Basic Thermodynamics(BME304) notes

BASIC THERMODYNAMICS

(Sub code:-BME304)
(AS PER CHOICE BASED CREDIT SYSTEM)

Prepared by:
Mr. Prakhyath Jain
Assistant Professor

DEPARTMENT OF MECHANICAL ENGINEERING

A J INSTITUTE OF ENGINEERING AND TECHNOLOGY
NH-66
KOTTARA CHOWKI
MANGALURU

Department of Mechanical Engineering, AJIET,Mangaluru 1

 VISION AND MISSION STATEMENT OF AJIET

Vision of the Institute

To produce top-quality engineers who are groomed for attaining excellence in their profession
and competitive enough to help in the growth of nation and global society.

Mission of the Institute

o To offer affordable high-quality graduate program in engineering with value education

and make the students socially responsible.
o To support and enhance the institutional environment to attain research excellence in
both faculty and students and to inspire them to push the boundaries of knowledge
base.
o To identify the common areas of interest amongst the individuals for the effective
industry- institute partnership in a sustainable way by systematically working together.
o To promote the entrepreneurial attitude and inculcate innovative ideas among the
engineering professionals.

Department of Mechanical Engineering

Vision of the Department

To create globally competent and self-reliant mechanical engineers adaptive to an

interdisciplinary environment contributing to society through development, authority and
entrepreneurship.

Mission of the Department

M 1. To offer high quality graduate program in the field of Mechanical Engineering with
value education to the students and make them responsive to societal needs.
M 2. To nurture the students with a global outlook for a sustainable future with high
moral and ethical values.
M 3. To strengthen collaboration with industries, academia and research organizations
to enrich learning environment, thus enhance research and entrepreneurship
culture.
M 4. To create awareness about the need of interdisciplinary applications through
alumni industry-institution interactions
 PROGRAM EDUCATIONAL OBJECTIVES (PEOs)
Prepare graduates with mathematical, scientific and engineering skills to design and
PEO1
develop energy efficient systems for sustainable development.
Excel graduates with high level of technical competency combined with research and
PEO2 complex problem-solving ability to generate innovative solutions in Mechanical and
multi-disciplinary areas.
PEO3 Equip graduates with modern tools, technology and advanced software’s for
deliberating engineering solutions.
Inculcate graduates with strong foundation in academic excellence, soft skills, leadership
PEO4
qualities, professional ethics, and social concerns and understand the need for lifelong
learning for a successful professional career.

PROGRAM OUTCOMES (POs)

Engineering knowledge: Apply the knowledge of mathematics, science, engineering fundamentals, and
PO1
specialization in Mechanical Engineering for the solution of complex engineering problems.
Problem analysis: Identify, formulate, research literature, and analyse complex engineering problems
PO2 reaching substantiated conclusions using first principles of mathematics, natural sciences, and engineering
sciences.
Design/development of solutions: Design solutions for complex engineering problems and design system
PO3 components or processes that meet the specified needs with appropriate consideration for public health and
safety, and cultural, societal, and environmental considerations.
Conduct investigations of complex problems: Use research-based knowledge and research methods
PO4 including design of experiments, analysis and interpretation of data, and synthesis of the information to
provide valid conclusions.
Modern tool usage: Create, select, and apply appropriate techniques, resources, and modern engineering
PO5 and IT tools, including prediction and modelling to complex engineering activities, with an understanding of
the limitations.
The engineer and society: Apply reasoning informed by the contextual knowledge to assess societal, health,
PO6 safety, legal, and cultural issues and the consequent responsibilities relevant to the professional engineering
practice

Environment and sustainability: Understand the impact of the professional engineering solutions in societal
PO7
and environmental contexts, and demonstrate the knowledge of, and need for sustainable development.
Ethics: Apply ethical principles and commit to professional ethics and responsibilities and norms of the
PO8
engineering practice.
Individual and team work: Function effectively as an individual, and as a member or leader in diverse
PO9
teams, and in multidisciplinary settings.
Communication: Communicate effectively on complex engineering activities with the engineering
PO10 community and with the society at large, such as, being able to comprehend and write effective reports and
design documentation, make effective presentations, and give and receive clear instructions.
Project Management and Finance: Demonstrate knowledge and understanding of the engineering and
PO11 management principles and apply these to one’s own work, as a member and leader in a team, to manage
projects and in multidisciplinary environment.
Life-long learning: Recognize the need for, and have the preparation and ability to engage in independent
PO12
and life-long learning in the broadest context of technological change.

PROGRAM SPECIFIC OUTCOMES (PSOs)

PSO1 Apply the knowledge of modern engineering tools to design and analyze the products and process
related to Mechanical Engineering systems
PSO2 Develop technical and interpersonal skills pertinent to mechanical and allied engineering for careers in
industry, academia and government organizations.
COURSE SYLLABUS

BASIC THERMODYNAMICS Semester 3rd

Course Code BME304 CIE Marks 50
Teaching Hours/Week 2:2:0:0 SEE Marks 50
(L:T:P: S)
Total Hours of 40 Total Marks 100
Pedagogy
Examination type (SEE) Theory
Module 1(08 hours)
Introduction and Review of fundamental concepts: Thermodynamic definition and scope,
Microscopic and Macroscopic approaches. 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 (The topics are Only for Self-study and not to be asked in
SEE. However, may be asked for CIE)

Zeroth law of thermodynamics, Temperature; concepts, scales, international fixed points

and measurement of temperature. Constant volume gas thermometer, constant pressure gas
thermometer, mercury in glass thermometer, thermocouples, electrical resistance
thermometer. Numerical.

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.
Module 2(08 hours)
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, Problems.

Extension of the First law to control volume; steady flow energy equation (SFEE),
Problems.
Module 3(08 hours)
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. 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. Problems
Module 4(08 hours)
 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. Problems

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. Problems.
Module 5(08 hours)
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 (Processes are not to be asked for SEE).

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.

Thermodynamic relations: Maxwell’s equations, TdS equation. Ratio of Heat capacities

and Energy equation, Joule-Kelvin effect, Clausius-Clapeyron equation.

Course outcomes
At the end of the course the student will be able to:
CO1 Understand the fundamentals of thermodynamics and evaluate energy
interactions across the boundary of thermodynamic systems.
CO2 Understand and apply 1st law of thermodynamics to closed and open systems
and determine quantity of energy transfers.
CO3 Evaluate the feasibility of cyclic and non-cyclic processes using 2nd law of
thermodynamics
CO4 Understand and apply the knowledge of entropy, reversibility and irreversibility
to solve numerical problems and Interpret the behaviour 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
 Suggested Learning Resources:

1. Text Books
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.
4. Thermodynamics- An Engineering Approach YunusA.Cenegal and Michael A.Boles
Tata McGraw Hill publications 2002

2. Web links and Video Lectures (e-Resources):

1. https://www.youtube.com/watch?v=9GMBpZZtjXM&list=PLD8E646BAB3366BC8
2. https://www.youtube.com/watch?v=jkdMtmXo664&list=PL3zvA_WajfGAwLuULHL0AG9fK
DgplYne
3. https://www.youtube.com/watch?v=1lk7XLOxtzs&list=PLkn3QISf55zy2Nlqr5F09oO2qcIw
NNfrZ&index=3
4. https://www.youtube.com/watch?v=Dy2UeVCSRYs&list=PL2_EyjPqHc10CTN7cHiM5xB2q
D7BHUry7
 Basic Thermodynamics(BME304) notes

Module: 1
FUNDAMENTAL CONCEPTS & DEFINITIONS

Introduction and Review of fundamental concepts: Thermodynamic definition and scope,

Microscopic and Macroscopic approaches. 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 (The topics are Only for Self-study and not to be asked in
SEE. However, may be asked for CIE)
Zeroth law of thermodynamics, Temperature; concepts, scales, international fixed points
and measurement of temperature. Constant volume gas thermometer, constant pressure gas
thermometer, mercury in glass thermometer, thermocouples, electrical resistance
thermometer. Numerical.
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.

Introduction:
Thermodynamics is the science of energy transfer which deals with the relations among heat,
work and properties of the systems.
The name thermodynamics is derived from the Greek words therme, meaning heat and
dynamis meaning power. Thus thermodynamics is basically the study of heat and power.

Application Area of Thermodynamics

Energy transfer is present in almost all the engineering activities. Hence, the principles of
thermodynamics are playing vital role in designing all the engineering equipments such as
internal combustion engines, rockets, jet engines, thermal and nuclear power plants,
refrigerators etc.

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.
Thermodynamics deals with three Es, 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

Macroscopic point of view: The macroscopic level is the level on which we live. We
measure most of the quantities on this level.

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Ex: Temperature measurement, pressure measurement, total volume measurement, specific

volume measurement.

The characteristics of macroscopic point of view are:

 Structure of the matter is not considered; no attention is focused on the behavior of
individual particles constituting the matter.
 The volumes considered are very large compared to molecular dimensions and the system
is regarded as continuum devoid of any voids and cavities.
 Study is made of overall effect of several molecules; the behavior and activities of the
molecules are averaged

Microscopic point of view:

Here matter is assumed to be made of numerous individual molecules. Microscopic point of
view will be used only to explain some phenomena that can’t be understood by macroscopic
means.
Ex: Velocity, position, energy
Temperature of a gas is a function of velocity of molecules.

Considers a system containing a cube of 25 mm containing mono atomic 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.

The characteristics of microscopic point of view are:

 Necessity of complete knowledge of the structure of the matter
 Requirement of a large number of variables for complete specification of the state of
matter
 Easy and precise measurement of variables is not possible
 It is complex, cumbersome and time consuming
Comparison between Macroscopic and Microscopic view points
Sl No Macroscopic Approach Microscopic Approach
1 A certain quantity of matter is A certain quantity of matter is
considered without taking into account considered by taking into account the
the events occurring at molecular events occurring at molecular level.
level.

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2 Analysis requires simple mathematical Advanced statistical and mathematical

formulas methods are needed for analysis.
3 The changes in properties can be felt Our senses cannot feel the changes
by our senses
4 Only a few properties are needed to Large number of variables are
describe the system required to describe the system
Substance. There must be something to perform energy transformations in
thermodynamics. 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.
System: A thermodynamic system is defined as a quantity of matter or region of space upon
which study is carried out

The system is also defined as any collection of matter or space of fixed identity upon
which maximum concentration is focused.
System is a specified portion of matter under study which is separated from rest of the
universe with a definite boundary.
Surrounding / Environment: Everything external to the system or boundary is called as
surroundings.

Boundary: The separation of system from surroundings is called as boundary. It may be

moving or fixed.

Note: System + Surroundings = Universe

The system is further divided into closed system, open system and isolated system

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Open System: The open system is one in which matter and energy crosses the boundary of
the system. Most of the 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.

Closed System: A closed system is a system of fixed mass. There is no mass transfer across
the system boundary and energy crosses the boundary.
Ex: A certain quantity of fluid in a cylinder bounded by a piston constitutes 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.

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.

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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: Every system has got certain characteristics, by virtue of which
its physical condition may be described. These characteristics are called properties. All the
properties are macroscopic in nature.
Ex: Pressure, Temperature, Volume etc
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
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.

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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.

Fig: Pressure measurement reference

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:

State: When all the properties of a system have definite values, the system is said to exist at a
definite state.
The state may be identified or described by certain observable macroscopic properties like
temperature, pressure and density. The state is specified or described by the properties. The

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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.
Change of state: Any operation in which one or more properties of system changes is called
as change of state.
Path: It is the route of change of state from one state to another. Path is the complete series of
states through which the system passes during a change from one given state to other state.
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

Fig: 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.

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) Polytrophic process 6) Throttling process

If the system passes through a series of equilibrium states during the process it is 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

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Note: It is clear that the transformation of a system from one fixed state to another state is
called a process.

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.

Representation of a reversible process An irreversible process

Cycle: It is a process who’s 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.

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Thermal Equilibrium:
If the temperature is the same throughout the entire system .i.e the system involves no
temperature differential

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.

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

Quasistatic process: (very slow process):

Quasi – static 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.
Ex: Rise in atmospheric temperature

Let us consider a system of gas contained in a cylinder. The system is in equilibrium

state, represented by p1, v1, T1. The weight W on the piston balances the upward force exerted
by the gas. If the weight is removed, there will be an unbalanced force between system and
surroundings and under gas pressure, the piston will move up till it hits the stops. Then the
system again comes to an equilibrium state, being described by p2, v2, T2. Hence
only initial and final states are identified.

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Now if the single weight W is made up of many very small pieces of weights, and
these weights are removed one by one very slowly from top of the piston.

This is a process which is a locus of all the equilibrium points passed through by the
system is known as quasistatic process. Infinite slowness is the feature of this process. It is
also known as reversible process.

Adiabatic and 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.

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Fig: Equality of temperature – Zeroth law of Thermodynamics

Temperature scales:
Two scales are commonly used for measurement of temperature namely, Fahrenheit and
Celsius.
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.
The relation Between kelvin and Celsius scale is K=oC + 273.15
In 1967 the CGPM (General Conference of Weights And Measures) defined the Kelvin as
1/273.16 of the temperature at the triple point of water

Thermometry
It may be defined as the act of measuring temperature with accuracy and precision. A
property or characteristic which changes its value as a function of temperature is called
thermometric property and corresponding substance is known as thermometric substance

Temperature scales
Celsius scale
The temperature of ice and steam points are fixed at 0 C and 100 C. There are 100 degrees
between the ice point and steam point

Fahrenheit scale:
The temperature of ice and steam points are 32 F and 212 F. There are 180 degrees between
the ice point and the steam point

Kelvin scale
A value of 273.15 K, 373.15 K and 273.16 K are assigned to ice point, steam point and triple
point

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Table:Thermometers and Thermometric Properties

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

Types of thermometers: Temperature of the given system can be measured with the
following types of thermometers.

1. Liquid in glass thermometer:

These thermometers use liquids as the thermometric substance and change in the lengh of
liquid column in the capillary with heat interactions is the characteristics used for temperature
measurement. Usually mercury and alcohol are used in these type of thermometers. The
figure below shows mercury in glass thermometer. It consists of a vertical tube with
graduations marked on it to show the temperature, one end of which is connected to a
thermometric bulb. A small quantity of mercury is filled in a capillary tube. Mercury has
lower specific heat and hence absorbs little heat from the body or source. When the bulb is
brought in contact with a hot system, there is change in volume of mercury which results in
rise or fall of mercury level in the capillary tube. The length of liquid column is used as a
thermometric property and is a measure of temperature
A small quantity of liquid enclosed in a glass capillary is called Liquid in glass thermometer.
In this type, the expansion of the liquid is used as the thermometric property. 𝑇(𝐿) =
𝐿
273.16 ( 𝐿𝑝 ) Where L & Ltp are thermometric properties (Length).

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Fig: Mercury in glass thermometer

2. Constant Volume Gas Thermometer:
This thermometer consists of a capillary tube (C),which connects thermometer bulb with a U-
tube manometer. A small amount of helium gas is contained in the bulb ‘B’. The left limb of
manometer is kept open to atmosphere and can be moved vertically and mercury level on the
right limb can be adjusted so that it just touches lip ‘L’ of the capillary. The pressure of the
gas in the bulb is used as a thermometric property and is given by
P= Patm+ 𝜌𝑚 gh
Where , Patm= Atmospheric pressure
𝜌𝑚 = Densiy of mercury
When the bulb is brought in contact with the system whose temperature is to be measured, it
comes in thermal equilibrium with the system. The gas in the bulb will be heated and
expanded, pushes mercury column downward on the right limb. This rises mercury column
on the left limb. The flexible limb is then adjusted so that the mercury again touches the lip
‘L”. The difference in mercury level ‘h’ is recorded and the pressure ‘P’ of the gas in the bulb
is estimated. Since the gas volume in the bulb is constant , from ideal gas equation we can
write
𝑉
∆𝑇 = ∆𝑃 (since PV=mRT)
𝑅
Since V is constant, R is constant
∆𝑇 ∝ ∆𝑃
i.e. the temperature rise is proportional to pressure rise
since for an ideal gas at constant volume,
𝑇∝𝑃
𝑇 𝑃
=
𝑇𝑡𝑝 𝑃𝑡𝑝
𝑃 𝑃
T= 𝑇𝑡𝑝 𝑃 =273.16
𝑡𝑝 𝑃𝑡𝑝
Where 𝑇𝑡𝑝 = 273.16 ℃ = Triple point of water

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Fig: Constant volume gas thermometer

3. Constant pressure gas thermometer:In this thermometer the mercury has to be

adjusted to keep pressure constant and the volume of gas V which would vary with the
temperature of the system and becomes thermometric property. The required temperature
𝑉
can be calculated using the equation T = 273.16𝑉
𝑡𝑝

4. Thermocouple: When two wires of different materials are joined at their ends with
different temperatures existing at the two junctions,
an electro motive force (emf) generated. The
generated emf may be used as a measure of the
temperature of one junction, if the temperature at the
other junction is known.
A thermocouple circuit is made up from joining two
wires A and B made of dissimilar metals. Due to
Seeback effect, a net e m f is generated in the circuit which depends on the difference in
temperature between the hot and cold junctions is, therefore, a thermometric property of
the circuit. This e m f can be measured by a micro voltmeter to a high degree of accuracy.
The metal pairs used are copper-constantan, chromel- alumel and platinum- platinum-
rhodium.
5. Electrical Resistance Thermometer: In the resistance thermometer, the change in
resistance of a metal wire due to its change in temperature is the thermometric property.
The wire, frequently, platinum, may be incorporated in a Wheatstone bridge circuit. The
platinum resistance thermometer measures temperature to a high degree of accuracy and
sensitivity, which makes it suitable as a standard for the calibration of other thermometers.

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In a restricted range, the following quadratic equation is

used,

R = R0 (1 + At + Bt2) where R0 is the resistance of the

platinum wire when it is surrounded by melting ice and A,
B are constants.

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.
Ice point is defined as the equilibrium temperature of a mixture of ice and air saturated liquid
water at a pressure of 1 atm. On the Celsius scale, ice point is 0°C. On Fahrenheit scale, it is
32 °F.
Table: Temperature of Fixed Points
Reference 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

Mechanical 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.

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Definition of Positive work is said to be done by a system if 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.

Consider as a system the battery and motor of fig a) and let the motor drive a fan. Let the fan
be replaced with a pulley and weight arrangement shown in fig b). As the motor turns, the
weight is raised, the sole effect external to the system being raising of weight. Thus for the
original system of fig a), one can conclude that work is crossing the boundary of the system,
since sole effect external to the system could be raising of a weight

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.
Power: 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.

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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 or work done in non flow process
(Expression for displacement work)

dx
Fig: a
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 = cross sectional area of piston
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
12 w1W2 or W1-2.
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 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.
1 Quasi-Static
Process

2
dV

V
Fig b:Quasi-Static pdV work

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Prove that work is a path function

1
p1 A
B

p2 2

a V1 b V2 V
Fig.C
From fig c, it is possible to take a system from state 1 to state 2 along quasistatic paths such
as A , B or C
Work done is given by area under 1-2
Work done along path A = area 1-A-2-b-a-1
Work done along Path B = area 1-B-2-b-a-1
Work done along path C = area 1-C-2-b-a-1
It is clear that these three areas are not same. Thus work depends on the path followed during
a process and not on end states. Hence work is a path function and and an inexact diffential
12 w1W2 or W1-2.
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

V
W1-2 =  p.dV
2
1 but dV = 0

 (Wd) 1-2 = 0

2. Constant pressure process: (Isobaric process).

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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

V1

W1-2 =  12 p.dV, where p = 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
But pV = constant =C
𝐶
p= 𝑉
𝐶
W1-2 =  12 p.dV=  12 .dV
𝑉
1 𝑉
=C  12 𝑉 .dV =C𝑙𝑛𝑉|𝑉21 = C[𝑙𝑛𝑉2 − 𝑙𝑛𝑉1 ]
𝑉
= Cln(𝑉2 )
1

But pV = p1V1 = p2V2= C

𝑉 𝑉
 W1-2 = p1V1 ln(𝑉2 )= p2V2 ln(𝑉2 )
1 1
where p1 = Initial pressure of the system

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V1 = Initial volume of the system

p2 = Final pressure of the system
V2 = Final volume of the system

4. Reversible adiabatic or isentropic process i.e., p𝑽𝜸 =Constant

Reversible Adiabatic process is a process in which there is no exchange of heat takes
place from the working substance to the surrounding or vice versa during its expansion or
compression. This is possible when the working system is made thermally insulated, that
is no heat can leave or enter it during the process.

W1-2 =  12 p.dV

𝛾 𝛾
But p𝑽𝜸 =Constant i.e., 𝑝𝑉 𝛾 = 𝑝1 𝑉1 =𝑝2 𝑉2 =C
𝐶
∴𝑝= 𝛾
𝑉
𝐶
W1-2 =  12 𝑉 𝛾 dV
2
= C ∫1 𝑉 −𝛾 dV

2
𝑉 −𝛾+1 𝐶 1−𝛾 1−𝛾
= C[ −𝛾+1 ]| = (𝑉2 − 𝑉1 )
1 1−𝛾
1 1−𝛾 1−𝛾
= (𝐶𝑉2 − 𝐶𝑉1 )
1−𝛾
1 𝛾 1−𝛾 𝛾 1−𝛾
= 1−𝛾 (𝑝2 𝑉2 𝑉2 − 𝑝1 𝑉1 𝑉1 )
1
= 1−𝛾 (𝑝2 𝑉2 − 𝑝1 𝑉1 )
𝑝2 𝑉2 −𝑝1 𝑉1 𝑝1 𝑉1 −𝑝2 𝑉2
= =
1−𝛾 𝛾−1
Where ‘𝛾’ is ratio of specific heats

5. Polytropic process, i.e., pVn = constant

A polytropic process is represented on a p-V diagram as shown below.

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Figure: Process in which pVn = Constant

W1-2 =  12 p.dV
But pVn = constant i.e., pV n  p1V1n  p2V2n =C
𝐶
∴𝑝= 𝑛
𝑉
𝐶
W1-2 =  12 𝑉 𝑛 dV
= C  12 V-n .dV

2
 V  n 1  𝐶
=C   = (𝑉21−𝑛 − 𝑉11−𝑛 )
  n  1 1
1−𝑛

1
= 1−𝑛 (𝐶𝑉21−𝑛 − 𝐶𝑉11−𝑛 )
1
= 1−𝑛 (𝑝2 𝑉2𝑛 𝑉21−𝑛 − 𝑝1 𝑉1𝑛 𝑉11−𝑛 )
1
= 1−𝑛 (𝑝2 𝑉2 − 𝑝1 𝑉1 )
𝑝2 𝑉2 −𝑝1 𝑉1 𝑝1 𝑉1 −𝑝2 𝑉2
= =
1−𝑛 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:

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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

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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

With in 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 

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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 = - σ dA when σ = surface tension (N/m)
 w = -  12 σ 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

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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.

Indicate in the following cases, the heat exchange and work exchange are positive, negative
or zero, and why

a) A body of mass 15 kg falls freely in a vacuum through a vertical distance of 30m. The
gravitational acceleration is 6 m/s2.
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

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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).

b) 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).

c) 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

d) 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.

e) Gas from a bottle is used to inflate a balloon which is originally flat. Consider gas as
system.
Ans: δW is Positive, δQ = 0

f) An insulated wire is stretched. Consider wire as a system.

Ans: δW is negative, δQ = 0

g) A mouse climbs 20 steps of a stair case. Consider mouse as the system.

Ans: δQ = δW = 0

h) Gas in an insulated cylinder expands as the piston is slowly moved outwards.

Ans: δQ = 0, δW is positive

i) 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.

j) 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

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k) 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)

i) 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

Theory Question Bank

1. Explain with examples the difference between a closed system, an open system and an
isolated system(JAN 2015, JULY 2016, JAN 2017, JAN 2018, JAN 2020)
2. State Zeroth law of thermodynamics and explain how this law is used to measure the
temperature of a given system(JAN 2018)
3. Define mean free path and clarify the difference between microscopic and
macroscopic approaches.(JAN 2009)
4. Define point function and path function(JAN 2012, JAN 2014)
5. Distinguish between (i) Intensive and Extensive properties (ii) Thermal and
Mechanical equilibrium (iii) Adiabatic and Dia-thermal boundary(JAN 2016, JAN
2017)
6. State Zeroth law of thermodynamics and clarify whether you can extend it to
Mechanical, Chemical and Electrical Equilibrium(JAN 2010)
7. Define (i) state (ii) Process (iii) System (iv) Quasi-static process(JULY 2015, JAULY
2017)
8. Explain what do you understand by thermodynamic equilibrium(JAN 2014)
9. Distinguish between macro and microscopic point of view of
thermodynamics(JUNE/JULY 2019)
10. Classify the following into intensive and extensive properties
Molecular weight, enthalpy,refractive index,quality of steam,entropy,roll strength of
glass(JUNE/JULY 2019)

11. Define Zeroth law of thermodynamics and explain the concept of temperature
measurement(JUNE/JULY 2019)
12. With examples briefly describe the terms

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 Basic Thermodynamics(BME304) notes

i. Macroscopic approach
ii. Intensive properties
iii. Closed sytems
iv. Quasistatic process (JUNE/JULY 2019, JAN 2020)
13. Define i. Thermodynamic Equilibrium ii. Zeroth law of thermodynamics(DEC
2019/JAN 2020)
14. With a neat sketch explain the working principle of
i. Electrical Resistance Thermometer
ii. Thermocouple (DEC 2019/JAN 2020)
15. Can you define and give examples to the following?i)closed system ii)Open system
iii)Isolated system(DEC 2019/JAN 2020)
16. Can you distinguish between the following
i) Microscopic and Macroscopic point of study
ii) Intensive and Extensive Properties
iii) Path and point functions(DEC 2019/JAN 2020)
17. Distinguish between heat and work in thermodynamics(JAN 2018)

18. State and explain Thermodynamic definition of work(JULY 2018)

19. Explain i) Isochoric process ii) Isobaric process iii) Isothermal process iv) Isentropic
process v) Polytropic process(JAN 2013, JULY 2015, DEC 2018/JAN 2019)
20. Show that heat and work are path functions(JAN 2018)
21. Derive an expression for displacement work in polytropic process(JULY 2010)

Problems

1. Develop a linear temperature scale ‘B’ where in ice and normal human body
temperature are assumed as two fixed points and assigned the values 00 B and 500 B
respectively. I f the temperature of human body on Celsius scale is 36.70 C, obtain
the relation between ‘ B ‘ scale and Celsius scale and find out water boiling
temperature in ‘ B’ . (VTU, JUNE/ JULY, 2013).
Solution:
Let the temperature be a linear function
Let t’= temperature on the B scale
Then t’=ax + b ……….. (1)
For ice point when, x=xi, t’=00
∴ 0=axi + b…………………… (a)
For normal human body temperature
When x= xb, t’=500
∴50= axb + b……………….. (b)
Solving for a and b we get
50
a=𝑋𝑏−𝑋𝑖
50𝑋𝑖
b= − 𝑋𝑏−𝑋𝑖

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 Basic Thermodynamics(BME304) notes

50 50𝑋𝑖
∴ Newton scale is given by t’=𝑋𝑏−𝑋𝑖 - 𝑋𝑏−𝑋𝑖
50(𝑋−𝑋𝑖 )
t’ = ……………(2)
𝑋𝑏−𝑋𝑖
Let t= temperature on the Celsius scale
t=a1x+b1
x=xi , t=00 C
∴0=a1xi+b1……..(c)
When x=xs, t=100 0 C
100=a1xs+b1……….. (d)
From equation (c ) and (d)
100
a1= 𝑋𝑠−𝑋𝑖
100𝑋𝑖
b1= − 𝑋𝑠−𝑋𝑖
100 𝑋 100𝑋𝑖
∴ t= 𝑋𝑠−𝑋𝑖 − 𝑋𝑠−𝑋𝑖
100(𝑋−𝑋𝑖)
t= 𝑋𝑠−𝑋𝑖
when, x= xb, t=36.7 0 C
(𝑋−𝑋𝑖) (36.7−0) 36.7
= = 100
𝑋𝑠−𝑋𝑖 100−0
Equation (2) can be written as
50(𝑋−𝑋𝑖 ) (𝑋𝑠−𝑋𝑖 )
t’ = 𝑋𝑠−𝑋𝑖 𝑋𝑏−𝑋𝑖
50(𝑋−𝑋𝑖 ) 100
t’ = ∗ 36.7
𝑋𝑠−𝑋𝑖
(𝑋−𝑋𝑖 )
Substituting for from equation (3) we have
𝑋𝑠−𝑋𝑖
𝑡 100
t’= 50* 100 * 36.7
50
t’= 36.7*t
Boiling point of water on B scale
50
t’=36.7*100= 136.24 0 B

2. The reading tA and tB of two Celsius thermometers A and B agree at the ice point (00
C) and the steam point (1000 C ) and are related by the equation tA = l+ m tB +
𝑡𝐵2 . Between these two points l, m and n are constants. When both are immersed in an
oil bath, A indicates 550 C and B indicates 500 C. Determine the values of l , m and
n, also find the reading on A if B reads 250 C ( DEC. 2012/10)
Solution:
As the two thermometers A and B agree at the ice point and steam point. We have at
ice point
tA= l+ mtB+ ntB2
0= l+ m*0 + n*0
∴ l=0 ……………. (1)
At steam point
100= l+ m*100 + n* 100 2

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 Basic Thermodynamics(BME304) notes

l= m + n*100
m = (1-100 n) ………. (2)
When A indicates 55 0 C, B indicates 50 0 C. Hence
55 = 50 m + 2500 n
∴11= 10 m + 500 n
Substituting for m in the above equation
11 = (1-100 n) 10 + 500 n = 10 -1000 n + 500 n
1
∴ n= − 500 ……… (3)

From equation (2)

100
m = 1- 100* n = 1+
500

600
m= 500

When thermometer B reads 25 0 C, we have

tA= l+ mtB+ ntB2

6 1
= 0 +5 * 25 + (− 500) * 25 2
= 30-1.25
=28.75 0 C

3. Sir Isaac Newton proposed a linear temperature scale wherein the ice point and the
normal human body temperature were assumed as the two fixed points and assigned
the temperatures of 00 and 12 0 respectively . If the temperature of the human body
on the Fahrenheit scale is 980 F, obtain the relation between the Newton scale and
Fahrenheit scale (JUN/FEB 2005)
Solution:
Let the temperature be a linear function
Let t’ = temperature on the Newton scale
Then t’ = ax + b……….. (1)
For ice point when x=xi, t’=00
∴ 0=axi +b…………………… (a)
For normal human body temperature
When x=xb, t’=120
∴12= a xb+b……………….. (b)
Solving for a and b we get
12
a=𝑋𝑏−𝑋𝑖
12𝑋𝑖
b= − 𝑋𝑏−𝑋𝑖
12 12𝑋𝑖
∴ Newton scale is given by t’=𝑋𝑏−𝑋𝑖 - 𝑋𝑏−𝑋𝑖

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 Basic Thermodynamics(BME304) notes

12(𝑋−𝑋𝑖 )
t’ = ……………(2)
𝑋𝑏−𝑋𝑖
Let t= temperature on the Fahrenheit scale
t=a1x+b1
x=xi , t=320 F
∴32=a1xi+b1……..(c)
When x=xs, t=212 0 F
212=a1xs+b1……….. (d)
From equation (c) and (d)
180
a1= 𝑋𝑠−𝑋𝑖
180𝑋𝑖
b1= 32 − 𝑋𝑠−𝑋𝑖
180 𝑋𝑖 180𝑋𝑖
∴ t= 𝑋𝑠−𝑋𝑖 + 32 − 𝑋𝑠−𝑋𝑖
180(𝑋−𝑋𝑖)
t=32 + ……….. (3)
𝑋𝑠−𝑋𝑖
when, x= xb, t=98 0 F
(𝑋𝑏−𝑋𝑖) (98−32) 66
𝑋𝑠−𝑋𝑖
= 180
=180
Equation (2) can be written as
12(𝑋−𝑋𝑖 ) (𝑋𝑠−𝑋𝑖 )
t’ = 𝑋𝑠−𝑋𝑖 𝑋𝑏−𝑋𝑖
(𝑋−𝑋𝑖 ) 12∗180
t’ = 𝑋𝑠−𝑋𝑖 ∗ 66
(𝑋−𝑋𝑖 )
Substituting for from equation (3) we have
𝑋𝑠−𝑋𝑖
(𝑡−32) 180∗12
t’=* = *
180 66
12
t’=66*(t-32)
2
t’=11*(t-32)

4. The temperature T on a thermometric scale is defined as T= a ln K + b where a and b

are constants. The values of K are found to be 1.83 and 6.78 at 00 C and 1000 C
respectively. Calculate the temperature for a value of K=2.42 (JULY / AUG 2005)
Solution:
T= a ln K + b
At ice point (00 C), 0= a ln 1.83 + b
At steam point (1000 C), 100= a ln 6.78 + b
Subtract (1) from (2)
100= a (ln 1.83- ln 6.78)
6.78
= a ln (1.83)
a = 76.355
From equation (1)
b= -a ln (1.83)
= - 76.355 ln(1.83)
=-46.14
For K=2.42

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 Basic Thermodynamics(BME304) notes

T= 76.355 ln (2.42) – 46.14

T= 21.34 0 C

5. A thermo couple with test junction at t0C on gas thermometer scale and reference
junction at ice point gives emf as e=0.2t-5x10-4t2 mv. The multivoltmeter is calibrated
at ice and steam point. What will be the reading on this thermometer where the gas
thermometer reads 700C.
Solution:

𝑒 = 0.2𝑡 − 5𝑥10−4 𝑡 2
At t=0,
𝑒 = 0.2𝑥0 − 5𝑥10−4 𝑥0 = 0
At t=100,
𝑒 = 0.2𝑥100 − 5𝑥10−4 𝑥1002 = 15𝑚𝑣
At t=70,
𝑒 = 0.2𝑥70 − 5𝑥10−4 𝑥702 = 11.55𝑚𝑣
From relation 𝑇 = 𝑎𝑒 + 𝑏
𝑒 − 𝑒𝑖 11.55 − 0
𝑇 = 100 = 100 = 770 𝐶
𝑒𝑠 − 𝑒𝑖 15 − 0

6. The temperature of a fluid is measured with a Celsius thermometer as well as

Fahrenheit thermometer. If the numerical reading is same for both thermometers,
what is temperature in degree Celsius and degree Fahrenheit. (JULY/AUG 2000)
Solution:

𝐿 − 𝐿𝑖
𝑇𝑐 = 100
𝐿𝑠 − 𝐿𝑖
𝐿 − 𝐿𝑖 𝑇𝑐
=
𝐿𝑠 − 𝐿𝑖 100

𝐿 − 𝐿𝑖
𝑇𝑓 = 32 + 180
𝐿𝑠 − 𝐿𝑖
𝑇𝑐
𝑇𝑓 = 32 + 180
100
𝑇𝑓 = 32 + 1.80𝑇𝑐
𝑇𝑓 = ±𝑇𝑐
𝑇𝑐 = 32 + 1.80𝑇𝑐
𝑇𝑐 = 𝑇𝑓 = −400
−𝑇𝑐 = 32 + 1.80𝑇𝑐
𝑇𝑐 = −11.430
𝑇𝑓 = 11.430

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 Basic Thermodynamics(BME304) notes

7. A temperature is graduated according to equation𝑇 = 100 + 3𝑇𝑐 , T is temperature on

this scale and Tc is temperature on Celsius scale. Find ice point and steam point on the
new scale, what is temperature in degree kelvin corresponding to 200 on the scale.
Solution:

At ice point Tc=0, 𝑇 = 100 + 3𝑥0 = 100

At steam point Tc=100, 𝑇 = 100 + 3𝑥100 = 400
AtT=20, 20 = 100 + 3𝑥𝑇𝑐
20 − 100
𝑇𝑐 = = −26.270 𝐶 = −26.27 + 273 = 246.48𝐾
3

8. A temperature scale of certain thermometers is given by relation T= alnp+b, where a

and b are constants. If at ice point and steam point the thermometric properties are 1.5
and 7.5. What will be the temperature corresponding to thermometric property of 3.5
on Celsius scale.(March 2001)
Solution:

At ice point 𝑎𝑙𝑛𝑝 + 𝑏 = 0

At steam point 𝑎𝑙𝑛𝑝 + 𝑏 = 100
𝑎𝑙𝑛1.5 + 𝑏 = 0
𝑎𝑙𝑛7.5 + 𝑏 = 100
Solve, 𝑎(𝑙𝑛7.5 − 𝑙𝑛1.5) = 100
a=62.112
𝑏 = −62.112𝑙𝑛1.5 = −25.18
𝑇 = 𝑎𝑙𝑛𝑝 + 𝑏 = 62.112𝑙𝑛3.5 + (−25.18) = 52.63

9. In 1709 sir Isaac newton proposed a linear temperature scale where ice point and
normal human body temperature were assumed as two fixed points with temperature 0
and 120 respectively. If the temperature of human body on the Celsius scale is 360C
obtain the relation between the newton scale and Celsius scale. If the temperature of
the normal human body is 980F on the Fahrenheit scale obtain the relation between
the newton scale and Fahrenheit scale. (Dec/Jan 2019)
Solution:

𝑇 = 𝑎 + 𝑏𝑥--------(a)
At ice point 𝑎 + 𝑏𝑥𝑖 = 0
At human body point 𝑎 + 𝑏𝑥𝑏 = 12
Solve 𝑏(𝑥𝑏 − 𝑥𝑖 ) = 12
12
𝑏=
𝑥𝑏 − 𝑥𝑖
12𝑥𝑖
𝑎=−
𝑥𝑏 − 𝑥𝑖
12𝑥𝑖 12𝑥
Substitute in a, 𝑇𝑛 = − 𝑥 +𝑥
𝑏 −𝑥𝑖 𝑏 −𝑥𝑖

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 Basic Thermodynamics(BME304) notes

12(𝑥 − 𝑥𝑖 )
𝑇𝑛 =
𝑥𝑏 − 𝑥𝑖
(𝑥 − 𝑥𝑖 ) 𝑇𝑛
=
(𝑥𝑏 − 𝑥𝑖 ) 12
At ice point 𝑎 + 𝑏𝑥𝑖 = 0
At human body point 𝑎 + 𝑏𝑥𝑏 = 36
Solve 𝑏(𝑥𝑏 − 𝑥𝑖 ) = 36
36
𝑏=
𝑥𝑏 − 𝑥𝑖
36𝑥𝑖
𝑎=−
𝑥𝑏 − 𝑥𝑖
36𝑥𝑖 36𝑥
Substitute in a, 𝑇𝑐 = − 𝑥 +𝑥
𝑏 −𝑥𝑖 𝑏 −𝑥𝑖
36(𝑥 − 𝑥𝑖 )
𝑇𝑐 =
𝑥𝑏 − 𝑥𝑖
𝑇𝑛
𝑇𝑐 = 36
12
𝑇𝑐 = 3𝑇𝑛
At ice point 𝑎 + 𝑏𝑥𝑖 = 32
At human body point 𝑎 + 𝑏𝑥𝑏 = 98
Solve 𝑏(𝑥𝑏 − 𝑥𝑖 ) = 66
66
𝑏=
𝑥𝑏 − 𝑥𝑖
66𝑥𝑖
𝑎 = 32 −
𝑥𝑏 − 𝑥𝑖
66𝑥𝑖 66𝑥
Substitute in a, 𝑇𝑓 = 32 − 𝑥 +𝑥
𝑏 −𝑥𝑖 𝑏 −𝑥𝑖
66(𝑥 − 𝑥𝑖 )
𝑇𝑓 = 32 +
𝑥𝑏 − 𝑥𝑖
66𝑇𝑛
𝑇𝑓 = 32 +
12
𝑇𝑓 = 32 + 5.5𝑇𝑛

10. The temperature T on a thermometric scale is defined in terms of thermometric property x by

T=alnx-b, the ice point and steam point are 00C and 1000. Experiments gave values of x as
1.86 and 6.81 at ice and steam point. Evaluate temperature on this scale for x=2.5.

Solution:
𝑇 = 𝑎𝑙𝑛𝑥 − 𝑏
𝑎𝑙𝑛𝑥𝑖 − 𝑏 = 0
𝑎𝑙𝑛𝑥𝑠 − 𝑏 = 100
𝑎(𝑙𝑛𝑥𝑠 − 𝑙𝑛𝑥𝑖 ) = 100
100
𝑎=
(𝑙𝑛𝑥𝑠 − 𝑙𝑛𝑥𝑖 )
𝑎𝑙𝑛𝑥𝑖 = 𝑏

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 Basic Thermodynamics(BME304) notes

100𝑙𝑛𝑥𝑖
𝑏=
(𝑙𝑛𝑥𝑠 − 𝑙𝑛𝑥𝑖 )
100𝑙𝑛𝑥 100𝑙𝑛𝑥𝑖
𝑇= −
(𝑙𝑛𝑥𝑠 − 𝑙𝑛𝑥𝑖 ) (𝑙𝑛𝑥𝑠 − 𝑙𝑛𝑥𝑖 )
100( 𝑙𝑛𝑥 − 𝑙𝑛𝑥𝑖 )
𝑇=
(𝑙𝑛𝑥𝑠 − 𝑙𝑛𝑥𝑖 )
100( 𝑙𝑛2.5 − 𝑙𝑛1.86)
𝑇= = 22.80
(𝑙𝑛6.81 − 𝑙𝑛1.86)

11.A constant volume gas thermometer containing helium gas gives reading of gas pressure
1000 and 1366 mm of mercury at ice and steam point. a) express the gas thermometer Celsius
temperature interms of gas pressure b) The thermometer left standing in the atmosphere
registers 1075 mm of mercury find the atmospheric temperature.
Solution:
𝑇 = 𝑎 + 𝑏𝑃
𝑎 + 1000𝑏 = 0
𝑎 + 1366𝑏 = 100
𝑏(1366 − 1000) = 100
b=0.2732
𝑎 = −1000𝑏 = −1000𝑥0.2732 = −273.2
𝑇 = −273.2 + 0.2732𝑃
𝑇 = −273.2 + 0.2732𝑥1075 = 20.490

12. The temperature T on a Celsius thermometer scale is defined in terms of a property P by

𝑇−𝐵
the relation 𝑃 = 𝑒 ( 𝐴 ) , where A and B are constants. Experiments gave P as 1.86 and 6.81 at
ice point and steam point. Find T when P=2.5.(DEC/JAN 2018)
Solution:
𝑇−𝐵
𝑃 = 𝑒( )
, taking log on both sides
𝐴

𝑇−𝐵
𝑙𝑛𝑃 = ( )
𝐴
𝑇 = 𝐴𝑙𝑛𝑃 + 𝐵
𝐴𝑙𝑛𝑃𝑖 + 𝐵 = 0
𝐴𝑙𝑛𝑃𝑠 + 𝐵 = 100
𝐴(𝑙𝑛𝑃𝑠 − 𝑙𝑛𝑃𝑖 ) = 100
100
𝐴=
(𝑙𝑛𝑃𝑠 − 𝑙𝑛𝑃𝑖 )
𝐵 = −𝐴𝑙𝑛𝑃𝑖
100𝑙𝑛𝑃𝑖
𝑏=−
(𝑙𝑛𝑃𝑠 − 𝑙𝑛𝑃𝑖 )
100𝑙𝑛𝑃 100𝑙𝑛𝑃𝑖
𝑇= −
(𝑙𝑛𝑃𝑠 − 𝑙𝑛𝑃𝑖 ) (𝑙𝑛𝑃𝑠 − 𝑙𝑛𝑃𝑖 )
100(𝑙𝑛𝑃 − 𝑙𝑛𝑃𝑖 )
𝑇=
(𝑙𝑛𝑃𝑠 − 𝑙𝑛𝑃𝑖 )

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 Basic Thermodynamics(BME304) notes

100( 𝑙𝑛2.5 − 𝑙𝑛1.86)

𝑇= = 22.80
(𝑙𝑛6.81 − 𝑙𝑛1.86)

13. A thermometer is calibrated at 00 marks with boiling point of carbon tetrachloride and
1000 mark with melting point of lead. When used to measure temperature of device indicates
160. Carbon tetra chloride boils at 76.750C and lead melts at 3270C. Convert the reading of
the device to the equivalent on Celsius scale.
Solution:
𝑇 = 𝑎 + 𝑏𝑥--------(a)
At ice point 𝑎 + 𝑏𝑥𝑖 = 76.75
At steam point 𝑎 + 𝑏𝑥𝑠 = 327
Solve 𝑏(𝑥𝑠 − 𝑥𝑖 ) = 250.25
250.25
𝑏=
𝑥𝑠 − 𝑥𝑖
250.25𝑥𝑖
𝑎 = 76.75 −
𝑥𝑠 − 𝑥𝑖
250.25𝑥𝑖 250.25𝑥
Substitute in a, 𝑇𝑐 = 76.75 − +
𝑥𝑠 −𝑥𝑖 𝑥𝑠 −𝑥𝑖
250.25(𝑥 − 𝑥𝑖 )
𝑇𝑐 = 76.75 +
𝑥𝑠 − 𝑥𝑖
𝑥 − 𝑥𝑖
𝑇𝑛 = 100
𝑥𝑠 − 𝑥𝑖
𝑥 − 𝑥𝑖 𝑇𝑛
=
𝑥𝑠 − 𝑥𝑖 100
𝑇𝑛
𝑇𝑐 = 76.75 + 250.25
100
𝑇𝑐 = 76.75 + 2.5025𝑇𝑛 = 116.790

14.A stationary mass of gas is compressed in a frictionless way from 1 bar and 0.1 m 3 to 5
bar and 0.03 m3. Assuming that pressure and volume are related by pVn = constant, find the
work done on the gas. (VTU JUNE / JULY 2015/16).

Solution:
The compression process is shown on the p-V diagram as shown below

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 Basic Thermodynamics(BME304) notes

Applying the gas law pVn= constant to state points

p1V1n= p2V2n = C
Or
n
p1  V2 
 
p 2  V1 

taking ln on both sides

𝑃 𝑉
ln (𝑃1 )=n ln(𝑉2 )
2 1
𝑃 1
ln( 1 ) ln( )
𝑃2 5
or n = 𝑉 == 0.03 =1.337
ln( 2 ) ln(
0.1
)
𝑉1

workdone during the process

𝑑𝑉
W1-2=  12 p.dV= C  12 𝑉 𝑛
𝐶
Or W1-2= 𝑛−1 (V1 1-n – V2 1-n)
p1V1  p 2V2
W1-2 =
n 1
1∗ 105 ∗0.1−5∗ 105 ∗0.03
= (1.337−1)
= -14.837 kNm/kg
The negative sign shows work of compression

15 An engine cylinder of diameter 22.5 cm has a stroke length of 37.5 cm. The swept volume
is 4 times the clearance volume. The pressure of the gas at the beginning of expansion stroke
is 1569 kpa. Find the workdone during expansion stroke assuming the process as reversible
adiabatic 𝛾 = 1.4.

Solution:

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 Basic Thermodynamics(BME304) notes

We have cylinder volume

𝛱
V2 = 4 * D2* L
𝛱
= 4 * (22.5* 10-2) 2* 37.5 * 10 -2
= 0.0149 m3
The process is shown on p-V diagram
As V2 = 4V1
𝑉2
V1 = 4
0.0149
= = 0.00373 m3
4
Applying the adiabatic law
p𝑉 𝛾 = C
𝑃2 𝑉
= ( 𝑉1 )𝛾
𝑃1 2
𝑉 0.00373 1.4
Or 𝑃2 = 𝑃1 ( 𝑉1 )𝛾 = 1569 ( 0.0149 ) = 225.29 kPa
2
Workdone during the process 1-2

𝑑𝑉
W1-2=  12 p.dV= C  12 𝑉 𝛾
p1V1  p 2V2
=
n 1
1569∗ 102 ∗0.00373−225.29∗ 102 ∗0.0149
= (1.4−1)
= 623.9 J/ kg

16. A gas is contained in a cylinder fitted with a piston loaded with a small number of
weights the initial pressure of the gas is 1.3 bar and the initial volume is 0.03 m 3. The
gas is now heated until the volume of the gas increases to 0.1 m3. Calculate the
workdone by the gas in the following process (i) pressure remains constant (ii)
temperature remains constant (iii) pV1.3 = C during the process. Sketch the processes
on p-V diagram. (JAN 2013/06)

Solution:
Given data

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P1= 1.3 bar, V1= 0.03 m3, V2= 0.1 m3

Different processes are shown on the p-V diagram below

(i) Constant pressure process

Workdone, W1-2 =  12 p.dV
=p (V2 – V1)
= 1.3 * 10 5 (0.1- 0.03)
=9.1 kJ/kg
(ii) Constant temperature process
Workdone, W1-2 =  12 p.dV
V2
= p1V1 ln
V1
0.1
= 1.3* 10 5 *0.03 ln (0.03)
=4.695 kJ/kg
(iii) For the polytropic process
We have, p1V11.3 = p2V21.3
𝑝1 𝑉
= (𝑉2 )1.3
𝑝2 1
𝑉
Or p2= p1(𝑉2 )1.3
1
0.03
= 1.3 * 10 5 ( 0.1 )1.3
= 0.2718 bar
Work done during the process
𝑝2𝑉2 −𝑝1𝑉1
W1-2 = (1−𝑛)
0.271∗100∗0.1 – 1.3∗100∗0.03
= (1−1.3)
= 3.97 kJ/kg

17.Consider the system shown in fig. Intial conditions of the gas are V1 = 0.1m3 and
p1=200 kPa. The ambient atmosphere pressure is 100 kPa .The spring excerts a force
which is proportional to the displacement from its equilibrium position. The gas is
heated until the volume is doubled at which point p2=600 kpa. Determine the work
done by the gas (AUG 2001).

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Solution:
Force balance at any position
pA= pa A +kx
The system is shown below

𝑣𝑜𝑙𝑢𝑚𝑒
Displacement = 𝑎𝑟𝑒𝑎
𝑘𝑉
pA= pa A + 𝐴
𝑘𝑉
pA= pa A + 𝐴2 …………………….. (1)
Work done is given by

W1-2 =  1 p.dV =  1 (pa+ 𝐴2 .)dV

2 2 𝑘𝑉

𝑘
= pa (V2- V1)+ 2𝐴2(V2 2- V12)

𝑘
= pa (V2- V1)+ 2𝐴2(V2- V1) (V2 + V1)

𝑘
= (V2- V1) [ pa + 2𝐴2 (V2 + V1)]

From equation (1)

𝑝2 − 𝑝𝑎 𝑝1 − 𝑝𝑎
= (V2- V1) [ pa + + ]
2 2

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𝑝1 + 𝑝2
= (V2- V1) [ ]
2

Substituting, 𝑝1 = 200 kPa 𝑝2 = 600 kPa

V1 = 0.1 m3, V2 = 2V1 = 0.2 m3, we have

200+ 600
Work done by the gas = (0.2-0.1) [ ]
2

= 40 kJ

18. An engine cylinder has a piston of area 0.12 m2 and contains gas at a pressure of
1.5 MPa. The gas expands according to a process which is represented by a straight
line on a p-V diagram. The final pressure is 0.15 MPa. Determine the magnitude and
direction of work transfer if the piston stroke is 0.30 m (JAN/FEB 2005, DEC/JAN
14)

Solution:
The system is shown on p-V diagram below

Workdone= W1-2= Area under the curve 1-2

1
= 2(V2- V1)[ p1+p2 ]
1
= 2 [ p1+p2 ](piston area* piston stroke)
1
= 2(1.5+0.15)*1000*(0.12*0.30)
= 29.7 kJ
W1-2 is positive value. Therefore work is done by the system

19.A gas undergoes a thermodynamic cycle consisting of the following process

(i) Process 1-2: constant pressure, p=1.4 bar, v1=0.028 m3, w2=10.5 kJ
(ii) Process 2-3 : Compression with pV= C, U3=U2
(iii) Process 3-1 : Constant volume, (U1-U3)= -26.4 kJ
There are no significant changes in KE and PE

1. Sketch the cycle on a p-V diagram

2.Calculate the network for the cycle in kJ
3.Calculate the heat transfer for process 1-2 (JUNE/JULY 2008)

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Solution:

For the process 1-2, we have

W 1-2 = p (V2- V1)

10.5 = 100*1.4 (V2 - 0.028)

∴ V2 = 0.103 m3

𝑉
For the process 2-3, W 2-3 = p2 V2 ln ( 𝑉3 )
2

0.028
= 100*1.4*0.103 ln (0.103)

= -18.78 kJ

For the process 3-1

( U2- U1) = 26.4 KJ

∴ Q 1-2 = W 1-2 + ( U2- U1)

= 10.5 +26.4

= 36.9 kJ

Networkdone = -18.782 +10.5

= -8.282 kJ

Net heat = Q 1-2 + Q 1-3 + Q 2-3

= 36.9 -26.4 -18.782

= -8.282 kJ

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20. A perfect gas is undergoing a process in which T 𝛼 V-2/5. Calculate the workdone
by the gas in going from state 1 in which pressure is 100 bar and volume is 4 m3 to the
state 2 in which volume is 2 m3 .Also calculate the final pressure (JAN /FEB 2007)

Solution:
Given that T 𝛼 V-2/5 and pV=mRT
∴p 𝛼 K V-7/5
K= p V7/5
K = 100 (4)7/5
K= 696.44
Work done by the gas , W=  1 p.dV =  1 K. V-7/5 dV
2 2

5 1 1
= − 2 K[ 2 – 2 ]
𝑉25 𝑉15

5 1 1
=− 2* 696.44 [ – 22/5 ]
42/5
W = 319.66 kJ

21 A balloon of flexible material is to be filled with air from a storage bottle until it
has a volume 0.7 m3. The atmospheric pressure is 1.013 bar. Determine the workdone
by the system comprising the air initially in the bottle, given that the ballon is light
and requires no stretching. (DEC/JAN 2010).

Solution:
At the end of the process the final boundary encloses 0.7 m3 of air in the ballon. Since
the balloon is light and requires no stretching the pressure on both sides are equal and
only the displacement work is present.
As the bottle is rigid the displacement work for the part of the boundary in contact
with the bottle is zero, therefore

Wd = Wd ballon+ Wd bottle
= Patm  1 dV + 0 (no change in volume of the bottle)
2

= 1* (0.7-0)*100
= 70 kJ

22 A cylinder piston assembly contains 0.5 grams of gas, as shown in fig. Intially , the
piston face at X=0, spring excerts no force on piston. As a result of heat transfer, the

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gas expands, raising the piston until it hits the stops. At this point the piston location
is X=0.05 m, and heat transfer stops. The force excerted by the spring varies linearly
with ‘X’ according to the equation F=kX, where k is the spring constant=10,000 N/m
.Take mass of piston =10 kg, area of piston =0.0078 m2, atmospheric pressure=1 bar
and specific internal energy at initial and final states as 214 kJ/kg and 337 kJ/kg
respectively. Determine initial pressure, work done and heat transfer in the process.
(JUNE /JULY 2009).

Solution:
Given
Cross sectional area of piston = A= 0.0078 m2
Mass of piston = mp = 10 kg
Internal energy, ui = 214 kJ/ kg , uf = 337 kJ/ kg
Atmospheric pressure, pa = 1 bar
𝑚𝑝
∴ Initial pressure, pi = pa + 𝐴
10∗9.81∗10−5
= 1+ 0.0078
= 1.12577 bar

For small displacement of piston dx, work done is p* A * dx, where p. A is gas force
at any position of piston= pa * A + mp g + kx
∴ displacement work for x=0 to x= 0.05 m
W=  1 ( pa * A + mp g + kx)dx
2

𝐾𝑋 2
= [pa * A*x + mp g*x + ] (Integrated from 0 to 0.05)
2
1000∗0.052
= 1*10 5* 0.0078*0.05 + 10*9.81*0.05+ 2
= 56.4 J
And Q = W + (Ui – Uf) = W+ m (ui – uf)
= 56.4+ 0.5+10 -3 (337-214) * 10 3
Q = 117.9 J

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Module :2

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 applications

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, Problems. Extension of the First
law to control volume; steady flow energy equation (SFEE), Problems

Introduction:
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 can not 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:

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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 W 1-2 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

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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,

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W
System
Q

The net energy transfer (Q-W) will be stored in the system. Energy in storage is neither 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
System
W1

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 following the
path A, and returns from state 2 to state 1 by following the path B or path C. So the system
undergoes a cycle.

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Writing the first law for path A

QA = ∆EA +WA (1)
And for path B
QB = ∆EB +WB (2)

The process A and B together constitute a cycle, for which

(∑ 𝑊) cycle= (∑ 𝑄) cycle
WA +WB = QA+QB
Or
QA-WA = WB-QB (3)
From equations (1), (2) and (3), it yields
∆EA =−∆EB (4)
Similarly, had the system returned from state 2 to state1 by following the path C instead of
path B
∆EA =−∆EC (5)
From equation (4) & (5)
∆EB =∆EC
Change in energy between two states of a system is the same, whatever path the system may
follow in undergoing that change of state. Therefore, energy has definite value for every state
of the system. Hence, it is a point function and property of the system.

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 can not 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 can not 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

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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(𝑚𝐶 2 )
Q = dU + + d (mgZ) + W
2
In the integral form this equation is, assuming ‘g’ is a constant

𝑚(𝐶22 −𝐶12 )
Q1-2 = U2 – U1 + + 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”.

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)

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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
∫ 𝑈 = CVT + k where k is a constant

For mass m, ∫ 𝑈 = m CVT

Any process between state 1 to state 2,
Change in int. energy = m CV (T2 – T1)
(U2 – U1) = m CV (T2 – T1)

Enthalpy: Enthalpy of a substance at any point is quantification of energy content in it,

which could be given by summation of internal energy and product of pressure and
volume.Enthalpy is very useful thermodynamic property for the analysis of engineering
systems
Mathematically, it is given as H=U+ PV
On unit mass basis, the specific enthalpy could be given as, h=u+Pv, where u is specific
internal energy in KJ/kg, v is specific volume in m3/kg
Specific heat at Constant Volume:
When heat interaction takes place at constant volume, δW = 0 and from 1st 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:

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a) Constant volume process (V = constant) or Prove that for constant volume process
heat transfer is equal to change in enthalpy
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) or For a constant pressure process heat transfer

is equal to change in enthalpy
Applying 1st law of thermodynamics to the process,
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)

Applying 1st law of thermodynamics to the process,
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

Applying 1st law of thermodynamics to the process,
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.

Relationship between Cp, Cv and R

Enthalpy is given by

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H= U + PV
Specific Enthalpy h= u+ Pv (1)
For perfect gas Pv = RT (2)
Substitute (2) in (1)
h= u +RT
Then, dh =du +R dT (3)
But, dh= Cp dT
du =Cv dT
Equation (3) becomes

Cp dT = Cv dT +RdT
Cp =Cv +R
R= Cp -Cv (4)
Divide equation (4) by Cv
𝑅 𝐶𝑝 𝐶𝑝
=𝐶 -1 But 𝐶 =𝛾
𝐶𝑉 𝑣 𝑣
∴ R = Cv(𝛾 − 1)
𝑹
Cv =𝜸−𝟏 (5)

𝐶𝑝
But 𝐶 =𝛾
𝑣
Cp = 𝛾Cv
From (5)
𝑹𝜸
Cp =𝜸−𝟏

Note:
For air, Cp =1.005 KJ/kg K , Cv =0.718 KJ/kg K

e) Poly tropic process (pVn = constant)

Applying 1st law of thermodynamics, Q1-2 = U2 – U1 + W1-2
(𝑃1 𝑉1 −𝑃2 𝑉2 )
= (U2 – U1) + But P1V1 = RT1, P2V2 = RT2
(𝑛−1)

R T1  T2 
= (U2 – U1) + But dU = CV (T2 – T1)
n 1
R T1  T2 
i.e., Q = CV (T2 – T1) +
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.

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Relationship between P,V and T for P 𝑽𝜸 =Constant

𝛾 𝛾
P1𝑉1 = P2𝑉2
𝑷𝟐 𝑽
= (𝑽𝟏 )𝛾
𝑷𝟏 𝟐
𝟏
𝑽 𝑷
∴ 𝑽𝟏 = ( 𝑷𝟐 )𝛾 (1)
𝟐 𝟏
For perfect gas
P1V1 = mRT1 (2)
P2V2 = mRT2 (3)
Divide (2) by (1)
𝑃2 𝑉2 𝑻
= 𝑻𝟐 (4)
𝑃1 𝑉1 𝟏
Sub (1) in (4)
𝜸−𝟏
𝑻𝟐 𝑷
=(𝑷𝟐 ) 𝜸
𝑻𝟏 𝟏

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.

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 Basic Thermodynamics(BME304) notes

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 p1,
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,

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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
dm1 [𝑃1 𝑣1 + 𝑢1 + 𝑍1 𝑔] δQ dm2 [𝑃2 𝑣2 + 𝑢2 + 𝑍2 𝑔]

The flow process is shown in fig. This analysis can be expressed mathematically as,
𝛿𝑄 − 𝛿𝑊 + dm1 [𝑃1 𝑣1 + 𝑢1 + 𝑍1 𝑔] = dm2 [𝑃2 𝑣2 + 𝑢2 + 𝑍2 𝑔] + d[E]0 (1)

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. per unit
time = mass leaving the C.V. per 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.

For a steady flow process, m  m 1  m 2 & d(E)0 = 0 as Q  f (T) & W  f (T)

Steady flow process

Steady flow means rate of flow of mass and energy across the control surface are constant

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 Basic Thermodynamics(BME304) notes

At steady state of system, any thermodynamic property will have fixed value at particular
location and will not alter with time

Steady flow energy equation (SFEE):

Let us consider a steady flow system in which one fixed fluid stream enters at section 1-1 and
leaves at section 2-2
A1 and A2 – Cross sectional area in m2
m1 and m2 - mass flow rate in kg/s
P1 and P2 – absolute pressure in N/m2
v1 and v2 - specific volume in m3/kg
u1 and u2 – specific internal energy in J/kg
C1 and C2 – velocity in m/s
Z1 and Z2 – elevation in m
𝑑𝑄
– Heat transfer rate
𝑑𝑇

𝑑𝑊
– Work transfer rate
𝑑𝑇

i) Mass balance
m1=m2
A1C1𝜌1 = A2C2𝜌2
𝐴1 𝐶1 𝐴2 𝐶2
=
𝑣1 𝑣2
𝑑𝑚1 𝑑𝑚2
This is called as continuity equation where m1 = m2 =
𝑑𝑇 𝑑𝑇
ii) Energy Balance

There are two types of work i) External work ii) flow work
External work refers to shaft work or electric work (Wx) (Which is outside the control
volume)
Flow work or displacement work at section 1-1 = - P1v1 dm1
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 Basic Thermodynamics(BME304) notes

Flow work at section 2-2 = P2v2dm2

Total work W = Wx - P1v1 dm1 - P2v2dm2
𝑑𝑊 𝛿𝑊𝑋 𝑑𝑚 𝑑𝑚
Work rate = - P1v1 𝑑𝑇1 + P2v2 𝑑𝑇2
𝑑𝑇 𝑑𝑇
𝛿𝑊 𝛿𝑊𝑋
∴ = – m1P1v1 +m2P2v2 (1)
𝑑𝑇 𝑑𝑇
Since there is no accumulation of energy
Energy in = Energy out
𝛿𝑄 𝛿𝑊
m1e1 +𝑑𝑇 = m2e2 + 𝑑𝑇 (2)
Substituting (1) in (2)

𝛿𝑄 𝛿𝑊𝑋
m1e1 +𝑑𝑇 = m2e2 + – m1P1v1 +m2P2v2
𝑑𝑇

𝛿𝑄 𝛿𝑊𝑋
m1e1 + m1P1v1 + = m2e2 +m2P2v2 +
𝑑𝑇 𝑑𝑇
e1 and e2 are energy carrying in and out of control volume
𝐶2
specific energy e= ek+ ep+ u = +Zg+u
2
𝐶2 𝛿𝑄 𝐶2 𝛿𝑊𝑋
∴ m1[ 21 + 𝑍1 𝑔 + 𝑢1 ]+m1P1v1 + 𝑑𝑇 = m2[ 22 + 𝑍2 𝑔 + 𝑢2 ]+m2P2v2 + 𝑑𝑇

𝐶2 𝛿𝑄 𝐶2 𝛿𝑊𝑋
m1[ 21 + 𝑍1 𝑔 + 𝑢1 + 𝑃1 𝑣1 ] + 𝑑𝑇 = m2[ 22 + 𝑍2 𝑔 + 𝑢2 + 𝑃2 𝑣2 ] + 𝑑𝑇

𝐶12 𝛿𝑄 𝐶22 𝛿𝑊𝑋

m1[ + 𝑍1 𝑔 + ℎ1 ] + = m2[ + 𝑍2 𝑔 + ℎ2 ] + (3)
2 𝑑𝑇 2 𝑑𝑇
In alternate form

𝐶 2 𝐶 2
m1[ 21 + 𝑍1 𝑔 + ℎ1 ] +𝑄̇ = m2[ 22 + 𝑍2 𝑔 + ℎ2 ] + 𝑊̇
Where 𝑄̇ and 𝑊̇ in kJ/s
As h= u + Pv

Eeqn (3) is called as SFEE based on unit time basis

𝑑𝑚
If m1=m2= 𝒎̇ = 𝑑𝑇
𝑑𝑚
Divide eqn (3) by 𝑑𝑇
𝐶12 𝛿𝑄 𝐶2 𝛿𝑊𝑋
[ 2 + 𝑍1 𝑔 + ℎ1 ] + 𝑑𝑚 = [ 22 + 𝑍2 𝑔 + ℎ2 ] + 𝑑𝑚

𝐶2 𝐶2
[ 21 + 𝑍1 𝑔 + ℎ1 ] + q = [ 22 + 𝑍2 𝑔 + ℎ2 ] + wx (4)
Where q and wx in kJ/kg
Eqn (4) is called as SFEE based on unit mass flow rate basis

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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)
From the 1 law of thermodynamics, we have δq – δW = du
st

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 device which is used to convert pressure energy into
kinetic energy. This results in decrease in enthalpy of the flowing fluid and increase in
kinetic energy of the flowing fluid
Features
 No work is done and therefore W= 0
 No heat transfer due to perfect insulation of the wall, Q=0
 Change in potential energy is negligible i,e. (Z1- Z2)g=0

C1 C2

Z1 Z2 = Z1

We have from SFEE,

𝐶12 −𝐶22
𝑚̇ [ + (𝑍1 − 𝑍2 )𝑔 + ℎ1 − ℎ2 ] +𝑄̇ = 𝑊̇
2
Applying the features

𝐶12 −𝐶22
𝑚̇ [ + ℎ1 − ℎ2 ] = 0
2

𝐶22 −𝐶12
= ℎ1 − ℎ2
2

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Increase in KE is equal to decrease in enthalpy of the fluid

C2 = √𝐶12 + 2(ℎ1 − ℎ2 )
As C1 ≪ C2 it is often neglected

C2 = √2(ℎ1 − ℎ2 )

Diffuser
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 C2 in a diffuser is very small, it is very often negligible.

ii) Steam or gas turbine

A turbine is a device used to generate power using the fluid which expands from high
pressure to low pressure
Features
 Work is done by the system and 𝑊̇ is positive
 Change in kinetic and potential energy is negligible
 Heat transfer is negligible due to insulation of the walls

W
C1 C2

Z1 Z2 = Z1

We have from SFEE,

𝐶12 −𝐶22
𝑚̇ [ + (𝑍1 − 𝑍2 )𝑔 + ℎ1 − ℎ2 ] +𝑄̇ = 𝑊̇
2

𝑊̇ = 𝑚̇(h1-h2)

iii) Rotary compressor

Rotary compressors are power absorbing device to obtain high pressure fluid at exit or
outlet
Features
 Work is done on the system to compress the fluid. Hence 𝑊̇ is negative
 Change in kinetic and potential energy is negligible
 Heat transfer is negligible due to insulation of the walls

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We have from SFEE,

𝐶12 −𝐶22
𝑚̇ [ + (𝑍1 − 𝑍2 )𝑔 + ℎ1 − ℎ2 ] +𝑄̇ = 𝑊̇
2
𝑚̇(h1 - h2) = −𝑊̇
𝑊̇ = 𝑚̇(h2-h1)

iv) Reciprocating compressor

A reciprocating compressor is a device used to increase the pressure of the fluid as
high as 1000 bar and to deliver a small quantity of the fluid. It has piston cylinder
arrangement to compress the fluid and a receiver to ensure uniform flow rate in the
control volume
Features
 Work is done on the system to compress the fluid. Hence 𝑊̇ is negative
 Change in kinetic and potential energy is negligible
 Heat lost to the surroundings. Hence 𝑄̇ is negative

We have from SFEE,

𝐶12 −𝐶22
𝑚̇ [ + (𝑍1 − 𝑍2 )𝑔 + ℎ1 − ℎ2 ] +𝑄̇ = 𝑊̇
2
𝑚̇[ℎ1 − ℎ2 ] - 𝑄̇ = −𝑊̇
𝑊̇ = 𝑚̇(h2-h1) + 𝑄̇

v) Centrifugal pump
A pump is a device used to convert mechanical energy into potential energy of liquid
using rotating wheels called rotors
Features
 Work is done on the system which is considered as negative
 Heat transfer is zero

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 Change in internal energy is zero due to no change in temperature of water

We have from SFEE,

𝐶12 −𝐶22
𝑚̇ [ + (𝑍1 − 𝑍2 )𝑔 + ℎ1 − ℎ2 ] +𝑄̇ = 𝑊̇
2
But h = u + Pv

̇
𝑚̇[𝑃1 𝑣1 + 𝑢1 − 𝑃2 𝑣2 + 𝑢2 + (𝑍1 − 𝑍2 )𝑔] = −𝑊
But u1-u2=0
−𝑊̇ = ̇ 𝑚[𝑃 𝑣 − 𝑃 𝑣 + (𝑍 − 𝑍 )𝑔] where , v1=v2 = 1
1 1 2 2 1 2 𝜌
𝜌 = density of liquid

vi) Hydraulic turbine

It is a prime mover which uses potential and kinetic energy of water to move the
runner of the turbine. Thus mechanical energy thus generated can be used to run a
generator to produce power
Features
 Work is done by the system and is considered as positive
 Heat transfer is negligible
 Change in internal energy is zero due to no change in temperature of water

We have from SFEE,

𝐶12 −𝐶22
𝑚̇ [ + (𝑍1 − 𝑍2 )𝑔 + ℎ1 − ℎ2 ] +𝑄̇ = 𝑊̇
2
But h = u + Pv
𝑚̇[𝑃1 𝑣1 + 𝑢1 − 𝑃2 𝑣2 + 𝑢2 + (𝑍1 − 𝑍2 )𝑔] = 𝑊̇

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But u1-u2=0
𝑊̇ =̇ 𝑚[𝑃1 𝑣1 − 𝑃2 𝑣2 + (𝑍1 − 𝑍2 )𝑔] where , v1=v2 = 𝜌
1

𝜌 = density of liquid

vii) Boiler
Boiler is an equipment or a pressure vessel used to generate steam. Steam thus
generated is used as a working fluid to run a steam turbine or is used for heating
industrial and residential buildings in cold weather or is used in process heating as in
sugar mills, textile and chemical industries
Features
 No work is done on the or by the system, therefore 𝑊̇ =0
 Changes in Potential and kinetic energy is negligible
 Heat transfer is positive , as heat is transferred to the system

We have from SFEE,

𝐶12 −𝐶22
𝑚̇ [ + (𝑍1 − 𝑍2 )𝑔 + ℎ1 − ℎ2 ] +𝑄̇ = 𝑊̇
2

𝑚̇[ℎ1 − ℎ2 ] +𝑄̇ = 0
𝑄̇ =𝑚̇[ℎ2 − ℎ1 ]

viii) Heat exchanger (Condenser)

A heat exchanger is a device in which heat is transferred from one fluid to another
fluid. A steam condenser is a type of heat exchanger in which steam after expansion
in the turbine condenses by exchanging heat with cold water flowing through the
tubes. Thus condenser uses both water and steam as flow fluids
Features
 No work is done, therefore 𝑊̇ =0
 No heat transfer due to perfect insulation
 Changes in Potential and kinetic energy is negligible
 𝑄̇ is positive

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 Basic Thermodynamics(BME304) notes

If 𝑚𝑤 and 𝑚𝑠 are the mass of water and steam, hs and hf are enthalpy of steam
and condensate and hw is the enthalpy of water, then
Heat lost by steam = Heat gained by water
ms(hs1-hf2) = mw(hw2-hw1)

ix) Evaporator
An evaporator extracts heat from the cooling cabinet of a refrigeration system. The
refrigerating liquid enters the evaporator and absorbs heat from the cooling cabinet and
leaves the cabinet in the form of a vapour, at constant pressure
Features
 No work is done and therefore 𝑊̇ =0
 Changes in Potential and kinetic energy is negligible
 𝑄̇ is positive

We have from SFEE,

𝐶12 −𝐶22
𝑚̇ [ + (𝑍1 − 𝑍2 )𝑔 + ℎ1 − ℎ2 ] +𝑄̇ = 𝑊̇
2

𝑚̇[ℎ1 − ℎ2 ] +𝑄̇ = 0
𝑄̇ =𝑚̇[ℎ2 − ℎ1 ]

x) Throttling Process: When a fluid steadily through a restricted passages like a partially
closed valve, orifice, porous plug etc., the pressure of the fluid drops substantially and the
process is called throttling.

Features

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 Heat transfer is zero

 Work transfer is zero
 Changes in potential and kinetic energy is negligible

1 2

1 2

We have from SFEE

𝐶12 −𝐶22
𝑚̇ [ + (𝑍1 − 𝑍2 )𝑔 + ℎ1 − ℎ2 ] +𝑄̇ = 𝑊̇
2
𝑚̇[ℎ1 − ℎ2 ] = 0
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.

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)

Theory question bank

1. Starting from first law for a closed system undergoing cyclic process obtain the first
law equation for a closed system undergoing a non cyclic process and show that
energy is a property of the system.(JAN 2012)
2. Give the precise statement of first law of thermodynamics as applied to a closed
system undergoing a process and hence prove internal energy is a property.(JAN
2018, JULY 2017, JAN 2016)
3. Starting from the first law equation for a closed system undergoing a non cyclic
process derive the equation for an open system under steady flow, steady state
situation. List all the assumptions made.(JULY 2012, JAN 2011)
4. State first law of thermodynamics for a cyclic process. Write the steady state, steady
flow energy equation based to unit time, identifying each term in the equation with its
unit(JAN 2018)
5. Show that energy is a property of the system. Define specific heat at constant volume
and constant pressure.(JAN 2018)

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 Basic Thermodynamics(BME304) notes

6. Derive the steady flow energy equation for a single stream of fluid entering and
leaving the control volume(JULY 2009)

Problems:

1..The working fluid, in a steady flow process flows at a rate of 220 kg/min. The fluid
rejects 100 kJ/s of heat passing through the system. The conditions of the fluid at inlet
and outlet are given as velocity=220 m/s, p1=6 bar, u1=2000 kJ/kg, v1=0.36 m3/kg
and velocity=140 m/s p2=1.2 bar, u2=1400 kJ/kg, v (=1.3 m3/kg. The suffix ‘1’
indicates condition at inlet and 2 at outlet. Determine the power capacity of the
system in MW.(JUNE/JULY 2009)

Solution:
Using SFEE, we have
𝑉2 𝑉2
M (u1+p1V1+ 21 + gz1) +Q = m (u2+p2V2+ 22 + gz2) +W
Since , z1 = z2 and Q is –ve, we have
𝑉2 𝑉2
2
∴ W = m(u2- u1 +(p2V2- p1V1) +2000 1
- 2000 ) –Q
220 2202 1402
= (2000- 1400 + (6*10 2*0.36- 1.2 * 10 2 *1.3) +2000 - ) –100
60 2000
= 2373.02 kJ/s
∴ Power input= 2.373 MW

2.In a thermal power plant operating in a steady state an adiabatic steam turbine
receives 1 kg/s of superheated steam at 3 MPa and 400 0 C. The steam enters the
turbine with a velocity of 10 m/s at an elevation of 10 m above the ground level.
The steam leaves the turbine at 0.1 bar with 10 % moisture content. The velocity
of steam at exit is 3 times that at inlet and the exit is at an elevation of 40 % of
inlet. Show that it is safe to ignore the changes in kinetic energy and potential
energy. (JUNE/JULY 2009)

Solution:
Given: P= 3 MPa , t= 400 0 C , h= 3232.5 kJ/kg , p= 0.1 bar
hf= 191.83 kJ/kg , hi = 2584.8 kJ/kg
From first law, we have
𝑉22 𝑉12
𝑚(ℎ2 + + gz2 ) + W = 𝑚(ℎ1 + + gz1 )+ Q
2 2
𝑊 𝑉22 𝑉12
∴ − 𝑚 = (ℎ2 -ℎ1 ) + - + g (z2 – z1)
2 2
But h2= x2hfg + (1-x2) hf
= 0.9(2584.8) +0.1(191.83)
=2345.5 kJ/kg
h2 – h1 = 2345.5-3232.5 = 887 kJ/kg
𝑉22 𝑉12 302 102
- = - = 400
2 2 2 2
g(z2 – z1) = 9.81(6-10)= -58.66

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Substituting
𝑊
− 𝑚 = -887*10 3 +400- 58.66
∴ W=886.66 KW for m=1
Power output of the turbine

P= 886.66 KW

If the KE changes are neglected

-W = (ℎ2 -ℎ1 ) + + g(z2 – z1)

=887.06 KW

887.06−886.66
∴ % error = ( )*100 =0.045 %
886.66

If the PE changes are neglected

𝑉22 𝑉12
-W = (ℎ2 -ℎ1 ) + -
2 2

= 886.6 KW

886.66−886.6
∴ % error = ( )*100 =0.0068 %
886.66

If both are neglected

% error = 0.003 %

It is safe to neglect KE and PE

3.A turbine operating under steady-flow conditions receives steam at the following
state. Pressure= 13.8 bar, specific volume=0.143 m3/kg, specific internal energy=2590
kJ/kg, velocity= 30 m/s.The state of the steam leaving the turbine is as
follows.Pressure=0.35 bar, specific volume=4.37 m3/kg, specific internal
energy=2360 kJ/kg, velocity=90 m/s. Heat is rejected to the surroundings at the rate
of 0.25 KW and the rate of steam flow through the turbine is 0.38 kg/s. Calculate the
power developed by the turbine.
Solution:
Applying SFEE we have
𝑉12 𝑉22 𝛿𝑄 𝑑𝑤
m[ - ] + ( U1- U2) +(p1V1 – p2 V2 )+𝛿𝑇 =
2 2 𝑑𝑡
Substituting the given values
302 902 13.8∗ 105 ∗0.143 0.35∗ 105 ∗4.37 𝑑𝑤
0.38 [2000 - 2000] + ( 2590- 2360) +( – )+ =
103 103 𝑑𝑡

𝑑𝑤
∴ 𝑑𝑡
=272.77 kJ

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 Basic Thermodynamics(BME304) notes

4. At the inlet to a certain nozzle, the enthalpy of the fluid is 30 kJ/kg and the
velocity of 60 m/s. At the exit of the nozzle, the enthalpy is 2790 kJ/kg. The
nozzle is horizontal and there is a heat loss of 100 kJ/kg from it. Calculate the
velocity of fluid at nozzle exit. Also find the mass flow rate of fluid if the inlet
area is 0.1 m2 and specific volume at inlet is 0.1 m3/kg. (DEC/JAN 2007)

Solution:
Given
h1 = 3025 kJ/ kg
h2 = 2790 kJ/ kg
V1 = 60 m/s
Q = -100 kJ/ kg
A = 0.19 m 2
V1 = 0.19 m3 / kg
Modified SFEE is given by
V2 = √2 𝑔𝑐 [ 𝑄 + (ℎ1 − ℎ2 )] + 𝑉12
=√2000[−100 + (3025 − 2790)] + 602
V2 = 523.07 m/s
𝐴1 ∗ 𝑉1
Mass flow rate m= 𝑣1
0.1∗ 60
= 0.19
m = 31.58 kg/s

5. Air flows steadily through a rotary compressor. At entry the air is 200C and 101
kPa. At exit the same air is at 2000C and 600 kPa. Assuming the flow to be adiabatic.
i)evaluate the workdone per unit mass of air if the velocities at inlet and exit are
negligible. ii) what would be the increase in work input if the velocities at inlet and
exit are 50 m/s and 110 m/s (DEC/JAN 2004)
Solution:
(i) Workdone per unit mass of air compressed
For adiabatic flow W = h1 – h2 = Cp ( T1- T2)
𝛾 1.4
But Cp = 𝛾−1 R = * 287 = 1004. 5 J/kg K
1.4−1
∴ Workdone = (h2 – h1) = 1004.5[ 20-200] = -180.81 kJ/kg
(ii) Increase in work input
Velocity at inlet V1 = 50 m/s
Velocity at outlet V2 = 110 m/s
From SFEE
𝑉22 𝑉12
W 1-2 =m [(ℎ2 -ℎ1 ) + - ] + Q 1-2
2 2
For adiabatic flow Q 1-2 = 0
𝑉22 𝑉12
W 1-2 = m[(ℎ2 -ℎ1 ) + - ]
2 2
𝑉22 𝑉12
= [(ℎ2 -ℎ1 ) + 2000 - 2000]

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 Basic Thermodynamics(BME304) notes

1102 502
= 180.81 +2000 - 2000
= 185.61 kJ/kg

6. A nozzle is a device for increasing the velocity of a steadily flowing stream. At the
inlet to a certain nozzle, the enthalpy of the fluid passing is 3000 kJ/kg and the
velocity is 60 m/s. At the discharge end, the enthalpy is 2762 kJ/kg. The nozzle is
horizontal and there is negligible heat loss from it.

i) Find the velocity at the exit section of the nozzle

ii) If the inlet area is 0.1 m2 and the specific volume at inlet is 0.187m3/kg find
the mass flow rate
iii) If the specific volume at the exit of the nozzle is 0.498m3/kg find the diameter
at the exit section of the nozzle (JUNE/JULY 2004)
Solution:

Applying SFEE
𝑉22 𝑉12
(ℎ2 + + gz2 ) + w = (ℎ1 + + gz1 )+ q
2 2
Nozzle is kept in horizontal position

z1 = z2 = 0

During flow no shaft work and negligible heat loss

∴ w=0 , q=0

∴ from equation (1)

𝑉22 𝑉2
- 2 = h1 –h2
2000 2000

h1 = 3000 kJ/kg

h2 = 2762 kJ/kg

V 1 = 60 m/s

𝑉22 602
- = 3000- 2762
2000 2000

𝑉22 = 479600

Velocity at the exit section of the nozzle, V2 = 692.53 m/s

𝐴1 ∗ 𝑉1
(i) Mass flow rate m= 𝑣1

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 Basic Thermodynamics(BME304) notes

𝐴1 = 0.1 m2
𝑣1 = 0.187 m3/kg
0.1∗60
m= 0.187
= 32.08 kg/s
(ii) Exit diameter of nozzle
Given that 𝑣2 = 0.498 m3/ kg
𝐴2 ∗ 𝑉2
We have, m= 𝑣2
𝐴2 ∗ 692.53
32.08 = 0.498
𝜋𝑑22
∴ 𝐴2 = 0.02306 m2 = 4
∴ Diameter at the exit of the nozzle d2 = 0.171 m

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 Basic Thermodynamics(BME304) notes

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. 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. Problems

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):

Fig: A closed system that under 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):

High Temperature

Q Q

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Low Temperature
 Basic Thermodynamics(BME304) notes

Let two systems, one at a high temperature and the 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. From experience we know that this process can take place. But the
reverse process in which heat is 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.

Thermal Energy reservoirs

A thermal energy reservoir (TER) is a large body of infinite heat capacity, capable of
absorbing or rejecting unlimited quantity of heat without undergoing any appreciable changes
in its thermodynamic coordinates.
Example: Atmosphere, Ocean

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:

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Let Q1= Heat transferred from a high temperature reservoir like a furnace to the working
fluid (water)
Q2= 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

Schematic representation of heat engine

Thermal Efficiency (th)
Energy output Energy Sought for
 th  
Energy input Energy that cos ts
𝑊𝑛𝑒𝑡 𝑄1 −𝑄2 𝑄
= = = 1 -𝑄2
𝑄1 𝑄1 1
The first law has put no restriction by which the whole heat energy Q1 cannot be converted
into work W, by reducing the transfer of heat to the low temperature reservoir to zero i.e., by

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 Basic Thermodynamics(BME304) notes

reducing Q2 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.

Reversed heat engines

In reversed heat engines the direction of flow of heat and work are exactly opposite.
These machines are used to remove heat from a body kept at a lower temperature and to
transfer this heat to a body at a higher temperature. Examples of reversed heat engines are
refrigerator and heat pump

Refrigerator:
A refrigerator is a device which working in a cycle delivers heat from low temperature region
to high temperature region. The purpose of refrigerator is to cool the space by absorbing heat
from it and to maintain this space at a temperature lower than that of the surroundings.
Refrigerators are used to preserve food items and drugs at low temperature.

Fig: Refrigerator
Heat cannot flow from a low temperature body to a high temperature body. But this can be
done by providing external work to the system.
Consider a simple vapour compression system.
W Amount of work done on the fluid (Refrigerant)
Q2 Amount of heat that is transferred to the fluid (Refrigerant) in the evaporator
(low temperature reservoir)
Q1 Heat transferred from the fluid to the coolant in the condenser (High temperature
reservoir)
At states 1 and 2 refrigerant will be in vapour phase
At states 3 and 4 the refrigerant will be in liquid phase

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Heat is absorbed in the evaporator and is rejected in the condenser. Work input is given to
run the compressor

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 Q2 for a
refrigerator,

𝐸𝑁𝐸𝑅𝐺𝑌 𝑆𝑂𝑈𝐺𝐻𝑇 𝐹𝑂𝑅 𝐷𝐸𝑆𝐼𝑅𝐸𝐷 𝐸𝐹𝐹𝐸𝐶𝑇 𝑄

COP = 𝐸𝑁𝐸𝑅𝐺𝑌 𝑇𝐻𝐴𝑇 𝐶𝑂𝑆𝑇𝑆 = = 𝑊2
𝑊𝑂𝑅𝐾 𝐼𝑁𝑃𝑈𝑇

𝑄2
COP = 𝑄
1 −𝑄2

Heat pump
A heat pump is a device which working in a cycle delivers heat from low temperature region
to a high temperature region. The purpose of the heat pump is to take the heat from low
temperature space and supply it to a high temperature sink for heating. Heat pumps are useful
to keep the rooms warm in winter season
When the system works as a heat pump, the main interest is the heat Q1.

Schematic representation of heat pump

Therefore for a heat pump.

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𝐸𝑁𝐸𝑅𝐺𝑌 𝑆𝑂𝑈𝐺𝐻𝑇 𝐹𝑂𝑅 𝐷𝐸𝑆𝐼𝑅𝐸𝐷 𝐸𝐹𝐹𝐸𝐶𝑇 𝑄

COP = 𝐸𝑁𝐸𝑅𝐺𝑌 𝑇𝐻𝐴𝑇 𝐶𝑂𝑆𝑇𝑆 = = 𝑊1
𝑊𝑂𝑅𝐾 𝐼𝑁𝑃𝑈𝑇
𝑄1
COP = 𝑄
1 −𝑄2
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.

Prove, (COP)R +1 =(COP)HP

𝑄1 𝑄1
(COP)HP = =
𝑊 𝑄1 −𝑄2
1
(COP)HP = 𝑄
1− 2
𝑄1
𝑄2 1
1-𝑄 = (𝐶𝑂𝑃)
1 𝐻𝑃
𝑄2 1
= 1-
𝑄1 (𝐶𝑂𝑃)𝐻𝑃
𝑄2 (𝐶𝑂𝑃)𝐻𝑃 −1
= (1)
𝑄1 (𝐶𝑂𝑃)𝐻𝑃
𝑄2 𝑄2
(COP)R = =𝑄
𝑊 1 −𝑄2
1
(COP)R =𝑄1
−1
𝑄2
𝑄1 1
-1 =(𝐶𝑂𝑃)
𝑄2 𝑅
𝑄1 1
=1+
𝑄2 (𝐶𝑂𝑃)𝑅
𝑄1 (𝐶𝑂𝑃)𝑅 +1
=
𝑄2 (𝐶𝑂𝑃)𝑅
𝑄2 (𝐶𝑂𝑃)𝑅
=(𝐶𝑂𝑃) (2)
𝑄1 𝑅 +1
Equating (1) and (2)
(𝐶𝑂𝑃)𝐻𝑃 −1 (𝐶𝑂𝑃)𝑅
= (3)
(𝐶𝑂𝑃)𝐻𝑃 (𝐶𝑂𝑃)𝑅 +1
Upon Rearranging (3), we get
(COP)HP = 1+(COP)R

PERPETUAL MOTION MACHINE OF FIRST KIND (PMMKI)

The first law of thermodynamics states that the energy can neither be created nor be
destroyed. It can only gets transformed from one form to another form. Perpetual Motion
Machine is the machine which violates the law of thermodynamics. A machine, which can
supply mechanical work continuously without consumption of any energy, violates the first
law of thermodynamics. Thus this machine is the Perpetual Motion Machine of the First kind
(PMM1). . All attempts made so for to make PMMKI have failed.
When a machine violates the second law or third law of thermodynamics then this machine is
called as PMM2 or PMM3 respectively. Perpetual Motion Machine is a hypothetical concept.

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 Basic Thermodynamics(BME304) notes

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 & produces 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.

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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.

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.

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Consider a heat engine that is operating in a cyclic process takes heat (Q1) from a high
temperature reservoir & converts completely into work (W), violating the Kelvin – Planck
statement. (fig a)
Let the work W, which is equal to Q1, be utilized to drive a heat pump as shown. Let the heat
pump take in Q2 amount of heat from a low temperature reservoir and pump (Q1 + Q2)
amount of heat to the high temperature reservoir.(fig b)
In fig c, both the heat engine and the heat pump are clubbed together to form a combined
system. since the output of the engine W is used to drive the heat pump, input to the
combined system is only from the Q2 amount of heat extracted from the low temperature
sink. This system rejects same amount of heat to high temperature source without any
external work input.This system violates clausius statement.
Thus violation of Kelvin plank statement leads to violation of clausius staement
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 Q2 from
LTR and transfer the heat equivalent amount of heat Q2 to the HTR violating the Clausius
statement. (fig a)

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 Basic Thermodynamics(BME304) notes

Let an amount of heat Q1, which is greater than Q2 , be transferred from high temperature
reservoir to a heat engine, an amount of heat Q2, be rejected by it to the LTR and an amount
of work W which is equal to (Q1 – Q2) be done by the heat engine on the surrounding.(fig b)
Consider fig c, in this case both the heat pump and the heat engine are combined together to
form a combined system. This system constitutes a device that receives(Q1 – Q2) amount of
heat from high temperature source and does an equivalent amount of work W=(Q1 – Q2).
Hence this system violated Kelvin planck statement. Thus violation of clausius statement
leads to violation of Kelvin planck statement.
The 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

reservoir reversible isothermal and two reversible adiabatic
processes. Since the processes in the cycle are all
QH reversible the Carnot cycle as a whole is reversible. The
Carnot cycle is independent of the nature of the working
CARNOT substance and it can work with any substance like gas,
Engine vapour, electric cell etc.

QL

Low
temperature
reservoir

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1) Process 1–2: The reversible or Carnot engine is brought in contact with the high
temperature reservoir .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:The carnot engine is removed from HTR and is thermally insulated. Gas
expands reversibly and adiabatically to temperature T2 to point 3. Work done is W23.

3) Process 3–4: The thermal insulation is removed and the carnot engine is brought in
contact with LTR and heat is transferred from the carnot engine to LTR .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: The reversible engine is removed from the LTR and is thermally
insulated. Gas is recompressed adiabatically and reversibly to point 1. The cycle is
now complete. Work done is W41

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The efficiency of the Carnot engine is given by

Work output Q1  Q 2
η carnot                 (1)
Heat input Q1 V
Q1  Heat added during process 1  2  mRT1 ln 2            (2)
V
V
Q 2  Heat rejected during process 3  4  mRT2 ln 31           (3)
V4
V V
mRT1 ln 2  mRT2 ln 3
Q  Q2 V1 V4
Therefore, η carnot  1 
Q1 V
mRT1 ln 2
V V V1
T1 ln 2  T2 ln 3
V1 V4
        (4)
V2
T1 ln
V1

Since process 2  3 is reversible adiabatic

1
V2  T2  γ 1
             (5)
V3  T1 
Process4  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

From the above equation we can have the following conclusions.

T1  T2
η carnot             (7 )
T1

T1  T2 T Low Temperatur e
ηcarnot  1  2 1           (8)
T1 T1 High Temperatur e

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.

Since Carnot cycle consists of reversible processes, it may be performed in either direction.

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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

For reversible heat pump and refrigerator

𝑄1 𝑄1 1 𝑇
(COP)HP = =𝑄 =𝑇 −𝑇
𝑊 1 −𝑄2 1 2
𝑄2 𝑄2 𝑇2
(COP)R = =𝑄 =𝑇 −𝑇
𝑊 1 −𝑄2 1 2

Carnot theorem
No heat engine operating between the two thermal reservoirs can be more efficient than
a reversible engine operating between the same two thermal reservoirs

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Consider a reversible engine R and irreversible engine I operating between same two
temperature reservoirs. Let us assume that irreversible engine I is more efficient than
reversible engine R.
∴ 𝜂I > 𝜂R
Let the irreversible engine I absorb energy as heat Q1 from the high temperature reservoir at
T1. It does work W1 and rejects heat Q to LTR at T2. Then the work done by this engine is
given by WI = Q1 – Q
𝑊𝐼 𝑄
𝜂I = = 1-𝑄
𝑄1 1
Consider a reversible engine R which works between same two temperature reservoirs. It
performs work WR by absorbing heat Q1 from HTR at T1 and rejecting heat Q2 to LTR at T2
WR = Q1 – Q2
𝑊𝑅 𝑄
𝜂 R= = 1-𝑄2
𝑄1 1
Since 𝜂I > 𝜂R
𝑄 𝑄
1-𝑄 >1-𝑄2 ∴ Q< 𝑄2
1 1

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∴WI = Q1 – Q>WR = Q1 – Q2
Therefore for the same amount of heat input, the irreversible engine does more work than the
reversible engine R
Since R is reversible, it can be made to run in the reverse order. When made to run in the
reverse order, it absorbs Q2 from reservoir at temperature T2 and rejects heat Q1 to reservoir
at T1, when work WR is done on the device.
Since WI is greater than WR, the engine R can be made to execute the cycle in the reverse
order utilizing part of the work done by engine I. The combination of the two is shown in fig
b
The net work delivered = WI–WR = (Q1 – Q) –(Q1 – Q2) =Q2 – Q
Thus the combined device absorbs heat (Q2-Q) from reservoir at T2 and does an equivalent
amount of work without exchanging any heat with reservoir at T1. This violates II law of
thermodynamics. Thus our assumption that efficiency of the irreversible engine is greater
than the efficiency of the reversible engine is wrong. Therefore reversible engine is the most
efficient engine.
Carnot corollary

All reversible engines operating between two given thermal reservoirs have the same
efficiency.

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Efficiency of a reversible heat engine does not depend on the working fluid, it depends only
on the temperature of the reservoirs between which it operates.
Let us assume the efficiency of reversible engine R1 is greater than the efficiency of the
reversible engine R2. The engine R1 absorbs heat Q1 from the thermal reservoir at T1 does
work 𝑊𝑅1 and rejects Heat Q to the reservoir at T2.
The engine R2 absorbs energy as heat Q1 from the reservoir at T1 does work𝑊𝑅2 and rejects
heat Q2 to the reservoir at T2
Then 𝑊𝑅1 = Q1 – Q
𝑊𝑅2 = Q1 – Q2
𝑊𝐼 𝑄
𝜂𝑅1 = = 1-𝑄
𝑄1 1
𝑊𝑅 𝑄
𝜂𝑅2 = = 1-𝑄2
𝑄1 1
By assumption𝜂𝑅1 > 𝜂𝑅2
𝑄 𝑄
1-𝑄 >1-𝑄2 Or Q< 𝑄2
1 1
∴ 𝑊𝑅1 > 𝑊𝑅2
Since R2 is a reversible engine, it can be made to execute the cycle in the reverse order. That
is when work 𝑊𝑅2 is performed on the device it absorbs heat Q2 from the reservoir at T2 and
rejects heat Q1 to the reservoir at T1.
Since 𝑊𝑅1 > 𝑊𝑅2 , R2 can be run as a heat pump utilizing part of the work done by R1. The
combination of the two devices is shown in fig b, the net work done by the device is given by
𝑊𝑅1 − 𝑊𝑅2 = (Q1 – Q) - (Q1 – Q2) =Q2 – Q
The resulting device absorbs heat Q2-Q from the reservoir at temperature T2 without requiring
any interaction with the second reservoir and delivers an equivalent amount of work. This is
a violation of Kelvin Planck statement of II law of thermodynamics. Hence the assumption
that 𝜂𝑅1 > 𝜂𝑅2 is incorrect.

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Now if we assume that reversible engine R2 is more efficient than the reversible engine R1 by
following the similar argument, we can arrive at the result

Hence it can be concluded that

𝜂𝑅1 = 𝜂𝑅2

ENTROPY
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.

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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."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:
Example 1.

One of the ideas

involved in the
concept of 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.

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Example 2.
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 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
TH TL
and 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
Q Q
in properties, suggesting that the quantities H and L represents property changes of the
TH TL

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working 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,

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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
T
Q
cycle 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.
T
is 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
Q R
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
T
or equal to zero.

Q
In symbols,  T
 0        (1)

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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

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Q
 T
 0 , the cycle is impossible since it violates the second law of thermodynamics.
ENTROPY IS A PROPERTY:

Proof that entropy is a property:

QR
Statement: For any system undergoing internally reversible cycle, the integral of is
T
QR
zero, in 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 Ap
2

Reversible Path B
1

X
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)

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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
T
fixed 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
C

X
Consider a system which executes a reversible cyclic process, from 1 along path A to 2, and
p
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)

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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 ( S2- 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
Q
divided by the absolute temperature. In symbols, dS 
T
Proof:

Irreversible Path A
2

Reversible Path BP
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)

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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  Q 
2

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
T
irreversible 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 dSIsolated  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:

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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 & si , 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)
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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:

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 Basic Thermodynamics(BME304) notes

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 T
Temperature =
TW1-2 Q
dS surroundings       (2)
T0
for a reversible process
δQ
The total change of entropy for the combined
system
Surroundings
Temperature =
T0V2 Q Q
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
dSopen system    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 

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 Basic Thermodynamics(BME304) notes

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  mc v  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

Department of Mechanical Engineering, AJIET,Mangaluru 103

 Basic Thermodynamics(BME304) notes

T2 2 p 2 T
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

Department of Mechanical Engineering, AJIET,Mangaluru 104

 Basic Thermodynamics(BME304) notes

 n    T2
S 2  S1  cv   ln
 n  1  T1

Theory Question Bank

1. Show that COP of a heat pump is greater than COP of a refrigerator by unity
2. What is a thermal energy reservoir? Give examples(JUNE/JULY 2018)
3. What is PMMK I and why it is impossible
4. What is PMMK II and why it is impossible(DEC 2017/JAN 2018)
5. Show that Kelvin Planck Statement and Clausius statements are
equivalent(JUNE/JULY 2017)
6. What are the limitations of first law of thermodynamics (JUNE/JULY 2017)
7. With a help of PV diagram explain carnot cycle
8. Prove that all reversible engines operating between same temperature limits have
same efficiencies
9. Prove that a reversible engine will have more efficiency than an irreversible engine
operating between the same temperature limits(JUNE/JULY 2018)
10. State Kelvin plank and Clausius statements of second law of thermodynamics(DEC
2017/JAN 2018)
11. State and prove Carnot theorem
12. State and prove Carnot corollary
13. State and prove claussius inequality and prove that entropy is a property.(JAN 2014,
JULY 2015, JAN 2013,JUNE/JULY 2019)
14. Show by invoking Kelvin Planck statement of second law that two reversible
adiabatic paths cannot intersect each other(JAN 2014)
15. Explain the principle of increase of entropy of universe.(JAN 2016, JULY
2017,JUNE/JULY 2019)
16. Define the terms available and unavailable energy(JAN 2018)
17. What is effectiveness of a system and how does it differ from efficiency (JAN 2012)
18. Briefly explain the terms
i.Thermal reservoir ii.Refrigerator iii.Heat pump iv.Clausius statement of II law
(JUNE/JULY 201

19. With the help of p-v diagram, derive an expression for the efficiency of a carnot
cycle(JUNE/JULY 2019)

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 Basic Thermodynamics(BME304) notes

Problems

1. A reversible engine operates between two reservoirs at temperatures of 6000 C and 400 C.
The engine drives a reversible refrigerator, which operates between 400C and -200 C. The
heat transfer to the engine is 2000 kJ and network output from combined engine and
refrigerator system is 360 kJ. Calculate heat transfer to the refrigerator and net transfer to the
reservoir at 400 C. (JUNE 2009)
Solution:

Efficiency of the heat engine is given by,

𝑇 313 𝑊
ᶯ𝐻𝐸 = 1- 𝑇2 = 1- 873 = 0.6415 = 𝑄 1
1 1
∴ 𝑊1 = 0.6415*2000 =1282.93 kJ
Also, 𝑄2 = 𝑄1-𝑊1 =2000-1282.93 =717.1 kJ
COP of the refrigerator is given by
3𝑇 253 𝑄
(COP) = 𝑇 −𝑇 =313−253 = 4.217=𝑊4
2 3 2
But 𝑊2 =𝑊1 - 360 = 1282.93-360 =922.93kJ
∴ 𝑄4 =𝑊2 * 4.217 = 922.93*4.217 =3892 kJ
And 𝑄3 = 𝑄4 +𝑊2 = 3892+922.93 =4814.93 kJ
Net heat transfer to 40 0 C (313 K) reservoir
= 𝑄2 + 𝑄3
=717.1+4814.93
= 5532.03kJ
2. It is proposed to produce 1000 kg of ice per hour from liquid water at 00 C in summer
when the ambient atmospheric temperature is 370 C. It is planned to use a heat engine to
operate the refrigeration plant. Hot water at 70℃, produced by solar heating acts as a source
to the heat engine which uses atmosphere as sink. Calculate i) the power required by the
refrigeration plant ii) the ratio of the energy extracted from freezing water to that absorbed by
the heat engine and iii) the rate of rejection of heat by both the devices. Take enthalpy of
fusion of water at 00 C as 333.43 kJ/kg (JAN 2009)
Solution:
The system arrangement is shown below

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 Basic Thermodynamics(BME304) notes

(i) Power required by the refrigeration plant

𝑄𝐿 𝑄𝐿 𝑇𝐿 273
COP R = = = =35−0 = 7.3784
𝑊 𝑄𝐻 −𝑄𝐿 𝑇𝐻 −𝑇𝐿
1000∗333.43
But, QL = = 92.619 KJ/s
3600
𝑄 92.619
Power required W = 𝐶𝑂𝑃𝐿 =7.3784 = 12.553 kW
𝑅
(ii) The ratio of energy extracted
𝑊 𝑄1 −𝑄2 𝑇 (273+37)
(iii) ᶯ=𝑄 = = 1- 𝑇2 = 1- =0.0962
1 𝑄1 1 273+70
𝑄𝐿 𝑄𝐿/ 𝑊 𝐶𝑂𝑃𝑅
Also, = = 1 = 0.7098
𝑄1 𝑄1 / 𝑊
ᶯ

(iv) The rate of rejection of heat

𝑄2 𝑇
We have, = 𝑇2
𝑄1 1
∴ Q2 = 0.9038 Q1
𝑄𝐻 𝑇
= 𝑇2
𝑄𝐿 1
∴ QH = 1.1355 QL
Rate of rejection to atmosphere

= Q2 + QH

= 0.9038 Q1 + 1.1355 QL = [0.9038 Q1 + 1.1355*0.7098]

=1.7098 Q1
𝑊
Q1 = = 129.68 kW
ᶯ

∴ QL + QH = 221.926 kW

3. Two reversible heat engines A and B are arranged in series, A rejecting heat to B through
and intermediate reservoir. Engine A receives 200 kJ at a temperature of 4210 C from a hot
source, while engine B is in communication with a cold sink at a temperature of 4.40 C. If the
work output of A is twice that of B, find i) the intermediate temperature between A and B ii)
the efficiency of each engine iii) the heat rejected to the cold sink (JUNE 2008)

Department of Mechanical Engineering, AJIET,Mangaluru 107

 Basic Thermodynamics(BME304) notes

Solution:
The system arrangement is shown below

Considering engine A,
𝑄𝐻 𝑇
= 𝑇𝐻
𝑄𝐿𝐴 1
694
∴ T1 = 200 𝑄𝐿𝐴
1 𝑇
Also, 𝑄𝐿𝐴 = 277.4 𝑄𝐿𝐵
694
1 𝑇
∴ T1 = 200 * 277.4 𝑄𝐿𝐵
∴ 𝑄𝐿𝐵 = 79.94 KJ
Given that, WA = 2 WB
(200- 𝑄𝐿𝐴 ) = 2(𝑄𝐿𝐴 – 79.94)
∴ 𝑄𝐿𝐴 = 119.96 kJ
Substituting in (1), we get T1 = 418.1 K
𝑇 418.1
∴ ᶯ𝐴 = 1- 𝑇1 = 1- =39.76%
𝐻 694
𝑇𝐿 277.4
ᶯ𝐵 = 1- = 1- 418.1 = 33.65%
𝑇1
4. A reversible heat engine works between the two reservoirs at 1400 K and 350 K
respectively. A reversible heat pump receives heat from the reservoir at 250 K and rejects the
heat to a reservoir at 350 K to which the heat engine also rejects the heat. The work output
from the engine is used to drive the heat pump. If the total heat supplied to the reservoir at
350 K is to be 100 KW, find the heat to be received by the heat engine (JAN 2007)
Solution:

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 Basic Thermodynamics(BME304) notes

Efficiency of the engine (E) is given by

𝑇 350
ᶯ = 1- 𝑇2 = 1- 1400 = 0.75
1
Work output, W = ᶯ* Q1 = 0.75 Q1
But, Q2 = Q1 – W = (1-0.75) Q1 =0.25 Q1
Considering the heat pump
2 𝑇 350
COP HP = 𝑇 −𝑇 =350−250 = 3.5
2 3
∴ Q4 = COP HP * W
= 3.5*0.75 Q1 = 2.625 Q1
But, Q2 + Q4 = 100 kW (given)
∴ (0.25+2.625) Q1 = 100
Q1 = 34.783 kW
Positive Q indicates that heat is received by the engine

5. A carnot refrigerator consumes 200 W of power in summer when the ambient atmosphere
is 400 C. 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. (FEB 2005)
Solution;
The arrangement is shown in the figure

Applying 1 law
We have, Q1= Q2+WR

Q1 = 20(T1 –T2) +200 …………………(1)

For carnot refrigerator
𝑄1 𝑄2
We have, =
𝑇1 𝑇2
𝑇1
Q1 = Q2 (𝑇 )
2
20( 𝑇1 − 𝑇2 )𝑇1
Q1 = ………………………(2)
𝑇2
Substituting (2) in (1) we have
20( 𝑇1 − 𝑇2 )𝑇1
= 20 (T1-T2) + 200
𝑇2

Department of Mechanical Engineering, AJIET,Mangaluru 109

 Basic Thermodynamics(BME304) notes

𝑇12 −𝑇1 ∗𝑇2

= T1- T2 +10
𝑇2
𝑇12 –T1*T2= T1*T2 -𝑇22 +10 T2

𝑇22 -2 T1*T2 -10 T2+ 𝑇12 = 0

Substituting for T1, we have
𝑇22 -2*313 *T2 -10 T2+ (313)2 = 0
𝑇22 -636 *T2 -10 T2+ (313)2 =0
∴ T2 = 318±56.17
Since T2 < T1
∴ T2 = 318-56.17 = 261.83 K
6. One kg of ice at -50C is exposed to the atmosphere which is at 200C. The ice melts and
comes into thermal equilibrium with the atmosphere. Determine the entropy increase of the
universe. Take Cpice=2.093kJ/kgK, Cpw=4.187kJ/kgK,,Lice=334kj/kg.(JULY2010, JUNE
2019).
Solution:
𝑇𝑠𝑎𝑡 𝐿𝑖𝑐𝑒 𝑇𝑠𝑎𝑡
𝑑𝑠𝑖𝑐𝑒 = 𝑚𝑖𝑐𝑒 [ 𝐶𝑝𝑖𝑐𝑒 𝑙𝑛 + + 𝐶𝑝𝑤 𝑙𝑛 ]
𝑇𝑖𝑐𝑒 273 273
0 + 273 334 20 + 273
𝑑𝑠𝑖𝑐𝑒 = 1 [2.093𝑙𝑛 ( )+ + 4.187𝑙𝑛 ( )] = 1.558 𝑘𝐽/𝐾
−5 + 273 273 0 + 273

𝑄 = 𝑚𝑖𝑐𝑒 [ 𝐶𝑝𝑖𝑐𝑒 (𝑇𝑠𝑎𝑡 − 𝑇𝑖𝑐𝑒 ) + 𝐿𝑖𝑐𝑒 + 𝐶𝑝𝑤 (𝑇𝑤 − 𝑇𝑠𝑎𝑡 )]

𝑄 = 1[2.093(273 − 268) + 334 + 4.187(293 − 273)]
Q=-428.21kJ
𝑄 −428.21
𝑑𝑠𝑎𝑡𝑚 = = = −1.462𝑘𝐽/𝐾
𝑇𝑎𝑡𝑚 20 + 273

𝑑𝑠𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = 𝑑𝑠𝑖𝑐𝑒 + 𝑑𝑠𝑎𝑡𝑚 = 1.558 − 1.462 = 0.096 𝑘𝐽/𝐾

7. m1 kg of water at T1 is isobarically and adiabatically mixed with m2 kg of water at T2

(T1>T2). Show that for equal masses of water, the entropy change of the mixture is given by
𝑇1 +𝑇2
𝑑𝑠 = 2𝑚𝐶𝑝 𝑙𝑛 [2√𝑇 ] and prove that the change is necessarily positive.(JAN2011)
𝑇 1 2
Solution:
𝑇1 +𝑇2
As the m and Cp are same , Mean temperature of mixture is 𝑇 = 2

𝑇 𝑇2
𝑑𝑠 = 𝑚𝐶𝑝 𝑙𝑛 − 𝑚𝐶𝑝 𝑙𝑛
𝑇1 𝑇

𝑇 𝑇
𝑑𝑠 = 𝑚𝐶𝑝 𝑙𝑛 + 𝑚𝐶𝑝 𝑙𝑛
𝑇1 𝑇2
𝑇1 + 𝑇2 𝑇1 + 𝑇2
𝑑𝑠 = 𝑚𝐶𝑝 𝑙𝑛 2 + 𝑚𝐶𝑝 𝑙𝑛 2
𝑇1 𝑇2

Department of Mechanical Engineering, AJIET,Mangaluru 110

 Basic Thermodynamics(BME304) notes

𝑇1 + 𝑇2 𝑇1 + 𝑇2
𝑑𝑠 = 𝑚𝐶𝑝 [𝑙𝑛 + 𝑙𝑛 ]
2𝑇1 2𝑇2
(𝑇1 + 𝑇2 )2
𝑑𝑠 = 𝑚𝐶𝑝 [𝑙𝑛 ]
4𝑇1 𝑇2
2
𝑇1 + 𝑇2
𝑑𝑠 = 𝑚𝐶𝑝 [𝑙𝑛 ( ) ]
2√𝑇1 𝑇2
𝑇1 + 𝑇2
𝑑𝑠 = 2𝑚𝐶𝑝 𝑙𝑛 ( )
2√𝑇1 𝑇2
𝑇1 +𝑇2
The arithmetic mean of is greater than geometric mean √𝑇1 𝑇2
2
𝑇 +𝑇
1 2
Hence (2√𝑇 ) is positive and the change is positive.
𝑇1 2

8. Two identical blocks of mass m are at temperatures T1 and T2 and act as source and sink
for the operation of a heat engine. Determine the maximum amount of work that can be
obtained is the specific heat of the blocks is C in both cases.(JAN2009)
Solution:
𝑇 𝑇2
𝑑𝑠 = 𝑚𝐶𝑝 𝑙𝑛 − 𝑚𝐶𝑝 𝑙𝑛 = 0
𝑇1 𝑇
𝑇 𝑇
𝑑𝑠 = 𝑚𝐶𝑝 𝑙𝑛 + 𝑚𝐶𝑝 𝑙𝑛 = 0
𝑇1 𝑇2
𝑇 𝑇
𝑚𝐶𝑝 [𝑙𝑛 + 𝑙𝑛 ] = 0
𝑇1 𝑇2
2
𝑇
𝑚𝐶𝑝 [𝑙𝑛 ]=0
𝑇1 𝑇2
𝑇 = √𝑇1 𝑇2
𝑊𝑜𝑟𝑘 = 𝑄𝑠 − 𝑄𝑅
𝑊𝑜𝑟𝑘 = 𝑚𝐶𝑝 (𝑇1 − 𝑇) − 𝑚𝐶𝑝 (𝑇 − 𝑇2 )
𝑊𝑜𝑟𝑘 = 𝑚𝐶𝑝 (𝑇1 − 2𝑇 + 𝑇2 )
𝑊𝑜𝑟𝑘 = 𝑚𝐶𝑝 (𝑇1 − 2√𝑇1 𝑇2 + 𝑇2 )
2
𝑊𝑜𝑟𝑘 = 𝑚𝐶𝑝 (√𝑇1 − √𝑇2 )

9. 10gm of water at 200C is converted into ice at -100C in a constant pressure process of one
atmosphere, calculate change in entropy for the process assuming that Cpw as 4.187kJ/kgK
for ice half of that of water(JULY 2019)

Solution:
𝑇𝑙 273
𝑑𝑠1 = 𝑚𝐶𝑝𝑤 𝑙𝑛 = 0.01𝑥4.187𝑙𝑛 ( ) = −0.00296𝑘𝐽/𝐾
𝑇𝑤 20 + 273
𝛿𝑄 0.01𝑥335
𝑑𝑠2 = = = 0.01227 𝑘𝐽/𝑘𝑔𝐾
𝑇 (0 + 273)
𝑇𝑖𝑐𝑒 −10 + 273
𝑑𝑠3 = 𝑚𝐶𝑝𝑖 𝑙𝑛 = 0.01𝑥2.093𝑙𝑛 ( ) = −0.00078𝑘𝐽/𝐾
𝑇𝑙 0 + 273
𝑑𝑠 = 𝑑𝑠1 + 𝑑𝑠2 + 𝑑𝑠3 = −0.00296 + 0.01227 − 0.00078 = 0.00853𝑘𝐽/𝐾

Department of Mechanical Engineering, AJIET,Mangaluru 111

 Basic Thermodynamics(BME304) notes

10. A heat engine is supplied with 278kJ/s of heat at a constant fixed temperature of 2830C
and heat rejection takes place at 50C. The following results were reported
i) 208kJ/s of heat rejected
ii) 139kJ/s of heat rejected
iii) 70kJ/s of heat rejected
Classify as reversible, irreversible and impossible cycles.(JULY2006/JULY2011)

Solution:
𝛿𝑄 𝑄1 𝑄2
𝑑𝑠 = ∮ = +
𝑇 𝑡ℎ 𝑡𝑙
𝑄1 𝑄2
𝑑𝑠 = − as Q2 is negative,
𝑡ℎ 𝑡𝑙
𝑄1 𝑄2 278 208
a) 𝑑𝑠 = − = 556 − 278 = −0.25 < 0 𝑖𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒
𝑡ℎ 𝑡𝑙
𝑄1 𝑄2 278 139
b) 𝑑𝑠 = − = 556 − 278 = 0 = 0 𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒
𝑡ℎ 𝑡𝑙
𝑄1 𝑄2 278 70
c) 𝑑𝑠 = − = 556 − 278 = 0.25 > 0 𝑖𝑚𝑝𝑜𝑠𝑠𝑖𝑏𝑙𝑒
𝑡ℎ 𝑡𝑙

11. A reversible heat engine operating between two thermal reservoirs at 8000 C and 30o
C respectively. It drives a reversible refrigerator operating between -150 C and 300 C. The
heat input to the heat engine is 1900 kJ and the network output from the combined plant
(engine and refrigerator both) is 290 KJ. Calculate the heat absorbed by the refrigerant
and the total heat transferred to 30 0 C reservoir (AUG 2005)
Solution:
The system arrangement is shown below

Carnot efficiency is given by

𝑇 303
ᶯ𝐻𝐸 = 1- 𝑇 𝐿 = 1- 1073 = 0.7176
𝐻
Work output from the carnot engine,
W =0.7176*Q1
= 0.7176 *1900
WTotal = 1363.47 kJ
Wnet = 290 KJ
WTotal = W RE + Wnet

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1363.47 = WRE +290

WRE = 1073.47 kJ
WTotal = Q1 –Q2

Q2 = Q1 - WTotal
= 1900-1363.47
= 536.53 kJ
3 𝑇 258
COP of RE = 𝑇 −𝑇 = = 303−258
2 3
= 5.733
𝑄
But COP = 𝑊 4
𝑅𝐸
5.733*1073.47 =Q4
Q4 = 6154.20 kJ
But Q3-Q4 = W
Q3 = Q4 + W
= 6154.20 +1073.47
Q3 = 7227.67 kJ
Total heat rejected at T2 = 30 0 C is
Q3 +Q2 = 7227.67+536.53
=7764.20 kJ
12. A reversible heat engine operates between two reservoirs at temperature 7000 C and 500
C. The engine drives a reversible refrigerator which operates between reservoirs at
temperatures of 500 C and- 250 C. The heat transfer to the engine is 2500 KJ and the network
output of the combined engine refrigerator plant is 400 KJ.

i) Determine the heat transfer to the refrigerant and the net heat transfer to the reservoir
at and 500 C.

ii) Determine the heat transfer to the refrigerant and the heat transfer to the reservoir at
500 C given that the efficiency of the heat engine and the COP of the refrigerator are each
45 percent of their maximum possible values. (AUG. 2001)
Solution:

( a) For the reversible heat engine

𝑇1 −𝑇2 973−323
ᶯ𝑡ℎ = = = 0.668 =66.8%
𝑇1 973
In terms of heat and work interactions
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𝑤𝑜𝑟𝑘 𝑖𝑛𝑝𝑢𝑡
ᶯ𝑡ℎ = 𝐻𝑒𝑎𝑡 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑
𝑊+400
0.668 = 2500
W = 1270 kJ
From first law
Q2 =2500-400-1270 =830 kJ
For the reversible refrigerator
4 𝑇 248
COP =𝑇 −𝑇 = 323−248 = 3.31
3 4
In terms of heat and work interactions,
𝑄
COP = 𝑊3
𝑄3
a. =
1270
Q3 = 4203. 7 kJ

Q4 = Q3 + W =4203.7 + 1270 = 5473.7 kJ

(a) Heat transfer to the refrigerator, Q3 = 4203.7 kJ

Net heat transfer to the reservoir at 50 0 C is Q4 – Q3 = 5473.7-4203.7 =1270 kJ

13. A reversible engine operates between 3 heat reservoirs 1000 K, 800 K and 600 K and
rejects heat to a reservoir at 300 K, the engine develops 10 KW and rejects 412 KJ/min. If
heat supplied by the reservoir at 1000 K is 60 % of heat supplied by the reservoir at 600
K, find quantity of heat supplied by each reservoir. (MARCH 2001)
Solution:

Work output= 60 kW
= 10*60
= 600 kJ/min
From first law of thermodynamics
Total heat supplied = workdone + heat rejected
= 600+412
= 1012 kJ/min
Let Q1 be the heat absorbed by the engine from the source at 600 K
Then, heat absorbed from the source at 1000 K is 0.6 Q1
∴ Heat taken from the source at 800 K
Q2 = 1012-Q1-0.6Q1

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= 1012 -1.6 Q1
As engine is reversible, clausius theorem becomes
𝑄1 𝑄2 𝑄3 𝑄4
+ + - =0
𝑇1 𝑇2 𝑇3 𝑇4
𝑄1 1012−1.6𝑄1 0.6𝑄1 412
+ + -300 =0
600 800 1000
∴ Q1 = 405 kJ/min (from source 600 K)
Q2 =1012-1.6*405 = 364 kJ/min (from source 800 K)
Q3 = 0.6 Q2 = 0.6*364 =218.4 kJ/min (from source 1000 K)

14. 5kg of copper block at 2000C is dropped to an insulated tank with 100kg of oil at
300C. Find the increase in entropy of the universe. Take Cpcu=0.4kJ/kgK, Cpoil=2.1kJ/kgK.
Solution:
𝑚𝑐𝑢 𝐶𝑝𝑐𝑢 (𝑇𝑐𝑢 − 𝑇) = 𝑚𝑜𝑖𝑙 𝐶𝑝𝑜𝑖𝑙 (𝑇 − 𝑇𝑜𝑖𝑙 )
5𝑥0.4(200 − 𝑇) = 100𝑥2.1(𝑇 − 30)
T= 31.60C
𝑇 304.6
𝑑𝑠𝑐𝑢 = 𝑚𝑐𝑢 𝐶𝑝𝑐𝑢 𝑙𝑛 = 5𝑥0.4𝑙𝑛 = −0.88𝑘𝐽/𝐾
𝑇𝑐𝑢 473
𝑇 304.6
𝑑𝑠𝑜𝑖𝑙 = 𝑚𝑜𝑖𝑙 𝐶𝑝𝑜𝑖𝑙 𝑙𝑛 = 100𝑥2.1𝑙𝑛 = 1.106𝑘𝐽/𝐾
𝑇𝑜𝑖𝑙 303

𝑑𝑠𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = 𝑑𝑠𝑐𝑢 + 𝑑𝑠𝑜𝑖𝑙 = −0.88 + 1.106 = 0.226 𝑘𝐽/𝐾

5. Estimate the entropy change for each of the universe due to each of the following
processes
i. A copper block of mass 0.5kg at 1000C is placed in a lake of water at 100C
ii. Two such blocks at 1000C and 00C respectively are joined together,
take for copper Cpcu=0.393kJ/kgK

Solution:
𝑄𝑐𝑢 = 𝑄𝑙𝑎𝑘𝑒 = 𝑚𝑐𝑢 𝐶𝑝𝑐𝑢 (𝑇2 − 𝑇1 ) = 0.5𝑥0.393(283 − 373) = −17.685𝑘𝐽
𝑇2 10 + 273
𝑑𝑠𝑐𝑜𝑝𝑝𝑒𝑟 = 𝑚𝑐𝑢 𝐶𝑝𝑐𝑢 𝑙𝑛 = 0.5𝑥0.393𝑙𝑛 = −0.05426𝑘𝐽/𝐾
𝑇1 100 + 273
𝛿𝑄 17.685
𝑑𝑠𝑙𝑎𝑘𝑒 = = = 0.0625 𝑘𝐽/𝑘𝑔𝐾(ℎ𝑒𝑎𝑡 𝑖𝑛𝑡𝑜 𝑙𝑎𝑘𝑒 𝑖𝑠 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒)
𝑇 (10 + 273)
𝑑𝑠𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = 𝑑𝑠𝑐𝑜𝑝𝑝𝑒𝑟 + 𝑑𝑠𝑙𝑎𝑘𝑒 = −0.05426 + 0.0625 = 0.00824 𝑘𝐽/𝐾

𝑚𝑎 𝐶𝑝𝑎 (𝑇𝑎 − 𝑇) = 𝑚𝑏 𝐶𝑝𝑏 (𝑇 − 𝑇𝑏 )

(𝑇𝑎 − 𝑇) = (𝑇 − 𝑇𝑏 )
(373 − 𝑇) = (𝑇 − 273)
T=323K or 500C
𝑇 323
𝑑𝑠𝑖 = 𝑚𝑎 𝐶𝑝𝑎 𝑙𝑛 = 0.5𝑥0.393𝑙𝑛 = −0.0283𝑘𝐽/𝐾
𝑇𝑎 373
𝑇𝑏 323
𝑑𝑠𝑏 = 𝑚𝑏 𝐶𝑝𝑏 𝑙𝑛 = 0.5𝑥0.393𝑙𝑛 = 0.033𝑘𝐽/𝐾
𝑇 273

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𝑑𝑠𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = 𝑑𝑠𝑎 + 𝑑𝑠𝑏 = −0.0283 + 0.033 = 0.00475 𝑘𝐽/𝐾

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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. Problems 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. Problems.

Introduction
A portion of the heat supplied to any engine must be rejected. No heat engine can have
efficiency equal to 100 percent.
The different sources of energy may be divided into two groups.

High grade energy

Energy that can be completely transformed into shaft work without any loss and hence is
fully utilizable
Ex: mechanical and electrical work, water, wind and tidal power, kinetic energy of jet etc.
Low grade energy
Energy of which only a certain portion can be converted into mechanical work
Ex: heat from thermal energy, heat from nuclear fission or fusion.

Available and unavailable energy

The portion of thermal energy input in cyclic engine which gets converted into mechanical
work is referred to as available energy.
The portion of thermal energy which is not utilizable and is rejected to the sink
(surroundings) is called unavailable energy.

Relation between increase in unavailable energy and increase in entropy

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𝑇
Consider any Carnot engine working between temperature limits T1 and T2 then rev = 1-𝑇2 .
1

For a given value of T1, rev increases with decrease in T2. The lowest possible temperature of
heat rejection is the ambient temperature T0.
𝑻 𝑾𝒎𝒂𝒙
Then max = 1-𝑻𝟎 =
𝟏 𝑸𝟏
𝑻𝟎
Wmax = (1-𝑻 ) Q1
𝟏
𝑸
= Q1 – T0 𝑻 𝟏
𝟏
= Q1 - T0 ∆S
Where ∆S is the change in entropy of the reservoir at temperature T1
Area abcd represents work done by the engine and hence this is the available energy or
portion of energy converted into work.
Area dcef represents the energy rejected to the sink or this denotes the unavailable energy or
a portion of the energy that cannot be converted into work.
A.E. = Available energy = Q1 - T0 ∆S
Q1 = A.E. +U.E.
Unavailable energy = Q1 – A.E.
= Q1 – (Q1 - T0 ∆S)
= T0 ∆S
Thus unavailable energy is equal to the product of the lowest temperature at which the heat is
rejected and the entropy change of the system during the process of supplying heat.

Now consider a finite process 1-2. Let Q, be the heat supplied to the engine reversibly at T1,
then
𝑻𝟎
Wmax =Q1 = (1- ) Q1
𝑻𝟏
𝑻
Wmax= Q1 - 𝑻𝟎 Q1 = A.E.
𝟏
The total work done is given by,
𝟐 𝟐 𝟐 𝑻𝟎
∫𝟏 𝑾𝒎𝒂𝒙 = ∫𝟏 𝐐𝟏 - ∫𝟏 𝑻𝟏
Q1
Wmax = 1Q2 – T0 (S2-S1)
A.E. = 1Q2 – T0 (S2-S1)
Unavailable energy U.E. = 1Q2 – A.E.
U.E. = T0 (S2-S1)
Maximum Work and Maximum Useful Work

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The availability of a system is defined as maximum useful work that can be obtained in a
process in which the system comes to equilibrium with the surroundings.
Consider a system which is initially at pressure P and temperature T while the surrounding
are at pressure P0 and temperature T0. Let the system undergo a process in which it delivers
some work and it reaches a state of thermodynamic equilibrium with the surroundings. When
once the system is in thermodynamic equilibrium with the surroundings, there is no
possibility of obtaining further work from the system (dead State). In such a situation the
total work delivered by the system will be Maximum. This is called as Maximum Work.
However, a part of the work done by the system is used in pushing the atmosphere and hence
it will not be available as useful work. As a result the Maximum useful work which is
obtainable from a system is always less than the maximum work done by the system in any
given process. Thus the maximum useful work delivered by the system is called availability
of the system.
Availability function for a Non Flow process
Consider a piston cylinder arrangement in which the fluid at p1, V1, T1 expands reversibly
to the state with parameters P0, V0, T0. The following energy interaction takes place.

The fluid expands and expansion work Wexp is obtained from the principle of energy
conservation.
Q = W + dU
-Q = Wexp + (U0-U1)
The heat interaction is negative as it leaves the system.
Wexp = (U1-U0) – Q
The heat rejected Q by the piston-cylinder assembly may be made to run a reversible heat
engine. The output from the reversible engine equals
𝑻
Weng = Q [1-𝑻𝟎 ]
𝟏
Weng= Q – T0 (S1-S0)
𝐓𝟏 −𝐓𝟎
[Weng= ]
𝐓𝟏
The sum of total of expansion work Wexp and the engine work Weng gives maximum work
obtainable from the arrangement.
Wmax= [(U1-U0)-Q] + [Q-T0(S1-S0)]
Wmax= (U1-U0) –T0(S1-S0)

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The piston moving outwards has to spend a work in pushing the atmosphere against its own
pressure. This work, which may be called as the surrounding work, is dissipated and is not
useful.
Wsur = P0 (V0-V1)
The energy available for work transfer less the work absorbed in moving the environment is
called the useful work or net-work.
Therefore Maximum useful available works can net-work,
Wnet = Wmax - Wsur
= (U1-U0)-T0(S1-S0) - P0(V0-V1)
Wnet= (U1+P0V1-T0S1) – (U0+P0V0-T0S0)
Wnet= A1-A2
Where A= (U+P0V-T0S) is known as non-flow availability function. The system consists of
three extensive properties (U,V & S) and also two intensive properties of one surroundings
(P0& T0).
When the system undergoes a change from state 1 to state 2, without reaching the dead state,
then
(Wu)max=Wnet = (A1-A0)-(A2-A0)
Wnet= A1-A2
Availability is a function of the properties of the surroundings as well as the end states of the
closed system.
Availability of a Steady flow System
Consider a steady flow system and let it be assumed that the flowing fluid has the following
properties and characteristics, Internal energy U, Volume V, Enthalpy H, Pressure P,
Velocity C and location Z.

The properties of the fluid would change when flowing through the system. Let subscript
1 indicates the properties of the system at inlet and subscript 0 are used to fluid parameters at
outlet.
The steady flow energy equation may then be written as
𝐂𝟏𝟐 𝐂𝟐
U1 + P1V1 + 𝟐
+ gZ1 – Q = U0+ P0V0+ 𝟐𝟎 +gZ0+Ws
Where,

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PV = Displacement or flow energy

C21
= Kinetic Energy
2
gZ = potential Energy

Neglecting potential and kinetic energy

U1 + P1V1- Q = U0+ P0V0+Ws
Shaft work Ws = (H1-H0) – Q
The heat Q rejected by the system may be made to run a reversible heat engine. The output
from this engine equals
𝐓
Weng = Q [1- 𝐓𝟎 ] = Q – T0 (S1- S0)
Maximum available useful work or net-work,
Wnet = Ws +Weng
= (H1- H0) –Q+Q – T0 (S1- S0)
= (H1-T0S1)-(H0-T0S0)
=B1-B0
Where [B= H-T0S] is known as the steady flow availability function.It is a composite
property of system and surroundings involving two extensive properties H and S of the
system and one intensive property T0 of the surroundings.
Effectiveness
It represents the fraction of maximum useful work actually utilized and is expressed as the
ratio of useful work to the maximum useful work.
𝑾𝒖
ε=
(𝑾𝒖 )𝒎𝒂𝒙
Irreversibility
It denotes the loss of work due to the fact that all real process are irreversible and is defined
as the difference between the maximum work output from the system and the expansion
work.
I = Wmax – W actual
Second Law Efficiency
The second law efficiency is defined as the ratio of the actual thermal efficiency to the
maximum possible thermal efficiency under the same conditions.
𝒕𝒉(𝒂𝒄𝒕𝒖𝒂𝒍)
= 𝒕𝒉(𝐦𝐚𝐱)

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PURE SUBSTANCES
It is a substance that has a uniform chemical composition throughout the system. Ex: Water,
N2, H2 and CO2.
A pure substance is one which has a homogeneous and invariable chemical
composition irrespective of the phase can phases in which it exists. A mixture of ice, water
and steam is one component system (pure substance), since the chemical composition of
these three different phases is the same.
Homogeneous in chemical composition means each part of the system must have the
same chemical constituents and the chemical elements must be combined chemically in the
same way.
Phase Diagrams (T.V. Diagram)

Consider the transfer of heat at constant pressure to a closed system of 1kg of water. Let the
initial state of water be at point 'a'. The constant pressure line a-b-c-d represents the
relationship between the temperature and the volume during the course of heat transfer. From
a to b, heat transfer produces an increases in temperature and a small increase in volume.
When point b is reached, part of the water begins to vaporize and a rapid increase in volume
takes place. Although both the temperature and the pressure remain unaltered, the change of
state is noted by the increase of the mass of the vapour and the decrease of the mass of the
liquid. The liquid state corresponds to point 'b' whereas the vapour state corresponds to point
‘c’. When point ‘c’ is reached, all the liquid has been converted into vapour. Further transfer
of heat to the system increases both the temperature and volume along portion 'c' and 'd' of
the constant pressure curve.
If the above heating process is repeated at different pressures, curves similar to a-b-c-
d are obtained. It is noted that there are two discontinuities in the slope of each of the
constant pressure lines, points ‘b’ and ‘c’ (with a constant temperature portion between
them). If the pressure is increased beyond a certain value called the critical pressure, the
discontinuities as well as the constant temperature portions disappear. In this case, there is no
definite transition between the liquid and vapour phases and the liquid changes to vapour
without any discontinuity. The limiting state at which no discontinuities are noticeable is
called the critical state and is represented by point 'f’. Line a-b-f is called saturation liquid
line, and line fcg called saturation vapour line. Both the lines meet at the critical point ‘f’.
Properties such as temperature, pressure and volume at the critical point are called critical

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properties. For water critical temperature, pressure specific volume is 2070C, 224 bar and
0.00064 m3/kg, respectively.

Pressure - Temperature Diagram

Consider 1 kg of ice at a pressure P and temperature Ta below the fusion temperature Tb.
Point b is located on the solid liquid line (fusion line) and determines the state at which the
solid is in equilibrium with its liquid.
Heat transfer to the ice at constant pressure results in a temperature increase to Tb.
with further transfer of heat, ice begins to liquefy at a constant temperature T b until all the
substance is transformed to the liquid state. The transfer of heat to the liquid will increase its
temperature to Tc at which evaporation begins, and the temperature remains constant till all
the liquid is evaporated. When all the liquid has evaporated, the temperature will again rise
upon further transfer of heat along c-d.
If the above process is repeated at different pressures, the corresponding point’s b and c can
be determined and the solid - Liquid and liquid vapour curves can be traced. These two
curves meet at a point on the P-T plane called triple point. Similarly the solid vapour line can
be determined for pressure values below the pressure of the triple point. In this case, heat
transfer to a solid will result first in raising its temperature to the solid vapour line and then
changing it directly into vapour. The solid vapour line (sublimation line) represents the state
in which the vapour is in equilibrium with its solid. The triple point defines a state in which
the solid, Liquid and vapour phases of a substance coexist in equilibrium.

Pressure Volume Diagram

Pressure volume diagram is somewhat similar to temperature volume diagram. However

in this case we have for example a constant temperature line a b c d which has two

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discontinuities one at b which represents saturated liquid state and another at c which is
saturated vapour state. The locus of all the saturated liquid states at different temperatures
gives saturated liquid line, while the locus of all the saturated vapour state, gives saturated
vapour line and these two lines meet at the critical point.
On the saturated liquid line the pure substance will be in saturated liquid state. The region
to the left of saturated liquid line is the compressed liquid or sub-cooled liquid region.
Similarly on the saturated vapour line the pure substance will be in vapour state. The region
to the right of saturated vapour line is super heated vapour region.

P-V-T Surface

The points which are represented on both the T-V and P-T diagrams can be shown on
one diagram. If the three coordinates P, V and T are plotted along rectangular axes is called
P-V-T surface. By projecting the surface on the P-T plane, the whole solid- vapour region
projects in to the sublimation curve, the whole liquid –vapour region projects into the fusion
curve. The critical point is denoted by the letter C1 and the triple point by T. The critical
isotherm is marked Tc.

Temperature- entropy diagram

Temperature - entropy diagram is more or less same as temperature- volume diagram.

As in T - v diagram, the saturated liquid and saturated vapour lines meet at critical point. At
any point on single phase region, constant volume lines are steeper than constant pressure
lines. In the two phase region constant pressure lines are horizontal,

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The h-s diagram for water

Enthalpy-entropy diagram is another diagram commonly used in engineering. This is
particularly useful in the analysis of steady flow devices such as nozzles, turbines and
compressors. Here enthalpy which is a primary property in the first law analysis of the steady
- flow devices is taken along y axis. When we consider steady flow of steam through an
adiabatic nozzle or turbine, for example, the vertical distance between the inlets and exist
states (dh) is a measure of work output, while the horizontal distance (DS) is a measure of
irreversibilities associated with the process. The h-s diagram is also called a “mollier
diagram”.

Saturated vapor and superheated vapor states of pure substance with water as example
Consider 1 kg of water at a temperature of 00C being heated in a container under constant
pressure. The temperature of water increases till the boiling point is reached. (The boiling
temperature depends on pressure and at atmospheric pressure of 1 bar, the boiling
temperature is 1000C). “The amount of heat absorbed by water in being heated upto
boiling temperature is known as the total heat of water and is approximately equal to
sensible heat of water”. It depends on the pressure at which the water is heated.
If the heating is continued after the boiling temperature is reached, it is seen that there
is no further increase in temperature so long as the pressure is constant, the heat supplied is
now utilized in converting water into steam and is known as "latent heat".
As long as there is some water left un-evaporated, in the container, the steam formed
will not be pure steam, but will have some water particles in suspension. Such steam is
known as “wet steam” and may be classed as vapour, “The ratio of the weight of the actual
dry steam to the weight of the wet steam is called the dryness fraction of steam”.
“When the last of these suspended water particles has evaporated, the steam is said to
be dry and is known as dry saturated steam”.
“If the heating of steam is continues beyond this stage, the steam is said to be the
super-heated steam”.

Enthalpy of change of phase (Latent heat)(hfg)

The latent heat is the quantity of heat absorbed by 1 kg of steam during evaporation and its
value varies with the pressure.

Dryness fraction (Quality)

The dryness fraction of wet steam is the ratio of the weight of actual dry steam to the total
weight of the wet steam containing it.

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𝐬 𝐖
Dryness fraction = x= 𝐖+𝐖
𝐬
Ws = Weight of dry steam contained in the steam considered.
W = Weight of the suspended particles of water.

Triple point
It is that state at which all these phases of a pure substance co-exists in equilibrium for water,
the triple point pressure and temperature are 0.006113 bar and 0.010C.

Critical Point
The critical point is that state beyond which it is difficult to distinguish between liquid and
vapour phases.
Or
It can also be defined as that state at which liquid can be converted to vapour completely
without any heat transfer.
Or
It can also be defined as that state at which the liquid-vapour saturation line suddenly
terminates. For water, the critical point pressure and temperature are 220.9 bar and 374.140C.

Sub-cooled liquid
The term sub-cooling refers to a liquid existing at a temperature below its normal boiling
point. For example, water boils at 373K; at room temperature (300K) the water is termed as
Sub-cooled.

Throttling Calorimeter

Sample of wet steam of mass m at pressure p1 is taken from the steam main through a
perforated sampling tube as shown in the figure.
Then it is throttled by the partially opened valve to a pressure P2 measured by a mercury
manometer and temperature T2 so that after throttling the steam is in the superheated region.
The process is shown on T-s and H-s diagram.

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The steady flow energy equation gives the enthalpy after throttling as equal to enthalpy
before throttling. It is a irreversible process hence joined by a dotted line. Thus the initial
state of the steam is P1, t1 and its dryness fraction is x1 and the final state of the superheated
steam is P2 .

T – s and h – s diagram for throttling calorimeter

Now h1 =h2
hf1+x1 hfg1 = h2
x1 =( h2 – hf1 ) / hfg1
With P2 and T2 being known, h2 can be found out from the superheated steam table. The
values of hf, hfg are taken from saturated steam table. thus quality of the wet steam x 1 can be
calculated.

Separating Calorimeter:
The quality of wet steam is usually defined by its dryness fraction. When the dryness
fraction, pressure and temperature of the steam are known, then the state of wet steam is fully
defined. In a steam plant it is at times necessary to know the state of the steam. For wet
steam, this entails finding the dryness fraction. When the steam is very wet, we make use of
a separating calorimeter. Construction of separating calorimeter is as shown in figure:
The steam is collected out of the main steam supply and enters the separator from the top.
The steam is forced to make a sharp turn when it hits the perforated cup (or any other
mechanism that produces the same effect). This results in a vortex motion in the steam, and
water separates out by the centrifugal action. The droplets then remain inside the separator
and are collected at the bottom, where the level can be recorded from the water glass. The dry
steam will pass out of the calorimeter into a small condenser for the collection of the
condensate. However, not all the water droplets remain in the collector tank. Some water
droplets pass through to the condenser, and hence this calorimeter only gives a close
approximation of the dryness fraction of the steam. From the results obtained from the two
collectors, the dryness fraction may then be found from
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑑𝑟𝑦 𝑠𝑡𝑒𝑎𝑚
Dryness fraction= 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑤𝑒𝑡 𝑠𝑡𝑒𝑎𝑚 𝑐𝑜𝑛𝑡𝑎𝑖𝑛𝑖𝑛𝑔 𝑑𝑟𝑦 𝑠𝑡𝑒𝑎𝑚

This can be expressed as:

𝑚
X=𝑚+𝑀

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Where, M is the mass of dry steam and m is the mass of suspended water separated in the
calorimeter in the same time.

Fig. Separating calorimeter

Determination of the dryness fraction of wet steam using combined separating and
throttling calorimeter

The wet steam from the boiler enters the separating calorimeter through the steam pipe. As it
passes down the central passage, it undergoes a sudden reversal of direction of motion when
it strikes the baffle plates. This causes the water, which has greater inertia to separate from
the mixture. The water collects in the inner chamber and the amount of water collected (m) is
indicated in the water quantity indicator.

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After the water particles are separated, the steam becomes drier but still it will be in wet
condition. This steam at pressure P1 and saturation temperature T1 enters the throttling
calorimeter. As the steam passes through the throttle valve, it undergoes expansion; the final
temperature is measured by a thermometer while the final pressure is measured by a
manometer.
M = mass of steam passing through the throttling calorimeter.
x = Dryness fraction of steam entering the separating calorimeter through the steam main
pipe.
x1 = Dryness fraction of steam as determined by separating calorimeter.
x2 = Dryness fraction of steam entering throttling calorimeter.
m= Weight of water separated in the separating calorimeter.

𝐌
Then x1 = 𝐌+𝐦 (1)
P1 = Initial pressure in Bar
P2 = Final pressure = Atmospheric pressure + manometer reading.
hf1= Enthalpy of water at pressure P1 in kj/kg
hfg1 = latent heat at pressure P1 in kj/kg
hg2 = Enthalpy of vapour at pressure P2 in kj/kg
Tsat2 = Saturation temperature at final pressure.
Tsup2 = Temperature of superheated steam as recorded by thermometer
During the throttling process, enthalpy remains constant.
Enthalpy before throttling at pressure P1 = Enthalpy after throttling at Pressure P2

hf1+ x2 hfg1 = hg2 +Cp (Tsup2 - Tsat2)

𝐡𝐠𝟐 +𝐂𝐩 (𝐓𝐬𝐮𝐩𝟐 − 𝐓𝐬𝐚𝐭𝟐 )− 𝐡𝐟𝟏

x2= 𝐡𝐟𝐠𝟏

But the quantity of dry steam entering the throttling calorimeter = Mx2

𝟐
𝐌𝐱
x = 𝐌+𝐦 (2)

From (1) and (2) x = x1 x2.

Vapourisation
It is the process that involves change from the liquid phase to vapour phase. Water vapours
can be obtained by evaporation and steam by boiling.
Evaporation
It is the process of vapour generation only from the surface of a liquid. Evaporation occurs at
any temperature; however its intensity increases with rise in temperature of the liquid.
Saturation Temperature
Boiling takes place at a definite temperature which depends upon physical properties of the
liquid and pressure. This temperature is denoted by Ts is called the saturation temperature
and it remains constant until all the liquid has transformed into vapour.

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Saturation Pressure
The pressure at a specific temperature at which the liquid boils or is in equilibrium with its
vapour is called saturation pressure.
Saturation point/ Boiling point
The steam is called saturated when the molecules escaping from the liquid become equal to
the molecules returning to it. The saturated steam has a maximum density at a given
temperature and is in thermal equilibrium with the liquid. The temperature of saturated steam
(vapour) and the liquid in contact with it is called the saturation point or boiling point. The
liquid at its boiling point at a specified pressure is called as saturated liquid.
Total heat of water
The amount of heat absorbed by water is being heated upto boiling temperature is known as
the total heat of water.
Sensible heat (hf)
It is the quantity of heat required to raise the temperature of 1kg of water from 00C to the
boiling point. Sensible heat increases as the pressure increases.
Wet steam
Water particles which are suspended in steam such steam are known as wet steam.
When the steam does not have any suspended water particle is called dry steam.

Total heat (enthalpy) of wet steam

The amount of heat required to convert, at constant pressure, 1 kg of water at freezing point,
into wet steam.
h= hf +xhfg

Total heat (enthalpy) of dry steam

The amount of heat required to convert, at constant pressure, 1 kg of water at freezing point,
into dry steam will be sum of the total heat of water and the latent heat.
hg = hf +hfg

Superheated steam
The heating of steam after it has become dry is known as superheating. The additional
heat supplied to the steam during superheating is known as heat of superheating steam.

Total heat (enthalpy) of superheated steam

The amount of heat required to convert, at constant pressure, 1 kg of water at freezing point,
into superheated steam
The total heat of 1 kg of superheated steam = hf +hfg+ Cps(TSup-TSat)= hg+ Cps(TSup-TSat)
TSup =Temperature of superheated steam
TSat = Saturation temperature at absolute pressure of P1

Volume of wet steam

If x is the dryness fraction of wet steam, then 1 kg of this steam will have x kg of dry
steam and (1-x) kg of water particles.

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Volume of wet steam = Vf +x Vg

But Vg=Vf+Vfg
Vfg= Vg - Vf
Volume of wet steam = Vf +x (Vg - Vf)
Vf is negligible compared to Vg
Volume of wet steam = x Vg
Vf = Volume of 1 kg of water.
Vg = volume of 1 kg of steam.

Volume of superheated steam(VSup)

This can be found out by applying general gas equation between saturated condition and
superheated condition
𝑃𝑣𝑆𝑎𝑡 𝑃𝑣𝑆𝑢𝑝
= as Pressure is constant
𝑇𝑆𝑎𝑡 𝑇𝑆𝑢𝑝
𝑣𝑆𝑎𝑡
𝑣𝑆𝑢𝑝 = 𝑇𝑆𝑢𝑝
𝑇𝑆𝑎𝑡

Theory Question :
1. Define available and Unavailable energy(DEC 2017/JAN 2018)
2. Define 1. Available energy 1. Unavailable energy 3. Effectiveness 4.
Irreversibility(JUNE /JULY 2017)
3. What is available , unavailable energy and second law efficiency(DEC 2016/JAN
2017,JUNE/JULY 2019)
4. Define the following:
i. Pure substance
ii. Triple point
iii. Critical point
iv. Quality
v. Sub-cooled liquid.(DEC 2011,JUNE/JULY 2019)
5. Sketch and explain separating and throttling calorimeter to find out the dryness
fraction of pure substances.(JUNE 2012,DEC 2018/JAN 2019, JUNE 2015,DEC
2017/JAN 2018 )
6. Draw phase equilibrium diagram for water on P-T coordinates indicating triple and
critical point.(JUNE 2012)
7. Draw phase equilibrium diagram for water on P-V coordinates and indicate relevant
parameters on it(DEC 2017/JAN 2018)
8. Sketch the T-P phase diagram for water. Mark on it the following: Solid region, liquid
region, vapour phase, triple point and critical point.(DEC 2012)
9. With neat sketches indicate varies parameter on typical T-S and H-S diagrams for a
pure substance.(JUNE 2013)
10. With a neat sketch, explain how throttling calorimeter can be used to measure the
dryness fraction of wet vapour.(JUNE 2013)
11. Draw the phase equilibrium diagram for a pure substance on T-S plot with relevant
constant property lines.(DEC 2013)

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12. What is the main objective of quality measurement? With a neat sketch, explain
throttling calorimeter.(DEC 2013,JUNE/JULY 2019)
13. Define dryness fraction of steam? What are the methods used to measure dryness
fraction? With a neat sketch explain any one of them.(JUNE 2014)
14. What is meant by a pure substance? Can we treat air as pure substance.(DEC 2014)
15. Name the widely used thermodynamic diagrams for a pure substance.(Dec 2014)
16. Define the followings:
i. Triple point
ii. Critical temperature
iii. Dryness fraction
iv. Saturation temperature(JUNE 2015)

Problems:
1. 1kg of air compressed polytropically from a pressure of 1bar and temperature of
300K to a pressure of 7bar and temperature of 373K. Determine the irreversibility
and reversibility measure assuming a sink Temperature of 298K.

Solution:
P1=1bar
T1= 300K
T0= 298K
T2= 373K
𝑛−1
𝑇2 𝑃2 𝑛
=
𝑇1 𝑃1
𝑛−1
373 7 𝑛
=
300 1
𝑛−1
1.24= 7 𝑛

n= 1.13
𝑃1 𝑉1 −𝑃2 𝑉2 𝑚𝑅(𝑇1 −𝑇2 ) 1∗0.287(300−373)
Wact= = =
𝑛−1 𝑛−1 1.13−1
Wact= -162 kJ/kg

Reversible work = Wr= (U1-U2) –T0(S1-S2)

𝑇 𝑃
= Cv(T1-T2) – T0[Cpln𝑇1 – mR ln𝑃1 ]
2 2
300 1
= 0.718(300-373) - 298[1.005 ln – 0.287ln ]
373 7
Wr=153.6kJ/kg

Irreversibility = Reversible work – Actual work

= -153.6-(-162) = 8.9kJ/kg

𝑊𝑢 −153.6
Reversibility measure =(𝑊 = = 0.9481
𝑢 )𝑚𝑎𝑥 −162

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2. Air at 5 bar and 5000C expands in a turbine to 1 bar and 2900C. During expansion
12kJ/kg of heat is lost to the surroundings which is at 0.98bar and 20 0C. Neglecting
changes in KE and PE, determine per kg of air
a. The decrease in availability
b. The maximum work required and
c. The irreversibility
For air, take Cp= 1.005 kJ/kg, h= Cp*T where Cp is constant
Solution:
P1=5bar
T1= 5000C
T2=2900C
P2=1bar
P0=0.98bar
T0=200C
m = 1kg
Change in availability for a flow process is
= B1- B2
= (h1-T0S1)-(h2-T0S2)
= (h1-h2) – T0(S1-S2)
𝑇 𝑃
= Cp (T1-T2) -T0[Cpln𝑇1 – mR ln𝑃1 ]
2 2
773 5
=1.005(773-563) -293[1.005 ln563 – 0.287ln1]
Change in availability = 253.05 kJ/kg
Maximum work = Change in availability = 253.05 kJ/kg
From steady flow energy equation, neglecting KE and PE
Q= h2-h1 +W
Q= Cp(T2-T1)+W
W= 223 kJ/kg
Irreversibility = I= Wmax-W
=253-223= 30kJ/kg

3. 0.2 kg of air initially at 575K temperature receives 300kJ/kg of heat reversibly at

constant pressure. Determine the available and unavailable energies of the heat
added. Take Cp for air =1.005kJ/kg and temperature of surrounding 300K.
Solution:
Q= mCp (T2-T1)
300=0.2*1.005 (T2-575)
T2= 2067.5K
Entropy change,
𝑇
ds= mCpln (𝑇2)
1
2067.5
= 0.2*1.005 ln 575
ds= 0.2572kJ/K
Unavailable work (energy) = T0ds

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= 800*0.2572
=77.16kJ
Available work (energy)
=Q- T0ds
=300-300*0.2572
= 222.84kJ

4. A pressure cooler contains 1.5kJ/kg of steam at 5 bar and 0.9 dryness. When the
gas was switched off, determine the quantity of heat rejected by the pressure in the
cooker falls to 1 bar.(JUNE 2010)
Solution:
P1= 5 bar P2= 1 bar
hf1=639.66KJ/kg hf2=417.33KJ/kg
hfg1= 1921.5KJ/kg hfg2= 2088.7KJ/kg
hg1= 2561.2 KJ/kg hg2= 2506.1 KJ/kg
3
vg1= 0.3749 m /kg vg2= 1.694 m3/kg
x1= 0.9
x1 vg1= x2 vg2
0.9∗0.3749
x2= =0.199
1.694
H1= hf1+x1hfg1
=639.66+0.9*1921.6
=2369.1KJ/kg
u1= H1-p1x1vg1
= 2369.1-5*100*0.3749*0.9
=2200.39KJ/kg
H2= 417.33+0.199*2088.7
=832.9813 KJ/kg
u2= H2-p2x2vg2
=832.9813-1*100*0.199*1.694
=799.27 KJ/kg
For constant volume process
Heat transferred= (u2-u1)
=799.27-2200.39
= -1401.12 KJ/kg
Total heat transfer= m (u2-u1)
= 1.5*1401.12
= 2101.68 KJ/kg

5. A vessel of volume 0.04m3 contains a mixture of saturated water and saturated

steam at a temperature of 2500C. The mass of the liquid present is 9kg. Find the
pressure, the mass, the specific volume, the enthalpy, the entropy and the internal
energy.(DEC 2011)
Solution:

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Psat =39.7 bar

hf= 1087.4KJ/kg
hg= 2800 KJ/kg
vg= 0.059749 m3/kg
vf= 0.0012486 m3/kg
Sf= 2.7965 kJ/kg K
Sg= 6.0685 kJ/kg K

𝑉 0.04
Mass of steam =M = 𝑉 = 0.059749 = 0.66946 kg
𝑔
M 0.66946
Dryness fraction x=M+m = 9.66946 = 0.0692
Specific volume = vf + x vfg
= vf + x(vg-vf)
=0.0012486+0.0692(0.059749-0.0012486)
= 0.005296 m3/kg
Specific Enthalpy H= hf+xhfg
= hf+ x(hg – hf)
= 1087.4 +0.0692 92800-0.1087)
= 1281.15 kJ/kg
Specific entropy =sf+xsfg
= sf+x (sg-sf)
= 2.7965+0.0692(6.0685-2.7965)
=3.0215kJ/kg K
H= u+pv
u= 1281.15-39.7*102*0.005296
u= 1260.124 kJ/kg
6. A pressure cooker contains 1.5kg of saturated steam at 5bar. Find quantity of heat
which is to be rejected so as to reduce quality to 60% dry. Determine the pressure
and temperature flow state.( DEC 2010)
Solution:
m= 1.5kg
P1= 5bar
x1= 1 saturated
x2= 0.6
hg1= 2748.7 kJ/kg
vg1= 0.3749 m3/kg
x1 vg1= x2 vg2
1*0.3749 = 0.6*vg2
vg2= 0.62483 m3/kg
Corresponding to vg2 =0.62483 m3/kg pressure and temperature are
P2= 2.875bar
T2= 1320C
hf2= 555.16kJ/kg
hfg2=2168.15kJ/kg
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u1= hg1-P1vg1 =2748.7-5*102*0.3749

= 3561.25 kJ/kg
u2= H2-P2x2v2
u2= (hf2+x2hfg2)-P2x2v2
= (555.16+0.6*2168.15)-2.875*102*0.62483
= 1676.42 kJ/kg
Constant volume process: work done is 0.
Heat transfer = u2-u1
= 1676.42-2561.25 = -884.83 kJ/kg
Heat rejected = 884.83 kJ/kg

7. Steam initially at 1.5 MPa, 3000C expands reversibly and adiabatically in a steam
turbine to 400C. Determine the ideal work output of the turbine per kg of steam
( JUNE 2012, DEC. 2013)
Solution:
P1= 1.5 MPa
h1= 3038.9 kJ/kg
S1= 6.9207 kJ/kg K
T1= 3000C
v1= 0.1697 m3/kg
At T2=400C, from saturated tables we have
P2= 0.07375 bar
hf2=167.5 kJ/kg
hfg2= 2406.9 KJ/kg
vg2= 19.546 m3/kg
Sf2= 0.5721 kJ/kg K
Sfg2= 7.6861 kJ/kg K
For reversible adiabatic expansion process
Entropy before expansion = entropy after expansion
S1= Sf2+ x2Sfg2
6.9207= 0.5721+x2*7.6861
x2= 0.825
u1= h1- P1v1
u1 = 3038.9- 1.5*1000*0.1697
= 3013.44 kJ/kg
u2= (hf2+x2hfg2)-P2x2v2
= (167.5+0.825*2406.9) – 0.07375*100*0.825*19.546
= 2034.267 kJ/kg
Q=0
Heat transferred= u2-u1+ work
0= 2034.267-3013.45+work
Work = 979.183 kJ/kg.

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8. 0.1 kg saturated steam expands reversibly from 10 to 1 bar in a piston- cylinder

device according PV1.3= constant. Find the work and heat interaction during
expansion process. (DEC. 2012)
Solution:
P1v11.3 = P2(x2 vg2)1.3
10*(0.19429)1.3= 1(x2*1.6937)1.3
x2= 0.674
𝑃1 𝑣1 − 𝑃2 𝑥2 𝑣2 (10∗102 ∗0.19429)− 1∗102 ∗0.674∗1.6937
work = =
𝑛−1 1.3−1
= 266.95 kJ/kg
u1= h1- P1v1
= 2776.2-10*102*0.19429
= 2581.91 kJ/kg
u2= (hf2+x2hfg2)-P2x2v2
= (417.51+0.674*2257.89)- (1*102*0.674*1.6937)
= 1825.172 kJ/kg
Heat transfer = u2-u1 + work
= -756.737 +266.95
= - 489.98 kJ/kg

9. Steam at 1 MPa and 2500C enters a nozzle with a velocity of 60 m/s and leaves the
nozzle at 10 KPa. Assuming the flow process to be isentropic and the mass flow rate
to be 1 kg/s Determine :
a. The exit velocity
b. The exit diameter of nozzle(JUNE 2013)
Solution:
P1=1MPa=1000KPa C1= 60m/s
P2=10KPa
T1= 2500C
m=1kg/s
At P1=1000KPa and T1= 2500C from superheated steam tables,
h1= 2943 kJ/kg, s1=6.9259kJ/kg K
To find the condition of steam after expansion,
At P2=10KPa from steam tables we get
Sf2 =0.64925 kJ/kg K hf2=191.83 kJ/kg
Sfg2= 7.50185 kJ/kg K hfg2= 2392.97 kJ/kg
Expansion is isentropic.
Entropy before expansion = entropy after expansion (S1=S2)
S1 =sf2+x2 sfg2
6.9259=0.64925+x2*7.50185
x2= 0.8366
h2= hf2+x2*hfg2
=191.83+0.8366*2392.97
=2193.78 kJ/kg

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For a nozzle applying steady flow energy equation

𝐶2 2 −𝐶1 2
q= (h2-h1) + *10-3 +g (z2-z1) +W
2
q=0, z2=z1, W=0
𝐶2 2 −𝐶1 2
(h2-h1) + *10-3=0
2
𝐶2 2 −𝐶1 2
= h1-h2
2000

𝐶2 2 = √𝐶12 + 2000(ℎ1 − ℎ2 )

= √602 + 2000(2943 − 2193.78)

= 1225.57 m/s
From continuity equation
𝐴2 𝐶2
m= 𝑣2
𝑣2 = specific volume V=C= velocity
𝐹𝑟𝑜𝑚 𝑠𝑡𝑒𝑎𝑚 𝑡𝑎𝑏𝑙𝑒𝑠 𝑎𝑡 0.1 𝑏𝑎𝑟
vg2= 14.675 m3/kg
v2= x2*vg2
2𝐴 ∗1225.57
1= 14.675∗0.8362
= 0.010012675 m3
𝜋𝑑22
= 0.010012675
4
d2= 0.129 m= 12.9 cm.

10. A rigid vessel of 2 m3 Volume is filled with superheated steam at 20bar and 3500C.
The vessel is cooled until the steam is just Dry saturated. Calculate the mass of
steam in the vessel: the final pressure of steam and amount of energy transferred as
heat to the surroundings.(JUNE 2014)
Solution:
V= 2m3
For superheated steam at 20bar and 3500C
v1= 0.13866 m3/kg
h1= 3138.6 kJ/kg
x2=1
Volume is constant
v1= vg2 = 0.13866 m3/kg = v2
𝑉 2
Mass= m= 𝑣 = 0.13866 = 14.42 kg
1
Corresponding to vg2 = 0.13866 m3/kg from saturated steam tables we get
P2= 14.5 bar
hg2= 2788.85 kJ/kg
u1= h1- P1v1
=3138.6-20*102*0.13866
= 2861.28 kJ/kg
u2= h2-P2x2v2

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= 2788.85- 14.5*102*0.13866
= 2587.793 kJ/kg
Change in internal energy = m (u2-u1) = 14.42 (2587.793-2861.28)
= -273.487
At constant volume work done is zero
Heat transfer = change in internal energy
= - 273.487 kJ

11. The following observations were recorded in an experiment with a combined

separating and throttling calorimeter. Pressure in the steam main 15bar, Mass of
water drained from the separator 0.55 kg, Mass of steam condensed after throttle
valve 4.2 kg, pressure and temperature after throttling 1 bar, 120 0C. Evaluate the
dryness fraction of the steam in the main.(DEC. 2014, JAN 2015)
Solution:
P1=15 bar P2= 1 bar
hf1= 844.6KJ/kg
hfg1= 1945.3KJ/kg hg2= 2675.4 KJ/kg
0
Tsat2= 99.63 C Tsup2= 1200C (given)
m= mass of water drained from separating calorimeter = 0.55 kg.
M= mass of steam condensed after throttling = 4.2 kg.
𝑀 4.2
x1= 𝑚+𝑀 = 0.55+4.2 = 0.8842
In throttling calorimeter,
Enthalpy before throttling = enthalpy after throttling
hf1+x2 hfg1 = hg2+Cp (Tsup2-Tsat2)
844.6+x2*1945.3 = 2675+2.1 (120-99.63)
x2= 0.963
x= x1*x2
x2= 0.8842*0.963
= 0.8515

12. Identify the type of steam in the following three cases, using the steam tables and
giving necessary calculation supporting your claim.
a. 2kg of steam at 8bar with an enthalpy of 5538.0 KJ at a temperature of
170.40C.
b. 1 kg of steam at 2550KPa occupies a volume of 0.2742 m3. Also find the steam
temperature.
c. 1 kg of steam at 60bar with an enthalpy of 2470.73kJ/kg. ( JULY 2015)
Solution:
a. m=2kg
p= 8bar
T=170.40C
5538
H= 5538 kJ = = 2769 kJ/kg
2
From steam tables at 8bar and 170.40C value of hg = H hence steam is saturated.

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b. From steam tables at a pressure of 2550kpa.

Vg=0.079915m3/kg Tsat=223.940C= 496.94 K
Since given volume is more than vg the steam is super heated
𝑃𝑉 𝑃𝑉
( 𝑇 )sup= ( 𝑇 )sat
0.2742∗496.94
Tsup= = 1704 K=14310C
0.079915
c. m=1kg
P=60bar
H= 2470.73kJ/kg
From steam tables at p=60bar, we get hg= 2609.7 kJ/kg
Since H< hg steam is wet.

13. Steam initially at a pressure of 15bar and 0.95 dry expands isentropically to 7.5 bar
and then throttled until it becomes just dry and saturated. Determine per kg of steam:
i) Change in internal energy
ii) Change in enthalpy
iii) Change in entropy(JUNE 2010)

Solution:
Process 1-2 isentropic
P1= 15 bar P2= 7.5 bar
hf1=844.6KJ/kg hf2=2055.7KJ/kg
hfg1= 1945.3KJ/kg hfg2= 2055.7KJ/kg
Sf1=2.3144 KJ/kg K Sf2=2.0187 KJ/kgK
Sfg1= 4.1272 KJ/kg K Sfg2= 4.6636 KJ/kg K
3
vg1= 0.13167 m /kg vg2= 0.25647 m3/kg
x1= 0.95
x1 vg1= x2 vg2
Entropy before expansion = Entropy after expansion
Sf1+x1 Sfg1= Sf2+x2 Sfg2
2.3144+0.95*4.1262=2.0187+x2*4.6636
x2= 0.9039
H1= hf1+x1hfg1
=844.6+0.95*1945.6
=2692.635KJ/kg
u1= H1-p1x1vg1
= 2692.635-15*100*0.13167*0.95
=2505.5KJ/kg
H2= 709+0.9039*2055.7
=2567.147 KJ/kg
u2= H2-p2x2vg2
=2567.147-7.5*100*0.9039*0.25647
=2393.123 KJ/kg
S1= sf1+x1+sfg1

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=2.3144+0.95*4.126
= 6.2342 KJ/kg K
Process 2-3 Throttling
x3= 1(dry saturated)
During throttling enthalpy is constant
hg3=H2=2567.143 KJ/kg
From steam tables, corresponding to hg = 2567.143
P3= 0.05 bar.
Sg3= 28.1945 m3/kg
U3=hg3-P3vg3 =2567.143-0.05*100*28.1945
= 2426.17 KJ/kg
Total change in enthalpy = H3-H1
= 2567.143-2692.635
= -125.48 KJ/kg
Total change in internal energy = u3-u1 = 2426.17-2505.5KJ/kg
Total change in enthalpy = s3-s1=8.396-6.2342 = 2.1617 KJ/kg K

14. Steam at 1bar and dryness fraction of 0.523 is heated in a rigid vessel until it
becomes saturated vapour. Calculate the heat transferred per kg of steam.(JAN 2016)
Solution:
P1= 1 bar
X1= 0.523
Hf1= 417.44 KJ/kg
Hfg1=2258 KJ/kg
vg1= 1.694 m3/kg
P2= 1 bar
x2= 1
H2= hg2= 2675.44 kJ/kg
H1= hf1+x1*hfg1
= 417.44+0.523*2258
= 1598.374kJ/kg
Heat transferred H2-H1 = 2675.44-1598.374
= 1077 kJ/kg

15. Determine the amount of heat, which should be supplied to 2 kg of water of 25 0C to

convert it into steam at 5 bar and 0.9 dry.(JAN 2018)
Solution:
m= 2kg
T1=250C
x=0.9
At 5 bar from steam tables
Hf = 640.12 KJ/kg
Hfg =2107.38 KJ/kg
H2= hf+x*hfg

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= 2536.762 kJ/kg
H1= enthalpy of water at 250C
= 104.77 KJ/kg
Heat required to convert 1 kg of water at 250C to wet steam = m (H2-H1)
= 2(2536.762-104.77)
= 4863.984 kJ
16. A rigid tank of 2m3 volume is filled with dry saturated steam at 0.2 MPa. Owing to
poor insulation of the tank, the pressure of steam is found to be 0.1 MPa after
sometime. Determine the final state of steam and the amount of energy transferred as
heat to the surroundings.(JUNE 2016)
Solution:
V= 2m3
P1=0.2MPa = 200 KPa
From steam tables
vg1= 0.8857 m3/kg
hg1= 2706.7 kJ/kg
x1=1
vg1= 0.8857 m3/kg
𝑉 2
Mass= m = 𝑣 = 0.8857 = 2.258 kg
𝑔1

P2= 0.1 MPa

vg2= 1.694m3/kg
hf2= 417.46 KJ/kg
hfg2= 2258 KJ/kg
Volume is constant.
V1=V2
vg1=x2*vg2
0.8857
x2= 1.694
= 0.5228
u1= hg1- P1vg1
=2706.7-200*0.8857
= 2529.56 kJ/kg
h2= hf2+x2*hfg2
=417.46+0.5228*2258
=1597.94KJ/kg
u2= h2-P2x2v2
= 1597.94- 1*102*1.694*0.5228
= 1509.38 kJ/kg
Change in internal energy = m (u2-u1) = 2.258 (1509.38-2529.56)
= -2303.56KJ
At constant volume work done is zero
Heat transfer = change in internal energy
=-2303.56 kJ

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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 (Processes are not to be asked for SEE).
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.
Thermodynamic relations: Maxwell’s equations, TdS equation. Ratio of Heat capacities and
Energy equation, Joule-Kelvin effect, Clausius-Clapeyron equation.

IDEAL GAS
An ideal gas is a gas having no forces of intermolecular attraction. The gases which follow
the gas laws at all range of pressures and temperatures are considered as ‘ideal gases’.
Consider a mixture of perfect gases a, b, c etc,existing in equilibrium at pressure P and
occupying a volume V at temperature T. Each constituent occupies the same volume that the
entire mixture occupies and each constituent is at the same temperature of the mixture.
PV=mRT
Where,
P= Pressure
V= Volume
m=mass
T=Temperature
R= Gas constant

The total mass of the mixture is equal to the sum of the masses of the individual gasses.
m=ma+mb+mc

Mass Fraction
It is the ratio of the mass of the constituent gas to the total mass of the mixture of perfect
gasses.

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𝒎𝒂 𝒎 𝒎
mfa= , mfb= 𝒎𝒃 , mfc= 𝒎𝒄
𝒎

mfa+mfb+mfc=1
The sum of the parts of mass fractions of the constituents in a mixture equals to unity.
Note:
When an analysis of gas mixture is made on the mass basis, it is called a gravimetric
analysis.

Mole fraction
The total number of moles of the mixtures is equal to the sum of the moles of the
individual gases.
n = na+ nb+ nc
The mole fraction of any component is the ratio of the number of moles of the
constituent’s gas to the total number of moles of the mixture of perfect gases.
𝒏𝒂 𝒏𝒃 𝒏𝒄
Xa= , Xb = , Xc=
𝒏 𝒏 𝒏
Xa+Xb+Xc=1

Gibb’s Dalton’s law

The total pressure of a mixture of perfect gases is equal to the sum of the partial
pressures of the constituent’s gases.
P= Pa +Pb+ Pc

Dalton’s law of partial pressure

The partial pressure of a gas in a mixture of perfect gases is the pressure that it
would exert if it alone occupied the whole volume of the mixture at the same temperature.
Consider a homogenous non reacting mixture of ideal gases a, b, c etc. at temperature
T, pressure P and occupying volume V.
Let us assume that each constituent of the mixture exists separately at temperature T and
volume V and pressure Pa, Pb, Pc etc. excerted by individual gases are measured separately.
An ideal gas may be defined as a substance that has the equation of state
Pv=RT (1)

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R is a constant having a particular value for each substance, and is called gas constant.
Multiply both sides of equation (1) by mass m; we get
PV=mRT (2)
The mass of a substance is equal to the product of the number of moles and the molecular
weight.
m =n x M (3)
Substituting in equation (2)
PV=nMRT
Product MR is a constant for all ideal gases and is called the universal gas constant denoted
by Rmol. Or 𝑅̅
For the constituent gases
PaV=naRmolT (4)
PbV=nbRmolT (5)
PcV=ncRmolT (6)
Adding (4),(5) and (6)
(Pa+Pb+Pc+…)V = (na+nb+nc+…)RmolT
From Dalton’s law of partial pressures,
P= Pa +Pb+ Pc
PV = nRmolT
(P=∑𝒊 𝐏𝐢 )
𝒏𝐢𝐑𝐦𝐨𝐥𝐓
Where, Pi = 𝐕
Represents the pressure component I would exert. This is called partial pressure of the ith
component of the gas mixture.

Amagat’s law
It states the sum of the partial volume of the constituent gases is equal to the total volume of
the mixture of perfect gases.
V=Va+Vb+Vc

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Volume fraction of any constituent gas is defined as the ratio of the volume of the constituent
gas to the total volume of the mixture of perfect gases.
𝐕𝒂 𝐕𝒃 𝐕
Vfa = , Vfb = , Vfc = 𝐕𝒄
𝐕 𝐕
Vfa+ Vfb+ Vfc= 1

Expression for gas constant R

For the mixture of gases
PV=mRT
For the constituent gases
PaV=naRaT
PbV=nbRbT
PcV=ncRcT
But from Dalton’s law of partial pressures.
P= Pa +Pb+ Pc

𝐦𝐑𝐓 𝐦𝐚 𝐑 𝐚 𝐓 𝐦𝐛 𝐑 𝐛 𝐓 𝐦𝐜 𝐑 𝐜 𝐓
= + +
𝐕 𝐕 𝐕 𝐕

𝒎 𝒎𝒃 𝒎𝒄
R= 𝒎𝒂 Ra + Rb + Rc
𝒎 𝒎

R = mfa Ra + mfbRb + mfcRc

Expression for Average molecular weight M

The mass of a substance is equal to the product of the number of moles and the molecular
weight.
For mixture of gases
m= nM (1)
Where, m=total mass of the mixture
n=number of moles of the mixture
M= Average Molecular weight of the mixture
For the constituent gases
ma =naMa (2)
mb = nbMb (3)
mc = ncMc (4)
But m= ma +mb+ mc
Substitute (1),(2),(3) and (4) in above equation
nM = naMa +nbMb + ncMc
𝒏𝒂 𝒏𝒃 𝒏
M= Ma + Mb + 𝒏𝒄 Mc
𝒏 𝒏
M= XaMa + XbMb +XcMc

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Where,
𝐕𝐚 𝒏𝒂 𝐏𝐚
Xa = = = = Mole fraction
𝐕 𝒏 𝐏

For mixture of perfect gases show that partial pressure ratio=mole fraction=volume
fraction
For the mixture
PV=mRT
PV=nMRT (m=Nm)
PV=n𝑹 ̅T (1)
For the constituent gas a
PaV=na𝑹 ̅T (2)
(2) / (1)
𝑷𝒂 𝒏𝒂
We get = =𝑿𝒂 = Mole f (3)
𝑷 𝒏
Again, For the mixture
PV=n𝑹̅T (4)
̅T
P𝑽𝒂 =na𝑹 (5)
(5)/(4)
𝐕𝐚 𝒏𝒂
We get, = = 𝑿𝒂 = Mole fracti (6)
𝐕 𝒏
From (3) and (6)
𝐕𝐚 𝒏𝒂 𝐏𝐚
Xa = = = = Mole fraction
𝐕 𝒏 𝐏

Internal energy and specific heats of an ideal gas mixture

The internal energy of a mixture of ideal gases is equal to the sum of the internal energies of
the constituent gases at the same pressure and temperature of the mixture
U=𝑼𝒂 + 𝑼𝒃 + 𝑼𝒄
𝑼
mu= maua+mbub+mcuc But u= 𝒎 U= mu
Differentiating, we get
mdu= madua+mbdub+mcduc
But, du= CvdT
m CvdT=maCvadT+ mbCvcdT+ mcCvcdT
𝒎𝒂 𝒎 𝒎
Cv= Cva + 𝒎𝒃Cvb + 𝒎𝒄Cvc
𝒎
Cv=mfa Cva +mfbCvb +mfcCvc

Enthalpy of an ideal gas mixture

The enthalpy of a mixture of perfect gases is equal to the sum of the enthalpies of the
constituent gases
H=𝑯𝒂 + 𝑯𝒃 + 𝑯𝒄

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𝑯
mh= maha+mbhb+mchc But h= 𝒎 H= mh
Differentiating, we get
mdh= madha+mbdhb+mcdhc
But, dh= CpdT
m CpdT=maCpadT+ mbCpcdT+ mcCpcdT
𝒎𝒂 𝒎 𝒎
Cv= Cpa + 𝒎𝒃Cpb + 𝒎𝒄Cpc
𝒎
Cv=mfa Cpa +mfbCpb +mfcCpc

Entropy of an ideal gas mixture

The entropy of a mixture of perfect gases is equal to the sum of the entropies of the
constituent gases
S=𝑺𝒂 + 𝑺𝒃 + 𝑺𝒄
𝑺
ms= masa+mbsb+mcsc But s= 𝒎 S= ms
Differentiating, we get
mds= madsa+mbdsb+mcdsc
𝒎𝒂 𝒎 𝒎
Cv= dsa + 𝒎𝒃dsb + 𝒎𝒄dsc
𝒎
Cv=mfa dsa +mfbdsb +mfcdsc
𝑻 𝑷
But dsa = [𝑪𝒑 𝒍𝒏 𝑻𝟐 − 𝑹𝒍𝒏 𝑷𝟐 ]
𝟏 𝟏

REAL GASES
A real gas is one which does not obey the ideal gas equation PV = mRT at all temperature
and pressures. No real gas actually follows the ideal gas equation of state at all ranges of
pressure and temperature.
The behavior of real gas approaches closely that of the ideal gas provided the following
assumptions are valid:
1. Any finite volume of a gas consists of a very large number of molecules.
2. The molecules are separated by distances large compared to their own dimensions and
are in a state of continuous motion.
3. Molecules exert no force on one another except when they collide.
4. Collisions of molecules with one another and with the walls of the container are
perfectly elastic.

Compressibility Factor
The deviation from ideal gas behavior at a given temperature and pressure can be
accurately predicted by the introduction of a correction factor called the compressibility
factor.
𝐏𝐯
Z = 𝐑𝐓

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For an ideal gas Z=1. For a real gas the value of Z is a measure of the deviation of the real
gas from the ideal gas.

Law of corresponding states

The ratio of pressure, temperature and specific volume of a real gas to the corresponding
critical values are called reduced properties.
𝐓
Reduced property Temperature TR = 𝐓𝐜
𝐏
Reduced property Pressure PR = 𝐏𝐜
𝐕
Reduced property Volume VR= 𝐕𝐜
Where,
R = reduced property
C = critical state
The compressibility factor of any one component substance is a function of only two
properties, usually temperature and pressure so that
Z= f (TR, PR)
This equation is called the law corresponding states.
Generalized compressibility chart
In this the compressibility factor Z is plotted as a function of reduced pressure and
temperature. According to these charts, one component substance which is at same reduced
pressure and temperature has the same compressibility factor.
It provides the deviation from ideal behavior and gives results with an accuracy of within 5
percent.
A gas which has a compressibility factor less than unity is more compressible than a perfect
gas

Vander Waal’s equation

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Real gases differ from ideal ones due to pressure of the intermolecular forces and also to the
finite molecular volumes. There are two corrections into the equation of state, Pv = RT,
𝐑𝐓
 Let the equation of state be presented in the form, v = , with increasing pressure,
𝐏
the volume decreases and if p→∞, then v→0. The molecules occupy a finite volume
and an allowance also needs to be made for the volume of voids existing between the
molecules. The finite volume available for molecular motion shall be equal to (v-b).
Where b= Vvoid. The quantity b represents the smallest volume to which the gas can
be compressed.
 Compared to an ideal gas the pressure exerted by a real gas will be smaller by a
quantity ∆P. This is directly proportional to the square of the density of gas, can
inversely proportional to the square of its specific volume.
𝒂
∆P = 𝒗𝟐 = aρ2
When these two corrections are introduced, we obtain the varder-waals equation of state.
𝒂
[P+𝒗𝟐] [v-b] = RT
b= to correct for the volume occupied by the gas molecules.
𝒂
= is a correction for the molecular forces.
𝒗𝟐
If the volume of one mole is considered, then the above equation can be written as,
 a
 P  v 2  v  b   R T
 

Determination of vander waal’s constants

The constants a and b can be estimated based on the behavior of pure substances at the
critical point
The constants at the critical point is given by
𝐝𝟐 𝐏 𝐝𝐏
(𝐝𝐯𝟐 )c = 0, ( 𝐝𝐯 )c = 0
From Vander waal’s equation
𝐑𝐓 𝐚
P = (𝐯−𝐛) – (𝐯𝟐 ) (1)
Differentiating equation (1) we get
𝐝𝐏 𝐑𝐓 𝟐𝐚
(𝐝𝐯 ) = - (𝐯−𝐛)𝟐 +𝐯𝟑
Differentiating above equation again
𝒅𝟐 𝑷 𝟐𝑹𝑻 𝟔𝒂
( 𝒅𝒗 ) = (𝒗−𝒃)𝟑 - 𝒗𝟒
Now
𝐝𝐏 𝐑𝐓
𝐜 𝟐𝐚
(𝐝𝐯 )c = - (𝐯 −𝐛)𝟐 +𝐯𝟑 = 0
(2)
𝐜 𝐜

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𝟐𝐚
RTc = 𝐯𝟑 ( vc –b)2 (3)
𝐜

Differentiating equation (2) we get

𝒅𝟐 𝑷 𝟐𝑹𝑻𝒄 𝟔𝒂
( 𝒅𝒗 )c = (𝒗 𝟑
- 𝒗𝟒 (4)
𝒄 −𝒃) 𝒄

𝟑𝒂
RTc = 𝒗𝟒 (vc – b)3 (5)
𝒄

From (3) and (5)

𝟐𝐚 𝟑𝒂
( vc –b)2 = (vc – b)3
𝐕𝐜𝟑 𝑽𝟒𝒄
2vc =3vc – 3b
vc= 3b (6)
Substituting (6) in (5)
𝟑𝒂 𝟖𝒂
RTc = (𝟑𝒃)𝟒(3b – b)3 = 𝟐𝟕𝒃
𝟖𝒂
Tc =𝟐𝟕𝒃𝑹 (7)
Substituting (6), (7) in (1)
𝐜 𝐑𝐓 𝐚
Pc = (𝐯 −𝐛 ) – (𝐯 𝟐 )
𝐜 𝐜
𝐑𝟖𝐚 𝐚 𝟒𝐚 𝐚 𝟒𝐚−𝟑𝐚
Pc = 𝟐𝟕𝐛𝐑(𝟑𝐛−𝐛) - (𝟑𝐛)𝟐 = 𝟐𝟕𝐛𝟐 - 𝟗𝐛𝟐 = 𝟐𝟕𝐛 𝟐

𝐚
Pc = 𝟐𝟕𝐛𝟐 (8)
From (6), (7) and (8)
From (8), a = 𝟐𝟕𝐛𝟐 Pc
𝟐𝟕𝒃𝑹𝑻𝒄
From (7), a= 𝟖
Equating a value
𝟐𝟕𝒃𝑹𝑻𝒄
𝟐𝟕𝐛𝟐 Pc = 𝟖
𝟏 𝐑𝐓𝐜
b= 𝟖 𝐏𝐜
Substituting b value in a value
𝟏 𝐑𝐓𝐜 𝟐
a = 27(𝟖 ) Pc
𝐏𝐜
𝟐𝟕 𝐑𝟐 𝐓𝐜𝟐
a = 𝟔𝟒 𝐏𝐜
𝟑 𝐑𝐓𝐜
vc=3b =𝟖 𝐏𝐜
𝟖 𝐏𝐜 𝐕𝐜
R= 𝟑 𝐓𝐜

Other Real gas equations

Beattie- Bridgeman Equation of State
̅𝑻
𝑹 𝑪 𝑨
P= ̅𝟐
(1- 𝑻𝟑 𝒗̅) (𝒗̅ + B) - 𝑽̅𝟐
𝒗

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𝒂
Where, A= A0 (1- 𝒗̅)
𝒃
B = B0 (1- 𝒗̅)
The constants A0, a, B0, b and c are given in tables.

Benedict- Webb- Rubin Equation of state

̅𝐓 ̅ 𝐓−𝐚 𝐯
𝐑 𝐂 𝟏 𝐛𝐑 𝐚𝛂 𝐜 𝚼 − 𝟐
P= ̅ 𝐓-A0- 𝟎𝟐 ) 𝟐 +
+ (B0𝐑 + 𝐯̅𝟔 + 𝐯̅𝟑 𝐓𝟐 (1- 𝐯̅𝟐 ) 𝐞 𝐯̅
𝐯̅ 𝐓 𝐯̅ 𝐯̅ 𝟑
Where constants a, A0, b, B0, c, C0, α and Υ are given in tables.
Table : Constants for Vander waals equation of state
Gas A B Zc = Pc v c / RTc
Kn-m4 /kg mol) 2 m3 /kg mol
Air 135.80 0.03665 0.284
O2 138.00 0.0318 0.290
N2 136.70 0.0386 0.291
H2O 551.70 0.0304 0.230
CH4 228.60 0.0427 0.290
CO 147.90 0.0393 0.293
CO2 365.60 0.0428 0.276
NH3 424.90 0.0373 0.242
H2 24.80 0.0266 0.304
He 3.42 0.0235 0.300

Table : Selected critical constants

Gas Tc Pc Vc
K Mpa (m3/kg mol ) ×102
Air 132.41 3.774 8.30
O2 154.78 5.080 7.43
N2 126.20 3.398 8.99
H2O 647.27 22.105 5.68
CH4 190.70 4.640 9.93
CO 132.91 3.496 9.30
CO2 304.20 7.386 9.55
NH3 405.40 11.277 7.24
H2 33.24 1.297 6.49
He 5.19 0.229 5.81

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Constants for Beattie –Bridgeman equation of state

Gas A0 A B0 b 104C
Helium 2.1886 0.05984 0.01400 0.0 0.0040
Argon 130.7802 0.02328 0.03931 0.0 5.99
Hydrogen 20.0117 -0.00506 0.02096 -0.04359 0.0504
Nitrogen 136.2315 0.02617 0.05046 -0.00691 4.20
Oxygen 151.0857 0.02562 0.04624 0.004208 4.80
Air 131.8441 0.01931 0.04611 -0.001101 4.34
CO2 507.2836 0.07132 0.10476 0.07235 66.00
CH4 230.80 0.01850 0.0590 -0.01580 12.82

Difference between ideal and real gases

Ideal gas Real gas
Ideal gas has no definite volume Real gas has definite mass
Ideal gas has no mass Real gas has mass
Collision of ideal gas particles is elastic Collision of real gas particles is non elastic
No energy involved during collision of Collision of particles involves energy transfer
particles in ideal gas
Pressure is high in ideal gascompared to real Pressure is low compared to ideal gas
gas
𝑎
Ideal gas follows the equation PV=mRT Real gas follows the equation [P+𝑣2 ] [v-b] =
RT

Gibbs and Helmholtz functions

The Helmholtz function defined as F = U – TS
For an infinitesimal reversible process
dF = dU – TdS –SdT (1)
𝜹𝑸
From first law, 𝜹𝑸 = 𝒅𝑼 + 𝜹𝑾, Entropy change , dS= 𝑻
𝜹𝑾 = 𝑷𝒅𝑽
Then Equation 1 becomes
TdS = dU +PdV (2)
Substituting (2) in (1)
dF = dU – dU – PdV–SdT
dF = - PdV–SdT
For a reversible isothermal process dF = - PdV
𝟐
F2 – F1 = - ∫𝟏 𝑷𝒅𝑽
Hence the change of the Helmholtz function during a reversible isothermal process equals
work done on the system. For a reversible isothermal and isochoric process,
dF = 0 and F= constant
These properties are useful in considering chemical reactions that take place isothermally and
isochorically.
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The Gibbs function is defined as G = H – TS

For an infinitesimal reversible process
dG = dH - TdS – SdT, (1)
Enthalpy H=U+PV
dH= dU+PdV+VdP
dU=dH-PdV-VdP
𝜹𝑸
From first law, 𝜹𝑸 = 𝒅𝑼 + 𝜹𝑾, Entropy change , dS= 𝑻
𝜹𝑾 = 𝑷𝒅𝑽
Then
TdS= dH-PdV-VdP+PdV
TdS= dH-VdP
dH = TdS + VdP (2)
Substituting (2) in (1)
dG = TdS + VdP – TdS – SdT
dG = -SdT + VdP
In the case of a reversible isothermal and isobaric process dG = 0 and G – constant.
This is a particularly important result in connection with processes involving a change of
phase.

Maxwell relations
Internal energy changes by an amount
dU = dQ – PdV, or dU = TdS – PdV
Where, U, T and P are all considered to be function of S and V.
Enthalpy changes by an amount
dH= dU + PdV +VdP, ordH = TdS + VdP
Where, H, T and V are all considered to be functions of S and P.
The Helmholtz function changes by an amount
dF =dU – TdS – SdT, or dF = - SdT – PdV
Where, F, S and P are all considered to be functions of T and V.
Gibbs function changes by an amount
dG = dH –TdS – SdT, ordG = - SdT + VdP
Where, G, S and V are all imagined to be the function of T and P.
Since U,H, F and G are actual functions, their differentials are exact differentials of the type
dz= Mdx+Ndy
where, z,M and N are all functions of x and y
𝜕𝑀 𝜕𝑁
∴( )=( )
𝜕𝑦 𝜕𝑥
Differentials dU, dH, dF and dG, we get
𝑻 𝑷
1. dU = TdS – PdV, Hence ( 𝑽)s = - (  𝑺)V
𝑻 𝑽
2. dH = TdS + VdP , Hence ( 𝑷)S=(  𝑺)P
𝑺 𝑷
3. dF = - SdT – PdV, Hence ( 𝑽)T= ( 𝑻)V

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𝑺 𝑽
4. dG = - SdT + VdP, Hence ( 𝑷)T= - ( 𝑻)P

The four equations on the right are known as Maxwell’s equations.

Clapeyron Equation
The clapeyron equation is an important relation involving the saturation pressure and
temperature, the enthalpy of evaporation and the specific volume of the two phases involved.
Consider the Maxwell’s third relation,
𝑺 𝑷
( 𝑽)T= ( 𝑻)V
Consider for example change of state from saturated liquid to saturated vapour of a pure
substance. This is a constant temperature process and therefore equation above equation can
be integrated between saturated liquid and saturated vapour state. Also when saturated state
are involved pressure and temperature are independent of volume.
𝑷 𝒅𝑷 (𝑺𝒈 −𝑺𝒇 ) 𝑺
( 𝑻)V= 𝒅𝑻 = (𝑽 = 𝒇𝒈
𝒈 −𝑽𝒇 ) 𝑽 𝒇𝒈

Sfg x T = L =hfg(latent heat)

𝐝𝐏 𝐡
= 𝐓(𝐕 𝐟𝐠−𝐕 )
𝐝𝐓 𝐠 𝐟

This is called clapeyron equation between liquid and vapour phases.

𝐝𝐏 𝐡
Between solid and liquid Phase 𝐝𝐓 = 𝐓(𝐕 𝐬𝐟−𝐕 )
𝐟 𝐬
Clausius Clapeyron Equation
𝐝𝐏 𝐡
= 𝐓(𝐕 𝐟𝐠−𝐕 )
𝐝𝐓 𝐠 𝐟

When Vg> 𝑉𝑓 Vg-Vf = Vg

𝐝𝐏 𝐡 𝐡𝐟𝐠 𝑹𝑻
= 𝐓𝐕𝐟𝐠 = 𝑹𝑻 Where Vg =
𝐝𝐓 𝐠 𝑻( ) 𝑷
𝑷
𝐝𝐏 𝐏𝐡𝐟𝐠
=
𝐝𝐓 𝐑𝐓 𝟐
Rearranging the terms
𝒅𝑷 𝒉𝒇𝒈 𝒅𝑻
=
𝑷 𝑹𝑻𝟐
Integrating the above equation
𝑷𝟐 𝒅𝑷 𝒉𝒇𝒈 𝑻𝟐 𝒅𝑻
∫𝑷 = ∫𝑻
𝟏 𝑷 𝟏 𝑻𝟐 𝑹
𝑷 𝒉 𝒇𝒈 −𝟏 𝑻
ln(𝑷)𝑷𝟐𝟏 = 𝑹 ( 𝑻 )𝑻𝟐𝟏
𝑷 𝒉 𝟏 𝟏
ln𝑷𝟐= 𝑹𝒇𝒈 [𝑻 − 𝑻 ]
𝟏 𝟏 𝟐
𝒉𝒇𝒈 𝟏
lnP= (𝑻)+Constant
𝑹

Joule – Thomson Coefficient

In a throttling process enthalpy remains constant whereas pressure and temperature varies.
Inversion Point:The point where the slope of the curve changes from positive to negative is
called an inversion point.

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Inversion Curve: If we draw the T vs P curve for different values of enthalpy (h) we get a
number of inversion points. The curve passing through all the inversion point is called the
inversion curve.

General relations for change in entropy, enthalpy, internal energy and specific heats.
Specific Heat of Ideal Gases:
From the definition of specific heat at constant volume and the specific heat at constant
pressure,
𝒅𝒖
Cv= 𝒅𝑻= f (T)
𝒅𝒉
Cp= 𝒅𝑻= f (T)
as u and h are functions of temperature, From the above equations, du = CV dT and dh = CP
dT For a mass of m kg of gas the equations becomedU = m cV dT and dH = m CP dT
On integrating we get,
𝑻
U2-U1=m∫𝑻 𝟐 𝑪𝒗 𝒅𝑻
𝟏
𝑻
H2-H1=m∫𝑻 𝟐 𝑪𝒑 𝒅𝑻
𝟏
Relation between specific heats for an ideal gas
For an ideal gas h =u+Pv= u + RT since Pv=RT
Therefore
𝒅𝒉 𝒅𝒖
= (𝒅𝑻) + 𝑹 (1)
𝒅𝑻
𝒅𝒖
But Cv= 𝒅𝑻= f (T)
𝒅𝒉
Cp= 𝒅𝑻= f (T)
CP= CV + R
CP - CV = R (2)
Dividing the equation (2) by CV, we get,
𝑹 𝑪𝒑
γ-1=𝑪 =𝜸
𝒗 𝑪𝒗
𝑹
or Cv= 𝜸−𝟏
Similarly, dividing the equation (2) by CP, we get
𝜸𝑹
Cp= 𝜸−𝟏
Change in internal energy

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Let an ideal gas of fixed mass m undergoes a finite change of state from temperature T1 to
temperature T2. Then the change in internal energy is given by
𝟐 𝑻
U2-U1= m (u2-u1) = m∫𝟏 𝒅𝒖 = m∫𝑻 𝟐 𝑪𝒗 𝒅𝑻
𝟏
To integrate the above equation we should know the functional relationship between CV and
dT. A perfect gas equation is one for which Cv is a constant.
Therefore, U2-U1= m Cv (T2 – T1).
Change in Enthalpy
𝟐 𝑻
We have H2-H1 = m (h2-h1) = m∫𝟏 𝒅𝒉 = m ∫𝑻 𝟐 𝑪𝒑 𝒅𝑻
𝟏
For a perfect gas CP is constant. Therefore the above equation can be integrated and we get
H2-H1= m CP (T2 – T1).
Change in Entropy
Let P1, v1, T1, S1 apply to the initial conditions of certain amount of gas. P2, v2, T2, S2, apply
to the final conditions after adding some heat.
From first law of TD,
δq = δw + du
δq = P.dv + du
Also by definition, du = Cv dT
Therefore δq = Pdv + CvdT (1)
Divide eqn (1) by T,
𝒅𝒒 𝒅𝑽 𝒅𝑻 𝜹𝒒
=P + Cv But =dS
𝑻 𝑻 𝑻 𝑻
𝑷 𝒅𝑻
dS= 𝑻 dV + Cv 𝑻
From perfect gas equation for unit mass of gas, Pv = RT, therefore P/T = R/v
𝑹 𝒅𝑻
dS= 𝑽 dV +Cv 𝑻
Therefore integrating,
𝟐 𝟐 𝐝𝐕 𝟐 𝐝𝐓
∫𝟏 𝐝𝐒 = ∫𝟏 𝐑 𝐕
+ ∫𝟏 𝐂𝐯 𝐓
i.e., the change in entropy is given by
𝑽 𝑻
S2-S1 = R ln𝑽𝟐 + Cv ln𝑻𝟐 (2)
𝟏 𝟏
Equation (2) also can be expressed in terms of pressure and volume.
𝑷𝟏 𝑽𝟏 𝑷𝟐 𝑽𝟐
=
𝑻𝟏 𝑻𝟐
𝑻𝟐 𝑷𝟐 𝑽𝟐
=𝑷 𝑽
𝑻𝟏 𝟏 𝟏
Substituting this in equation (2) we get,
𝑽 𝑷
S1-S2 = ( Cv+R) ln𝑽𝟐 + Cv ln 𝑷𝟐
𝟏 𝟏
But CP – Cv = R, i.e., Cv + R = CP
𝑽 𝑷
S1-S2 = Cp ln 𝑽𝟐 +Cv ln 𝑷𝟐 (3)
𝟏 𝟏
Equation (2) can also be represented in terms of temperature and volume.
𝑷𝟏 𝑽𝟏 𝑷𝟐 𝑽𝟐
=
𝑻𝟏 𝑻𝟐
𝑽𝟐 𝑷𝟐 𝑻𝟐
=𝑷
𝑽𝟏 𝟏 𝑻𝟏

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Substituting this in equation (2) we get

𝑷 𝑻𝟐 𝑻
S1-S2 = R ln 𝑷𝟏 + Cv ln 𝑻𝟐
𝟐 𝑻𝟏 𝟏
𝑻𝟐 𝑷𝟐
Or S1-S2 = Cp ln 𝑻 - R ln 𝑷 (4)
𝟏 𝟏

Theory Questions:
1. Write a note on compressibility factor and compressibility chart. (AUG
2001)(FEB.2003)
2. Write down Vander Waal’s and Bridege man equation.( AUG 2001)
3. Define critical properties and reduced properties.(MARCH 2001)
4. What do you mean by reduced Properties?( FEB 2003)
5. Obtain expressions for the constants a, b and R in terms of the critical properties for a
vander waal gas (DEC 2011, JUNE/JULY 2019,DEC/JAN 2019,JUNE/JULY 2019)
6. Write a note on compressibility factor and compressibility chart. (DEC 2011)
7. State Gibb’s Dalton Law of partial pressures and hence derive and expression for the
gas constant R of a mixture of gases.(JUNE 2012)
8. Write a brief note on compressibility factor and compressibility chart. (JUNE 2012)
9. Explain the following:
i. Compressibility factor(JUNE/JULY 2019)
ii. Law of corresponding states(JUNE/JULY 2019)
iii. Compressibility chart
iv. Vander waals equation of state.(DEC 2012)
10. State and explain Amagat’s law.(JUNE 2013)
11. State and explain Law of corresponding states.(JUNE 2013)
12. Explain the following:
i. Generalized compressibility chart
ii. Law of corresponding states
iii. Compressibility factor.(DEC 2013)
13. Derive Van der wall’s constants in terms of critical properties.(DEC 2013)
14. Write notes on the following:
i. Dalton’s law of partial Pressures. (JUNE/JULY 2019)
ii. Van der waal’s equation of states.
iii. Generalized compressibility chart.(JUNE 2014, DEC 2018)
15. Explain :
i. Dalton’s law of partial Pressures.
ii. Amagat’s Law of additive volumes
iii. Law of corresponding states.
16. Ideal gas (DEC 2014, JUNE/JULY 2019, (DEC/JAN 2019)
17. Explain generalized compressibility chart.(DEC 2014)

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18. Write notes on the following;

i. Compressibility factor
ii. Compressibility chart.
iii. Law of corresponding states
iv. Real gas.(JUNE 2015, JUNE/JULY 2019 )
19. Define the terms partial pressure, mole fraction and volume fraction of gas
constituent in a mixture.(JUNE 2015)
20. Define the following terms
i. Saturated air ii. Wet bulb temperature iii. Specific humidity iv. Dew point
temperature (JUNE/JULY 2019)
21. Derive an expression for the change in entropy of an ideal gas(JUNE/JULY 2019)
22. Define i. DBT ii.WBT iii. Specific humidity iv. Relative humidity(DEC/JAN
2019)
23. Write a note on Maxwell’s relations(DEC 2017/JAN 2018,DEC 2016/JAN 2017,JUNE /JULY
2016)
24. Write maxwell’s relations and their importance in thermodynamics(DEC2016/JAN
2017)
25. Derive Clausius Clapeyron equation for evaporation of liquid and explain the
significance (DEC 2016/JAN 2017,JUNE/JULY 2016)

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Problems
1. A mixture of gases contains 1kg of CO2 and 1.5 kg of N2. The pressure and
temperature of the mixture are 3.5 bar and 270C. Find
a) The mass and mole fraction of each constituent gas.
b) Average molecular weight
c) The partial pressure.
d) The specific gas constant
e) The volume
f) The density
g) The partial volume and volume fraction(JUNE 2012)

Solution:
𝑚𝐶𝑜2 = 1kg
𝑚𝐶𝑜2 = 1.5 kg
P1 = 3.5 bar
T1 = 270C =300K
𝑚𝑐𝑜2 1
Mass fraction 𝑚𝑓𝐶𝑜2 = = (1+1.5) = 0.4
𝑚

𝑚 𝑁2 1.5
𝑚𝑓𝑁2 = = (1+1.5) = 0.6
𝑚

𝑚𝑐𝑜2 1
Number of moles 𝑛𝐶𝑜2 = 𝑀 = 44 = 0.0227 mole
𝑐𝑜2
𝑚 𝑁2 1.5
𝑛𝑁2 = 𝑀 = = 0.0535 mole
𝑁2 28

𝑛𝑐𝑜2 0.0227
Mole fraction 𝑋𝐶𝑜2 = = (0.0277+0.0535) = 0.2976
𝑛
𝑛𝑁2 0.0535
𝑋𝑁2 = = (0.0277+0.0535) = 0.7014
𝑛
Rmix = 𝑚𝑓𝑁2 𝑅𝑁2 + 𝑚𝑓𝐶𝑜2 𝑅𝐶𝑜2
̅
R ̅
R
𝑚𝑓𝑁2 M + 𝑚𝑓𝐶𝑜2 M
N2 Co2
8.314 8.314
= 0.6 x + 0.4 x
28 44
Rmix = 0.2537 kJ /Kg K
̅
R 8.314
Mmix = R = 0.2537 = 32.76 Kg/ mole
𝑚𝑖𝑖
Partial pressure ratio = mole fraction.
𝑃𝑁 2
= 𝑋𝑁2
𝑃
𝑃𝑁2 = 𝑃 ∗ 𝑋𝑁2 = 3.5 x 0.7014 = 2.45 bar
Similarly 𝑃𝐶𝑜2 = 𝑃 ∗ 𝑋𝐶𝑜2 = 3.5 x 0.2976 = 1.0416 bar
𝑚𝑅𝑇 2.5 x 0.2537 x 300
Vmix = ( )mix = = 0.5436 m3
𝑃 3.5 x 100
𝑀𝑎𝑠𝑠 2.5
Density = 𝑉𝑜𝑙𝑢𝑚𝑒 = 0.5436 = 4.598 kg/m3

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𝑚𝑁2 𝑅𝑁 𝑇 8.314 300

2
Partial volume 𝑉𝑁2 = = 1.5 x x 3.5 x 102 = 0.3817 m3
𝑃 28
𝑚𝐶𝑜2 𝑅𝐶𝑜 𝑇 8.314 300
2
𝑉𝐶𝑜2 = =1x x 3.5 x 102 = 0.1613 m3
𝑃 44
Volume fraction = mole fraction
𝑉𝑓𝑁2 = 𝑋𝑁2 = 0.7014
𝑉𝑓𝐶𝑜2 = 𝑋𝐶𝑜2 = 0.2976

2. A cubic tank of 1 m side contains a mixture of 2 Kg of N2 and 3 Kg of an unknown

gas. The mixture pressure and temperature are 280 KPa and 350K. determine
a) Molecular weight and gas constant of the unknown gas.
b) The volumetric analysis.(JUNE 2009)

Solution:
V= volume = 1m3
P =280 KPa.
𝑚𝑁2 = 2Kg
Mass of unknown gas mu = 3kg
P = 280KPa
T = 350K
𝑃𝑉 280∗1
Rmix = ( 𝑚𝑇)mix = 5∗350 = 0.16 kJ/kg K

𝑚 𝑁2 2
𝑚𝑓𝑁2 = = (2+5) = 0.4
𝑚
𝑚 𝑓𝑢 3
𝑚𝑓𝑢 = = (2+3) = 0.6
𝑚
̅
R 8.314
𝑅𝑁2 = M = = 0.296 kJ/Kg K
N2 28
Rmix = 𝑚𝑓𝑁2 𝑅𝑁2 + 𝑚𝑓𝑢 𝑅𝑢

0.16 = (0.4*0.296) + 0.6*𝑅𝑢

𝑢𝑛𝑘𝑛𝑜𝑤𝑛 𝑔𝑎𝑠 𝑅𝑢 = 0.0693 kJ/Kg K

̅
𝑀𝑢 𝑅𝑢 = R

̅
R 8.314
𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑊𝑒𝑖𝑔ℎ𝑡 𝑀𝑢 = R = 0.0693= 119.97 Kg/ mole
𝑢

𝑚𝑁2 2
𝑇ℎ𝑒 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑛𝑁2 = 𝑀 = 28 = 0.07142 mole
𝑁2
𝑚𝑢 3
𝑛𝑢 = 𝑀 = 119.97 = 0.025 mole
𝑢

Total number of moles n = 0.07142 +0.025

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= 0.09642 mole

𝑛𝑁 2 0.07142
𝑀𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑋𝑁2 = = 0.09642 = 0.7407
𝑛

𝑛𝑢 0.025
𝑋𝑢 = = 0.09642 = 0.2592
𝑛

But volume fraction = mole fraction

𝑉𝑓𝑁2 = 𝑋𝑁2 = 0.7407
𝑉𝑢 = 𝑋𝑢 = 0.2592
Volumetric composition will be N2 = 74.07%
Unknown gas = 25.92%

3. A gaseous mixture has the following volumetric analysis O2 = 30%, CO2 = 40%, N2=
30% Determine
a. The analysis on mass basis
b. Molecular weight of the mixture and
c. The partial pressure of each component if the total pressure is 100KPa
and temperature is 320C.
Solution:
𝑉𝑓𝑂2 = 0.3
𝑉𝑓𝐶𝑜2 = 0.4
𝑉𝑓𝑁2 = 0.3
Partial pressure ratio = volume fraction
𝑃 𝑂2
= 𝑉𝑓𝑂2
𝑃
𝑃𝑂2 = P * 𝑉𝑓𝑂2 =100*0.3 = 30KPa
𝑃𝐶𝑂2 = P * 𝑉𝑓𝐶𝑂2 = 100*0.4 = 40KPa
𝑃𝑁2 = P * 𝑉𝑓𝑁2 = 100*0.3 = 30KPa

Again mole fraction = Volume fraction

𝑋𝑂2 = 𝑉𝑓𝑂2
Molecular weight of the mixture
𝑋𝑂2 𝑀𝑂2 + 𝑋𝐶𝑂2 𝑀𝐶𝑂2 + 𝑋𝑁2 𝑀𝑁2
(0.3*32) + (0.4*44) +(0.3*28)
Mmix= 35.6kJ/Kg mole
𝑛𝑂2 𝑚𝑂2 ⁄𝑀𝑂2 𝑚𝑂2 𝑀𝑚𝑖𝑥 𝑀
𝑋𝑂2 = = = * = 𝑚𝑓𝑜2 * 𝑀𝑚𝑖𝑥
𝑛 𝑚⁄𝑀𝑚𝑖𝑥 𝑚 𝑀𝑂2 𝑂2
𝑀𝑂2 0.3∗32
𝑚𝑓𝑜2 = 𝑋𝑂2 *𝑀 = = 0.2696
𝑚𝑖𝑥 35.6
𝑀𝐶𝑂2 0.4∗44
𝑚𝑓𝐶𝑜2 = 𝑋𝐶𝑂2 *𝑀 = 35.6 = 0.4943
𝑚𝑖𝑥
𝑀𝑁2 0.3∗28
𝑚𝑓𝑁2 = 𝑋𝑁2 *𝑀 = 35.6 = 0.2395
𝑚𝑖𝑥
Mass analysis of the mixture is

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O2= 26.96%
CO2= 49.43%
N2 = 23.95%
4. Specific heats of a gas are given by Cp = a +KT and Cv = b +KT, where a, b and K
are constants and T is in K. 1.5 Kg of this gas occupying a volume of 0.06m3at
5.6MPa expands isentropically until the temperature is 2400C. If a=0.946, b=0.662
and K=10-4. Calculate the work done in the expansion.
(DECEMBER 2011)
Solution:
Cp - Cv = R
a+KT – b- KT
a-b=R
0.946-0.662 = 0.284 kJ/Kg K
T2 = 240+273= 513K
𝑃 𝑉
1 1 5.6∗103 ∗0.06
T1 = 𝑚𝑅 = = 789K
1.5∗0.284
𝑇 789
W= − ∫𝑇 2 𝑚𝐶𝑣 𝑑𝑇= − ∫240 𝑚(𝑏 + 𝐾𝑇)𝑑𝑇
1
W=1.5[0.662(789-513) +10-4*0.5((789)2-(513)2)]
W= 1.5(182.71+19.97)
W=304kJ
5. A mixture of ideal gases consists of 3kg of N2 and 54kg of CO2 at a pressure of
300KPa and a temperature of 200C. Find
a. Mole fraction of each constituent.
b. The equivalent molecular weight of mixture
c. The equivalent gas constant of the mixture
d. The partial pressure of each gas.(JULY 2016)
Solution:
𝑚𝑁2 = 3kg
𝑚𝐶𝑜2 = 54 kg
P = 300KPa
T = 200C =293K
Number of Moles
𝑚𝑐𝑜2 54
𝑛𝐶𝑜2 = 𝑀 = 44 =1.2272 mole
𝑐𝑜2
𝑚 𝑁2 3
𝑛𝑁2 = 𝑀 = 28 = 0.1071 mole
𝑁2

n = 0.10714+1.2272 = 1.3343
Mole fraction
𝑛𝑐𝑜2 1.2272
𝑋𝐶𝑜2 = = (1.3343) = 0.9197
𝑛
𝑛𝑁2 0.1071
𝑋𝑁2 = = 1.3343 = 0.08026
𝑛
Equivalent molecular weight of the mixture
Mmix= 𝑀𝑁2 * 𝑋𝑁2 + 𝑀𝐶𝑂2 * 𝑋𝐶𝑂2
Mmix = 28*0.0802 + 0.9149*44

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Mmix = 42.72 kJ/kg mole

Equivalent gas constant of the mixture
̅
R 8.314
Rmix= M = 42.72 = 0.23 kJ/kg K
𝑚𝑖𝑥
Partial pressure ratio = mole fraction.
𝑃𝑁 2
= 𝑋𝑁2
𝑃
𝑃𝑁2 = 𝑃 x𝑋𝑁2 = 300 x 0.0802 = 24.06KPa
𝑃𝐶𝑜2 = 𝑃 x𝑋𝐶𝑜2 = 300 x 0.919 = 275.7KPa

6. 5kg of argon gas undergoes a change of state at constant internal energy. Initial
pressure and temperature are 6atm and 300K respectively. The final volume
occupied by the gas is 3 times that occupied initially. Assume ideal gas behavior,
Determine:
a. The final temperature of the gas.
b. The final pressure of the gas
c. The entropy change of the gas due to change of state. (DECEMBER 2012)

Solution:
m = 5kg
P1 = 6atm= 6 bar
T1 = 300K
V2 =3 V1
M=40
̅
R 8.314
𝑅𝑎𝑟𝑔𝑜𝑛 = M = = 0.20785 kJ/kg K
argon 40
Since internal energy constant T2= T1= 300K
P1V1= mRT1
5∗0.20785∗300
V1 = = 0.519625m3
6∗102
V2=3*0.51962 = 1.5588 m3
P2V2= mRT2
5∗0.20785∗300
P2= = 200KPa
1.5588
𝑇 𝑉
S2-S1 = mCvln(𝑇2) + mRln (𝑉2 )
1 1
S2-S1 = 5*0.20785 ln(3)
S2-S1 = 1.14 kJ/kg K

7. A gas at a pressure of 1.4 MN/m2 and 3600 is expanded adiabatically to a pressure of

100 kN/m2. The gas is then heated at constant volume until it attains 3600C when its
pressure is found to be 220kN/m2. Finally it is compressed isothermally to the
original pressure of 1.4 MN/m2. Sketch the process on P-V and T-S diagram. For
0.23 kg of gas, evaluate the following work transfer, heat transfer, change in internal
energy and change in entropy during each process. Assume the following data for
the gas.

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Cp = 1.005 kJ/kg K
Cv= 0.718 kJ/kg K
R= 0.287 kJ/kg K
 = 1.4

Solution:
M=0.23kg
P1= 1.4 MN/m2=1400KPa
T1= 3600C
P2= 100KN/m2= 100KPa
T3= 3600C
P3=220KPa
Process 1-2 adiabatic
2-3 constant volume
3-1 isothermal
Process 1-2 adiabatic
Q =0
−1
𝑃
T2= T1 (𝑃2 ) 𝑌
1
100 1.4−1
T2= 633 ( ) 1.4 = 297.82K
1400

𝑃1 𝑉1 −𝑃2 𝑉2 𝑚𝑅(𝑇1 −𝑇2 ) 0.23∗0.287(633−297.82)

W= = = = 22.1 KJ
−1 −1 1.4−1
Q = U2 –U1+W
U2-U1= -22.1 kJ
S2-S1 =0
Process 2-3: constant volume.
W=0
U2-U1 = mCv (T3-T2)

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=0.23*0.718 (633-297.82)
=55.35kJ
Q= (U2-U1) = 55.35kJ
𝑇 𝑉
S3-S2 = mCvln𝑇3 + mR ln𝑉3
2 2
633
= 0.23*0.718 ln (297.82) + 0
S3-S2 = 0.1245kJ/K
Process 3-1: Isothermal

Change in internal energy = U1-U3=0

𝑉 𝑃 220
Work W= P3V3ln𝑉1 = mrT3ln𝑃3 = 0.23*0.287*633 ln 1400 = - 77.32 kJ
3 1
Heat generated Q = -77.32+0
Q = -77.32 KJ
𝑇 𝑃
Change in entropy= S1-S3= mCpln𝑇3 – mRln 𝑃3
1 1
220
= - 0.23 *0.287 ln1400 +0
S1-S3=0.122kJ/K

8. Determine the pressure exerted by CO2 in a container of 1.5m3 capacity when it

contains 5kg at 270C
a. Using ideal gas.
b. Using van der Waal’s equation.(DEC. 2011,2013, JUNE 2014)
Solution:
V=1.5m3
m =5kg
T = 270C= 300K
For CO2 – vander Waal’s constant
a= 364.3 KPa (m3/kg mol)2
b= 0.0427 m3 kg/mole
𝑚 5
Number of moles, n=𝑀 = 44 = 0.1136
𝑉 15
Molar specific volume = 𝑣̅ = 𝑛 = 0.1136 = 13.2 m3/ mol
a. Using ideal gas equation
𝑚𝑇𝑅̅ ̅
R
PV= mRT = (𝑅𝑎 = )
𝑀 Ma
𝑚𝑇𝑅̅ 5∗8.314∗300
P= = = 188.95KPa
𝑀𝑉 44∗1.5
b. Using vander Waal’s equation
𝑎
[P+𝑣̅2 ] [𝑣̅ -b] =RT
𝑅̅ T 𝑎 8.314∗300 364.3
P= 𝑣̅−𝑏 - 𝑣̅2 = 13.2−0.0427 - 13.22 = 183.576KPa

9. Determine the pressure in a steel vessel having a volume of 15 litres and containing
3.4 kg nitrogen at 4000C by using

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a. Ideal gas equation

b. Vander waal’s equation
c. Also calculate the compressibility factor by using the answer obtained from the
vander-waal’s equation.(JUNE 2013)
Solution:
V= 15 litres = 0.015m3
m=3.4kg
T=4000C=673K
̅
R 8.314
For nitrogen R= M = = 0.2969 kJ/kg K
28
PV=mRT
3.4∗0.2969∗673
P= = 45295.46 KPa
0.015
From the tables for N2vanderwaal constant are
a= 136.4 KNm4/(Kg mol)2
b= 0.0386 m3/kg mol
𝑚 3.4
n= Number of moles = = = 0.1214
𝑀 28
Molar specific volume
𝑉 0.015
𝑣̅ = 𝑛 = 0.1214 = 0.1235 m3/ mole
𝑖
[P+𝑣̅2 ] [𝑣̅ -b] =RT
𝑅̅ T 𝑎 8.314∗673 136.4
P= 𝑣̅−𝑏 - 𝑣2 = 0.1235−0.0386- 0.12352 = 56961.91 KPa
Pv=ZRT
𝑉 0.015
v= 𝑚 = = 0.0044 m3/Kg
3.4
Pv 56961.91∗0.0044
Z= RT = = 1.25
0.2969∗673

10. A vessel of 2.75 m3 capacity contains 5kg of oxygen at 300K. Determine the pressure
executed by oxygen using vander-waal’s equation compare the results obtained if
oxygen is treated as ideal gas. The constants appearing in the vanderwaal’s equation
have the values a= 139.35 kNm4/ (kg mol)2 and b= 0.0314 m3/kg mol. (JUNE 2009)
Solution:
V= 2.75 m3
m= 5kg
T=300K
𝑚 5
n= Number of moles = = 32 = 0.15625
𝑀
Volume occupied by 1kg mole of oxygen
𝑉 2.75
𝑣̅ = 𝑛 = 0.15625 =17.6 m3
𝑎
[P+𝑣̅2 ] [𝑣̅ -b] =RT
𝑅̅ T 𝑎 8.314∗300 139.35
P= 𝑣̅−𝑏 - 𝑣2 = 17.6−0.0314- = 141.55 KPa
17.62
Gas constant for oxygen,
̅
R 8.314
𝑅𝑜 = M = = 0.2598 kJ/kg K
𝑜 32

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Using the ideal gas equation, PV= mRT

mRT 5∗0.2598∗300
P= = = 141.70 KPa
V 2.75

11. Determine the specific volume of H2 gas when its pressure is 60bar and temperature
is 100K.
a. By using compressibility chart
b. By using varderwaal’s equation for H2
Tc = -239.760C Pc =12.92 bar a= 25.105 kNm2/kg mole
b= 0.0262m3/kg mole.( JAN 2011)
Solution:
Tc= 273-239.76= 33.240C
P=60bar
T=100K
T 100
TR= T = 33.24 = 3.008
𝑐
P 60
PR= P = 12.92 = 4.65
𝑐
From chart,
PR and TR
Z= 1.035
̅
R 8.314
𝑅𝐻2 = M = = 4.157
𝐻2 2
Pv= ZRT
1.035∗8.314∗100
Specific Volume = v= = 0.0717 m3/kg
60∗2∗102
By using varder-waal’s equation
𝑎
[P+𝑣̅2 ] [𝑣̅ -b] =RT
0.25105∗102
[60*105+ ] [𝑣̅ -0.02622] =8.314*100
𝑣̅ 2
Volume 𝑣̅ = 0.14 m3/ mole
V
Specific volume 𝑣̅ = 𝑚 = 0.07 m3/kg
m
Number of mole = n= 𝑀 = 0.5

12. A mixture of gases has the following volumetric composition CO2=12%, O2=
4%,N2=82% CO=2% calculate
i. The gravimetric composition
ii. Molecular weight of mixture
iii. R for mixture (JUNE 2011)
Solution:
Volume fraction = mole fraction
XCO2= 0.12
XN2= 0.82
XO2= 0.04
XCO= 0.02

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Molecular weight of the mixture,

Mmix = XCO2 MCO2 + XO2 MO2 +XN2 MN2 +XCO MCO
= (0.12*44) + (0.04*32) + (0.82*28)+(0.02*28)
=30.08 KJ/kg mole.
Gas constant of the mixture
̅
R
𝑅𝑁2 = M
N2
8.314
= 30.08
= 0.276 KJ/KgK
𝑚𝐶𝑂2
Mass fraction = 𝑚𝑓𝐶𝑂2 = 𝑚
𝑀𝐶𝑂2
𝑚𝑓𝐶𝑂2 = 𝑋𝐶𝑂2 *𝑀
𝑚𝑖𝑥
44
= 0.12* 30.08
= 0.1755
𝑀𝑂2
𝑚𝑓𝑂2 = 𝑋𝑂2 *𝑀
𝑚𝑖𝑥
32
= 0.04*30.08
= 0.0425
𝑀𝑁2
𝑚𝑓𝑁2 = 𝑋𝑁2 *𝑀
𝑚𝑖𝑥
28
=0.82*30.08
=0.764
𝑀
𝑚𝑓𝐶𝑂 = 𝑋𝐶𝑂 *𝑀 𝐶𝑂
𝑚𝑖𝑥
28
= 0.02*30.08
= 0.0186
Gravimetric composition is CO2 = 17.5%, O2=4.25%, N2 = 76.4%, CO= 18.6%.

13. A gas mixture consists of 6 mol of H2 and 4 mol of N2. Determine the mass of each
gas constant of the mixture.(JAN.2014)
Solution:
nH2= 6
MH2= 2
nN2= 4
MN2= 28
mH2= nH2*MH2
= 6*2= 12 kg
mN2= nN2*MN2
= 4*28 = 112 kg
𝑚𝐻2 12
𝑚𝑓𝐻2 = = 112+12= 0.09677
𝑚
𝑚𝑁2 112
𝑚𝑓𝑁2 = = 112+12= 0.9032
𝑚
̅
R 8.314
𝑅𝑁2 = M = = 0.296 kJ/kgK
N2 28

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̅
R 8.314
𝑅𝐻2 = M = = 4.157 kJ/kgK
H2 2

14. A gaseous mixture consists of 1 kg of oxygen and 2 kg of nitrogen is initially at a

pressure of 150 kpa and a temperature of 200C. It is heated at constant pressure
until its temperature reaches 1000C. Determine:
i. Change in enthalpy
ii. Change in entropy and
iii. Change in internal energy(JAN. 2018)
Solution:
𝑚𝑜2 = 1kg
𝑚𝑁2 = 2 kg
m=1+2= 3 kg
Mole fraction
𝑚 𝑜2 1
𝑚𝑓𝑜2 = = (1+2) = 0.334
𝑚
𝑚 𝑁2 2
𝑚𝑓𝑁2 = = (1+2) = 0.667
𝑚
̅
R 8.314
𝑅𝑂2 = M = = 0.262
O2 32
̅
R 8.314
𝑅𝑁2 = M = = 0.291
N2 28
Rmix= mfo2*RO2+mfN2*RN2
= 0.334*0.262+0.667*0.291
= 0.2853 kJ/kgK
Cp for the mixture
Cpmix = mfo2*CpO2+mfN2*CpN2
= 0.877*0.334+1.0292*0.667
=0.985 kJ/kg K
Cv = Cp – R = 0.985 – 0.2853
= 0.6897 kJ/kg K
Change in enthalpy = H2-H1 = mCp (T2-T1)
= 5* 0.985 (100-30)
=394 kJ/kg
Change in internal energy = U2-U1 = mCv (T2-T1)
=5*0.6997 (100-20)
= 280 kJ/kg
𝑇 𝑃
S2-S1 = m [Cp ln𝑇2 - R ln 𝑃2 ]
1 1
100+273
= 5[0.985ln 20+273 - 0]
= 1.189 kJ

15. Find the gas constant and apparent molar mass of a mixture of 2kg O 2 and 3kg N2
given that the universal gas constant is 8314.3 J/kg K, molar masses of O2 and N2 are
respectively 32 and 28.(JULY 2018)

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Solution:
mO2= 2kg
mN2= 3kg
mtotal= 5kg
𝑚𝑂2 2
mfO2= = 5 = 0.4
𝑚
𝑚𝑁2 3
mfN2= = 5 = 0.6
𝑚
1
Mmix= 𝑚𝑓𝑂2 𝑚𝑓𝑁
2
+
𝑀𝑂 𝑀𝑁
2 2
1
= 0.4 0.6
+
32 28
= 29.47 kg/kg mole
̅
R 8.314
Rmix= M = 29.47 = 0.282 kJ/kg K.
𝑚𝑖𝑥

16. Compute from Vander Waal’s equation, the pressure exerted by 1kg of CO2 at
10000C if the specific volume is 1m3/kg. Also compare the results obtained if CO2 is
treated as an ideal gas. Take a= 362.85 ,b= 0.0423, R= 8.314 (JULY 2016)
Solution:
Ideal gas equation
𝑅̅
Pv= RT = 𝑀T
8.314
P*1= *373
44
P= 70.48KPa
n.M = m
1
n= 44
𝑉
Molar specific volume 𝑣̅ = 𝑛 = 44 m3/ mole
𝑎
Vander Waal’s equation [P+𝑣̅2 ] [𝑣̅ -b] =𝑅̅ T
362.85
[P+ ] [44-0.0423] =8.314*373
442
P= 62.36 KPa

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