2.2.

DEFINITION OF THERMODYNAMICS
Thermodynamics may be defined as follows :
•Thermodynamics is an axiomatic science which deals with the relations among heat,
work and properties of system which are in equilibrium. It describes state and changes
in state of physical systems.

Or
Thermodynamics is the science of the regularities governing processes of energy
Conversion.

Or
Thermodynamics is the science that deals with the interaction between energy and
material systems.
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2.3. THERMODYNAMIC SYSTEMS
2.3.1. System, Boundary and Surroundings
System.A system is a finite quantity of matter or a prescribed region of space (Refer Fig. 2.2)
Boundary. The actual or hypothetical envelope enclosing the system is the boundary of
the system. The boundary may be fixed or it may move, as and when a system containing a gas is
compressed or expanded. The boundary may be real or imaginary. It is not difficult to envisage a
real boundary but an example of imaginary boundary would be one drawn around a system con
sisting of the fresh mixture about to enterthe cylinder of an I.C. engine together with the remanants
of the last cylinder charge after the exhaust process (Refer Fig. 2.3).

Convenient
Gurroundings imaginary
Boundary Real boundary
boundary
System

System System
Cylinder
Piston
Surrounding Piston

Fig. 2.2. The system. Fig. 2.3. The real and imaginary boundaries.
 -Convenient
Gurroundings imaginary
Boundary
Real boundary
boundary
System

System System
Cylinder
Piston
SurrOunding Piston

Fig. 2.2. The system. Fig. 2.3. The real and imaginary boundaries.

2.3.2. Closed System

Refer to Fig. 2.4. If the boundary of the system is impervious to the flow of matter, it is
called a closed system.An example of this system is mass of gas orvapour contained in an engine
cylinder, the boundary of which is drawn by the cylinder walls, the cylinder head and piston
crown. Here the boundary is continuous and no matter may enter or leave.
 Mass remains constant Out
regardless variation of Mass non-necessarily
boundaries Constant

Gas Gas

In

Fig. 2.4. Closed system. Fig. 2.5. Open system.

2.3.3. Open System

Refer to Fig. 2.5. An open system is one in which matter flows into or out of the system.
Most of the engineering systems are open.
2.3.4. Isolated System
An isolated system is that systemn which exchanges neither energy nor matter with any
other system or with environment.
2.3.5. Adiabatic System
An adiabatic system is one which is thermally insulated from its surroundings. It can,
however, exchange work with its surroundings. If it does not, it becomes an isolated system.
Phase. A phase is a quantity of matter which is homogeneous throughout in chemical
composition and physical structure.
2.3.6. Homogeneous System
A system which consists of a single phase is termed as homogeneous system. Examples :

Mixture of air and water vapour, water plus nitric acid and octane plus heptane.
2.3.7. Heterogeneous System
A system which consists of two or more phases is called a heterogeneous system. Examples :
Water plus steam,ice plus water and water plus oil.
2.14. ZEROTH LAW OF THERMODYNAMICS
Zeroth law of thermodynamics' that if two systems are each equal in tem
states
perature to a third, they are equal in temperature to each other.

2 3

Fig. 2.7. Zeroth law of thermodynamics.

Example. Refer Fig. 2.7. System 1 may consist of a mass of gas enclosed in a rigid vessel
fitted with a pressure gauge. If there is no change of pressure when this system is brought into
contact with system 2 a block of iron, then the two systems are equal in temperature (assuming
that the systems 1 and 2 do not react each other chemically or electrically). Experiment reveals
that if system '1 is brought into contact with a third system 3again with no change of properties
then systems 2 and 3 will show no change in their properties when brought into contact provided
they do not react with each other chemically or electrically. Therefore, 2 and 3 must be in
equilibrium.
This law was enunciated by R.H. Fowler in the year 1931. However, since the first and
second laws already existed at that time, it was designated as zeroth law so that it
precedes the first and second laws to form a logical sequence.
 These approaches are discussed (in a comparative way) below :

S.No. Macroscopic approach Microscopic approach

1. In this approach a certain quantity ofmatter is The approach considers thatthe system is made
considered without taking into account the events up of a very large number of discrete particles
occurring at molecular level. In other words this known as molecules. These molecules have
approach to thermodynamics is concerned with different velocities and energies. The values of
gross or overall behaviour. This is known as theseenergies are constantly changing with time.
classical thermodynamics. This approach to thermodynamics which is
concerned directly with the structure of the
matter is known as statistical thermodynamics.

2 The of macroscopic system requires

analysis The behaviour of the system is found by using
simple mathematical formulae. statistical methods asthe numberof molecules is

very large. So advanced statistical and mathe

matical methods are needed to explain the
changes in the system.

3. The values of the properties of the system are The properties like velocity, momentum,impulse,
their average values. For example, consider a kineticenergy, force ofimpactete. which describe
sample ofa gasina closed container. Thepressure the molecule cannot be easily measured by
of the gas is the average value of the pressure instruments. Our senses cannot feel them.
exerted by millions of individual molecules.
Similarly thetemperature ofthis gas is the average
value oftranslational kinetic energies ofmillions
of individual molecules. These properties like
pressure and temperature can be measured very
easily. The changes in properties can be felt by
Our senses.

4. In order to describe a system only a few properties Large number ofvariables areneeded to describe
are needed. a system.So the approach is complicated.
2.15. THE THERMOMETER AND THERMOMETRIC PROPERTY
2.15.1. Introduction
The zeroth law of thermodynamicsprovides the basis for the measurement of tempera
ture. It enables us to compare temperatures of two bodies 1' and 2 with the help of a
third body ´3' and say that the temperature of 1 is the same as the temperature of 2
without actually bringing 1and 2 in thermal contact. In practice, body 3 in the
zeroth law is called the thermometer, It is brought into thermal equilibrium with a set
of standard temperature of a body 2,and is thus calibrated. Later, when any other body
1is brought in thermal communication with the thermometer, we say that the body 1
has attained equality of temperature with the thermometer,and hence with body 2.
This way, the body 1 has the tenmperature of body 2
given for example by, say the
height of mercury column in the thermometer '3.
The height of mnercury column in a thernmometer, therefore, becomnes a thermometric
property.
There are other methods of temperature measurement which utilize various other proper
ties of materials, that are functions of temperature, as thermometric properties.
Six differentkinds of thermometers,and the names of the corresponding thermometric
properties employed are given below :
Thermometer Thermometric property
1. Constant volumes gas Pressure (p)
2. Constant pressure gas Volume ()
3. Alcohol or mercury-in-glass Length (L)
4. Electric resistance Resistance (R)
5. Thermocouple Electromotive force (E)
6. Radiation (pyrometer) Intensity of radiation (I or )
2.6. THERMODYNAMIC EQULIBRIUM
Asystem is in thermodynamic equilibrium if the temperature and pressure at all points
are same ; there should be no velocity gradient ;
the chemical equilibrium is also necessary.
Systems under temperature and pressure equilibrium but not under chemical equilibrium are
sometimes said to be in metastable equilibrium conditions. It is only under thermodynamic equi
librium conditions that the properties of a system can be fixed.

Thus for attaining a state of thermodynamic equilibrium the following three types of equi
librium states must be achieved :
 1. Thermal
equilibrium. The temperature of the system does not change with time and
has same value at all points of the system.
2. Mechanical equilibrium. There are no unbalanced within the system or between
forces
the surroundings. The pressure in the system is same at all points and does not change with
respect to time.

3.Chemical equilibrium. No chemical reaction takes place in the system and the chemi
cal composition which is same throughout the system does not vary with time.
2.18. REVERSIBLE AND IRREVERSIBLE PROCESSES
Reversible process. A reversible process (also sometimes PA
known as quasi-static process) is one which can be stopped at any
stage and reversed so that the system and surroundings are exactly
restored to their initial states. Equilibrium
states
This process has the following characteristics:
1. It must pass through the samne states on the reversed path
as were initially visited on the forward path.
ttH2
2. This process when undone will leave no history of events in
the surroundings.
3. It must pass through a continuous series of equilibrium
Fig. 2.29. Reversible process.
states.

No real process is truely reversible but some processes may approach reversibility, to close
approximation.
2.9. PROCESS
A process occurs when the system undergoes a change in a state or an energy transfer at a
steady state. A process may be non-flow in which a fixed mass within the defined boundary is
undergoing a change of state. Example : A substance which is being heated in a closed cylinder
undergoes a non-flow process (Fig. 2.4). Closed systems undergo non-flow processes. A process
may be a flow process in which mass is entering and leaving through the boundary of an open
system. In a steady flow process (Fig. 2.5) mass is crossing the boundary from surroundings at
entry, and an equal mass is crossing the boundary at the exit so that the total mass of the system
remains constant. In an open system it is necessary to take account of the work delivered from the
surroundings to the system at entry to cause the mass to enter, and also of the work delivered from
the system at surroundings to cause the mass to leave, as well as any heat or work crossing the
boundary of the system.
Quasi-static process. Quasi means 'almost'. A quasi-static process is also called a re

versible process. This process is a succession of equilibrium states and infinite slowness is its

characteristic feature.
 Examples.Some examples of nearly reversible processes are :
()Frictionless relative motion.
(ü) Expansion and compression of spring.
(ii) Frictionless adiabatic expansion or compression of fluid.
(iv) Polytropic expansion or compression of fluid.
(v)Isothermal expansion or compression.
(vi) Electrolysis.

Irreversible process. An irreversible process is one in which heat is transferred through

a finite temperature.

Examples.
(i)Relative motion with friction (iü)Combustion
(üüi) Diffusion (iv)Free expansion
(v) Throttling (vi) Electricity flow through a resistance
(viü) Heat transfer (viüi)Plastic deformation.

An irreversible process is usually represented by a dotted (or PA

discontinuous) line joining the end states to indicate that the inter
mediate states are indeterminate (Fig. 2.30).
Irreversibilities are of two types : Nonequilibrium
states
External irreversibilities. These are associated with
1.

dissipating effects outside the working fluid.

Example. Mechanical friction occurring during a process
due to some external source.
Internal irreversibilities. These are associated with
2. V
dissipating effects within the working fluid. Fig. 2.30. Irreversibleprocess.
Example. Unrestricted expansion of gas, viscosity and
inertia of the gas.
Comparison of Work and Heat
Similarities :
()Both are path functions and inexact differentials.
(ü)Both are boundary phenomenon i.e., both are recognized at the boundaries of the system
as they cross them.
(üüi)Both are associated with a process, not a state. Unlike properties, work or heat has no
meaning at a state.
(iv) Systems possess energy, but not work or heat.
Dissimilarities :
()In heat transfer temperature difference is required.

(ü) In a stable system there cannot be work transfer, however, there is no restriction for the
transfer of heat.
(ii) The sole external to the system could be reduced to rise ofa weight but in the case
effect
of a heat transfer other effects are also observed.
2.11. POINT FUNCTION
When two properties locate a point on the graph (co-ordinate axes) then those properties
are called as point function.
Examples. Pressure, temperature, volume etc.

dV= -V,(an exact

V, differential).

2.12. PATH FUNCTION

There are certain quantities which cannot be located on a graph by a point but are given by
the area or so, on that graph. In that case, the area on the graph, pertaining to the particular
process, is a function of the path of the process. Such quantities are called path functions.
Examples. Heat, work etc.

Heat and work are inexact differentials. Their change cannot be written as difference be

tween their end states.

Thus8Q Q,- and is shown as ,,or Q-2

2

Similarly SW # W,- W, and is shown as W, or W,2

Note. The operator 8is used to denote inexact differentials and operator d is used to denote exact
differentials.
 Qucsi- Static pacegsi
that
I3 he poocess (8 Caied out Buch cay
at every éatnt g the stery depants nty
boginitesimally Bcn thezmyic eguiboicry ns

Buch Peocess called 8 Quasí- sttic PeocesS.

AB 8 2ua8i-static paccegg, 1,2,3, 4....Sy3tem
themasrmonlcpoCeHS.
P A Quazi-salic
PoDCes3

Fguiliboium
Sales -PSen

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welghts slonly re by one the peSRUTe e g he gaz
dispace piston gndvally. it (s guasi- tatc
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othez hand 2 oe e
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gas paeESUIe e don't Cosdn tha ooss te
¿s done beeayse té iz ot En a Buetained moomer.
 Wooh done duzing Quaai-static pooceSS nd
Displacennent

F-PxA

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Position Positon

Qu8i-gtattc
) Process
wosh loonsBer

Consiabn piston clendee aegenent qs Erocon

in gce. Let Be Pieton moves Slooly er
Bmmae isplacerment dbe'the poce88 assm
-ed that guasi-static pooceS8.

Let ==Tn'ttal poessure ? tbe System

y = Tnital voeone a the setem
The
thenmeraniçs
Let tße

Zuiltbricn
Ptor 0Ne tds to
qulzbrion
a o

R=PoegsLeze l Syetern in fnal pitio.

 ohen ece aetig
F þxA A= azea a te pttn
The bngintestmal o cooos done by the gas'
Bletd

dw= Fx de (dv- Axdse =initteBinal

- þAxdb d'eplacement voume).

The coos done by the ga8 cchen piston ove8

toom tnitial POBition to fal on be obtaiad 4/1

by tntegoating above eguator.

2
dw=
Y. 2

Wi-aJ pdr
TL E8 alled dsplacement noas pdv orh.
Lirnltaton
To Depegent ook
w byp.dv the followin9
Cenditioos TDUst be
be BatiEZfed.
OThe System 8 a
takeplace n on-oes ysten.
PceS8 ¿3 a quasi-static
peoce88.
Boudany o systenn should
toct moe o osde
coetS ray be tanBeed.
Eectdue to goavity,
Bovce negliyible.
agretc,
magnetc. v8cays
ALL aove Condition Shuld beSalsfied
Sirmullomeoy Then he opoesfon
w=Adv valid.
Thezmoolyamic poocessi
Tt 8 degted as
change slate Bo thee

al zuilibacen slate to anoteer theznal

Gulibtem sate ts called therynalc
Pooes3. Pa

TYpes poegg
|Deycltc poess: I er the end thornsy

niC Poocess, the System ones back to ieg

Coginal state . then pcess ts calld as a

yele pooes3.
DNon- cycltc
thermenamte pacess,
peo cegs!. T aftey the
be sate of
d
the
of
sstem
lon the éniil géate, then poces
l8 dzerent

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cny chonges.
* TE e3 also alled gutsi- gtatic pooceES. NO Dl
Poocess is Peeely oevegsibe. But ome poe88eg
ay appach everaibilty to clase appocmation,
Eei- Pcton less zelative rotfon

ToeveGBible poeces:- A poocegs cshen OverEed

leoves soe mok on the sstem aguTCLENlengs
& carmet Cocd to the bniteal ate ystem
coitbout termal aput Buch poccess te aled
Cooevessible pDceBS.
Eel
To paove thot sk es
Considen
sa a

a
path
cloeed System cdee
nction :
gotng a chonge g state oc
1 to S.

aab connecttrg he d gale

|E.
voerstoceter deing pooce8
- l-a-a= azea beloo he
cuVe |-a
=
oek tocNBzer owring pOceB8 I-b-&
= asea belo the cave I-b
= b[ pal

Soce azea beloo the csve I-a-a 8 not egual

to the aea beloc the Cuzve I-b-, it tollows
that coots tonaer dlepends on the peth the
8ystem paRees trogh begre aiviog at the
tnal Btate. Thenefore cDoss t& a path fecttos

dv-wosk gor vazous thertrodynamics Quosi-sta

-tec) pooceae8:
Conzlant poes2uze poocegs :- (T8obaric pocess

Pr

Wi

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 Conséant oltane poCCE8 (Tsochoafe
PA

V=V, dv=o (artea

Caeve
unen th.
30)
W-2

O Conskant émperalwee pcess(sothesm)

Beut þv =C, PV, =V,=C

Wi-a

V
Ve
-kyx V = hvlg
V Wi-z =
hvlg

palytoptc pooceas :- (pc)

P^
P W-z =pdv
but pvn=c

T py? = v=bvn=c
þ

cohee n is costant.

V
dv
 = hy -n+)

= Pv, (v)
=
n-I

O TBentaopic pocess ;- (Revexsible aabati

2
(Pvec)
pvec
-

dv

Jv -n+I

= Ry°vw72
-94)

Wi-2 = -
|-9
hy,.vY*

Þy,-BV