Unit I: Introduction (4 hrs)

Definition and Scope of Engineering Thermodynamics, Value of energy to society,

Microscopic versus Macroscopic Viewpoint, Concepts and Definitions - System,
Surroundings, Boundary and Universe; Closed Systems, Open Systems, and
Isolated Systems, Thermodynamic Properties: Intensive, Extensive and Specific
Properties, Thermodynamic Equilibrium, State, Process, and Path Cyclic Process,
Quasi-equilibrium Process, Reversible and Irreversible Process, Common
Properties: Pressure, Specific Volume, Temperature, Zeroth Law of
Thermodynamics, Equality of Temperature.

Definition and Scope of Engineering Thermodynamics:

"Engineering thermodynamics is the branch of applied science which deals with

energy transfer and its effect on the state or condition of a system".

Essentially, thermodynamics concern to the study of:

 Interaction of system and surroundings

 Energy and its transformation.
 Relationship between heat, work and physical properties such as pressure,
volume and temperature of the working substance employed to obtain energy
conversion.
 Feasibility of a process and the concept of equilibrium processes.
Notable applications of engineering thermodynamics in the field of energy
technology are:
 Power producing devices e.g. internal combustion engines and gas turbines,
steam and nuclear power plants.
 Power consuming devices e.g. fans, blowers and compressors, refrigeration and
air-conditioning plants.
Value of energy to society:
 Energy plays a unique and critical role in the world; no activity of any kind can
take place without the movement or conversion of energy.
 In the industrialized world the development of energy resources has become
essential for agriculture, transportation, information technology, communication
that have become necessity of a developed society.
 For developing nations, the need for reliable and affordable energy is more
fundamental. It can improve and even save lives. In these countries, reliable
energy supports expanded industry, modern agriculture, increased trade and
improved transportation. These are the building blocks that help people escape
poverty and create better lives.

Microscopic versus Macroscopic Viewpoint: There are two approaches for

investigating the behavior of a system. They are Macroscopic and Microscopic
view point.

In the macroscopic view point which is followed in classical thermodynamics

(Classical thermodynamics is the description of the states
of thermodynamic systems at near-equilibrium that uses macroscopic, measurable
properties).

 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.
 Study is made of overall effect of several molecules; the behavior and
activities of the molecules are averaged i.e. their effect integrated.

In the microscopic view point which is followed in statistical thermodynamics

(Statistical thermodynamics is a theory that uses molecular properties to predict the
behavior of macroscopic quantities of compounds) in which the matter is
considered to be comprised of a large number of tiny particles called molecules.
The salient aspects of microscopic view point are:
 Necessity of complete knowledge of the structure of matter
 Requirement of a large number of variables for complete specification of the
state of matter.
  Easy and precise measurement is not possible of the variables used to
describe the state of matter.
Difference between Macroscopic and Microscopic view point
Macroscopic view point Microscopic view point
1. Attention is focused on a certain 1. Matter constituting the system is
quantity of matter without taking into considered to comprise a large number
account the event occurring at of discrete particles called molecules.
molecular level. These molecules have different
velocities and energies, and these
parameters constantly change with time.
2. Analysis is concerned with gross or 2. A knowledge of the structure of matter is
overall behavior of the system, and this essential in analyzing the behavior of the
approach is adopted in the study of system, and this approach is adopted in
classical thermodynamics. the study of statistical thermodynamics.
3. A few properties are needed to describe 3. Large numbers of variables are needed to
the system. describe the system.
4. The properties like pressure, volume 4. The properties like velocity, momentum
and temperature etc are needed to and kinetic energy which describe the
describe the system can be easily behavior of the molecules can neither be
measured and felt by our sense. felt by our sense nor easily measured by
instruments.
5. The properties of the system are their 5. The properties are defined for each
average values. molecule individually.
6. The macroscopic approach requires 6. Number of molecules is very large and
simple mathematical formulae for as such the microscopic approach
analyzing the system. requires advanced statistical and
mathematical methods to explain any
change in the system.

Concepts and Definitions - System, Surroundings, Boundary and Universe

System: A thermodynamic system represents a prescribed and fixed quantity of

matter under consideration to analyze a problem to study the changes in its
properties due to change of energy in the form of heat and work. The system may
be quantity of steam, mixture of vapor and gas or a piston-cylinder assembly of an
IC engine and its contents. For the description of a thermodynamic system, some
of the following quantities need to be specified.
  Quantity as well as composition of the matter
 Measurable properties such as pressure, temperature and volume of the
system.
 Energy of the system
"So any component or collection of certain components which is
performing certain specific task or activity is called system". If we analyze
this system thermodynamic perspective i.e. with reference to thermodynamic
parameters, then this system is called a thermodynamic system. We can also
define thermodynamic system as a part of the universe which is to be studied or
analyzed.
Surroundings: The combination of matter and space, external to the system
that may be influenced by changes in the system is called surroundings or
environment. All the material or medium outside to the system is called
surroundings and the medium which separates system from its surroundings is
called boundary. System and surroundings taken together is sometimes called
universe.

Universe

Boundary

System

Surroundings

Fig: System, surroundings, boundary and universe

The boundary represents the limit to the system and may be either real or
imaginary and may change shape, volume position or orientation relative to
observer.
Closed Systems, Open Systems, and Isolated Systems

Thermodynamic systems can be classified into

a) Closed system
b) Open system
c) Isolated system

a) Closed system: A closed system can exchange energy in the form of heat and
work with its environment but there is no mass transfer across the system
boundary. The mass within the system remains the same and constant, though
the volume can change against the flexible boundary. Further, the physical
nature and chemical composition of the mass may change. Thus a liquid may
evaporate, a gay may condense or a chemical reaction may occur between two
or more components of the system. Examples of closed system are : Cylinder
fitted with a movable piston, motor-car battery, pressure cooker, kitchen
refrigerator etc.
b) Open system: An open system has mass exchange with surroundings along
with transfer of energy in the form of heat and work. The mass within the
system does not necessarily remain constant; it main change depending upon
mass inflow and mass outflow. Examples of open system are: Water wheel,
motor car engine, steam generator (boiler). Most of the engineering devices are
open systems involving flows of fluids through them.
c) Isolated system:
This system is completely sealed. Neither matter nor heat can transfer to or from
the surroundings. In case of an isolated system there is no interaction between
system and surroundings. A closed rigid and insulated container is an example of
isolated system.

Figure: Thermos.
Thermodynamic Properties: Intensive, Extensive and Specific Properties
Thermodynamic Properties: A thermodynamic property refers to the
characteristics which can be used to describe the condition or state of a system.
Example: temperature, pressure, chemical composition, color, volume, energy etc.
The salient aspects of a thermodynamic property are:
 It is a measurable characteristic describing a system and helps to distinguish
one system from other.
 It has definite unique value when the system is in a particular state.
 It is dependent only on the state of the system, it does not depend on the path
of or route the system follows to attain that particular state.
 Its differential is exact
 If P is a thermodynamic property with dP representing its differential
change, then the integral between initial state 1 to final state 2 of the system
2
will have only value given by ∫1 dP = (P2 – P1)
 Since thermodynamic property is a function of the state of a system, it is
referred to as a point function or state function.
There are two kinds of thermodynamic properties namely intensive and extensive.
a) Intensive property: Intensive property is independent of the mass of the
system. Its value remains the same whether one considers the whole system or
only a part of it. Examples are pressure, temperature, density, composition,
viscosity, thermal conductivity, electrical potential. An intensive property is a
property of matter that does not change as the amount of matter changes. The
ratio of two extensive properties, however, is an intensive property (e.g.,
density is mass per unit volume).

b) Extensive property: Extensive property depends on mass or extent of the

system; its value depends on how big a portion of the system is being
considered. Examples include energy, volume, entropy, enthalpy, mass etc.
 Let a system with value of a certain characteristic/ property P be divided into
a number of parts. If P1, P2, P3 etc denote the value of that property for various
parts of the system, then
For an intensive property:
P = P1 = P2 = P3 = ...
For an extensive property:
P = P1+ P2 + P3 + ...
c) Specific property: An extensive property expressed per unit mass of the
system. Examples include specific volume, specific energy, specific entropy,
specific enthalpy etc.
V E
specific volume v = and specific energy e =
𝑚 𝑚
Where V, E and m are volume, energy and mass of the system respectively.
Like extensive properties, specific properties are additive.
Thermodynamic Equilibrium:
Equilibrium is the concept associated with the absence of tendency for spontaneous
change in the value of any macroscopic property of the system when it is isolated
from its surroundings.
"A system is said to be in thermodynamic equilibrium if there is no change in any
properties of the system when it is isolated from its surroundings."
"A system is said to be thermodynamic equilibrium if all intensive properties have
same value throughout the system."
For system to be in thermodynamic equilibrium, it should satisfy the following
equilibrium conditions: thermal equilibrium, mechanical equilibrium and chemical
equilibrium.
For a system to be in a thermal equilibrium there should not be any temperature
difference within the system. For a system to be in a mechanical equilibrium there
should not be any pressure difference or unbalanced force/moment within the
system. Similarly for a system to be in a chemical equilibrium there should not be
any chemical reaction during the observation interval.
 Thermodynamic Process

The path followed by a system when it undergoes from one equilibrium state to
another is called a thermodynamic process. Thermodynamic process can also be
defined as a locus of states through which system passes while undergoing change
from one equilibrium state
P
to another. T P

P2 2 T2 2 P2 2

Gas P1 T1 P1
1 1 1
V V T
V 1 = V2 V 1 = V2 T1 T2
Figure: Property diagram constant volume heating process

Q
P T P

P 1=P 2 1 2 T2 2 P 1=P 2 1 2

Gas T1
1

V1 V2 V V1 V T
V2 T1 T2
Figure: Property diagram constant pressure heating process
Q

P T P

P1 1 T1= T 2 1 2 P1 1
1

Gas 2
P2
P2 2

V1 V2 V V1 V T 1 = T2 T
V2
Q Figure: Property diagram constant temperature heating process
Thermodynamics process is described with the help of property diagrams such as
P-V, T-V, P-T, h-s, T-s, P-h diagrams etc. Thermodynamic process represents a
transition in which a system changes from one state to another.

1
A
Process
2
3
Pressure

B
Process

Volume

Path: The locus of the series of states through which a system passes in going
from initial state to its final state constitutes the path. A complete specification of
the path is referred to as a process.

Cyclic Process: When a system in a given state undergoes through a series of

processes such that the final state is identical with the initial state a cyclic process
or cycle is said to have been executed. A process is said to be a cyclic process, if
the initial state of the system is restored by number of different processes in series.
For a cyclic process, initial and final states are identical. Figure shows a cyclic
process consisting of three different processes.
P
3

2
1
V
Fig: Cyclic Process
 Quasi-equilibrium Process: Quasi means 'almost'. A quasi-static process is also
called a reversible process. This is a succession of equilibrium states and finite
slowness is its characteristic feature.
Stops
Stops

Final State Weights

W Weight
Piston
Piston

System boundary
Initial State p1 ,v1 ,t1
p1 v1 Gas
Gas t1 System boundary

Fig. 1 Transition between two equilibrium states Fig. 2 Infinitely slow transition of a system by
by an unbalanced force infinitesimal force
1 1
p1
Equilibrium process
p Quasi-static process

p2 2
2

v1 v2
v v

Fig. 3 Plot representing the transition between two Fig. 4 A quasi-static process
equilibrium states

Let us consider a system of gas contained in a cylinder in Fig. 1. The system

initially is in equilibrium state, represented by the properties p1, v1, t1. The weight
on the piston just balances the upward force exerted by the gas. If the weight is
removed, there will be an unbalanced force between the system and the
surroundings, and under gas pressure, the piston will move up till it hits the stops.
The system again comes to an equilibrium state, being described by the properties
p2, v2, t2. But the intermediate states passed through by the system are non-
equilibrium states which cannot be described by thermodynamic coordinates.

Figure 3 shows points 1 and 2 as the initial and final equilibrium states joined by a
dotted line, which has got no meaning otherwise. Now if the single weight on the
piston is made up of many very small pieces of weights and these weights are
removed one by one very slowly from the top of the piston, at any instant of the
upward travel of the piston, if the gas system is isolated, the departure of the state
of the system from the thermodynamic equilibrium state will be infinitesimally
small. So every state passed through by the small will be an equilibrium state. Such
a process, which is but a locus of all the equilibrium points passed through by the
system, is known as a quasi-static process. Infinite slowness is the characteristic
feature of a quasi-static process. A quasi-static process 1-2 is thus a succession of
equilibrium states. So a quasi-static path of the succession of equilibrium states
Fig. 2 and Fig. 4 is also a reversible process. A reversible process is performed in
both ways from 1 to 2 and 2 to 1 involving infinite time in executing each of the
processes.

Reversible and Irreversible Process:

Reversible Process: A thermodynamics process is reversible if the system passes

through a continuous series of equilibrium states.
 Net heat and work exchange between the system and surroundings (for original
+ reverse process) is zero.
 Why reversible processes are of interest? Consume least work in the case of
work consuming devices and generate maximum work in the case of work-
producing devices.
 Reversible processes serve as theoretical limits for the corresponding
irreversible ones.
The following conditions need to be satisfied for a process to be reversible
 There should be no friction, solid or fluid.
 The heat exchange to or from the system, if any, should be only through
infinitely small temperature difference.
 The process should be quasi-static; it should proceed at infinitely slow speed.
For this the pressure difference between the system and surroundings must be
infinitely small.
 It leaves no trace of its occurrence in the system and surroundings. When a
process is reversibly done, no after effects or changes are evident either in the
system or in the surroundings.
 No wastage of energy accompanies a reversible process; a system going
through a reversible process results in maximum efficiency.

1
Equilibrium states

Reversible and quasi-static

Property B

process

Property A

Quasi-static and Reversible process

Some of the operations that can be idealized as reversible process are:

 Motion without friction
 Restricted and controlled expansion or compression.
 Elastic stretching of a solid
 Electric circuit with zero resistance.
 Polarization and magnetization and electrolysis.
Irreversible Process: A process is irreversible if the system passes through a
sequence of non- equilibrium states. During such a process, the properties of the
system do not have a unique value and accordingly cannot be located on any
property diagram. When an irreversible process is made to proceed in the
backward direction, the original state of the system is not restored.
1

Backward direction
Property B

Forward direction
2

Property A

Irreversible process

An irreversible process is identified by the following characteristics:

 It can be carried out in one direction

 It occurs at a finite rate
 It cannot be reversed without causing permanent changes in the surroundings.
 The system is never in equilibrium state at any instant during an irreversible
process.
Processes are rendered irreversible as a result of degradation of energy by such
factors like friction, turbulence, diffusion, diffusion, throttling and combustion.
Some notable examples of irreversible process are:
 Spontaneous chemical reaction
 Viscous flow; fluid flow with friction
 Inelastic (plastic) deformation and hysteresis effects.
 Diffusion of gases; mixing of dissimilar gases
 Energy transfer as heat with finite temperature differences
 Free expansion and throttling process.
Common Properties: Pressure, Specific Volume, Temperature

Pressure: Pressure is defined as force per unit area. It is denoted by P and is

expressed in N/m2 or Pascal (Pa). Sometimes pressure is also expressed in bar or
atm.

1 bar = 100 kPa = 105 Pa.

1 atm = 101.325 kPa = 1.01325 x 105 Pa.

We deal with three pressure terms in thermodynamics: atmospheric pressure(P atm),

gauge pressure (Pgauge) and absolute pressure(Pabs).

i) Atmospheric pressure (Patm): Pressure exerted by the ambient (atmosphere,

climate, environment) air on any surface is called atmospheric pressure.
Atmospheric pressure is measured by barometer. Barometer gives atmospheric
in terms of height of the mercury column z baro as
Patm = 𝜌𝐻𝑔 g zbaro
Where𝜌𝐻𝑔 , the density of mercury and g is the local gravitational acceleration.
The standard atmospheric pressure is defined as the pressure produced by column
of mercury 760mm high, the specific gravity of mercury being 13.5951 and the
acceleration due to gravity being 9.80665m/s2.
From equation: Patm = 𝝆𝑯𝒈 g zbaro ............................(i)
760
= (13.5951 × 1000) × 9.80665 ×
1000
2
= 101325N/ m
= 1.01325 ×105 Pa = 1.01325 bar.
ii) Absolute pressure ( pabs ) : Pressure been defined as the force per unit area
due to interaction of fluid particles amongst themselves. Pressure intensity
measured from the state of vacuum or zero pressure is called absolute
pressure. "Pressure of a system expressed relative to perfect vacuum is
called absolute pressure. Hence, Patm, Pgauge and Pabs can be represented on a
pressure scale as shown in figure and are related as
Pabs = Patm + Pgauge ..................................... (ii)

Gauge pressure

Atmospheric pressure line

Vacuum
Absolute
pressure
(greater than Absolute Atmospheric pressure
atmospheric pressure (less
pressure) than atmospheric
pressure)
Absolute zero pressure

Relationship between absolute, gauge and atmospheric pressure

iii) Gauge pressure (Pg) and vacuum pressure (Pvac) : Instruments and gauges
used to measure fluid pressure generally measure the difference between the
unknown pressure p and the existing pressure pat as shown in figure.

Pat
Gauge

Gauge reads (p-pat)

Fluid pressure p

Fig. Gauge pressure

When the unknown pressure is more than atmospheric pressure, the pressure
recorded by the instrument is called gauge pressure. A pressure reading below the
atmospheric pressure is known as vacuum or negative pressure.
Pabs = Pat - Pvac .........................................(iii)

Specific volume (v): Specific volume represents the volume per unit mass of the
substance; specific volume is the reciprocal of density.
𝑉 1
𝑣= ; 𝑣=
𝑚 𝜌
The specific volume has the unit m3/kg.
The concept of specific volume is found to be practically more useful in the study
of flow of gases and vapors.
Specific gravity(s): Refers to the ratio of specific weight( or mass density) of a
fluid to the specific weight of a standard fluid. For liquids the standard fluid is
water at 40C, and for gases the standard fluid is taken either air at 0 0C or hydrogen
at the same temperature. Specific gravity is dimensionless and has no units.
A statement that specific gravity of mercury is 13.6 implies that mercury is 13.6
times heavier than water.
Temperature: Temperature may be defined as the

(i) degree of hotness and coldness of a body or an environment measured on a

definite scale.
(ii) driving force or potential causing the flow of energy as heat
(iii) parameter which determines whether or not a system is in thermal
equilibrium with another system.
(iv) It is also defined as a property of a system which defines the direction and
magnitude of heat transfer.
If the temperature of the system is higher than that of the surroundings, heat
transfer takes place from the system to the surroundings while if the
temperature of the system is less than that of the surroundings, heat transfer
takes place from the system to the surroundings to the system. Similarly,
magnitude of the heat transfer is also proportional to the temperature difference
between the system and the surroundings.
 Temperature is measured by thermometer. Commonly used scales for
temperature are 0C, 0F and K. Temperature expressed in Kelvin scale is called
absolute temperature.
C−0 F−32 K−273
= = Scale Freezing Point Boiling Point
100−0 212−32 373−273
0
C F−32 K−273 C 0 100
= = 0
F 32 212
5 9 5
K 273 373

Equality of Temperature and Zeroth Law of Thermodynamics:

Equality of Temperature:
 Two systems are equal in temperature if no change occurs in any property
when they are brought into communication.
 Two systems are said to have equal temperatures, if there is no change in
any properties of both the system when they are brought in contact with each
other.

Sphere

Gas

Figure: An arrangement for equality of temperature

Consider two systems, perfectly insulated from the surroundings and at
different temperatures. When they are bought into physical contact, the energy in
the form of heat will flow from the hot system to the cold system, and there would
occur changes in their physical properties such as length, electrical resistance etc.
After a sufficient long time of contact, no further change occurs and thermal
equilibrium is established. The two systems are then said to have the same
temperature.
Zeroth Law of Thermodynamics: When two systems have equality of
temperature (thermal equilibrium) to a third system, they in turn have equality of
temperature (thermal equilibrium) with each other.
 Consider two systems S1 and S3 which are in thermal equilibrium with each
other. Accordingly no change occurs in their physical properties when they are
brought into good contact. It is assumed that the systems S 1 and S3 do not react
each other chemically or electrically. Likewise, let the system S3 be separately
equal in temperature to another system S2 so that no change occurs when they
communicate with each other. It is then observed that the systems S 1 and S2 will
not undergo any physical changes when brought into contact. The systems S 1 and
S2 are then taken to be in thermal equilibrium, i.e. equal in temperature to each
other.
S3

S2 S2

Concept of Zeroth law

The Zeroth law provides the basis for the measurement of temperature of a system.
The temperature measuring device (thermometer) is brought into contact with a
system A which is at a temperature level (the reference temperature) and the two
are allowed to reach a state of thermal equilibrium.

Note: Water boils at a lower temperature at high altitudes, because

The boiling point of water is lower at higher altitudes due to the decreased
atmospheric pressure. A liquid boils when its vapor pressure exceeds the local
total pressure. As the atmospheric pressure drops, the Vapor pressure
increases more than the local pressure at an even lower temperature. At sea
level water boils at 100°C. For each 500 ft increase in elevation, the boiling
point of water is lowered by approximately 0.5°C.