MECHANICAL ENGINEERING

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THERMODYNAMICS

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First Edition : 2017

Typeset at : IES Master Publication, New Delhi-110016

 CONTENTS

1. Basics of Thermodynamics and First law .................................................. 01–51

2. Second Law of Thermodynamics ................................................................ 52–83

3. Entropy ......................................................................................................... 84–126

4. Availability and Irreversibility .................................................................. 127–149

5. Pure Substrances ..................................................................................... 150–167

6. Gases and Gaseous Mixtures ................................................................ 168–210

7. Thermodynamic Relations ........................................................................ 211–231

8. Compressible flow and Shocks ............................................................... 232-296

 1
INTRODUCTION

Introduction  It is the science dealing with energy (heat) and its conversion into
work along change in properties of the system in equilibrium.
Types of System
 Word thermodynamics originated during men’s endeavor to convert
Microscopic and heat into work i.e. during heat engine invention. It derived from two
Macroscopic Approach Greek words namely THERME means heat and DYNAMICS means
power (force+velocity).
Types of
 In the initial phase it was assumed that conversion of heat into
Thermodynamic
work is all about thermodynamics. But later it was felt that every
Properties wake of our life is controlled by thermodynamics. Or in other words
Thermodynamic the basic fundamentals of thermodynamics are based upon the
natural processes and observations that we feel in daily ife.
Equilibrium
 These common observations are natural processes. For example -
Pure Substance balance i.e. equilibrium, flow of heat from high temperature to low
temperature, water flows from high elevation to low elevation, aging
Temperature Concept
of life of living organism, conservation of energy etc.
p.dV work or  It is observed that all the above mentioned observations or processes
Boundary Work have a directional sense and rhythm to occur in a direction.

Free Expansion  Based upon these natural processes and common observations, four
LAWS OF THERMODYNAMICS are drived. So these laws have no
First Law of mathematical back up and proved empirically only. Firmness of
Thermodynamics these laws are proved by their wide applications and still not violated.
The four laws of thermodynamics are,
Unsteady Flow
1. Zeroth Law of thermodynamics
Processes
2. First law of thermodynamics.
3. Second law of thermodynamics.
4. Third law of thermodynamics.
2 Chapter-1 : Basics of Thermodynamics and First law

System
Boundary
Thermodynamic system is defined as a quantity of matter or region in
space upon which thermodynamic analysis is done for a particular System
problem.
Surroundings/ environment
Surrou ndings
Everything outside the thermodynamic system is non as surroundings.

System Boundary
The system and surrounding separating line or boundary is called system boundary. The boundary of
system may be either fixed or moving. It may also be either real or imaginary.

TYPES OF SYSTEM
Thermodynamics system are divided in three groups namely,
(1) Closed System. (2) Open system. (3) Isolated System.
(1) Closed System or Control Mass Energy Transfer : (Heat or work)

It is a system of fixed mass i.e. mass can Boundary

not change or cross the system boundary
System
but energy can cross. (The volume of closed
system is changing i.e. cylinder piston
machine) i.e. boundary is moving. Environment
or (No mass/matter movement)
Surroundings
Example:
(i) A constant amount of matter in cylinder-piston system, here the mass of the system is constant
and volume can change i.e. boundary moving, energy can transfer through conducting wall of
system.
(ii) A steel container containing fluid having no outlet – no material movement across the boundary
but energy can transfer across conducting wall.
(2) Open System or Control Volume
In this system the energy as well as mass can cross the system boundary. Generally boundary is
fixed and a specific region or space of system is selected for analysis purpose.
Boundary

Mass Energy
System

Example: Compressor, pump, turbine etc.

(3) Isolated System
This system has no interaction with surrounding i.e. neither mass nor energy can transfer the
system boundary. It is a fixed mass and fixed energy system e.g. coffee in insulated thermo flask,
universe is itself an isolated system. This is a special case of close system.
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 Mechanical Engineering (Study Package) 3

X
No energy transfer
Surroundings

No mass/matter transfer
X
System matrix
System Mass transfer Energy Transfer
Open system Yes Yes
Closed No Yes
Isolated No No

Control Volume and Control Surface

For the analysis of open system such as compressor and turbine, attention is focussed on a certain
volume surrounding the machine called control volume enclosed by control surface. Here matter as well
as energy can cross the control surface.
Energy

Mass in Work

Control
Volume

Mass out

Control Surface (dashed)

MICROSCOPIC AND MACROSCOPIC APPROACH

Microscopic Approach
Here the study is focussed at molecular level i.e behaviour of molecules is studied. This study is also
known as statistical thermodynamics. This is done when the density is very low.
Macroscopic Approach
When the density is high, the individual molecular study is not possible so it is done on whole system
i.e. average of system, the study is called macroscopic and is also called classical thermodynamics.
Thermodynamic Properties
To analyse a thermodynamic system, some variables are required such as volume, temperature, pressure
etc. These variables are called properties of system. These are macroscopic in nature. These are the
coordinates of system. When all the properties have definite value, the system is said to exist in definite
state.
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4 Chapter-1 : Basics of Thermodynamics and First law

TYPES OF THERMODYNAMIC PROPERTIES

There are two types of thermodynamic propertetis
(1) Intensive property
These are independent of mass or size of system e.g. pressure, temperature, density, thermal
conductivity, dielectric constant, thermal expansion coefficient etc.
(2) Extensive Property
These properties depend on mass or size of system. If system is divided into two parts all extensive
properties are halved. e.g. volume, kinetic energy, potential energy etc.

NOTE Specific properties are intensive e.g. [extensive property per unit mass]. Energy per
unit mass, volume per unit mass etc. But work and heat are not properties.

Some Important Points

Units of Pressure: S.I. unit – pascal (Pa):
1 Pa = 1 N/m2-similarly kilopascal – 103 N/m2
Mega Pa = 106 N/m2
1 bar = 105 N/m2
Standard atmospheric.1 atm = 101.325 kPa = 1.013×105 N/m2 (Pa)
The unit of 1 mm Hg Pressure is torr,
 1.0 torr = 133 Pa = 1 mm Hg
One gram mole of gas = Molecular weight (gm) of substance. e.g. one gram mole of oxygen = 32
gram oxygen.

Change of State
An operation which brings change in one or more properties is called change of state.

Path
The series of states during change of state is called path of change of state.

Process
When the path of change of state is completely specified i.e. mode of change of stated again i.e. constant
volume, constant pressure etc. It is called as process e.g. isobaric process, isothermal process etc.

Cycle
A
A series of changes of state or processes in such a way that the final 1
state is same as initial is called as cycle. P
B
2
 The change in property in a cycle is always zero because of same
initial and final state. V
A  B - Process
1–2–1 cycle
 Minimum two processes are required for a cycle.
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 Mechanical Engineering (Study Package) 5

Quasi-Static Process
A process which is carried out with infinitely small pressure gradient and slowly is called quasi-static
process. Some points about it are,
 All the states on the process are equilibrium states.
 Infinite slowness is the characteristic feature of this process.
 A frictionless quasi-static process is a reversible process.
 Quasi-means almost i.e. the process is almost static.
P P
1 Equilibrium states
1
State 1 & 2 are in
Equilibrium states
Quasi-static
process
This process
cannot be defined

2 2
V V

Fast/Practical Process Slow/Impractical Process

Here points 1 and 2 are in Infinitely slow process

equilibrium so only coordinates of 1 (Impractical): All the points

and 2 can be determine but any between 1 and 2 are in equilibrium.

other points in between has no So has definite value.

meaning.

Reversible and Irreversible Processes

The process is called a reversible process if it can be completely reversed. It implies that when carried
out in the opposite direction the system follows the same succession of states as it followed in the
forward direction. Thus, the system is restored to the initial conditions. In addition, the interactions
between the system and the surroundings are also equal and opposite in direction. Hence, not only the
system but the surroundings also are restored to the initial conditions. Accordingly, if a process is
reversible, then when it is reversed, the system and the surroundings both come back to the original
states, and no trace of the history of the forward process is left.
THERMODYNAMIC EQUILIBRIUM
A system is said to be in thermodynamic equilibrium if it is in three types of equilibrium.
(1) Mechanical Equilibrium
Equality of force or pressure throughout system if the system is in equilibrium with environment,
the pressure will be equal to atmospheric pressure.
(2) Chemical Equilibrium
Equality of chemical potenital i.e. no chemical reaction, no change of concentration i.e. no mass
diffusion throughout the system.
(3) Thermal Equilibrium
Temperature is unirform throughout the system.
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6 Chapter-1 : Basics of Thermodynamics and First law

NOTE If system is in thermodyanic equlibrium, there will be no change in any macroscopic

property.

PURE SUBSTANCE
A substance is pure if,
 Homogeneous in composition – Chemical composition of each part of system is same.
 Homogeneous in chemical aggregation – Chemical compound in the system must be combined
in the same way in every part of the system.
 Invariable in chemical aggregation – Chemical compostion doesn’t change in time.
Change in phase is possible here.
 A pure substance does not have to be of a single chemical element or compound so a mixture of
various chemical compounds also qualify a pure substance.
Example of pure substances
Atmospheric air, steam–water mixture, combustoin products of fuel.
But mixture of air and liquid air is not pure substance because relative proportion of oxygen and
nitrogen are different in two phases.
Homogeneous and Heterogeneous Systems
Any substance in single phase e.g. mixture of air water vapour, water and nitric acid is called
homogeneous system and if a system has more than one phase, it is called heterogeneous system.

TEMPERATURE CONCEPT
 Temperature is the property which differentiate between hot and cold body.
 To understand this concept, temperature bears the relationship with thermodynamics, as forces
with statics and velocity with dynamics.
 In order to understand the quantitative measure of temperature, a reference body is selected in such
a way that there should be a reference physical characterstic which vary with temperature.
 The reference body is called as thermometer and characterstic as thermometric property.
 The basis of temperature measurement is Zeroth law of thermodynamics.
Zeroth Law of Thermodynamics B
“If a body A is in thermal equilibrium with body B and body B is in
thermal equilibrium with body C, then A and C will be in thermal
equilibrium”. A C

Temperature Measurement Method Before 1954

This method of temperature measurement was based upon two reference points namely ice point
assigned value 0°C and steam point assigned value 100°C.
Temperature (x) was assumed linear function of thermometric property x.
 (x) = ax + b. ...(i) where ‘a’ and ‘b’ are conslants
At ice point, i(x) = axi + b ...(ii)

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