BTD Notes

|| Jai Sri Gurudev ||
Sri AdichunchanagiriShikshana Trust®
SJB INSTITUTE OF TECHNOLOGY

(Affiliated to Visvesvaraya Technological University, Belagavi & Approved by AICTE, New Delhi. Accredited with NAAC ‘A’ grade)
Department of Mechanical Engineering
Course Material
BASIC THERMODYNAMICS
Semester &Section: 3rd Semester ‘A’ section

Subject Name: Basic Thermodynamics
Subject Code: 18ME33
Faculty Name: Naveena kumar R. R.
Designation: Assistant Professor
Academic year: ODD Semester-2021-2022

CONTENTS
1. Vision, Mission
2. POs, PSOs & PEOs
3. Blooms Taxonomy
4. Objectives and Outcomes
5. Course Syllabus
6. Lecture Notes (Unit-wise)
a. Notes
b. Industry applications relevant to the concepts covered
c. Assignment Question with self learning Materials
Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. Page 2

Vision of the Institute

 To become a recognized technical education center with global perspective.
Mission of the Institute

To provide learning opportunities that fosters students ethical values,
intelligent development in science & technology and social responsibility
so that they become sensible and contributing members of the society.
Vision of the Department

 To become a center of excellence and a platform in diversified fields for the
aspirants in Mechanical Engineering.
Mission of the Department

 To impart comprehensive education in the field of mechanical engineering to
produce highly accomplished graduates
 To endow high profile technical & soft skill trainings to foster
professionalism and ethical values among students
 To inculcate innovative thinking among students through projects and
research work

PROGRAMOUTCOMES
1. Engineering knowledge: Apply the knowledge of mathematics, science, engineeringfundamentals, and
an engineering specialization to the solution of complex engineeringproblems.
2. Problem analysis: Identify, formulate, review research literature, and analyze complex engineering
problems reaching substantiated conclusions using first principles of mathematics, natural sciences, and
engineeringsciences.
3. Design/development of solutions: Design solutions for complex engineering
problemsanddesignsystemcomponentsorprocessesthatmeetthespecifiedneedswithappropriate
consideration for the public health and safety, and the cultural, societal, andenvironmentalconsiderations.
4. Conduct investigations of complex problems: Use research-based knowledge andresearch methods
includingdesign ofexperiments, analysisand interpretation
ofdata,andsynthesisoftheinformationtoprovidevalidconclusions.
5. Modern tool usage: Create, select, and apply appropriate techniques, resources,
andmodernengineeringandITtoolsincludingpredictionandmodelingtocomplexengineeringactivitieswithan
understandingofthelimitations.
6. The engineer and society: Apply reasoning informed by the contextual knowledge
toassesssocietal,health,safety,legalandculturalissuesandtheconsequentresponsibilitiesrelevanttotheprofess
ionalengineeringpractice.
7. Environment and sustainability: Understand the impact of the professional engineeringsolutions in
societal and environmental contexts, and demonstrate the knowledge of,
andneedforsustainabledevelopment.
8. Ethics: Apply ethical principles and commit to professional ethics and responsibilities
andnormsoftheengineering practice.
9. Individual and teamwork: Function effectively as an individual, and as a member
orleaderindiverseteams, andinmultidisciplinarysettings.
10. Communication: Communicate effectively on complex engineering activities with theengineering
community and with society at large, such as, being able to comprehend andwrite effective reports and
design documentation, make effective presentations, and giveand receiveclearinstructions.
11. Project management and finance: Demonstrate knowledge and understanding of theengineering and
management principles and apply these to one‟s own work, as a memberandleaderinateam,
tomanageprojectsandinmultidisciplinaryenvironments.
12. Life-long learning: Recognize the need for and have the preparation and ability toengage in independent
and life-long learning in the broadest context of technologicalchange.

PROGRAM EDUCATIONAL OBJECTIVES (PEO’S)
Enable the Graduates in Mechanical Engineering to:

PEO-1: Progress their career as a professionalin mechanical engineering and
Inter-disciplinary fields.
PEO-2: Become successful entrepreneur with social responsibilities and ethical
values.
PEO-3: Pursue higher education and involve in research of allied areas in
Mechanical Engineering.
PROGRAM SPECIFIC OUTCOMES (PSO’S)
After successful completion of Mechanical Engineering program, the graduates will

be able to:
PSO1: Apply the Knowledge & Skill of Mechanical Engineering on Design,
Manufacturing and Thermal platforms to address the real-life problem of the society.
PSO2: Design and implement new ideas with the help of CAD/CAM and Industrial
Automation tools.

Blooms Taxonomy

B. E. MECHANICAL ENGINEERING
Choice Based Credit System (CBCS) and Outcome Based Education (OBE)
SEMESTER - III
Course Code 18ME33 CIE Marks 40

Teaching Hours/Week (L:T:P) 3:0:0 SEE Marks 60
Credits 03 Exam Hours 03
Course Learning Objectives:

 Learn about thermodynamic system and its equilibrium
 Understand various forms of energy - heat transfer and work
 Study the basic laws of thermodynamics including, zeroth law, first law and second law.
 Interpret the behaviour of pure substances and its application in practical problems.
 Study of Ideal and real gases and evaluation of thermodynamic properties
Module-1
Fundamental Concepts & Definitions: Thermodynamic definition and scope, Microscopic and
Macroscopic approaches. Some practical applications of engineering thermodynamic Systems,
Characteristics of system boundary and control surface, examples. Thermodynamic properties;
definition and units, intensive, extensive properties, specific properties, pressure, specific volume,
Thermodynamic state, state point, state diagram, path and process, quasi-static process, cyclic and non-
cyclic; processes; Thermodynamic equilibrium; definition, mechanical equilibrium; diathermic wall,
thermal equilibrium, chemical equilibrium, Zeroth law of thermodynamics, Temperature; concepts,
scales, international fixed points and measurement of temperature. Constant volume gas thermometer,
constant pressure gasthermometer, mercury in glass thermometer.
Module-2
Work and Heat: Mechanics, definition of work and its limitations.Thermodynamic definition of work;
examples, sign convention. Displacement work; as a part of a system boundary, as a whole of a system
boundary, expressions for displacement work in various processes through p-v diagrams. Shaft work;
Electrical work. Other types of work. Heat; definition, units and sign convention. Problems.
First Law of Thermodynamics: Joules experiments, equivalence of heat and work. Statement of the First
law of thermodynamics, extension of the First law to non - cyclic processes, energy, energy as a
property, modes of energy, Extension of the First law to control volume; steady flow energy
equation(SFEE), important
Module-3
Second Law of Thermodynamics: Limitations of first law of thermodynamics, Thermal reservoir, heat
engine and heat pump: Schematic representation, efficiency and COP. Reversed heat engine, schematic
representation, importance and superiority of a reversible heat engine and irreversible processes,
internal and external reversibility. Kelvin - Planck statement of the Second law of Thermodynamics;
PMM I and PMM II, Clausius statement of Second law of Thermodynamics, Equivalence of the two
statements; Carnot cycle, Carnot principles. Problems

Entropy: Clausius inequality, Statement- proof, Entropy- definition, a property, change of entropy,
entropy as a quantitative test for irreversibility, principle of increase in entropy, entropy as a
coordinate.
Module-4
Availability, Irreversibility and General Thermodynamic relations. Introduction, Availability (Exergy),
Unavailable energy, Relation between increase in unavailable energy and increase in entropy.
Maximum work, maximum useful work for a system and control volume, irreversibility. Pure
Substances: P-T and P-V diagrams, triple point and critical points. Sub-cooled liquid, saturated liquid,
mixture of saturated liquid and vapor, saturated vapor and superheated vapor states of pure substance
with water as example. Enthalpy of change of phase (Latent heat). Dryness fraction (quality), T-S and H-
S diagrams, representation of various processes on these diagrams. Steam tables and its use. Throttling
calorimeter, separating and throttling calorimeter.
Module-5
Ideal gases: Ideal gas mixtures, Daltons law of partial pressures, Amagat’s law of additive volumes,
evaluation of properties of perfect and ideal gases, Air- Water mixtures and related properties.
Real gases: Introduction, Van-der Waal's Equation of state, Van-der Waal's constants in terms of critical
properties, Beattie-Bridgeman equation, Law of corresponding states, compressibility factor;
compressibility chart. Difference between Ideal and real gases.
Course Outcomes: At the end of the course, the student will be able to:
CO1: Explain fundamentals of thermodynamics and evaluate energy interactions across the boundary
of thermodynamic systems.
CO2: Evaluate the feasibility of cyclic and non-cyclic processes using 2nd law of thermodynamics.
CO3: Apply the knowledge of entropy, reversibility and irreversibility to solve numerical problems and
apply 1st law of thermodynamics to closed and open systems and determine quantity of energy
transfers and change in properties.
CO4: Interpret the behavior of pure substances and its application in practical problems.
CO5: Recognize differences between ideal and real gases and evaluate thermodynamic properties of
ideal and real gas mixtures using various relations.
Question paper pattern:

 The question paper will have ten full questions carrying equal marks.
 Each full question will be for 20 marks.
 There will be two full questions (with a maximum of four sub- questions) from each module.
 Each full question will have sub- question covering all the topics under a module.
 The students will have to answer five full questions, selecting one full question from each module.
Textbooks
1. Basic and Applied Thermodynamics, P.K.Nag, Tata McGraw Hill 2nd Ed., 2002
2. Basic Engineering Thermodynamics, A.Venkatesh Universities Press, 2008
3. Basic Thermodynamics,, B.K Venkanna, Swati B. Wadavadagi PHI, New Delhi 2010
Reference Books
1. Thermodynamics- An, Engineering Approach, YunusA.Cenegal and Michael A.Boles Tata McGraw Hill
publications 2002
2. An Introduction to Thermodynamcis, Y.V.C.Rao Wiley Eastern 1993,
3. Engineering Thermodynamics .B.Jones and G.A.Hawkins John Wiley and Sons.

Module 1
FUNDAMENTAL CONCEPTS AND DEFINITIONS
INTRODUCTION:
Thermodynamics is the science of energy transfer and its effect on the physical properties of
substances. The alternate definition is: thermodynamics is the science that deals with work
and heat and these properties of substances that bear a relation to heat and work. Like all
sciences, the basis of thermodynamics is experimental observation.
Thermodynamics (from the Greek therme, meaning "heat" and dynamis, meaning "power") is
a branch of physics that studies the effects of changes in temperature, pressure, and volume on
physical systems at the macroscopic scale by analyzing the collective motion of their particles
using statisticsThis subject was developed mainly by
1) Carnot 2) Mayer 3) Clausius 4) Joule
5) Kelvin 6) Maxwell 7) Plank 8) Gibbs
A thermodynamic system is a device or combination of devices containing a quantity of matter

that is being studied. A typical thermodynamic system - heat moves from hot (boiler) to cold
(condenser), and work is extracted, in this case by a series of pistons.
A typical thermodynamic system
The study of thermodynamics is the basis of such fields as steam power plants, IC
Engines, Gas dynamics and aerodynamics, fluid mechanics, Refrigeration and Air conditioning
and

A Steam Power Plant
Thermodynamics deals with four laws. Namely Zeroth law, first law, second law
and Third law of thermodynamics. Fortunately, there is no mathematical proof for any of
these laws of thermodynamics, like physical laws, but they are deduced from experimental
observations.
Refrigeration Cycle
Thermodynamics deals with three E’s, namely Energy, Equilibrium and Entropy.
Thermodynamics also talks about study of materials, chemical reactions, plasmas and other
biological reactions.

Macroscopic and Microscopic point of view:
This study deals with macroscopic, as opposed to microscopic or statistical thermodynamics.

In microscopic thermodynamics individual molecule is considered and analysis of collective
molecular action. In macroscopic thermodynamics, we concern ourselves with the overall
effect of the individual molecular interaction.
Macroscopic point of view: The macroscopic level is the level on which we live. We measure
most of the quantities on this level.
Ex: Temperature measurement, pressure measurement, total volume measurement, specific
volume measurement. Thus, microscopic point of view will be used only to explain some
phenomena that can’t be understood by macroscopic means.
Microscopic point of view: Considers a system containing a cube of 25 mm containing

monoatomic gas at atmospheric pressure and temperature. This volume contains approx. 1020
atoms. To describe the position of each atom in a coordinate system we require three
equations. To describe the velocity of each atom we have to specify 3 velocity components.
Thus to describe completely the behavior of the system from a microscopic point of view we
must deal at least 6*1020 equations. It is a hopeless computational task.
The other approach that reduces number of variables to a few that can be handled is the
macroscopic point of view of Classical Thermodynamics. It concerns with the gross or average
effect of many molecules and can be measured by instruments. This measurement is the time-
averaged influence of many molecules.
In the present study, we concentrate on macroscopic point of view.
Statistical thermodynamics, classical thermodynamics deals with the significance of

microscopic point of approach. From the macroscopic point of view it is very clear that
continuum has to be there in the system because we are not concerned with the behavior of
the individual molecule.
Substance: What follows will be illustrations of the thermodynamics, one must be able to
solve problems and to do what the part of the problem must be enumerated. The first
consideration is that there must be something performing the energy transformations. This
something is called a substance. Ex: In case of IC engine gasoline and air mixture constitutes
the substance. In steam turbine the substance is steam.
The substance may be further divided into sub categories, namely pure substance i.e. if it is
homogeneous in nature- i.e. if it does not undergo chemical reaction and is not a mechanical
mixture of different spices. The other substance is a mixture substance which is not a pure
substance.

Thermodynamic System:
A substance does not exist alone. It must be contained. This brings us to the concept of a
system.
In thermodynamics a system is defined as any collection of matter or space of fixed identity,
the concept is one of the most important thermodynamics.
Concept of a Boundary
System boundary: When a system is defined, let us say, fluid in a cylinder, what separates the
fluid from the cylinder wall and the piston and everything external to the piston-cylinder? it is
the system boundary. Everything not in the system is called the surrounding. Note that piston
can be raised or lowered, but the system, matter of fixed identity is constant.
The system is further divided into closed system, open system and isolated system.
Thermodynamic System
A Thermodynamic system is defined as a quantity of matter or a region in space upon

which attention is concentrated in the analysis of a problem. Everything external to the system
is called the surrounding or environment. The system is separated from the surrounding by
the system boundary. Boundary may be either fixed or moving. A system and its surrounding
together comprise a universe.

A System, Surroundings and Boundary
Open System: The open system is one in which matter crosses the boundary of the system.
There may be energy transfer also. Most of th4e engineering devices are generally open
systems. Ex: An air compressor in which air enters at low pressure and leave at high pressure
and there is energy transfer across the system boundary.
An Open System
Closed System: A closed system is a system of fixed mass. There is no mass transfer across the
system boundary. Ex: A certain quantity of fluid in a cylinder bounded by a piston constitutes
a closed system.
A Closed System
Isolated System: The isolated system is one in which there is no interaction between the
system and surrounding. It is of the fixed mass and energy and there is no mass or energy
transfer across the system boundary.
Control Volume and Control Surface:

In thermodynamic analysis of an open system such as air compressor, gas turbine in which
there is a flow of mass into and out of the system, attention is focused on a certain volume in
space surrounding the compressor known as control volume, bounded by a surface called the
control surface. Matter as well as energy can cross the control surface.

Gas turbine
Homogeneous and Heterogeneous system:

A quantity of matter homogeneous throughout in chemical composition and physical structure
is called a phase. Every substance can exist in any one of the three phases viz. Solid, Liquid or
gas.
A system consisting of a single phase is called a homogeneous system while a system

consisting of more than one phase is known as a heterogeneous system.
THERMODYNAMIC PROPERTIES
Thermodynamic properties are taken from a macroscopic perspective. We are dealing with
quantities that can either directly or indirectly be measured or counted. Therefore, the matter
of units becomes an important consideration.
Mass, length and time are considered as fundamental physical quantities, they are related by
Newton's second law of motion, which states that the force acting on a body is proportional to
the product of mass and acceleration in the direction of force.
i.e. F= m * a
Mass – kg Length – m Time – s

This is adopted by CGPM- General Conference of Weights and Measures
In thermodynamics temperature is also considered as fundamental unit in Kelvin.
Energy: One of the very important concepts in a study of thermodynamics is the concept of
energy. It is defined as the capacity to do work. It is also defined as the capability to produce an
effect
When considered from molecular point of view, three general forms of energy become
important.

1) Intermolecular potential energy.
2) Molecular kinetic energy
3) Intermolecular energy.
The energy is the important concept which depends on the mass, velocity, intermolecular
attraction. In all intermolecular internal energy is most difficult to evaluate.
Specific Volume: It is a macroscopic property and defined as the volume occupied by unit
mass. It is reciprocal of density and its unit is m3/ kg. The specific volume of a system in a
gravitational field may vary from point to point. Specific volume increases as the elevation
increases. Thus the definition of specific volume involves the specific volume of a substance at
a point in a system.
Pressure: The pressure in a fluid at rest at a given point is the same in all directions. We define
pressure as the normal component of force per unit area. Its unit is pascal or N/m2. When
dealing with liquids and gases we ordinarily speak of pressure. For solids we speak of stresses.
Two other units not part of international system continue to be widely used are
Bar = 105 Pa = 0.1MPa and standard atmosphere is 1 atm = 101325 Pa.
In most thermodynamic investigations, we are concerned with absolute pressure. Most
pressure vacuum gauges however read the difference between the absolute pressure and the
atmospheric pressure at the gauge. This refers to as gauge pressure.
Pabs1
Ordinary Pressure gauge P = Pabs1 – P atm
Patm Ordinary vacuum gauge
P = P atm – P abs2
Pabs2
Barometric reads atmospheric pressure

Temperature: It is a fundamental property of thermodynamics and defined as the hotness of
the body. Temperature first of all as a sense of hotness or coldness when we touch an object.
We also learn that when a hot body and a cold body are brought into contact the hot body
becomes cooler and cold body becomes warmer. Because of these difficulties in defining
temperature we define equality of temperature.
Property: It is defined as any quantity that depends on the state of the system and is
independent of the path ( i.e. the prior history) by which the system arrived at the given state.
Conversely the state is specified or described by the properties and later we will consider the
number of independent properties a substance can have, i.e, the minimum number of
properties that must be specified to fix the state of a substance.
Thermodynamic properties can be divided into 2 general classes: intensive and extensive
properties:
Intensive property: An intensive property is independent of mass; thus intensive property

value remains same even if the matter is divided into two equal parts. Ex: pressure,
temperature, density etc.
Extensive Property: The value of an extensive property varies directly with the mass, i.e. if a
quantity of matter in given state is divided into 2 equal parts, the properties will have the half
the original values. Ex: mass, total volume, total enthalpy, total energy etc.
Thermodynamic State Point:

The state may be identified or described by certain observable macroscopic properties; some familiar
one are temperature, pressure and density. The state is specified or described by the properties. The
state point can be indicated on a thermodynamic coordinate system. Thermodynamic coordinate
system includes pressure volume diagram, temperature volume diagram, temperature entropy
diagram, enthalpy entropy diagram, pressure enthalpy diagram so on and so forth.
These co-ordinate systems represent thermodynamic state of a substance. Consider a system

not undergoing any change. At this point all the properties can be measured or calculated
throughout the entire system, which gives us a set of properties that completely, describes the
condition or the state of the system.
Thermodynamics deals with equilibrium state. When a system undergoes any change
then change of state will occur.

Weights
Piston
Gas
Cylinder
Piston Cylinder arrangement
Process: Whenever one or more of the properties of a system change we say that a change in
state has occurred. For ex: in a piston and cylinder arrangement, if weight is removed from the
piston rises and change in state occurs in which pressure decreases and specific volume
increases. The path of succession of states through which the system passes is called process.
Path: Path is the complete series of states through which the system passes during a change
from one given state to other state. It is clear that the transformation of a system from one
fixed state to another state is called a process.
The thermodynamic processes that are commonly met within engineering practice are 1) Constant
pressure process (Isobaric) 2) Constant volume process(Isochoric) 3)Constant temperature process(
Isothermal) 4) Reversible adiabatic process (Isentropic process) 5) Polytropic, process 6) Throttling
process.
If the system passes through a series of equilibrium states during the process it’s called
reversible process. On the other hand the system passes through a series of non-equilibrium
states during a process it is called irreversible process. The state of the processes cannot be
plotted on the co-ordinate systems since the path of the process is not defined.
Generally the system is in equilibrium in the beginning and at the end of the process, the
reversible process can be plotted on the coordinate diagram by continuous line and an
irreversible process by a dotted line.

1 1
P P
V
2
2
V V
Representation of a reversible process An irreversible process
Quasi – static process (very slow process) :

Quasi – meaning almost, static meaning infinite slowness. Thus quasi-static process is infinitely
slow transition of a system. Infinite slowness is the characteristic feature of a quasi-static
process. A quasi-static process is a succession of equilibrium states. It is a reversible process.
Cycle: It is a process whose initial and final states are same. Thus at the end of a cycle all the
properties of a working fluid have the same values as they had in the initial states.
There are 2 types of cycles. viz. thermodynamic cycle and mechanical cycle.

Thermodynamic cycle:
It is one in which the working substance is re circulated. Ex: water that circulates through
steam power plant and refrigerant that passes through refrigeration plant are the examples of
thermodynamic cycle. There is change of phase during the process but the end states do not
change
Mechanical cycle:
In case of a mechanical cycle the working substance is not re circulated. In an IC engine air and
fuel are burnt in the engine, converted into the products of combustion and are then exhausted
into the atmosphere. Hence this type of cycle is called mechanical cycle.
Thermodynamic Equilibrium:
The word equilibrium implies a state of balance. In an equilibrium state, there are no
unbalanced potentials within the system or driving forces. Thus, a system in equilibrium
experiences no changes when it is isolated from its surroundings.
There are many types of equilibrium. A system is not in thermodynamic equilibrium unless the
condition of all the relevant types of equilibrium are satisfied, which includes 1) Thermal
equilibrium 2) Mechanical equilibrium 3) Phase equilibrium and 4) Chemical equilibrium.
Thermal Equilibrium:
If the temperature is the same throughout the entire system .i.e the system involves no
temperature differential which is the driving force or heat flow then we say system is in
thermal equilibrium.
Mechanical equilibrium:
It is related to pressure, velocity. A system is in mechanical equilibrium if there is no change in
pressure, velocity, specific volume at any point of the system with respect to time. However the
pressure may vary within the system with elevation as well as resultant of gravitational effects.
However there should not be any imbalance of forces. Then we say the system is in mechanical
equilibrium
Phase equilibrium:
If a system involves two phases it is in phase equilibrium when the mass of each phase reaches
equilibrium level and stays there.
Chemical equilibrium:
If the systems chemical composition does not change with time, i.e., no chemical reaction occur
then we say the system is in chemical equilibrium.
Thus if all thermal, mechanical, phase and chemical equilibrium exist for a system then we say
the system exist in thermodynamic equilibrium

Diathermic wall:
A wall which is impermeable to the flow of heat is an adiabatic wall, where as a wall which
permits the flow of heat is a diathermic wall. Thus heat flow takes place through this wall.
Zeroth law of Thermodynamics:

It states that when two bodies have equality of temperature with the third body, they in turn
have equality of temperature with each other.
When a body A is in thermal equilibrium with body B and also separately with body C then B
and C will be in thermal equilibrium with each other.
Equality of temperature – Zeroth law of Thermodynamics.
Temperature scales:
Two scales are commonly used for measurement of temperature namely, Fahrenheit after
Gabriel Fahrenheit (1686-1736) and Celsius. The Celsius scale was formerly called the
centigrade scale but is now designated the Celsius scale after Anders Celsius (1701-1744), the
Swedish astronomer who devised this scale.
In SI units of temperature scale we use absolute temperature scale or absolute scale of

temperature which comes from second law of thermodynamics and its unit is Kelvin.

Table: Thermometers and Thermometric Properties
Thermometric
Thermometer Symbol
property
Constant volume gas thermometer
Pressure P
Constant pressure gas thermometer
Volume V
Electrical Resistance thermometer
Resistance R
Thermocouple
Thermal e.m.f. e
Mercury in glass thermometer Length L
The absolute scale is related the Celsius scale is the Kelvin scale after William Thompson,
1824-1907, who is also known as Lord Kelvin and is designated K. The relation is K= oC +
273.15
In 1967 the CGPM defined the Kelvin as 1/273.16 of the temperature at the triple point of
water.
In order to obtain a quantitative measure of temperature a reference body is used, and a

certain physical characteristic of this body which changes with temperature is selected. The
changes in the selected characteristic may be taken as an indication of change in temperature.
The selected characteristic is called the thermometric property and the reference body which
is used in the determination of temperature is called the thermometer.
A Very common thermometer consists of a small amount of Mercury in an evacuated capillary

tube. In this case the extension of the mercury in the tube is used as the thermometric
property.
A common Mercury thermometer Mercury-in-glass thermometer

Presently temperature of triple point of water which is an easily reproducible state is now the
standard fixed point of thermometry.

International practical temperature scale: an international temperature scale was adopted at

the seventh general conference on weights and measures held in 1927. It was not to replace
the Celsius or ideal gas scales, but to provide a scale that could be easily and rapidly used to
calibrate scientific and industrial instruments.
International practical scale agrees with Celsius scale at the defining fixed points listed
in following table.
Table: Temperature of Fixed Points

Temperature in 0C
Normal boiling point of oxygen -182.97
Triple point of water (standard) +0.01
Normal boiling point of water 100.0
Normal boiling point of sulphur 444.60
Normal melting point antimony 630.50
Normal melting point of silver 960.80
Normal melting point of gold 1063.0
Numerical Examples with Solutions:
1) A tank contains mixture of 20kg of nitrogen and 20 kg of carbon monoxide. The total tank
volume is 20m3. Determine the density and specific volume of the mixture.
Solution:
Total mass of the mixture: 20 kg N2 + 20 kg CO = 40 kg mixture
Specific volume = volume / mass = 20 m3 / 40kg = 0.5 m3/kg
Density of mixture = mass / volume = 1/sp. vol = 1/ 0.5 = 2 kg / m3. Ans.
2) An automobile has a 1200 kg mass and is accelerated to 7m/s2. Determine the force
required to perform this acceleration.
Solution:
Force required F = m * a = 1200 * 7 =8400 kg m /s2 = 8400 N. Ans.

3) The emf in a thermocouple with the test junction at t0C on gas thermometer scale and
reference junction at ice point is given by e = 0.20 t – 5 * 10-4 t2 m V. the milli voltmeter is
calibrated at ice and steam points. What will this thermometer read in a place where gas
thermometer reads 500C?
Solution:
At ice point, when t = 0oC, e= 0 mV.
At steam point, when t=100oC, e= 0.20 * 100 – 5* 10-4 * (100)2 = 15 mV
At t = 50oC, e = 0.20 * 50 – 5* 10-4 * (50)2 = 15 mV = 8.75 mV
When the gas thermometer reads 50oC, the thermocouple will read
t = 100/15 * 8.75 or 58.33 oC. Ans.
4) A barometer to measure absolute pressure shows a mercury column height of 725mm. The
temperature is such that the density of the mercury is 13550 kg/m3. Find the ambient
pressure.
Solution:
Ambient pressure = ρ * g * h = 13550 * 9.81* 725 / 1000 = 96371Pa
or P = 0.9637 bar. Ans.
5) The temperature t on a Celsius thermometric scale is defined in terms of a property p by the

relation p = e(t-B)/A, where A and B are constants. Experiment gives values of p of 1.86 and
6.81 at the ice and steam point respectively. Obtain relation for t and also find the temperature
t for the reading of p = 2.5
Solution:
At ice point, t = 0oC, p= 1.86 Hence 1.86 = e(0-B)/A
1.86 = e –B/A or eB/A = 1/1.86 and ln eB/A = ln 1/1.86
B/A = - 0.62058 --------------- (1)
At steam point, t=100oC, p= 6.81 6.81 = e(100-B)/A

ln 6.81 = (100 - B) /A = 1.9184
1.9184 A + B =100--------------------------(2)
Solving equations (1) and (2)

A = 77.05 and B = -47.81 hence p = e [t – (-47.81) ] / 77.05

The temperature at p=2.5, 2.5 = e (t+47.81)/77.05

ln 2.5 =( t + 47.81) / 77.05 or t + 47.81 = 0.9163 77.05
or t = 22.79 0C Ans.
6) A hiker is carrying a barometer that measures 101.3 kPa at the base of the mountain. The
barometer reads 85 kPa at the top of the mountain. The average air density is 1.21kg/m 3.
Determine the height of the mountain.
Solution:
Pressure at the base of the mountain = ρ1 * g * h1.
h1= p / (ρ1 * g ) = 101.3 *1000 / (9.81 * 1.21) = 8534 m.
Also at the top of the mountain p = ρ2 * g * h2.

h2 = p / (ρ2 * g ) = 85 *1000 / (9.81 * 1.21) = 7161 m.
Hence the height of the mountain = h1- h2 = 8534 – 7161= 1373 m. Ans.
7) A lunar excursion module (LEM) weighs 1500 kgf at sea level; on earth. What will be its
weight on the surface of the moon, where g =1.7 m/s2? On the surface of the moon, what will
be the force in kgf required to accelerate the module at 10m/s2?
Solution:
The mass m of the LEM is given by W = mg/g0
1500 kgf = m * { (9.806 m/s2 ) / ( 9.806 kg/ kgf * m/s2 )}
i.e. m=1500 kg
The weight of the LEM on the moon would be
W = 1500 kg * {(1.7 m / s2) / (9.806 kg / kgf * m/s2 ) } Ans.
The force required to accelerate the module at 10 m/s2
= [ 1500 kg / (9.806 kg/kgf * m/s2) ] * 10 m/s2 = 1530 kgf Ans.
8) A cannon ball of 5 kg acts on a piston in a cylinder of 0.15m diameter. As the gunpowder is

burnt, a pressure of 7 MPa is created in the gas behind the ball. What is the acceleration of the
ball if the cylinder is pointing horizontally?
Solution:
Mass of the cannon ball = 5 kg
Diameter of the cylinder = 0.15 m
Force = Area * Pressure = (π / 4) * (0.15)2 *7* 106 = 123716.25 N Ans.
F = m*a Hence a = F /m = 123716.25 / 5 = 24743.25 m / s2 Ans.

Module 2
WORK & HEAT
Mechanics definition of work: Work is done when the point of application of a force moves in the
direction of the force. The amount of work is equal to the product of the force and the distance
through which the point of application moves in the direction of the force. i.e., work is identified
only when a force moves its point of application through an observable distance.
Mathematically, W =  12 F.dx
However, when treating thermodynamics from a macroscopic point of view, it is advantageous to tie
in the definition work with the concepts of systems, properties and processes.
Thermodynamic definition of work: It is a kind of interaction that would occur at the system
boundaries. It can be positive or negative.
Definition of Positive work is said to be done by a system when the „sole effect‟ external to the
system could be reduced to the raising of a weight.
Comments: The word „sole effect‟ indicates that the raising of weight should be the only interaction
between the system and surroundings in order to say that there is work interaction between the
system and the surroundings. The phrase „external to the system‟ indicates that the work is a
boundary phenomenon. The magnitude of work interaction depends upon the system boundary. This
is illustrated with an example.
Figure 1: Equivalence of Current Work Interaction between the System and the Surroundings

Figure 2: System Comprising of Battery, Switch & Resistance Coil
For the two systems shown in figure, system (1) comprising battery alone has work interaction with
the surroundings, whereas for system (2) which includes motor, weights etc along with the battery,
the work interaction is zero.
The word „could be reduced to‟ indicates that it is not necessary that weights should actually be
raised in order to say that there is work interaction between the system and the surroundings. It is
just sufficient to have an effect which is equivalent to the raising of weight.
Here an electrical storage battery constitutes system 1 whose terminals are connected to an electrical
resistance coil through a switch. The circuit external to the battery constitutes the surroundings.
When the switch is closed, the current flow through the coil, and the resistance (surroundings)
become warmer and the charge of the battery (system) decreases. Obviously there has been
interaction between the system and the surroundings. According to mechanics this interaction cannot
be classified as work because their has been no action of force through a distance or of torque
through an angle. However, as per thermodynamics concepts, the battery (system) does work as the
electrical energy crosses the system boundary. Further, the electrical resistance can be replaced by an
ideal frictionless motor pulley arrangement which can wind a string and thereby raise suspended
weight. The sole effect, external to the system, is raising of a weight. As such interaction of battery
with resistance coil is a work.
Sign Conventions for work:
Work is said to be positive, if it is done by the system on the surroundings
System Positive work
Work is said to be negative, if it is done on the system by the surroundings
System Negative work
Therefore, Wsystem + Wsurroundings = Zero

The unit of work is N-m or Joule. The rate at which work is done by, or upon, the system is known
as power. The unit of power is J/s or watt.
Work is one of the forms in which a system and its surroundings can interact with each other. There
are various types of work transfer which can get involved between them.
Work done at the moving boundary of a system (Expression for displacement work)
dx
Consider a piston-cylinder arrangement which contains certain working fluid undergoing quasi-static
process.
Let p = Pressure exerted by the fluid on the piston

A = Area of c/s of the cylinder
dx = displacement of the piston when the system has undergone an infinitesimal change
of state.
 Displacement work: dw = Force x displacement
= p.A x dx
i.e., dw = p.dV
Where dv is the infinitesimal change in volume of the system. If the system undergoes a finite
change of state from state (1) to state (2). Then the displacement work is given by
12 dw  12 p.dV
The integration of above equation can be done only if the relationship between P and v during the
process is known i.e., if the path of the process is well defined. Hence, work is a path function. As
work depends on the path of the process which it follows, there will be different values of work for
different process between two given states. Hence the differentials of the path functions are in exact
differentials. The symbol δ will be used to designate inexact differentials. The magnitude of the
work transfer by the system during the process from state (1) to state (2) containing unit mass of the
fluid will be written as,  12 w1W2 or W1-2.
The process can be represented by a full line on an appropriate thermodynamic coordinate system (in
this case p-V diagram) and the area under the curve gives the work done by the system during the
process. p
1
A
B
Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. C Page 27
p2 2
1 Quasi-Static
Process
p
2
dV
Quasi-Static pdV work Work-a path function
Inspection of the pV diagram above shows that just by specifying the end states 1 and 2 does not
determine the area (or work); the nature of the curve needs to be known. The curve may be arched
upwards or it may sag downwards, and the area under the curve will vary accordingly. For the same
initial and final states, the work done by the system in following the paths A, B and C are different.
Therefore the work is a path function and not a point function. Accordingly the work transfer across
the system boundaries is not classified as a thermodynamic property.
The expression w = pdV holds good under the following restrictions

i) The system is closed
ii) There is no friction within the system
iii) The pressure and all other properties are the same on all the boundaries of the system
iv) The system is not influenced by motion, gravity, capillarity, electricity and magnetism
Expression for Displacement work for various Quasi-Static Processes (pdV work):
1. Constant volume process: (Isochoric Process).

For a constant volume process i.e., V = constant (dV = 0 ) as represented in the p-V diagram
below.
1
p p1
p2 2
W1-2 =  12 p.dV but dV = 0
 (Wd) 1-2 = 0

2. Constant pressure process: (Isobaric process).

For a closed system undergo a constant pressure process from state 1 (volume V1 and pressure
p1) to a final state 2 (volume V2). The process is represented in the p-V diagram as shown below.
p1 = p2 1 2
P
W1-2
V1 V2
W1-2 =  12 p.dV, where pV = constant

 W1-2 = p  12 dV = p (V2 – V1)
 (Wd) 1-2 = p (V2 – V1)
3. Hyperbolic process i.e., pV = constant:
The hyperbolic expansion process from state 1 to state 2 is represented on a p-V diagram as
shown below.
Process in which pV = Constant

W1-2 =  12 p.dV
p1V1
But pV = constant i.e., pV = p1V1, p
V
W1-2 =  12 p.dV

p1V1 dV
  12 .dV  p1V1  12
V V
= p1 V1 [ln V2 – ln V1] where p1 = Initial pressure of the system

V1 = Initial volume of the system
p2 = Final pressure of the system
V2 = Final volume of the system
V2
i.e., (Wd) 1-2 = p1V1 ln
V1
4. Polytropic process, i.e., pVn = constant

A polytropic process is represented on a p-V diagram as shown below.
Figure: Process in which pVn = Constant

W1-2 =  12 p.dV
p1V1n
But pVn = constant i.e., pV n  p1V1n  p2V2n p
Vn
p1V1n
W1-2 =  12 .dV
Vn
= p1 V1n  12 V-n .dV
2
 V  n 1 
= p1 V1 n
  = 
p1V1n 1n
V2  V11n 
  n  1 1 1 n
p1V1n .v12n  p1V1
= but p1V1n = p2V2n
1 n

p 2V2  p1V1
=
1 n
p1V1  p 2V2
(Wd) 1-2 =
n 1
Where „n‟ is called the index of expansion or compression
Note: 1. Work is a transient phenomenon i.e., it is present only during a process. Mathematically
speaking, work is a path function.
  12 dw = w2 – w1 is wrong
= w1-2 i.e., w is inexact differentials.
2. For irreversible process w ≠  12 P.dv

Other Types of Work Transfer
1. Shaft Work:
Shaft work
Let Ft = Tangential force on the shaft

R = Radius of the shaft
d = Angular displacement of the shaft in an interval of time „dt‟
 Shaft work in time interval „dt‟, is dWs = Ft. AA1
= Ft. R.d
i.e., Ws =T.d
dWs d
 Work done / unit time =  T. = T.ω where ω = angular velocity, T = Torque
dt dt
2N
But ω = where N = rpm of the shaft
60

2NT
Shaft work, Ws = watts
60
2. Stirring Work: Stirring work is nothing but shaft work is done on the system by using a stirrer
which is driven by a shaft.
Figure3: Paddle-wheel work

As the weight is lowered, and the paddle wheel turns, there is work transfer into the system which
gets stirred. Since the volume of the system remains constant,  pdv = 0. If m is the mass of the
weight lowered through a distance dz and T is the torque transmitted by the shaft in rotating through
an angle d, the differential work transfer to the fluid is given by
w = mgdz = Td
and the total work transfer is w =  12 mgdz =  12 W1dz =  12 Td where W1 is the weight lowered
3. Electrical Work: When a current flows through a resistor, taken as system, there is work transfer
into the system. This is because the current can drive a motor, the motor can drive a pulley and the
pulley can raise a weight.
System boundary
I
I
The current I, flows is given by,
dC
I= where C = charge in coulombs
d
 = time in seconds
Thus dC is the charge crossing a system boundary during time d. If E is the voltage potential,
the work is w = E.dC
= EI d
 w =  12 EI d

dw
The electrical work is, w = lim = EI
δ 0 d
This is the rate at which work is transferred.
4. Work done in stretching a wire: Consider a wire as the system. If the length of the wire in which
there is a tension Ŧ is changed from L to L + dL, the infinitesimal amount of work that is done is
equal to, w = - Ŧ dL
The -ve sign is used because a positive value of dL means an expansion of the wire, for which
work must be done on the wire i.e., negative work.
For a finite change of length, w = -  12 Ŧ dL
Within the elastic limits, if E is the modulus of the elasticity,  is the stress, ε is the strain, and A
is the cross sectional area, then
Ŧ = A = E.ε.A
Therefore w = - E.ε.AdL
But dε = dL/L or dL = L x dε
 w = - Ŧ dL = - E.ε.A. L dε
i.e., w = -EAL  12 ε d ε
AL 2
=-
2
 2  12 
5. Work done in changing the area of a surface film: A film on the surface of a liquid has a
surface tension which is a property of the liquid and the surroundings. The surface tension acts to
make the surface area of the liquid a minimum. It has the unit of force per unit length.
The work done on a homogeneous liquid film in changing its surface area by an infinitesimal
amount dA is
w = - ζ dA when ζ = surface tension (N/m)
 w = -  12 ζ dA
6. Magnetization of a paramagnetic field: The work done per unit volume on a magnetic material
through which the magnetic and magnetization fields are uniform is,
w = - H.dI
i.e., w = -  12 H.dI
Where H = field strength
I = Component of the magnetization field in the direction of the field.
-ve sign provides that an increase in magnetization (+ve dI) involves -ve work.

Note: It may be noted in the above expressions that the work is equal to the integral of the product of
an intensive property and the change in its related extensive property. These expressions are valid
only for infinitesimally slow quasi-static process.
Network Transfer: The network interaction between the system and the surroundings for any
process will be the algebraic sum of all types of work interaction that has taken place between the
system and the surroundings.
Therefore if W1-2 represents the net work transfer then,

W1-2 = (Wd)1-2 ± (Ws)1-2 ± (We)1-2 ± (Wmag)1-2 ± ......
+ve sign has to be used when the work transfer takes place from the system to the surroundings and
–ve sign to be used when work transfer is from the surroundings to the system.
Heat: Heat is a mode of energy transfer that takes place between the system and the surroundings
solely due to the temperature difference. Thus, heat is a transient phenomenon. It can be recognized
only during a process. It is not a thermodynamic property of the system. Like work, heat is a path
function i.e., the magnitude of heat transfer between the system and surroundings depends upon the
type of process the system is undergoing.
Heat transfer always takes place from a region of higher temperature to a region of low temperature.
The magnitude of the heat transfer into unit mass of the fluid in the system during a process from
state (1) to state (2) will be written as 12 q1 q2 or q12 and not as 12 q  q1  q2
 12 q represents the total heat transfer that takes place when the system undergoes a change of state
from state 1 to state 2.
+ve System -ve

Sign Convention: System
Heat transfer is considered as positive if it takes place from the surroundings to the system and it is
considered as negative if it takes place from the system to the surroundings.
During an adiabatic process, Q = 0
Units: Since heat is a form of energy transfer it will have the same units as that of energy. In SI units
it is expressed in Joules (J) or Kilo Joules (kJ).
Comparison between work and heat:
Similarities:
 Both are path functions and inexact differentials.

 Both are boundary phenomenon i.e., both are recognized at the boundaries of the system as they
cross them.
 Both represent transient phenomenon; these energy interactions occur only when a system
undergoes change of state i.e., both are associated with a process, not a state. Unlike properties,
work or heat has no meaning at a state.
 A system possesses energy, but not work or heat.
 Concepts of heat and work are associated not with a „store‟ but with a „process‟.
Dissimilarities:
 Heat is energy interaction due to temperature difference only; work is by reasons other than
temperature difference.
 In a stable system, there cannot be work transfer; however there is no restriction for the transfer
of heat.
 The sole effect external to the system could be reduced to rise of a weight but in the case of a
heat transfer other effects are also observed.
 Heat is a low grade energy whereas work is a high grade energy.
Problems:
1. Evaluate the work done in the following processes. The systems to be considered are underlined.
a) An agent slowly raises a body of mass 2 kg a distance of 3 mts in a gravitational field of

standard acceleration.
Solution: By definition, considering agent as the system, it does positive work. The magnitude of
work is measured by the product of the weight its lifts and the distance through which it is lifted.
W = + mg .l = 2 x 9.81 x 3 = + 58.86 J
Work done by the agent = + 58.86 J
Because, work is done by the agent, work is done on the body to the same amount.
 Work done on the body = 58.86 J
or Work done by the body = - 58.86 J
b) A mass of 1 tonne is suspended from a pulley block. An agent slowly raises the mass against
the standard gravitational acceleration by 2m.
Solution: By definition, considering agent as the system, it does positive work.

W = + mg .l = 1000 x9.81 x2 = 19620 J = 19.62 kJ
 Work done by the agent = 19.62 kJ

Because, work is done by the agent, work is done on the mass to the same amount.
Work done on the mass = 19.62 kJ
or Work done by the mass = - 19.62 kJ
c) After raising the mass as in (b), the mass falls freely through the same vertical distance of 2
m. The drag force of the atmosphere on the body is 50 N.
Actual Surroundings Fictitious Surroundings
+ +
Zero 50 N
mass
1 tonne 1 tonne
50 N No drag
Force
Solution: Considering mass as a system (w r t. fictitious surroundings)

W = F x l = 50 x 30 = 1500 J = 1.5 kJ
Work done by the mass = 1.5 kJ
Work done by the atmosphere = - 1.5 kJ
Or Work done on the atmosphere = 1.5 kJ
d) A body of mass 15 kg falls freely in a vacuum through a vertical distance of 30m. The
gravitational acceleration is 6 m/s2.
e)
Solution: Considering body as a system, as it is falling freely there is no interaction with the system
boundary and hence work done by the body is zero. (In other words, the work done by the body is
zero as it can lift no weight. All that is happening as the body is falling freely is that its PE is
decreasing and its KE is increasing accordingly).
f) A rat weighing 5.0 N climbs a stair 0.2 m in height.

Solution: Wrat = 0 (since there is no interaction between the system and its surroundings).
2. Indicate in the following cases, the heat exchange and work exchange are positive, negative or
zero, and why
a) A copper block of 1 kg heated to 1000 C is dipped into water at 150 C. Consider copper as
system.

Ans: δW = 0, δQ is negative
b) Heat is added to a gas in a rigid container such that pressure and temperature increases.
Consider gas as system,
Ans: δW = 0, δQ is positive.
c) Gas from a bottle is used to inflate a balloon which is originally flat. Consider gas as system.
Ans: δW is Positive, δQ = 0
d) An insulated wire is stretched. Consider wire as a system.

Ans: δW is negative, δQ = 0
e) A mouse climbs 20 steps of a stair case. Consider mouse as the system.

Ans: δQ = δW = 0
f) Gas in an insulated cylinder expands as the piston is slowly moved outwards.

Ans: δQ = 0, δW is positive
g) A closed rigid vessel containing steam at a temperature of 2000C is left standing in an

atmosphere which is at 200C. Consider steam as the system.
Ans: For a closed rigid vessel, there is no change in volume and accordingly work done is zero.
i.e., δW = 0. Since the steam is at a temperature higher than that of the surrounding atmosphere,
the heat is rejected to the atmosphere. i.e., heat interaction is negative or δQ is negative.
h) The air in a tyre and connecting pump the pump plunger is pushed down, forcing air into the
tyre. The tyre, pump walls and connecting tube can be thought of to be non-conducting.
Consider air as a system.
Ans: δW is negative and δQ = 0
i) An electric current flows steadily through a resistor which is immersed in running water.
Ans: Considering resistor as system, current flows through the resistance i.e., electrical work is done
on the system δWe is negative
Due to the flow of current the resistor gets heated up resulting in heat transfer to the surrounding
cold water from the resistor.
δQ is negative (heat transfer from the system)
j) A container with rigid non-conducting walls holds a complete electrical circuit consisting of
a heating element and charged storage battery. The temperature and pressure of the air in the
container increases.
Ans: No interaction taking place across the boundary. The system boundary does not move as the
walls are rigid. δW = 0
The walls are non-conducting  though the temperature inside the system increase, no heat
transfer to the surroundings can take place  δQ = 0

k) 0.1 kg of gas contained in an insulated cylinder expands moving the piston slowly outwards
Ans: The cylinder is insulated  No. heat transfer is possible  δQ = 0
The gas expands the system boundary expands  δWd is positive
Problems:
3. Gas from a bottle of compressed helium is used to inflate a balloon originally folded completely
flat, to a volume of 0.25 m3. If the barometer reads 760 mm of mercury, how much work is done
by the system comprising the helium initially in the bottle, if the balloon is light and requires no
stretching. Sketch the system before and after the process.
Solution:
The firm line S1 shows the boundary of the system before the process, and the dotted line S2 shows
the boundary after the process.
Total displacement work is given by

(Wd)1-2 = (Wd)bottle portion of the system + (Wd)Balloon portion of the system
Since there is no displacement of the bottle portion of the system boundary, it follows that (Wd)bottle
=0
= 0 + (Wd)Balloon
The balloon is expanding against a constant atmosphere pressure of 760 mm of mercury,

i.e., p = wh
= 9810 (13.6) 0.76 = 1.01396 x 105 N/m2 = 101.396 kPa
(Wd)balloon =  pdV = p  12 dV
= p (V2 – V1)
= 101.396 (0.25 – 0)
= 25.349 kJ
4. Determine the work done by the air which enters an evacuated bottle from the atmosphere when
the cork is opened, atmospheric air rushes into it. If the atmospheric pressure is 101.396 kPa and
0.6m3 of air (measured at atmosphere conditions) enters the bottle.

Solution:
No work is done by the part of the boundary in contact with the bottle. Work is done only by the
moving part external to the bottle. The pressure over this moving part is uniform at 101.396 kPa
 Displacement work done by the system,
Wd = (Wd)bottle + (Wd)atmosphere
= 0 +  12 p.dV
= p (V2 – V1) = 101.396 (0 – 0.6)
= - 60.8 kJ
Negative, because the boundary is contracting. Thus the surroundings do positive work at the
boundary and the work done by the air negative
5. A spherical balloon has a diameter of 25 cm and contains air at a pressure of 1.5 x 10 5Pa. The
diameter of the balloon increases to 30 cm in a certain process and during this process the
pressure is proportional to the diameter. Calculate the work done by the air inside the balloon
during this process.
Solution:
State 1 (p1, D1)
D1
D2 State 2 (p2, D2)
D1 = 0.25 m, D2 = 0.3 m,
p α D,
p1 = 1.5 x 105 N/m2
We have W1-2 =  12 p.d V --- (1)
D 3
But, volume of sphere = V =
6


 dV = . 3D2.dD
6
p
Also, p α D i.e., = constant = K
D
p p p p
  1  2  p  1 .D
D D1 D2 D1
p1 
Equation (1) becomes, W1-2 =  12 .D. 3 D2. dD
D1 6
2
 p1  p1  D 4 
= ,  D =2
1
3
 
2 D1 2 D1  4  1
 p1  D24  D14 
= .  
2 D1  4 
 1.5 x105  0.34  0.254 

= .  
2 0.25  4 
W1-2 = 988.13 J
Positive sign indicates that work is done by the system.
6. Gas from a bottle of compressed helium is used to inflate an inelastic flexible balloon, originally
folded completely flat to a volume of 0.5 m3. If the barometer reads 760 mm of Hg, what is the
amount of work done upon the atmosphere by the balloon (50.66 kJ)
7. When the valve of the evacuated bottle is opened, atmosphere air rushes into it. If the atmosphere
pressure is 101.325 KPa, and 1.2 m3 of air (measured at atmosphere conditions) enters the bottle,
calculate the work done by the air (-60.8 kJ).
8. A gas system, confined by a piston and cylinder, undergoes a change of state such that the
product of pressure and volume remains constant. If the process begins at a pressure of 3 bar and
a volume 0.015m3 and proceeds until the pressure falls to half its initial value, determine the
magnitude and direction of the work flow.
Solution:
pV = C i.e., hyperbolic process or p1 V1 = p2 V2

Given, p1 = 3 x 105 Pa V1 = 0.015 m3 p2 = 1.5 x 105 m3
V2 = ? W1-2 = ?

p1V1 3x10 5 x0.015

We have, p1V1 = p2 V2  V2 = = 5
= 0.03 m3
p2 1.5 x10
V2
Displacement work, (Wd)1-2 =  12 p.dV = p1V1 ln
V1
= 3119.16 J = 3.1192 kJ
Positive sign indicates work is done by the system on the surroundings.
9. A certain amount of gas is compressed from 1 bar and 0.1m3 to 5 bar and 0.03m3. The process is
according to the law pVn = K. Determine the magnitude and direction of work.
Solution: Given: p1 = 1 bar; V1 = 0.1 m3; p2 = 5 bar; V2 = 0.03
We have for a polytropic process,
p V  p 2V2
Displacement work, = (Wd)1-2 = 1 1
n 1
To find the compression index n, we have,
p1V1n  p2V2n  C
n
p V 
i.e., 1   2 
p 2  V1 
Taking log‟s on both sides we have
p V
ln 1  n. ln 2
p2 V1
1
ln
n  5  1.34
0.03
ln
0.1
1x10 5 0.1  5 x10 5 0.03

(Wd)1-2 = = - 14706 J = - 14.706 kJ
1.34  1
i.e., work done on the gas = 14.706 kJ
10. A gas confined in a cylinder by a piston is at pressure of 3 bar and a volume of 0.015 m3. The
final pressure is 1.5 bar. Determine the magnitude and direction of work transfer for the
1 1
following processes. i) p α V, ii) p α , iii) p α V2 and iv) p α 2
V V
5 3 5
Solution: Given: p1 = 3 x 10 Pa; V1 = 0.015 m ; p2 = 1.5 x 10 Pa V2 = ? (Wd) = ?
p p p
i) p α V i.e.,  1  C  2
V V1 V2

We have, (Wd)1-2 =  12 p.dV

p1V p 2
=  12 .dV  1  1 V.dV
V1 V1
=
p1 2
2V1

V2  V12 
p1 p 2 V1 1.5
we have  V2 = p2  0.015 = 0.0075 m3
V1 V2 p1 3
3x105
 (Wd)1-2 = [0.00752 – 0.015]2 = - 1.688 kJ
20.015
-ve sign indicates that work is done on the system
1
ii) p α i.e., pV = C
V
Ans: (Wd)1-2 = 3.1192 kJ
p1 p p p 2  V12
iii) p α V2 i.e., 2
 22  C  2 V2 = = 0.0106 m3
V1 V2 V p1
(Wd)1-2 =  12 p.dV
p1 2
=  12 V .dV
V12
p1 2 2
=  1 V .dV
V12

p1 3
3V12

V2  V13 
=
3x105

0.01063  0.0153 = -0.9707 kJ 
30.015
2
-ve sign indicates that work is done on the system
1
iv) p α i.e., pV2 = C = p1V12 = p2V22
V2
p1V12 3x0.015 2
V2 =  = 0.0212 m3
p2 1.5
p1V12 1
We have (Wd)1-2 =  12 p.dV =  12 .dV = p1V12  12 .dV
V2 V2

= p1V12  2  1V 1 
2
1
2
 1
= p1V12  
 V 1

 1 1
= p1V12    
 V2 V1 
1 1
= p1V12   
 V1 V2 
Substituting the given values, we get (Wd)1-2 = 1.316 kJ
+ve sign indicates that work is done by the system
11. A non-flow reversible process occurs for which p = 3V2 + 1/V where p is in N/cm2 and V is in
m3. What is the work done when V changes from 0.5 m2 to 1 m3.
Solution: We have (Wd)1-2 =  12 p.dV
 1
= 104  12  3V 2  dV
 V
=  12 3 V2 dV +  12 dV/V
3 V 
 
= 104  V23  V13  ln 2 
3 V1 

 
= 104  12  0.53  ln
1 

 0.5 
= 1.568 x 104J = 15.86 kJ
12. A system consists of a cylinder and piston machine. The external normal load applied to the
piston is given by F = - 7000 + 15000L Newton‟s, where L is the distance in mts from the closed
and of the cylinder to the piston. How much work is done when the piston moves from the
position L = 1m to L = 1.5 m. Sketch the p-V diagram for this process and show the work done.
Solution: Given: F = - 7000 + 15000 L
We have Work done = (Wd)1-2 =  pdV
=  12 p.A.dL
= A  12 p.dL
F  7000  15000 L
But p = 
A A
  7000  15000 L 
(Wd)1-2 = A  12   . DL
 A 
=  LL12 (-7000 + 15000L). dL
= - 7000 (L2 – L1) + 15000/2 (L22 – L12)
= - 7000 (0.5) + 15000/2 (1.25)
= - 3500 + 9375
= 5875 J = 5.875 kJ

Sketching of p-V diagram:
F 8000 9500 11000 12500 14000 15500
L 1 1.1 1.2 1.3 1.4 1.5
20000
15000
p= F/A
10000
5000
0
1 1.2 1.4
V= A x L
13. An insulated system contains a mixture of ice and water. A paddle wheel is rotated in the system
at 100rpm. Torque applied to the shaft is 3 N-m. In order to effect the transformation of 1 kg of
ice to liquid water 300 kJ of heat must be transferred to the system. Determine the length of time
the paddle wheel must be rotated in order to achieve 2.5 kg reduction in the quantity of ice.
Solution: Given: T = 3 N-m ; N = 1000 rpm
2NT
Paddle work (done on the system), Ws =
60
2 (1000)3
= = 314 N-m/s = 314 J/s
60
In order to have a reduction of 2.5 kg of ice into water, the paddle work required is
300 (2.5) = 750 kJ
Length of time for which the paddle wheel should be operated, is
750 x103
= 2388.5 sec i.e., 39.8 minutes
314
14. A system containing 5 kg of a substance is stirred with a torque of 1 N-m at a speed of 500 rpm
for 24 hrs. The system mean while expands from 1.5m3 to 2.0m3 against a constant pressure of 5
bar. Determine the magnitude and direction of net work transfer.
Solution: The system is associated with two interactions with the surroundings i.e., stirring work
(surroundings to the system) and displacement work
i.e., W1-2 = Wst(1-2) + (Wd)1-2
Stirring work, Wst = 2 NT / 60
2 5001
= = 52.359 n-m/sec
60
Wst = 52.359 x 24 x 60 x 60
= 4523893 J = 4523.893 kJ
This is a negative work, as the work is done on the system by the surroundings
Displacement work, (Wd)1-2 =  12 pdV
= p (V2 – V1)
= 5 x 105 (2 - 1.5)

= 250000 J = 250 kJ
Net work transfer W1-2 = - 4523.893 + 250
= - 4273.89 kJ
Negative indicated that net work transfer takes place from the surroundings to the system.
15. A mass of 1.5 kg of a substance is compressed in a quasi-static process from 0.1 MPa to 0.7
MPa. The initial pressure density of the substance is 1.16 kg/m3. Determine the magnitude of
work done on the substance if i) process is pV = C and pV1-4 = C
Solution: Given: m = 1.5 kg p1 = 0.1 x 106 Pa p2 0.7 x 106 MPa 1 = 1.16 kg/m3
Since  = 1.16 kg/m3 and m = 1.5 kg, volume V1 = m/ = 1.293 m3
Case i) pV = C
pV 0.1
i.e., pV = p1V1 = p2V2 or V2  1 1  x1.293  0.185m 3
p2 0.7
We have (Wd)1-2 =  12 p.dV
p1V1
=  12 .dV
V
V2
i.e., (Wd)1-2 = p1V1 ln
V1
0.185
= 0.1 x 106 x 1.293 ln
1.293
= - 251595 J = - 251.595 kJ
Negative sign indicates that work is done on the system
Case ii) pV1-4 = C

1 / 1.4
 p1V11.4 
p1V11-4
i.e., = p2V2 = V2 = 
1-4
 = 0.322 m
3
 p2 
p V  p 2V2
We have, adiabatic process (Wd)1-2 = 1 1
 1
0.1x106 1.293  0.7 x106 (0.322)
=
0.4
= - 240381 J = - 240.381 kJ
16. O2 is compressed in a quasi static process according to the relation pV1-2 = C. The initial
conditions are 98 KPa and 200 C and the final pressure is 1000 KPa. Assuming an ideal gas
behaviour, determine the work required to compress 100 kg of O2. Compare this work with the
work of isothermal compression, i.e., pV = C.
Solution: p1 =98 x 103 Pa, T1 = 2930 K, p2 = 1000 x 103Pa, m = 100 kg
We have for polytropic process,

p1V1  p 2V2
(Wd)1-2 =
n 1
mR(T1  T2 )

n 1
R 8.3143
But gas constant, R   = 0.2598 kJ
M 32
Also for polytropic process we have
n 1 / n 0.2
T2  p 2   1000  1.2
  T2 = 293   = 431.52 K
0
T1  p1   98 
100(0.259)(293  431.52)
 (Wd)1-2 =
0.2
= -17938.34 kJ
Case ii) for isothermal process, we have

V
(Wd)1-2 = p1V1 ln 2
V1
Considering oxygen to be a perfect gas, we have pV = mRT
p
(Wd)1-2 = mRT1 ln 1 since, pV = C = p1V1 = p2V2 i.e., V2/V1 = p1/p2
p2
= -17626.94 kJ
17. The following data refer to a12 Cylinder, single-acting, two-stroke marine Diesel engine:
Cylinder diameter-0.8m
Stroke of piston-1.2m
Area of indicator diagram-5.5E10-4 m2
Length of diagram-0.06m
Spring value-147 MPa per m
Find the net rate of work transfer from the gas to the piston in kW.
Solution: Mean effective pressure, Pm, is given by
a
Pm  d *spring constant
ld
5.5  10 4 m 2 MPa
  147
0.06 m
=1.35 MPa
One engine cycle is completed in two strokes of the piston or one revolution of the crank shaft.
Work done in one minute= Pm LAN


 1.35  1.2  (0.8) 2  150
4
=122 MJ
Since the engine is single-acting, and it has 12 cylinders, each contributing an equal power, the rate
of work transfer from the gas to the piston is given by
W=12212 MJ/min
=24.4 MJ/s
=24.4 MW = 24,400 kW
18. A gas system has mass m, occupies a volume V at a pressure of p and temperature T. These
 a 
properties are related by the equation  p  2 V  b  mRT where a, b and R are constants.
 V 
Obtain an expression for the displacement work done by this gas system during a constant
temperature process where the gas expands from 1 m3 to 10 m3 at a temperature of 293 K.
Assume a = 15.7 x 104 Nm4, b = 1.07 x 10-2 and R = 0.278kJ/kg-K.
 a 
Solution: For a given gas,  p  2 V  b  mRT
 V 
 mRT a 
Solving for p we get, p    2
 V  b  V 
Displacement work = (Wd)1-2 = pdv
V2
 mRT a   V  b   1 1 
   2  dv  mRT ln  2   a  
V1 
V  b V  
 1V  b    V2 V1 
On substituting the values we get, (Wd)1-2 = 1744.8 x 103J = 1744.8 kJ
FIRST LAW OF THERMODYNAMICS
First Law of Thermodynamics: Joule‟s Experiments, Equivalence of heat work. Statement of the 1 st
law of thermodynamics, extension of the 1st law to non cyclic processes, energy, energy as a
property, modes of energy, pure substance; Definition, two property rule, specific heat at constant
volume, enthalpy, specific heat at constant pressure. Extension of the 1st law to control volume;
Steady state-steady flow energy equation, important applications, analysis of unsteady processes
such as filling and evacuation of vessels with and without heat transfer.
The first law of thermodynamics is often called as the law of the conservation of energy, with
particular reference to heat energy and mechanical energy i.e., work.
First law of thermodynamics for a closed system undergoing a cyclic process

The transfer of heat and the performance of work may both cause the same effect in a system.
Energy which enters a system as heat may leave the system as work, or energy which enters the
system as work may leave as heat. Hence, by the law of conservation of energy, the net work done

by the system is equal to the net heat supplied to the system. The first law of thermodynamics can
therefore be stated as follows:
“When a system undergoes a thermodynamic cyclic process, then the net heat supplied to the system
from the surroundings is equal to the net work done by the system on its surrounding”.
i.e.,  Q =  W where  represents the sum for a complete cycle.
The first law of thermodynamics cannot be proved analytically, but experimental evidence has
repeatedly confirms its validity and since no phenomenon has been shown to contradict it, therefore
the first law is accepted as a „law of nature‟.
Joule’s Experiment:
Figure: Joule‟s Experiment Figure: Cycle completed by a system

with two energy interactions i.e.,
work transfer followed by heat
transfer
Figure shows the experiment for checking the first law of thermodynamics. The work input to the
paddle wheel is measured by the fall of weight, while the corresponding temperature rise of liquid in
the insulated container is measured by the thermometer.
The process 1-2 undergone by the system is shown in figure i.e., W1-2. Let the insulation be
removed. The system and the surrounding interact by heat transfer till the system returns to its
original temperature, attaining the condition of thermal equilibrium with the atmosphere. The
amount of heat transfer Q2-1 from the system during this process 2-1 is shown in figure. The system
thus executes a cycle, which consists of a definite amount of work input W1-2 to the system followed
by the transfer of an amount of heat Q2-1 from the system.
Joule carried out many such experiments with different type of work interactions in a variety of
systems, he found that the net work input the fluid system was always proportional to the net heat
transferred from the system regardless of work interaction. Based on this experimental evidence
Joule stated that,
“When a system (closed system) is undergoing a cyclic process, the net heat transfer to the system is
directly proportional to the net work done by the system”. This statement is referred to as the first
law for a closed system undergoing a cyclic process.

i.e.,  Q   W
If both heat transfer and work transfer are expressed in same units as in the S.I. units then the
constant of proportionality in the above equation will be unity and hence the mathematical form of
first law for a system undergoing a cyclic process can be written as
i.e.,  Q =  W
If the cycle involves many more heat and work quantities as shown in figure, the same result will be
found.
Figure: Cyclic Process on a Property Diagram
For this cyclic process the statement of first law can be written as
 Q   W
1 2 3 4 1 1 2 3 4 1
The cyclic integral in the above equation can be split into a series of non cyclic integral as
12 Q   32 Q   34 Q  14 Q  12 W   32 W   34 W  14 W
or 1Q2 + 2Q3 + 3Q4 + 4Q1 = 1W2 + 2W3 + 3W4 + 4W1

i.e.,  Q =  W
or (∑Q)cycle = (∑W)cycle
This is the first law for a closed system undergoing a cyclic process. i.e., it is stated as
“When a closed system is undergoing a cyclic process the algebraic sum of heat transfers is equal to
the algebraic sum of the work transfers”.
First law for a closed system undergoing a non-cyclic process (i.e., for a change of state):
If a system undergoes a change of state during which both heat transfer and work transfer are
involved, the net energy transfer will be stored or accumulated within the system.

If Q is the amount of heat transferred to the system and W is the amount of work transferred from
the system during the process as shown in figure,
W
System
Q
The net energy transfer (Q-W) will be stored in the system. Energy in storage is either heat or work
and is given the name internal energy or simply, the energy of the system.
Q-W = ∆E where ∆E is the increase in the energy of the system

or Q = ∆E + W
If there are more energy transfer quantities involved in the process as shown in figure.
Q3 Q2
Q1
W1 System
W2 W3 W4
First law gives
(Q2 + Q3 – Q1) = ∆E + (W2 + W3 – W1 – W4)
i.e., energy is thus conserved in the operation. Therefore the first law is a particular formulation of
the principle of the conservation of energy. It can be shown that the energy has a definite value at
every state of a system and is therefore, a property of a system.
Energy – A property of the system:
Figure: First law to a non cyclic process
Consider a system that undergoes a cycle, changing from state 1 to state 2 by process A and
returning from state 2 to state 1 by process B.
We have from 1st law of thermodynamics,  Q   W

For the process, 1-A-2-B-1,  Q   W

1 A 2  B 1 1 A 2  B 1
Considering the two separate processes, we have

 Q B 12 Q A 12 W  B 12 W
2
A 1 --- (1)
Now consider another cycle, the system changing from state 1 to state 2 by process A, as before and
returning to state 1 by process C. For this cycle we can write
 Q C  12 Q A 12 W  C 12 W

2
A 1 --- (2)
Subtracting (2) from (1), we get
 Q  C 12 Q  B 12 W  C 12 W

1
B 2
Or, by rearranging, B 12 Q  W  C  12 Q  W 
Since B and C represent arbitrary processes between state 1 to state 2, we conclude that the quantity
(Q - W) is the same for all processes between state 1 and state 2.  (Q - W) depends only on
the initial and final states and not on the path followed between the two states. This is a point
function and differential is a property of the system. This property is called the energy of the system,
E. Therefore, we can write
Q - W = dE
Or Q = dE + W
If it is integrated between initial and final states, 1 and 2, we get
Q1-2 = E2 – E1 + W1-2
i.e., Q1-2 - W1-2 = E2 – E1
The above equation is the statement of first law for a closed system undergoing a non cyclic process,
where Q1-2 represents the net heat transfer between the system and the surroundings during the
process, W1-2 represents net work transfer between the system and the surroundings during the
process and (E2 – E1) represents the change in the energy of the system during the process.
Classification of Energy of the System:
The energy E is an extensive property and the specific energy e = E/m (J/kg) is an intensive
property. Energy E represents the total energy of the system.
i.e., E = kinetic energy (KE) + Potential Energy (PE) + remaining forms of energy.
Since K.E and P.E are macroscopic quantities and can be measured very easily and so they are
considered separately in thermodynamics. The remaining energies (associated with the motion and
position of the molecules, energy associated with the structure of the atom, chemical energy etc),

which cannot be measured directly and is the summation of all microscopic energies is called
internal energy of the system.
Internal energy:
It is the energy associated with internal structure of matter. This energy cannot be determined in its
absolute values. But it is possible to determine the change in internal energy of the system
undergoing a process by first law of thermodynamics.
 Total energy E = KE + PE + IE
Since the terms comprising E are point functions, we can write
dE = d(KE) + d (PE) + dU
The first law of thermodynamics for a change of state of a system may therefore be written as
Q = dU + d (KE) + d (PE) + W
In words this equation states that as a system undergoes a change of state, energy may cross the
boundary as either heat or work, and each may be positive or negative. The net change in the energy
of the system will be exactly equal to the net energy that crosses the boundary of the system. The
energy of the system may change in any of three ways, namely, by a change in IE, KE or P.E
Sub. For KE and PE in the above equation
d (mV 2 )
Q = dU + + d (mgZ) + W
2
In the integral form this equation is, assuming „g‟ is a constant
Q1-2 = U2 – U1 +
 
m V22  V12
+ mg (Z2 – Z1) + W1-2
2
In most of the situations the changes in KE and PE are very small, when compared with the changes
in internal energies. Thus KE and PE changes can be neglected.
Q = dU + W
or Q1-2 = U2 – U1 + W1-2
Law of conservation of energy (2nd corollary of first law of thermodynamics)
From first law of thermodynamics Q1-2 = E2 – E1 + W1-2
This equation in effect, a statement of the conservation of energy. The net change of the energy of
the system is always equal to the net transfer of energy across the system boundary as heat and work.
For an isolated system, Q = 0, W = 0 E2 – E1 = 0
For an isolated system, the energy of the system remains constant.

Therefore, the first law of thermodynamics. may also be stated as follows, “Heat and work are
mutually convertible but since energy can neither be created nor destroyed, the total energy
associated with an energy conversion remains constant”.
Perpetual Machine of first kind (3rd Corollary):

Any system which violates the first law of thermodynamics is called the Perpetual Motion machine
of first kind. i.e., “It is impossible to construct a perpetual motion machine of first kind”. A perpetual
machine is one which can do continuous work without receiving energy from other systems or
surroundings. It will create energy on its own and thus violates first law. But from our experience we
also know that it is impossible to construct such a machine, as frictional resistance would not allow it
to run for an indefinite period.
The Pure Substance

The system encountered in thermodynamics is often quite less complex and consists of fluids that
don not change chemically, or exhibit significant electrical, magnetic or capillary effects. These
relatively simple systems are given the generic name the Pure Substance.
Definition
A system is set to be a pure substance if it is (i) homogeneous in chemical composition, (ii)
homogeneous in chemical aggregation and (iii) invariable in chemical aggregation.
Homogeneous in chemical composition means that the composition of each part of the system is
same as the composition of any other part. Homogeneous in chemical aggregation implies that the
chemical elements must be chemically combined in the same way in all parts of the system.
Invariable in chemical aggregation means that the chemical aggregation should not vary with respect
to time.
Steam H2 + ½ O2 H2 + O2
(Gas) (Gas)
Water Water Water

(i) (ii) (iii)
(i) (ii) (iii)

Water
Satisfies condition (i)

Water Satisfies condition (i) Does not satisfies condition (i)
Satisfies condition (ii) Water condition (ii) Satisfies condition (iii)
Does not satisfies
Figure Illustration of the definition of pure substance
In figure three systems are shown. The system (i) shown in the figure is a mixture of steam and
water. It is homogeneous in chemical composition because in every part of the system we have, for

every atom of oxygen we have two atoms of hydrogen, whether the sample is taken from steam or
water. The same is through for system (ii) consisting of water and uncombined mixture of hydrogen
and oxygen. System (iii) however is not homogeneous in chemical composition because in the upper
part of the system hydrogen and oxygen are present in the ratio 1:1 where as in the bottom portion
they are present in the ratio 2:1.
System (i) also satisfies condition (ii), because both hydrogen and oxygen have combined
chemically in every part of the system. System (ii) on the other hand does not satisfies condition (ii)
because the bottom part of the system has two elements namely hydrogen and oxygen have
chemically combined where as in the upper part of the system the (ii) elements appear as a mixture
of two individual gases.
Invariable in chemical aggregation means that the state of chemical combination of the system
should not change with time. Thus the mixture of hydrogen and oxygen, if it is changing into steam
during the time the system was under consideration, then the systems chemical aggregation is
varying with time and hence this system is not a pure substance. Thus the system (i) is a pure
substance where as the systems (ii) and (iii) are not pure substances.
The Two Property Rule for a Pure Substance

The thermodynamics state of a pure substance of a given mass can be fixed by specifying two
independent properties provided (i) the substance is in equilibrium and (ii) the effects of gravity,
motion, capillarity, electricity and magnetism are negligible.
The above rule indicates that if the values of two properties of a pure substance are fixed then the
values for all other properties are fixed. This means that there is a definite relation between the two
independent properties and each of the other properties. Each of these relations is called “Equation
of state” for a pure substance. The equation of state for a pure substance can be in any one of the
following forms: (i) Algebraic equation (example: perfect gas equation), (ii) Tables (example: steam
tables) and (iii) Charts (example: Mollier chart for steam).
Specific heat, C
When interaction of heat takes place between a closed system and its surroundings, the
internal energy of the system changes. If δQ is the amount of heat transferred to raise the
temperature of 1 kg of substance by dT, then, specific heat C = δQ/dT
As we know, the specific heat of gas depends not only on the temperature but also upon the type of
the heating process. i.e., specific heat of a gas depends on whether the gas is heated under constant
volume or under constant pressure process.
 We have dQ = m CV. dT for a rev. non-flow process at constant volume

and dQ = m Cp. dT for a rev. non-flow process at constant pressure
For a perfect gas, Cp & CV are constant for any one gas at all pressure and temperatures. Hence,
integrating above equations.
Flow of heat in a rev. constant pressure process = m Cp (T2 – T1)

Flow of heat in a rev. constant volume process = m CV (T2 – T1)
The internal energy of a perfect gas is a function of temperature only. i.e, u = f (T), to evaluate this
function, let 1 kg of gas be heated at constant volume
From non-flow energy equation, δQ = dU + δW

δW = 0 since volume remains constant
δQ = dU = CV. dT
Int. U = CVT + k where k is a constant
For mass m, Int. energy = m CVT
Any process between state 1 to state 2,
Change in int. energy = m CV (T2 – T1)

(U2 – U1) = m CV (T2 – T1)
We can also find the relationship between Cp & CV & shown that
Cp R rR
Cp – Cv = R ;  ; Cv  & CP 
CV r 1 r  1
Enthalpy: Consider a system undergoing a quasi equilibrium constant pressure process. We have
from 1st law of thermodynamics for a non-flow process,
Q1-2 = U2 – U1 + W1-2
W1-2 =  12 pdv
Since pressure is constant W1-2 = p (V2 – V1)
Q1-2 = U2 – U1 + p (V2 – V1)
= (U2 + p2V2) – (U1 + p1V1)
i.e., heat transfer during the process is given in terms of the change in the quantity (U + pV) between
initial and final states. Therefore, it find more convenient in thermodynamics to define this sum as a
property called Enthalpy (H)
i.e., H = U + pV
In a constant pressure quasi equilibrium process, the heat transfer is equal to the change in
enthalpy which includes both the change in internal energy and the work for this particular process.
The enthalpy of a fluid is the property of the fluid, since it consists of the sum of a property and the
product of the two properties. Since enthalpy is a property, like internal energy, pressure, specific
volume and temperature, it can be introduced into any problem whether the process is a flow or a
non-flow process.
For a perfect gas, we have h = u + pV
= CV T + RT = (CV + R) T = CpT
i.e., h = CpT & H = mCpT
For any process, δQ = dH = mCpdT
For a process between states 1 & 2
Change in enthalpy = (H2 – H1) = mCp (T2 – T1)

Specific heat at Constant Volume:

When heat interaction takes place at constant volume, δW = 0 and from 1 st law of thermodynamics,
for unit mass, (δq)V = dU
The amount of heat supplied or removed per degree change in temperature, when the system is kept
under constant volume, is called as the specific heat at constant volume,
 Q   dU 
Or CV =     
 dT  V  dT  V
Or dU = CV dT
Specific heat at Constant pressure:

When heat interaction is at constant pressure, (δq)p = dh
The amount of heat added or removed per degree change in temperature, when the system is kept
under constant pressure, is called as the specific heat at constant pressure.
 Q   dh 
Or Cp =     
 dT  p  dT  p
Or dh = Cp. dT
Application of 1st law of thermodynamics to non-flow or closed system:
a) Constant volume process (V = constant)

Applying 1st law of thermodynamics to the process,
Q1-2 = U2 – U1 + W1-2
= U2 – U1 + 0
i.e., Q1-2 = CV (T2 – T1)
For mass „m‟ of a substance, Q = mCV (T2 – T1)
b) Constant pressure (p = Constant)

Q1-2 = u2 – u1 + W1-2
The work done, W1-2 =  12 p dV = p (V2 – V1)
i.e., Q1-2 = u2 – u1 + p (V2 – V1) = (u2 + pV2) – (u1 + pV1)
= h2 – h1
i.e., Q = Cp (T2 – T1)
For mass „m‟ of a substance, Q = mCp (T2 – T1)
c) Constant temperature process (Isothermal process, T = constant)

Q1-2 = U2 – U1 + W1-2

= CV (T2 – T2) + W1-2
i.e., Q1-2 = W1-2  T1  T2
Q1-2 = p1V1 lnV2/V1
= p1 V1 ln p1/p2
d) Reversible adiabatic process (pV) = constant

Q1-2 = U2 – U1 + W1-2
O = u2 – U1 + W1-2 --- (1)
p V  p 2V2
Or (U1 – U2) = 1 1
 1
RT1  T2 
(U1 – U2) =
 1
The above equation is true for an adiabatic process whether the process is reversible or not. In
an adiabatic experiment, the work done W1-2 by the fluid is at the expense of a reduction in the
internal energy of the fluid. Similarly in an adiabatic composition process, all the work done on
the fluid goes to increase the internal energy of the fluid.
To derive pV = C: For a reversible adiabatic process

We have δq = du + δu
For a reversible process, δw = p dV
δq = du+ p dV
= O  For an adiabatic process δq = 0
Also for a perfect gas, pV = RT or p = RT
V
dV
dU + RT
V
Also, u = CV T or du = CV dT
dV
CV dT + RT
V
dT dV
or CV R 0
T V
Int., CV ln T + R ln V = constant
Sub. T = pV/R
Cv ln Pv  R ln v = constant
R
pV R
Or ln  ln V = constant
R CV

R R
Also, CV = or   1
  1 CV
pV
ln  (  1) ln V = constant
R
pV
ln  ln V  1 = constant
R
pVxV  1
or ln = constant
R
pV r
i.e., ln = constant
R
pV r
or = econstant = constant
R
i.e., pV = constant
we have pV = RT
RT
or p =
V
sub. This value of p in pV = C
RT 
V = C or TV-1 = constant --- (a)
V
RT
Also, V = sub. This in equation pressure = C
P

 RT 
p   = constant
 p 
T2 T
  1 = constant or   1 
= constant --- (b)
p  
  
p
For a reversible adiabatic process for a perfect gas between states 1 & 2, we can write
r
p V 
p1V1 = p2V2 or 2   1  --- (c)
p1  V2 
 1
T V 
T1V1-1 = T2V2 -1
or 2   1  --- (d)
T1  V2 
r 1
T1 T2 T p  r
r 1
 r 1
or 2   2  --- (e)
p1 r
p2 r T1  p1 

The work done in an adiabatic process is W = u1 – u2
The gain in I.E. of a perfect gas, is u2 – u1 = CV (T2 – T1)
W = CV (T1 – T2)
R
But CV =
 1
R(T1  T2 )
W =
 1
p1V1  p 2V2
Using pV = RT, W =
 1
e) Poly tropic process (PVn = constant)

Applying 1st law of thermodynamics, Q1-2 = u2 – u1 + W1-2
RT1  T2 
= (u2 – u1) +
n 1
RT1  T2 
i.e., Q = - CV (T1 – T2)
n 1
R   n
Also CV = sub. & simplifying Q =  W
 1  n 1 
In a poly tropic process, the index n depends on the heat and work quantities during the process.

Problems:
1. In a cyclic process, heat temperature are + 14.7 kJ, -25.2 kJ, -3.56 kJ and +31.5 kJ. What is the
net work for this cyclic process.
Solution: 1st law of thermodynamics for a cyclic process is  Q   W
i.e., Net work = 14.7 – 25.2 -3.56 + 31.5
= 17.44 kJ
2. Consider a cyclic process in a closed system which includes three heat interactions, namely Q 1 =
20 kJ, Q2 = -6kJ, and Q3 = -4 kJ and two work interactions for which W1 = 4500 N-m. Compute
the magnitude of the second work interaction W2 in Nm.
Solution: We have for a closed system undergoing cyclic process,
 Q   W
20000 – 6000 – 4000 = 4500 + W2
W2 = 5500 Nm
3. When the state of a system changes from state 1 to state 3 along the path 1-2-3 as shown in
figure, 80 kJ of heat flows into the system and the system does 30 kJ of work. (a) How much
heat flows into the system along the path 1-4-3 if work done by the system is 10 kJ (b) when the
state of the system is returned from state 3 to state 1 along the curved path, the work done on the
system is 20 kJ. Does the system absorb or liberate heat? Find its magnitude. (c) If U1 = 0 and U4
= 40kJ, find the heat absorbed in the process 1-4 and 4-3 respectively.
Solution:
2 3
A
p
1 4
V
a) Along the path 1-2-3,

From 1st law of thermodynamics, Q1-3 = U3-U1 + W1-3
From the data given, 80 = (U3 – U1) + 30
(U3 – U1) = 50 kJ
Along the path 1-4-3, we have

Q1-3 = U3 – U1 + W1-3
From the data given, Q1-3 = 50 + 10
= 60 kJ  U is property of a system
i.e., Work is done by the system
b) Along the path 3-A-1,

(U1 – U3) = Q3-1 – W3-1
Or Q3-1 = (U1 – U3) + W3-1
= -50 -20 = -70 kJ
Negative sign indicates that heat is liberated from the system.
c) Along the path 1-4

Q1-4 = U4 – U1 + W1-4
= 40-0+10 (since W1-4-3 = W1-4 + W4-3 = 10 + 0 = 10)
= 50 kJ
Positive sign indicates heat is absorbed by the system
Along the path 4-3

Q4-3 = U3 – U4 + W4-3
= 50 – 40 + 0 = 10 kJ
4. A domestic refrigerator is loaded with food and the door closed. During a certain period the
machine consumes 1 kWh of energy and the internal energy of the system drops by 5000 kJ.
Find the net heat transfer for the system.
Solution: W1-2 = 1kWhr = -1 x3600 kJ U2 – U1 = -5000 kJ
From 1st law, Q1-2 = (U2-U1) + W1-2
= -5000 -3600 = -8600 kJ = - 8.6 MJ
5. For the following process in a closed system find the missing data (all in kJ)
Process Q W U1 U2 ∆U

a) 35 20 -10 5 15
b) 15 -6 -27 -6 21
c) -7 10 20 3 -17
d) -27 -7 28 8 -20
Solution: Process (a): Q = ∆U + W
= U2 – U1 + W1-2 but U2-U1 = 15 U2 = 5
= 15 + 20 = 35 kJ
Process (b): Q = U2 – U1 + W
15 = -6-U1-6
27 = -U1 U1 = -27 kJ
∆U = U2 – U1 = - 6 + 27 = 21 kJ
Process (c) - 7 = U2 – 20 + 10
U2 = 3 kJ ∆U = 3-20 = -17 kJ
Process (d) ∆U = U2 – U1 = - 20
= 8 – U1 = - 20 U1 = 28 kJ
A = 8 – 28 – 7 = - 27 kJ
6. A fluid system, contained in a piston and cylinder machine, passes through a complete cycle of
four processes. The sum of all heat transferred during a cycle is -340 kJ. The system completes
200 cycles minutes. Complete the following table showing the method for each item, and
compute the net rate of work output in kW.
Process Q (kJ/min) W (kJ/min) ∆E (kJ/min)
1-2 0 4340 -4340
2-3 42000 0 42000
3-4 -4200 69000 -73200
4-1 -105800 -141340 35540
Solution: Given  Q = -340 kJ,
cycle
No. of cycle = 200 cycles / min
Process 1-2: Q1-2 = (E2 – E1) + W1-2

0 = ∆E + W1-2
∆E = -4340 kJ/min
Process 2-3: 42000 = ∆E + 0
Q1-2 = 42000 kJ/min
Process 3-4: -4200 = -73200 + W3-4
W3-4 = 69000 kJ/min
Process 4-1:  Q = -340 kJ
cycle
The system completes 200 cycle/min

  Q = -340 x 200 = - 68000 kJ / min
cycle

But, Q1-2 + Q2-3 + Q3-4 + Q4-1 = -68000
Q4-1 = - 68000 – 0 – 42000 + 4200
= - 105800 kJ/min
Also, dE = 0, since cyclic integral of any property is zero
(∆E)1-2 + (∆E)2-3 + (∆E)3-4 + (∆E)4-1 = 0
-4340 + 42000 – 73200 + (∆E)4-1 =0
(∆E)4-1 = 35540 kJ/min
Therefore Q4-1 = (∆E)4-1 + W4-1

- 105800 = 35540 + W4-1
W4-1 = -141340 kJ/min
Since  Q   W
cycle cycle
= - 68000 kJ/min
 68000
Rate of work output = = 1133.33 kW
60

First Law of Thermodynamics to open system:
In the case of closed system there is only energy transfer across the system boundary. But in many
engineering applications we come across open systems where in both mass and energy transfer takes
place. The energies that cross the system boundary are as follows.
1) Internal energy: Each kg of matter has the internal energy „u‟ and as the matter crosses the
system boundary the energy of the system changes by „u‟ for every kg mass of the matter that
crosses the system boundary.
2) Kinetic energy: Since the matter that crosses the system boundary will have some velocity say
V each kg of matter carries a K.E. ( V 2 / 2 ) thus causing the energy of the system to change by
this amount for every kg of matter entering the system boundary.
3) Potential energy: P.E. is measured with reference to some base. Thus „Z‟ is the elevation of the
matter that is crossing the system boundary, then each kg of matter will possess a P.E. of gZ.
4) Flow energy or Flow work: This energy is not directly associated with the matter crossing the
system boundary. But it is associated with the fact that there must be some pumping process
which is responsible for the movement of the matter across the system boundary. Thus external
to the system there must be some force which forces the matter across the system boundary and
the energy associated with this is called flow energy.
Flow Work: Consider a flow process in which a fluid of mass dm1 is pushed into the system at
section 1 and a mass dm2 is forced out of the system at section 2 as shown in fig.
A1
dm1 1 2
p1 p2, dm2
F1 F2
1 2
dl1 dl2

In order to force the fluid to flow across the boundary of the system against a pressure p 1, work is
done on the boundary of the system. The amount of work done is δW = - F1.dl1,
Where F1 is the force and dl1 is the infinitesimal displacement, but F1 = p1A1
δW = - p1A1 dl1 = - p1dv1
i.e., the flow work at section 1 = - p1v1
Similarly, the work done by the system to force the fluid out of the system at section 2 = + p2v2
Hence net flow work = p2V2 – p1V1
For unit mass, the flow work is (p2V2 – p1V1). Flow work is expressed entirely in terms properties of
the system. The net flow work depends out on the end state of the fluid and it is a thermodynamics
property. Also the fluid contains energies like internal energy, potential energy and due to the
motion of the fluid, kinetic energy, in addition to the flow work. When a fluid enters an open system,
these properties will be carried into the system. Similarly when the fluid leaves the system, it carries
these energies out of the system. Thus in an open system, there is a change in energy of the system.
5. Control Volume: The first and most important step in the analysis of an open system is to
imagine a certain region enclosing the system. This region having imaginary boundary is called
control volume, which can be defined as follows.
A C.V. is any volume of fixed shape, and of fixed position and orientation relative to the observer.
Across the boundaries of the C.V. apart from mass flow, energy transfer in the form of heat and
work can take place just as similar to the energy transfer across the boundaries of a system.
Thus the difference between C.V. and system are

i) The system boundary may and usually does change shape, position, orientation relative to the
observer. The C.V. does not by definition.
ii) Matter may and usually does flow across the system boundary of the C.V. No such flow
takes place across the system boundary by definition.
First law of thermodynamics for an open system (Flow process):
We have 1st law of thermodynamics to a closed system as,

δQ – δW = dU + d(KE) + d (PE)
= d [E]0
The subscript O refers to the states of the system within the boundary. In the case of open system,
energy is transferred into & out of the system not only by heat and work but also by the fluid that
enters into and leaves the boundary of the system in the form of internal energy, gravitational
potential energy, kinetic energy in addition to the energy in the flow work. Thus, when the first law
is applied to an open system, the energy entering into the system must be equal to the energy leaving
the system in addition to any accumulation of energy within the system.
δW
d[E]0
δQ
 V2   V2 
dm1  p1v1  u1  1  gZ1  dm2  p 2 v 2  u 2  2  gZ 2 
 2   2 
The flow process is shown in fig. This analysis can be expressed mathematically as,
 V12 
Q  W  dm1  p1v1  u1   gZ1 
 2 
 V22 
 dm2  p 2 v2  u 2   gZ 2   d E 0 --- (1)
 2 
Where state (1) is the entering condition and state (2) is the leaving condition of the fluid. This is a
general equation of the first law of thermodynamics applied to open system.
Note: The equation is valid to both open and closed system. For closed system, dm1=0 & dm2 =0
Energy Equation for open system: The general form of first law of thermodynamics applied to an
open system is called steady-flow energy equation (SFEE) i.e., the rate at which the fluid flows
through the C.V. is constant or steady flow. SFEE is developed on the basis of the following
assumptions.
i) The mass flow rate through the C.V. is constant, i.e., mass entering the C.V. / unit time =
mass leaving the C.V. /unit time. This implies that mass within the C.V. does not change.
ii) The state and energy of a fluid at the entrance and exit do not vary with time, i.e., there is no
change in energy within the C.V.
iii) The rates of heat and work transfer into or out of the C.V. do not vary with time.
 m
For a steady flow process, m  2 & d(E)0 = 0 as Q  f (T) & W  f (T)
1  m
SFEE on the basis unit mass:
Energy entering to the system = energy leaving the system
 V12   V22 
i.e., u1  p1v1   gZ1   Q  W  u 2  p 2 v2   gZ 2 
 2   2 
 V2   V2 
or h1  1  gZ1   Q  W h2  2  gZ 2 
 2   2 

 V2 
or Q  W    h   gZ 2 
 2 
Where Q = heat transfer across the C.V, W = shaft work across the C.V, h = Enthalpy,
V = velocity, Z = elevation and g = gravitational acceleration
SFEE on the basis of unit time:

 V2 
Q  W  m
  h   gZ 
 2 
Where Q = heat transfer/unit time; W = shaft work / unit time, m =mass flow rate / unit time
Hence it can be written as,
 V2   V2 
Q  m  u1  p1v1  1  gZ1  = W s  m  u 2  p1v2  2  gZ 2 
 2   2 
Where m  1  1 A1V1 and m
 2   2 A2V2 Where  = density A = cross sectional area
1  m
But m 2  m

 
V 2  V22
 Q  m h1  h2   1
 
 g Z1  Z 2   W s
 2 
This is the Steady Flow Energy Equation
Displacement work for a flow process (open system):
From SFEE, when changes in kinetic & potential energies are neglected, δq – δW = dh
Or δW = δq – dh --- (1)
st
From the 1 law of thermodynamics, we have δq – δW = du
For a rev. process, δW = Pdv
δq = du + Pdv
Also, from the definition of enthalpy, h = u + pv
Or dh = du + d (pv)
Sub δq & dh in equation (i)
δW = [du + p.dv] – [du + d (pv)]
= p.dv – p.dv – v.dp W = - vdp
Note: With negligible PE & KE, for a non-flow rev. process, the work interaction is equal to  12 p.dv
where as for a steady-flow rev. process, it is equal to   12 vdp

Application of SFEE:
i) Nozzle and Diffuser: Nozzle is a duct of varying c/s area in which the velocity increases
with a corresponding drop in pressure. Since the flow through the nozzle occurs at a very
high speed, there is hardly any time for a fluid to gain or loose heat and hence flow of the
fluid is assumed to be adiabatic. And also there is no work interaction during the process, i.e.,
Ws = 0, Q = 0, Z1 = Z2
V1 V2
Z1 Z2 = Z 1
We have from SFEE, Q –W = h + PE + KE

V22  V12
0 = h2 – h1 +
2
 h1  h2  V22  V12 
1
2
i.e., the gain in KE during the process is equal to the decrease in enthalpy of the fluid. Diffuser is
a device to increase the pressure of a fluid during flow with a corresponding decrease in KE.
Thus its function is reverse to that of a nozzle. As final velocity V2 in a diffuser is very small, it
is very often negligible.
ii) Turbine and Compressor (rotary): Turbine is a device which produces work by expanding
a high pressure fluid to a low pressure. The fluid is first accelerated in a set of nozzle and
then directed through curved moving blades which are fixed on the rotor shaft. The direction
of the fluid changes which it flows through the moving blades, due to which there is a change
in momentum and a force exerted on the blades producing torque on the rotor shaft. Since the
velocity of flow of the fluid through the turbine is very high, the flow process is generally
assumed to be adiabatic, hence heat transfer q = 0. The change in PE is neglected as it is
negligible.
W1-2
V1 V2
Z1 Z2 = Z 1
SFEE is W1-2 = (h1 – h2) – ½ (V22 – V12)

If mass flow rate is m , then,
W12  m h1  h2   m V22  V12  Watts

1
2
i.e., power developed by the turbine
Compressor is a device in which work is done on the fluid to raise its pressure. A rotary
compressor can be regarded as a reversed turbine. Since work is done on the system, the rate of
work in the above equation is negative and the enthalpy after compression h 2 will be greater than
the enthalpy before compression h1.
iii) Throttling Process: When a fluid steadily through restricted passages like a partially closed
valve, orifice, porous plug etc., the pressure of the fluid drops substantially and the process is
called throttling. In a throttling process, expansion of the fluid takes place so rapidly that no
heat transfer is possible between the system and the surroundings. Hence the process is
assumed to occur adiabatically. The work transfer in this process is zero.
1 2
1 2
SFEE is Q1-2 – W1-2 = h + KE + PE

We have, Q = 0; W = 0; Z1 = Z2, V1  V2
0 – 0 = h2 – h1 + 0 + 0 i.e., h1 = h2
In a throttling process, the enthalpy remains constant. The throttling process is irreversible because
when a fluid is throttled, it passes through a series of non-equilibrium states.
iv) Heat Exchanger: A heat exchanger is a device in which heat is transferred from one fluid to
another. It is used to add or reduced heat energy of the fluid flowing through the device.
Radiator in an automobile, condenser in a steam power and refrigeration plants, evaporator in
a refrigerator are examples of heat exchangers. There will be no work interaction during the
flow of the fluid through any heat exchanger.
Eg: i) Steam condenser: Used to condense the steam. It a device in which steam loses heat as it
passes over the tubes through which water is flowing.

Figure: Heat Exchanger
We have KE = 0, PE = 0 (as their values are very small compared to enthalpies)
W = 0 (since neither any work is developed nor absorbed)
SFEE is Q = h2 – h1
i.e., h1 – Q = h2 --- (1)
Where Q = heat lost by 1 kg of steam passing through the condenser.
Assuming there are no other heat interactions except the heat transfer between steam and water,
then Q = heat gained by water passing through the condenser.
  
 m w hw2  hw1  m wCw Tw2  Tw1 
Substituting Q in the above equation (1),
h 2 - h1  m
 w C w (Tw - Tw )
2 1
 w = mass of cooling water passing through the condenser

Where m
Cw = specific heat of water
In a condenser there are 2 steady flow streams namely (i) Vapour that losses heat (ii) The coolant
(water) that receives heat.
Let m w = mass flow rate of coolant
 s = mass flow rate of steam
m
h1w = Enthalpy-coolant entry
h1s = Enthalpy-steam entry
h2w, h2s = Enthalpy of coolant, steam at exit
 w h1w + m
m  s h1s = m
 w h2w + m
 s h2s
m w h2 s  h1s 
or 
m s h1w  h2 w 
ii) Evaporator: An evaporator is a component of a refrigeration system and is used to extract

heat from the chamber which is to be kept at low temperature. The refrigerating liquid enters the

evaporator, absorbs latent heat from the chamber at constant pressure and comes out as a vapour.
SFEE is
m h1 + Q = m h2 Since W = 0, KE = PE = 0
 Q = m (h2 – h1)
Q is taken as positive because heat flows from the chamber to the evaporator coil.
Figure: Evaporator
v) Boiler: It is equipment used for the generation of the steam. Thermal energy released by
combustion of fuel is transferred to water which vaporizes and gets converted into steam at
the desired pressure and temperature. The steam thus generated is used for
a. Producing mechanical work by expanding it in steam engine or steam turbine.
b. Heating the residential and industrial buildings in cold weather and
c. Performing certain processes in the sugar mills, chemical and textile industries.
1. Velocity change is negligible V1 = V2

2. Change in elevation is also negligible Z2 = Z1
3. Work done = 0
SFEE is h1 + q = h2
q = h2 – h1
= (u2 – u1) + (p2 v2 – p1 v1)

Problems:
1. 12 kg of a fluid per minute goes through a reversible steady flow process. The properties of fluid
at the inlet are p1 = 1.4 bar, 1 = 25 kg/m3, V1 = 120 m/s & u1 = 920 kJ/kg and at the exit are p2 =
5.6 bar, 2 = 5 kg/m3, V2 = 180 m/s and u2 = 720 kJ/kg. During the passage, the fluid rejects 60
kJ/s and raises through 60m. Determine i) the change in enthalpy ii) work done during the
process.
Solution: i) Change in enthalpy h = (u + pV)
= (720 x 103 – 920 x 103) + (5.6 x 105 x 1/5 – 1.4 x 105 x 1/25)
= - 93.6 kJ
ii) SFEE for unit time basis is Q  W  m h  KE  PE  --- (1)
V22  V12 180 2  120 2
KE   = 9000 J = 9 kJ/kg
2 2
PE = g (Z2 – Z1) = 9.81 (60) = 0.589 kJ/kg
Substituting in equation (1), - 60  W = 12/60 [- 93.6 + 9 + 0.589]
W = - 43.2 kW
Negative sign indicates work is done on the fluid in the reversible steady flow process.
2. In the turbine of a gas turbine unit the gases flow through the turbine at 17 kg/s and the power
developed by the turbine is 14000 kW. The enthalpies of the gases at inlet and outlet are 1200
kJ/kg and 360 kJ/kg respectively, and the velocities of the gases at inlet and outlet are 60 m/s and
150 m/s respectively. Calculate the rate at which the heat is rejected from the turbine. Find also
the area of the inlet pipe given that the specific volume of the gases at inlet is 0.5 m3/kg.
Solution: m = 17 kg/s v1 = 0.45 m3/kg
14000
P = 1400kW Work done W  = 823.53 kJ/kg
17
h1 = 1200kJ/kg h2 = 360kJ/kg V1 = 60m/s V2 = 150 m/s
We have SFEE, Q –W = h + PE + KE

V22  V12
 KE   9.45kJ / kg
2
h  h2  h1  840kJ / kg
PE = 0
Substituting in SFEE equation,
 Q – 823.53 = – 840 + 0 + 9.45
Q = - 7.02 kJ/kg
i.e., heat rejected = 7.02 x 17 = 119.34 kW
1
Also, we have m  1 A1V1  A1V1
v1

1
17  A1 (60) A1 = 0.142 m2
0.5
3. Air flows steadily at the rate of 0.4 kg/s through an air compressor entering at 6 m/s with a
pressure of 1 bar and a specific volume of 0.85 m3/kg, and leaving at 4.5 m/s with a pressure of
6.9 bar and a specific volume of a 0.16 m3/kg. The internal energy of air leaving is 88 kJ/kg
greater than that of the air entering. Cooling water in a jacket surrounding the cylinder absorbs
heat from the air at the rate of 59 kJ/s. Calculate the power required to drive the compressor and
the inlet and outlet pipe cross sectional areas.
Solution: m = 0.4 kg/s V1 = 6m/s p1 = 1 x 105Pa
v1 = 0.85 m3/kg V2 = 4.5 m/s P2 = 6.9 x 105Pa v2 =0.16m3/kg
u = 88 kJ/kg Q = - 59 kJ/s W  ?
pv = 6.9 x 105 x 0.16 – 1 x 105 x 0.85 = 25.4 kJ/kg
u = 88 kJ/kg
h =  (u + pv) = 113.4 kJ/kg
SFEE for unit time basis is given by,
Q  W  m h  KE  PE 
V22  V12
KE    7.88 J / kg
2
PE = 0
Substituting in the SFEE equation,
 7.88 
 59  W  0.4113.4   0
 1000 
W  104.4kW
Negative sign indicates work is done in the air compressor i.e., power input to the compressor.
  1 A1V1   2 A2V2
ii) We have m
1 1
 A1V1  A2V2
v1 v2
m v1
 A1   0.057 m 2
V1
m v2
A2   0.0142 m 2
V2
4. A turbine operating under steady flow conditions receives steam at the following state. pressure
13.8 bar, specific volume 0.143 m3/kg, i.e., 2590 kJ/kg, velocity 30 m/s. The state of the steam
leaving the turbine is pressure 0.35 bar, specific volume 4.37 m3/kg, i.e., 2360 kJ/kg, velocity 90

m/s. Heat is lost to the surroundings at the rate of 0.25 kJ/s. If the rate of steam flow is 0.38 kg/s,
what is the power developed by the turbine? (102.8 kW).
5. At the inlet to a certain nozzle the enthalpy of the fluid is 3025 kJ/kg and the velocity is 60 m/s.
At the exit from the nozzle the enthalpy is 2790 kJ/kg. The nozzle is horizontal and there is
negligible heat loss from it. i) Find the velocity at the nozzle exit. ii) If the inlet area is 0.1 m 2
and specific volume at inlet is 0.19 m3/kg, find the rate of flow of fluid. iii) If the specific volume
at the nozzle exit is 0.5 m3/kg, find the exit area of the nozzle.
Solution: h1 = 3025 kJ/kg V1 = 60 m/s h2 = 2790 kJ/kg Z2 = Z1 Q=0
SFEE is Q – W = h + PE + KE
For a nozzle, W = 0, Q = 0, PE = 0
Substituting in SFEE, we get
V12  V22 V 2  V22
 h  i.e., h2  h1  1
2 2
or 2 (h2 – h1) = V12  V22 V2  V12  2h2  h1 
= 688.2 m/s
 1  1 A1V1
ii) m

1
. A1V1 
1
0.1 60  31.6kg / s
v1 0.19
 2   2 A2V2
iii) m
. A2 688.2 A2 = 0.0229 m2

1
31.6 
0.5
6. In a steam power plant 1.5 kg of water is supplied per second to the boiler. The enthalpy and
velocity of water entering the boiler are 800 kJ/kg and 10 m/s. Heat at the rate of 2200 kJ/kg of
water is supplied to the water. The steam after passing through the turbine comes out with a
velocity of 50 m/s and enthalpy of 2520kJ/kg. The boiler inlet is 5m above the turbine exit. The
heat loss from the boiler is 1800 kJ/m and from the turbine 600 kJ/min. Determine the power
capacity of the turbine, considering boiler and turbine as single unit.
Solution: m = 1.5 kg/s h1 = 800 kJ/kg V1 = 10 m/s Q = 2200 kJ/kg
V2 = 50 m/s h2 = 2520 kJ/kg Z1 = 5 m Z2 = 0 W=?
Heat loss from boiler and turbine is 1800 + 600 = 2400 kJ/min
40
= 40 kJ/sec = = 26.67 kJ/kg
1 .5
Net heat added to the water in the boiler Q = 2200 – 26.67 = 2173.33 kJ/kg
SFEE is Q - W = h + KE + PE --- (1)
h = h2 – h1 = 2500 – 800 = 1720 kJ/kg
V22  V12 50 2  10 2
KE    1200 J / kg  1.2kJ / kg
2 2
PE = g (Z2 – Z1) = 9.81 (0-5) = - 49.05 J/kg = -49.05 x 10-3kJ/kg

Substituting in (1), 2173.33 – W = 1720 + 1.2 – 49.05 x 10-3
W = 452.18 kJ/kg
Power capacity of the turbine P = 452.18 x 1.5 = 678.27 kW
7. A centrifugal air compressor used in gas turbine receives air at 100 KPa and 300 K and it
discharges air at 400 KPa and 500 K. The velocity of air leaving the compressor is 100 m/s.
Neglecting the velocity at the entry of the compressor, determine the power required to drive the
compressor if the mass flow rate is 15 kg/sec. Take Cp(air) = 1 kJ/kgK, and assume that there is
no heat transfer from the compressor to the surroundings.
Solution: p1 = 100 x 103N/m2 T1 = 300 K p2 = 400 x 103N/m2 T2 = 500K
V2 = 100 m/s W = ? m = 15 kg/s Cp = 1kJ/kgK Q = 0
SFEE is Q – W = h + KE + PE
h = m Cp (T2 – T1) = 15 (1) (500 – 300)
= 3000 kJ/s = 3000 / 15 = 200 kJ/kg
V22 100 2
KE    5000 J / kg  5kJ / kg
2 2
Substituting in SFEE we have
0 – W = 200 + 5 = 205 kJ/kg
i.e., W = - 205 kJ/kg = - 205 x 15 kJ/s = - 3075 kW
Negative sign indicates work is done on the centrifugal air compressor
Power required = 3075 kW
8. In a water cooled compressor 0.5 kg of air is compressed/sec. A shaft input of 60 kW is required

to run the compressor. Heat lost to the cooling water is 30% of input and 10% of the input is lost
in bearings and other frictional effects. Air enters the compressor at 1 bar and 200C. Neglecting
the changes in KE & PE, determine the exit air temperature. Take Cp = 1kJ/kg0C air.
Solution: m = 0.5 kg/s W = 60 kW HL = (30% + 10%) input = 40% input
5 2 0
p1 = 1 x 10 N/m t1 = 20 C
SFEE is Q – W = h + KE + PE
KE = 0, PE = 0
60
W = 60 kW = 60 kJ/sec  = 120 kJ/kg
0.5
Heat lost to the surroundings = 40% (input) = 0.4 (120)
= 48 kJ/kg
Substituting in SFEE we have
- 48 – (-120) = h
But h = Cp (t2 – t1)
- 48 + 120 = Cp (t2 – t1)
i.e., 72 = 1 (t2 – 20)
t2 = 920C

9. A petrol engine develops 50 kW brake power. The fuel and air flow rates are 10 kg and 107
kg/hr. The temperature of fuel air mixture entering the engine is 200C and temperature of gases
leaving the engine is 5000C. The heat transfer rate from the engine to the cooling water
circulated is 50kJ/s and that to the surroundings 10 kJ/s. Evaluate the increase in the specific
enthalpy of the mixture as it flows through the engine.
Solution: W = 50 kW = 50 kJ/s = 1538.46 kJ/kg m = (10 + 107)kg/hr = 0.0325 kg/s
0 0
t1 = 20 C t2 = 500 C QL = 50 + 10 = 60 kJ/s = 1846.15 kJ/kg
SFEE is QL – W = h + KE + PE but KE = PE = 0
Substituting in SFEE, we have
- 1846.15 – 1538.46 = h
h = - 3384.61 kJ/kg
= - 109.99 kJ/sec
Negative sign indicates there is decrease in enthalpy of the mixture.
10. Air at a temperature of 150C passes through a heat exchanger at a velocity of 30 m/s where its
temperature is raised to 8000C. It then enters a turbine with the same velocity of 30 m/s and
expands until the temperature falls to 6500C. On leaving the turbine, the air is taken at a velocity
of 60 m/s to a nozzle where it expands until the temperature has fallen to 5000C. If the air flow
rate is 2 kg/s, calculate i) the rate of heat transfer to the air, ii) the power output from the turbine
assuming no heat loss, and iii) the velocity at exit from the nozzle, assuming no heat loss. Take
the enthalpy of air as h = Cpt, where Cp = 1.005 kJ/kg0C.
Solution: t1 = 150C, V1 = 30 m/s, t2 = 8000C V2 = 30 m/s t3 = 6500C
V3 = 60 m/s t4 = 5000C m = 2 kg/s
i) Heat exchanger: Q = ?
Q – W = (h + KE + PE) but KE = PE = 0
Q = Cp (t2 – t1)
= 1.005 (800 – 15) = 788.93 kJ/kg
or Q = 1577.85 kJ/s
ii) Turbine: W = ?
Q – W = h + KE + PE, but Q = 0, PE = 0
h = Cp (t3 – t2) = (650 – 800) 1.005 = - 150.75 kJ/kg
V32  V22 60 2  30 2
KE    1350 J / kg  1.35kJ / kg
2 2
- W = - 150.75 + 1.35
W = 149.4 kJ/kg
= 149.4 x 2 = 298.8 kW
iii) Nozzle: V4 =?
Q – W = h + KE + PE, but Q = 0, W = 0, PE = 0

V42  V32
(h3 – h4) =
2
i.e., 2Cp (t3 – t4) = V4  V32
2
2 (1.005) (650 – 500) + 602 = V42

V4 = 552.36 m/s
11. A 260 mm dia cylinder fitted with a frictionless leak pro of piston contains 0.02 kg of steam at a
pressure of 6 x 105 N/m2 and a temperature of 2000C. As the piston moves slowly outwards
through a distance of 305 mm the steam undergoes a fully resisted expansion according to the
law pVn = a constant to a final pressure 1 x 105N/m2. Determine i) value of the index n ii) work
done by the steam iii) Magnitude and sign of heat transfer.
Solution: d = 0.26 m, m = 0.02 kg p1 = 6 x 105Pa t1 = 2000C
l = 0.305 m, pVn = C p2 = 1 x 105Pa
 
Stroke volume = d 2 l  0.26 0.305  0.016193m 3
2
4 4
Considering steam as a perfect gas, p1V1 = mRT1,
0.02 287  473
V1  5
 4.525 x 10 3 m 3
6 x 10
Final volume = V2 = V1 + stroke volume
= 4.525 x 10-3 + 0.016193
= 0.020693m3
i) n =? p1 V1n = p2V2n
n
p1  V2 
n
6 x10 5  0.20693 
or    i.e.,    n  1.179
p 2  V1  1x10 5  4.525 x10 3 
p V  p 2V2
ii) Work done. 1 1  3.607kJ
n 1
  n  1.4  1.179 
iii) For reversible polytropic process, Q W    3.607
 n 1   0.179 
= 4.453 kJ
12. Air flows steadily at the rate of 0.5 kg/s through an air compressor, entering at 7 m/s velocity,
100 KPa pressure, 0.95 m3/kg volume, and leaving at 5 m/s velocity, 700 KPa pressure and 0.19
m3/kg. The internal energy of the air leaving is 93 kJ/kg greater than that of the air entering.
Cooling water in the compressor jackets absorbs heat from the air at the rate of 58 kW. i)
compute the rate of shaft work in kW ii) find the ratio of the inlet pipe dia to outlet pipe
diameter.
Solution: m = 0.5 kg/s V1 = 7 m/s p1 = 100 x 103Pa V1 = 0.95 m3/kg

V2 = 5 m/s p2 = 700 x 103Pa v2 = 0.19 m3/kg (u2 – u1) = 93 kJ/kg
58
QL = 58 kJ/s   116kJ / kg Z1 = Z2
0.5
Q – W = h + KE + PE --- (1)
h = (U + pV) = (U2 – U1) + (p2V2 – p1V1)
= 93 x 103 + [700 x 103 x 0.19 – 100 x 103 x 0.95]
= 131000 J/kg = 131 kJ/kg
V22  V12
KE   12 J / kg  12 x10 3 kJ / kg
2
PE = 0
Equation (1) becomes, - 116 – W = 131 – 12 x 10-3
W = - 246.99 kJ/kg
= - 246.99 x 0.5 = - 123.49 kW
Negative sign indicates shaft work done on the compressor.
ii) m = 1A1V1 = 2A2V2

AV AV A Vv
 1 1  2 2  1  2 1  3.5714
v1 v2 A2 V1v 2
 2
d1
4 d1
 3.5714   1.8898
 2 d2
d2
4
13. A gas flows into a turbine with an initial pressure of 7 bar, specific volume 0.2 m3 and velocity
150 m/s. The corresponding values of pressure, specific volume and velocity at the exit are 3.5
bar, 0.5 m3 and 300 m/s respectively. During the expansion of gas in the turbine its internal
energy decreases by 92 kJ/kg and loss due to radiation was 13 kJ/kg. What amount of shaft work
is developed per kg of gas flow.
14. The compressor of a large gas turbine receives air from the surroundings at 95 KPa and 200C.
The air is compressed to 800 KPa according to the relation pV1.3 = constant. The inlet velocity is
negligible and the outlet velocity is 100 m/s. The power input to the compressor is 2500 kW,
20% of which is removed as heat from the compressor. What is the mass flow rate of the air?
Take Cp = 1.01 kJ/kg0K for air.
Solution: p1 = 95 x 103N/m2 T1 = 293 k p2 = 800 x 103N/m2
pV1-3 = C V2 = 100 m/s W = - 2500 kW Q = - 0.2 (2500) = -500 kW
m = ? Cp = 1.01 kJ/kg0K
n 1 0.3
T p  n
 800  1.3
we have 2   2   T2  293   479.09 K
0
T1  p1   95 

 V2 
Q  W  m  h  2  gZ 
 2 
 100 2 
- 500 + 2500  m 1.01479.09  293  x10 3 
 2 
 m = 10.365 kg/sec
15. The steam supply to an engine is comprised of two streams which mix before entering the
engine. One stream is supplied at the rate of 0.01 kg/s with an enthalpy of 2950 kJ/kg and a
velocity of 20 m/s. The other stream is supplied at the rate of 0.1 kg/s with an enthalpy of 2569
kJ/kg and a velocity of 120 m/s. At the exit from the engine the fluid leaves as two streams, one
of water at the rate of 0.001 kg/s with an enthalpy of 420 kJ/kg and the other of steam. The fluid
velocity at the exit are negligible. The engine develops a shaft power of 25 kW. The heat
transfer is negligible. Evaluate the enthalpy of the second exit stream. (Ans. 2462 kJ/kg)
16. A perfect gas flows through a nozzle where it expands in a reversible adiabatic manner. The inlet
conditions are 22 bar, 5000C, 38 m/s. At exit the pressure is 2 bar. Determine the exit velocity
and exit area if the flow rate is 4 kg/s. Take R = 190 J/kg-0k and  = 1.35
r 1
 T p 
R, h  C p T2  T1 , 2   2 
r
[hint: C p 
 1 T1  p1 
1
p2v2 = RT2 v2 = 0.3933 m3/kg  2  m = 2A2V2 ]
v2
Ans.: V2 = 726 m/s , A2 = 0.002167 m2
17. A steam turbine operate under steady flow conditions receiving steam at the following state:
Pressure 15 bar, internal energy 2700 kJ/kg, velocity 300 m/s, specific volume 0.17 m3/kg and
velocity 100 m/s.
The exhaust of steam from the turbine is at 0.1 bar with internal energy 2175 kJ/kg, specific
volume 15m3/kg and velocity 300 m/s. The intake is 3 m above the exhaust. The turbine
develops 35 kW and heat loss over the surface of turbine is 20kJ/kg. Determine the steam flow
rate through the turbine. [Ans.: 0.0614 kg/s]
18. Determine the power required to drive a pump which raises the water pressure from 1 bar at
entry to 25 bar at exit and delivers 2000 kg/hr of water. Neglect changes in volume, elevation
and velocity and assume specific volume of water to be 0.001045m3/kg.
Solution: We have Q  W  m h  KE  PE 
Q  0, KE = 0, PE = 0
Substituting in the SFEE equation,
u = 0  Water does not experience any change in temperature

 v p2  p1 
m but v1 = v2
 W = - 1.393 kW
19. In a conference hall comfortable temperature conditions are maintained in winter by circulating
hot water through a piping system. The water enters the piping system at 3 bar pressure and 50 0C
temperature (enthalpy = 240 kJ/kg) and leaves at 2.5 bar pressure and 300C temperature
(enthalpy = 195 kJ/kg). The exit from the piping system is 15 m above the entry. If 30 MJ/hr of
heat needs to be supplied to the hall, make calculation for the quantity of water circulated
through the pipe per minute. Assume that there are no pumps in the system and that the change
in KE is negligible.
Solution: Q – W = (h + KE + PE)
W = 0, KE = 0
9.81(15)
Q = (195 – 240) +
1000
= - 44.853 kJ/kg
30 x10 6
Mass of water to be circulated =  11.15kg / min
44.853x10 3 x60
Unsteady flow process: In a steady flow process we have assumed that the mass and energy within
the system remain constant and do not vary with time. In an unsteady flow process, mass and energy
within the control volume vary continuously. The fluid flow into and out of the system.
Example: Filling or evacuation of a tank, (internal energy as well as mass of the tank changes with
time), the condition of water in the cylinder jacket of an I.C. engine (is time dependant)
Analysis: Consider the flow of a fluid through a pipe line into the cylinder. Let m1 be the mass of the
fluid initially in the cylinder at pressure p1, temperature t1 and m2 the final mass in the cylinder at
pressure p2, temperature t2. The mass that flows into the cylinder is thus (m2 – m1).
There are two ways for solving problems involving unsteady flow (i) Closed system analysis (ii)
Control volume analysis
(i) Closed system analysis:

Pipe line
System
Boundar
Cylinder
y
(System)

Since no mass crosses the boundary of the system, the boundary of the system is selected in such a
way that it includes not only the cylinder but also that portion of the fluid in the pipe line which will
be introduced eventually into the cylinder as shown in figure. That means the system has variable
boundaries which at the final state will be the same as that of the cylinder. Initially energy of the
system E1 is composed of the internal energy of the mass initially in the cylinder, m 1u1 plus the
 V p2 
energy of the fluid which will eventually flow the pipe line into the cylinder, (m2 – m1) u p  
 2 
where the subscript „p‟ refers to the condition of the fluid in the pipe line. At the final state, energy
E2 of the fluid in the system will be equal to m2u2.
Neglecting the change in PE, the change in energy is,

  V p2 
E2 – E1 = m2u2 - m1u1  m2  m1 u p  
  2 
To find out work done on the system, consider a mass in the pipe line (m2 – m1) which is
subjected to a controlled pressure Pp. The flow work due to the flow of mass (m2 – m1) into the
cylinder from the (m2 – m1) vp in the pipe line to a zero volume is
W = Pp [0 – (m2 – m1) vp] = - (m2 – m1) Pp vp

Where vp is the specific volume of the fluid in the pipeline.
Applying 1st law of thermodynamics,
 
 
V p2 
Q  m2  m1 Pp v p  m2 u 2  m1u1  m2  m1 u p  
 
 2 

But hp = up + Ppvp,
Above equation becomes,
 V p2 
Q  m2 u 2  m1u1  m2  m1 h p   --- (1)
 2 
(ii) Control Volume analysis:
Pipe line
C.V
Boundary
Cylinder
(Control Volume)

The cylinder itself is taken as the control volume as shown in figure. In this case, there is no
work interaction. Using the general equation 1st law and considering no mass flows out of the
control volume and neglecting the change in PE, as in the earlier case we have
 V p2  d
Q  m 2  m 1 h p 
  U 
 2  d
 V p2 
or Q  m2  m1 h p    m2 u 2  m1u1 --- (2)
 2 
If the tank would have been thermally insulated and initially empty, Q = 0 and m 1 = 0 substituting
V p2
into equation (1) and simplifying, we get h p   u2 --- (3)
2
Also if KE in the pipe line is not appreciable, hp = u2 i.e., the specific enthalpy of the fluid in the pipe
line is equal to the specific internal energy of the fluid in the cylinder at the final state.
Note: The tank emptying process is the reverse of filling process i.e., there is flow of fluid from the
tank (cylinder) to the surroundings.
Analogous to filling process, applying 1st law, of thermodynamics, we have
 V p2 
Q  m1u1  m2 u 2  m1  m2 h p   --- (4)
 2 
Where hp and Vp are the specific enthalpy and velocity of leaving fluid.
For no heat transfer and negligible exit velocity,

(m1 – m2) hp = m1u1 – m2u2
Further if the tank is to be fully emptied (m2 = 0)
i.e., m1hp = m1u1
or hp = u1
i.e., the specific enthalpy of the fluid in the cylinder is equal to the specific internal energy of
the fluid in the pipe line at the final state.
Problems:
1. A household gas cylinder initially evacuated is filled by 15 kg gas supply of enthalpy 625 kJ/kg.
After filling, the gas in the cylinder has the following parameters: pressure 10 bar, enthalpy 750
kJ/kg and specific volume 0.0487 m3/kg. Evaluate the heat received by the cylinder from the
surroundings.
Solution: Given: m2 = 15 kg hp = 625 kJ/kg P2 = 10 bar h2 = 750 kJ/kg
3
v2 = 0.0487 m /kg

SFEE to the filling process is
 V p2 
Q = m2u2 – m1u1 – (m2 – m1) h p  
 2 
The cylinder is initially evacuated i.e., m1 = 0, also V p  0
i.e., Q = m2u2 – m2hp

= m2 [(h2 – p2v2) – hp]
 10 x10 5 0.0487   
 15 750  3
  625
 10  
= 1144.5 kJ
2. An insulated and rigid tank contains 5 m3 of air at 10 bar and 425 K. The air is then let off to
atmosphere through a valve. Determine the work obtainable by utilizing the KE of the discharge
air. Take Cp = 1 kJ/kg K, CV = 0.714 kJ/kg0-K atmosphere pressure = 1 bar.
Solution: Given: V1 = V2 = 5 m3 P1 = 10 bar T1 = 425 K
The situation corresponds to emptying process, for which the energy balance equation is,
V p2
Q + (m1 – m2) h p   m1u1  m2 u 2
2
Insulated and rigid tank i.e., Q = 0
 V p2 
m1  m2 h p    m1u1  m2 u 2 Suffix „p‟ refers to discharge condition.
 2 
V p2
Or m1  m2   m1u1  m2 u 2  m1  m2 h p
2
= m1CVT1 – m2CVT2 – (m1 – m2) CpT2 --- (1)
Cp 1
We have,     1.4 p2 = 1 bar, R = Cp – CV = 0.286 kJ/kg K
CV 0.714
 1
P 
0.286
T r
1
 2   2  i.e., T2  425   220 K
T1  P1   10 
10 x10 5 x5
Also, p1V1 = m1RT1  m1   41.14kg
286425
1x10 5 x5
& p2V2 = m2RT2  m2 
 7.95kg
286220
Substitute in equation (1) on RHS, we have
V p2
m1  m2  = 41.14 (0.714) (425) – 7.95 (0.714) (220)
2

- (41.14 – 7.95) (1.0) (220)
= 3933.35 kJ
3. A vessel of constant volume 0.3 m3 contains air at 1.5 bar and is connected via a valve, to a large
main carrying air at a temperature of 380C and high pressure. The valve is opened allowing air to
enter the vessel and raising the pressure there in to 7.5 bar. Assuming the vessel and valve to be
thermally insulated, find the mass of air entering the vessel.
Solution: The situation corresponds to filling process, for which the energy balance equation is,
 V p2 
Q  m2  m1 h p    m2 u 2  m1u1
 2 
With thermally insulated and neglecting KE of air,
(m2 – m1)hp = m2u2 – m1u1
or (m2 – m1) CpTp = m2CVT2 – m1CVT1
Air is a perfect gas, i.e., pV = mRT
p2V p1V
i.e., m2T2  and m1T1  Given V1  V2  V
R R
 m2  m1 C pT p  CV
 p2  p1 
V
R
or m2  m1   . .  p 2  p1 
1 1 V
Tp r R

1 1 0.3
. . 7.5  1.5105
311 1.4 287
= 1.44 kg
= Mass of the air entering
4. After the completion of exhaust stroke of an I.C. engine the piston cylinder assembly remains
filled up with 1 x 10-4kg of combustible products at 800 K. During the subsequent suction stroke,
the piston moves outward and 16 x 10-4 kg of air at 290 K is sucked inside the cylinder. The
suction process occurs at constant pressure and heat interaction is negligible. Evaluate the
temperature of gases at the end of suction stroke. For air and gases, take Cp = 1kJ/kg
Solution: The energy equation for the filling process is,

 V2 
Q  m2  m1 h p  p   m2 u 2  m1u1  W
2
 
With no heat interaction and negligible KE of air in the supply line, above equation reduces to,
(m2 – m1) hp = m2u2 – m1u1 + W
The suction occurs at constant pressure i.e., W   12 pdV  pV2  V1 
= p (m2v2 – m1v1)
= m2 (p2v2 – p1v1)

Substituting in the above equation for W, we have
(m2 – m1) hp = m2u2 – m1u1 + m2 (p2v2 – p1v1)
= m2 (u2 + p2v2) – m1 (u1 + p1v1)
= m2h2 – m1h1
Or (m2 – m1) CpTp = m2CpT2 – m1CpT1
Or (m2 – m1) Tp = m2T2 – m1T1
Substitute the given data, we get
(16 x 10-4 – 1 x 10-4) 290 = 16 x 10-4 x T2 – 1 x 10-4 x 800
T2 = 321.87 K (Temperature of gas at the end of suction stroke)
5. An air receiver of volume 6 m3 contains air at 15 bar and 40.50C. A valve is opened and some air
is allowed to blow out to atmosphere. The pressure of the air in the receiver drops rapidly to 12
bar when the valve is then closed. Calculate the mass of air which has left the receiver.
Solution: The situation correspond to emptying process for which the energy balance equation is,
 V2 
Q  m1  m2 h p  p   m1u1  m2 u 2
2
 
But Q = 0, Vp = 0
i.e., (m1- m2) hp = m1u1 – m2u2
Or (m1 – m2) CpTp = m1CVT1 – m2CVT2
p1V pV
From perfect gas equation, p1V1 = m1RT1 i.e., m1T1  , Similarly m2T2  2
R R
C
m1  m2   V . V  p1  p2 
C pT p R
i.e., Mass of air left the receiver, m1  m2   .  p1  p 2 

1 V
 .T p R

1
.
6
15  1210 5
1.4313.5 287
= 14.3 kg
p1V1
Also, m1   100.03kg
RT1
m2 = 85.74 kg
6. The internal energy of air is given, at ordinary temperature by, u = u0 + 0.718t. Where u is in
kJ/kg, u0 is any arbitrary value of u at 00C, kJ/kg and t is temperature in 0C. Also for air, pv =
3
0.287 (t + 273) where p is in KPa and v is in m /kg.
i) An evacuated bottle is fitted with a valve through which air from the atmosphere, at 760 mm
oxygen and 250C, is allowed to flow slowly to fill the bottle. If no heat transfer to or from the
air in the bottle, what will its temperature be when the pressure in the bottle reaches 760 mm
Hg?

ii) If the bottle initially contains 0.03 m3 of air at 400 mm Hg and 250C, what will the
temperature be when the pressure in the bottle reaches 760 mm of Hg?
Solution: u = u0 + 0.718t
pv = 0.287 (t + 273)
Using above equation determine Cv, Cp i.e., Cv = du/dt = 0.718 kJ/kg -0k
 u  pv  = 1.005 kJ/kg-0k
dh d
& Cp 
dt dt
i) Situation corresponds to filling process, for which the energy balance equation is,
 V p2 
Q  m2  m1 h p    m2 u 2  m1u1
 2 
Heat transfer Q = 0, evacuated bottle, m1 = 0 and negligible KE, Vp = 0
m2hp = m2u2
Or hp = u2
i.e., CpTp = CVT2
Cp
 T2  Tp
CV
= Tp = 1.4 (298)
= 417.120K or 144.120C
ii) Energy balance equation is, (m2 – m1) hp = m2 u2 – m1 u1
i.e., (m2 – m1) CpTp = m2CVT2 – m1CVT1
Using perfect gas equation, p1V1 = m1RT1
But p1 = ωh
= 9810 (13.6) (400 x 10-3) = 53366.4 N/m2
53366.40.03
 m1   0.0187kg
287298
Similarly p2V2 = m2RT2
P2 = ωh = 9810 (13.6) (760 x 10-3)
= 101396.2 N/m2
101396.20.03
 m2   V1  V2
287T2 
10.59

T2
Substituting in energy balance equation,
 10.59 
 0.0187  1005298  718T2  0.0187 718 298
10.59

 T2  T2
Solving, T2 = 344.920K or 71.920C

7. The internal energy of air is given by u = u0 + 0.718 t also for air, pv = 0.287 (t + 273). A mass
of air is stirred by a paddle wheel in an insulated constant volume tank. The velocities due to
stirring make a negligible contribution to the internal energy of the air. Air flows out through a
small valve in the tank at a rate controlled to keep the temperature in the tank constant. At a
certain instant the conditions are as follows: tank volume 0.12m3, pressure 1 MPa,
0
temperature 150 C and power to paddle wheel 0.1 kW. Find the rate of flow of air out of the tank
at this instant.
Solution: The energy balance equation for emptying process is,
 V p2 

Q – Ws + (m1 – m2) h p    m1u1  m2 u 2
 2 
 
Insulated tank, Q = 0, there is no change in i.e., of air in the tank. Internal energy, u = 0 and
KE = 0
- Ws + (m1 – m2) hp = 0
i.e., (m1 – m2) = Ws/hp
Or rate of flow of air out of the tank at this instant
0.1
  h p  C pT p
1.005 425
= 2.3412 x 10-4 kg/s
= 0.843 kg/hr
8. A certain water heater operates under steady flow conditions receiving 4.2 kg/s of water at 750C
temperature, enthalpy 314 kJ/kg. The water is heated by mixing with steam which is supplied to
the heater at temperature 1000C and enthalpy 2676 kJ/kg. The mixture leaves the heater as liquid
water at temperature 1000C and enthalpy 419 kJ/kg. How much steam must be supplied to the
heater per hour.
Solution: Energy entering = energy leaving

 V2   V2 
Q  m
 1 h1  1  gZ1   m 2 h2  2  gZ 2 
 2   2 
 V2 
 m 3 h3  3  gZ 3   W
 2 
By the nature of the process, W  0 KE = 0 PE = 0 Q  0
 1h1  m 2 h2  m 3 h3
i.e., m
4.2314  m
 2 2676  4.2  m
 2 419
 2  0.196kg / s
m
= 705 kg/hr

MODULE 3
SECOND LAW OF THERMODYNAMICS
The first law states that when a closed system undergoes a cyclic process, the cyclic integral of the
heat is equal to the cyclic integral of the work. It places no restrictions on the direction of the heat
and the work.
As no restrictions are imposed on the direction in which the process may proceed, the cycle may be
reversed and it will not violate the first law.
Example (1):
A closed system that undergoes a cycle involving work and heat.
In the example considered the system undergoes a cycle in which work is first done on the system by
the paddle wheel as the weight is lowered. Then let the cycle be completed by transferring heat to
the surrounding.
From experience it has been learnt that we cannot reverse this cycle. i.e., if we transfer heat to the
gas, as shown by the dotted line, the temperature of the gas will increase, but the paddle wheel will
not turn and lift the weigh. This system can operate in a cycle in which the heat and work transfers
are both negative, but it cannot operate in a cycle when both are positive, even though this would not
violate the first law.
Example (2):
Let two systems, one at a high temperature and the

High Temperature other at a low temperature undergoes a process in
which a quantity of heat is transferred from the high –
temperature system to the low temperature system.
Q Q
From experience we know that this process can take
place. But the reverse process in which heat is
Low Temperature transferred from the low temperature system to the
high temperature system does not occur and that it is

impossible to complete the cycle by heat transfer
only.
These two examples lead us to the consideration of the heat engine and heat pump (i.e., refrigerator).
Experience tells us that the reversed processes described above do not happen. The total energy of
each system would remain constant in the reversed process and thus there would be no violation of
the first law. It follows that there must be some other natural principle in addition to the first law
and not deducible from it, which governs the direction in which a process can take place in an
isolated system. This principle is the Second law of thermodynamics.
Example (3) Work of the mechanical form, can be converted completely into heat
Consider the pushing of a block over a rough surface. The work used in pushing the block to
overcome friction produces a heating effect on the block and the surface. To restore the temperature
of the system to its original value, heat, equivalent in amount to the work input must be removed
from the system. But from experience the converse of the operation is impossible. The heat that
was removed will not of its own accord flow back into system, restore the block to its original
position and deliver an amount of work equivalent to the original work input. Furthermore, heating
the block will obviously not cause it to move, either.
The first law does not answer many questions (1) why there cannot be complete transformation of
heat into work but work can be completely transformed into heat. (2) Why some processes can
proceed in one direction but not in the other and the first law in no way explain, why it is possible
for certain processes to take place but impossible for other processes to occur.
The second law does provide answers to these questions. The second law is broad and the heart of
the second law is a property called Entropy.
Heat Engine:
Any device which converts heat into work. Consider a heat engine as a system which work in a
thermodynamic cycle and converts a portion of the heat into the work, when the heat transfer occur
from a body at higher temperature to a low temperature body. E.g., steam power plant,
Thermocouple etc.
Gas turbines are also called heat engines though they do not work in a thermodynamic cycle
Steam power plant:
Let QH = Heat transferred from a high temperature reservoir like a furnace to the working fluid
(water)
QL= Heat rejected from the steam to the low temperature reservoir like coolant in the condenser.

W= Amount of work done by the fluid during the cycle to run the generator or any other devices.
A steam turbine power plant

Thermal Efficiency (th)
Energy output Energy Sought for

 th  
Energy input Energy that cos ts
W Q  QL Q
  H 1 L
QH QH QH
The first law has put no restriction by which the whole heat energy QH cannot be converted into
work W, by reducing the transfer of heat to the low temperature reservoir to zero i.e., by reducing
QL to zero. The th in that case would have 100%. But from experience such performance is
impossible. During the process there will always be some loss of energy. This is also one of the
limitation of the first law.
Refrigerator:
QH
Condenser Heat cannot flow from a low temperature

body to a high temperature body. But this can
Compressor
be done by providing external work to the
Expansion
valve system.
Evaporator
W
Evaporator
QL

Consider a simple vapour compression system.
W Amount of work done on the fluid (Refrigerant)
QL Amount of heat that is transferred to the fluid (Refrigerant) in the evaporator (low
temperature reservoir)
QH Heat transferred from the fluid to the coolant in the condenser (High temperature reservoir)
The efficiency of a refrigerator is given by the term COP.
When the system works as refrigerator, the main interest is the net cooling effect QL for a
refrigerator,
Energy sought for QL

COP  
Energy that cos ts W
QL

QH  QL
When the system works as a heat pump, the main interest is the heat QH . Therefore for a heat pump.
QH QH
COP  
W QH  QL
This illustration shows the limitation of the first law. From these we conclude that there must be
some physical principle which though not derivable from the first law, directs the direction and
extent up to which energy can be converted into one form to the other form. This principle is the
second law of thermodynamics.
Second law like first law has no mathematical proof. It is based on the results of countless
observations in nature.
PERPETUAL MOTION MACHINE OF FIRST KIND (PMMKI)
No machine can produce energy without corresponding expenditure of energy without

corresponding expenditure of energy i.e., it is impossible to construct a PMMK of first kind. The
machine violates the first law of thermodynamics. All attempts made so for to make PMMKI have
failed, thus showing the validity of the first law.

Second law of Thermodynamics

There are two classical statements of the second law of thermodynamics
1) Kelvin – Planck statement

2) Clausius statement
Kelvin – Planck statement

“It is impossible to construct a device which will operate in a cycle & produce no effect other than
the raising of a weight and the exchange of heat with a single reservoir”
i.e., it is impossible to construct an engine which will operate in a cycle will produce no effect other
than the transfer of heat from a single thermal reservoir and the performance of an equivalent
amount of work”.
No actual or ideal engine operating in cycles can convert into work all the heat supplied to the
working substance, it must discharge some heat into a naturally accessible sink because of this
aspect and the second law is often referred as the law of degradation of energy.
The statement implies that it is impossible to construct a heat engine that working in a cyclic process
can absorb an amount of heat from a high temperature reservoir and can do an equivalent amount of
work. In other words it is not possible to construct a heat engine having thermal efficiency of 100
percent.

Constant Temp
System
QH
Steadily
W
operating system
IMPOSSIBLE POSSIBLE
nd
A directional implication of the 2 Law
PERPETUAL MOTION MACHINE OF SECOND KIND (PMMKII)
Without violating the first law a machine can be imagined

which would continuously absorb heat from a single thermal
reservoir and would convert this heat completely into work.
The efficiency of such a machine would be 100%. This
machine is called PMMK II. A machine of this kind will
violate the second law of thermodynamics and hence does not
exist.
Clausius Statement
It is impossible to construct a heat pump which operating in a cycle will produce no effect other than
the transfer of heat from a low temperature thermal reservoir to a higher temperature thermal
reservoir.
That is in order to transfer heat from a low temperature thermal reservoir to a high temperature
thermal reservoir work must be done on the system by the surroundings.

IMPOSSIBLE POSSIBLE
Although the Kelvin – Planck and Clausius statements appear to be different, they are really
equivalent in the sense that a violation of one statement involves violation of the other.
Although the Kelvin – Planck and Clausius statements appear to be different, they are really
equivalent in the sense that a violation of one statement involves violation of the other.
Proof of violation of the Kelvin – Plank statement results in violation of the Clausius statement.
Consider a heat engine that is operating in a cyclic process takes heat (QH) from a high temperature
reservoir & converts completely into work (W), violating the Kelvin – Planck statement.
Let the work W, which is equal to QH, be utilized to drive a heat pump as shown. Let the heat pump
take in QL amount of heat from a low temperature reservoir and pump (QH + QL) amount of heat to
the high temperature reservoir.

From the diagrams we see that a part of heat QH, pumped to the high temperature reservoir is
delivered to the heat engine, while there remains a heat flow QL, from the low temperature reservoir
to the high temperature reservoir, which in fact violates the Clausius statement.
Proof of violation of the Clausius statement results in violation of the Kelvin – Planck
statement.
Consider a heat pump that operating in a cyclic process takes in an amount of heat QL from LTR and
transfer the heat equivalent amount of heat QL to the HTR violating the Clausius statement.
Let an amount of heat QH, which is greater than QL, be transferred from high temperature reservoir
to a heat engine, an amount of heat QL, be rejected by it to the LTR and an amount of work W which
is equal to (QH – QL ) be done by the heat engine on the surrounding.
Since there is no change in heat transfer in the LTR, the heat pump, the HTR and the heat engine
together can be considered as a device which absorbs an amount of heat (QH – QL) from the HTR
and produce an equal amount of work W = QH – QL which in fact violates the Kelvin – Planks
statement.
Reversibility and Irreversibility

If 100% efficiency is unattainable, what is the max possible efficiency which can be attained and
what factors promote the attainment of this max value? In trying to answer these questions,
thermodynamics has invented & used the concept of reversibility, absolute temperature and entropy.
Reversible Process:
-for a system is defined as a process which once having taken place, can be reversed and leaves no
change in either the system or surroundings. Only ideal processes can do this and restore both
system and surroundings to their initial states. Hence an ideal process must be a reversible process.

No real process is truly reversible but some processes may approach reversibility, to a close
approximation.
Example:
1) Frictionless relative motion

2) Extension and compression of a spring
3) Frictionless adiabatic expansion or compression of fluid.
4) Polytropic expansion or compression etc.,
The conditions for a process to be reversible may be given as follows:
i) There should be no friction

ii) There should be no heat transfer across finite temperature difference.
iii) Both the system and surrounding be stored to original state after the process is reversed.
Any process which is not reversible is irreversible.
Example: Movement of solids with friction, A flow of viscous fluid in pipes and passages mixing of
two different substances, A combustion process.
Every quasistatic process is reversible, because a quasistatic process is of an infinite succession of

equilibrium states.
Examples of Irreversible processes:
(i) Solid Friction (ii) Free expansion

Proof that heat transfer through a finite

temperature difference is irreversible
Heat transfer through a finite Heat transfer through a finite

temperature difference temperature difference is irreversible
Proof that Unrestrained expansion

makes process irreversible
INTIAL STATE REVERSED PROCESS

CARNOT cycle:
To convert heat continuously into work, at least two thermal reservoirs are required, one will be a
HTR (Heat source) which will supply heat to the heat engine and the other will be a low temperature
reservoir LTR (sink) to which the heat rejected by the heat engine will flow.
Carnot was the first man to introduce the concept of reversible cycle. The CARNOT engine works
between HTR & LTR.
High temp The Carnot cycle consists of an alternate series of two reversible
reservoir isothermal and two reversible adiabatic processes. Since the
processes in the cycle are all reversible the Carnot cycle as a
QH whole is reversible.
W
CARNOT
Engine The Carnot cycle is independent of the nature of the working
substance and it can work with any substance like gas, vapour,
QL electric cell etc.,
Low
temperature
reservoir
CARNOT CYCLE ENGINE CARNOT CYCLE

1) Process 1–2: Gas expands isothermally absorbing heat Q1 from the source at Temperature T1.
Work done during this process is given by the area under 1 – 2 (W12)
2) Process 2–3: During this process cylinder is thermally isolated from the heat reservoir and the
head is insulated by the piece of perfect insulator. Gas expands reversibly and
adiabatically to temperature T2 to point 3. Work done is W23.
3) Process 3–4: Cylinder is in contact with the heat reservoir at T2. Gas is isothermally and
reversibly compressed to point 4 rejecting an amount of heat Q2 to the sink. The
work done on the W34.
4) Process 4–1: Cylinder is again isolated thermally from the thermal reservoir; gas is recompressed
adiabatically and reversibly to point 1. The cycle is now complete. Work done is
W41
The efficiency of the Carnot engine is given by,
Work output Q1  Q 2
η carnot                 (1)
Heat input Q1
V2
Q1  Heat added during process 1  2  mRT1 ln            (2)
V1
V3
Q 2  Heat rejected during process 3  4  mRT2 ln           (3)
V4
V2 V V V
mRT1 ln  mRT2 ln 3 T1 ln 2  T2 ln 3
Q1  Q 2 V1 V4 V1 V4
Therefore, η carnot           (4)
Q1 V2 V2
mRT1 ln T1 ln
V1 V1
Since process 2  3 is reversible adiabatic
1
V2  T2  γ 1
             (5)
V3  T1 
Process 4  1is also reversible adiabatic

1
V1  T2  γ 1 V V V V
   , Therefore , 2  1 or 2  3           (6)
V4  T1  V3 V4 V1 V4

T1  T2
η carnot             (7 )
T1
T1  T2 T Low Temperature
ηcarnot  1  2 1           (8)
T1 T1 High Temperature
From the above equation we can have the following conclusions.
Even in an ideal cycle, it is impossible to convert all the energy received as heat from the
source into mechanical work. We have to reject some of the energy as heat to a receiver at a
lower temperature than the source (sink).
The part of the heat which is converted into work is the available energy. The remainder of the heat
which is to be rejected to the sink is unavailable energy.
Carnot cycle is the most efficient cycle, but it is impossible to carry out the Carnot cycle in real
engines because of the following reasons.
i) To achieve isothermal process, the piston must move very slowly allowing heat interchange
to keep temperature constant.
ii) To achieve adiabatic process the piston must move very fast so that the heat interchange is
negligible due to very short time available.
The isothermal & adiabatic processes take place in the same stroke which means that for part of the
stroke the piston must move very slowly and for remaining part, it must move very fast. But this is
not possible.
Since Carnot cycle consists of reversible processes, it may be performed in either direction.

High temp
TH
reservoir
QH
CARNOT W
Heat Pump
QL
Low temperature
TL
reservoir
Carnot heat pump with a gas
Reversible adiabatic
Process 1 - 4 Temperature falls down from TH to TL
expansion
Reversible isothermal
Process 4 - 3 Temperature remains constant
expansion
Reversible adiabatic
Process 3 - 2 Temperature increases from TL to TH
Compression
Reversible isothermal
Process 2 - 1 Temperature remains constant
Compression
QH QH TH
COP of heat pump =  
W QH  QL TH  TL
QL QL TL
COP of refrigerator =  
W QH  QL TH  TL

Problems:
A heat engine works on the Carnot cycle between temperature 900 C & 200 C. If the engine
receives heat at the higher temperature at the rate of 60 kW, calculate the power of the engine.
TH = 900 + 273 = 1173 k
TL = 200 + 273 = 473 k
TH  TL 1173  473
 th    0.597
TH 1173
. .
W W .
Also, th   .  W  th QH
QH Q
H
.
W = 0.597 x 60 = 35.82 kW
CARNOT theorem and corollary
“An irreversible heat engine cannot have efficiency greater than a reversible one operating between
the given two temperatures”.
That is reversible engine is maximum
This theorem can be proved by a process of reasoning.
Fig. (a) Fig. (b) Fig. (c)

Imagine a reversible engine R as shown in fig (a). The thermal efficiency of the engine is therefore
40
 40% Now if this engine is reversed 40 KJ of heat will be necessary to drive it, 60 KJ will be
100
taken from LTR and 100 KJ will be discharged to the HTR.
In fig (b) an irreversible engine I is driving the reversible engine R.
Now for a moment, let us assume that the irreversible engine I is more efficient than the reversible
engine R, say I = 50%, Then, since it takes 40 KJ to drive R, engine I will need to take
W 40
QH    80 KJ from HTR and it will reject 40 KJ to the LTR.
 I 0.5
We now observe that, we have in fig (b) an isolated system where in the reversible engine R
discharges 100-80 = 20 KJ more to the HTR than the irreversible engine I takes from the HTR more
ever, the reversible engine R takes 60-40 = 20 KJ more from the cold reservoir than the irreversible
engine I rejects to the LTR.
In other words, for the assumed condition that I is more efficient than R, we find that heat is being
moved continuously from LTR to HTR without the external aid.
Instead of simply moving the heat as shown in fig (b), we could direct the flow of energy from the
reversible engine directly into the irreversible engine, as in fig (c), whose efficiency is 50% would
allow to drive engine R, and at the same time deliver 10 KJ of work to something outside of the
system. This means the system exchanges heat with a single reservoir and delivers work.
These events have never been known to happen.
 We say that the assumption that I is more efficient than R is impossible.
 I  R
Corollary
rev, engine = f (TH, TL)
All reversible engines have the same efficiency when working between the same two temperatures.
Consider two reversible engines R1 and R2, operating between the two temperatures. If we imagine
R1 driving R2 backward, then Carnot theorem states that.
R  R
1 2
If R2 drives R1 backward, then
R  R
2 1

It therefore follows that
R  R
1 2
If this were not so, the more efficient engine could be used to run the less efficient engine in the
reverse direction and the net result would the transfer of heat from a body at low temperature to a
high temperature body. This is impossible according to the second law.
Suppose R1 & R2 are two reversible engines

working between the two same reservoirs as
shown let us assume that R1 is more efficient than
R2.
By our assumption
WR1  WR2
  
i.e., QH  QLR1  QH  QLR2 

i.e., QLR2  QLR1 
& WR1  WR2 

= QLR2  QLR1  …………………. (1)
Now let engine R2 be reversed so that it abstracts heat QLR2 from LTR at TL and delivers heat QH to
HTR at TH. Since the heat required by R1 is also QH we can replace the reservoir 1 by a conductor
between R1 & R2. This new combination would become a PMMK II because it would abstract a net
 
amount of heat QLR2  QLR1 from the single reservoir at TL and convert it completely into work.
Wnet  WR1  WR2  QLR2  QLR1
But this is impossible; hence the corollary must be true.
The Thermodynamics Temperature Scale
Zeroth law provides a basis for temperature measurement, but it has some short comings, since the
measurement of temperature depends on the thermometric property of a particulars substance and on
the mode of working of the thermometer.

We know that the  of a reversible engine operating between two thermal reservoirs at different
temperatures depends only on the temperatures of the reservoir and is independent of the nature of
the working fluid.
With this principle lord Kelvin decided a temperature scale that is independent of the thermometric
property of the working substance and this is the Kelvin temperature scale or thermodynamic
temperature scale or absolute temperature scale.
The concept of this temperature scale may be developed as follows.
QL
 th  1    TL , TH  ......................(1)
1
QH
Where, T  absolute temperature
There are many functional relations possible to relate QL & QH to TL & TH , which will serve to
define the absolute scale. the relation that has been selected for the thermodynamic scale of
temperature is
TH QH
 ........................(2)
TL QL
The Carnot efficiency may be expressed as
QL T
 th  1   1  L ......................(3)
1
QH TH
This means that if th1 of a Carnot cycle operating between two given constant temperature
reservoirs is known, the ratio of the to absolute temperature is also known, in order to assign values
of absolute temperature, however one other relation between TL and TH must be known.

Construction of Kevin temperature scale
Thermal reservoir Consider a series of reversible engines operating between

at T1 thermal temperature reservoirs in the following way. R1
absorbs an amount of heat Q1 from a thermal reservoir at
Q1 T1 and rejects heat Q2 to a thermal reservoir at T2. R2
absorbs an amount of heat Q2 from the reservoir at T2 and
WR1 rejects Q3 to a reservoir at T3 and so on. The temperatures
R1 are selected in such a way that the work done by each
engine is the same i.e.,
Q2
Thermal reservoir WR1  WR2  WR3          W

TL
at T2
Or
Q2
(Q1 – Q2) = (Q2 – Q3) = (Q3 – Q4) = ----- = W (1)
WR2
R2
From the definition of Kelvin temperature scale we have
Q3
Thermal reservoir Q1 T Q T Q T
 1 , 2  2 , 3  3      etc
at T3 Q2 T2 Q3 T3 Q4 T4
Q1 Q Q
  2  3           (2)
T1 T2 T3
On solving equations (1) & (2) we get
T1 – T2 = T2 – T3 = T3 – T4 = - - - - - - (3)

From this equations we conclude that the reversible engines operating in series in this way as shown
in Fig develops equal work when the temperature difference across them are equal.
Now a decision to be made on the magnitude of the degree of the Kelvin temperature scale. This is
usually done by choosing the steam point and the ice point at one atmosphere as the reference
temperatures. As the difference between these points s is 100 degrees, we can write
Ts - Ti = 100 ………….. (4)
Steam pt ice pt
On the other equation involving Ts & Ti can be derived experimentally by finding out the 
of a reversible engine operating between the steam point and the ice point. The efficiency
 = 26.80%
Ti Ti
Hence,  R  1   0.2680   0.7320 ...........(5)
Ts Ts
Solving (4) & (5), we get
Ts = 373:15 K, Ti = 273.15 K
K = C + 273.15
 Relationship between K & C is given by

Problems (on second Law of thermodynamics)
Problem 1. An engineer claims to have developed an engine which develops 3.4 kW while
consuming 0.44 Kg of fuel of calorific value of calorific value of 41870 kJ / kg in one hour. The
maximum and minimum temperatures recorded in the cycle are 1400 C & 350 C respectively is
the claim of the engineer genuine (Sept./Oct. 1996)
Solution:
Temperature of source, TH = 1400 C = 1673 K
Temperature of sink, TL = 350 C = 673 K
We know that the thermal efficiency of the CARNOT cycle is the maximum between the specified
temperature limits and is given as.
QL T
 carnot  1  1 L
QH TH
TL 623
i.e.,  carnot  1  1  0.628
TH 1673
= 62.8%
The thermal efficiency of the engine developed by the engineer is given as

. .
QL W
 thermal  1  .
 .
QH QH
.
We have, W  3.4 kW
. 0.44 x 41870
QH   5.12 kW
3600
3.4
&  thermal   0.664 or 66.4%
5.12
Since  thermal   Carnot, Engineer claim is not genuine Answer

Problem 2. Two Carnot engines A and B are connected in series between two thermal reservoirs
maintained at 100 k and 100 k respectively. Engine A receives 1680 kJ of heat from the high
temperature reservoir and rejects heat to Carnot engine B. Engine B takes in the heat rejected by
engine A and rejects heat to the low temperature reservoir. If engines A and B have equal thermal
efficiencies determine (1) The heat rejected by engine B (2) The temperature at which heat is
rejected by engine A and (3) The work done during the process by engines A and B respectively.
Solution:
QHA = 1680 KJ
High temp
reservoir
TH = 1000 K
 A  B
QHA = 1680 KJ
WA = QHA - QLA We have,

HE A
QLA = QHB
Q LA
A  1 
QHA
WB = QHB - QLB
HE B
TLA
1
TL = THB TH
QLB
QLB
& B  1 
Low temperature QHB
reservoir TL =
100 K
TL
1
THB
i) Given  A   B
TLA T
 1 1 L
TH THB
TL T T T
i.e,  LA  L  LA  THB  TLA 
THB TH TLA TH

i.e., T 2 LA  TL  TH  100  1000
= 100000 K2
[ TLA = THB = 316.23 K, i.e., the temperature at which heat is rejected by engine A]
ii) We have also
TLA 316.23
 A  B  1  1
TH 1000
= 0.684 or 68.4%
The heat rejected by engine B
QLA T T
B  1   1  LH  1  L
QHB THB TLA
QLB T T
i.e,  L  QLB  QHB L        (1)
QHB TLA TLA
We have,
QLA T
A  1   1  LA
QHA TH
TLA 316.23
i.e., QLA  QHA  1680 
TH 1000
= 531.27 KJ = QHB
100
Substituting this in (1) we get QLB  531.27   168KJ Ans.
316.23
iii) Work done
WA = QHA – QLA = 1680 – 531.27 = 1148.73 KJ

WB = QHB – QLB = 531.27 – 168 = 363.27 KJ
Problem 3. A reversible refrigerator operates between 35 C and -12 C. If the heat rejected to
reservoir is 1.3 kW, determine the rate at which to heat is leaking into the refrigerator.
Solutions: Reversible refrigerator
TH = 35 C = 308 K
TL = -12 C = 261 K
. .
QL QL
(COP) Ref = .
 .
W QH  QL
TL
TH = 308 K  ( It is a reversible refrigerator)
TH  TL
. . .
QH  W  QL
.
.
Ref W QL TL 261
i.e,  
.
QH  QL
.
TH  TL 308  261
.
QL
= 5.553
TL = 261 K
i.e, Q L  5.553  Q H  Q L   5.553 Q H  5.553 Q L

. . . . . .
 
. . . .
i.e., Q L  5.553 Q L  5.553 Q H
.
. 5.553 . 5.553
i.e., Q L   QH   1.3 = 1.102 kW Ans.
6.553 6.553

Problem 4. A reversible power cycle is used to drive heat pump cycle. The power cycle takes in Q 1
heat units at T1 K and rejects Q2 at T2 K. The heat pump abstract Q4 from the sink at T4 k and
discharges Q3 units of heat to a reservoir at T3 K. Develop an expression for the ratio Q4 / Q1 in
terms of the four temperatures
Solution:-
Source T1 K Source T3 K
Q1 Q3  W  Q4   Q1  Q2   Q4
W  Q1  Q2
HE HP
Q2 Q4
Sink Sink
T2 K T4 K
We have
For reversible power cycle,
Q1  Q2 T1  T2
thermal            (1)
Q1 T1
For reversible heat pump cycle,
Q3 T3
(COP) H.P           (2)
Q3  Q4 T3  T4
Multiply (1) by (2), we get
Q1  Q2 

Q3 T  T2   T3
 1
Q1 Q3  Q4 T1 T3  T4 
Considering LHS,

Since Q3  Q4  W  Q1  Q2 , we get
Q1  Q2 Q3 Q W  Q4
x  3 
Q1 Q1  Q2 Q1 Q1

Q1  Q2   Q4 
Q1  Q2  
Q4
Q1 Q1 Q1
 T  T2  Q4
  1  
 T1  Q1
On substitution in the above equation
 T1  T2  Q4  T  T2  T3
   =   1  x
 T1  Q1  T1  T3  T4 
Q4  T1  T2   T3   T1  T2 
i.e.,         
Q1  T1   T3  T4    T1 
 T  T2   T3 
  1    1
 T1   T3  T4  
 T  T2   T3  T 3  T4 
  1   
 T1   T3  T4 
 T  T2   T4 
  1     Ans
 T1   T3  T4 

Problem 5. A Heat engine is used to drive a heat pump. The heat transfers from the heat engine
and from the heat pump are used to heat the water circulating through the radiators of a building.
The efficiency of the heat engine is 27% and the coefficient performance of heat pump is 4.
Evaluate the ratio of heat transfer to the circulating water to the heat transfer to the heat engine.
Solution:-
 HE  27%
(COP)HP = 4
We have
Heat rejected from heat engine = QL1
Heat transfer from heat pump = QH 2
Heat transfer from circulating water = QL1  QH 2
 The ratio of heat transfer to the circulating water to the heat transfer to the engine
QL1  QH 2
=        (1)
QH1
We also have,
QH1  QL1
 HE   0.27        (2)
QH1

QH 2
(COP) HP   4        (3)
QH 2 _ QL2
We have from (2),
QL1  QH1  0.27 QH1  0.73QH1        (4)
From (3),

QH 2  4  QH 2  QL2  4  QH1  QL1   
 4  QH 1  0.73QH 1   1.08QH 1        5
Substituting in equation (1), We obtain
Q  QH 2  0.73QH 1  1.08QH 1
  1.81 Ans.
L1
QH 1 QH 1
Problem 6. It is proposed to construct a refrigeration plant for a cold storage to be maintained at -

3C. The ambient temperature is 27C. If 5 x 106 kJ /hr of energy has to be continuously removed
from the cold storage, calculate the maximum power required to run.
Problem 7. There are three reservoirs at temperatures of 827C, 127C and 27C parallel. A
reversible heat engine operates between 827C and 127C and a reversible refrigerator operates
between 27C and 127C respectively 502 kJ of heat are extracted from the reservoir at 827C by the
heat engine and 251 kJ of heat are abstracted by the refrigerator from the reservoir at 27C. Find the
net amount of heat delivered to the reservoir at 127C.
Can the heat engine drive the refrigerator and still deliver some net amount of work? If so how
much?
Solutions: Given: Reversible heat engine and refrigerator
QHE QLE QHR QLR

HE Ref T3 = 27C
T1 = 827C T2 = 127C 251 kJ
502 kJ
= 1100k = 400k = 300k
WHE WRe f

QLE T
For heat engine   1  1  2
QHE T1
QLR T3
For Refrigerator (COP) Re f  1  
QHR  QLR T2  T3
400
We have   1   0.636
1100
WHE
Also,  0.636  WHE  0.636  502 = 319.27 kJ
QHE
T3 300
& (COP) Re f    3.0
T2  T3 400  300
QLR
Also  3.0  QLR  3.0 QHR  QLR 
QHR  QLR
QLR  3QHR  3QLR  3QHR  4QLR
4 4
i.e., QHR QHR   251 = 334.67 kJ
3 3
For HE, QLE  QHE  WHE  502  319.27  182.73 k J
Net amount of Heat delivered
QLE  QHR = 182.73 + 334.67 = 517.4 kJ Ans.
WRe f i.e. work required to drive the refrigerator
 QHR  QLR  334.67  251 = 83.67 kJ
Since WHE  WRe f Heat engine drives the refrigerator and still deliver some net amount of work
i.e, WHE  WRe f = 319.27 – 83.67 = 235.6 kJ

THE THERMODYNAMIC TEMPERATURE SCALE
A Temperature scale that is independent of the properties of the substances that are used to measure
temperature is called a Thermodynamic scale of temperature. It can be defined with the help of
reversible heat engines.
The thermal efficiency of a reversible engine is given by
QL T
 th, rev  1   1 L
QH TH
i.e., th, rev   f TH , TL           (1)
QL
Also,  f TH , TL           (2)
QH
If some functional relationship is assigned between TH, TL and QH, QL equation (2) then becomes the
definition of a temperature scale.
This functional form of f TH , TL  can be developed by considering the three reversible heat
engines as shown.
Engines R1 & R2 can be combined into one reversible

engine operating between the same reservoirs as
engine R3 and thus this combined engine will have
the same efficiency as engine R3
Using equation (2) we can write for engines R1,

R2 and R3 respectively.
Q1 Q
 f T1 , T2 , 2  f T2 , T3 
Q2 Q3
Q1
and  f T1 , T3 
Q3
Q1
Also can be expressed as
Q3
Q1 Q1 Q2
 
Q3 Q2 Q3
i.e., f T1 , T3   f T1 , T2   f T2 , T3 

From the above equation we see that, the left hand side is a function of T1 and T3, the right hand side
too must be a function of T1 and T3, only and not T2. That is the value of the product on R.H.S is
independent of T2. To satisfy this condition, the function f must have the following form:
 T1   T2 
f T1 , T2   & f T2 , T3  
 T2   T3 
So that,
 T1 
 f T1, T3  
Q1
       (3)
Q3  T3 
For a reversible heat engine operating between two reservoirs at TH & TL, equation (3) can be
written as:
QH  TH 
        (4)
QL  TL 
This is the only condition that the second law stipulates on the ratio of heat flows to and from the
reversible heat engines. Since the function  (T) is completely arbitrary, several values of it will
satisfy equation (4). Lord Kelvin first proposed taking  (T) = T to define thermodynamic
temperature scale as:
 QH  TH
             (5)
 QL  rev TL
This scale is called the Kelvin scale and the temperatures on this scale are called absolute
temperatures.
With equation (5) the thermodynamic scale is not completely defined, since it gives only a ratio of
the absolute temperatures. The triple point of water is assigned the value 273.15 k. The magnitude
of a Kelvin is defined as 1/273.15 of the temperature interval between absolute zero and triple point
temperature of water. The magnitudes of temperature units on the Kelvin and Celsius scales are
identical (1k = 1C) the temperature on the scales are related by a constant 273.15 (the temperature
of the ice point) as:
T (C) = T (k) – 273.15 *
Additional Problems:
Problem 8. There are two ways of increasing the efficiency of a Carnot heat engine:
i) Lowering the temperature T2 of the low temperature reservoir by ∆T, while keeping the
temperature T1 of the high temperature reservoir a constant.

ii) Increasing the temperature T1 by ∆T, while keeping the temperature T2 a constant. Which is more
effective? Prove your answer.
Problem 9. An inventor claims that his engine has the following:

Specifications
Heating value of the fuel: 74500 kJ / kg, Temperature limits: 750 0 C and 25 0C
Power developed: 75 kW,
Fuel burned: 0.07 kg / min
State whether the claim is valid or not.
Problem 11. A Carnot refrigerator consumes 200 W of power in summer when the ambient
atmosphere is 40 0C. The rate of energy leak into the refrigerator is estimated at 20 W per degree
Celsius temperature difference between the ambient atmosphere and the cold space of the
refrigerator. If the refrigerator is continuously operated, determine the temperature at which the cold
space is maintained.
Problem 12. Direct heat engine operating between two reservoirs at 327 0C and 27 0C drives a
refrigerator operating between 27 0C and 13 0C. The efficiency of the heat engine and the COP of the
refrigerator are each 70% of their maximum values. The heat transferred to the direct heat engine is
500 kJ. The net heat rejected by the engine and the refrigerator to the reservoir at 27 0C is 400 kJ.
Find the net work output of the engine-refrigerator combination. Draw the schematic representation.
Problem 13. A reversible heat engine operates between two reservoirs at constant temperature of
160 0C and 20 0C. The work output from the engine is 15 kJ / sec. Determine: i) Efficiency of the
cycle ii) Heat transfer from the reservoir at 160 0C iii) heat rejected to the reservoir at 20 0C. If the
engine is reversed and operates as a heat pump between the same two reservoirs, determine the COP
of the heat pump & the power required when the heat transfer from the reservoir at 20 0C is 300 kJ /
min.
Problem 14. A cyclic heat engine operates between a source temperature of 800 0 C and a sink
temperature of 30 0C. What is the least rate of heat rejection per kW net output of the engine?
Problem 15. A reversible heat engine operates with two environments. In the first it draws 12000
kW from a source at 400 0C and in the second it draws 25000 kW from a source at 100 0C. In both
the operations the engine rejects heat to a thermal sink at 20 0C. Determine the operation in which
the heat engine delivers more power.

ENTROPY
The first law of thermodynamics introduces the concept of the internal energy U, and this term helps
us to understand the nature of energy, as defined by the first law. In the similar way the second law
introduces the concept of entropy S, like internal energy it is also a thermodynamic property and is
defined only in terms of mathematical operations.
General Discussion:
For a system undergoing a quasistatic process, work done at the boundary is given by,
W  P dV      (1)
Since a reversible process is a quasistatic process this relation gives the work done at the boundary
of a system during a reversible process.
Considering a reversible cycle in which only work involved is done at the boundary of the system,
we have
 Q   W   P dV      (2)
Form the equation (2) ,Work is given by the cyclic integral of product of two properties
viz. P is an intensive property & dV is change in an extensive property.
For a reversible cycle when work (which is a path function) is defined by the product of two
properties one is intensive and the other is change in an extensive property, why can‟t Heat (which is
also a path function) is defined by the cyclic integral of product of two properties one intensive and
the other change in an extensive property.
Yes, the intensive property most closely associated with heat is temperature and the other extensive
property for this answer is ENTROPY. Total entropy is denoted by capital letter S and lower case „s‟
represents the specific entropy, i.e. entropy / unit mass.

If entropy is an extensive property then what exactly is entropy?
Entropy is –
1. The amount of Energy that is not available for work during a certain process
2. A measure of the disorder of a system.
3. Measure of disorganization or degradation in the universe that reduces available energy, or
tendency of available energy to dwindle. Chaos, opposite of order.
4. The state of disorder in a thermodynamic system: the more energy the higher the entropy.
5. A measure of the dispersal or degradation of energy.
6.A measure of the disorder or randomness in a closed system. For example, the entropy
of an unburned piece of wood and its surroundings is lower than the entropy of the ashes, burnt
remains, and warmed surroundings due to burning that piece of wood.
7.The scientific measure of the disorder in a system; the greater the disorder, the greater the
entropy.
8.The thermodynamic entropy S, often simply called the entropy in the context of
thermodynamics, is a measure of the amount of energy in a physical system that cannot be used to
do work. It is also a measure of the disorder present in a system. The SI unit of entropy is J·K-1
(joule per Kelvin), which is the same unit as heat capacity.
9."Entropy" is defined as a measure of unusable energy within a closed or isolated system (the
universe for example). As usable energy decreases and unusable energy increases, "entropy"
increases. Entropy is also a gauge of randomness or chaos within a closed system. As usable energy
is irretrievably lost, disorganization, randomness and chaos increase.
Understanding entropy: One of the ideas involved in the concept of

Example 1. entropy is that nature tends from order to
disorder in isolated systems. This tells us that
the right hand box of molecules happened
before the left. Using Newton's laws to
describe the motion of the molecules would
not tell you which came first.
For a glass of water the number of molecules is

astronomical. The jumble of ice chips may look
more disordered in comparison to the glass of
Example 2. water which looks uniform and homogeneous.
But the ice chips place limits on the number of
ways the molecules can be arranged. The water
molecules in the glass of water can be arranged
in many more ways; they have greater
"multiplicity" and therefore greater entropy.

Solids have lesser entropy than liquids. Statistically, in solids the atoms or molecules are in their
fixed places, whereas in liquids and even more in gases you never know exactly where to find them.
The fixed sequence of atoms in solids reflects a higher ordered state.
Consider a body which is heated and another one is cooled. What happens to the entropy of the two
bodies? Entropy increases on heating. Does disorder increase, too?
Yes, it does. We know that heat is stored in a piece of matter as the random motion of particles. The
hotter a body, the more its atoms and molecules jiggle around. It is not difficult to identify disorder
by faster jiggling motion.
CLAUSIUS THEOREM:
The thermal efficiency of reversible Carnot cycle is given by the expression,
QL T Q Q
Carnot  1   1  L or H  L        (1)
QH TH TH TL
Where TH and TL are the temperatures of high temperature thermal reservoir and low temperature
thermal reservoir respectively, and QH is the heat supplied and QL is the heat rejected by the Carnot
engine.
Considering the usual sign convention, +ve for the heat absorbed and –ve for the heat rejected, we
may write,
QH Q Q Q
  L or H  L  0          (2)
TH TL TH TL
QH Q
Equation (2) shows that the sum of the quantities and L , associated with absorption and
TH TL
rejection of heat by the fluid of a reversible heat engine is zero for the entire cycle. Since the
working fluid returns to its initial state at the end of the cycle, it undergoes no net change in
Q Q
properties, suggesting that the quantities H and L represents property changes of the working
TH TL
fluid because their sum is zero for the cycle and this is the characteristic of a property or state
function. The amount of heat transfer is known to depend on the path of the process. However if the
heat is divided by the temperature at which the transfer takes place, the result is independent on the
path.
The above conclusion is for the Carnot reversible cycle. But it can be proved that the conclusion is
valid for any reversible cycle.

Consider any arbitrary reversible cycle a-b-c-d-a as shown. In such cycle absorption and rejection of
heat do not occur at two constant temperatures but take place at continuously changing temperatures.
j b
m
f
Pressure e
c
a
k
n
g
d h
Volume
The cycle can be now broken into an infinite number elementary Carnot cycle by drawing a series
of infinitely close adiabatic lines, eh, fg, mn, etc. efgh, fmng etc represents elementary Carnot cycle
in which sections ef, gh etc can be considered as isothermal lines.
For any differential Carnot cycle, efgh, let QH1 be the heat absorbed during isothermal process ef and
QL1 be the heat rejected during the isothermal process gh. The temperature of ef is TH1 and gh
process is TL1.Then we may write,
QH 1 Q
 L1
TH 1 TL1
Using proper sign convention +ve for the absorption of heat and -ve for rejection, we get,
QH 1 Q
 L1  0          (1)
TH 1 TL1
Similarly,
QH 2 Q
 L 2  0          (2) for the cycle fmng
TH 2 TL 2
From these relations we see that the algebraic sum of the ratios of the amounts of heat transferred to
the absolute temperature for the Carnot cycles taken together is equal to zero, thus,
 QH 1 Q  Q Q 
  L1    H 2  L 2            0
 TH 1 TL1   TH 2 TL 2 

 QH QL 
i.e.   T    0          (3)
 H TL 
Q
As the number of Carnot cycles is very large, the sum of the terms over the complete cycle
T
Q
becomes equal to the cyclic integral of , We may , therefore write
T
Q
 R
T
 0        (4)
Q
Where R represents reversible cycle. This result is known as CLAUSIUS THEOREM. is
T
known as ENTROPY.
ENTROPY:
Definition: Entropy , S is a property of system such that its increase S2 - S1 as the system changes
from state 1 to state 2 is given by,
2
QR
S 2  S1            (1)
1
T
QR
In differential form equation (1) can be written as dS 
T
THE CLAUSIUS INEQUALITY:

Q
When any system undergoes a cyclic process, the integral around the cycle of is less than or
T
equal to zero.
Q
In symbols,  T
 0        (1)
Where δQ is an infinitesimal heat transfer, T is absolute temperature of the part of the system to
which heat transfer δQ occurs.
PROOF:
For any reversible cycle from Clausius theorem,
Q
 R
T
 0        (2)

From the Carnot‟s theorem we know that the efficiency of an irreversible engine is less than that of a
reversible engine, i.e.  I  R

Where  I is efficiency of the irreversible engine and  R is efficiency of the reversible engine.
 Q   Q 
Hence, 1   L   1   L             (3)
 QH  I  QH  R
Where I and R represents irreversible and reversible processes respectively.
For a reversible engine, the ratio of the heat absorbed and heat rejected is equal to the ratio of the
absolute temperatures. Therefore
 Q  T   Q   TL 
1   L   1   L             (4) i.e.  L    
 QH I  TH   QH  I  TH 
 Q   T   Q   Q 
or  H    H  i.e.  H    L   0        (5)
 QL  I  TL   TH  I  TL  I
Using sign conventions of +ve for absorption of heat and –ve for the rejection of heat, we get,
 QH   QL 
      0        (6)
 TH  I  TL  I
From this we see that the algebraic sum of the ratios of the amounts of heat transferred to the
absolute temperature for a cyclic irreversible process is always less than zero,
Q
 I
T
 0        (7)
Q
Combining equations (2) and (7), we get  T
 0        (8)
This is known as CLAUSIUS INEQUALITY.
CLAUSIUS INEQUALITY is helpful in determining whether the process is reversible or not.

Q Q
If  T
 0 , the cycle is reversible,  T
 0 , the cycle is irreversible and possible and
Q
 T
 0 , the cycle is impossible since it violates the second law of thermodynamics.
ILLUSTRATION OF CLAUSIUS INEQUALITY:
Example 1. Consider the flow of heat from the reservoir at temp T1 to that at T2 across the conductor
as shown. Conductor is the system. In the steady state there is no change in the state of the system.
A Clausius
T1 δQ1 δQ2 T2
Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. inequality Page 125
Let δQ1 = 1000 kJ , T1 = 500 K, T2 = 250 K

Since δQ1 = 1000 kJ, δQ2 = -1000 kJ
Q Q
T 
1000 1000
500

250
 2.5 kJ / K , Hence T  0 , proved.
Example 2. E is the system which executes a cyclic process.
Q 1000 600
T  
500 250
 0.4 kJ / K
500
K However, if E were a reversible engine, then work
1000 δW would have been,
kJ 1000 (500  250 )
E δ W   500 kJ and
W 500
600 kJ
Q 1000 1000  500
T 
500

250
 0 kJ / K
250
K Hence
Example 3.
Q
A heat engine receives reversibly 420 kJ/ cycle
 0 ofproved
heat from a source at 327 0C, and rejects heat
0 T
reversibly to a sink at 27 C. There are no other heat transfers. For each of the three hypothetical
Q
amounts of heat rejected, in (a), (b) and (c) below, compute the cyclic integral of . From these
T
results show which case is irreversible, which reversible and which impossible. (a) 210 kJ / cycle
rejected (b) 105 kJ / cycle rejected and (c) 315 kJ / cycle rejected.

Case (a)
Q 420 210 Q
T  
600 300
 0 , Since 
T
 0 , reversible
Case (b)
Q 420 105 Q
T  
600 300
 0.35 , Since 
T
 0 , Impossible
Case (c)
Q 420 315 Q
T  
600 300
  0.35 , Since 
T
 0 , irreversible
ENTROPY IS A PROPERTY:
Proof that entropy is a property:
QR
Statement: For any system undergoing internally reversible cycle, the integral of is zero, in
T
QR
symbols,  T
 0      (1)
Let the system executes a cyclic process, starting at state 1, proceeding to state 2 along the reversible
path A, and returning state 1 along a different path B.
Reversible Path A
2
X Reversible Path B
1
QR
From the Clausius inequality we have along path 1A2B1,  T
 0      (2)

Since the process is reversible, we may reverse it and thus cause the system to retrace its path
precisely. Let the element of heat transfer corresponding to the system boundary at temperature T be
δQ’R , for this reversed process.
Q ' R
Then we have along path 1B2A1,  T
 0      (3)
But, since the second cycle is simple the first one with the direction reversed, we have,
QR '   QR      (4)

QR
Therefore, statement (3) becomes; along path 1B2A1,   T
 0      (5)
QR
or  T
 0      (6)
Comparing statements (2) and (6) we see that they can be both true simultaneously only
QR
if,  T
 0      (7) , hence Entropy is a property.
QR
Statement: The integral of , when a system executes any reversible process between fixed
T
end states, is independent of the path of the process.
2 QR 2 QR
In symbols, for arbitrary paths A and B, 
1A T

1B T
Reversible Path A
2
Y
Reversible Path B
Reversible Path C
1
Consider a system which executes a reversible cyclic process, from 1 along path A to 2, and back
along path C to 1.Then we have,

QR 2 QR 1 QR


AC
T

1A T

2C T
 0      (1)
Similarly, for the reversible cyclic process 1B2C1, we can write,
QR 2 QR 1 QR


BC
T

1B T

2C T
 0      (2)
From equations (1) and (2) we get, i.e. (1) – (2) gives,
2 QR 1 QR 2 QR 1 QR

1A T

2C T

1B T

2C T
 0      (2)
2 QR 2 QR
i.e. 
1A T

1B T
     (3)
2 QR
Path A and path B are arbitrary and  1 T
has the same value for any reversible
path between (1) and (2) , hence from the definition of entropy we may write ( S 2- S1) has the same
value for any reversible path between 1 and 2 . Therefore ENTROPY is a property.
CALCULATION OF ENTROPY CHANGE FOR DIFFERENT PROCESS
Entropy change in IRREVERSIBLE process:

For a process that occurs irreversibly, the change in entropy is greater than the heat change divided
by the absolute temperature. In symbols,
Q
dS 
T
Proof:
Irreversible Path A
2
Reversible Path B
1

Consider an arbitrary irreversible cycle 1-A-2-B-1 as shown in figure. The path 1 to 2 (1-A-2) is
traversed irreversibly and the path 2 to 1 ( 2-B-1) reversibly. From the Clausius Inequality, we have
Q
 T
 0 , for the cycle which is irreversible and
Q
 T
 0 , for the cycle which is reversible ---------------------------- (1)
Since the entropy is a thermodynamic property, we can write

2 1
 dS   dS I   dS R  0      (2)
1A 2B
1 1 QR
For a reversible process we have, 2B
dS R  
2B T
     (3)
Substituting this in equation (2), we get
2 1 QR
1A
dS I  
2B T
 0      (4)
Using equation (1), for an irreversible cycle,
Q 2  Q  1  Q 
 T
 
1A
 
 T I
2 B  T  R  0      (5)
Now subtracting equation (5) from equation (4), we get
2 2  Q 

1A
dS I  1A  T  I      (6)
For small changes in states the above expression can be written as,
 Q 
dS I         (7)
 T I
Where the subscript I represents the irreversible process. The equation (7) states that in an
Q
irreversible process the change in entropy is greater than . Therefore we can write,
T
Q
dS I  , where equality sign is for reversible process and inequality sign is for irreversible
T
process.

IMPORTANT: The effect of irreversibility is always to increase the entropy of the system. If an
isolated system is considered, from the first law of thermodynamics the internal energy of the system
will remain constant. Q  0 , from the above expression dS Isolated  0 , i.e., the entropy of an
isolated system either increases or remains constant. This is a corollary of the second law of
thermodynamics and this explains the principle of increase in entropy.
MATHEMATICAL EXPRESSION OF THE SECOND LAW:
Q  TdS for reversible processes and Q  TdS for irreversible processes
The above equation may be regarded as the analytical expression of the second law of
thermodynamics.
ENTROPY CHANGES FOR AN OPEN SYSTEM:

In an open system the entropy is increased because the mass that crosses the boundary of the system
has entropy. Thus for an open system, we may write,
Q
dS   mi si  me se      (1)
T
Where, mi and me are the masses entering and leaving the system & s i , s e are the entropies.
As the mass mi enters the system, the entropy is increased by an amount mi si , similarly as the
mass me leaves the system, the entropy decreases by an amount me se
In steady flow process there is no change in the mass of the system and mi  me  m . We can
write, therefore
Q
m ( se  si )       (2)
T
For steady flow adiabatic process s e  si ( since Q  0 ) i.e. in a steady flow adiabatic process
the entropy of the fluid leaving must be equal to or greater than the entropy of the fluid coming in.
Since the equality sign holds for a reversible process, we conclude that for a reversible steady – flow
adiabatic process,
se  si      (3)
IMPORTANT RELATIONS FOR A PURE SUBSTANCE INVOLVING ENTROPY

PURE SUBSTANCE:
A pure substance has a homogeneous and invariable chemical composition even though there occurs
a phase change.
The first law for a closed system is given by,
Q  dE  W        (1)
In the absence of changes in kinetic and potential energies the equation (1) can be written as

Q  dU  W        (2)
For a reversible process Q  TdS
Therefore equation (2) becomes
TdS  dU  W        (3)
The work done at the boundary of a system during a reversible process is given by
W  PdV          (4)
Substituting this in equation (3), we get
TdS  dU  PdV        (5)
From equation (5) we realize that it involves only changes in properties and involves no path
functions. Therefore we conclude that this equation is valid for all processes, both reversible and
irreversible and that it applies to the substance undergoing a change of state as the result of flow
across the boundary of the open system as well as to the substance comprises a closed system.
In terms of per unit mass the equation (5) can be written as
Tds  du  Pdv        (6)
dU  d H  PV 
Since
 dH  PdV  VdP (since H = U + PV)
TdS  dH  PdV VdP  PdV  dH VdP
Therefore TdS  dH  PdV VdP  PdV  dH VdP
i.e. TdS  dH VdP
In terms of unit mass, Tds  dh  vdP
dh  vdP
or ds       (7)
T

PRINCIPLE OF THE INCREASE OF ENTROPY:
Entropy Change for the System + Surroundings

Consider the process shown. Let δQ is the heat transfer from a system at temperature T to the
surroundings at temperature T0, and δW is the work of this process (either +ve or –ve ). Using the
principle of increase in entropy
δW Q
dS system        (1)
System Temperature T
=T
Q
dS surroundings       (2)
T0
for a reversible process
δQ
The total change of entropy for the combined
Surroundings
system
Q Q
Temperature = T0
dS system  dS surroundings   
T T0
 1 1 
or dS system  dS surroundings  Q    
 T T0 
The same conclusion can be had for an open system, because the change in the entropy of the system
would be
Q
dSopensystem    mi si  me se
T
The change in the entropy of the surroundings would be,

Q
dS surroundings   mi si  me se
T0
Q Q
dS system  dS surroundings   
T T0
Therefore,  1 1  since T  T0 and it follows
or dS system  dS surroundings  Q    
 T T0 

1 1
that    0 and therefore dS system  dS surroundings  0
T T0
This means that processes involving an interaction of a system and its surroundings will take place
only if the net entropy change is greater than zero or in the limit remains constant. The entropy
attains its maximum value when the system reaches a stable equilibrium state from a non
equilibrium state.
ENTROPY FOR AN IDEAL GAS :
Let the ideal gas undergoes a change of state from state 1 to state 2. Let T1 , V1 and T2 , V2 be the
temperatures and volumes at state 1 and 2 respectively.
TdS  dU  PdV        (1)

We have, dU P
or dS   dV
T T
P mR
Since, dU  m cv dT and  where m is the mass and R is the gas constant, we get
T V
dT dV
dS  mcv  mR therefore
T V
T2 2 V 2 T
dT dV dT V
S 2  S1  m  c v mR  m  cv  m R ln 2        (2)
T1
T V1
V T1
T V1
If cv = constant, then
T2 V
S 2  S1  m cv ln  m R ln 2        (3)
T1 V1
TdS  dH VdP
Similarly, we have dH V
or dS   dP      (4)
T T
V mR dT dP
Since, dH  mc p dT &  we get, dS  mc p  mR
T P T P
T2 2 p T2
dT dP dT P
Therefore, S 2  S1  m  c p  m R  cv  m  cp  m R ln 2        (5)
T1
T p1
P T1
T P1

T2 P
If cp = constant, then S 2  S1  m c p ln  m R ln 2        (6)
T1 P1
For general case ( process ), change of entropy is given by,
T2 V T P
S 2  S1  m cv ln  m R ln 2  m c p ln 2  m R ln 2          (7)
T1 V1 T1 P1
or in specific values,
T2 v T P
s 2  s1  cv ln  R ln 2  c p ln 2  R ln 2          (8)
T1 v1 T1 P1
SPECIAL CASES:
a) Constant temperature process ( Isothermal process), T = Constant
V2 P v P
S 2  S1  m R ln   m R ln 2 or in specific values s 2  s1  R ln 2   R ln 2
V1 P1 v1 P1
b) Constant volume process , V = Constant
T2 T
S 2  S1  m cv ln or in specific values s 2  s1  cv ln 2
T1 T1
c) Constant pressure process , P = Constant
T2 T
S 2  S1  m c p ln or in specific values s 2  s1  c p ln 2
T1 T1
d) Reversible adiabatic process or isentropic process, S = Constant
Change in entropy is zero, S 2  S1  0 or S 2  S1
e) Polytropic process
 n    T2
S 2  S1  c v   ln
 n  1  T1

Problems on entropy:
Problem No.1. One kg of water at 273 K is brought into contact with a heat reservoir at 373 K.
When the water has reached 373 K, find the entropy change of water, the heat reservoir and of the
universe.
Solution: Let T1 be the temperature of water, T2 be the temperature of heat reservoir. Since reservoir
is at higher temperature than that of water, when water is brought into contact with the reservoir heat
transfer occurs from reservoir to water and takes place through a finite temperature difference
(irreversible). The entropy of water would increase and that of reservoir decrease so that net entropy
change of the water and the reservoir together would be +ve definite. To find the entropy change of
water we have to assume a reversible path between end states, which are at equilibrium.
1) Entropy of water
Heat reservoir
T2
dT T2
T2 = 373 K S water   m c p  m c p ln
T1
T T1
373
 1 x 4.187 ln  1.3068 kJ / K
273
Q
System (water)
T1 = 273 K
2) The temperature of the reservoir remains same irrespective of the amount of the heat withdrawn.
Amount of heat absorbed by the system from the reservoir,
Q  mc p T2  T1  1 x 4,187 373  273  418.7 kJ
Therefore, Entropy change of reservoir,
Q 418.7
S reservoir     1.1225 kJ / K (-ve sign indicates decrease in entropy)
T2 373
3) Entropy change of the universe
S universe  S water  S reservoir 1.3068 1.1225  0.1843 kJ / K

.Problem No.2. Two kg of air is heated from 270C to 4270C while the pressure changes from 100
kPa to 600 kPa. Calculate the change of entropy.R = 0.257 kJ / kg K, Cp = 1.005 kJ / kg K.
Solution: Given:
m = 2 kg
T1 = 27 + 273 = 300K P1 = 100 kPa
T2 = 427 + 273 = 700K P2 = 600 kPa
The general equation used for the calculation of change of entropy is given by,
T P  700   600 
S air  S 2  S1  m c p ln 2  m R ln 2  2 x 1.005 ln    2 x 0.257 ln 
T1 P1  300   100 
 0.7821 kJ / K
Problem No.3. Ten grams of water at 20 0C is converted into ice at - 10 0C at constant atmospheric
pressure. Assuming specific heat of liquid water to remain constant at 4.184 J / g 0C and that of ice
to be half of this value, and taking the latent heat of fusion of ice at 0 0C to be 335 J / g, calculate the
total entropy change of the system.
Solution: Given :
m = 10 gm
Water is available at Ice is to be formed at
temperature T1 = 20 0C = 293 k temperature T4 = -10 0C = 263 K
Cp(water) = 4.184 J / g 0C Cp(ice) = ½ x 4.184 J / g 0C
= 4.184 kJ / kg 0C = ½ x 4.184 kJ / kg 0C
∆SIII ∆SII ∆SI

Total entropy change of water (system) as it is converted into ice will be
STotal  S I  S II  S III        (1)
a) S I i.e. entropy change of the system as it is cooled from 20 0C to 0 0C.
273
dT 273 10 273
S I   mc
293
p
T
 mcp ln 
293 1000
x 4.184 ln
293
  2.958 x 103 kJ / K
b) S II i.e. entropy change of water at 0 0C.to become ice at 0 0C
mQL 10 335
S II    x   0.0123 kJ / K
T 1000 273
c) S III i.e. entropy change of ice as it is cooled from 0 0C to -10 0C
263
dT 263 10 4.184 263
S III   mc
273
p ( ice )
T
 mc p (ice ) ln 
273 1000
x
2
ln
273
  7.807 x 10 4 kJ / K
Therefore total entropy change of water as it is converted into ice will be
STotal  S I  S II  S III   2.958 x103  (0.0123)  (7.807 x104 )

  0.01604 kJ / K

Problem No.4. A reversible engine as shown in figure during a cycle of operation draws 5MJ from
the 400 K reservoir and does 840 kJ of work. Find the amount and direction of heat interaction with
other reservoirs.
300 K
200 K
400 K
Q2
Q3 Q1 = 5 MJ
W = 840 kJ
Solution:
Let us assume that Q2 and Q3 are the heat rejected by the engine to the reservoir at 300 K and 200 K
respectively.
Q Q1 Q2 Q3
From the Clausius theorem we have  T
 0 i.e.    0    (1)
T1 T2 T3
And also, Q1 W  Q2  Q3    (2)
Consider equation (1), Q1  5 MJ , T1  400 K , T2  300 K , T3  200 K
Using –ve sign for heat rejected in the equation, we have
5 x10 6 Q2 Q3
   0,
400 300 200
Q Q
i.e.12500  2  3  0
300 200
2Q2  3Q3 12500 x 600  7500000      (3)
and equation (2) gives, Q2  Q3  5x10  840 x10  4160000      (4)

6 3
Solving equations (3) and (4), we get

Q3   0.82 MJ and Q2   4.98 MJ

Therefore the direction of heat interaction with the reservoirs are as follows
300 K
200 K
Q2 = 4.98 MJ 400 K
Q3 = 0.82 MJ Q1 = 5 MJ
W = 840 kJ
Problem No.5. Two kg of water at 80 0C are mixed adiabatically with 3 kg of water at 30 0C in a

constant pressure process of 1 atmosphere. Find the increase in the entropy of the total mass of water
due to mixing process. Cp of water = 4.187 kJ / kg K.
Solution:
Subsystem 1
2 kg of water at 80 0C
Subsystem 2
3 kg of water at 30 0C
And t1› t2
Let tf be the equilibrium temperature of the mixture of two subsystems

i.e. Subsystem 1 + Subsystem 2 and the final temperature tf is such that t2 ‹ tf ‹ t1. Since energy
interaction is exclusively confined to the two fluids, the system being isolated.
m1c p1 t1  t f   m2 c p 2 t f  t 2  therefore

m1c p1t1  m2 c p 2 t 2
tf  since Cp1= Cp2 , tf will be given by
m1c p1  m2 c p 2

m1t1  m2t 2 (2 x80)  (3x30)

tf    50 0C
m1  m2 (2  3)
Entropy change for the fluid subsystem 1,

Tf
dT Tf 323
S1   m1c p  m1c p ln  2 x 4.187 ln
T1
T T1 353
  0.7437 kJ / K
This will be negative since T f  T1
Entropy change for the fluid subsystem 2,
Tf
dT Tf 323
S 2   m2 c p  m2 c p ln  3 x 4.187 ln
T2
T T2 303
 0.8028 kJ / K
Increase in the entropy of the total mass of water due to mixing
S  S1  S 2   0.7437  0.8028  0.0591kJ / K
Since S is + ve definite, the mixing process is irreversible.
Problem No.6. A steel tool of mass 0.5 kg at a temperature of 350 0C is plunged suddenly into an
insulated vessel containing 10 kg of oil at a temperature of 20 0C. After a time the temperature of the
contents of the vessel becomes uniform. Assuming the heat transfer to the atmosphere to be zero,
and that none of the oil evaporates; evaluate the increase in entropy of the final contents of the
vessel. Take Cp of oil = 1.88 kJ /Kg K and Cp of steel = 0.48 kJ /Kg K
Solution: Given
Steel Oil
ts = 350 0C toil = 20 0C
ms = 0.5 kg moil = 10 kg
C steel = 0.48 kJ /Kg K C oil = 1.88 kJ /Kg K

We take the steel and the oil as our system. Applying the principle of conservation of energy for this
process, we get
Q  W  U  KE  PE      (1)

Where Q  0, W  0, KE  0, PE  0
Therefore U steel  U oil  0      (2)
Let tf be the final temperature of the contents of the vessel. We have for the energy balance
ms csteel t s  t f   moil coil t f  t o  therefore

ms csteel t s  moil coilt 0 (0.5  0.48  350)  (10 1.88  20)
tf    24.16 0 C
ms csteel  moil coil (0.5  0.48)  (10 1.88)
Now, entropy change for steel is,
Tf
dT Tf (24.16  273)
S steel   ms csteel  ms csteel ln  0.5  0.48 ln
TS
T Ts (350  273)
  0.178 kJ / K
And, entropy change for oil is
Tf
dT Tf (24.16  273)
S oil   moil coil  moil coil ln  10 1.88 ln
T0
T To (20  273)
 0.26504 kJ / K
Therefore change in entropy of the final contents of the vessel,
S  S steel  Soil   0.178  0.26504  0.08704 kJ / K
Problem No.7. Calculate the entropy change of the universe as a result of the following processes
1. A copper block of mass 0.6 kg and specific heat 150 J/kg K at 100 0C is placed in a lake at 8
0
C.
2. Two such blocks at 100 0C and 0 0C are joined together.

Solution:
Given:
Case i) m  0.6 kg, Cc 150 J / kg K  0.150 kJ / kg K ,
Tc 100 0C  373 K , Tl  8 0C  281 K
Suniverse  SCopperblock  SLake
When hot copper block is put into lake, the block shall cool down to the lake temperature since lake
is big and treated as sink.
T   281 
i) SCopperblock  m CC ln  L   0.6  0.150  ln  
 
TC  373 
  0.0255 kJ / K
Heat lost by Copper Block  Heat gained by lake

 mC c ( TC  TL )
 0.6  0.150  (373  281)  8.28 kJ
8.28
S Lake   0.0295 kJ / K
281
Therefore Suniverse  SCopperblock  S Lake

  0.0255  0.0295  0.004 kJ / K
Case ii ) m  0.6 kg, Cc1  Cc 2  150 J / kg K  0.150 kJ / kg K ,

Tc1 100 0C  373 K , Tc 2  0 0C  273 K
Let Tm be the equilibrium temperature of the two copper blocks when they communicate. i.e.
Copper block 1 + Copper block 2 and the final temperature Tm is such that Tc2 ‹ Tm ‹ Tc1. Since
energy interaction is exclusively confined to the two blocks, the system being isolated.

mcc1 Tc1  Tm   mcc 2 Tm  Tc 2  therefore

mcc1Tc1  mcc 2Tc 2 373  273
Tm    323 K
m cc1  m cc 2 2
Tm
dT T 323
S I Block   mcc1  mcc1 ln m  0.6  0.150 ln
Tc1
T Tc1 373
  0.01295 kJ / K
Tm
dT T 323
S II Block   mcc 2  mcc 2 ln m  0.6  0.150 ln
Tc 2
T Tc 2 273
 0.01514 kJ / K
Therefore Suniverse  S I block  S II block

 0.01295  0.01514  0.00219 kJ / K
Problem No.8. A heat engine is supplied with 278 kJ / s of heat at a constant fixed temperature of
283 0C and the heat rejections take place at 5 0C. The following results were reported.
i) 208 kJ / s of heat rejected. ii) 139 kJ / s of heat rejected. iii) 70 kJ / s of heat rejected.
Classify which of the results report a reversible cycle, irreversible cycle or impossible cycle.
Solution:
Case (i)
Q Q
T 
278 208

556 278
  0.2482 , Since T  0 irreversib le

Case (ii)
Q 278 139 Q
T  
556 278
0 , Since T  0 reversible
Case (iii)
Q Q
T 
278 70

556 278
 0.2482 , Since T  0 impossible
Problem No.9. 0.5 kg of ice block at -10 0C is brought into contact with 5 kg copper block at 80 0C
in an insulated container. Determine the change in entropy of i) ice block ii) copper block iii) the
universe.
Given specific heat of ice = 2 kJ / kg K, Specific heat of water = 4.2 kJ / kg K, Specific heat of
copper = 0.5 kJ / kg K, enthalpy of fusion of water at 0 0C = 334 kJ / kg.
Problem No.10. An inventor reports that she has a refrigeration compressor that receives saturated
Freon-12 vapor at -20 0C and delivers the vapor at 1 MPa, 50 0C. The compression process is
adiabatic. Does the process described violate the second law?
Solution:
State 1. Condition of Freon -12 at inlet to compressor– saturated vapor at -20 0C
State 2. Condition of Freon -12 at the exit of compressor – 1 MPa and 50 0C
Referring the Freon -12 tables we get, at state 1, s1= 0.7082 kJ/kg K and at state 2,
s2= 0.7021 kJ /kg K
For a steady state, steady flow, adiabatic process we can write second law as,s2≥ s1, but for the
given adiabatic process, s1> s2 therefore the process involve a violation of the second law and would
not be possible.
Problem No.11.One kg of ice at -5 0C is exposed to the atmosphere which is at 20 0C. The ice melts
and comes into thermal equilibrium with the atmosphere. i) Determine the entropy increase of the
universe.

Heat absorbed by ice from the atmosphere is given by,
Q  1 2.093 (0  (5))  1 333.3  1 4.187  (20  0)

 427.5 kJ
Entropy change of the atmosphere
Q 427.5
S atmosphere     1.46 kJ / K
T 293
a) S I , entropy change of the system(ice) as it is heated from -5 0C to 0 0C.
273
dT 273 273
S I   mc
268
p
T
 mc p ln
268
1 2.093 ln
268
  0.0389 kJ / K
b) S II , entropy change of the system(ice) as it melts at 0 0C to become water at
0 0C.
333.3
S II   1.22 kJ / K
273
c) S III , entropy change of water as it is heated from 0 0C to 20 0C
293
dT 293 293
S III  
273
mc p
T
 mc p ln
273
1 4.187 ln
273
 0.296 kJ / K
Therefore total entropy change of ice as it melts into water will be
STotal  S I  S II  S III  0.0389  1.22  0.296

1.5594 kJ / K
Therefore entropy change of universe will be,
S universe  S system  S atmosphere  1.5594  1.46  0.0949 kJ / K

Problem No.12. A 5 kg copper block at a temperature of 200 0C is dropped into an insulated tank
containing 100 kg of oil at a temperature of 30 0C. Find the increase in entropy of the universe due to
this process when copper block and the oil reach thermal equilibrium. Assume that the specific heats
of copper and oil are respectively 0.4 kJ /Kg K and 2.1 kJ /Kg K.
Solution: Given
Copper block Oil
tc = 200 0C toil = 30 0C
mc = 5 kg moil = 100 kg
Ccopper block = 0.4 kJ /Kg K C oil = 2.1 kJ /Kg K
We take the copper block and the oil as our system. Applying the principle of conservation of energy
for this process, we get
Q  W  U  KE  PE      (1)

Where Q  0, W  0, KE  0, PE  0
Therefore U copperblock  U oil  0      (2)
Let tm be the final temperature of the contents of the tank. We have for the energy balance
mc ccopperblock t c  t m   moil coil t m  t o  therefore

mc ccopperblockt c  moil coilt 0 (5  0.4  200)  (100  2.1 30)
tf    31.6 0 C
mc ccopperblock  moil coil (5  0.4)  (100  2.1)
Now, entropy change for copper block is,
(31.6  273)
Tm
dT T
S copperblock   mc ccopperblock  mc ccopperblock ln m  5  0.4 ln
Tc
T Tc (200  273)
  0.8802 kJ / K
Now, entropy change for oil is
(31.6  273)
Tm
dT T
S oil   moil coil  moil coil ln m  100  2.1 ln
T0
T To (30  273)
 1.106 kJ / K
Therefore change in entropy of the final contents of the vessel,
S  Scopperblock  Soil   0.8802 1.106  0.2258 kJ / K

PROPERTY DIAGRAMS WITH ENTROPY AS A COORDINATE:
T Reversible
Adiabatic
s
T
Irreversible
Adiabatic
This diagram is useful to analyze the nature of the thermodynamic systems to visualize the changes
of state that occurs in various processes. This diagram possesses the following features.
1. Area on the diagram have the dimensions of heat
2. In the mixed-phase region, the constant pressure lines are horizontal
3. In a reversible process the area under the curve is equal to the heat transfer in the
corresponding process
4. Vertical lines represents isentropic processes
5. In a reversible cycle, the area enclosed by the curve representing the process is equal to the
net heat transfer to the fluid and so, from the first law is also equal to the net work.
If the substance executes a Carnot cycle, its path on the T-s diagram is a rectangle.
TH
T
b c Processes:
Process a-b: Isentropic Process
Process b-c: Isothermal Process

a d
T Process c-d: Isentropic Process
Department of Mechanical
L Engineering, SJBIT-Naveena kumar R. R. Page 148
Process d-a: Isothermal Process
s
Efficiency of the Carnot engine is given by,
Area abcda TH ( s 2  s1 )  TL ( s 2  s1 ) TH  TL T
 th    1  L
Area fbcef TH ( s 2  s1 ) TH TH
An irreversible process is represented by a line tending to the right, for this entropy always increases.
THE ENTHALPY –ENTROPY (h-s) diagram or MOLLIER diagram
In the enthalpy-entropy diagram the pressure and temperature lines naturally coincide in the two-
phase region.
Entropy postulations:
1. The entropy content of an isolated system can never decrease.
2. The entropy of any substance approaches a constant value as its temperature approaches
absolute zero.
3. For a perfect crystalline substance, its entropy is zero at the absolute zero of temperature.
The nature of Entropy:
1. Entropy is a primitive concept
2. Every system has entropy
3. Entropy is an extensive property
4. Entropy is that –it is an index of that portion of energy content in a system that is not
available to do work
5. Entropy content of an isolated system is not conserved.

Available and Unavailable energy:

We have,
High Grade Energy Low Grade Energy
1 Mechanical Work 1 Heat or Thermal energy
2 Electrical Energy 2 Heat derived from nuclear fission or
3 Water power fusion
4 Wind power 3 Heat derived from combustion of fossil
5 Kinetic Energy of a jet fuels
6 Tidal power
The complete conversion of low grade energy, heat into high grade energy, shaft work is impossible.
That part of the low grade energy which is available for conversion is called as available energy,
while the part which, according to the 2nd law of thermodynamics, must be rejected is known as
unavailable energy.
If a cyclic heat engine is considered, the maximum work output obtainable from a certain heat input
is called the available energy (A.E.), or the available part of the energy supplied. The minimum
energy that has to be rejected to the sink is the unavailable energy (U.E.).
Therefore,
Q1  A. E. U . E. or Wmax  Q1  U . E.          (1)
For a reversible cycle,
T
 rev 1  2        (2)
T1
For a given temperature T1,  rev will increase with the decrease of T2. The lowest practicable
temperature of heat rejection is the temperature of the surroundings, T0.
T
Therefore,  rev 1  0
T1
 T 
And Wmax  1  0  Q1        (3)
 T1 

Consider a finite process X-Y , heat is supplied reversibly to a heat engine. Taking an elementary
cycle, if Q1 is the heat received by the engine reversibly at T1, then
T1  T0 T
Wmax  Q1  Q1  0 Q1  A. E.
T1 T1
For the heat engine receiving heat for the whole process X-Y, and rejecting heat at T0
Y Y Y
T0
 Wmax   Q1  
X X
T
X 1
Q1
Wmax   A. E.  QXY  T0 sY  s X 
or U . E.  QXY  Wmax i.e U . E.  T0 sY  s X .
The U.E. is thus the product of the lowest temperature of heat rejection, and the change of entropy of
the system during the process of supplying heat.

Module 4
AVAILABILITY, IRREVERSIBILITY AND GENERAL

THERMODYNAMIC RELATIONS
Reversible and Irreversible Processes
Consider an ideal gas that is held in half of a thermally insulated container by a wall in the
middle of the container. The other half of the container is under vacuum with no molecules
inside. Now, if we remove the wall in the middle quickly, the gas expands and fills up the entire
container immediately, as shown in Figure.
A gas expanding from half of a container to the entire container (a) before and (b) after the
wall in the middle is removed.
Because half of the container is under vacuum before the gas expands there, we do not expect
any work to be done by the system—that is, —because no force from the vacuum is
exerted on the gas during the expansion. If the container is thermally insulated from the rest of
the environment, we do not expect any heat transfer to the system either, so . Then the
first law of thermodynamics leads to the change of the internal energy of the system,
For an ideal gas, if the internal energy doesn’t change, then the temperature stays the same.
Thus, the equation of state of the ideal gas gives us the final pressure of the gas, where is
the pressure of the gas before the expansion. The volume is doubled and the pressure is
halved, but nothing else seems to have changed during the expansion.

All of this discussion is based on what we have learned so far and makes sense. Here is what
puzzles us: Can all the molecules go backward to the original half of the container in some
future time? Our intuition tells us that this is going to be very unlikely, even though nothing we
have learned so far prevents such an event from happening, regardless of how small the
probability is. What we are really asking is whether the expansion into the vacuum half of the
container is reversible.
A reversible process is a process in which the system and environment can be restored to
exactly the same initial states that they were in before the process occurred, if we go backward
along the path of the process. The necessary condition for a reversible process is therefore the
quasi-static requirement. Note that it is quite easy to restore a system to its original state; the
hard part is to have its environment restored to its original state at the same time. For
example, in the example of an ideal gas expanding into vacuum to twice its original volume, we
can easily push it back with a piston and restore its temperature and pressure by removing
some heat from the gas. The problem is that we cannot do it without changing something in its
surroundings, such as dumping some heat there.
A reversible process is truly an ideal process that rarely happens. We can make certain
processes close to reversible and therefore use the consequences of the corresponding
reversible processes as a starting point or reference. In reality, almost all processes are
irreversible, and some properties of the environment are altered when the properties of the
system are restored. The expansion of an ideal gas, as we have just outlined, is irreversible
because the process is not even quasi-static, that is, not in an equilibrium state at any moment
of the expansion.
From the microscopic point of view, a particle described by Newton’s second law can go
backward if we flip the direction of time. But this is not the case, in practical terms, in a
macroscopic system with more than particles or molecules, where numerous collisions
between these molecules tend to erase any trace of memory of the initial trajectory of each of
the particles. For example, we can actually estimate the chance for all the particles in the
expanded gas to go back to the original half of the container, but the current age of the
universe is still not long enough for it to happen even once.

An irreversible process is what we encounter in reality almost all the time. The system and its
environment cannot be restored to their original states at the same time. Because this is what
happens in nature, it is also called a natural process. The sign of an irreversible process comes
from the finite gradient between the states occurring in the actual process. For example, when
heat flows from one object to another, there is a finite temperature difference (gradient)
between the two objects. More importantly, at any given moment of the process, the system
most likely is not at equilibrium or in a well-defined state. This phenomenon is
called irreversibility.
Let us see another example of irreversibility in thermal processes. Consider two objects in
thermal contact: one at temperature and the other at temperature , as shown
in Figure.
Spontaneous heat flow from an object at higher temperature to another at lower
temperature
We know from common personal experience that heat flows from a hotter object to a colder
one. For example, when we hold a few pieces of ice in our hands, we feel cold because heat has
left our hands into the ice. The opposite is true when we hold one end of a metal rod while
keeping the other end over a fire. Based on all of the experiments that have been done on
spontaneous heat transfer, the following statement summarizes the governing principle:
Second Law of Thermodynamics (Clausius statement)
Heat never flows spontaneously from a colder object to a hotter object.
This statement turns out to be one of several different ways of stating the second law of
thermodynamics. The form of this statement is credited to German physicist
Rudolf Clausius (1822−1888) and is referred to as the Clausius statement of the second law of

thermodynamics. The word “spontaneously” here means no other effort has been made by a
third party, or one that is neither the hotter nor colder object. We will introduce some other
major statements of the second law and show that they imply each other. In fact, all the
different statements of the second law of thermodynamics can be shown to be equivalent, and
all lead to the irreversibility of spontaneous heat flow between macroscopic objects of a very
large number of molecules or particles.
Both isothermal and adiabatic processes sketched on a pV graph (discussed in The First Law of
Thermodynamics) are reversible in principle because the system is always at an equilibrium
state at any point of the processes and can go forward or backward along the given curves.
Other idealized processes can be represented by pV curves; (Figure) summarizes the most
common reversible processes.
Summary of Simple Thermodynamic Processes
Process Constant Quantity and Resulting Fact
Isobaric Constant pressure
Isochoric Constant volume
Isothermal Constant temperature
Adiabatic No heat transfer
Availability, Irreversibility and General Thermodynamic relations

There are many forms in which an energy can exist. But even under ideal conditions all these
forms cannot be converted completely into work. This indicates that energy has two parts:
Available part, Unavailable part Available energy: is the maximum portion of energy which
could be converted into useful work by ideal processes which reduce the system to a dead
state (a state in equilibrium with the earth and its atmosphere). Because there can be only one
value for maximum work which the system alone could do while descending to its dead state, it
follows immediately that „Available energy‟ is a property. Unavailable energy: A system which
has a pressure difference from that of surroundings, work can be obtained from an expansion
process, and if the system has a different temperature, heat can be transferred to a cycle and

work can be obtained. But when the temperature and pressure becomes equal to that of the
earth, transfer of energy ceases, and although the system contains internal energy, this energy
is 4.1. Available energy referred to a cycle: The available energy (A.E.) or the available part of
the energy supplied is the maximum work output obtainable from a certain heat input in a
cyclic heat engine (Fig. 6.1). The minimumenergy that has to be rejected to the sink by the
second law is called the unavailable energy (U.E.), or the unavailable part of the energy
supplied.
Q1 = A.E. + U.E.
or Wmax = A.E. = Q1 – U.E.
For the given values of the source temperature T1 and sink temperature T2, the reversible
efficiency,
PURE SUBSTANCE
Pure Substance
A substance that has a fixed chemical composition throughout is called a pure substance such
as water, air, and nitrogen.
A pure substance does not have to be of a single element or compound. A mixture of two or
more phases of a pure substance is still a pure substance as long as the chemical composition
of all phases is the same.
Phases of a Pure Substance

A pure substance may exist in different phases. There are three principal phases solid, liquid,
and gas.
A phase: is defined as having a distinct molecular arrangement that is homogenous throughout
and separated from others (if any) by easily identifiable boundary surfaces.
A substance may have several phases within a principal phase, each with a different molecular
structure. For example, carbon may exist as graphite or diamond in the solid phase, and ice
may exist in seven different phases at high pressure.
Molecular bonds are the strongest in solids and the weakest in gases.

Solid: the molecules are arranged in a three-dimensional pattern (lattice) throughout the solid.
The molecules cannot move relative to each other; however, they continually oscillate about
their equilibrium position.
Liquid: the molecular spacing in liquid phase is not much different from that of the solid phase
(generally slightly higher), except the molecules are no longer at fixed positions relative to
each other.
Gas: the molecules are far apart from each other, and a molecular order does not exist. Gas
molecules move randomly, and continually collide with each other and the walls of the
container they are in.
Molecules in the gas phase are at a considerably higher energy level than they are in liquids or
solid phases.
Phase-Change Processes of Pure Substances

Consider a process where a pure substance starts as a solid and is heated up at constant
pressure until it all becomes gas. Depending on the prevailing pressure, the matter will pass
through various phase transformations. At P0:
1. Solid
2. Mixed phase of liquid and solid
3. Sub-cooled or compressed liquid (means it is not about to vaporize)
4. Wet vapor or saturated liquid-vapor mixture, the temperature will stop rising until the
liquid is completely vaporized.
5. Superheated vapor (a vapor that is not about to condense).

Fig. 1: T-v diagram for the heating process of a pure substance.
 At a given pressure, the temperature at which a pure substance starts boiling is called the
saturation temperature, Tsat.
 Likewise, at a given temperature, the pressure at which a pure substance starts boiling is
called the saturation pressure, Psat.
 During a phase-change process, pressure and temperature are dependent properties, Tsat =
f (Psat).
 The critical point is the point at which the liquid and vapor phases are not distinguishable

 The “triple point” is the point at which the liquid, solid, and vapor phases can exist
together. On P-v or T-v diagrams, these triple-phase states form a line called the triple line.
Table 1: Critical and triple point for water and oxygen.
Critical Point Triple Point
P (atm) T (K /°C) P (atm) T (K /°C)
H2O 218 647.30/(374.14) 0.006 273.17 (0.01)
O2 50.136 154.80/(−118.36) 0.0015 54.16/(−219)
Vapor Dome
The general shape of a P-v diagram for a pure substance is very similar to that of a T-v diagram.
P
critical point
SUPERHEATED VAPOR
sat. vapor line
REGION
COMPRESSED
LIQUID T2 = const. >T1
REGION
SATURATED LIQUID-
sat. liquid VAPOR REGION
T1 = const
line
Fig. 2: P-v diagram of a pure substance.

The P-T or Phase Change Diagram
This is called phase diagram since all three phases are separated from each other by three
lines. Most pure substances exhibit the same behavior.
 One exception is water. Water expands upon freezing.

Fig. 3: phase diagram of pure substances.

There are two ways that a substance can pass from solid phase to vapor phase i) it melts first
into a liquid and subsequently evaporates, ii) it evaporates directly without melting
(sublimation).
 the sublimation line separates the solid and the vapor.
 the vaporization line separates the liquid and vapor regions
 the melting or fusion line separates the solid and liquid.
 these three lines meet at the triple point.
 if P<PTP , the solid phase can change directly to a vapor phase
 at P<PTP the pure substance cannot exist in the liquid phase. Normally (P>PTP ) the
substance melts into a liquid and then evaporates.
 matter (like CO2) which has a triple point above 1 atm sublimate under atmospheric
conditions (dry ice)
 for water (as the most common working fluid) we are mainly interested in the liquid
and vapor regions. Hence, we are mostly interested in boiling and condensation.

Property Tables
For most substances, the relationships among thermodynamic properties are too complex to
be expressed by simple equations. Thus, properties are frequently presented in the form of
tables, see Table A-4.
The subscript “f” is used to denote properties of a saturated liquid and “g” for saturated vapor.
Another subscript, “fg”, denotes the difference between the saturated vapor and saturated
liquid values of the same property.
For example:
vf = specific volume of saturated liquid
vg = specific volume of saturated vapor
vfg = difference between vg and vf ( vfg = vg – vf)
Enthalpy: is a property defined as H = U + PV (kJ) or h = u + Pv (kJ/kg) (per mass unit).
Enthalpy of vaporization (or latent heat): 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 increase, and becomes zero at the critical point.
1- Saturated Liquid-Vapor Mixture
During vaporization, a mixture of part liquid part vapor exists. To analyze this mixture, we
need to know the proportions of the liquid and vapor in the mixture. The ratio of the mass of
vapor to the mass of the total mixture is called quality, x:
m vapor
x mtotal  mliquid  mvapor  m f  m g
m total
Saturated liquid-vapor mixture is treated as a combination of two sub-systems (two phases).

The properties of the “mixture” are the average properties of the saturated liquid-vapor
mixture.

V  V f  Vg
mt v ave  m f v f  m g v g
m f  mt  m g  mt v ave  mt  m g v f  m g v g
dividing by m t
v ave  1  x v f  xv g and x  m g / mt
v ave  v f  xv fg m 3
/ kg 
or,
v ave  v f
x
v fg
P or critical point
T
sat.
sat.
vapor
liquid
states
states
sat. vapor
sat. liquid
Fig. 4: The relative amounts of liquid and vapor phases (quality x) are used to calculate the
mixture properties.
Similarly,
u ave  u f  xu fg
have  h f  xh fg
Or in general, it can be summarized as yave = yf +x.yfg. Note that:

0  x 1
y f  y ave  y g
Note: pressure and temperature are dependent in the saturated mixture region.

Fig. 5: Quality defined only for saturated liquid-vapor mixture.
Example 1: Saturated liquid-vapor mixture

A closed, rigid container of volume 0.5 m3 is placed on a hot plate. Initially the container holds
a two-phase mixture of saturated liquid water and saturated water vapor at P1= 1 bar with a
quality of 0.5. After heating, the pressure in the container is P2=1.5 bar. Indicate the initial and
final states on a T-v diagram, and determine:
a) the temperature, in °C, at each state.
b) the mass of vapor present at each state, in kg.
c) if heating continues, determine the pressure, in bar, when the container holds only saturated
vapor.
Solution:
Assumptions:
1. Water in the container is a closed system.
2. States 1, 2, and 3 are equilibrium states.
3. The volume of container remains constant.

Two independent properties are required to fix state 1 and 2. At the initial state, the pressure
and quality are known. Thus state 1 is known, as mentioned in the problem. The specific
volume at state 1 is found using the given quality:
v1  v f 1  x1 v g1  v f 1 
From Table A - 5 at P  1 bar  100 kPa
v1  0.001043  0.5 (1.694  0.001043)  0.8475 m 3 / kg

At state 2, the pressure is known. Volume and mass remain constant during the heating
process within the container, so v2=v1. For P2= 0.15 MPa, Table A-5 gives vf2= 0.001053 and
vg2=1.1593 m3/kg. Since
vf2 < v2 < vg2
State 2 must be in the two-phase region as well. Since state 1 and 2 are in the two-phase liquid-
vapor region, the temperatures correspond to the saturation temperatures for the given. Table
A-5:
T1 = 99.63 °C and T2 = 111.4 °C
To find the mass of water vapor present, we first find the total mass, m.
V 0.5m 3
m   0.59kg
v 0.8475m 3 / kg
m g1  x1 m  0.50.59kg   0.295kg
3
P2 = 1.5 bar
2
P1 = 1 bar
1
The mass of vapor at state 2 is found similarly using quality x2. From Table A-5, for P2 = 1.5 bar,
we have:
v vf2
x2 
vg 2  v f 2
0.8475  0.001053
x2   0.731
1.159  0.001053
mg 2  0.731 0.59kg   0.431 kg

If heating continued, state 3 would be on the saturated vapor line, as shown in on the T-v
diagram above. Thus, the pressure would be the corresponding saturation pressure.
Interpolating in Table A-5 at vg = 0.8475 m3 /kg, we get P3 = 2.11 bar.
2- Superheated Vapor
Superheated region is a single phase region (vapor only), temperature and pressure are no
longer dependent. See Table A-6 for superheated vapor properties.
If T>> Tcritical or P<<Pcritical, then the vapor can be approximated as an “ideal gas”.
3- Compressed (or Sub-cooled) Liquid
The properties of a liquid are relatively independent of pressure (incompressible).
A general approximation is to treat compressed liquid as saturated liquid at the given
saturation temperature.
y  y f @T
The property most affected by pressure is enthalpy. For enthalpy use the following
approximation:
h  h f @ T  v f P  Psat 
The Ideal-Gas Equation of State

Any equation that relates the pressure, temperature, and specific volume of a substance is
called an equation of state.
The simplest and best known equation of state for substances in the gas phase is the ideal-gas
equation of state.
Gas and vapor are often used as synonymous words. The vapor phase of a substance is called a
gas when it is above the critical temperature. Vapor usually implies a gas that is not far from a
state of condensation.
It is experimentally observed that at a low pressure the volume of a gas is proportional to its
temperature:
Pv  RT
Where R is the gas constant. The above equation is called the ideal-gas equation of state (ideal
gas relation). Since R is a constant for a gas, one can write:
P1v1 P2 v 2
R 
T1 T2

where 1 and 2 denote two states of an ideal gas. The constant R is different for each gas; see
Table 2-3 in Cengel book.
Ru = 8.314 kJ / (kmol. K) is the universal gas constant, R = Ru /M.
The molar mass, M (kg/kmol): is defined as the mass of one mole of a substance. The mass of a
system is equal to the product of its molar mass M and the mole number N:
m  MN (kg)
See Table A-1 for R and M for several substances. An ideal gas is an imaginary substance that
obeys the relation Pv = RT. It is experimentally observed that the ideal gas closely approximate
the P-v-T behavior of real gases at low densities.
 In the range of practical interest, many familiar gases such as air, nitrogen, oxygen,
hydrogen, helium, argon, neon, and CO2 can be treated as ideal gases with negligible
error.
 Water vapor (in general see Fig. 4-49 Cengel book), refrigerant vapor in refrigerators
should not be treated as ideal gases.
 Water vapor at pressures below 10 kPa can be treated as an ideal gas, regardless of
temperature.
Compressibility Factor
The assumption of ideal gas relation implies that:
 the gas particles take up negligible volume
 the intermolecular potential energy between particles is small
 particles act independent of one another

However, real gases deviate from ideal gas behavior. This deviation at given temperature and
pressure can be accurately accounted for by introduction of a correction factor called the
compressibility factor Z.
Pv
Z or Pv  ZRT
RT
or Z = vactual / videal. Obviously, Z=1 for ideal gases.
Gases behave very much the same at temperatures and pressures normalized with respect to
their critical temperatures and pressures.

P T
PR  and TR 
Pcr Tcr
Here PR and TR are called the reduced pressure and temperature, respectively.
By curve-fitting all the data, the general compressibility chart is obtained which can be used
for all gases.
Fig. 6: Z factor, general compressibility chart.

From the Z chart, one can conclude:
 at very low pressure (PR <<1), the gases behave as an ideal gas regardless of
temperature
 at high temperatures (TR>2), ideal gas behavior can be assumed.
 the deviation is highest in the vicinity of the critical point.

Example 2: Ideal Gas
Determine the specific volume of R-134a at 1 MPa and 50°C, using (a) ideal gas equation (b)
the generalized compressibility chart. Compare the values obtained with the actual value of
0.02171 m3/kg.
Solution:
From Table A-1, for R-134a, R = 0.0815 kPa.m3/(kg.K), Pcr = 4.067 MPa, and Tcr = 374.3 K
(a) Ideal gas equation of state

v
RT

 
0.0815 kPa.m 3 / kg.K  323 K 
 0.02632 m 3 / kg
P 1000 kPa
Comparing with the tabulated value, using ideal gas equation one would get an error of
(0.02632-0.02171)/0.02171=0.212 or 21.2%.
(b) To determine the correction factor Z,
P 1MPa
PR    0.246
Pcr 4.067 MPa
T 323K
TR    0.863
Tcr 374.3K
From Fig. A-28, Z= 0.84. Thus,
v = Z videal = 0.84 (0.02632 m3/kg) =0.02211 m3/kg
The error is less than 2%.
Therefore, in the absence of exact tabulated data, the generalized compressibility chart can be
used with confidence.
p-V diagram for water (solid-liquid-vapor region)
If we heat ice at different vapor pressures and note down the corresponding change in
volumes, the saturation state points for solid, liquid and vapor (state from which a change of
phase may occur without change of pressure and temperature) for different pressures may be
obtained on a p-V diagram.
By joining the saturated solid states at various pressures, a saturated solid line ‘ECA’ is
obtained. Similarly, by joining all the saturated liquid states with respect to solidification and
by joining all the saturated liquid states with respect to vaporization, saturated liquid
lines ‘FG’ and ‘HG’ are obtained. Finally, by joining all the vapor states at various
pressures saturated vapor line ‘HB’ is obtained and a phase equilibrium diagram of water on
p-v co-ordinates will be formed as shown in Fig.

The horizontal portion ‘AB’ of constant pressure or temperature in Fig. 19.1 represents the
transition from saturated solid directly into saturated vapor called sublimation. There is
obviously one such line ‘CGD’ in this figure, the part ‘CG’ of which is the boundary between the
liquid-vapor region (L+V) and the solid-vapor region (S+V) and the remaining part ‘GD’ of
which is boundary between the solid-liquid region (S+L) and the solid-vapor region (S+V). This
‘CGD’ line is called the triple point. Triple point is the only point at which three phases of a
pure substance coexist. In the case of ordinary water , the triple point is at a pressure of
4.58 mm of Hg and a temperature of 0.01OC, and the line extends from a volume of 1 cm3/g
(saturated liquid) to a volume of 206000 cm3/g (saturated vapor)
p-T DIAGRAM FOR WATER
If the pure substance is heated at low pressure until its triple point (pressure and temperature
at which three phases of a pure substance coexist) is reached and while heating the vapor
pressure of a solid is measured at various temperatures and then plotted on a p-T diagram,
shown in Fig. 19.6. These plotted points represent the coexistence of solid and vapor and the
line through these points is called sublimation curve.
If the pure substance at triple point is further heated until the critical point is reached and
while heating the vapor pressure of a liquid is measured at various temperatures and then
plotted on a p-T diagram, the results will appear as shown in Fig. 19.6. The results of these
plotted points represent the coexistence of liquid and vapor and the line through these points
is called vaporization curve.

On the other hand, if the substance at the triple point is compressed until there is no vapor left
on the resulting mixture of solid and liquid phase and the pressure on the resulting mixture of
solid and liquid is increased further, the temperature will have to be changed for equilibrium
to exist between the solid and the liquid. Measurements of these pressures and temperatures
give rise to a third curve on the p-T diagram, starting at the triple point and continuing
indefinitely. This is fusion curve.
 The points on the sublimation curve represent the coexistence of solid and vapor.
 The points on the vaporization curve represent the coexistence of liquid and vapor.
 The points on the fusion curve represent the coexistence of liquid and solid.
In the particular case of water, the sublimation curve is called the frost line,
the vaporization curve is called the steam line, and the fusion curve is called the ice line.
The slopes of the sublimation and the vaporization curves for all substances are positive. The
slope of the fusion curve, however, may be positive or negative. The fusion curve of most
substances has a positive slope. Water is one of the important exceptions. Any substance, such
as water, which expands upon freezing, has a fusion curve with a negative slope (represented
by solid line in Figure 19.6), where as opposite is true for substance such as CO 2, which
contracts upon freezing i.e. the substance which contracts upon freezing, has a fusion curve
with a positive slope (represented by dotted line in Figure 19.6). In other words, in the case of
water, the freezing temperature decreases with an increase in pressure while for CO 2, the
freezing temperature increases as the pressure increases.

TRIPLE POINT
The pressure and temperature at which three phases of a pure substance coexist is
called triple point. The triple point is merely the point of intersection of the sublimation and
vaporization curves, It has been found that on a ‘p-T’ diagram the triple point is represented by
a point (Fig. 19.6) and on a ‘p-v’ diagram it is a line (Fig. 19.3), and on a ‘u-v’ diagram it is a
triangle. In the case of ordinary water, the triple point is at a pressure of 4.58 mm Hg and a
temperature of 0.01OC.
P-V-T Behaviour of Pure Substances
A typical P-T diagram showing the relationship between pressure and temperature of a
pure substance is shown below:
The three lines 1-2, 2-3 and 2-C display conditions of P and T at which two phases may co-
exist in equilibrium, and are boundaries for the single-phase regions of solid, liquid and vapour
(gas).
Line 1-2 is known as the sublimation curve, and it separates the solid from the gas regions.
Line 2-3 is known as the fusion curve, and it separates the solid and liquid regions. Line 2-C is
known as the vapourization curve, and it separates the liquid and the gas regions. All three
lines meet at Point 2, known as the Triple Point. This is a point where all 3 phases can co-exist
in equilibrium.
The vapourization curve 2-C terminates at point C, known as the Critical Point. The pressure
and temperature corresponding to this point are known as the critical pressure PC and critical

temperature TC respectively. These are the highest pressure and temperature at which a pure
substance can exist in vapour-liquid equilibrium.
At the critical point, the liquid and gas phases become indistinguishable, because their
properties are the same. This observation is different from ordinary condition whereby the
boundary between liquid and gas is very clear. For example, consider a path such as the one
from A to B that lead from the liquid region to the gas region without crossing the
vapourization curve 2-C. The transition from liquid to gas is gradual. On the other hand, paths
that cross the vapourization curve will involve a vapourization or condensation step, where an
abrupt change from liquid to gas occurs.
The shaded area shows the area existing at pressure and temperature greater than PC and TC.
This region is called the fluid region.
The gas region is sometimes divided into 2 parts, as indicated by the dotted vertical line
through temperature TC. A vapour region is the region to the left of this line and represent a
gas that can be condensed either by compression at constant temperature or by cooling at
constant pressure. The region everywhere to the right of this line, including the fluid region, is
termed supercritical.
P-V Diagram for Pure Substance
The P-T Diagram does not provide any information about volume. It merely displays the phase
boundaries on as a function of pressure and temperature. The P-V Diagram - see Figure below -
displays the regions (areas) where 2 phases of solid/liquid, solid/vapour, and liquid/vapour
co-exist in equilibrium. For a given P and T, the relative amounts of the phases determine the
molar (or specific) volume. On the P-V Diagram, the triple point appears as a horizontal line,
where all 3 phases co-exist at a single temperature and pressure.

Isotherms are lines of constant temperature and these are superimposed on the P-V Diagram
as shown in the Figure below:
Point C is the critical point. VC is the critical volume at this point. The isotherm labelled T >
TC does not cross a phase boundary. The lines labelled T1 and T2 are isotherms for subcritical
temperatures, and they consist of 3 segments. The horizontal segment of each isotherm
represents all possible mixtures of liquid and vapour in equilibrium, ranging from 100% liquid
at the left end (curve B-C) to 100% vapour at the right end (curve D-C). Curve B-C represents
saturated liquid at their boiling points, and curve D-C represent saturated vapours at their
condensation points.
The 2-phase liquid-vapour region lies under the curve BCD, whereas subcooled liquid and
superheated vapour regions lie to the left and right, respectively. Subcooled liquid exists at
temperatures below the boiling point for the given pressure. Superheated vapour exists at
temperatures above the boiling point for the given pressure.
Isotherms in the subcooled liquid region are very steep, because liquid volumes change little
with large changes in pressure.
The horizontal segments of the isotherms in the 2-phase region become progressively shorter
at higher temperatures, being ultimately reduced to a point at C, the critical point.
Problems
1. Two kilograms of water at 25°C are placed in a piston cylinder device under 100 kPa
pressure as shown in the diagram (State (1)). Heat is added to the water at constant
pressure until the piston reaches the stops at a total volume of 0.4 m3 (State (2)). More heat
is then added at constant volume until the temperature of the water reaches 300°C (State

(3)). Determine (a) the quality of the fluid and the mass of the vapor at state (2), and (b) the
pressure of the fluid at state (3).
Solution:
Step 1: Always draw a complete diagram of the states and processes of the problem and
include all the relevant information on the diagram. In this case there are three states and two
processes (constant pressure and constant volume).
Step 2: In the case of a closed system with a phase change fluid, always sketch
a T_v or P_v diagram indicating all the relevant states and processes on the diagram. As
mentioned above this diagram will not be drawn to scale, however it will help to define the
problem and the approach to solution. In the case of steam, as we determine various values
from the steam tables we add these values to the diagram, typically as shown below:
Notice that the T_v diagram is based exclusively on intensive properties, hence mass is not
indicated on the diagram. Thus we indicate on the diagram that in order to determine the

quality at state (2) we need to first evaluate the specific volume v2, which can then be
compared to the saturation values vf and vg at the pressure of 100 kPa.
Thus v2 = V / m = 0.4 [m3] / 2 [kg] = 0.2 [m3 / kg]
Concerning state (3), the problem statement did not specify that it is in the superheat
region. We needed to first determine the saturated vapor specific volume vg at 300°C. This
value is 0.0216 m3 / kg, which is much less than the specific volume v3 of 0.2 m3 / kg, thus
placing state (3) well into the superheated region. Thus the two intensive properties which
we use to determine the pressure at state (3) are T3 = 300°C, and v3 = 0.2 m3 / kg. On
scanning the superheat tables we find that the closest values lie somewhere between 1.2
MPa and 1.4 MPa, thus we use linear interpolation techniqes to determine the actual
pressure P3 as shown below:
2 - Two kilograms of water at 25°C are placed in a piston cylinder device under 3.2 MPa
pressure as shown in the diagram (State (1)). Heat is added to the water at constant
pressure until the temperature of the fluid reaches 350°C (State (2)). Determine the final
volume of the fluid at state (2).

In this example since the pressure is known (3.2 MPa) and remains constant throughout
the process, we find it convenient to draw a P-v diagram indicating the process (1) - (2) as
follows.
As in the previous example, on scanning the superheat tables we find that we need to
interpolate between pressure P = 3.0 MPa and P = 3.5 MPa in order to determine the
specific volume at the required pressure of 3.2 MPa as follows:
MEASUREMENT OF DRYNESS FRACTION

Throttling Calorimeter

Principle: The principle of the throttling calorimeter is to throttle the wet steam so that it
becomes superheated.
Material: Refer Fig. 26.1. The Throttling Calorimeter consists of inner chamber and outer
chamber. The pressure gauge attached to the outer casing and thermometer in inner chamber
gives the pressure and temperature of steam after throttling, respectively. In order to prevent
any heat transfer from and to the system, the outer chamber is insulated.
Procedure: A sample of wet steam at pressure ‘p1’ is taken from the main steam pipe of boiler
into the inner chamber of the throttling calorimeter through a sampling tube and orifice
throttling valve. This wet steam sample is throttled in orifice throttling valve before it enters
into the calorimeter. Normally, pressure desired after throttled is few mm of Hg slightly above
atmospheric pressure. The steam of the inner chamber is first allowed to flow down wards
then flows upwards and finally turns downwards in the annular space between the inner and
outer chamber. This is done so that the steam should flow long enough to ensure constant
temperature of throttled steam.
During steam sampling: Note down the following observations:
 Pressure of the wet steam before throttling = p2 bar
 Pressure of the superheated steam after throttling = p2 bar
 Temperature of the superheated steam after throttling = tsup,2 °C
For the accurate result from the throttling calorimeter, the necessary condition is that the
steam should be in a superheated state after throttling. In general, 5°C of superheating is most
desirable i.e. 5°C more than the saturation temperature corresponding to recorded pressure
after throttling ‘p2’.

The process ‘1-2’ on h-s diagram in Fig. 26.2, represent the throttling process in orifice
throttling valve of throttling calorimeter.
Calculations of dryness fraction of wet steam, x1:
Properties of wet steam before throttling at point ‘1’ by using Steam Tables:
Enthalpy of a saturated water corresponding to pressure p1 = hf,1, kJ/kg.
Latent heat of evaporation corresponding to pressure p1 = hfg,1,kJ/kg
Properties of superheated steam after throttling at point ‘2’ by using Steam Tables:
Enthalpy of a superheated steam corresponding to pressure p2 and temperature tsup,2 =
hsup,2, kJ/kg.
Since during throttling process, the enthalpy remains constant, hence
Enthalpy of wet steam before throttling valve at point ‘1’ corresponding to pressure
p1 = Enthalpy superheated steam after throttling valve at point ‘2’ corresponding to pressure
p2
or h1 = hsup,2 ……….(26.1)
Where, Enthalpy of wet steam at point ‘1’ corresponding to pressure p1 is given by ,
h1= hf,1 + x1. hfg,1 …….(26.2)
By using equation (26.2) in equation (26.1), we have
hf,1 + x1. hfg,1 = hsup,2
or
…….(26.3)
An alternative method to find ‘x1’ when superheated steam is treated as an ideal gas:
Then, enthalpy of a superheated throttled steam corresponding to pressure p 2 and
temperature tsup,2 is calculated by
hsup,2 = hg,2 + Cp(tsup,2 - tg,2) , kJ/kg. …….(26.4)
where Cp is sp. heat of superheated steam = 2.607 kJ/kg K
By using equations (26.2) and (26.4) in equation (26.1), we have
hf,1 + x1. hfg,1 = hg,2 + Cp(tsup,2 - tg,2)
or …….(26.5)
With the above equation (26.3) or (26.5) we can easily calculate the value of the dryness
fraction.
Drawback

We can not use this method for finding out the dryness fraction of very wet steam because the
required 5°C superheated steam after throttling cannot be achieved with the very wet steam.
Problem 1: The following data refer to a throttling calorimeter.

Pressure in the main steam pipe = 10 bar, Pressure after throttling = 1.2 bar, Temperature
after throttling = 120°C. Assuming Cp = 2.303 kJ/kg K for steam after throttling. Calculate the
(a) Dryness fraction.
(b) Minimum degree of wetness which can be shown by this calorimeter for this steam. If the
wetness is beyond the range of this calorimeter suggest another method.
Solution:
Given: Steam at state ‘1’: Pressure in the main steam pipe before throttling, p1 = 10 bar:
By using steam table (for dry saturated steam):
For state 1, From steam tables for dry saturated steam at p1 = 10 bar, we have
hf,1 = 763 kJ/kg, hfg,1 = 2015 kJ/kg
Given: Steam at state ‘2’: Pressure after throttling, p2 = 1.2 bar; Temperature after throttling,
t2 = 120°C;
For state 2, From steam tables for dry saturated steam at p2 = 1.2 bar, we have
ts,2 =104.8°C,
Since, t2 = 120°C > ts,2 =104.8°C the condition of steam at state ‘2’ is superheated. Therefore,
tsup,2 = t2 = 120°C
By using steam table (for superheated steam)
For superheated state 2, From steam tables for superheated steam at p2 = 1.2 bar and
tsup,2 = 120°C, we have

hsup,2 = 2714.81 kJ/kg
Given: Assuming Cp = 2.303 kJ/kg K for steam after throttling. Calculate the
(a) Determine the dryness fraction of steam in main steam pipe:

Formula: During throttling process enthalpy remains constant.
i.e. h1= hsup,2
Since the steam is wet at state ‘1’: h1= hf,1+ x1. hfg,1
Therefore, hf,1+ x1. hfg,1 = hsup,2
or
Answer: Dryness fraction, x1 = = 0.9686
(b) Determine the minimum degree of wetness

For minimum degree of wetness, the condition of
steam after throttling should be at least 5°C
superheated at 1.2 bar pressure.
Therefore superheat temperature at point ‘2’,
tsup,2 = tsat °C + 5°C =104.8 + 5 = 109.8°C
For superheated state 2, From steam tables for
superheated steam at p2 = 1.2 bar and tsup,2 =
109.8°C, we have
hsup,2 = 2687 kJ/kg
Formula: Since, during throttling process enthalpy remains constant.

i.e. h1= hsup,2
or hf,1+ x1. hfg,1 = hsup,2 (as condition of steam at point ‘1’ is wet)
or
Answer: The minimum degree of wetness
x1 = = 0.9582
If the dryness fraction is lower than 95.28%, a combination of separating and throttling
calorimeter will be used.

COMBINED SEPARATING AND THROTTLING CALORIMETER

A combined separating and throttling calorimeter is used to remove the drawback of
Separating Calorimeter (i.e. water particles from wet steam are not fully separated) and the
drawback of Throttling Calorimeter (i.e. not suitable for very wet steam).
Principle: In this calorimeter
 The moisture from wet steam sample is first removed in separating calorimeter, so that
dryness fraction of wet steam sample is increased above 0.95 before steam sample is
entering into throttling calorimeter. During this process pressure and temperature
remains constant.
 The sample coming out from separating calorimeter is then passed through throttling
calorimeter where it expands to superheated steam.
Material: Refer Fig. 26.2. It consists of a combined separating calorimeter and throttling
calorimeter as discussed in previous sections.
Procedure: A sample of wet steam from main steam pipe (represented by point ‘A’ in Fig.
26.2) is first enters the separating calorimeter through a sampling tube. While passing through
separating calorimeter, most of the moisture from wet steam is separated out and collected in
the inner chamber of the separating calorimeter where it is measure with scale. Now,
comparatively dry steam having dryness fraction above 0.95 from separating calorimeter
(represented by point ‘B’ in Fig. 26.2) is passed into throttling calorimeter through throttling
valve where it expands to superheated steam (represented by point ‘C’ in Fig. 26.2). The
superheated steam after passing through throttling calorimeter is then exhausted from
throttling calorimeter into a condenser, provided at the bottom of the throttling calorimeter,
where it is finally condensed and measured.
The representation of separating-throttling processes of combined separating and throttling
calorimeter on T-s and h-s diagrams is shown in Fig.
During steam sampling: Note down the following observations:
 Pressure before throttling = p1 (say) bar
 Pressure after throttling = p2 (say) bar
 Temperature of a throttled superheated steam = tsup,C (say), oC
After steam sampling: Note down the following observations:

 Mass of condensate collected in the container provided at the bottom of throttling
calorimeter (i.e. mass of steam coming from separating calorimeter into throttling
calorimeter through throttling valve) = M (say),kg
 Mass of water collected in the inner chamber of the separating calorimeter (i.e. mass of
water separated in the separating calorimeter = m (say),kg

Calculations of dryness fraction of wet steam, x:
 Partial dryness fraction of wet steam coming from main steam pipe, measured by
separating calorimeter alone,
 Dryness fraction of steam entering into throttling calorimeter from separating

calorimeter through throttling valve, measured by throttling calorimeter alone (by
using equation 26.3)
Where,
hf,B is enthalpy of saturated water at p1 (from steam tables) , kJ/kg.
hfg,B is Latent heat of vapouization at p1 (from steam tables),kJ/kg
hsup,C is enthalpy of a throttled superheated steam corresponding to pressure p2 and
temperature tsup,C (from superheated steam table),kJ/kg .
 Mass of dry steam in the wet steam sample collected from main steam pipe = the mass
of dry steam entering the throttling calorimeter = x2 . M
Finally, The total dryness fraction of wet steam collected from main steam pipe measure
by Combined Separating and Throttling Calorimeter
By using equation (26.6) in above equation, we have

x = x1.x2
This shows that the dryness fraction of steam measured from combined separating and
throttling calorimeter is the product of dryness fraction x1 and x2 measured by separating and
throttling calorimeter respectively.
Among all methods, this method of determining the dryness fraction of steam is the
most satisfactory.
Problem : In a test on a combined separating and throttling calorimeter, the following data
were obtained:-
Pressure in the steam main = 14 bar,

Pressure of steam after throttling = 13.2 cm of Hg gauge,
Mass of steam collected in the separator = 0.8 kg/min ,
Discharge from throttling calorimeter = 10 kg/min,
Temperature of steam after throttling = 115°C,
Barometer = 76 cm of Hg.
Calculate (a) the dryness fraction of steam in the main, (b) the velocity of flow in the steam
main, if the diameter is 12 cm and the flow of steam is 130 kg/min, (c) the mass of water
required to condense the steam after the throttling calorimeter if the temperature rise of the
cooling water is l2°C.
Solution:
Given: Steam before throttling (state ‘1’): Pressure in steam main before throttling, p1 = 14
bar:
For state 1, From steam tables for dry saturated steam at p1 = 14 bar, we have
hf,1 = 830 kJ/kg, hfg,1 = 1960 kJ/kg, vg,1 = 0.1408 m3/kg
Given: Steam after throttling (state ‘2’):
Pressure of steam after throttling, p2 = 13.2 cm of Hg gauge
p2 = 76+13.2 = 89.2 cm of Hg.
Temperature after throttling, t2 = 115°C;

For state 2, From steam tables for dry saturated steam at p2 = 1.1889 bar, we have
ts,2= 104.8°C, hg,2 = 2683 kJ/kg,
Since, t2 = 115°C > ts,2 =104.8°C the condition of steam at state ‘2’ is superheated.
Therefore, tsup,2 = t2 = 115°C
For superheated state 2, From steam tables for superheated steam at p 2 = 1.1889 bar and
tsup,2 = 115°C, we have
hsup,2 = 2704.3 kJ/kg
Given: Mass of steam collected in the separator, m = 0.8 kg/min;
Discharge from throttling calorimeter, M = 10 kg/min,

(a) Determine the dryness fraction of steam in the main:
Formula: The dryness fraction of steam from separating and throttling calorimeter is
calculated by the equation:
x = x1. x2
where, x1 = Dryness fraction of steam measured by separating calorimeter,
x2 = Dryness fraction of steam measured by throttling calorimeter
Finding unknown, x1 and x2:
Dryness fraction of steam measured by separating calorimeter,
Dryness fraction of steam measured by throttling calorimeter,
x2 = = 0.956
Answer: x = x1.x2 = 0.9256 x 0.956 = 0.885
(b) Determine the velocity of flow in the steam main, if the diameter is 12 cm and the
flow of steam is 130 kg/min
Given:
Diameter of pipe, d = 12 cm = 0.12 m
Formula: From continuity equation,
or velocity = C1 =
Finding unknown, v1
Sp. volume of steam in the main pipe for wet steam, v1 = x vg,1
= 0.885 x 0.1408
= 0.1246 m3/kg
Answer: Velocity = C1 = =1432.2 m/min

(c) Determine the mass of water required to condense the steam after the throttling
calorimeter if the temperature rise of the cooling water is l2°C.
Given: Temperature rise of the cooling water, Δt = l2°C
Formula: If mass of water be required in the condenser to remove the superheat and latent
heat of M mass of steam from throttling calorimeter, then
M (hsup,2 – ts,2) = x Cp x Δt
Answer: M (hsup,2 – ts,2) = x Cp x Δt
10 (2704.3 – 104.8) = x 12 x 4.18
or = 518.24 kg/min

MODULE 5
IDEAL GASES AND REAL GASES

Usually, the word 'real gas' refers to a gas that does not function as an ideal gas. The
interactions between gaseous molecules can explain their behaviour. Such intermolecular
interactions between gas particles are the explanation of why the ideal gas law does not
adhere to real gases. A real gas can therefore be characterized as non-ideal gases whose
molecules occupy a given amount of space and are capable of interacting with one another. In
this article, we will study the real gas definition, real gas equation, and ideal and real gases in
detail.
Real Gas Definition
A real gas is defined as a gas that at all standard pressure and temperature conditions does not
obey gas laws. It deviates from its ideal behaviour as the gas becomes huge and voluminous.
True gases have velocity, mass, and volume. They liquefy when cooled to their boiling point.
The space filled by gas is not small when compared to the total volume of gas.
Ideal and Real Gas Equation
An ideal gas is defined as a gas that obeys gas laws at all pressure and temperature conditions.
Ideal gases have velocity as well as mass. They have no volume. The volume taken up by the
gas is small as compared to the overall volume of the gas. It does not condense and triple-point
does not exist.
The ideal gas law is the equation of the state of a hypothetical ideal gas, also called the general
gas equation. Under many conditions, it is a reasonable approximation of the behaviour of
several gases, but it has many limitations. In 1834, Benoît Paul Émile Clapeyron first described
it as a variation of the empirical law of Boyle, the law of Charles, the law of Avogadro, and the
law of Gay-Lussac. In an empirical form, the ideal gas law is also written:
pV=nRT
Real Gas Law
By explicitly including the effects of molecular size and intermolecular forces, the Dutch
physicist Johannes van der Waals modified the ideal gas law to explain the behaviour of real
gases. The Van der Waal real gas equation is given below-
Real gas law equation,
=(P+an2/V2) (V-nb)=nRT

Where a and b represent the empirical constant which is unique for each gas.
n2/V2 represents the concentration of gas.
P represents pressure
R represents a universal gas constant and T is the temperature
Ideal and Real Gases
The difference below shows the properties of real gas and ideal gas, and also the ideal and real
gas behaviour.
Ideal Gas Real Gas
No definite volume Definite volume
Elastic Collision of particles Non-elastic collisions between particles
No intermolecular attraction force Intermolecular attraction force
Does not really exists in the environment and

It really exists in the environment
is a hypothetical gas
The pressure is less when compared to

High pressure
Ideal gas
Independent Interacts with others
Obeys PV = nRT Obeys p + ((n2a )/V2) (V – nb ) = nRT
The three fundamental gas laws discover the relationship of pressure, temperature, volume
and amount of gas. Boyle's Law tells us that the volume of gas increases as the pressure
decreases. Charles' Law tells us that the volume of gas increases as the temperature increases.
And Avogadro's Law tell us that the volume of gas increases as the amount of gas increases.
The ideal gas law is the combination of the three simple gas laws.

Ideal Gases
Ideal gas, or perfect gas, is the theoretical substance that helps establish the relationship of
four gas variables, pressure(P), volume(V), the amount of gas(n)and temperature(T). It has
characters described as follow:
1. The particles in the gas are extremely small, so the gas does not occupy any spaces.
2. The ideal gas has constant, random and straight-line motion.
3. No forces between the particles of the gas. Particles only collide elastically with each
other and with the walls of container.
Real Gases
Real gas, in contrast, has real volume and the collision of the particles is not elastic, because
there are attractive forces between particles. As a result, the volume of real gas is much larger
than of the ideal gas, and the pressure of real gas is lower than of ideal gas. All real gases tend
to perform ideal gas behavior at low pressure and relatively high temperature.
The compressiblity factor (Z) tells us how much the real gases differ from ideal gas behavior.
Z=PV/nRT (Gas Laws.1)
For ideal gases, Z=1 For real gases, Z≠1
Boyle's Law
In 1662, Robert Boyle discovered the correlation between Pressure (P)and Volume
(V) (assuming Temperature(T) and Amount of Gas(n) remain constant):
P∝1/V→PV=x
(Gas Laws.2)
where x is a constant depending on amount of gas at a given temperature.
 Pressure is inversely proportional to Volume

Another form of the equation (assuming there are 2 sets of conditions, and setting both
constants to eachother) that might help solve problems is:
P1V1=x=P2 V2
Charles' Law
In 1787, French physicists Jacques Charles, discovered the correlation
between Temperature(T) and Volume(V) (assuming Pressure (P) and Amount of Gas(n) remain
constant):
V∝T→V=yT
where y is a constant depending on amount of gas and pressure. Volume is directly
proportional to Temperature
Another form of the equation (assuming there are 2 sets of conditions, and setting both
constants to eachother) that might help solve problems is:
V1/T1=y=V2/T2
REAL GASES
Real gases do not obey ideal gas equation under all conditions. They nearly obey ideal gas
equation at higher temperatures and very low pressures. However they show deviations from
ideality at low temperatures and high pressures.
The deviations from ideal gas behaviour can be illustrated as follows:
The isotherms obtained by plotting pressure, P against volume, V for real gases do not coincide
with that of ideal gas, as shown below.

It is clear from above graphs that the volume of real gas is more than or less than expected
in certain cases. The deviation from ideal gas behaviour can also be expressed by
compressibility factor, Z.
Compressibility factor (Z):
The ratio of PV to nRT is known as compressibility factor.
(or)
The ratio of volume of real gas, Vreal to the ideal volume of that gas, Vperfect calculated by
ideal gas equation is known as compressibility factor.
But from ideal gas equation:

PVperfect = nRT
or
Therefore
* For ideal or perfect gases, the compressibility factor, Z = 1.

* But for real gases, Z ≠1.
* For ideal or perfect gases, the compressibility factor, Z = 1.
* But for real gases, Z ≠1.

Case-I : If Z>1
* Vreal > Videal
* The repulsion forces become more significant than the attractive forces.
* The gas cannot be compressed easily.
* Usually the Z > 1 for so called permanent gases like He, H2 etc.
Case-II: If Z < 1
* Vreal < Videal
* The attractive forces are more significant than the repulsive forces.
* The gas can be liquefied easily.
* Usually the Z < 1 for gases like NH3, CO2, SO2 etc.
The isotherms for one mole of different gases, plotted against the Z value and pressure, P at
0 oC are shown below:
* For gases like He, H2 the Z value increases with increase in pressure (positive deviation).
It is because, the repulsive forces become more significant and the attractive forces become
less dominant. Hence these gases are difficult to be condensed.
* For gases like CH4, CO2, NH3 etc., the Z value decreases initially (negative deviation) but
increases at higher pressures.
It is because: at low pressures, the attraction forces are more dominant over the repulsion
forces, whereas at higher pressures the repulsion forces become significant as the molecules
approach closer to each other.

* But for all the gases, the Z value approaches one at very low pressures, indicating the
ideal behaviour.
Also consider the following graphs of Z vs P for a particular gas, N2 at different
temperatures.
In above graphs, the curves are approaching the horizontal line with increase in the
temperature i.e., the gases approach ideal behaviour at higher temperatures.
VAN DER WAALS EQUATION : DERIVATION
The deviations from ideal gas behaviour can be ascertained to the following faulty
assumptions by kinetic theory of gases.
* The real volume of the gas molecules is negligible when compared to the volume of the
container.
* There are no forces of attraction or repulsion between the gas molecules.
Hence van der Waal suggested the following corrections:

* The gas molecules possess finite volume and hence should not be neglected. It is
especially true at high pressures and low temperatures and should be accounted for.
* In case of real gases, both the forces of attraction as well as repulsion operate between
gas molecules.
Note: If the gases obey the kinetic theory of gases, then they cannot be compressed since
the attractions between the gas molecules is negligible.

Also the following corrections are applied by van der Waals to the ideal gas equation:
Volume correction:
The volume available for the gas molecules is less than the volume of the container, V.
The available volume is obtained by subtracting excluded volume of ‘n’ moles of gas, nb
from the volume of the container.
Available volume = V - nb
Where 'b' is a constant characteristic of a gas.
The ideal gas equation can be written after correcting for this as:
P(V-nb) = nRT
Pressure correction:
The pressure of the real gas is less than the expected pressure due to attractions between
the molecules. These attractions slow down the motion of gas molecules and result in:
i) reduction of frequency of collissions over the walls and
ii) reduction in the force with which the molecules strike the walls.
Hence
Pideal = Preal + p
Where p = reduction in pressure
However the reduction in pressure is proportional to the square of molar concentration,
n/V.
One factor for reduction in frequency of collisions and the second factor for reduction in
strength of their impulses on the walls.
or
where ‘a’ is a proportionality constant characteristic of a gas.

Therefore:

Now the ideal gas equation can be modified once again by introducing this pressure
correction as:
This is known as van der Waals equation of state.

For one mole of a gas, the equation can be written as:
Where Vm = volume occupied by one mole of a real gas
Remember that:
P = observed pressure of the real gas
V = volume occupied by the real gas and is equal to the volume of the container.
whereas, (V - nb) = available volume for gas molecules
Units of ‘a’ and ‘b’:

For ‘a’ ----------- atm L2 mol-2
For ‘b’ ----------- L. mol-1
CHARACTERISTICS OF VAN DER WAALS CONSTANTS: a & b
* ‘a’ is called van der Waals constant of attraction. Higher values of ‘a’ indicate greater
attraction between gas molecules. The easily compressible gases like ammonia, HCl possess
higher ‘a’ values.
Greater the value of ‘a’ for a gas easier is the liquefaction.
* ‘b’ is called excluded volume of the gas.
Where NA = Avogadro number and r = radius of molecule

* For a given gas, the numerical value of ‘a’ is greater than that of ‘b’.

* The Boyle's temperature (TB) and inversion temperature (Ti) are related to the two van
der Waals constants as:
Note:
Boyle’s temperature is the temperature at which the gases obey the ideal gas laws over a
wide range of pressures.
Inversion temperature is the temperature at which the Joule Thompson coefficient
changes its sign i.e., from positive to negative or vice versa.
MERITS & APPLICATIONS OF VAN DER WAAL'S EQUATION
* The Vander Waal's equation holds good for real gases up to moderately high pressures.
* It explains the isotherms of PV/RT vs P for various gases.
* From this equation it is possible to obtain expressions for Boyle's temperature, critical
constants and inversion temperature in terms of the Vander Waal's constants 'a' and 'b'.
Liquefaction of gases: The isotherms plotted between P vs V at different temperatures for
one mole of CO2 gas are shown below.
Following conclusions can be drawn from these graphs:

* At higher temperatures, say 50 oC, the isotherms show ideal behaviour.
* As the temperature is lowered, the isotherms show deviation from ideal behaviour.
* At 30.98 oC, carbon dioxide remains as gas up to 73 atm. But liquid appears for the first
time at 73 atm (represented by point ‘O’). Hence 30.98 oC is called critical temperature for CO2.

And above 73 atm. there is a steep rise in the pressure. This steep portion of the curve
represents the isotherm of liquid state for which small decrease in volume results in steep rise
in the pressure.
* At even lower temperature, 20 oC, the liquid appears at point ‘A’. Further compression
does not change the pressure up to point ‘B’. After point, B the curve again becomes steep
representing the isotherm for liquid CO2.
Critical PROPERTIES
Critical Temperature (Tc): It is the temperature above which a gas cannot be liquefied by
applying pressure.
Critical Pressure (Pc): It is the minimum pressure required to cause liquefaction at critical
temperature, Tc.
Critical Volume (Vc): It is the volume occupied by one mole of a gas at Tc and Pc.
Vc = 3b
Super critical fluid: The dense fluid obtained by compressing a gas above its critical
temperature is called super critical fluid.
* It is not a liquid though its density is similar to that of liquid.
* It is not a gas due to high density and no distinct surface that separates it from the vapour
phase.
* It can be used as a solvent.
E.g. The super critical fluid of CO2 is used in the extraction of caffeine from coffee beans.
Derivation of critical constants from van der Waals constant:

The van der Waals equation for n moles is

From the equation we can derive the values of critical constants Pc, Vc and Tc in terms of a and
b, the van der Waals constants, On expanding the above equation
When the above equation is rearranged in powers of V
The equation (6.26) is a cubic equation in V. On solving this equation, we will get three
solutions. At the critical point all these three solutions of V are equal to the critical volume VC.
The pressure and temperature becomes Pc and Tc respectively
V = VC
V – VC = 0
(V – VC)3 = 0
V3 - 3VCV3 + 3VC2V - VC3 = 0 .......(6.27)
As equation (6.26) is identical with equation (6.27), we can equate the coefficients of V2, V and
constant terms in (6.26) and (6.27).

i.e. VC = 3b ------- (6.31)

when equation (6.31) is substituted in (6.29)
substituting the values of Vc and Pc in equation (6.28),

The critical constants can be calculated using the values of van der waals constant of a gas and
vice versa.
DALTON'S LAW OF PARTIAL PRESSURES

Dalton's law of partial pressures states that the total pressure of a mixture of gases is the sum
of the partial pressures of its components:
PTotal=Pgas 1+Pgas 2+Pgas 3...
where the partial pressure of each gas is the pressure that the gas would exert if it was the only
gas in the container. That is because we assume there are no attractive forces between the
gases.

Dalton's law of partial pressure can also be expressed in terms of the mole fraction of a gas in
the mixture. The mole fraction of a gas is the number of moles of that gas divided by the total
moles of gas in the mixture, and it is often abbreviated as xxx:
AMAGAT’S LAW OF PARTIAL VOLUMES
Amagat’s law of partial volumes asserts that the volume of a mixture is equal to the sum of the
partial volumes of its components. For a mixture of components AA, BB, CC, etc., Amagat’s law
gives the volume as
Vmixture=VA+VB+VC+…
For real gases, Amagat’s law is usually an even better approximation than Dalton’s law66.
Again, for mixtures of ideal gases, it is exact. For an ideal gas, the partial volume is
VA=Nart/Pmixture
Since nmixture=nA+nB+nC+…
we have, for a mixture of ideal gases,
Vmixture=nmixtureRT/Pmixture
=(nA+nB+nC+…)RT/Pmixture
=VA+VB+VC+…

Applied to the mixture, the ideal-gas equation yields Amagat’s law. Also, we
have VA=xAVmixture
Beattie-Bridgman equation
An equation of state that relates the pressure, volume, and temperature of a gas and the gas
constant. The Beattie-Bridgman equation uses empirical constants to take into account the
reduction in the effective number of molecules due to various types of molecular aggregation.
It is given by
P=RT(1 – ϵ)(V+B)/V 2 – A/V 2,
where P is the pressure,
T is the thermodynamic temperature,
V is the volume,
R is the gas constant,
and A, B, and ϵ are constants related to five empirical constants A 0, B 0, a, b, and c by: A=A 0(1 –
a/V), B=B 0(1 – b/V), and ϵ=c/VT 3.
P=RT(1 – ϵ)(V+B)/V 2 – A/V 2
Problems
1. Carbon Dioxide gas is stored in a 100 liter tank at 6 MPa and 30°C. Determine the mass of
CO2 in the tank based on (a) values obtained from the CO2 tables of data, (b) the ideal gas
equation of state, and (c) the generalized compressibility chart. Compare (b) and (c) to (a) and
determine the percentage error in each case.
Solution Approach:
We first determine the Critical Point data for CO2 from the Table of Critical Point Data of
Various Substances

After evaluating the Reduced Pressure and Reduced Temperature we plot them on
the Generalized Compressibility Chart in order to determine the Compressibility Factor, as
shown below
The actual value of specific volume va is obtained from the CO2 Superheat Tables

The general rule is that if P << PCR or if T >> TCR then you are probably dealing with an ideal
gas. If in doubt always check the Compressibility Factor Z on the Compressibility Chart.
2. You may wonder why we would be interested in knowing the value of air pressure at 3000m
altitude. In the following example we continue with the above development in order to
evaluate the payload that can be lifted to an altitude of 3000m using a small hot air balloon
(Volume =1000 m3) having an empty mass of 100kg. Assume that the temperature of the air in
the balloon is 100°C.
Solution Approach:
In this case we develop the solution in terms of a force balance between the bouyancy force
(weight of the displaced air) and the gravity force including the weight of the hot air, the
balloon empty mass, and the payload mass. The maximum altitude occurs when those two
forces are equal, as follows:


3. A piston-cylinder device contains 0.5 kg saturated liquid water at a pressure of 200 kPa.
Heat is added and the steam expands at constant pressure until it reaches 300°C.
 a) Draw a diagram representing the process showing the initial and final states of the
system.
 b) Sketch this process on a T-v (temperature-specific volume) diagram with respect to
the saturation lines, critical point, and relevant constant pressure lines, clearly
indicating the initial and final states.
 c) Using steam tables determine the initial temperature of the steam prior to heating.
 d) Using steam tables determine the final volume of the steam after heating
 e) Using the ideal gas equation of state determine the final volume of the steam after
heating. Determine the percentage error of using this method compared to that of using
the steam tables.
Note: The critical point data and the ideal gas constant for steam can be found on the first page
of the steam tables.
Solution Approach:
Even if questions a) and b) were not required, this should always be the first priority item in
solving a thermodynamic problem.

c) Since state (1) is specified as saturated liquid at 200 kPa, we use the saturated pressure
steam tables to determine that T1 = Tsat@ 200kPa = 120.2°C.
d) From the T-v diagram we determine that state (2) is in the superheated region, thus we use
the superheated steam tables to determine that v2 = v200kPa,300°C = 1.3162 m3/kg. Thus V2 =
m,v2 = (0,5kg).(1.3162 m3/kg) = 0.658 m3 (658 liters)
Note that in doing a units check we find that the following conversion appears so often that we
feel it should be added to our Units Conversion Survival Kit (recall Chapter 1):
Finally we determine the percentage error of using the ideal gas equation at state (2)

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|| Jai Sri Gurudev ||

Sri AdichunchanagiriShikshana Trust®

SJB INSTITUTE OF TECHNOLOGY

Department of Mechanical Engineering

Semester &Section: 3rd Semester ‘A’ section

Academic year: ODD Semester-2021-2022

2. POs, PSOs & PEOs

4. Objectives and Outcomes

6. Lecture Notes (Unit-wise)

b. Industry applications relevant to the concepts covered

c. Assignment Question with self learning Materials

Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. Page 2

Vision of the Institute

Mission of the Institute

Vision of the Department

Mission of the Department

Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. Page 3

Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. Page 4

PROGRAM EDUCATIONAL OBJECTIVES (PEO’S)

Enable the Graduates in Mechanical Engineering to:

PROGRAM SPECIFIC OUTCOMES (PSO’S)

After successful completion of Mechanical Engineering program, the graduates will

Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. Page 5

Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. Page 6

Course Code 18ME33 CIE Marks 40

Course Learning Objectives:

Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. Page 7

Question paper pattern:

Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. Page 8

A thermodynamic system is a device or combination of devices containing a quantity of matter

A typical thermodynamic system

Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. Page 9

A Steam Power Plant

Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. Page 10

This study deals with macroscopic, as opposed to microscopic or statistical thermodynamics.

Microscopic point of view: Considers a system containing a cube of 25 mm containing

Statistical thermodynamics, classical thermodynamics deals with the significance of

Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. Page 11

A Thermodynamic system is defined as a quantity of matter or a region in space upon

Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. Page 12

A System, Surroundings and Boundary

Control Volume and Control Surface:

Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. Page 13

Homogeneous and Heterogeneous system:

A system consisting of a single phase is called a homogeneous system while a system

Mass – kg Length – m Time – s

Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. Page 14

Patm Ordinary vacuum gauge

Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. Page 15

Intensive property: An intensive property is independent of mass; thus intensive property

Thermodynamic State Point:

These co-ordinate systems represent thermodynamic state of a substance. Consider a system

Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. Page 16

Piston Cylinder arrangement

Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. Page 17

Quasi – static process (very slow process) :

Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. Page 18

Department of Mechanical Engineering, SJBIT-Naveena kumar R. R. Page 19

Zeroth law of Thermodynamics:

Force = Area * Pressure = (π / 4) * (0.15)2 7 106 = 123716.25 N Ans.