UNIVERSAL COLLEGE OF ENGINEERING & TECHNOLOGY

(Approved by AICTE, New Delhi & Affiliated to JNTUK, Kakinada)

DEPARTMENT OF MECHANICAL ENGINEERING

THERMODYNAMICS
UNIT -1
WINNY DASARI
ASST.PROFESSOR
 SYLLABUS

UNIT – I
Introduction: Basic Concepts : System, boundary, Surrounding, Universe, control
volume, Types of Systems, Macroscopic and Microscopic viewpoints, Concept of
Continuum, Thermodynamic Equilibrium, State, Property, Process - Reversible, Quasi
static & Irreversible Processes, cycle, Causes of Irreversibility. Energy in State and in
Transition - Types, Work and Heat, Point and Path function.

Zeroth Law of Thermodynamics – Concept of Temperature – Principles of

Thermometry – Reference Points – Const. Volume gas Thermometer – Scales of
Temperature.
 TEXTBOO
KS

1. Engineering Thermodynamics, PK Nag 6th

Edn , McGraw Hill.

2. Fundamentals of Thermodynamics – Sonntag,

Borgnakke, Van Wylen, 6th Edn, Wiley
What is Thermodynamics ?
 The branch of science that deals with energy levels and the transfer of energy
between systems and between different states of matter.
 Thermodynamics is the study of the conversion of energy into work and heat and its
relation to macroscopic variables such as temperature, volume and pressure.
 The word thermodynamics is derived from Greek words “Thermo” means heat or
hot “dynamikos” means study of matter in motion.

System : The part of the universe that is under consideration. It is separated from the
rest of the universe by it’s boundaries.

Surrounding : Everything external to system is surrounding.

Boundary : The above two are separated by an envelope called boundary.

Universe : The presence of System, Surroundings, Boundary are in the universe.

Types of Systems
Thermodynamic
Systems

1. Open System 2. Closed System 3. Isolated System

1. Open System : this is a system in which

both matter and energy is being exchanged
with the surroundings. Eg : Open lid pan and
a piston cylinder with inlets and outlets.
2.Closed System : this is a system in which
only energy is being exchanged with the
surroundings. No mass interactions or
exchange takes place. Eg : piston in
cylinder with out any inlet and outlet.
3. Isolated System : this is a system in
which no matter or energy is being
exchanged with the surroundings. Eg : Hot
liquid in thermo flask.
Macroscopic and Microscopic viewpoints
MACROSCOPIC AND MICROSCOPIC VIEWPOINT OF THERMODYNAMICS

The behaviour of a matter can be studied at two levels: a) Macroscopic. b)

Microscopic. Macroscopic ( or classical thermodynamics):
• In this approach, a certain quantity of matter is considered, without taking into
account the events occurring at the molecular level.

• This macroscopic approach to the study of thermodynamics that does not

require knowledge of the behaviour of individual particles.
• Macroscopic thermodynamics is only concerned with the effects of the action of
many molecules, and these effects can be perceived by human senses.
• The macroscopic observations are completely independent of the
assumptions regarding the nature of matter.

Example: A movi ng car, a falling stone from a cliff, etc.

Microscopic (or statistical thermodynamics):
• From the microscopic viewpoint, matter is composed of a large number of small
molecules and atoms.
• This microscopic approach to the study of thermodynamics that require
knowledge of the behaviour of indiv idual pa1ticles.

• Microscopic thermodynamics is concerned with the effects of the action of

many molecules, and these effects cannot be perceived by human senses.
• The microscopic observations are completely dependent on the assumptions
regarding the nature of matter.

• Example: Individual molecules present in air, etc.

Control Volume
 1. ZEROTH LAW

2. FIRST LAW
LAWS OF
THERMODYNAMIC
S
3. SECOND LAW

4. THIRD LAW
1. Zeroth Law : If two systems are both in thermal equilibrium with a third system then
they are in thermal equilibrium with each other.
 3. Second Law :
ENTROPY: It is the measure of disorder in the system. All systems gain entropy
over time.

The second law of thermodynamics states that the total entropy of both a system and its
surroundings will NEVER decrease.

 It is impossible to build a cyclic machine that converts heat into work with 100%
efficiency . Kelvin’s statement of the second law.
 Heat does not ‘flow*’ from a colder body to a hotter body, without an concomitant
change outside of the two bodies Clausius’s statement of the second law.
This law also governs the direction of process
The total entropy of the universe always increases.

ΔS universe ≥ 0
ΔS universe = ΔS system + ΔS Surrounding
 3. Third Law :
The third law of thermodynamics states that the entropy of a system approaches a
constant value as the temperature approaches absolute zero. The entropy of a system
at absolute zero is typically zero, and in all cases is determined only by the number of
different ground states it has.

 The entropy of a perfect crystal of any pure substance approaches zero as the
temperature approaches absolute zero.

Where ΔS = entropy or change in entropy,

T = Temperature
Thermodynamic Equilibrium

Thermodynamic equilibrium, condition or state of a thermodynamic system, the

properties of which do not change with time and that can be changed to another
condition only at the expense of effects on other systems.

 A particularly important concept is thermodynamic equilibrium, in which there is no

tendency for the state of a system to change spontaneously.

 Equilibrium means the state of balance of a system within itself and between
system and surroundings. Thus for attending a state of Thermodynamic
equilibrium following three types of equilibrium states the system must
achieve.

1. Thermal Equilibrium
2. Mechanical Equilibrium
3. Chemical Equilibrium
1. Thermal Equilibrium
For a system to be in thermal equilibrium there should not be any temperature gradient
in the system. For a system to be in thermal equilibrium it is not necessary that the
system should be in mechanical and chemical equilibrium.
2. Mechanical Equilibrium
For a system to be in mechanical equilibrium there should be any pressure unbalancing
either in the interior of the system or between the system and the surroundings.

3. Chemical Equilibrium
For a system to be in chemical equilibrium there should be equality of chemical
potential i.e., there should not be any chemical reactions.
 Heat & Work
Heat : Heat is the transfer of thermal energy between systems.
Thermodynamic definition of heat: It is the energy in transition between the system
and the surroundings by virtue of the difference in temperature.
Work : It is the transfer of mechanical energy between two systems.
Thermodynamic definition of work: Positive work is done by a system when the sole
effect external to the system could be reduced to the rise of a weight.
 Both heat and work in the form of energy with units as joule.

 Work done BY the system is +ve

 Obviously work done ON the system is –ve
 Heat given TO the system is +ve
 Obviously Heat rejected by the system is -ve
Concept of Continuum
QUASI-STATIC PROCESS

Quasi-static process is called a slow process in thermodynamics. It is a process that

occurs infinitesimally slow. All the states in a quasi-static process are in equilibrium. The
process in which at each moment the system is in thermodynamic equilibrium with the
surrounding is known as a quasi-static process.
Reversible & Irreversible Processes
Reversible : A thermodynamic process (state i → state f ) is said to be reversible if the
process can be turned back such that both the system and the surroundings return to
their original states, with no other change anywhere else in the universe.
 As we know, in reality, no such processes as reversible processes can exist. Thus, the
reversible processes can easily be defined as idealizations or models of real
processes, on which the limits of the system or device are to be defined.
 They help us in incurring the maximum efficiency a system can provide in ideal
working conditions and thus the target design that can be set.
Examples of Reversible Process
Here, we have listed a few examples of Reversible Process:
 Extension of springs
 Slow adiabatic compression or expansion of gases
 Electrolysis (with no resistance in the electrolyte)
 The frictionless motion of solids
 Slow isothermal compression or expansion of gases
 A reversible process is one where an infinitesimal change in the conditions of the
surroundings leads to a ‘reversal’ of the process.
 If a block of material (at T) is in contact with surrounding at (T-δT), then ‘heat will flow’
into the surrounding. Now if the temperature of the surrounding is increased to
(T+δT), then the direction of heat flow will be reversed.
Irreversible : An irreversible process can be defined as a process in which the system
and the surroundings do not return to their original condition once the process is
initiated.
Taking an example of an automobile engine, that has travelled a distance with the aid of
fuel equal to an amount ‘x’. During the process, the fuel burns to provide energy to the
engine, converting itself into smoke and heat energy. We cannot retrieve the energy lost
by the fuel and cannot get back the original form. There are many factors/Causes due
to which the irreversibility of a process occurs, namely:
1.The friction that converts the energy of the fuel to heat energy
2.The unrestrained expansion of the fluid which prevents from regaining the original form
of the fuel Heat transfer through a finite temperature, the reverse of which is not possible
as the forward process, in this case, is spontaneous
3.Mixing of two different substances which cannot be separated as the process of
intermixing is again spontaneous in nature, the reverse of which is not feasible.
Thus, some processes are reversible while others are irreversible in nature depending
upon their ability to return to their original state from their final state.
Examples of Irreversible Processes
A few examples of Irreversible Processes are:
•Relative motion with friction
•Throttling
•Heat transfer
•Diffusion
•Electricity flow through a resistance

How to visualize a ‘reversible’ equivalent to a ‘irreversible’ processes?

 Let us keep one example in mind as to how we can (sometimes) construct a
‘reversible’ equivalent to a ‘irreversible’ processes.
 Let us consider the example of the freezing of ‘undercooled water’* at –5˚C (at 1 atm
pressure). This freezing of undercooled water is irreversible (P1 below).
 We can visualize this process as taking place in three reversible steps.
 Hence making the entire process reversible (P2 below).
Thermodynamic Properties of a system
Properties are those characteristics of the system which can be used for defining the
system. Such as volume, pressure, temperature, viscosity etc.
Classification of properties of a thermodynamic system
The thermodynamic properties may be classified into two categories:
1.Intensive property 2.Extensive property
1.Intensive property: Intensive properties are those properties which have same value
for any part of the system or these are those properties that are independent of the mass
of the system. Such as temperature, pressure and density.
2.Extensive property: Extensive properties are those properties which depend upon
the mass of the system and do not maintain the same value for any path of the system.
Such as mass, enthalpy, volume and energy etc.

Path: If all the changes of states of the system are plotted, then line joining the change
of states of the system is known as path.
Process: A process is a complete description of change of state of a thermodynamic
system through a specified path.
Cycle: A thermodynamic cycle is defined as the series of state of changes such that the
initial state is identical with the final state.
Point and Path Functions

Point Functions: Point function are those function which depend upon the initial and
final point of the curve and is not affected by the path of the curve ,even if the path of the
function is changed but the initial and the final points are the same then the function will
give the same value .
• They depend on the state only, and not on how a system reaches that state. All
properties are point functions.
Process A: V2 - V1 = 3 m3
Process B: V2 - V1 = 3 m3
Path Functions: On the other hand path function are those functions whose value
depends upon the path traced by them .If their path is changed keeping the initial and
final point same , their value will change.
• Their magnitudes depend on the path followed during a process as well as the end
states. Work (W), heat (Q) are path functions.
Process A: WA = 10 kJ
Process B: WB = 7 kJ
Zeroth Law of Thermodynamics
CONSTANT VOLUME GAS THERMOMETER
 CONSTANT VOULME
Change in GAS THERMOMETER
temperature

CONSTANT PRESSURE
GAS THERMOMETER
 TEMPERATURE SCALES

Freezing point of water known as ice point and boiling point of water known as steam
point are taken as the reference states for all types of temperature scales.
The various types as temperature scales in use are :
a) Celsius scale
b) Fahrenheit scale
c) Kelvin scale
d) Rankine scale
A Gas of volume 6000cm³ at a pressure of 100 kPa is compressed quasi statically
according to PV2 = constant until the volume becomes 2000cm³. Determine the final
pressures and work transfer
W