilibrium
6.2 Ideal Gas Reactions
6.3 Ideal Solution Reactions
6.4 Temperature And Pressure Dependence of Keq
7 LEVEL 1 CONCEPT BASED MCQS 151
8 LEVEL 2 CONCEPT BASED MCQS 174
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CHAPTER 1
INTRODUCTION
1.1 INTRODUCTION
The word THERMODYNAMICS means ―Heat in Motion‖.
―THERMODYNAMICS is basically a branch of science which focuses on the

study of energy transfer and its effect on various physical properties of the
system.‖
―THERMODYNAMICS is the study of three E‘s i.e. Energy, Entropy and
Equilibrium.‖
―THERMODYNAMICS is a science that governs following:
 Energy and its transformation.
 Feasibility of a process involving transformation of energy.
 Feasibility of a process involving transfer of energy.
 Equilibrium process.
Thus, we can say that THERMODYNAMICS deals with energy conversion,
energy exchange and the direction of exchange.
Thermodynamics is the branch of science that embodies the principles of

energy transformation in macroscopic systems. The general restrictions which
experience has shown to apply to all such transformations are known as the
laws of thermodynamics. These laws are primitive; they cannot be derived from
anything more basic. The first law of thermodynamics states that energy is
conserved; that although it can be altered in form and transferred from one
place to another, the total quantity remains constant. Thus, the first law of
thermodynamics depends on the concept of energy; but, conversely, energy is
an essential thermodynamic function because it allows the first law to be
formulated. This coupling is characteristic of the primitive concepts of
thermodynamics.
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THERMODYNAMIC SYSTEM
 System is that part of universe which is under investigation or under
the study of observer.
 Properties of the system are observed when the exchange of energy i.e.
work or heat, takes place.
 There is no arbitrary rule for selection of system but proper selection
makes the calculations easy.
SURROUNDINGS
 The remaining portion of universe which is external to the system is
called as surrounding.
 The exchange of energy takes place between system and
surroundings; hence surroundings may be influenced by the changes
taking place in system.
UNIVERSE
 System and surroundings together constitutes Universe i.e.
System + Surroundings = Universe.
Figure 1.1
SYSTEM BOUNDARY
 System and surroundings in the universe are separated by System
boundary.
 A system boundary has zero thickness.
 Boundary may be Real or Hypothetical and Fixed or Moving.
 It is a surface, and since a surface is a two-dimensional object, it has
zero volume. Thus, it attains neither mass nor volume.
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Figure 1.2
If heat (energy) exchange doesn’t take place across body it is called adiabatic
boundary otherwise it will be diathermic boundary.
DIFFERENCE BETWEEN SURROUNDINGS, IMMEDIATE SURROUNDINGS

AND ENVIRONMENT
 Surroundings are everything outside the system boundaries.
 The immediate surroundings refer to the portion of the surroundings
that is affected by the process, and
 Environment refers to the region beyond the immediate surroundings
whose properties are not affected by the process at any point.
1.2 CLASSIFICATION OF THERMODYNAMIC SYSTEM

On the basis of mass and energy transfer across / through the system
boundaries, a thermodynamic system can be classified as follows:
1.2.1 CLOSED SYSTEM (OR NON FLOW SYSTEM)

The system which can exchange energy with surroundings but which cannot
transfer matter across the boundaries are known as closed system.
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Closed System
 Heat and work (energy) crosses the boundary.
 No mass transfer takes place i.e. mass of system is fixed, hence it is also
called as NON FLOW SYSTEM.
 Due to fixed mass, we also define closed system as CONTROL MASS.
 Boundary of the system is not fixed but arbitrarily selected.
 Since boundary may change, volume of the system is not necessarily
fixed.
 Energy transfer can be experienced only at boundaries.
 e.g. Piston cylinder arrangement, gas being compressed by a piston in a
closed cylinder.
The fluid contained in the cylinder can receive or reject heat, can expand
or contract, hence changing the volume, but no matter (fluid) can flow
out or into the cylinder, i.e. mass remains fixed.
1.2.2 OPEN SYSTEM (OR FLOW SYSTEM)

The system that can exchange both energy and matter with their environment.
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 Heat and work crosses the boundary.

 Mass transfer also takes place i.e. mass of system is not fixed; hence it is
also called as FLOW SYSTEM.
 System boundary is known as CONTROL SURFACE which always
remains fixed.
 Volume of the system does not change; hence open system is also
defined as CONTROL VOLUME.
 e.g. Steam generator or boiler
A steam generator converts water into steam by gaining heat from
furnace. Hence water flows into the system and steam flows out of the
system; hence matter is crossing the boundary of system.
1.2.3 ISOLATED SYSTEM

An isolated system exchanges neither matter nor energy with its surroundings.
Isolated System
 Heat and work does NOT cross the boundary.
 Mass of the system remains fixed i.e. No mass transfer takes place.
 e.g. Thermos flask.
 Neither heat flows into/out of the system nor the matter flows.
Classify the following as open, close or isolated system with suitable reasons:
 Cooling system of engine of a car
 Pressure cooker
 Air compressor
Thus, a special type of closed system that does not interact with its
surroundings is called an Isolated System.
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GATE Tip
Open system
 Heat and work crosses the boundary. Mass transfer also takes place
i.e. mass of system is not fixed
 Known as FLOW SYSTEM.
 Volume of the system does not change.
Closed System
 Heat and work (energy) crosses the boundary. No mass transfer takes
place.
 Known as NON FLOW SYSTEM.
 Volume of the system change.
Isolated System
 Heat and work does not cross the boundary. No mass transfer takes place.
Past GATE Questions on GATE Tip
Q.1 A closed thermodynamic system is one in which

(a) There is no energy or mass transfer across the boundary
(b) There is no mass transfer, but energy transfer exists
(c) There is no energy transfer, but mass transfer exists
(d) Both energy and mass transfer take place across the boundary, but
the mass transfer is controlled by valves
Q.2 Which of the following statements are true?

(a) A closed system is necessarily an isolated system
(b) An isolated system is necessarily a closed system
(c) A system cannot be both closed and isolated.
(d) The concepts of closed and isolated in regards to a system are
independent concepts.
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Q.3 Which of these Cases would be best suited for using a control volume
approach in the thermodynamic analysis of the system?
(a) Compression of air in a cylinder
(b) Expansion of gases in a cylinder after combustion
(c) Air in a balloon
(d) Air Filling in a Cycle tyre from any compressor
Solutions
1) (b) As we know that In closed system only energy transfer will happen.
2) Statement (b) is true. Because for isolated system ,system should be a closed
system at first.
3) All Systems (a) to (c) are closed systems, so we can‘t use control mass for
these cases. Only system (d) is an open system with a fixed boundary because
here mass flow and energy transfer both are taking place so option (d) will be
answer.
1.3 BASIC TERMINOLOGIES

There are some basic terms one should know for the good study of
thermodynamics:
1.3.1 HOMOGENEOUS AND HETEROGENEOUS SYSTEM

 A phase is defined as the quantity of matter which is homogeneous
throughout in chemical composition i.e. chemical composition does not
vary within system; and physical structure i.e. solid, liquid or gas.
 The system consisting of single phase is called a homogeneous system.
e.g. air, mixture of water and sugar etc.
 The system which consists of more than one phase is called
heterogeneous system. e.g. mixture of water and oil etc.
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MACROSCOPIC AND MICROSCOPIC VIEWPOINT

Macroscopic Viewpoint Microscopic Viewpoint
1. A certain quantity of matter is 1. The behaviour of matter is
under investigation without described by summing up
focusing on the events taking behaviour of each molecule.
place at molecular level.
2. Properties that define the system 2. Since properties are concerned
can be measured and can be felt with individual molecule, they
by human senses. cannot be felt by human senses.
3. Observations are based on 3. Exact observations are carried

assumption (properties are out by considering the structure
average values) since structure of of matter.
matter is not considered at all.
4. The analysis of approach
4. The analysis of this approach
requires a large no. of
requires simple mathematical
molecules so behaviour of the
formula.
molecules is studied by using
advanced statistical and
mathematical methods.
 Macroscopic viewpoint is an engineering approach while

microscopic viewpoint is a scientific approach.
1.3.2 THERMODYNAMIC EQUILIBRIUM

When a system is in equilibrium with regard to all possible changes in state,
the system is in thermodynamic equilibrium. For example, if the gas that
comprises a system is in thermal equilibrium, the temperature will be the same
throughout the entire system.
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1.3.3 CONTROL VOLUME

A control volume is a fixed region in space chosen for the thermodynamic study
of mass and energy balances for flowing systems. The boundary of the control
volume may be a real or imaginary envelope. The control surface is the
boundary of the control volume.
1.3.4 STEADY STATE

Steady state is that circumstance in which there is no accumulation of mass or
energy within the control volume, and the properties at any point within the
system are independent of time.
1.3.5 THERMODYNAMIC PROCESS

Whenever one or more of the properties of a system change, a change in the
state of the system occurs. The path of the succession of states through which
the system passes is called the thermodynamic process. One example of a
thermodynamic process is increasing the temperature of a fluid while
maintaining a constant pressure. Another example is increasing the pressure
of a confined gas while maintaining a constant temperature.
1.3.5.1 CYCLIC PROCESS

When a system in a given initial state goes through a number of different
changes in state (going through various processes) and finally returns to its
initial values, the system has undergone a cyclic process or cycle. Therefore, at
the conclusion of a cycle, all the properties have the same value they had at the
beginning. Steam (water) that circulates through a closed cooling loop
undergoes a cycle.
1.3.5.2 REVERSIBLE PROCESS

A reversible process for a system is defined as a process that, once having
taken place, can be reversed, and in so doing leaves no change in either the
system or surroundings. In other words the system and surroundings are
returned to their original condition before the process took place. In reality,
there are no truly reversible processes; however, for analysis purposes, one
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uses reversible to make the analysis simpler, and to determine maximum

theoretical efficiencies. Therefore, the reversible process is an appropriate
starting point on which to base engineering study and calculation. Although
the reversible process can be approximated, it can never be matched by real
processes.
One way to make real processes approximate reversible process is to carry out
the process in a series of small or infinitesimal steps. For example, heat
transfer may be considered reversible if it occurs due to a small temperature
difference between the system and its surroundings. For example, transferring
heat across a temperature difference of 0.00001 °F "appears" to be more
reversible than for transferring heat across a temperature difference of 100 °F.
Therefore, by cooling or heating the system in a number of infinitesimally small
steps, we can approximate a reversible process.
1.3.5.3 IRREVERSIBLE PROCESS

An irreversible process is a process that cannot return both the system and the
surroundings to their original conditions. That is, the system and the
surroundings would not return to their original conditions if the process was
reversed. For example, an automobile engine does not give back the fuel it took
to drive up a hill as it coasts back down the hill. There are many factors that
make a process irreversible. Four of the most common causes of irreversibility
are friction, unrestrained expansion of a fluid, heat transfer through a finite
temperature difference, and mixing of two different substances. These factors
are present in real, irreversible processes and prevent these processes from
being reversible.
1.3.5.4 ADIABATIC PROCESS

An adiabatic process is one in which there is no heat transfer into or out of the
system. The system can be considered to be perfectly insulated.
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1.3.5.5 ISENTROPIC PROCESS

An isentropic process is one in which the entropy of the fluid remains constant.
This will be true if the process the system goes through is reversible and
adiabatic. An isentropic process can also be called a constant entropy process.
1.3.5.6 POLYTROPIC PROCESS

When a gas undergoes a reversible process in which there is heat transfer, the
process frequently takes place in such a manner that a plot of the Log P
(pressure) vs. Log V (volume) is a straight line. Or stated in equation form PVn =
constant. This type of process is called a polytropic process. An example of a
polytropic process is the expansion of the combustion gasses in the cylinder of
a water-cooled reciprocating engine.
1.3.5.7 THROTTLING PROCESS

A throttling process is defined as a process in which there is no change in
enthalpy from state one to state two, h1 = h2 ; no work is done, W = 0; and the
process is adiabatic, Q = 0. To better understand the theory of the ideal
throttling process let‘s compare what we can observe with the above theoretical
assumptions.
1.4 PROPERTIES OF A SYSTEM

 Properties are the descriptive and measurable characteristics of the
system.
 Properties describe the state of a system i.e. has a definite value when
system is in a particular state.
 These are macroscopic in nature and hence, can be measured very
easily.
 Their differential is exact i.e. value can be determined by simply
integrating from one state to another.
 They depend only upon the state of system but not on the path followed
by the process, hence are Point function or State function.
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 Temperature, pressure, volume energy etc. are the various properties of

system.
GATE Tip
Gate Tip: Thus, Properties are macroscopic characteristics of a system such as
mass, volume, energy, pressure and temperature etc. to which numerical values
can be assigned at a given time without knowledge of the past history of the
system.
Check for a property:

 An expression is a property of the system if its differential is exact.
e.g. Expression 𝑝 𝑑𝑣 + 𝑣 𝑑𝑝 is an exact differential of 𝑑(𝑝𝑣),hence is a
property. But 𝑝 𝑑𝑣 𝑜𝑟 𝑣 𝑑𝑝 alone are not exact differential, hence are not
the property of system.
 Expression 𝑑𝑃 = 𝑀 𝑑𝑥 + 𝑁 𝑑𝑦 is exact differential if
∂M ∂N
=
∂y 𝑥 ∂x 𝑦
INTENSIVE AND EXTENSIVE PROPERTIES
 Properties of system may be classified as Intensive or Extensive
properties.
 INTENSIVE PROPERTIES are those which are independent of mass of

system.
 Property of small portion of the system defines the property of whole of
the system.
 Intensive properties are expressed in lower case letters except Pressure
(P), temperature (T).
 All the specific properties are intensive properties.
 e.g. Pressure (P), temperature (T), density(𝜌) etc.
 EXTENSIVE PROPERTIES are mass dependent. Hence their value

depends upon the size of the system.
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 An extensive property when expressed as per unit mass becomes an

intensive property (Specific property).
 Extensive properties are expressed in upper case letter except mass.
 e.g. mass (m), energy (E), enthalpy (H), entropy (S) etc.
Extensive
 . = intensive
Extensive
GATE Tip
Intensive properties are those which will be unchanged by any process, whereas those
properties whose values are increased or decreased in proportion to the enlargement
or reduction of the system are called extensive properties.
If the system consists of mixture of different phases, the phases are separated from
each other by phase boundary. The thermodynamic properties change abruptly at the
phase boundary, even though the intensive properties like temperature and pressure
are identical.
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Past GATE Questions on Concept
Q.1 Here two systems S1 and S2 as shown in Figure 2.1.Both the systems
are in similar states. S3 is the combined system of S1 and S2. Is the
value of property for S3 same as that for S1 and S2 or will have some
other value?
Ans 1: If property is intensive then S3 will also have same value as S1 and S2
and if property is extensive then it will not have same value as S1 and S2.
Q.2 Which of the following are intensive properties?

1. Kinetic energy 2. Specific enthalpy
3. Pressure 4. Entropy
Select the correct answer using the code given below:
(a) 1 and 3
(b) 2 and 3
(c) 1, 3 and 4
(d) 2 and 4
Ans. 2: Specific Enthalpy is defined as enthalpy per unit mass so it will not
depend on mass and Pressure will not depend on mass also. Thus both Specific
Enthalpy and Pressure both will be treated as intensive property.
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STATE OF A SYSTEM
 State of a system is the condition of system at any point of time.
 The state of a simple compressible system can be completely
specified by two independent, intensive properties. (This is also
called two property rule or state postulates) Gibb‘s phase rule
F=C–P+2
 When one or more than one property of system changes, then a change
of state of system takes place.
Note:
 A system is called a simple compressible system in the absence of
electrical, magnetic, gravitational, motion, and surface tension effects.
(These effects are nearly negligible in the most of the engineering
problems )
 Two properties are independent if one property can be varied while the
other one is held constant.
 Temperature and specific volume, for example, are always independent

properties, and together they can fix the state of a simple compressible
system
Dialogue box….
Temperature and pressure, however, are independent properties for single-
phase systems, but are dependent properties for multiphase systems. Explain.
THERMODYNAMIC PROCESS, PATH AND CYCLE

 Any change that a system undergoes from one equilibrium state to
another is called a process
 The series of states through which a system passes during a process is
called the path of the process
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 When change of state takes place in such a way that the initial and final
states of system are identical, then the process is called thermodynamic
cycle.
THERMODYNAMIC EQUILIBRIUM
 A system is said to be in thermodynamic equilibrium if the conditions are
satisfied for:
 Mechanical equilibrium
 Chemical equilibrium
 Thermal equilibrium
 Phase equilibrium
Mechanical equilibrium in system exists when there is no change in pressure
at any point of system with time i.e. uniformity of pressure. It also means that
there is no any unbalanced force. In other words, there is no pressure gradient
within the system.
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 The variation of pressure as a result of gravity in most

thermodynamic systems is relatively small and usually
disregarded.
 Still water contained in a tank is also considered to be in
mechanical equilibrium, though the pressure increases as one
move downward from free water surface.
 Chemical equilibrium in a system exists when there is no change in

chemical composition with time i.e. no chemical reaction takes place.
 Thermal equilibrium in a system exists when there is no temperature
differential within system.
 Temperature is same throughout the entire system.
 Fluids comprising the system are not chemically reactive
since it may raise temperature of system by chemical
reaction.
 Phase equilibrium in a multiphase system exists when the mass of each
phase reaches an equilibrium level and stays there.
Note:
 A system is said to be in non-equilibrium state if any one of the
above condition is not satisfied by the system.
 In non-equilibrium, states passed by the system cannot be
described by thermodynamic properties which represent the
system as a whole.
When a system remains in equilibrium state, it should not undergo any changes
on its own.
QUASI-STATIC PROCESS
 When a process proceeds in such a manner that the system remains
infinitesimally close to an equilibrium state at all times, it is called a
quasi-static, or quasi-equilibrium, process.
 Thus, clear state properties (pressure, temperature etc.) can be assigned
to the system at every moment. A quasi-static process can thus be
represented by a set of continuous points on a state-space diagram (e.g.,
a p − V diagram or a T − v diagram).
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Features of Quasi-Static Process

 A quasi-equilibrium process is a sufficiently slow process that allows the
system to adjust itself internally so that properties in one part of the
system do not change any faster than those at other parts.
 Frictionless quasi-static processes are reversible.

 These are idealized process and not the true representation of actual
process.
 Every state passed may be regarded as equilibrium state.
 Infinite slow process and easy to analyze.
 All work producing devices work on this principle.
GATE Tip
A process is said to be reversible if the system and its surroundings are

restored to their respective initial states by reversing the direction of the
process. A reversible process has to be quasi-static, but a quasi – static process
is not necessarily reversible.
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Examples:
Quasi-static: Slow expansion of a piston and cylinder system such that
pressure and volume can be clearly defined at every point in time.
Non quasi-static: Sudden expansion of the piston-cylinder system. Pressure in
the system cannot be specified at every point in time.
Quasi-static: Two bodies exchanging energy in the form of heat such that the
temperature of each body is clearly defined at every point of time.
Non quasi-static: Rapid removal of energy from one surface of a reasonably large
system such that there is no unique temperature for the system.
Reversible Process
A process in which an infinitesimal change in the driving potential can reverse
the direction of the process.
Example: A piston expanding against an external pressure. The driving
potential is the pressure difference which is infinitesimal. At any stage, if the
external pressure is increased infinitesimally, the piston should start moving
the opposite way.
Or Else: Heat transfer occurring due to a temperature difference between two
bodies. The temperature difference between the two bodies is infinitesimal. If
the temperature of body receiving energy is changed infinitesimally, the
direction of heat transfer also changes.
NOTE: A reversible process is necessarily quasi-static though the opposite is
not true. For example, consider heat exchange between a really well insulated
vessel at temperature T1 and the surroundings which are at T2 far lesser than
T1. Changing either T1 or T2 does not reverse the direction of the process,
though it is slow enough to be quasi-static.
Q.3 Which Of The Following Is/Are Reversible Process(es)?

1. Isentropic expansion
2. Slow heating of water from a hot source
3. Constant pressure heating of an ideal gas from a constant
temperature source
4. Evaporation of a liquid at constant temperature
Select the correct answer using the code given below:
(a) 1 Only
(b) 1 And 2
(c) 2 And 3
(d) 1 And 4
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Ans:
(d) Isentropic expansion and evaporation of a liquid at constant temperature.
Isentropic expansion is also known as reversible adiabatic process (which will
be discussed in later chapter).
CONCEPT OF CONTINUUM
Despite the large gaps between molecules, a substance can be treated as
a continuum because of the very large number of molecules even in an
extremely small volume.
It assumes a continuous distribution of mass within the matter or

system with no empty space, instead of the actual conglomeration of
separate molecules.
If the mean free path is very small as compared with some characteristic
length in the flow domain (i.e., the molecular density is very high) then
the gas can be treated as a continuous medium. If the mean free path is
large in comparison to some characteristic length, the gas cannot be
considered continuous.
 The continuum idealization allows us

 to treat properties as point functions and
 to assume the properties vary continually in space with no
jump discontinuities.
 This idealization is valid as long as the size of the system we deal with is
large relative to the space between the molecules.
PATH FUNCTION AND POINT FUNCTION

Point Functions
 They depend only upon the initial and final condition (state) of the
system but not on the path followed by the system.
 They have exact differential i.e. their integration can be carried out
simply.
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 Differential amount is represented by symbol ―d‖ i.e. small change in

volume will be expressed as dV.
 Change in value can be expressed as the difference between initial and
final value.
2
𝑑𝑉 = 𝑉2 − 𝑉1
1
 Thermodynamic properties are point functions since for a given state
there is a definite value for each property and is independent of the path
the system follows during the change of state.
 In a cycle, since initial and final states are identical, the cyclic integral of
a property (point function) is always zero i.e. 𝑉 = 0, 𝑃 = 0, 𝑇 = 0.
Path Functions
 They depend upon the path followed by the system.
 They have inexact differential.
 Differential amount is represented by symbol 𝛿 i.e. for small work done
𝛿𝑊 and small heat transfer 𝛿𝑄
 Work and heat are the path functions.
 Change in the value can NOT be expressed as the difference between
initial and final value.
𝛿𝑊 ≠ 𝑊2 − 𝑊1 ≠ ΔW
=W1-2 (but not ΔW)
 Before integration, multiplication with integrating factor is required.
WORKING SUBSTANCE
 A working substance refers to a fluid in thermodynamic devices to serve
as a medium for transport of energy between the system and
surroundings.
 Fluid may be gas, vapour, liquid or any nonreactive mixture of these
constituents.
 Working substance may change their phase during processes occurring
in the system.
 Example – refrigerants used in refrigeration and air-conditioners, water
vapour used in steam power plants.
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GATE Tip
Intensive Property
 Independent of mass
Extensive Property
 mass dependent.
 value depends upon the size of the system.
Specific property
 An extensive property when expressed as per unit mass becomes an
intensive property.
Point Functions
 They depend only upon the initial and final condition
 not on the path followed by the system.
 exact differential
 Cyclic integral of a property (point function) is always zero
Path Functions
 Depend upon the path followed by the system.
 Inexact differential.
1.4.2 FUNDAMENTAL PROPERTIES

There are following fundamental properties which are used to describe the
state of a system. Such as
1.4.2.1 VOLUME
Space occupied by the system in three dimensions is called volume of the
system.
Unit: m3, litre, c.c.
and 1 m3 = 103 litre = 106 c.c.
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1.4.2.2 PRESSURE
Force exerted by the gaseous system perpendicular to the unit surface area.
Mathematically,
Normal Component of Force
Pr essure 
Area
Units: Pa, N / m2, atm…
And 1 atm = 101.325 kPa = 101325 N / m2
 Standard Atmospheric Pressure

Weight of air column per 1 m2 area is called standard atmospheric pressure.
Since it is not practically possible to determine the infinite height of air column
thus we take a equivalent column of same weight filled with Mercury (Hg), and
it comes to be 760 mm height.
Hence we can say that
1 atm  760 mm Hg
Hence,
From Hydrostatic law, we know that
P   gh
Therefore,
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1 atm 
kg m
P  13595.1 3
  9.80665  2   0.760  m
m s
N
P  101325.01 2
m
P  101.325 kPa
P  1.01325 bar
and 1 bar  105 Pa
1.4.2.3 FORCE
Force is which may change or tends to change the state of the system.
Force  Rate of change of momentum
d (mv )
F
dt
 dv dm 
F  m v
 dt dt 
Since, m is the mass (i.e. matter contained by the body) of the body which is
independent of the time and place.
Thus equation becomes:
dv
F m
dt
F  ma
F  k .ma
Where k is the proportionality constant.
According to Force law:
1 kgf  k  1 kg m  9.81 sm2
1 1
 k  (say )
9.81 gc
gc  constant value of g everywhere
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1
F ma
gc
1 m
 1kg f   1kg m  9.81 2
gc s
kg m .m
 g c  9.81
kg f .s 2
Example 1.1 A body having mass 70 kgm weighing 70 kgf at g = 9.81 m / s2,
when it placed at a place where the value of g becomes 5 m / s2.
What will be the weight of the body?
Solution: From Newton‘s second law, we know that
1
W  mg
gc
1  kgf .s 2  m
W     70(kg )  5  2 
9.81  kg m .m  s 
 W  36.67788kg f
 Relationship between kgf and N

m kg .m
F  70kg m  5  2   350 m2  350N
s  s
hence, Mathematically
F W
 350N  36.67788kg f
 1kgf  9.81N
1.4.2.4 VELOCITY
Velocity may be defined as the distance travelled by the body per unit time.
Distance travelled by the body d
v 
Time taken by the body to travel that distance t
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1.4.2.5 TEMPERATURE
Temperature may be defined as the thermal potential of a system responsible
for energy transfer (i.e. heat transfer).
According to science,
Temperature is the measure of average kinetic energy of gases.
 THERMAL EQUILIBRIUM
When a body is brought into contact with another body that is at a different
temperature, heat is transferred from the body at higher temperature to the
one at lower temperature until both bodies attain the same temperature as
shown in figure. At that point, the heat transfer stops, and the two bodies are
said to have reached thermal equilibrium. The equality of temperature is the
only requirement for thermal equilibrium.
1.4.2 ZEROTH LAW OF THERMODYNAMICS

The zeroth law of thermodynamics states that if two bodies are in thermal
equilibrium with a third body, they are also in thermal equilibrium with each
other. It may seem silly that such an obvious fact is called one of the basic laws
of thermodynamics. However, it cannot be concluded from the other laws of
thermodynamics, and it serves as a basis for the validity of temperature
measurement. By replacing the third body with a thermometer, the zeroth law
can be restated as two bodies are in thermal equilibrium if both have the same
temperature reading even if they are not in contact.
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 TEMPERATURE SCALES
Temperature scales enable us to use a common basis for temperature
measurements. All temperature scales are based on some easily reproducible
states such as the freezing and boiling points of water, which are also called
the ice point and the steam point, respectively.
A mixture of ice and water that is in equilibrium with air saturated with vapor
at 1 atm pressure is said to be at the ice point.
A mixture of liquid water and water vapor (with no air) in equilibrium at 1 atm
pressure is said to be at the steam point.
The temperature scales used in the SI and in the English system are the
Celsius scale and the Fahrenheit scale, respectively.
On the Celsius scale, the ice and steam points were originally assigned the
values of 0 and 100°C, respectively.
The corresponding values on the Fahrenheit scale are 32 and 212°F. These are
often referred to as two-point scales since temperature values are assigned at
two different points.
In thermodynamics, it is very desirable to have a temperature scale that is

independent of the properties of any substance or substances. Such a
temperature scale is called a thermodynamic temperature scale, which is
developed later in conjunction with the second law of thermodynamics.
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The thermodynamic temperature scale in the SI is the Kelvin scale. The

temperature unit on this scale is the kelvin, which is designated by K (not °K).
The lowest temperature on the Kelvin scale is absolute zero, or 0 K. Then it
follows that only one nonzero reference point needs to be assigned to establish
the slope of this linear scale. Using nonconventional refrigeration techniques,
scientists have approached absolute zero kelvin (they achieved 0.000000002 K
in 1989).
The thermodynamic temperature scale in the English system is the Rankine
scale, named after William Rankine (1820–1872). The temperature unit on this
scale is the rankine, which is designated by R.
The Kelvin scale is related to the Celsius scale by

T (K )  T (0 C )  273.15
The Rankine scale is related to the Fahrenheit scale by
T (R )  T (0 F )  459.67
The temperature scales in the two unit systems are related by
T (R )  1.8  T (K )
T (0 F )  1.8  T (0 C )  32
The reference temperature chosen in the original Kelvin scale was 273.15 K (or
0°C), which is the temperature at which water freezes (or ice melts) and water
exists as a solid – liquid mixture in equilibrium under standard atmospheric
pressure (the ice point).
At the Tenth General Conference on Weights and Measures in 1954, the
reference point was changed to a much more precisely reproducible point, the
triple point of water (the state at which all three phases of water coexist in
equilibrium), which is assigned the value 273.16 K.
The Celsius scale was also redefined at this conference in terms of the ideal gas
temperature scale and a single fixed point, which is again the triple point of
water with an assigned value of 0.01°C. The boiling temperature of water (the
steam point) was experimentally determined to be again 100.00°C.
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We emphasize that the magnitudes of each division of 1 K and 1°C are identical
as shown in figure. Therefore, when we are dealing with temperature
differences T , the temperature interval on both scales is the same. Raising the
temperature of a substance by 10°C is the same as raising it by 10 K. That is
T (K )  T (0 C )
T (R )  T (0 F )
1.5 IDEAL GAS

An ideal gas is one in which the distance between the molecules is so large that
the inter molecular forces are negligible and the volume occupied by the
molecules is only a negligible fraction of the total volume. It follows from kinetic
theory that for such a fluid the product of pressure and volume varies linearly
with temperature. This is stated mathematically by the ideal gas equation PV =
RT, where R is a constant known as the ideal gas constant and V is the molar
volume of the gas.
Mathematically, we write the equation of state, as follows
PV  nRT
1.6 AVOGADRO’S HYPOTHESIS

It states that,
―All gases contain equal no. of molecules in a given volume at NTP.‖
i.e. Avogadro‘s number , NA  6.023  1026 no. of molecules
NA  6.023  1023 no. of kilo  molecules
in 22.41 m 3 Volume
E.g. H2  In 22.41 m3  6.023  1026 no. of molecules of 2 kilogram mass  1 kgmol
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1.7 ENERGY, WORK AND HEAT

Heat and work are the two ways in which energy can be transferred across the
boundary of a system. One of the most important discoveries in
thermodynamics was that work could be converted into an equivalent amount
of heat and that heat could be converted into work.
1.7.2 ENERGY
Energy is defined as the capacity of a system to perform work or produce heat.
1.7.2.1 POTENTIAL ENERGY

Potential energy (PE) is defined as the energy of position. Using English system
units, it is defined by Equation
mgz
PE 
gc
where:
PE = potential energy (N – m)
m = mass (kgm)
z = height above some reference level (m)
g = acceleration due to gravity (m / s2)
gc = gravitational constant = 9.81 m – kgm / kgf - s2
1.7.2.2 KINETIC ENERGY

Kinetic energy (KE) is the energy of motion. Using English system units, it is
defined by Equation
mv 2
KE 
2gc
where:
KE = kinetic energy (N – m)
v = velocity (m / sec)
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1.7.2.3 SPECIFIC INTERNAL ENERGY

The specific internal energy (u) of a substance is its internal energy per unit
mass. It equals the total internal energy (U) divided by the total mass (m).
i.e.
U
u
m
where:
u = specific internal energy (J / kg)
U = internal energy (J)
1.7.2.4 SPECIFIC P-V ENERGY

In addition to the internal energy (U), another form of energy exists that is
important in understanding energy transfer systems. This form of energy is
called P – V energy because it arises from the pressure (P) and the volume (V) of
a fluid. It is numerically equal to PV, the product of pressure and volume.
Because energy is defined as the capacity of a system to perform work, a
system where pressure and volume are permitted to expand performs work on
its surroundings. Therefore, a fluid under pressure has the capacity to perform
work. In engineering applications, the units of P-V energy, also called flow
energy, are the units of pressure times volume (kgf per square meter times
cubic meter), which equals kgf – m (kgf – m).
The specific P-V energy of a substance is the P-V energy per unit mass. It
equals the total P-V divided by the total mass m, or the product of the pressure
P and the specific volume ν, and is written as Pν.
PV
Pv 
m
where:
P = pressure (kgf / m2)
V = volume (m3)
ν = specific volume (m3 / kgm)
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1.7.2.5 SPECIFIC ENTHALPY

Specific enthalpy (h) is defined as h = u + Pν, where u is the specific internal
energy (J / kg) of the system being studied, P is the pressure of the system (kgf
/ m2), and ν is the specific volume (m3 / kgm) of the system. Enthalpy is usually
used in connection with an "open" system problem in thermodynamics.
Enthalpy is a property of a substance, like pressure, temperature, and volume,
but it cannot be measured directly. Normally, the enthalpy of a substance is
given with respect to some reference value.
For example, the specific enthalpy of water or steam is given using the
reference that the specific enthalpy of water is zero at .01°C and normal
atmospheric pressure. The fact that the absolute value of specific enthalpy is
unknown is not a problem, however, because it is the change in specific
enthalpy (∆h) and not the absolute value that is important in practical
problems.
1.7.3 WORK
Work is a form of energy, but it is energy in transit. Work is not a property of a
system. Work is a process done by or on a system, but a system contains no
work. This distinction between the forms of energy that are properties of a
system and the forms of energy that are transferred to and from a system is
important to the understanding of energy transfer systems.
Work is defined for mechanical systems as the action of a force on an object

through a distance. It equals the product of the force (F) times the
displacement (d).
W  F.d
where:
W = work (m – kgf)
F = force (kgf)
d = displacement (m)
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Work  Unit Force  Unit Displacement

 W  1 N 1 m
 1J 1N m
1.7.4 HEAT
Heat, like work, is energy in transit. The transfer of energy as heat, however,
occurs at the molecular level as a result of a temperature difference. The
symbol Q is used to denote heat. In engineering applications, the unit of heat is
the calorie (cal).
As with work, the amount of heat transferred depends upon the path and not
simply on the initial and final conditions of the system. Also, as with work, it is
important to distinguish between heat added to a system from its surroundings
and heat removed from a system to its surroundings. A positive value for heat
indicates that heat is added to the system by its surroundings. This is in
contrast to work that is positive when energy is transferred from the system
and negative when transferred to the system. The symbol q is sometimes used
to indicate the heat added to or removed from a system per unit mass. It equals
the total heat (Q) added or removed divided by the mass (m). The term "specific
heat" is not used for q since specific heat is used for another parameter. The
quantity represented by q is referred to simply as the heat transferred per unit
mass.
Q
q
m
where:
q = heat transferred per unit mass (cal / kgm)
Q = heat transferred (cal)
The amount of heat is required to raised the temperature of 1 kg of water (as

15 to 16°C) is the 1 kcal.
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Past GATE Questions
1. Which of the following is correct?

a. Absolute pressure = Gauge pressure + Atmospheric pressure
b. Gauge pressure = Absolute pressure + Atmospheric pressure
c. Atmospheric pressure = Absolute pressure + Gauge pressure
d. Absolute pressure = Gauge pressure × Atmospheric pressure
2. Which of the following is an example of closed system?

a. Thermosflask
b. Pressure cooker
c. Steam turbine
d. All of above
3. Which of the following expressions are true?
1 𝑑𝑊 ≠ 0, 2 𝑑𝑃 = 0 ,
(3) 𝛿𝑄 = 0
a. 1, 2
b. 1
c. 2
d. 2, 3
4. A diathermic wall allows flow of

a. Heat and matter
b. Only heat
c. Only matter
d. None of these
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5. Atm is…..
a. 1.01325 Mpa
b. 1.0 Mpa
c. 1.005 Mpa
d. 760 Kpa
6. The Barometer reading 760 mm hg equals
a. 90 cm hg Gauge
b. 40 cm hg Vacuum
c. 10.336 m H2o Gauge
d. 3.1 Bar
7. A 30 m high vertical column of a fluid of density 1878 kg/m3 exists in a

place where g = 9.65 m/s2. What is the pressure at the base of the
column?
a. 501.45 Kpa
b. 600.25 Kpa
c. 644.67 Kpa
d. 543.68 Kpa
Answers and Hints:
1-a 2-b 3-c 4-b 5-a 6-c 7- hint (p = ρgh)
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CHAPTER 2
LAWS OF THERMODYNAMICS
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
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Explanation:
 W   Q (both are in same units)
  W     W     Q  A    Q B
2 1 2 1
For cycle 1  A  2  B  1  A B
...(1)
1 2 1 2
  W     W     Q  A    Q C
2 1 2 1
For cycle 1  A  2  C  1  A C
...(2)
1 2 1 2
Subtracting equation (2) from (1), we get:
2  W B  2  W C  2  Q B  2  Q C
1 1 1 1
  Q     W C    Q B    W B
1 1 1 1
 C
2 2 2 2
  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
THERMODYNAMICS - CH
For a cyclic process,

1 2  Q2 1 W2  U2  U1
1
23  Q3 2 W3  U3  U2
2
34 Q4 3 W4  U 4  U3
3
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
THERMODYNAMICS - CH
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 thermo dynamic cycle and produces net
amount of positive work having heat exchange with at least two thermal
reservoirs.
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Energy balance:
Energy in = Energy out
 QH = Wnet + QL
Wnet  QH  QL
From first law of thermodynamics,
 Q   W
  QH   0   QL   0  
 Q
 W
 WT  WP  Wnet  
 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
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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:
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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
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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
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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
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 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
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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.
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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 Q L and Wnet,in
by W net ,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
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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
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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 QH is lost to the
outside air through piping and other devices, and COP HP 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 averaged COP of 2 to 3.
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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 QL 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.
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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.
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2.4.4 CLAUSIUS INEQUALITIES

The work done is given as
 W    Q    Q
1 H
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
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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 are called Clausius Inequalities.
2.5 ENTROPY
 Q 
For   T
Re v
0
For reversible cycle, 1–A–2–B–1
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2  Q  1  Q 
 1  T   2  T   0
 A  B
…(i)
For reversible cycle, 1–A–2–C–1

2  Q  1  Q 
 1  T   2  T   0
 A  C
…(ii)
Subtracting equation (ii) from (i), we get

1  Q  1  Q 
      0
2
 T B 2  T C
1  Q  1  Q 
 2  T 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.
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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.
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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.
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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 
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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
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2.6.2.6 WORK DONE

V2 V
W2  PV
1 1 1 ln  P2V2 ln 2
V1 V1
P1 V
1 W2  mRT1 ln  P2V2 ln 2
P2 V1

V2
Q2  PV
1 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 
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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
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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
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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
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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
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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
And work done is given by
1 1  P2V2
PV
W2 
1
 1
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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
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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.
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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.
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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
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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
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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
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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:
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(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.
(c) The COP of an ideal Carnot refrigerator.
Solution:
(a) HA = 656, HB = 724 and HC = HD = 144. From equation
H A  HD 656  144
COP    7.53
HB  H A 724  656
(b) HA = 652, HB = 758 and HC = HD = 159. From equation
H A  HD 652  159
COP    3.49
HB  H A  758  652   1/ 0.75
(c) For Carnot cycle, COP is given by equation

T2 266
COP    7.8
T1  T2 300  266
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Past GATE Questions based on first law of

thermodynamics
1. A closed system is cooled reversely from 1000C to 500C. If no work is done on

the system.
(A) Its internal energy (U) decreases and its entropy (S) increases,
(B) U and S both decrease,
(C) U decreases but S is constant,
(D) U is constant but S decreases,
2. The equation dU = TdS – PdV is applicable to infinitesimal changes occurring in

:
(A) an open system of constant composition,
(B) a closed system of constant composition,
(C) an open system with changes in composition,
(D) a closed system with changes in composition
Answer Key:
1-B 2-D
Past GATE Questions on second law of

thermodynamics
1. The second law of thermodynamics states that,

(A) The energy change of a system undergoing any reversible process is zero.
(B) It is not possible to transfer heat from a lower temperature to a
higher temperature.
(C) The total energy of the system and surroundings remain constant.
(D) None of the above.
Answer key:
1-C
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Past GATE Questions on Carnot cycle
1. A Carnot cycle consists of the following steps :

A) two isothermals and two isentropics,
B) two isobarics and two isothermals
C) two isochorics and two isobarics,
D) two isothermals & two isochorics
2. The thermal efficiency of a reversible heat engine operating between two

given thermal reservoirs is 0.4. The device is used either as a refrigerator or as
a heat pump between the same reservoirs. Then the coefficient of performance
as a refrigerator (COP)R and the coefficient of performance as a heat pump
(COP)HP are
A) (COP)R = (COP)HP = 0.6,
B) (COP)R = 2.5; (COP)HP = 1.5,
C) (COP)R = 1.5; (COP)HP = 2.5,
D) (COP)R = (COP)HP = 2.5,
3. The following heat engine produces power of 100,000 kW. The heat
engine operates between 800 K and 300 K. It has a thermal efficiency equal
to 50% of that of the Carnet Engine for the same temperatures. The rate at
which heat is absorbed from the hot reservoir is
A) 100,000 kW B) 160,000 kW
C) 200,000 kW D) 320,000 Kw
4. A cyclic engine exchanges heat with two reservoirs maintained at 100

and 3000C, respectively. The maximum work (in J) that can be obtained from
1000 J of heat extracted from the hot reservoir is
A) 349 B) 651 C) 667 D) 1000
5. Which one of the following statements in 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.
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6. A Carnot heat engine cycle is working with an ideal gas. The work
performed by the gas during the adiabatic expansion and compression
steps, W1 and W2 respectively, are related as
A) | W1 | > | W2 | B) | W1 | < | W2 |
C) W1 = W2 D) W1 = – W2
7. A heat engine operates at 75% of the maximum possible efficiency. The

ratio of the heat source temperature (in K) to the heat sink temperature
(in K) is 5/3. The fraction of the heat supplied that is converted to work
is
A) 0.2 B) 0.3 C) 0.4 D) 0.6
8. Which of the following represents the Carnot cycle ( ideal engine ) ?
9. For a Carnot refrigerator operating between 40°C and 25°C, the

coefficient of performance is
A) 1 B) 1.67 C) 19.88 D) 39.74
Answer Key:
1-A 2-C 3-D 4-A 5-C 6-D 7-B 8-C 9-C
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CHAPTER 3
PURE SUBSTANCE
3.1 PURE SUBSTANCE

A pure substance is one whose chemical composition does not change during
thermodynamic processes. Water and refrigerants are examples of pure
substances. These days emphasis is on the use mixture of refrigerants. The
properties of mixtures also require understanding of the properties of pure
substances.
Water is a substance of prime importance in refrigeration and air-conditioning.
It exists in three states namely, solid ice, liquid water and water vapour and
undergoes transformation from one state to another. Steam and hot water are
used for heating of buildings while chilled water is used for cooling of
buildings.
If a liquid (pure substance) is heated at constant pressure, the temperature at
which it boils is called saturation temperature. This temperature will remain
constant during heating until all the liquid boils off. At this temperature, the
liquid and the associated vapor at same temperature are in equilibrium and are
called saturated liquid and vapor respectively. The saturation temperature of a
pure substance is a function of pressure only. At atmospheric pressure, the
saturation temperature is called normal boiling point. Similarly, if the vapor of
a pure substance is cooled at constant pressure, the temperature at which the
condensation starts is called dew point temperature. For a pure substance,
dew point and boiling point are same at a given pressure.
Similarly, when a solid is heated at constant, it melts at a definite temperature
called melting point. Similarly cooling of a liquid causes freezing at the freezing
point. The melting point and freezing point are same at same pressure for a
pure substance and the solid and liquid are in equilibrium at this temperature.
For all pure substances there is a temperature at which all the three phases
exist in equilibrium. This is called triple point.
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The liquid – vapor phase diagram of pure substance is conveniently shown in

temperature-entropy diagram or pressure-enthalpy diagram or p-v diagram.
3.2 CRITICAL POINT

Above figures show the critical point. The temperature, pressure and specific
volume at critical point are denoted by Tc, Pc and vc, respectively. A liquid below
the critical pressure when heated first becomes a mixture of liquid and vapor
and then becomes saturated vapor and finally a superheated vapor. At critical
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point there is no distinction between liquid state and vapor state; these two
merge together. At constant pressure greater than critical pressure, PC when
liquid is heated in supercritical region, there is no distinction between liquid
and vapor; as a result if heating is done in a transparent tube, the meniscus of
liquid and vapor does not appear as transformation from liquid to vapor takes
place. At pressures below critical pressure, when a liquid is heated there is a
clear-cut meniscus between liquid and vapor, until all the liquid evaporates.
For water:
Triple point: 0.1oC, 0.006112 bar
Critical point: 221.2 bar, 647.3K and 0.00317 m3 / kg
3.3 SATURATED LIQUID AND SATURATED VAPOR STATES

The properties of saturated liquid and saturated vapor for water are listed in
steam tables. The subscript f is used to denote properties of a saturated liquid,
and the subscript g to denote the properties of saturated vapor. These symbols
are commonly used in thermodynamics and originated from German. Another
subscript commonly used is fg, which denotes the difference between the
saturated vapor and saturated liquid values of the same property. For example,
the quantity hfg is called the enthalpy of vaporization (or latent heat of
vaporization). It represents the amount of energy needed to vaporize a unit
mass of saturated liquid at a given temperature or pressure. It decreases as the
temperature or pressure increases and becomes zero at the critical point.
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3.4 SATURATED LIQUID–VAPOR MIXTURE

During a vaporization process, a substance exists as part liquid and part
vapor. That is, it is a mixture of saturated liquid and saturated vapor. To
analyze this mixture properly, we need to know the proportions of the liquid
and vapor phases in the mixture. This is done by defining a new property called
the quality x as the ratio of the mass of vapor to the total mass of the mixture:
mvapor
x
mtotal
Where, mtotal  mvapor  mliquid
Quality has significance for saturated mixtures only. It has no meaning in the
compressed liquid or superheated vapor regions. Its value is between 0 and 1.
The quality of a system that consists of saturated liquid is 0 (or 0 percent), and
the quality of a system consisting of saturated vapor is 1 (or 100 percent). In
saturated mixtures, quality can serve as one of the two independent intensive
properties needed to describe a state. Note that the properties of the saturated
liquid are the same whether it exists alone or in a mixture with saturated
vapor. During the vaporization process, only the amount of saturated liquid
changes, not its properties. The same can be said about a saturated vapor. A
saturated mixture can be treated as a combination of two subsystems: the
saturated liquid and the saturated vapor.
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3.5 SUPERHEATED VAPOR

In the region to the right of the saturated vapor line and at temperatures above
the critical point temperature, a substance exists as superheated vapor. Since
the superheated region is a single - phase region (vapor phase only),
temperature and pressure are no longer dependent properties and they can
conveniently be used as the two independent properties in the tables.
Compared to saturated vapor, superheated vapor is characterized by
Lower pressures (P = Psat at a given T)
Higher temperatures (T = Tsat at a given P)
Higher specific volumes (v = vg at a given P or T)
Higher internal energies (u = ug at a given P or T)
Higher enthalpies (h = hg at a given P or T)
3.6 COMPRESSED LIQUID

Compressed liquid tables are not as commonly available, and one reason for
the lack of compressed liquid data is the relative independence of compressed
liquid properties from pressure. Variation of properties of compressed liquid
with pressure is very mild. Increasing the pressure 100 times often causes
proper-ties to change less than 1 percent.
In the absence of compressed liquid data, a general approximation is to treat
compressed liquid as saturated liquid at the given temperature. This is because
the compressed liquid properties depend on temperature much more strongly
than they do on pressure.
In general, a compressed liquid is characterized by
Higher pressures (P = Psat at a given T)
Lower temperatures (T = Tsat at a given P)
Lower specific volumes (v = vf at a given P or T)
Lower internal energies (u = uf at a given P or T)
Lower enthalpies (h = hf at a given P or T)
But unlike superheated vapor, the compressed liquid properties are not much
different from the corresponding saturated liquid values.
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3.7 COMPRESSIBILITY FACTOR

The ideal-gas equation is very simple and thus very convenient to use.
However, gases deviate from ideal-gas behavior significantly at states near the
saturation region and the critical point. This deviation from ideal-gas behavior
at a given temperature and pressure can accurately be accounted for by the
introduction of a correction factor called the compressibility factor Z defined as
Pv
Z
RT
3.8 VAN DER WAALS EQUATION OF STATE
The van der Waals equation of state was proposed in 1873, and it has two
constants that are determined from the behavior of a substance at the critical
point. It is given by
 a 
 P  v 2  V  b   RT
 
Van der Waals intended to improve the ideal-gas equation of state by including
two of the effects not considered in the ideal-gas model: the inter-molecular
attraction forces and the volume occupied by the molecules them-selves. The
term a / v2 accounts for the intermolecular forces, and b accounts for the
volume occupied by the gas molecules.
The determination of the two constants appearing in this equation is based on
the observation that the critical isotherm on a P – v diagram has a horizontal
inflection point at the critical point. Thus, the first and the second derivatives
of P with respect to vat the critical point must be zero. That is,
 P    2P 
 v  0 and  2 0
 T Ta constant   v T Ta constant
The van der Waals equation may be considered as the ideal gas law, ―improved‖
due to two independent reasons:
 Molecules are thought as particles with volume, not material points. Thus V
cannot be too little, less than some constant. So we get (V − b) instead of
V.
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 While ideal gas molecules do not interact, we consider molecules attracting

others within a distance of several molecules' radii. It makes no effect inside
the material, but surface molecules are attracted into the material from the
surface. We see this as diminishing of pressure on the outer shell (which is
used in the ideal gas law), so we write (p + something) instead of p.
3.9 REDLICH–KWONG EQUATION OF STATE
Introduced in 1949 the Redlich–Kwong equation of state was a considerable

improvement over other equations of the time. It is still of interest primarily
due to its relatively simple form. While superior to the van der Waals equation
of state, it performs poorly with respect to the liquid phase and thus cannot be
used for accurately calculating vapor-liquid equilibria. However, it can be used
in conjunction with separate liquid-phase correlations for this purpose.
The Redlich–Kwong equation is adequate for calculation of gas phase properties

when the ratio of the pressure to the critical pressure (reduced pressure) is less
than about one-half of the ratio of the temperature to the critical temperature
(reduced temperature):
3.10 VIRIAL EQUATION OF STATE
The virial expansion, also called the virial equation of state, is the most
interesting and versatile of the equations of state for gases. The virial
expansion is a power series in powers of the variable, n/V, and has the form,
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The coefficient, B(T), is a function of temperature and is called the "second

virial coefficient. C(T) is called the third virial coefficient, and so on. The
expansion is, in principle, an infinite series, and as such should be valid for all
isotropic substances. In practice, however, terms above the third virial
coefficient are rarely used in chemical thermodynamics.
Notice that we have set the quantity pV/nRT equal to Z. This quantity (Z) is
called the "compression factor." It is a useful measure of the deviation of a real
gas from an ideal gas. For an ideal gas the compression factor is equal to 1.
Problem :
One kilo mole CO2 occupies a volume of 0.381 m3 at 313 K. Compare the
pressure given by
a) Ideal gas equation
b) Vander waal‘s equation. Take the Vanderwaals constant to be a= 0.365

Nm4 / mol2 and b = 4.28 X10-5 m3 /mol.
Solution
The molar Volume of CO2 is V= 0381 x10-3 m3/mol
a) Ideal gas equation P= RT/V =8.314(313)/(0.318x10-3)= 68.30 x 105

N/m2= 68.30 bar
b) Vanderwaal‘s equation may be arranged as

P = (RT/ V-b)-a/V2= [8.314(313)/ (0.318 x 10-3)- (0.428 x 10-4)]-0.365/ (0.381x10-3)2
= 5.18 x105 N/m2 = 51.8 bar
Problem :
Reported values for the virial coefficients of isopropanol vapor at 200°C are:
B = -388 cm3/mol and C = -26000 cm6/mol2. Calculate V and Z for isopropanol

vapor at 200 °C and 10 bar by (1) the ideal gas equation; (2) two-term virial
equation.
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Solution:
(1) For an ideal gas, Z = 1:

RT 83.14  473.15 3
V   3934 cm
P 10 mol
(2) Two-term virial equation:
RT 3 PV
V  B  3934  388  3546 cm Z  0.9014
P mol RT
Past GATE Questions on different equation of state
1. Ideal gas law is applicable at,

(A). low T, low P
(B). high T, high P
(C). low T, high P
(D). high T, low P
2. The kinetic energy of gas molecules is zero at

(A) 00C, (B) 2730C, (C) 1000C, (D) -2730C,
3. Which of the following is true for Virial equation of state

(A) Virial coefficients are universal constants.
(B) Virial coefficient B represents three body interactions.
(C) Virial coefficients are functions of temperature only.
(D) For some gases, Virial equations and ideal gas equations are the
same.
4. In van der Waals equation of state, what are the criteria applied at the
critical point in determine the parameters ‗a‘ and ‗b‘ ?
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5. Match the following :

(A) Heat (i) State Function
(B) Internal energy (ii) Path Function
(C ) Work
(D ) Entropy
(A) (a)-(ii); (b)-(i); (c)-(i); (d)-(i) (B) (a)-(ii); (b)-(i); (c)-(ii); (d)-(ii)
(C) (a)-(ii); (b)-(ii); (c)-(i); (d)-(i) (D) (a)-(ii); (b)-(i); (c)-(ii); (d)-(i)
6. 6. The molar density of water vapor at the normal boiling point of water is
33 mol/m3. The compressibility factor under these conditions is close
to which ONE of the following? R = 8.314 J/(mol K)
(A) 0.75 (B) 1 (C) 1.25 (D) 1.5
7. 7. The state of an ideal gas is changed from (T1, P1) to T2, P2) in a constant
volume process. To calculate the change in enthalpy, Δh, ALL of the
following properties/variables are required.
A) CV , P1 , P2 B) CP , T1 , T2
C) CP , T1 , T2 , P1 , P2 D) CV , P1 , P2 , T1 , T2
8. Parameters ‗a‘ and ‗b‘ in the van der Waals and other cubic equations of
state represent
A) a – molecular weight b – molecular polarity
B) a – molecular size b – molecular attraction
C) a – molecular size b – molecular speed
D) a – molecular attraction b – molecular size
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Problem:
9. The work done by one mole of a van der Waals fluid undergoing reversible
isothermal expansion from initial volume Vi to final volume Vf is
Answer Key:
1-D 2-A 3-C 4-A 5-D 6-B 7-B 8-D 9-D
Explanatory Answer:
7. Ans: (B)
Explanation: The change in enthalpy,
h = CP  T
 Cp, T1, T2 is required.
8.Ans: (D)
Explanation: van der waals equation
 a 
 p  2  (V – b) = RT
 V 
Here, a is molecular attraction and b is molecular size.
9. Ans: (D)
Explanation: ν dw equation of state  P + a2   υ - b  = RT
 u 
The (boundary work done =  P dυ
Vf  RT a 
∴w= V   υ - b  -  dυ
u 2 
i

V
a f
= RT ln (υ - b) VVf +
i υ Vi
= RT ln
 Vf - b   1 1
⟸ Option (d) is correct answer.
+a - 
 Vi - b   Vf Vi 
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Past GATE Questions on equation of state and

thermodynamic laws
1. A system undergoes a change from a given initial state to a given final

state either by an irreversible process or by a reversible process. Then
A) ∆ SI is always > ∆SR B) ∆SI is sometimes > ∆SR,
C) ∆SI is always < ∆SR, D) ∆ SI is always = ∆SR,
2. A change in state involving a decrease in entropy can be spontaneous

only if
A) it is exothermic
B) it is isenthalpic
C) it takes place isothermally
D) it takes place at constant volume
3. It is desired to bring about a certain change in the state of a system by

performing work on the system under adiabatic conditions.
A) The amount of work needed is path-dependent,
B) Work alone cannot bring about such a change of state,
C) The amount of work needed is independent of path,
D) More information is needed to conclude anything about the path
dependence or otherwise of the work needed.
4. On a P-V diagram of an ideal gas, suppose a reversible adiabatic line

intersects a reversible isothermal line at point A. Then at point A, the

slope of the reversible adiabatic line   and the slope of the reversible
 V S

isothermal line   are related as
 V T
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
     
A)      B)      
 V S  V T  V S  V T 
   1 
C)       D)     
 V S  V T  V S   V T
5. High pressure steam is expanded adiabatically and reversibly through a

well insulated turbine which produces some shaft work. If the enthalpy
change and entropy change across the turbine are represented by ∆H
and ∆S, respectively, for this process :
A) ∆H = 0 and ∆S = 0 B) ∆H ≠ 0 and ∆S = 0
C) ∆H ≠ 0 and ∆S ≠ 0 D) ∆H = 0 and ∆S ≠ 0
6. Air enters an adiabatic compressor at 300 K. The exit temperature for a

compression ratio of 3, assuming air to be an ideal gas (y = Cp/Cv = 7/5)
and the process to be reversible, is
A) 300 (3 2/7) B) 300 (3 3/5) C) 300 (3 3/7) D) 300 (3 5/7)
7. Steam undergoes isentropic expansion in a turbine from 5000 kPa and

400 0C (entropy = 6.65 kJ/kg K) to 150 kPa (entropy of saturated liquid
= 1.4336 kJ/kg K, entropy of saturated vapour = 7.2234 kJ/kg K). The
exit condition of steam is
A) superheatedvapour
B) partially condensed vapour with quality of 0.9
C) saturated vapour
D) partially condensed vapour with quality of 0.1
8. 1 m3 of an ideal gas at 500 K and 1000 kPa expands reversibly to 5 times

its initial volume in an insulated container. If the specific heat capacity
(at constant pressure) of the gas is 21 J/mol K, the final temperature will
be
A) 35 K B) 174 K C) 274 K D) 154 K
THERMODYNAMICS - CH
9. One mole of Nitrogen at 8 bar and 600 K is contained in a piston-

cylinder arrangement. It is brought to 1 bar isothermally against a
resisting pressure of 1 bar. The work done (in Joules) by the gas is –
A) 30554 B) 10373 C) 4988.4 D) 4364.9
10. For an ideal gas mixture undergoing a reversible gaseous phase

chemical reaction, the equilibrium constant
A) is independent of pressure
B) increases with pressure,
C) decreases with pressure,
D) increases/decreases with pressure depending on the stoichiometric
coefficients of the reaction.
11. A car tyre of volume 0.057 m3 is inflated to 300 kPa at 300 K. After the
car is driven for ten hours, the pressure in the tyre increases to 330
kPa. Assume air is an ideal gas and Cv for air is 21 J/(mol K). The
change in the internal energy of air ini the tyre in J/mol is
A) 380 B) 630 C) 760 D) 880
12. A gas obeys P (v-b) = RT. The work obtained from reversible isothermal
expansion of one mole of this gas from an initial molar volume vi to a
final molar volume vf is
 Vf   Vf  b   Vf   Vf  b 
A) RT ln   B) RT ln   C) RT ln   D) RT ln  
 Vi   Vi   Vi  b   Vi  b 
13. A frictionless cylinder piston assembly contains an ideal gas. Initially

pressure (P1) = 100 kPa, temperature (T1) = 500 K and volume (V1) = 700
x 10-6 m3. This system is supplied with 100 J of heat and pressure is
maintained constant at 100 kPa. The enthalpy variation is given by H
(J/mol) = 30000 + 50 T; where T is the temperature in K, and the
universal gas constant R = 8.314 J/(mole K).
THERMODYNAMICS - CH
(A) The final volume of the gas (V2) in m3 is
A) 700 x 10-6 B) 866.32 x 10-6

C) 934.29 x 10-6 D) 1000.23 x 10-6
(B) The change in internal energy of the gas in J is

A) 0 B) 100
C) 23.43 D) 83.37
14. For the isentropic expansion of an ideal gas from the initial conditions
ρ1, T1 to the final conditions ρ2, T2, which one of the following relations is
valid? (  = Cp/Cv)
 1

  T   1   T1  1  1   T1   1   T1  
A)  1    2  B)    C)    D)   
 2   T1   2   T2   2   T2   2   T2 
15. The change in entropy of the system, ΔSsys, undergoing a cyclic

irreversible process is
A) greater than 0 C) less than zero
B) equal to zero D) equal to the ΔSsurroundings
16. For the two paths as shown in the figure, one reversible and one
irreversible, to change the state of the system from a to b,
A) ΔU, Q, W are same B) ΔU, is same

C) Q, W are same D) ΔU, Q, are different.
THERMODYNAMICS - CH
17. 2 kg of steam in a piston-cylinder device at 400 kPa and 175 °C

undergoes a mechanically reversible, isothermal compression to a final
pressure such that the steam becomes just saturated. What is the work,
W, required for the process.
Data :
T = 175°C, P = 400 kPa – v = 0.503 m3/kg, u = 2606 kJ/kg, s = 7.055
kJ/kg-K
T = 175°C, satd. vapor – v = 0.216 m3/kg, u = 2579 kJ/kg, s = 6.622
kJ/kg-K
A) 0 kJ B) 230 kJ C) 334 kJ D) 388 kJ
18. An ideal gas at temperature T1 and pressure P1 is compressed

isothermally to pressure P2 (> P1) in a closed system. Which ONE of
the following is TRUE for internal energy (U) and Gibbs free energy (G)
of the gas at the two states ?
A) U1 = U2, G1> G2 B) U1 = U2, G1< G2
C) U1> U2, G1 = G2 D) U1< U2, G1 = G2
5
19. An ideal gas with molar heat capacity Cp = R (where R = 8.314 J/mol.K)
2
is compressed adiabatically from 1 bar and 300 K to pressure P2 in a

closed system. The final temperature after compression is 600 K and the
mechanical efficiency of compression is 50%.
(A) The final pressure P2 (in bar) is
A) 23/4 B) 25/4 C) 23/2 D) 25/2
(B) The work required for compression (in kJ/mol) is

A) 3.74 B) 6.24 C) 7.48 D) 12.48
THERMODYNAMICS - CH
Answer Key:
1-C 2-A 3-A 4-C 5-B 6-A
7-B 8-B 9-B 10-D 11-B 12-D
13(a)-C 13(b)-D 14-B 15-A 16-B 17-C
18-B 19(a)-D 19(b)-D
Explanatory answer:
4.Ans: [C]
Explanation: For reversible isothermal,

pV = C
Differentiating w.r.t. V,
p 
V   +p=0
 V T
 p  P
  =– … (i)
 V T V
For reversible adiabatic,
pV  = C
Differentiating w.r.t. V,
p
V    + p   V  – 1 = 0
 V S
 p  P
  = – … (ii)
 V S V
From Eqs.(i) and (ii),
 p   p 
  =  
 V S  V T
5.Ans: [B]
Explanation: For reversible adiabatic process ,
∆S=0 and ∆H ≠0
6.Ans: [A]
Explanation: For adiabatic process,
THERMODYNAMICS - CH
pV  = Constant

 nRT 
Or p  = Constant
 p 
T
= Constant
p  1
T1 T
Or 1
 2 1
p1 p2
1
 p  
T T  2 
2 1
 p1 
1
 p2  
T2 = T1  
 p1 
Given, T1 = 300 K
p2 7
= 3,  
p1 5
7 
 7/5
 T2 = 300  3 5 1
T2 = 300  32/7
7. Ans: [B]
Explanation: Let the quality of steam is x.
Since, entropy is constant in an isentropic process.
 Sinitial = x  Svap + (1 – x)  Sliq
Putting values,
6.65 = x  7.2234 + (1 – x)  1.4336
X = 0.9
The exit condition of steam is partially condensed vapour with quality of
0.9
8.Ans: [B]
Explanation: Insulated container  Adiabatic process
For adiabatic process,
pV  = Constant
 nRT  
Or   V = Constant, for ideal gas
 V 
Or TV  -1 = Constant
THERMODYNAMICS - CH
 T1V1  -1 = T2V2  -1
1
 V1 
T2 = T1   … (i)
 V2 
Given, T1 = 500 K, V1 = 1 m3, V2 = 5 m3
Cp = 21 J/mol – K
Since, Cp – CV = R
 CV = Cp – R
CV = 21 – 8.314 = 12.686 J/mol – K
Cp
And 
CV
21
 = 1.655
12.686
Putting all values in Eq. (i),
1.6551
T2 = 500   
1
 5
T2 = 174 K
9. Ans:[B]
Explanation: Given, n = 1, T = 600 K
P1 = 8 bar, p2 = 1 bar
Work done in isothermal process
 p1 
W = nRT ln  
 p2 
= 1  8.314  600  ln  
8
1
= 10373 J
10. Ans: [D]

Explanation: Assume the reaction,
aA + bB  cC and dD
The equilibrium constant,
y cC y dD
K= (p)c + d – a – b
y aA y bB
Where, yi is mole fraction of I and p is total pressure. It can be seen that
K will increase or decrease with pressure depending on the stoichiometric
coefficients of the reaction.
THERMODYNAMICS - CH
11. Ans: [B]

Explanation: For constant volume process,
P1 P2

T1 T2
Here, P1 = 300 kPa, P2 = 330 kPa
T1 = 300 K
Putting values,
300 330

300 T2
T2 = 330 K
Change in internal energy,
 V = CV  T
 V = 2.1  (300 – 300)
 V = 630 J/mol
12. Ans: [D]

Explanation: Given, p (V – b) = RT
Work done for reversible isothermal process,
W =  p dV
Vf RT
W=  dV
Vi Vb
W = RT [ln (Vf – b) – ln (Vfi– b)]
V b
W = RT ln  f 
 Vi  b 
13(a).Ans: [B]
Explanation: Given, p1 = 100 kPa = 105 Pa
V1 = 700  10 – 6 m3, T1 = 500 K
The number of moles of gas,
p1V1
n=
RT1
105  700 106
n=
8.314  500
= 0.0168
Given, H (J/mol) = 30000 + 50 T
It is given a constant pressure process.
dH
 = Cp = 50 J/mol – K
dT

THERMODYNAMICS - CH
Now, 100 J of heat is supplied,

 100 = nCp  T
100 = 0.0168  50  (T2 – T1)
T2 – 500 = 119
T = 619 K
For constant pressure,
V1 V2

T1 V2
V1T2
V2 =
T1
6
V2 = 700 10  619
500
V2 = 866.6  10 – 6 m3
13(b). Ans: [D]

Explanation:  h =  U + p  V
U = h - pV
 U = 100 – 100  103
 (866.6  10 –6 – 700  10 – 6)
 U = 83.34 J
14.Ans: [B]
CP
Explanation: Give,  =
CV
For isentropic expansion of ideal gas,
pV  – K … (i)
Also, pV = nRT
V1 T1 P2
  
V2 T2 P1
From Eq.(i),

p1  V2 
 
p2  V1 
 
p1  p1  T 
   2 
p2  p2   T1 

THERMODYNAMICS - CH
1 
 p1  T 
   2 
 p2   T1 

p1  T2 1
 
p2  T1 

p1  T1  1
 
p2  T2 
15.Ans: [A]
Explantion: For an irreversible process,  Ssys > 0
16. Ans:[B]
Explanation:  U is a point to point function while Q and W depend on the
process.
  U is same in two cases.
17.Ans: [C]
Explanation: From Maxwell relation,
dU = T dS – dW
dW = T dS – dU
Work required for the process,
 W = m [T (S2 – S1) – (U2 – U1)]
Here, m = 2 kg, T = 1750C = 448 K
S1 = 7.055 kJ/kg – K, S2 = 6.622 kJ/kg – K
U1 = 2606 kJ/kg , U2 = 2579 kJ/kg
Putting values,
 W = 2  [448  (6.622 – 7.055) – (2579 – 2606)]
 W = – 334 KJ
Work done by the system
= –  W = 334 KJ
18.Ans: [B]
Explanation: Internal energy U = f (T)
= Constant for isothermal process
 U1 = U2
Change in Gibbs free energy,
 p2 
G = RT ln  
 p1 

THERMODYNAMICS - CH
For p2 > p1, G = G2 – G1 > 0

 G2 > G1
19(a).Ans: [D]
5
Explanation: Given, Cp = R
2
Cp – Cv = R
5 3
 Cv = R – R = R
2 2
Cp 5
 
Cv 3
For adiabatic compression,
  
 
P2  T  1 
= 2 
P1  T1 
Here, P1 = 1 bar, T1 = 300 K
T1 = 600 K, P2 =?
Putting values,
 5/3 
P2  600   5/31
 
1  300 
P2 = 25/2 bar
19(b).Ans:[D]
Explanation: Work done in ideal case,
 1

RT1  P2   
Wideal =    1
  1  P1  
 
Putting values,
  5/3 1 
 
 5 / 3  8.314  300  25/2   5/3  
Wideal =  1   1
5
1   
3
 5 2
 
= 6235.5   2 2 5  1
 
= 6235.5 J/mol
Given, the mechanical efficiency of compression is 50%.
Actual work required
6235.5
= = 12471 J/mol = 12.47kJ/mol
0.5

THERMODYNAMICS - CH
CHAPTER 4
THERMODYNAMIC RELATIONS
EQUILIBRIUM AND STABILITY
MAXWELL’S EQUATION
 A pure substance existing in a single phase has only two independent
variables. Of the eight quantities p, V, T, S, U, H, F (Helmholtz
fascination), and Gibbs function) only one may be substance undergoing
an infinitesimal reversible process
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
𝐻 = 𝑈 + 𝑃𝑉
𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃
𝐹 = 𝑈 − 𝑇𝑆
𝑑𝐹 = 𝑑𝑈 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇
𝐺 = 𝐻 − 𝑇𝑆
𝑑𝐺 = 𝑑𝐻 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇
 Since U, H, and G are thermodynamic properties and exact differentials
of the type
𝑑𝑧 = 𝑀 𝑑𝑥 + 𝑁 𝑑𝑦, then
𝜕𝑀 𝜕𝑁
=
𝜕𝑦 𝑋
𝜕𝑋 𝑌
𝜕𝑇 𝜕𝑃
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 → =− ... (4.1)
𝜕𝑉 𝑆 𝜕𝑆 𝑉
𝜕𝑇 𝜕𝑉
𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 → = ... (4.2)
𝜕𝑃 𝑆 𝜕𝑆 𝑃
𝜕𝑃 𝜕𝑆
𝑑𝐹 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇 → = ... (4.3)
𝜕𝑇 𝑉 𝜕𝑉 𝑇
𝜕𝑉 𝜕𝑆
𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 → =− ... (4.4)
𝜕𝑇 𝑃 𝜕𝑃 𝑇
These four are called Maxwell‘s equation

THERMODYNAMICS - CH
TdS EQUATION
 Let entropy be the function of T and V.

𝜕𝑆 𝜕𝑆
𝑑𝑆 = 𝑑𝑇 + 𝑑𝑉
𝜕𝑆 𝜕𝑆
𝑇𝑑𝑆 = 𝑇 𝑑𝑇 + 𝑇 𝑑𝑉
𝜕𝑆 𝜕𝑆 𝜕𝑃
Since 𝑇 𝑑𝑇 = 𝐶𝑣 & =
𝜕𝑇 𝑉 𝜕𝑉 𝑇 𝜕𝑇 𝑉
𝜕𝑃
𝑇𝑑𝑆 = 𝐶𝑣 𝑑𝑇 + 𝑇 𝑑𝑉 ... (4.5)
𝜕𝑇 𝑉
This is known as the first TdS equation

 If S = f(T, p)
𝜕𝑆 𝜕𝑆
𝑑𝑆 = 𝑑𝑇 + 𝑑𝑃
𝜕𝑆 𝜕𝑆
𝑇𝑑𝑆 = 𝑇 𝑑𝑇 + 𝑇 𝑑𝑃
𝜕𝑆 𝜕𝑆 𝜕𝑉
Since, 𝑇 = 𝐶𝑝 & =−
𝜕𝑇 𝑃 𝜕𝑃 𝑇 𝜕𝑇 𝑃
𝜕𝑉
𝑇𝑑𝑆 = 𝐶𝑝 𝑑𝑇 − 𝑇 𝑑𝑃 ... (4.6)
𝜕𝑇 𝑃
This is known as second TdS equation.
HEAT CAPACITY RELATIONSHIPS

 Difference of heat capacities
Equating first and second TdS equation,

THERMODYNAMICS - CH
𝜕𝑃 𝜕𝑉
𝑇𝑑𝑆 = 𝐶𝑣 𝑑𝑇 + 𝑇 𝑑𝑉 = 𝐶𝑝 𝑑𝑇 − 𝑇 𝑑𝑃
𝜕𝑇 𝑉 𝜕𝑇 𝑃
𝜕𝑃 𝜕𝑉
𝐶𝑝 − 𝐶𝑣 𝑑𝑇 = 𝑇 𝑑𝑉 + 𝑇 𝑑𝑃
𝜕𝑃 𝜕𝑉
𝑇 𝑇
𝑑𝑇 = 𝑑𝑉 + 𝑑𝑃
𝐶𝑝 − 𝐶𝑣 𝐶𝑝 − 𝐶𝑣
𝜕𝑇 𝜕𝑇
𝑑𝑇 = 𝑑𝑉 + 𝑑𝑃
𝜕𝑉 𝑃 𝜕𝑃 𝑉
Again
𝜕𝑃 𝜕𝑉
𝑇 𝜕𝑇 𝑇 𝜕𝑇
= & =
𝐶𝑝 − 𝐶𝑣 𝜕𝑉 𝑃 𝐶𝑝 − 𝐶𝑣 𝜕𝑃 𝑉
Both these equations give

𝜕𝑃 𝜕𝑉
𝐶𝑝 − 𝐶𝑣 = 𝑇
But
𝜕𝑃 𝜕𝑉 𝜕𝑉
= −1
𝜕𝑇 𝑉 𝜕𝑇 𝑃 𝜕𝑃 𝑇
𝜕𝑉 2 𝜕𝑃
𝐶𝑝 − 𝐶𝑣 = −𝑇 ...(4.7)
𝜕𝑇 𝑃 𝜕𝑉 𝑇
This is very important equation in thermodynamics. It indicates the following

important fact.
𝜕𝑉 2 𝜕𝑃
(a) Since is always positive, and for any substance is negative,
𝜕𝑇 𝑃 𝜕𝑉 𝑇
𝐶𝑝 − 𝐶𝑣 is always positive. Therefore, Cp is always greater than Cv.
(b) 𝐴𝑠 𝑇 → 0𝐾 𝑖. 𝑒. 𝑎𝑡 𝑎𝑏𝑠𝑜𝑙𝑢𝑡𝑒 𝑧𝑒𝑟𝑜, 𝐶𝑝 = 𝐶𝑣
𝜕𝑉
(c) When = 0 (e.g., for water at 40 C, when density is maximum, or
𝜕𝑇 𝑃
specific volume minimum) 𝐶𝑝 = 𝐶𝑣

THERMODYNAMICS - CH
(d) For an ideal gas, 𝑃𝑉 = 𝑚𝑅𝑇
𝜕𝑉 𝑚𝑅 𝑉
= =
𝜕𝑇 𝑃 𝑃 𝑇
𝜕𝑃 𝑚𝑅𝑇
And =−
𝜕𝑉 𝑇 𝑉2
𝐶𝑝 − 𝐶𝑣 = 𝑚𝑅
𝐶𝑝 − 𝐶𝑣 = 𝑅
 Specific heat relationships can be expressed in terms of volume
expansivity
1 𝜕𝑉
𝑣𝑜𝑙𝑢𝑚𝑒 𝑒𝑥𝑝𝑎𝑛𝑠𝑖𝑣𝑖𝑡𝑦 = 𝛽 =
𝑉 𝜕𝑇 𝑃
1 𝜕𝑉
𝑖𝑠𝑜𝑡𝑕𝑒𝑟𝑚𝑎𝑙 𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑏𝑖𝑙𝑖𝑡𝑦 = 𝑘 𝑇 = −
𝑉 𝜕𝑝 𝑇
Substituting in equation (63)..

𝑇𝑉𝛽 2
𝐶𝑝 − 𝐶𝑣 = ... (4.8)
𝑘𝑇
It is called the Mayer relation in honor of the German physician and physicist
J. R. Mayer (1814–1878). We can draw several conclusions from this equation:
 The isothermal compressibility is a positive quantity for all
substances in all phases. The volume expansivity could be negative
for some substances (such as liquid water below 4°C), but its square
is always positive or zero. The temperature T in this relation is
thermodynamic temperature, which is also positive. Therefore we
conclude that the constant pressure specific heat is always greater
than or equal to the constant volume specific heat.
 The difference between 𝑐𝑝 𝑎𝑛𝑑 𝑐𝑣 approaches zero as the absolute
temperature approaches zero.
 The two specific heats are identical for truly incompressible
substances since v =constant. The difference between the two
specific heats is very small and is usually disregarded for
substances that are nearly incompressible, such as liquids and
solids.

THERMODYNAMICS - CH
 Ratio of Heat Capacities

At constant value of S, values TdS equations becomes,
𝜕𝑃
𝐶𝑣 𝑑𝑇 = −𝑇 𝑑𝑉𝑠
𝜕𝑇 𝑉
𝜕𝑉
𝐶𝑝 𝑑𝑇 = 𝑇 𝑑𝑃𝑠
𝜕𝑇 𝑃
𝐶𝑝 𝜕𝑉 𝜕𝑇 𝜕𝑃
=−
𝐶𝑣 𝜕𝑇 𝑃 𝜕𝑃 𝑉 𝜕𝑉 𝑠
𝜕𝑃
𝜕𝑉 𝑠
= 𝜕𝑃
=𝛾
𝜕𝑉 𝑇
Since   1,
 p   p 
 V    V 
 s  T
2.5
Ws  h 2s  h1  
1
vdp
= Area 1 - 2s - 3 - 4 - 1
The adiabatic compressibility (ks) is defined as
1  V 
ks    
V  p s
1  V 

Cp V  p 
  
Cv 1  V 
 
V  p s
k
 
ks

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ENERGY EQUATION
For a reversible process between two equilibrium states,
𝒅𝑼 = 𝑻𝒅𝑺 − 𝑷𝒅𝑽
Substituting first TdS relation,

𝜕𝑃
𝒅𝑼 = 𝐶𝑣 𝑑𝑇 + 𝑇 𝑑𝑉 − 𝑃𝑑𝑉
𝜕𝑇 𝑉
𝜕𝑃
= 𝐶𝑣 𝑑𝑇 + 𝑇 − 𝑃 𝑑𝑉
𝜕𝑇 𝑉
If U=f(T,V)
𝝏𝑼 𝝏𝑼
𝒅𝑼 = 𝒅𝑻 + 𝒅𝑽
𝝏𝑻 𝑽 𝝏𝑽 𝑻
𝝏𝑼 𝜕𝑃
𝒅𝑽 = 𝑇 −𝑃 ... (4.9)
𝝏𝑽 𝑻 𝜕𝑇 𝑉
𝑻𝒉𝒊𝒔 𝒊𝒔 𝒌𝒏𝒐𝒘𝒏 𝒔 𝒆𝒏𝒆𝒓𝒈𝒚 𝒆𝒒𝒖𝒂𝒕𝒊𝒐𝒏.
CLAUSIUS CLAPEYRON EQUATION

𝑣 = 1 − 𝑥 𝑣𝑙 + 𝑥𝑣𝑔
𝑠 = 1 − 𝑥 𝑠𝑓 + 𝑥𝑠𝑔
𝑣 = 𝑣𝑔 + 𝑥𝑣𝑓𝑔
𝑠 = 𝑠𝑔 + 𝑥𝑠𝑓𝑔
𝜕𝑃 𝜕𝑆
=
 During a phase change process, the pressure is the saturation pressure,

which depends on the temperature only and is independent of the
specific volume.
That is, 𝑃𝑠𝑎𝑡 = 𝑓 (𝑇𝑠𝑎𝑡 ).

THERMODYNAMICS - CH
𝜕𝑃
 Therefore, the partial derivative can be expressed as a total
𝜕𝑇 𝑉
𝜕𝑃
derivative , which is the slope of the saturation curve on a PT
𝜕𝑇 𝑠𝑎𝑡
diagram at a specified saturation state.

 This slope is independent of the specific volume, and thus it can be
treated as a constant during the integration of between two saturation
states at the same temperature.
 For an isothermal liquid–vapor phase change process, for example, the
integration yields
𝜕𝑃
𝑠𝑓𝑔 = 𝑣𝑓𝑔
𝜕𝑇 𝑠𝑎𝑡
𝜕𝑃 𝑠𝑓𝑔
=
𝜕𝑇 𝑠𝑎𝑡 𝑣𝑓𝑔
During this process the pressure also remains constant.

𝑑𝑕 = 𝑇𝑑𝑠 + 𝑣𝑑𝑃
𝑔 𝑔
𝑑𝑕 = 𝑇𝑑𝑠
𝑓 𝑓
𝑕𝑓𝑔 = 𝑇𝑠𝑓𝑔
𝜕𝑃 𝑕𝑓𝑔
=
𝜕𝑇 𝑠𝑎𝑡 𝑇𝑣𝑓𝑔
 This is called the Clapeyron equation.
 This is an important thermodynamic relation since it enables us to
determine the enthalpy of vaporization hfg at a given temperature by
simply measuring the slope of the saturation curve on a PT diagram and
the specific volume of saturated liquid and saturated vapor at the given
temperature.
 The Clapeyron equation is applicable to any phase change process that
occurs at constant temperature and pressure.
𝜕𝑃 𝑕 12
= ... (4.10)
𝜕𝑇 𝑠𝑎𝑡 𝑇𝑣12

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INTERNAL ENERGY CHANGE FOR AN IDEAL GAS
U= f(V, T)
𝝏𝑼 𝝏𝑼
𝒅𝑼 = 𝒅𝑻 + 𝒅𝑽
𝝏𝑻 𝑽 𝝏𝑽 𝑻
𝝏𝑼
𝒅𝑼 = 𝒄𝒗 𝒅𝑻 + 𝒅𝑽 ... (4.11)
𝝏𝑽 𝑻
𝜕𝑆 𝜕𝑆
S=f(V, T) 𝑑𝑆 = 𝑑𝑇 + 𝑑𝑉
Also,𝑑𝑢 = 𝑇𝑑𝑠 − 𝑉𝑑𝑃 ... (4.12)
𝜕𝑆 𝜕𝑆
𝑑𝑢 = 𝑇 𝑑𝑇 + − 𝑃 𝑑𝑉 ... (4.13)
𝜕𝑆 𝒄𝒗
=
𝜕𝑇 𝑉 𝑇
𝝏𝑼 𝜕𝑆 𝜕𝑃
=𝑇 −𝑃 =
𝝏𝑻 𝑽 𝜕𝑉 𝑇
𝜕𝑇 𝑉
𝜕𝑃
=𝑇 −𝑃
𝜕𝑇 𝑉
𝜕𝑃
𝒅𝑼 = 𝒄𝒗 𝒅𝑻 + 𝑇 − 𝑃 𝒅𝑽 ... (4.14)
𝜕𝑇 𝑉
ENTHALPY CHANGES
𝜕𝑕 𝜕𝑕
h=f (P,T ) 𝑑𝑕 = 𝑑𝑇 + 𝑑𝑃

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𝜕𝑕
𝑑𝑕 = 𝑐𝑝 𝑑𝑇 + 𝑑𝑃
𝜕𝑃 𝑇
𝜕𝑆 𝜕𝑆
S=f(P, T) 𝑑𝑆 = 𝑑𝑇 + 𝑑𝑃
Enthalpy relation:𝑑𝑕 = 𝑇𝑑𝑠 + 𝑣𝑑𝑃
𝜕𝑆 𝜕𝑆
𝑑𝑕 = 𝑇 𝑑𝑇 + + 𝑣 𝑑𝑃
𝜕𝑆 𝑐𝑝
Since =
𝜕𝑇 𝑃 𝑇
𝜕𝑕 𝜕𝑆
=𝑉+𝑇
𝜕𝑃 𝑇 𝜕𝑃 𝑇
𝜕𝑕 𝜕𝑉
=𝑉−𝑇
𝜕𝑃 𝑇 𝜕𝑇 𝑃
𝜕𝑉
𝑑𝑕 = 𝑐𝑝 𝑑𝑇 + 𝑉 − 𝑇 𝑑𝑃 ... (4.15)
𝜕𝑇 𝑃
ENTROPY CHANGES
𝒄𝒗 𝜕𝑃
𝒅𝒔 = 𝒅𝑻 + 𝑑𝑉 ... (4.16)
𝑻 𝜕𝑇 𝑉
𝒄𝒑 𝜕𝑣
𝒅𝒔 = 𝒅𝑻 − 𝑑𝑃 ... (4.17)
𝑻 𝜕𝑇 𝑝

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THE JOULE THOMSON COEFFICIENT

 The temperature behavior of a fluid during a throttling (h
=constant)process is described by the Joule Thomson coefficient,
defined as
𝜕𝑃
𝜇= ... (4.18)
𝜕𝑇 𝑕
 Thus the Joule Thomson coefficient is a measure of the change in

temperature with pressure during a constant enthalpy process.
 Joule Thomson coefficient represents the slope of h= constant lines on a
TP diagram. Such diagrams can be easily constructed from temperature
and pressure measurements alone during throttling processes.
 Some constant enthalpy lines on the TP diagram pass through a point of
zero slopes or zero Joule Thomson coefficient.
 The line that passes through these points is called the inversion line,
and the temperature at a point where a constant enthalpy line intersects
the inversion line is called the inversion temperature.
 The temperature at the intersection of the P = 0 line (ordinate) and the
upper part of the inversion line is called the maximum inversion
temperature.
 Notice that the slopes of the h =constant lines are negative at states to
the right of the inversion line and positive to the left of the inversion line.
 Direction of decreasing pressure, that is, from right to left. Therefore, the
temperature of a fluid increases during a throttling process that takes
place on the right hand side of the inversion line.
 However, the fluid temperature decreases during a throttling process
that takes place on the left hand side of the inversion line.
 It is clear from this diagram that a cooling effect cannot be achieved by
throttling unless the fluid is below its maximum inversion temperature.
This presents a problem for substances whose maximum inversion
temperature is well below room temperature.
 For hydrogen, for example, the maximum inversion temperature is 68°C.
Thus hydrogen must be cooled below this temperature if any further
cooling is to be achieved by throttling.

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𝜕𝑉
𝑑𝑕 = 𝑐𝑝 𝑑𝑇 + 𝑉 − 𝑇 𝑑𝑃 ... (4.19)
𝜕𝑇 𝑃
1 𝜕𝑉 𝜕𝑇
−𝑐 𝑉 −𝑇 = =𝜇 ... (4.20)
𝑝 𝜕𝑇 𝑃 𝜕𝑃 𝑕
Past GATE Questions on thermodynamic relations
1. Maxwell‘s relation corresponding to the identity,

is
2. The Maxwell relation derived from the differential expression for the Helmholtz
free energy (dA) is :

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3. Which of the following identities can be most easily used to verify steam table
data for superheated steam –
 T      T   V 
(A)      (B)      
 V S  S V   S  S 
    S   V   S 
(C)       (D)     
 T V  V T  T    T
4. For a pure substance, the Maxwell‘s relation obtained from the fundamental
property relation du = Tds – Pdv is
(A)  T / V S     / SV (B)   / T V   S / V T
(C)  T / S   V / S (D)  V / T     S /  T
Answer Key:
1-D 2-D 3-D 4-A
Explanatory Answer:
2. : [D] We have,
a = U – TS
da = dU – TdS – SdT
da = (TdS – pdV) – TdS – SdT
da = – pdV – SdT … (i)
Partial differentiation w.r.t. V,
 a 
  =–p … (ii)
 V T
Also, from Eq. (i),
 a 
  =–S … (iii)
 T  V
From Eq. (ii),
   a    p 
 T  V      T  … (iv)
  T  V  V
From Eq. (iii),
   a    S 
 V  T      V  … (v)
  V T  T

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Therefore, from Eq. (iv) and (v),

 p   S 
  =  
 T  V  V T
 p   S 
Or   =  
 T  V  V T
3. [D] We can verify steam table data for

 V   S 
   
 T  p  p T
4. [A] Given, dU = T dS – pV
Maxwell relation,
 T   p 
   
 V S  S  V

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CHAPTER 5
SOLUTION THERMODYNAMICS
5.1 FUGACITY
The concept of fugacity is widely used in solution thermodynamics to represent
the behavior of real gases. The name fugacity is derived from the Latin for
‗fleetness‘ or the ‗escaping tendency‘. It has been used extensively in the study
of phase and chemical reaction equilibria involving gases at high pressures.
Though the ‗fugacity‘ is mainly applied to mixtures, the present discussion is
limited to pure gases.
For an infinitesimal reversible change occurring in the system under
isothermal conditions, Gibbs – Helmholtz equation dG  SdT  VdP reduces to
dG  VdP
For one mol of an ideal gas V in the above equation may be replaced by RT / P,
so that
dP
dG  RT  RTd  ln P  …(i)
P
This equation is only applicable for ideal gases. If, however, we represent the
influence of pressure on Gibbs free energy of real gases by a similar
relationship, then the true pressure in the above equation should be replaced
by an ‗effective‘ pressure, which we call fugacity f of the gas. The following
equation, thus, provides the partial definition of fugacity.
dG  VdP  RTd ln f  …(ii)
This equation satisfied by all gases whether ideal or real. Integration of this
equation gives
G  RT ln f   C …(iii)
Where C is a constant of integration that depends upon the temperature and

nature of the gas.
Fugacity has same dimension as pressure, usually atmospheric or bar.

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5.1.1 FUGACITY COEFFICIENT

The ratio of fugacity to pressure is referred to as fugacity coefficient and s
denoted by  . It is dimensionless and depends on nature of the gas, the
pressure and the temperature. Integrating the equation dG  RTd ln f  between
pressures f and f 0,
f
G  G0  RT ln …(iv)
f0
Since f 0  P 0 and f  P ,we can write the above equation as

P
G  G0  RT ln  RT ln
P0
5.1.2 EFFECT OF TEMPERATURE AND PRESSURE ON FUGACITY
The effect of temperature on the fugacity can be expressed as
  ln f  H  H0
 T   …(v)
 P RT 2
Where H is the molar enthalpy of the gas at the given pressure and H0is the
enthalpy at a very low pressure. H0 – H can be treated as the increase of
enthalpy accompanying the expansion of the gas from pressure P to zero
pressure at constant temperature.
The effect of pressure on the fugacity can be expressed as
  ln f  V
 P   RT …(vi)
 T
5.1.3 CALCULATION OF FUGACITY OF PURE GASES

The fugacity can be determined by the following methods
5.1.3.1 USING COMPRESSIBILITY FACTOR, Z

The compressibility factor Z of a real gas is the ratio of its volume to the volume
of an ideal gas at the same temperature and pressure.
PV
Z …(vii)
RT
Introducing this in equation (vi), we get
THERMODYNAMICS - CH
f P  Z  1
ln    dP …(viii)
P 0
 P 
5.1.3.2 USING RESIDUAL VOLUME

The residual volume  is defined as the difference between V and the volume
occupied by one mole of an ideal gas at the same temperature and pressure.
RT
 V  …(ix)
P
Substitution of this value in equation (ii) gives,
f 1 P
ln 
P RT  0
 dP …(x)
5.1.3.3 USING ENTHALPY AND ENTROPY DATA

Equation (iv) indicates the free energy change between the given state where
free energy and fugacity are G and f respectively, and a standard state where
the free energy and fugacity are G0 and f0 respectively. By the definition of free
energy, G  H  TS , and , G0  H 0  TS0 where H 0 and S0 are the enthalpy and
entropy values at the standard state. Using these equation (iv) becomes
ln
f
f
0

1 
RT     
H  H 0  T S  S 0  …(xi)
5.1.4 FUGACITY OF SOLIDS AND LIQUIDS

Every solid or liquid has a definite vapor pressure although it may be
immeasurably small, in some cases. At this pressure, the solid (or the liquid)
will be in equilibrium with its vapor. When two phases of a substance are in
thermodynamic equilibrium, the molar free energies in both phases should be
equal. Hence, at low pressure the fugacity of solids and liquids is same as their
vapors. Hence, we can say that
f L  fV
f S  fV

THERMODYNAMICS - CH
If vapor pressure is not very high, the fugacity of the vapor would be equal to
the vapor pressure; hence the fugacity of liquid (or a solid) is approximately the
same, as its vapor pressure.
If the vapor pressure is very high and the vapor cannot be treated as ideal gas
its fugacity is related to the saturation pressure as in equation:
2
VP s
f sat
 …(xii)
RT
PS is the saturation pressure of the gas and fsatis the saturation fugacity. The
fugacity of the liquid at any other pressure P is readily obtained as
ln
f
f
sat

V
RT

P  Ps  …(xiii)
5.2 ACTIVITY
It is defined as the ratio of the fugacity to the fugacity at standard state.
f
a sat
…(xiv)
f
or, ln  a  
V
RT

P  P0  …(xv)
The concept of activity is particularly useful in the study of solutions.
5.2.1 EFFECT OF PRESSURE AND TEMPERATURE ON ACTIVITY

The effect of temperature can be expressed as
  ln a   H0  H 
 T    RT 2  …(xvi)
 P  
The effect of pressure can be expressed as
  ln a   V 
 P    RT  …(xvii)
 T  

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5.3 PARTIAL MOLAR PROPERTIES

Partial Molar Properties of a particular component in a mixture measures the
contribution of that component to the mixture property.
Let Mt = total molar properties of solution (extensive quantity)
Mi = Partial molar property of component i (intensive quantity)
M = Molar property
 M t 
Mi    …(xviii)
 ni T ,P ,ni  j
5.3.1 PARTIAL PROPERTIES OF SOLUTION

Consider any thermodynamic extensive property (such as free energy, heat
capacity, etc.) its value, for a homogeneous system, being completely
determined by the temperature, pressure and the amount of various
constituents present. Let M be the molar property of a solution and Mt be the
total property. Then, M t  N.M , where N is the total no. of moles of all
constituents. The solution property is a function represented by
M t  T , P,n1, n2,....
If there is a small change in the pressure, temperature and the amounts of
various constituents, then
 M t   M t   M t   M t 
dM t    dP    dT    dn  ......    dni
 P T ,N  T P ,N  
1
 1 T ,P ,n2,...
n  i T ,P ,n j  i
n
At constant temperature and pressure, dP and dT are zero, so that equation

becomes
n
 M t 
dM t     dni
i 1  ni T ,P ,n
j i
The partial derivatives appearing on the R.H.S. are, by equation (xviii), the
partial molar properties M i . i.e., at constant temperature and pressure,
n
dM t   Mi dni …(xix)
i 1
Then for a binary solution,

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2
dM   Mi dni
t
i 1
 dM  M1dn1  M2dn2
t
On integration. We get
 M t  M1n1  M2n2

 M t  M1x1n  M2 x2n  M1x1  M2 x2 n 
Mt
  M1x1  M2 x2
n
 M  M1x1  M2 x2 …(xx)
Thus molar volume V of a solution made up of components 1,2 can be written

as
V  V1x1  V2 x2
Proof:
Consider a binary mixture containing n1 moles of component 1 and n2 moles of
component 2.
The total no. of moles, n = n1 + n2
Total volume of solution Vt = n.V = (n1 + n2).V
Differentiating with respect to n1 and keeping n2 constant, we get
 V t  V
   V   n1  n2 
 ni T ,P ,n2 n1
V
 V1  V   n1  n2  …(a)
n1
n2
x2 
Now, n1  n2
  n1  n2  x2  n2
Differentiating with respect to n1 keeping n2 constant,

 x2  n2
  
 n1 T ,P ,n2  n1  n2 
2
 x   x2
 2  …(b)
 n1 T ,P ,n2  n1  n2 

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From equation (a) and (b), we get

 x 
 V1  V   2  V
 n1 
Therefore,
V V 
 V1  V  x2  V  x2 
x2 x1 
 …(xxi)
V V 
 V2  V  x1  V  x1
x1 x2 
5.4 CHEMICAL POTENTIAL

The chemical potential (  ) is used as an index of chemical equilibrium in the
same manner as temperature and pressure are used as indices of thermal and
mechanical equilibrium.
The chemical potential  i of a component i in a solution is same as its partial
molar free energy in the solution, Gi . That is, chemical potential of a

component i in a solution can be defined as
 Gt 
i  Gi    …(xxii)
 ni T ,P ,n j
5.4.1 EFFECT OF TEMPERATURE AND PRESSURE ON CHEMICAL

POTENTIAL
The effect of temperature on chemical potential can be defined as
 i 
 T   Si …(xxiii)
 P ,N
Where Si is the partial molar entropy of the component i in the solution. This
result, though gives the variation of chemical potential with temperature, can
be put in more useful form as follows: since
G  H  TS, Gi  Hi  TSi , i  Hi  TSi

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i  H i
We can write Si 
T
Therefore, we get
   i T   Hi
   2 …(xxiv)
 T P ,N T
The effect of pressure on chemical potential can be given as
 i 
 P   Vi …(xxv)
 T ,N
The rate of change of chemical potential with pressure is thus equal to the
partial molar volume of the constituent.
5.5 FUGACITY IN SOLUTIONS

For pure fluids, the definition of fugacity is provided by the equation
dG  RTd  ln f 
f
lim 1
P 0 P
The fugacity of a component iin a solution (gaseous, liquid or solid) is defined

by

 
d i  RTd ln fi …(xxvi)

fi
lim  1
P 0 p
i

Here  i is the chemical potential, fi is the fugacity and pi is the partial pressure
of component i in the solution. For an ideal gas mixture, the fugacity of a
component is equal to its partial pressure. All gaseous mixtures behave ideally
on approaching zero pressure. The partial pressure s defined as product of
total pressure and mole fraction of i (yi) in the mixture.
pi  y i P …(xxvii)

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5.5.1 FUGACITY IN GASEOUS SOLUTION

The fugacity of a component i in a gaseous solution is given by the following
equation

  fi  1 P RT 
lni   ln     Vi 
P 
dP …(xxviii)
 pi  RT 
0

Where i denotes the fugacity coefficient in solution.
 
 fi fi
i   …(xxix)
pi y i P
5.6 LEWIS – RANDALL RULE (LEWIS FUGACITY RULE)

It states that “fugacity of a component in an ideal solution is directly proportional
to mole fraction of component in the solution.“

fi  xi fi 
  
for liquid solution 
  …(xxx)
fi  y i fi 
 
for gaseous soltion 

Where, f iis the fugacity of component i in pure state.
This model is valid only when
 Pressure tends to zero.
 Component is present in excess amount in solution.
 Physical properties of all components are nearly same.
5.7 IDEAL SOLUTION

The solution is called ideal under following cases:
 The solution in which, partial molar volume is equal to molar volume.
 When there is no inter molecular forces between molecules.
 When there is no change when the components are mixed together.
5.8 RAOULT’S LAW

It states that “Partial pressure of any component is directly proportional to its
molar composition in liquid phase at vapor liquid equilibrium.”

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pi  xi pis …(xxxi)
This expression is known as Raoult‘s law. It is simplified form of Lewis –

Randall rule. Whereas the Lewis – Randall rule is obeyed by all ideal solutions,
the Raoult‘s law is applicable to ideal solutions if the vapor phase with which it
is in equilibrium is an ideal gas.
5.9 HENRY’S LAW

The solubility of the gases in liquids is usually very low, the mole fraction of a
gas in a saturated liquid solution is very small. The solute gas obeys Henry‘s
law and therefore its fugacity (or the partial pressure) would be directly
proportional to its mole fraction, the proportionality constant being Henry‘s law
constant.
pi
xi  …(xxxii)
Ki
5.10 ACTIVITY IN SOLUTIONS

The activity of a component in a solution can be defined in a similar way. It is
the ratio of fugacity of a component in solution in a given condition to the
fugacity of that component in the standard state. It is denoted by ai.

fi
ai  0 …(xxxiii)
fi
The concept of activity plays an important role in solution thermodynamics

because activity can be related to composition directly. For example, let the
standard state for a substance be the pure component at the temperature and
pressure of the solution. Then the activity of that component becomes equal to
its mole fraction in the case of ideal solutions and is strong function of mole
fraction in the case of real solutions.
 
fi fi
ai  0 
fi fi

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
For ideal solutions as fi  xi fi , the activity ai  xi . For real solutions, the activity
ai   i xi .
5.11 ACTIVITY COEFFICIENT

Activity coefficient measure the extent to which the real solution departs from
ideality. Activity coefficient of the component i in solution is denoted by  i and
is defined by the following relationship.

fi   i xi fi 0 …(xxxiv)
Where f i 0 is the fugacity in the standard state. For ideal solutions  i  1. And we
have

fi  xi f i 0
This is same as the Lewis – Randall rule with the pure liquid at system
pressure as standard state.
If the activity coefficients are defined with the reference to an ideal dilute
solution. Then
1  1 as x1  1 (solvent)
2 1 as x2  0 (solute)
5.11.1 EFFECT OF TEMPERATURE AND PRESSURE ON ACTIVITY

COEFFICIENT
The effect of temperature on activity coefficient is nearly same as that on
fugacity, and can be given as
  ln  i  Hi  Hi
 T   RT 2 …(xxxv)
 P
 
Where the term Hi  Hi is the partial heat of mixing of component i from its
pure state to the solution of given composition both in the same state of
aggregation and pressure.
The effect of pressure on activity coefficient is nearly same as that on fugacity,
and can be given as

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  ln  i  Vi  Vi
 P   RT …(xxxvi)
 T
The molar volumes Vi and Vi correspond to the particular phase under

consideration.
5.12 GIBBS – DUHEM EQUATIONS

In a mixture, the partial molar properties of the components are related to one
another by one of the most useful equations in thermodynamics, the Gibbs –
Duhem equations. It tells us how the partial molar properties changes with
compositions at constant temperature and pressure.
The Gibbs – Duhem equation is given as
 n dM i i 0 …(xxxvii)
 For a binary mixture

Consider a binary mixture made up of components 1 and 2 whose mole
fractions in the solution are x1and x2respectively. Equation (xxxvii) can be
written as
n1dM1  n2dM2  0
 n1dM1  n2dM2
 x1dM1   x2dM2
Where M1 and M2 are the partial molar properties of components 1 and 2

respectively.
Dividing by dx1on both side of the equation, we get
M1 M2
x1   x2  dx1  dx2 
x1 x1
M1 M2
 x1  x2 …(xxxviii)
x1 x2
Other useful form of Gibbs –Duhem equation:

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5.13 EXCESS PROPERTIES

The excess property ME is defined as the difference between the actual property
of a solution and the property that would have as an ideal solution at the same
temperature, pressure, and composition. Thus,
M E  M  M id …(xxxix)
M is the molar property of the solution and Mid is the property of an ideal
solution under the same conditions.
The excess property change of mixing is defined in a similar manner.
M E  M  M id …(xxxx)
M E is the excess property change of mixing, M and M id are the property

changes of mixing for a real solution and an ideal solution respectively, both
under the same conditions.
5.14 ACTIVITY COEFFICIENT EQUATIONS

There are many relations to calculate the activity coefficient through
compositions but most appropriate one is Van – Laar equations, which is given
as
ln  1  Z22 .A 

 …(xxxxi)
ln  2  Z1 .B 
2

where
x1 x2
Z1  and Z2 
x1  x2 .  B A  x2  x1.  A B 
and
2 2
 x ln  2   x ln  
A  ln  1  1  2  and B  ln  2  1  1 1 
 x1 ln  1   x2 ln  2 

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Example 4.1
At 300K, 1 bar the volumetric data for liquid mixture of Benzene and Cyclo
Hexane are V  109.4  106  16.8  106 x  2.64  106 x 2 where x is the mole
fraction of Benzene, find VB at x = 0.4
Solution:
We know that
V V
 V  (1  x )
x x
VB  109.4  10  16.8  10 6 x  2.64  10 6 x 2 
6
(1  x )  16.8  106  2.64  2  10 6 x 

x 0.4
 VB  90.90  10 6
Example 4.2
The fugacity of component 1 in binary liquid mixture of components 1 and 2 at

298 K and 20 bar is given by f1  50x1  80x12  40x13

Where where f1 is in bar and xi is the mole fraction of component 1. Determine:
(a) The fugacity f 1of pure component 1.
(b) The fugacity coefficient 1
(c) The Henry‘s law constant K1
(d) The activity coefficient  1
Solution:
(a) When the mole fraction approaches unity, the fugacity of component in the
solution becomes equal to the fugacity of the pure component. That is,

f1  f1 when x  1. Therefore, f1  50  80  40  10 bar
(b) 1  f1 / P  10 / 20  0.5
(c) By equation, Henry‘s Law constant is

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
K1  lim
f1
x1 0 x
 
 lim 50  80 x1  40 x12  50 bar
x1 0
1
(d) The activity coefficient is given as


1 
f1

 50  80 x1  40 x12 
 5  8 x1  4 x12
x1f1 10 x1
Past GATE Questions on solution thermodynamics
1. The partial molar enthalpy of a component in an ideal binary gas mixture

of composition z, at a temperature T and pressure P, is a function only of
A) T, B) T and P, C) T, P and Z, D) T and Z,
2. If mi , , miR , miE are molar, partial molar, residual and excess

properties respectively for a pure species ―i‖ , the mixture property M of a
binary non-ideal mixture of components 1 and 2, is given by
A) x1 + x2 B) x1 m1R + x2 m2R
C) x1 m1 + x2 m2 D) x1 m1E + x2 m2E
3. The molar volume (v) of a binary mixture, of species 1 and 2 having mole
fractions x1 and x2 respectively is given by v = 220 x1 + 180 x2 + x1 x2 (90
x1 + 50 x2). The partial molar volume of species 2 at x2 = 0.3 is
A) 183.06 B) 212.34 C) 229.54 D) 256.26
Answer Key :
1-B 2-A 3-B

THERMODYNAMICS - CH
Explanatory Answer:
1.Ans:[B]
Explanation: Partial molar enthalpy = f (T, p)
Past GATE Questions on concept of Fugacity
1. For water at 300 0C, it has a vapour pressure 8592.7 kPa and fugacity
6738.9 kPa. Under these conditions, one mole of water in liquid phase
has a volume 25.28 cm3, and that in vapour phase 391.1
cm3. Fugacity of water (in kPa) at 9000 kPa will be
A) 6738.9 B) 6753.5 C) 7058.3 D) 9000
2. As pressure approaches zero, the ratio of fugacity to pressure (f/P) for a

gas approaches
(A) Zero (B) Unity
(C) Infinity (D) an indeterminate value
Answer Key:
1-B 2-B
Explanatory Answer:
1.Ans: [B]
Explanation: Given, PS = 8592.7 kPa,
T = 3000C = 573 K
fS = 6738.9 kPa
Vliq = 25.28 cm3 = 25.28  10 –6 m3
P = 900 kPa
Fugacity of water,
 Vliq  p  pS  
f = fS exp  
 RT 

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f = 6738.9
 25.28 106   9000 103  8592.7 103  
x exp   = 6753.5 kPa
 8.314  573 
2. Ans: [b]
Explanation: As p  0,
Fugacity f  p
f 
And lim
p0  = 1
p
Past GATE Questions: Past Gate Questions
1. One mole feed of a binary mixture of a given composition is flash vapourised at

a fixed P and T. If Raoult‘s law is obeyed, then changing the feed composition
would effect.
A) the product composition but not the fraction vapourized,
B) the product composition as well as the fraction vapourized,
C) the fraction vapourized but not the product composition,
D) neither the product composition nor the fraction vapourized
2. If the heat of solution of an ideal gas in a liquid is negative, then its solubility at
a given partial pressure varies with the temperature as
A) Solubility increases as temperature increases,
B) Solubility decreases as temperature increases,
C) Solubility is independent of temperature,
D) Solubility increases or decreases with temperature depending on the Gibb‘s
free energy change of solution.
3. In a binary liquid solution of components A and B, if component A exhibits

positive deviation from Raoult‘s law, then components B,
A) exhibits positive deviation from Raoult‘s law,
B) exhibits negative deviation from Raoult‘s law,

THERMODYNAMICS - CH
C) obeys Raoult‘s law,

D) may exhibit either positive or negative deviation from Raoult‘s law.
4. When dilute aqueous solutions of two salts are mixed, the process is associated
with
A) decrease in temperature
B) increase in temperature
C) no change in temperature
D) change in temperature which is a function of composition
5. A perfectly insulated container of volume V is divided into two equal halves by a

partition. One side is under vacuum while the other side has one mole of an
ideal gas (with constant heat capacity) at 298 K. If the partition is broken, the
final temperature of the gas in the container
(A) will be greater than 298 K (B) will be 298 K
(C) will be less than 298 K (D) cannot be determined.
6. For a binary mixture at constant temperature and pressure, which ONE of the
following relations between activity coefficient ( γi) and mole fraction (xi) is
thermodynamically consistent ?
(A) ln γ1 = –1 + 2 x1 , ln γ2 =
(B) ln γ1 = –1 + 2 x1 , ln γ2 =
(C) ln γ1 = –1 + 2 x1 , ln γ2 =
(D) ln γ1 = –1 + 2 x1 , ln γ2 =
Answer Key :
1-C 2-B 3-A 4-B 5-C 6-D

THERMODYNAMICS - CH
CHAPTER 6
CHEMICAL REACTION EQUILIBRIUM
A reversible reaction can be described by an equilibrium constant Keq. Consider

for example the reaction,
A  2B  C
K
eq
The equilibrium constant related to the equilibrium concentrations in moles /

molecules per volume of the species involved:
Where, the powers of the concentrations are determined by the stoichiometric

coefficients. Notice that we can consider the case of irreversible reactions as
just a special subset of reversible ones, in which the equilibrium constant is
very large.
REACTION
Why does a reaction occur?
Bonds are broken, and bonds are formed. If the bonds that form are different
than the bonds broken, then a chemical reaction occurred.
Chemical Equilibrium
Most chemical reactions do not continue until all of the reactants are used up.
Most reactions are on-going, reversible processes; preceding in both the
forward direction to give products and in the reverse direction to give the
original reactant.
We indicate an equilibrium reaction with a double arrow:

Reactants <=>Products
In an equilibrium reaction, initially the rate of the forward reaction is very fast.
As more products are formed, the rate of the reverse reaction speeds up. When
the rates of the forward and reverse reactions are the same, the system is at
equilibrium
CHEMICAL REACTIONS
For a reaction to be energetically favorable, the Gibbs energy for products
should be lower than the Gibbs energy for reactants.
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“Directionality” of Chemical Reactions G  H  T S

The directionality of a chemical reaction at fixed P,T is governed by the Gibbs
free energy minimum principle. Two factors are at play: the entropy and the
enthalpy. Since the change in G is equal to the maximum ―useful‖ work which
can be accomplished by the reaction, then ∆G<0 indicates that the reaction will
proceed “spontaneously”.
H S G  H  T S
+ reaction will go spontaneously
+ + Reaction needs input of energy to
go
The sign of  G Depends on the sign of  G
+ + Depends on the
relative values of  H, 
S and T
PROBLEM:
Molar values of  H and  S for the reaction of dissolving of NH4CI in water at

standard conditions (P=1 bar, T=298 K) are 34.7 kJ/mol and 0.167 kJ/(Kmol),
respectively.
(1) Does the reaction proceed spontaneously under these conditions?
(2) How does the entropy of the environment and the Universe change in this
reversible process?
 G =  H-T  S  34.7  298 0.167  15.1J / mol  0

 G<0, thus the reaction proceeds spontaneously
The ―reversible‖ energy (heat) for this process:
revers
qsyst  T S syst  298  0.167  49.8kJ / mol
qenv q 49.8kJ / mol
Senv    sys    0.167kJ /  K  mol 
T T 298K
Sunivers  S syst  Senv  0.167kJ /  K  mol   0.167kJ /  K  mol   0

THERMODYNAMICS - CH
Problem:
Consider the reaction of oxidation of methane CH4 + 0.5 O2  4 CH3OH For

this reaction  H = -164 kJ/mol,  S = -162 J/mol x K
(a) Find the temperature range where this reaction proceeds spontaneously.
(b) Calculate the energy transferred to the environment as heat at standard

conditions (T= 298 K, P = 1 bar) assuming that this process is reversible.
(c) Calculate the change in the entropy of environment,  Sevn at standard

conditions assuming that this process is reversible What is the total entropy
change for the ―Universe‖ (the system + environment) if the process is
reversible?
(a) For this reaction to proceed spontaneously,  G must be negative:

164kJ / mol
 G=  H-T  S<0 T   103 K
162 J /  mol  K 
(b) The energy transferred to the environment as heat:

revers
qsyst  H  G  T S  298K   162 J / K  mol    48.28kJ / mol
qenv   qsyst  48.28kJ / mol
qenv 48.28kJ / mol

(c) Senv   162 J / K  mol
T 298K
For reversible processes: Stotal  Ssystem  Senv  0
Equilibrium criteria to chemical reactions:
The total Gibbs energy, Gt of a closed system at constant T and P must

decrease during an irreversible process and that the condition of equilibrium is
reached when Gt attains a minimum value.
At equilibrium state,
 dGt  T , P  0.
The law of mass action The reaction Quotient
2SO2  g   O2 g   2SO3 g  Kc  0.041
For a system NOT at Equilibrium the reaction quotient indicates the direction
the reaction must shift to reach equilibrium
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Since QC > KC reaction must shift left

1
2
QC  444  Kc 
 0.5  0.009 
2
Reaction Quotient
When Q > K the reaction must shift left
When Q < K the reaction must shift right
Q equals K at only at equilibrium
In 1884 the French chemist and engineer Henry-Louis Le Chatelier proposed

one of the central concepts of chemical equilibria. Le Chatelier's principle can
be stated as follows: A change in one of the variables that describe a
system at equilibrium produces a shift in the position of the equilibrium
that counteracts the effect of this change.
Le Chatelier's principle describes what happens to a system when something

momentarily takes it away from equilibrium. This section focuses on three
ways in which we can change the conditions of a chemical reaction at
equilibrium:
(1) changing the concentration of one of the components of the reaction
(2) changing the pressure on the system
(3) changing the temperature at which the reaction is run.
Applying Le Châtelier’s Principle
What effect do each of the following changes have on the equilibrium posit ion
for this reversible react ion?
PCI5 g   heat  PCI3 g   CI 2 g 

a. addition of Cl2 b. increase in pressure
c. removal of heat d. removal of PCl3 as it is formed
a. Addition of product, shifts the equilibrium to the left, forming more PCI5
b. The equation shows 2 mol of gaseous product and 1 mol of gaseous

reactant. The increase in pressure is relieved if the equilibrium shifts to the
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left, because a decrease in the number of moles of gaseous substances

produces a decrease in pressure.
c. The removal of heat causes the equilibrium to shift to the left, because the
reverse reaction is heat-producing.
d. The removal of PCI3 causes the equilibrium to shift to the right to produce
more PCI3
Problem:
How is the equilibrium position of this reaction affected by the following

changes?
C(s) + H2O(g) + heat  CO(g) + H2(g)

a. lowering the temperature
b. increasing the pressure
c. removing hydrogen
d. adding water vapor
a. left b. left c. right d. right
5.1 CHEMICAL REACTION EQUILIBRIUM

First, let‘s understand a reacting system from the point of view of macroscopic
thermodynamic potentials. We will take the specific reaction above as an
example, and consider the behavior of a system at constant temperature and
pressure. At constant T and P, the relevant thermodynamic potential is the
Gibbs free energy and at equilibrium, it is at a minimum.
Consider that we have an initial system of components A, B and C, If reactions

are not permitted, and we can independently control the respective amounts of
the species, the Gibbs free energy of the system is given by
G(T , P, NA , NB , NC )
What happens now if we allow the reaction to proceed? In this case, the
numbers of molecules of each species can change, subject to a certain
conservation rule. That rule says that the changes in mole numbers are related
by the stoichiometric coefficients:

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dNA  dNC
dNB  2dNC
These equations say that for every A molecule we get due to the reaction, we
have to lose a C one. Similarly, for every C molecule we lose, we also get two B
molecules. Here, there is one macroscopic degree of freedom that can vary due
to the reaction. You could think of that as the number of C molecules that
react. If we know how much C has reacted, we instantly know how much A and
B have reacted by the considerations above. More generally, there is one
reaction and hence one extent of reaction.
If the reaction is allowed to proceed from some initial specified composition of
the three components, at equilibrium the Gibbs free energy will be minimized.
The change in G with the amount of the species, at constant T and P is:
 dG   dG   dG 
dG    dNA    dNB    dNC
 A T ,P ,NB ,NC
dN  B T ,P ,NA ,NC
dN  C T ,P ,NA ,NB
dN
dG   AdNA  B dNB  C dNC
But using the stoichiometric considerations above, we find that:
At equilibrium the Gibbs free energy is minimized, dG = 0. This means that the
reaction reaches equilibrium when the chemical potentials satisfy the
condition:
Thus, we find that:

The thermodynamic quantity that predicts chemical reaction equilibrium is the
chemical potential.
Notice that the condition for chemical potential equality reduces the number of
macroscopic degrees of freedom. If we specify, T, P, NA and NB we know that
there is a reaction between A, B and C then NC is automatically specified by
solving the chemical potential equality above (recall that the chemical
potentials are functions of composition).
In other words,
For every reversible reaction in a system, the number of macroscopic degrees of
freedom is reduced by one

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For the general case, we can introduce a notation for reactions that reads as
follows:
where  i is a stoichiometric coefficient and Mi, is the chemical symbol for

component i. The  i ' s are defined such that they take on negative values for
reactants (the left hand side of the reaction) and positive for products (the right
hand side). Our previous example would be:
A  2B  C  0
dNi   i d
5.2 IDEAL GAS REACTIONS

We have already derived many expressions for the chemical potential of simple
multi-component systems in previous lectures. For ideal gas mixtures, for
example, we can write the equilibrium condition using i   i0  kBT ln Pi where Pi
is the partial pressure of component i :

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Notice that the right hand side is independent of pressure and composition,
since  i0 is only function of temperature. Therefore, we can write this expression
as:
In other words, the equilibrium state for a mixture of ideal gases is given by the
point at which the product of the component partial pressures, raised to the
stoichiometric coefficients, equals a temperature-dependent equilibrium
constant. If this had been the case of a non ideal gas, the mixture fugacity
would have replaced the partial pressures.

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For the simple example above, we find that the equilibrium conditions reduce
to:
5.3 IDEAL SOLUTION REACTIONS

Recall that, for an ideal solution, i   i*  kBT ln xi . Substituting this expression
into the equilibrium condition,

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5.4 TEMPERATURE AND PRESSURE DEPENDENCE OF Keq

Consider the temperature-derivative of the logarithm of the ideal gas
equilibrium constant:
This equation gives the Van’t Hoff relation. It shows that a plot of the
logarithm of the equilibrium constant versus the inverse temperature has a
slope given by the negative enthalpy of reaction. Such a plot is called a Van’t
Hoff plot. When these kinds of plots are

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Example 5.1
Derive the relationship between the mole fraction of the components taking
part in the reaction and the extent of the reaction.
Solution:
Let niobe the no. of moles of the species initially present in the system and nithe
number of moles present after the reaction. Then ni  nio  ni where ni is the
change in the number of moles of i due to the reaction. Integration of equation,

ni   i  d   i 
0
 ni  nio   i 
The mole fraction of component i in the reaction mixture is yi.
ni nio   i 
yi  
 ni  nio    i
nio   i 
yi 
no  
Example 5.2
The standard heat of formation and standard free energy of formation of
ammonia at 298 K are – 46100 J / mol and – 16500 J / mol respectively.
Calculate the equilibrium constant for the reaction
N2 (g )  3H2 (g ) 
 2NH3 (g )
At 500 K assuming that the standard heat of reaction is constant in the
temperature range 298 to 500 K.
Solution:
The standard free energy of reaction is estimated from equation
G0  
products
 i Gi0,f  
reac tan ts
 i Gi0,f
The second summation yields zero as the free energy of formation of the
elements are zero.
G0  
products
 i Gi0,f  2  16500  33000 J / mol

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Using equation,
G0 33000
ln K     133195
RT 8314  298
Therefore,
K at 298 K  6.0895  105
The standard heat of reaction at 298 K = 2 x – 46100 = – 92200 J / mol. This is
assumed constant within the temperature range involved. Now using equation
to evaluate the equilibrium constant.
K H 0  1 1 
ln    
K1 R  T T1 
K 92200  1 1 
 ln    15.0344
6.0895  10 5
8314  500 298 

Therefore, the equilibrium constant at 500 K, K = 0.18
Example 5.3
Ammonia synthesis reaction is represented by
N2 (g )  3H2 (g ) 
 2NH3 (g )
The reactant stream consists of 1 mol N2, 3 mol H2 and 2 mol argon. The
temperature and pressure of the reaction are 675 K and 20 bar. The
equilibrium constant for the reaction is 2 x 10-4. Determine how the conversion
of nitrogen is affected by the presence of argon.
Solution:
The total no. of moles of the initial mixture, n0 = 1 + 3 + 2 = 6.
   i  1 3  2  2
ni 0   i  ni 0   i 
yi  
n0   6  2

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Component i nio, mol yi
N2 ‒1 1 1    6  2 
H2 ‒3 3 3 1     6  2 
NH3 +2 0 2  6  2 
Ar 2
no 6
K 
Ky  P  KP 2
K
2  6  2  
2
 2  104  202
1     6  2   3 1     6  2  
2
 (3   )
  0.3674
(1   )2
On solving, we get  =0.1022. thus, it is seen that the conversion of nitrogen
decreases to 10.22%.

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Past GATE Questions on reaction equilibrium
1. The equilibrium constant, K, for a chemical reaction depends on

A)temperature only, B) pressure only,
C) temperature and pressure, D) ratio of reactant
2. At a given temperature, K1, K2 and K3 are the equilibrium constants for

the following reaction 1, 2, 3 respectively :
CH4 (g) + H2O (g) CO (g) + 3 H2 (g) (1)
CO (g) + H2O (g) CO2 (g) + H2 (g) (2)
CH4 (g) + 2 H2O (g) CO2 (g) + 4 H2 (g) (3)
A) K3 = K1 K2 B) K3 = (K1 K2)0.5
C) K3 = (K1 + K2) / 2 D) K3 = (K1 K2)2
3. At standard conditions,
N2 + 2O2 2NO2 ∆G0 = 100 kJ/mol
NO + ½ O2 NO2 ∆G0 = – 35 kJ/mol
The standard free energy of formation of NO in kJ/mol is
A) 15 B) 30 C) 85 (D) 170
4. For a reversible exothermic gas phase reaction, A + B ↔ C, the

equilibrium conversion will increase with
A) increase in pressure and increase in temperature
B) decrease in pressure and increase in temperature
C) increase in pressure and decrease in temperature
D) decrease in pressure and decrease in temperature
Answer Key:
1-A 2-A 3-C 4-C

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CHAPTER 7
CONCEPT BASED QUESTIONS

LEVEL 1
1. Generation of heat by frication is an example of a/an……….change
(a) Isothermal (b) Irreversible
(c) Adiabatic (d) Reversible
2. Internal energy change of a system over one complete cycle in a cycle

process is
(a) Zero (b) +ve
(c) –ve (d) Dependent on the path
3. The work done in an adiabatic change in a particular gas depends upon

changes in the……….only.
(a) Temperature (b) Specific heat
(c) Volume (d) Pressure
4. An ideal monatomic gas is taken round the cycle ABCDA as shown below
in the P.V diagram
The work done during the cycle is

(a) PV (b) 2PV
(c) PV/2 (d) 0

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5. A thermodynamic system is taken form state A to B along ACB and is

brought back to A along BDA as shown below in the P-V diagram
The net work done during the complete cycle is given by he area covered
by
(a) P1ACBP2P (b) ACBB1A1A
(c) ACBDA (d) ADBB1A1A
6. An ideal gas is taken around the cycle ABCA as shown in P-V diagram
below
The work done by the gas during the cycle is equal to

(a) 12P1 V1 (b) 6 P1 V1
(c) 3P1 V1 (d) P1 V1

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7. Linde gas liquefaction process employs cooling

(a) By throttling
(b) By expansion in an engine
(c) At constant pressure
(d) None of these
8. If atmospheric temperature and dew point are nearly equal, then the
relative humidity is
(a) Zero (b) 50%
(c) Almost 100% (d) unpredictable
9. Which of the following is not reversible process

(a) Expansion of an ideal gas against constant pressure
(b) Atmospheric pressure vaporization of water at 100 C
(c) Solution of NaCI in water at 50 C
(d) None of these
10. …..….. Law of thermodynamics ascertains the direction of a particular

spontaneous pressure.
(a) Zeroth (b) First
(c) Second (d) Third
11. Pick out the wrong statement.

(a) The conversion for a gas phase reaction increases with decrease in
pressure if there is an increase in volume accompanying the reaction
(b) With increase in temperature, the equilibrium constant increases for
an exothermic reaction
(c) The equilibrium constant of a reaction depends upon temperature
only
(d) The conversion for gas phase reaction there is a decrease in volume
accompanying the reaction

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12. Which of the following non flow reversible compression processes require
maximum work?
(a) Adiabatic process (b) Isothermal process
(c) Isobaric process (d) All require same work
13. The root mean square speed of molecules of a gas is equal to

2KT 3KT
(a) (b)
m m
6KT 3KT
(c) (d)
m m
Where, m = mass of the molecule
K = Boltzmann‘s constant.
T= absolute temperature
14. Pick out the wrong statement

(a) Activity co-efficient is dimensionless
(b) In case of an ideal gas, the fugacity is equal to its pressure.
(c) In a mixture of ideal gases, the fugacity of a component is equal to the
partial pressure of the component.
(d) The fugacity co-efficient is zero for an ideal gas.
15. With increase in temperature the internal energy of a substance

(a) Increase
(b) Decreases
(c) Remains unchanged
(d) May increase or decrease; depends on the substance

(a) Trout ion‘s ratio of non polar liquids is calculated using Kistyakowsky
equation
(b) Thermal efficiency of a Carnot engine is always less than 1.

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(c) An equation relating pressure volume and temperature of gas is called

ideal gas equation
(d) None of these
17. The efficiency of an Otto engine compared to that of a diesel engine for the
same compression ratio will be
(a) more
(b) Less
(c) Same
(d) Data insufficient to predict
18. The value of joule Thomson co-efficient in case where cooling occurs after
the throttling process is
(a) 0 (b) 
(c) +ve (d) –ve
19. A large iceberg melts at the base, but not at he top because of the reason
that
(a) Ice at the base contains impurities which lowers its melting point .
(b) Due to the high pressure at the base, its melting pint reduces.
(c) The iceberg remains in a warmer condition at the base.
(d) All (a), (b) and (c)
20. A two stage compressor is used to compress an ideal gas the gas is cooled
to the initial temperature after each stage the intermediate pressure for
the minimum total work requirement should be equal to the ……….mean
of P1 an P2
(a) Logarithmic (b) Arithmetic
(c) Geometric (d) Harmonic

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21. What happens in a reversible adiabatic expansion process?

(a) Heating takes place
(b) Cooling takes place
(c) Pressure is constant
(d) Temperature is constant
22. A system in which there is exchange of energy but not of mass, is called
a/an……….system.
(a) Isolated (b) Open
(c) Insulated (d) Closed
23. Kopp‘s rule is used to calculate the heat capacity of

(a) Solids (b) Liquids
(c) Gases (d) All (a), (b) & (c)
24. Pick out the correct statement.

(a) The available energy in an isolated system for all irreversible (real)
processes decreases
(b) The efficiency of a carnot engine increases if the sink temperature is
decreased
(c) The reversible work compression in non flow process under
isothermal condition is the change in Helmholtz free energy
25. In the equation PV n  if the value of n = 1, then it represents a

reversible……….process
(a) Isothermal (b) Isobaric
(c) Polytrophic (d) Adiabatic

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26. For a stable phase at constant pressure and temperature the fugacity of
cache component in a binary system……….as its mole fraction increases
(a) Decreases (b) Increases
(c) Remains same (d) Deceases linearly
27. A refrigeration cycle is he same as a ……….cycle.

(a) Turbine (b) Heat engine
(c) Reversed heat engine (d) None of these
28. For multicomponent multiple phases to be in equilibrium at the same

pressure and temperature, the ……….of each component must be same in
all phases
(a) Chemical potential
(b) Both (a) and (b)
(c) Both (a) and (b)
(d) Neither (a) nor (b)
29. Trouton‘s ratio is given by

(a) b / Tb (b) b / Tb
(c) Tb / b (d) Tb / b
30. ………. Increases with increase in pressure

(a) The melting point of wax
(b) The boiling point of liquid
31. The difference between isothermal compressibility and adiabatic

compressibility for an ideal gas an
(a) 0 (b) –ve
(c) + ve (d) 
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32. Entropy of a substance remains constant during an ……….change

(a) Reversible isothermal
(b) Irreversible isothermal
(c) Reversible adiabatic
(d) None of these
33. The specific heat of saturated water vapor at 100 C is

(a)  (b) –ve
(c) 0 (d) +ve
34. Any substance above its critical temperature exists as

(a) Saturated vapor (b) Solid
(C) Gas (d) liquid
35. Which of the following is affected by the temperature?

(a) Fugacity
(b) Activity co-efficient
(c) Free energy
(d) all (a), (b) & (c)
36. The third law of thermodynamic states that the

(a) Heat capacity of a crystalline solid is zero at absolute zero
temperature.
(b) Heat transfer form law temperature to high temperature source is not
possible without external work
(c) Gases having same reduced properties behave similarly
(d) None of theses

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37. Vapor which is at a pressure smaller than the saturation pressure for the
temperature involved is called a……….vapor
(a) Superheated (b) De-superheated
(c) Non condensable (d) None of these
38. The variation of heat of reaction with temperature at constant pressure is

given by the ……….law
(a) Kelvin‘s (b) Antoine‘s
(c) Kirchhoff‘s (d) None of these
39. For a cyclic process, a fixed ratio between heat and work
(a) Always exists (b) May exist
(c) Never exists (d) is difficult to predict
40. One ton of refrigeration is defined as the heat rate corresponding to

melting of one ton of ice in one
(a) Hour (b) Day
(c) Minute (d) Second
41. Those solutions in which there is no volume change upon mixing the
components in the liquid state and which when diluted for not undergo
any heat change (i.e. heat of dilution is zero), are called……….solution
(a) Ideal (b) Real
(c) Isotonic (d) None of these

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42. Clausius – Clayperon equation gives accurate result, when the

(a) Vapor pressure is relatively low and the temperature does not vary
over wide limits
(b) Vapor obeys the ideal gas law and the latent heat of vaporization is
constant
(c) Volume in the liquid state is negligible compared with that in the
vapor state

(a) System (of partially miscible liquid pairs), in which the mutual
solubility increases with rise in temperature are said to possess an
upper consolute temperature
(b) Systems, in which the mutual solubility increases with decrease in
temperature are said to possess lower consolute temperature
(c) Nicotine water system shows both an upper as well as a lower
consolute temperature implying that they are partially miscible
between these two limiting temperatures
(d) None of these
44. If the molar heat capacities CP or C  of the reactants and products of a
chemical reaction are identical, then with the increase in temperature, the
heat of reactions will
(a) Increase
(b) Decrease
(c) Remain unaltered
(d) Increase or decrease: depends on the particular reaction

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

 CO2 ; H-94 kcal What will the the valve of
45. Consider the reaction O2 
H  94 kcal. What will be the valve of H for the reaction? CO2  C  O2
(a) – 94 kcal (b) + 94 kcal
(c) > 94 kcal (d) < - 94 kcal
46. ―The fugacity of a gas in a mixture is equal to the product of its mole
fraction and its fugacity in the pure state at he total pressure of the
mixture ― This is
(a) The statement as per Gibbs – Helmholtz
(b) Called Levis – randall rule
(c) Henry‘s law
(d) None of these
47. At constant temperature and pressure for one mole of a pure substance
the ratio of the free energy to the chemical potential is
(a) Zero (b) One
(c) Infinity (d) Negative
48. Gibbs – Duhem equation

(a) States that n1d1  n2d  2  ....n j d j  0, for a system of definite composition
at constant temperature and pressure
(b) Applies only to binary systems
(c) Finds no application in gas liquid equilibrium involved in distillation
(d) None of these
49. Solubility of a substance which dissolves with an increase in volume and

liberation of heat will be favored by the
(a) Low pressure and high temperature.
(b) Low pressure and low temperature
(c) High pressure and low temperature
(d) High pressure and high temperature

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50. While dissolving a gas into a liquid at a constant temperature, the ratio of
the concentration of the gas in the solution phase and in the gaseous
phase is
(a) Infinity (b) Unity
(c) Constant (d) Negative
51. A domestic refrigerator has a/an……….cooled condenser.

(a) Water (b) Air
(c) Evaporative (d) Gas


52. In the ammonia syntheses reaction. N2  3H2 
 2NH3 kcal. The formation
of NH3 well be favored by
(a) High temperature
(b) Low pressure
(c) Low temperature only
(d) Both low temperature and high pressure.


53. In the reaction, H2 + I2 
 2HI, addition of an inert gas will
(a) Increase the partial pressure of H 2
(b) Increase the partial pressure of I2

(c) Increase the total pressure and hence shift the equilibrium towards
the right
(d) Not affect the equilibrium conditions
54. At absolute zero temperature, all substance have the same

(a) Heat capacity
(b) Crystalline structure
(c) Entropy
(d) None of these

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55. For an ideal gas, the activity co-efficient is

(a) Directly proportional to pressure
(b) Inversely proportional to pressure
(c) Unity at all pressure
(d) None of these
56. When liquid and vapor phase of multi-component system are in

equilibrium (at a given temperature and pressure) then chemical potential
of each component is
(a) Same in both the phases
(b) Zero in both the phases
(c) More in vapor phase
(d) More in liquid phase
57. When liquid and vapor phases of one component system are in equilibrium
(at a given temperature and pressure), the molar free energy is
(a) More in vapor phase
(b) More in liquid phase
(c) Same in both the phases
(d) Replaced by potential which is more In vapor phase
58. Pick out the correct statement

(a) A real gas expansion in vacuum gets heated up.
(b) An ideal gas on expansion in vacuum gets cooled
(c) An ideal gas on expansion in vacuum gets heated up
(d) A real gas on expansion in vacuum cools down whereas ideal gas
remains unaffected.

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59. Choose the condition that must be specified in order to liquefy CO2 (triple
point for CO2 IS - 57 C and 5.2 atm.
(a) Pressure must be kept below 5.2 atm
(b) Temperature must be kept above - 57 C
(c) Pressure must be kept below 5.2 atm and temperature must be kept
above 57 C
(d) Pressure and temperature must be kept below 5.2 and - 57 C
respectively.
60. The principle applied in liquefaction of gases is

(a) Adiabatic expansion
(b) Joule – Thomson effect
61. When a system in equilibrium is subjected to a change in temperature

pressure or concentration the equilibrium is displaced in a direction which
tends to undo the effect of the change this is called the
(a) Le-Chatelier principle
(b) Kopp‘s rule
(c) Law of corresponding state
(d) Arrhenius hypothesis
62. The energy of activation of exothermic reaction is

(a) Zero
(b) Negative
(c) Very large compared to that for endothermic reaction
(d) Not possible to predict

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63. Which of the following is not an intensive property

(a) Volume
(b) Density
(c) Temperature
(d) Pressure
64. Lowering of condenser temperature (keeping the evaporator temperature

constant) in case of vapor compression refrigeration system results in
(a) Increased COP
(b) Same COP
(c) Decreased COP
(d) Increased or decreased COP depending upon the type of refrigerant
65. In vapor compression refrigeration system if the evaporator temperature

and the condenser temperatures are - 13 C and 37 C respectively, the
Carnot COP will be
(a) 5.2 (b) 6.2
(c) 0.168 (d) Data insufficient,
66. Pick out the undesirable property for a good refrigerant

(a) High thermal conductivity
(b) Low freezing point
(c) Large latent heat of vaporization
(d) High viscosity
67. In joule Thomson plug experiment the

(a) Enthalpy does remain constant
(b) Entire apparatus is exposed to surrounding
(c) Temperature remains constant
(d) None of these

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68. Fugacity co-efficient of a substance is the ratio of its fugacity to

(a) Mole fraction
(b) Activity
(c) Pressure
(d) Activity co-efficient
69. Equilibrium constant of a reaction varies with the

(a) Initial concentration of the reactant (b) Pressure
(c) Temperature (d) None of these
70. An irreversible process

(a) Is the analog of linear frictionless motion in machines?
(b) is an idealized visualization of be behavior of a system
(c) Yields the maximum amount of work.
(d) Yields an amount of work less than that of a reversible process
71. First law of thermodynamics deals with the

(a) Direction of energy transfer (b) Reversible processes only
(c) Irreversible processes only (d) None of these
72. Which of the following processes cannot be made reversible even under
ideal condition of operation?
(a) Free expansion of a gas
(b) Compression of air in a compressor
(c) Expansion of steam in a turbine
(d) All (a) (b) & (c)
73. Which of the following is a thermodynamics property of a system?

(a) Concentration (b) Mass
(c) Temperature (d) Entropy

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74. Maxwell‘s relation corresponding to the identity dH  dS=V dP   i dni is
 T   P   S   V 
(a)  V     S  (b)  P    T 
 S.ni  V ,ni  T ,ni  P ,ni
 S   P   S   P 
(c)  V    T  (d)  V    T 
 T ,ni  V ,ni  T ,ni  V ,ni
75. The Maxwell relation derived from the differential expression for the
Helmholtz free energy ( dA )is
 T   P   S   V 
(a)  V     S  (b)  P     T 
 S    T  P
 V   T   V   T 
(c)  S    P  (d)  S    P 
 P  S  P  S
76. Two substances are in equilibrium in a reversible chemical reaction if the

concentration of each substance is doubled than the value of the
equilibrium constant will be
(a) Same
(b) Doubled
(c) Halved
(d) One fourth of its original value
77. In a reversible chemical reaction

(a) Addition of inert gas favors the or ward reaction when  x is positive
(b) Pressure has no effect o equilibrium when  n = 0,
(c) Addition of inert gas has no effect on the equilibrium constant at
constant volume for any value of x  e, e  or zero)

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78. ……….calorimeter is normally used for measuring the dryness fraction of

steam when it is very low
(a) Bucket
(b) Throttling
(c) A combination of separating & steam
(d) Separating
79. Claude‘s liquefaction process employs the cooling of gases by

(a) Expansion in an engine
(b) Following a constant pressure cycle
(c) Throttling
(d) None of these
80. Gases are cooled in joule Thomson expansion when it is……….inversion

temperature
(a) Below (b) At
(c) Above (d) Either ‗b‘ or ‗c‘

(a) The chemical potential of a pure substance depends upon the
temperature and pressure
(b) The chemical potential of a component in a system is directly
proportional to the escaping tendency of that component
(c) The chemical potential of ith species (  ) in an ideal gas mixture
approaches zero as the pressure or mole fraction (xi) tends to be zero
at constant temperature
(d) The chemical potential of species ‗I‘ in the mixture ( i ) is
   nG  
mathematically represented as, i    where n, ni
 ni T ,P ,ni
respectively denote the total number of moles of ith species and all
mole numbers except ith species. ‗G‘ is Gibbs molar free energy

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82. Match the T-S diagrams of various thermodynamics cycles
List I
P. Diesel cycle
Q. Otto cycle
R. Carnot refrigeration cycle
S. Brayton cycle
(a) P – (ii), Q – (i), R – (iv), S – (iii)

(b) P – (i), Q – (iii), R – (i), S – (iv)
(c) P – (ii), Q – (iii), R – (iv), S – (i)
(d) P – (iii), Q – (i), R – (iv), S – (ii)

(a) Minimum number of degree of freedom of a system is zero
(b) Degree of freedom of a system containing a gaseous mixture of
helium, carbon dioxide and hydrogen is 4.
(c) For a two phase system in equilibrium made up of four non reacting
chemical species the number of degrees of freedom is 4.
(d) Enthalpy and internal energy change is zero during phase change
processes like melting evaporation and sublimation

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84. Minimum number of phases that exists in a system is 1. Number of

chemical species in a colloidal system
(a) 1 (b) 2
(c) 4 (d) 3
85. A refrigeration cycle is a reversed heat engine. Which of the following has
the maximum value of the co-efficient of performance (COP) for a given
refrigeration effect?
(a) Vapor compression cycle using expansion valve
(b) Air refrigeration cycle
(c) Vapor compression cycle using expansion engine
(d) Carnot refrigeration cycle
86. Chemical potential (an intensive property) of a substance is a force that

drives the chemical system to equilibrium and is equal to its partial molar
properties the ratio of chemical potential to free energy of a pure
substance at constant temperature and pressure is
(a) 0 (b) 1
(c)  (d) None of these
87. 4 kg moles of an ideal gas expands in vacuum spontaneously the work

done is
(a) 4J (b) 
(c) 0 (d) 8J
88. Entropy is a/an

(a) State function
(b) Macroscopic property
(c) Extensive property
(d) None of these

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89. Heat is added at constant temperature in an ideal ……….cycle

(a) Stirling (b) Brayton
(c) Rankine (d) None of these
90. The eccentric factor of a material '  ' is defined as

   log10  Prsat Tr 1  0.7
where, Prsat 
Reduced vapor pressure Tr = reduced temperature. The value of eccentric
factor is always
(a) >2 (b) <1
(c) >1 (d) <3
91. Which of the following is Clausius ideal gas under the condition that the
molar volume of liquid is negligible compared to that of the vapor
d In p Hap
(a) 
dt RT Q
d Inp RT Q
(b) 
dt Hap
dp RT Q
(c) 
dt Hap
dp Hapor
(d) 
dT RT Q
92. The free energy change for a chemical reaction is given by

(a) RT InK
(b) – RT InK
(c) – R Ink
(d) T InK

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(a) Compression ratio of an Otto engine is comparatively higher than a
diesel engine
(b) Efficiency of an Otto engine is higher than that of a diesel engine for
the same compression ratio
(c) Otto engine efficiency decreases with the rise in compression ratio due
to decrease in work produced per quantity of the heat
(d) Diesel engine normally operates at lower compression ratio than an
Otto engine for an equal output of work

(a) Entropy and enthalpy are path function
(b) In a closed system the energy can be exchanged with the surrounding
while matter cannot be exchanged
(c) All the natural process are reversible in nature
(d) Work is a state function
95. Chemical engineering thermodynamics is concerned with the ……….in/of

chemical processes
(a) Reaction mechanism
(b) Energy transformation form one form to the another
(c) Energy transformation form one form to the another
(d) None of these
96. For a constant volume process……….by the system is used only to

increase the internal energy
(a) Heat absorbed
(b) Work done
(c) Both (a) & (b)

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 E 
97.   is the mathematical expression for
 T v
(a) Cv
(b) Enthalpy change
(c) Free energy change
(d) None of these
 H 
98.   is the mathematical expression for
 T P
(a) Cv
(b) Entropy change
(c) Gibbs tree energy
(d) none of these
99. Frost on coding coils

(a) Increases COP of the system
(b) Increases heat transfer
(c) Decreases power consumption
(d) Acts as an insulator causing increased power consumption
100. In a vapor compression refrigeration system liquid suction heat exchanger

is used to
(a) Keep the COP constant.
(b) Prevent the liquid refrigerant form entering the compressor.
(c) Sub cools the liquid refrigerant form leaving the condenser.
(d) Sub cools the vapor refrigerant form the evaporator.

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ANSWER KEY
1 (b) 21 (b) 41 (a) 61 (a) 81 (c)

2 (a) 22 (c) 42 (d) 62 (d) 82 (c)
3 (a) 23 (a) 43 (d) 63 (a) 83 (d)
4 (a) 24 (d) 44 (c) 64 (a) 84 (c)
5 (c) 25 (a) 45 (b) 65 (a) 85 (d)
6 (c) 26 (b) 46 (a) 66 (d) 86 (b)
7 (a) 27 (c) 47 (b) 67 (d) 87 (d)
8 (c) 28 (c) 48 (a) 68 (c) 88 (d)
9 (c) 29 (a) 49 (b) 69 (c) 89 (a)
10 (c) 30 (c) 50 (c) 70 (d) 90 (b)
11 (b) 31 (b) 51 (a) 71 (a) 91 (a)
12 (a) 32 (c) 52 (d) 72 (a) 92 (b)
13 (b) 33 (b) 53 (d) 73 (d) 93 (b)
14 (d) 34 (c) 54 (a) 74 (d) 94 (c)
15 (a) 35 (d) 55 (c) 75 (d) 95 (c)
16 (c) 36 (a) 56 (a) 76 (a) 96 (a)
17 (a) 37 (a) 57 (c) 77 (d) 97 (d)
18 (c) 38 (c) 58 (d) 78 (c) 98 (d)
19 (b) 39 (a) 59 (d) 79 (a) 99 (d)
20 (c) 40 (d) 60 (c) 80 (a) 100 (d)

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CHAPTER 8
LEVEL 2
1. In an ideal vapor compression refrigeration cycle, the specific enthalpy of

refrigerant (in kJ/kg) at the following sates is given as:
Inlet of condenser: 283 0C Exit of condenser: 116 0C
The COP of this cycle is
(a) 2.27 (b) 2.75
(c) 3.27 (d) 3.75
2. A vapor absorption refrigeration system is a heat pump with three thermal

reservoirs as shown in the figure. A refrigeration effect of 100 W is required
at 250 K, when the heat source is available at 400 K. Heat rejection
occurs at 300 k The minimum value of heat required (in W)is

(a) 167 (b) 100

(c) 80 (d) 20
3. The working temperature is evaporator and condenser coils of a

refrigerator are 23 C and 27C . The COP of the refrigerator is 0.8 of the
maximum COP for a power input of 1 kW , the refrigeration effect
produced will be………. kW
(a) 4 (b) 8
(c) 5 (d) 2.5

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4. Power (kW) per ton of refrigeration is expressed as

(a) 3.5/COP (b) COP/3.5
(c) 3.5 x COP (d) 2 x COP
5. Round the clock cooling of an apartment having a load of 300 MT/day

requires on air conditioning plant of capacity about
(a) 1 ton (b) 5 tons
(c) 10 tons (d) 100 tons
6. Consider the following statements sub-cooling in the condenser of a

refrigeration system Is advisable when
1. Expansion valve is at a higher elevation than condenser.
2. There is a large pressure drop in the connecting condenser to the
expansion valve.
3. The refrigeration effect is to be increased.
4. The compressor work is to be reduced which of the statement are
correct
(a) 1 and 2 (b) 1, 3 and 4
(c) 2, 3 and 4 (d) 1, 2 and 3
7. A solar absorption refrigeration system has generator temperature of 87 C

evaporator temperature of 3 C, 27C each then its maximum possible COP
is
(a) 10 (b) 9
(c) 1.80 (d) 1.50
8. A one ton capacity water cooler cools water steadily form 35 C and 20 C
The specific heat of water is 4.18 kJ / kg.k the water flow rate will be
nearly……….1/hr
(a) 13.33 (b) 3.33
(c) 200 (d) 250

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9. Match List I (Expansion device) with List II (Operation) and select the
correct answer using the codes given below the lists:
List I List II
A. Float valve 1. Constant degree of super heat at
evaporation exit pressure
B. Automatic expansion valve 2. Constant degree of super heat at
evaporator inlet pressure
C. Internally equalized thermostatic 3. Constant level of refrigerant in the
expansion valve evaporator.
D. Externally equalized thermostatic 4. Constant pressure in he
valve evaporator codes:
A B C D
(a) 1 2 4 3
(b) 3 2 4 1
(c) 3 4 2 1
(d) 1 4 2 3
10. The vapor compression refrigeration cycle is represented a shown in the

figure with state ‗1‘ being the exit of the evaporator. The co-ordinate
system used in this figure is
(a) p–h
(b) T–s
(c) p-s
(d) T–h

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11. The bypass factor of single cooling coil in an air conditioner is 0.7 The
bypass factor of three such cooling coils with the same apparatus dew
point are kept one behind the other will be
(a) 0.210
(b) 0.292
(c) 0.343
(d) 0.412
12. Consider the following statements

1. The recommended outside air required per person for an auditorium
is approximately 0.25 m3 minutes.
2. Outside air for ventilation purpose causes sensible heat load and also
latent heat load
3. The sensible heat factor for an auditorium is generally kept as 0.7?
Which of these statements are correct?
(a) 1 and 2
(b) 2 and 3
(c) 1 and 3
(d) 1.2 and 3
13. The discharge pressure of the compressor in the refrigeration system goes
up due to the
(a) Lower volumetric efficiency of the compressor
(b) Large size of the condenser
(c) Formation of scale in the compressor.
(d) Undercharge of the refrigerant

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14. Consider the following parameters:

1. Dry bulb temperature
2. Humidity ratio
3. Air velocity
4. Solar radiation intensity
Which of these parameters are taken into account for determining effective
temperature for human comfort?
(a) 1 and 2
(b) 1 and 4
(c) 2, 3 and4
(d) 1, 2 and 4
15. The COP a heat pump  IIP and the COP f a refrigerator  ref relate as
(a) HP  ref  1 (b) HP  ref  1

(c) ref  HP  1 (d) HP  ref  0
16. The enthalpies at the beginning of compression at the end of compression

and at the end of condensation are respectively 185 kJ / kg . 210 kJ / kg
and 85 kJ / kg . The COP of the vapor compression refrigeration system is
(a) 0.25 (b) 5.4
(c) 4 (d) 1.35
17. The turbo machine used to circulate refrigerant in a large refrigeration

plant is
(a) A centrifugal compressor
(b) A radial turbine
(c) An axial compressor
(d) An axial turbine

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18. In milk chilling plants the used secondary refrigerant if

(a) Ammonia solution
(b) Sodium silicate
(c) Glycol
(d) Brine
19. Air cooling is used for Freon compressors whereas water jacketing is
adopted for cooling ammonia compressors this is be cause
(a) Latent heat of ammonia is higher than that of Freon
(b) Thermal conductivity of water is higher than that of air
(c) Specific heat of water is higher than that of air
(d) Of the larger super heat horn of ammonia compression cycle
20. A monatomic ideal gas = 1.67 molecular weight = 40) is compressed

adiabatically form 0.1 MPa , 300 k to 0.2 MPa the universal gas constant
is 8.314 kJ.mole 1 k 1 the work o compression of Gas ( in kJ.kg is
(a) 29.7
(b) 19.9
(c) 13.3
(d) 0
21. A single stage vapor compression refrigeration sys tem can be used to
produce ultra low temperature because
(a) Refrigerants for ultra low temperature are not available
(b) Lubricants for ultra low tempera rue are not available
(c) Volumetric efficiency will decrease considerably
(d) Heat leakage into the system will be excessive.

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22. Consider the following statements Moisture should be received form

refrigerants to avoids
1. Compressor seal failure
2. Freezing at expansion valve
3. Restriction to refrigerant flow
4. Corrosion of steel parts of the statements.
(a) 1, 2, and 4 are correct
(b) 1 and 2 are correct
(c) 2, 3 and 4 are correct
(d) 1, 3 and 4 are correct
23. Match List I and List II and select the correct answer
List I List II
A. Freon 22 1. Centrifugal sys tem
B. Freon 22 2. Low temperature cold storage
C. Freon 11 3. Window type a/c unit
D. Ammonia 4. Ice plants
A B C D
(a) 3 2 1 4
(b) 3 1 2 4
(c) 1 2 4 3
(d) 1 2 4 3

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24. Consider the following statements/ in thermoelectric refrigeration the co-

efficient of performance is a function of
1. Electrical conductivity of materials
2. Peltier coefficient
3. See back coefficients
4. Temperature at cold and hot junctions
5. Thermal conductivity of materials of the statements
(a) 1, 3, 4 and 5 are correct
(b) 1, 2, 4 and 5 are correct
(c) 1, 2, 4 and 5 are correct
(d) 2, 3, 4 and 5 are correct
25. In an air standard Otto cycle, the compression ratio is 10. The condition at
the beginning of the compression process is 100 kPa and 27 C Heat added
at constant volume is 1500 kJ / kg heat is rejected during the other
constant volume process in the cycle specific gas constant of air = 0.287
kJ / kg K. The mean effective pressure (in kPa) of the cycle is
(a) 103
(b) 310
(c) 515
(d) 1032

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26. The inlet and outlet conditions steam for an adiabatic steam turbine are a
indicated in the notations as usually followed: if the mass flow rate of
steam through the turbine is 20 kg/s the power output of the turbine
(inMW) is pressure undergoes a reversible steady flow process.
The gas at inlet and outlet of the compressors is designated as state 1 and
state 2 respectively. Potential and kinetic energy changes are to be
ignored. The following notations are used:
V = specific volume and
P = pressure of the gas
The specific work required to be supplied to the compressor for this gas
compression process is
1 1
(a)  p.du
2
(b)  .dp
2
(c) V2  P2  P1  (d) P2 V1  V2 
27. A heat transformer is a device that transfers a a part of the heat supplied
to it at an intermediate temperature to a high temperature reservoir, while
rejecting the remaining part to a low temperature heat sink. In such a heat
transformer, 100 Kj of heat is supplied at 350 K. the maximum amount of
heat in Kj that can be transferred to 400 K, when the rest is rejected to
heat sink at 300 K is
(a) 12.50 (b) 14.29
(c) 57.14 (d) 33.33

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28. In a steady state flow process taking place in a device with a single inlet
and single outlet the work done per unit mass flow rate is given by,
inlet
w  
outlet
V .dp, where  is the specific volume and p is the pressure. The
expression for w given above is

(a) Valid only If the process is both reversible and adiabatic
(b) Valid only if the process is both reversible and isothermal
(c) Valid for any reversible process
inlet
(d) Incorrect it must be, w = 
outlet
p.d
29. Which of the following is not an assumption made for the Clausius –
Clayperon equation
(a) The vapor act as ideal gas
(b) Applicable below and away from the critical point
(c) Heat of vaporization is independent of temperature
(d) The vapors are real gases
30. 2 moles of oxygen are mixed adiabatically with another 2 moles of oxygen
in mixing chamber, so that the final total pressure and temperature of the
mixture becomes same as that of the individual components at their initial
states. The universal gas contestant due to mixing, mole of oxygen, is
given by
(a) – R In 2
(b) 0
(c) R In 2
(d) R In 4

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31. A balloon containing an ideal gas is initially kept in an evacuated and

insulated room. The balloon ruptures and the gas fills up the entire room.
Which one of the following statements is true at the end of the above
process?
(a) The internal energy of the gas decreases from its initial value, but the
enthalpy remains constant
(b) The internal energy of the gas increase from its initial value but the
enthalpy remains constant
(c) Both internal energy and he enthalpy of the gas remains constant
(d) Both internal energy and the enthalpy of the gas increase.
32. Which combination of the following statements is true? the incorporation

of a pre-heater in a steam power plant
P. always increases the thermal efficiency of the plant
Q. always increases the dryness fraction of steam at condenser inlet
R. always increases the mean temperature of heat addition
S. always increases the specific work output
(a) P and s
(b) Q and S
(c) Q, R and S
(d) P, Q and R

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32. A thermodynamic cycle with an ideal gas as working fluid is shown below:
The above cycle is represented on T-S plane by
(a)
(b)
(c)
(d)

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34. Water has a critical specific volume of 0.003155m3/kg. A closed and rigid
steel tank of volume 0.025 m contains a mixture of water and steam at 0.1
MPa. The mass of the mixture is 10 kg. The tank is now slowly heated. The
liquid level inside the tank .
(a) Will rise
(b) Will fall
(c) Will remain constant
(d) May rise or fall depending upon the amount of heat transferred
35. Group I shows different heat addition processes in power cycles. Likewise
group II shows different heat removal process. Group III lists power cycles.
Match items form group I, II & III.
Group I Group II Group III
P. Pressure constant S. Pressure constant 1. Rankine cycle
Q. Volume constant T. Volume constant 2. Otto cycle
R. Temperature constant U. Temperature constant 3. Carnot cycle
4. Diesel cycle
5. Bray ton cycle
(a) P – S – 5, R – U – 3, P – S – 1, Q – T – 2
(b) P – S – 1, R – U – 3, P – S – 4, P – T – 2
(c) R – T – 3, P – S – 1, P – T – 4, Q – S – 5
(d) P – T – 4, R – S – 3, P – S – 1, P – S – 5

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36. Match items form groups I, II, III, IV and V

Group I Group II Group III Group IV Group V
When added to Differential Function Phenomenon
the system is
E heat G positive I exact K path M transient
E work H negative J inexact L point N boundary
(a) F – G – J – K – M, E – G– I – K – N,
(b) E – G – I – K – M, F – H – I – K – N
(c) F – H – J – L – N, E – H – I – L – M
(d) E – G – J – K – N, F – H – J – K – M
37. Determine the correctness or otherwise of the following Assertion (a) and
the Reason (r)
Assertion (q): In a power plant working on a Rankin cycle, the
regenerative feed water heating improves the efficiency of the steam
turbine
Reason (r): The regenerative feed water heating raises the average
temperature of heat addition in Rankin cycle
(a) Both (q) and (r) are true and (r) is the correct reason for (a)
(b) Both (q) and (r) are true but (r) is NOT the correct reason for (a)
(c) Both (q) and (r) are false
(d) (q) is false but (r) is true

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38. A reversible thermodynamic cycle containing only three process ad

producing work is to be constricted. The constraints are
(i) There must be one isothermal process
(ii) There must be one isotropic process
(iii) The maximum and minimum cycle pressure and clearance volume are
fixed and
(iv) Polytrophic processes are not allowed than the number of possible
cycles is
(a) 1 (b) 2
(c) 3 (d) 4
39. The following four figures have been drawn to represent a factious
thermodynamic cycle on the p   and T – s plane
According to the first law of thermodynamics equal areas are enclosed by

figures
(a) 1&2
(b) 1&4
(c) 1&3
(d) 2&3

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40. Dew point temperature of air to one atmospheric pressure (1.013 bar ) is
18 C The air dry bulb temperature is 30 C The saturation pressure of water
at 18 C and 30 C are 0.2062 bar and 0.04241 respectively. The specific
heats of air and water vapor respectively are 1.005 and 1.88 kJ / kg and
the latent heat of vaporization of water at 0 C is 2500 kJ / kg the specific
humidity ( kJ / kg of dry air ) & enthalpy ( kJ / kg of dry air) of this moist
respectively are
(a) 0.1051 % 52.64
(b) 0.01291 & 63.15
(c) 0.01481 & 78.60
(d) 0.01532 & 81.40
41. A sterling cycle and Carnot cycle operate between 50 C their efficiencies
are s and c respectively. In this case which of the following statements is
true?
(a) s  c
(b) s  c
(c) s  c
(d) The sign of s - c  depends upon the working fluid used
42. Consider an actual regenerative Rankine cycle with one open feed water
heater for each kg is steam entering the turbine if ‗m‘ kg steam with a
specific enthalpy of ' h1 ' is bled form the turbine and the specific enthalpy
of liquid water entering the heater is ' h2 ' specific enthalpy of saturated
liquid leaving the heater is equal to
(a) mh1  (h2  h1 )
(b) h1  m(h2  h1 )
(c) h2  m(h2  h1 )
(d) mh2  (h2  h1 )s

THERMODYNAMICS - CH
43. In a new temperature scale say   the boiling and freezing points of water
at one atmosphere are 100  and 300  respectively correlate this scale
with the centigrade scale. The reading of 0  un the centigrade scale is
……….  C
(a) 0
(b) 50
(c) 100
(d) 150
44. The definition of 1 K as per internationally accepted temperature scale is

(a) 1/100th the difference between normal boiling point and normal
freezing point of water
(b) 1/273.15th the normal freezing point of water
(c) 10 times the difference between the triple point of water and normal
freezing point of water
(d) 1/273.16th the of the triple point of water
45. Mach List I with List II and select the correct answer form the codes given
below the lists:
List I List II
(Heat Engines)
A. Gs turbine 1. Constant volume heat addition and constant
volume heat refection
B. Petrol engine 2. Constant pressure heat addition and
constant volume heat rejection
C. sterling engine 3. Constant pressure heat addition and
constant pressure heat rejection
D. Diesel engine 4. Heat addition at constant volume followed by
heat addition at constant temperature

THERMODYNAMICS - CH
A B C D
(a) 1 2 3 4
(b) 3 1 4 2
(c) 2 4 1 3
(d) 4 2 1 3
46. Consider the following statements: when dry saturated steam is throttled
form a higher pressure to a lower pressure the
(a) Pressure decreases and volume increases
(b) Temperature decrease and the steam becomes superheated
(c) Temperature and the dryness fraction increase
(d) Entropy increase without any change in enthalpy
47. In which one of the following situations the entropy change will be
negative?
(a) Air expands isothermally form 6 bars to 3 bars
(b) Air us compressed to half the volume at constant pressure
(c) Heat is supplied to air at constant volume till the pressure becomes
three fold
(d) Air expands isentropically from 6 bar to 3 bar
48. Which of the following sets of thermodynamic laws/relations is directly

involved in determining the final properties during an adiabatic mixing
process?
(a) The first and second low of thermodynamic
(b) The second law of thermodynamics and steady flow relations
(c) Perfect gas relationships and steady flow relations
(d) The first law of thermodynamics and perfect gas relationship

THERMODYNAMICS - CH
49. Consider the following processes

1. Constant pressure heat addition
2. Adiabatic compression
3. Adiabatic expansion
4. Constant pressure heat rejection
The correct sequence of these processes in Rankine cycle is
(a) 1, 2, 3, 4
(b) 2, 1, 4, 3
(c) 2, 1, 4, 3
(d) 1, 2, 4, 3
50. In a surface condenser used in a steam power station, undercooking of

condensate is undesirable as this would
(a) Not absorbs the gases in steam
(b) Reduce efficiency of the plant
(c) Increase the cooling water requirement
(d) Increases thermal stresses in the condenser
51. The upper convolute temperature for two partially miscible liquids is the
temperature at which
(a) Two conjugate phase coexist
(b) A homogenous phase (single phase solution is formed)
(c) The vapor pressure of the two phases become equal
(d) None of these
52. For binary zoetrope

(a) The dew point and bubble point curves are separated by the P1Vap - P2Vap
(b) P1Vap  P2Vap
(c) Both a & b

(d) Neither a nor b

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53. For the vapor liquid equilibrium of a binary mixture the correct of the
critical point is
(a) The temperature above which the liquid phase does not exit and
corresponding saturation pressure
(b) The temperature to which the mixture must be heated for smooth
transition from vapor to liquid phase without showing any phase
transition and corresponding saturation pressure
(c) Meeting point of the bubble point and dew point line in a P.T diagram
for the specific composition
(d) The temperatures and pressure where the vapor liquid equilibrium
ratio for both the components simultaneously unity
54. At a constant temperature and pressure and for a mixture of benzene and
isopropyl benzene vapor which of the following identities is TRUE?
(a) hmix  x1h1  x2h2
(b) hmix  x1h1  x2 h2
h1  h2
(c) hmix 
x1h1  x2h2
h1  h2
(d) hmix 
x1h1  x2 h2
55. For a particular reaction the plot of In k s. I/T is a straight line. K is the
equilibrium constant fo he reaction. This means that
(a) Heat of reaction is zero
(b) Heat of reaction is independent of temperature
(c) The specific heat of the reactants and products are identical
(d) Heat of reaction is a linear function of temperature

THERMODYNAMICS - CH
56. For the gas phase reaction system N2  O2  NO; 2NO +O2  2NO2, the
degrees of freedom (F) at equilibrium are
(a) F=1
(b) F=2
(c) F=3
(d) F=4
57. For an ideal solution which of the following equations NOT TRUE?
(a) Partial molar enthalpy of a species is equal to its pure molar enthalpy
(b) Partial molar entropy of a species is equal to its pure molar entropy
(c) Chemical potential of a species is equal to pure molar Gibbs free
energy
(d) None of these
58. The activity coefficient of benzene in a benzene – toluene mixture is

assumed to be equal to
(a) Critical temperature of benzene
(b) Vapor pressure of benzene
(c) Mole fraction of benzene in the mixture
(d) Unity
59. For a heat pump the coefficient of performance is defined as, COP =
T2
(a)
T1  T2
T1
(b)
T2  T1
T1
(c)
T1  T2
T2
(d)
T2  T1

THERMODYNAMICS - CH
60. The Gibbs –Duhem equation is applicable for

(a) Molar Gibbs free energy only
(b) Molar Gibbs free energy and excess Gibbs free energy only
(c) Chemical potential molar Gibbs free energy and excess Gibbs free
energy only
(d) Any partial molar property
61. The fugacity of a solid is approximately equal to

(a) 1
(b) 0
(c) 10
(d) 100
62. What is the change in fugacity when a saturated liquid on heating is

converted to saturated vapor?
(a) 0
(b) 3
(c) 1
(d) 
63. Which of the following assumption are inherent in Clausius – Clayperon

equation?
(a) Specific molar volume of the liquid is very small compared to specific
molar volume of the gas and as a result an be neglected
(b) Saturated vapor obeys ideal gas law
(c) The molar heat of vaporization is independent of temperature
(d) All a, b & c

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64. Raoult‘s law applies to

(a) Any liquid solution
(b) Idea liquid solution only
(c) No ideal liquid solution
(d) Ideal gas mixture
65. In h – s diagram, the dome shaped region is for

(a) Vapor only
(b) Liquid only
(c) Vapor liquid mixture
(d) Super heated vapor
P H
66. The Clayperon equation  can be used for
TGT  g v
T .DV
(a) VLE (vapor liquid equilibrium only)
(b) SLE (solid liquid equilibrium only)
(c) SVE (solid – vapor equilibrium only
(d) Equilibrium between any two coexisting phases.
67. For an ideal gas joule Thompson expansion would always result in
(a) Increase in temperature
(b) Decrease in temperature
(c) Temperature remaining unchanged
(d) Unpredictable.
68. For an ideal gas the joule – Thomson coefficient is always

(a) >0
(b) <0
(c) =0
(d) 0

THERMODYNAMICS - CH
69. The critical compressibility factor value for water is

(a) 0.23
(b) 0.35
(c) 1.0
(d) 0
70. The cubic equation of state can be represented as z3  aZ 2  bZ  g  0,

where z is the compressibility factor for CH4 at one particular temperature
and pressure cuic equation of state has one real root and tow imaginary
roots; therefore the state of the substance is
(a) Mixture of liquid and vapor
(b) Either liquid or vapor but not a mixture
(c) Impossible to have imaginary roots for a physically meaningful state
of the substance
(d) Liquid
71. Critical pressure of a substance is defined as the

(a) Pressure at which saturated liquid and vapor are in equilibrium
(b) Pressure at which an azeotrope is formed when mixed with steam
(c) Pressure above which the state of a substance may not be
distinguished between liquid and vapor
(d) None of these
72. The law of corresponding states is that all fluids at ……….same

(a) Critical temperature and pressure will have the same critical volume
(b) Reduced temperature and pressure will have the same reduced
volume
(c) Temperature and pressure will have the same specific volume
(d) None of these

THERMODYNAMICS - CH
73. Compressed air throttled through a needle valve to atmospheric pressure

the throttling processes is
(a) Isenthalpic
(b) Isentropic
(c) Isobaric
(d) isothermal
pvap (T2 ) H  1 1 
74. The ClausiusClayperon equation In     is applicable for
pvap (T1 ) R  T2 T2 
(a) VLE (vapor liquid equilibrium only)
(b) SLE (solid liquid equilibrium only )
(c) SVE (solid vapor equilibrium only)
(d) Equilibrium between any tow coexisting phases
75. For the above compressor problem, the amount of heat (Kj/mol) removed
by the cooling jacket is
(a) 0
(b) 1.06
(c) 13.20
(d) 13.20
76. For the above heat exchanger problem, the heat supplied to the gas is
equal to the increase in
(a) Enthalpy
(b) Internal energy
(c) Both a & b
(d) Neither ‗a‘ nor ‗b‘

THERMODYNAMICS - CH
77. When water is boiling in a beaker open to atmosphere, the latent heat of
evaporation to be supplied is equal to difference in specific ……….of steam
and water
(a) Internal energies
(b) Enthalpies
(c) Entropies
(d) All (a), (b), &(c)
78. A system consists of mixture of ice and water. Amount of ice being 0.5 mol
and water being 0.5 mol. What is the sp. Heat of the mixture (cal/mole.K)
(sp. Heat of water is 18 cal/mol. K and that of ice is 9 cal/mol. K)?
(a) 0
(b) 18
(c) 9
(d) 
79. For an ideal gas specific internal energy is a function of

(a) Temperature only
(b) Temperature and pressure
(c) Total entropy remains constant
(d) None of these
80. A cylinder L1 containing LPG at 10 bars and 298 K is connected and is being
used to fill another cylinder L2 initially at 1 bar and 295 K. the final
temperature of L1 is T1 and that of L2 is T2 Then
(a) T1>T2
(b) T1 = T2
(c) T1<T2
(d) Unpredictable

THERMODYNAMICS - CH
81. An adiabatic steady state turbine is he source for a small electric

generator. Steam the motive fluid, enters at 600 C and 10 bar steam is
exhausted from the turbine at 1 atm pressure and 400 C Estimate the
work done by turbine (kJ / kg steam)
(a) – 401.7
(b) 401.7
(c) – 632.2
(d) 632.2
82. Match the following as:

A. Boyles‘ law (Isobaric) (i) Pv/T = constant
B. Charle‘s law (Isobaric) (ii) vT  cons tan t
C. Charles law (isometric) (iii) PT = constant
D. General law (iv) Pv = constant
(a) I – D, ii – B, iii – C, iv – A
(b) I – D, ii – C, iii – B, iv – A
(c) I – D, ii – A, iii- B, iv – C
(d) I – A, ii – B, iii – C, iv – D
83. Match the following values of R (universal gas constant) with proper units
which of the following approximation are true
(a) hu
(b) Cp  C
(c)  /   0
(d) All (a), (b)&(c)

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84. Match the following values of R (universal gas constant) with proper units:
(I) litre atm/ mole K  A. 0.0821
(II) litre atm/mol. K C B. 10.73
(III) cal/ mole  K C. 1.987
(iv) atm ft 3 / Ib mole R D. 0.7302
(a) I – A, II – B, III – C, IV – D
(b) I – D, II – C, III – B, IV – A
(c) I – A, II – B, III – D, IV – C
(d) I – B, II- A, III – C, IV – D
85. Which of the following identities can be most easily used to verify steam
table data for superheated steam table data for superheated steam?
 T   P 
(a)  V      S 
 S  V
 T   V 
(b)  P    S 
 s  
 P   S 
(c)   T     V 
 V  T
 V   S 
(d)  T      P 
 P  T

THERMODYNAMICS - CH
86. Which of the following conditions are satisfied at the critical point by the P
– V – T relation of a real fluid?
  2P   P 
(a)  2 2   0
  P T  V T
  2P   P 
(b)  2   0;  T  0
 V T  V 
  2P   P 
(c)  2 T  0;  T  0
 V   V 
  2P   P 
(d)  2 T  0;  T  0
 V   V 
87. A reasonable general expression for vapor liquid phase equilibrium at low
to moderate pressure is t y i  y i xi FT0 where t is a vapor fugacity coefficient,
t is the liquid activity coefficient and f 0 is the fugacity of pure component i
the ki value    Ki xi as therefore in general, a function of
(a) Temperature only

(b) Temperature and pressure only
(c) Temperature pressure and liquid composition only
(d) Temperature pressure and liquid composition xi and vapor
composition yi
88. The vapor pressures of benzene and toluene are 3 and 4/3 atmospheres
respectively A liquid feed of 0.4 moles of benzene and 0.6 moles of toluene
is vaporized assuming that the products are in equilibrium, the vapor
phase mole fraction of benzene is
(a) 0.4
(b) 06.
(c) 0.8
(d) 0.2

THERMODYNAMICS - CH
89. Maxwell‘s relation corresponding to the identity, dH = ds + V. dp - idni is
 T   P 
(a)  V   S 
 S ni  V ni
  S   V 
(b)   P   T 
 T ni  Pni
 S   P 
(c)  V    T 
 T ni  V ni
  T   V 
(d)  P   S 
 Sni  Pni
90. Which of the following is true for Virial equation of state?

(a) Virial coefficients are universal constants
(b) Virial coefficients B represent three body interactions
(c) Virialcoefficients are functions of temperature only
(d) For some gases, Virial equations and ideal gas equations are the
same
91. A liquid mixture contains 30% o – xylene, 60 % p – xylene and 10 % m –

xylene (all percentages in w/w) which of the following statements would be
true in respect of this mixture
(a) The mixture exhibits an azeotrope at 101.3 kPa
(b) The composition of the mixture in percent by volume is :o – xylene 30,
p – xylene 60 and , m – xylene 10
(c) The composition of the mixture in mol per cent is : 0 xylene 30, p –
xylene 60 and m –xylne 10
(d) The mixture contains optical isomers.

THERMODYNAMICS - CH
92. A system undergoes a change form a given initial state to a given final
state either by an irreversible process or by a reversible process then
(a) S1 is alwyas > SR (b) S1 is sometime >SR
(c) S1 is aLWAYS < SR (d) S1 isalways = SR
Where SI is always > SR are the entropy changes of the system for the
irreversible and reversible processes, respectively.
93. For an ideal gas the slope of the pressure volume curve at a givne point
will be
(a) Steeper for an isothermal than for an adiabatic process
(b) Steeper for an adiabatic than for an isothermal process
(c) Identical for both the process
(d) Of opposite signs
94. Which of the following refrigerant system uses vacuum for operation
(a) Vapor absorption system using ammonia water.
(b) Vapor compression system using R – II
(c) Vapor absorption system using lithium bromide water
(d) Vapor compression system using HFC 134a.
95. Match the expression for various thermodynamic equations/relations

List I List II
I. Gibbs Duhem equation  B
A. log P  P 1  
 T
II. Lewis = Randall rule B. TA  K.TB  C
III. Diuhring rule 2

 d ln ri 
C. x i   0
i 1  dxi T , P
IV. Cox equation B

D. ln(P sat )  A 
T C

THERMODYNAMICS - CH
(a) I – A, II – B, III – C, IV – D
(b) I – D, II – C, III – B, IV – A
(c) I – A, II – B, III – D, IV – C
(d) I – B, II- A, III – C, IV – D
96. Unit of Planck‘s constant in the relation E  h is

(a) Joule
(b) Joule/sec
(c) Joule/kmol
(d) Joule.sec
97. The temperature at the joule – Thomson coefficient changes sing is known
as the inversion temperature joule Thomson co – efficient is zero at the
inversion temperature The inversion temperature of helium is……….  C
(a) 80
(b) – 80
(c) 240
(d) – 240
98. Brayton cycle can be used as idealized cycle for simple gas turbine when a
simple gas turbine cycle is modified with overcooling heat and exhaust
heat exchange the modified cycle will give higher
(a) Thermal efficiency
(b) Power output
(c) Both (a) & (b)
(d) Nether (a) nor (B)

THERMODYNAMICS - CH
99. The chemical potential of any constituent of an ideal solution does not
depend upon the ……..of the solution
(a) Pressure
(b) Temperature
(c) Composition
(d) Viscosity
100. Phase rule for finding the degree of freedom is F = C – P – R + 2. Here 2

stands for
(a) Temperature & pressure variables of the system
(b) Two reacting components (since at least two reactants are required for
the reaction to occur)
(c) Tow dependent equations (e.g. a component balance and the overall
mass balance)
(d) Temperature & the equation y1  y 2  .....  1

THERMODYNAMICS - CH
ANSWER KEY
1 (a) 21 (a) 41 (c) 61 (a) 81 (b)
2 (a) 22 (a) 42 (c) 62 (a) 82 (a)
3 (a) 23 (d) 43 (d) 63 (d) 83 (d)
4 (a) 24 (b) 44 (d) 64 (b) 84 (a)
5 (a) 25 (d) 45 (b) 65 (c) 85 (d)
6 (c) 26 (a) 46 (a) 66 (d) 86 (a)
7 (d) 27 (b) 47 (a) 67 (c) 87 (c)
8 (c) 28 (c) 48 (d) 68 (c) 88 (b)
9 (c) 29 (d) 49 (c) 69 (b) 89 (d)
10 (c) 30 (b) 50 (c) 70 (b) 90 (c)
11 (c) 31 (c) 51 (b) 71 (c) 91 (a)
12 (c) 32 (b) 52 (d) 72 (b) 92 (d)
13 (b) 33 (c) 53 (c) 73 (a) 93 (b)
14 (d) 34 (b) 54 (b) 74 (a) 94 (a)
15 (b) 35 (a) 55 (b) 75 (b) 95 (b)
16 (c) 36 (a) 56 (c) 76 (a) 96 (d)
17 (c) 37 (d) 57 (b) 77 (b) 97 (d)
18 (c) 38 (a) 58 (d) 78 (d) 98 (c)
19 (a) 39 (a) 59 (d) 79 (a) 99 (d)
20 (a) 40 (b) 60 (d) 80 (c) 100 (a)

THERMODYNAMICS - CH

THERMODYNAMICS - CH

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THERMODYNAMICS - CH

2.6.4.4 Change in Internal Energy

4 THERMODYNAMIC EQUATIONS 104

5 SOLUTION THERMODYNAMICS 117

6 CHEMICAL REACTION EQUILIBRIUM 135

7 LEVEL 1 CONCEPT BASED MCQS 151

8 LEVEL 2 CONCEPT BASED MCQS 174

―THERMODYNAMICS is basically a branch of science which focuses on the

Thermodynamics is the branch of science that embodies the principles of

DIFFERENCE BETWEEN SURROUNDINGS, IMMEDIATE SURROUNDINGS

1.2 CLASSIFICATION OF THERMODYNAMIC SYSTEM

1.2.1 CLOSED SYSTEM (OR NON FLOW SYSTEM)

1.2.2 OPEN SYSTEM (OR FLOW SYSTEM)

 Heat and work crosses the boundary.

1.2.3 ISOLATED SYSTEM

Past GATE Questions on GATE Tip

Q.1 A closed thermodynamic system is one in which

Q.2 Which of the following statements are true?

1.3 BASIC TERMINOLOGIES

1.3.1 HOMOGENEOUS AND HETEROGENEOUS SYSTEM

MACROSCOPIC AND MICROSCOPIC VIEWPOINT

3. Observations are based on 3. Exact observations are carried

 Macroscopic viewpoint is an engineering approach while

1.3.2 THERMODYNAMIC EQUILIBRIUM

1.3.3 CONTROL VOLUME

1.3.4 STEADY STATE

1.3.5 THERMODYNAMIC PROCESS

1.3.5.1 CYCLIC PROCESS

1.3.5.2 REVERSIBLE PROCESS

uses reversible to make the analysis simpler, and to determine maximum

1.3.5.3 IRREVERSIBLE PROCESS

1.3.5.4 ADIABATIC PROCESS

1.3.5.5 ISENTROPIC PROCESS

1.3.5.6 POLYTROPIC PROCESS

1.3.5.7 THROTTLING PROCESS

1.4 PROPERTIES OF A SYSTEM

 Temperature, pressure, volume energy etc. are the various properties of

Check for a property:

 INTENSIVE PROPERTIES are those which are independent of mass of

 EXTENSIVE PROPERTIES are mass dependent. Hence their value

 An extensive property when expressed as per unit mass becomes an

Past GATE Questions on Concept

Q.2 Which of the following are intensive properties?

 Temperature and specific volume, for example, are always independent

THERMODYNAMIC PROCESS, PATH AND CYCLE

 The variation of pressure as a result of gravity in most

 Chemical equilibrium in a system exists when there is no change in

Features of Quasi-Static Process

 Frictionless quasi-static processes are reversible.

A process is said to be reversible if the system and its surroundings are

Q.3 Which Of The Following Is/Are Reversible Process(es)?

It assumes a continuous distribution of mass within the matter or

 The continuum idealization allows us

PATH FUNCTION AND POINT FUNCTION

 Differential amount is represented by symbol ―d‖ i.e. small change in

1.4.2 FUNDAMENTAL PROPERTIES

 Standard Atmospheric Pressure

gc  constant value of g everywhere

 Relationship between kgf and N