THERMODYNAMICS

2.1 Zeroth law of thermodynamics

The sense of touch is the simplest way distinguish hot bodies from coldbodies. By touch
to distinguish This
we can arrange b0dies in the order of their hotness. We speak of this as our temperateeful
is a very subjective procedure for determining the temperature of abody and certainly notvol
tor purp0ses of sCience. Further, the range of our temperature sense is limited. What we need s a
obiective, numerical, measure of temperature.
The first step toward attaining an objective measure of the temperature sense is to sel Upa
criterion of equality of temperature. Let an obiect 4 which feels cold to the hand and an identical
object Bwhich feels hot be placed in contact with each other. After asufficient length of time, 4 and
Bgive rise to the same temperature sensation. Then, Aand Bare said to be in thermal equilibrium
with each other."Two bodies are in thermal equilibrium" means that the two bodies are in states such
that, if the two were connected, the combined system would be in thermal equilibrium. Iftwo bodies
are in thermalequilibrium when placed in contact, then by definition their temperatures are egual.
Conversely, if the temperatures of two bodies are equal, they will be in thermal equilibrium when
placed in contact.
The logical and operational test for thermalequilibrium is to use a third or test bodysuch as a
thermometer. This is summarised in apostulate often called the zeroth law of thermodynamics
Statement. IfA and Bare in thermal equilibrium with a third body C(the thermometer) thon
equilibrium with each other.
Aand B are in thermal know when two beakers of water are at the same
Explanation. Thus ifwe want to whether temperature
their properties change with time. We
contact and see
to bring them into
it is unnecessary to
walel (004y A) and wait until somne n r o w e
insert such as(body
a thermometer
thermometer, C) inofone
the length mercuryol column in a glass capillary, becomes constant. Then
the beake
oy definition, the thermometer has the same temperature as the water in the beaker A. We next repeat
the procedure with the other beaker of water (body B). If the lengths of the mercury columns are the
same, the temperatures of Aand Bare equal. Experiment shows that if the two beakers are brought
properties take place.
their
into contact, no changes in the basis ofoconcept of temperature. All
be said Significance.
to possess a This
property forms
lawthat ensures their beingin thermal equilibrium these
with three
one another. This
systems
property is known as temperature. We may, therefore. define the temperature of a system as can the
nal
thermal
Systems. It is determines
property that
if two or
obvious thatwhether systems
System is in
nottheare equilibrium, withwill
not in thermal equilibrium, they the be at different
neighbouring
temperatures. Speakingloosely, the essence ofthe zeroth law is : there exists a useful quantity called

temperature.
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 THERMAL PHYSICs
24

2.2 First Law of thermodynamics

system is equal to the algebraic sum of the
Statement. The amount of heat supplied to a external work done by the system.
the amount of
change in internal energy of the system and
of thermodynamics is
Explanation. The differential form of the first law
dQ = dU+ dW
dQ = amount of heat supplied to the system
dU =increase in internal energy of the system
dW external work done by the system.
units supplied must be balanced by the external
In all transformations, the energy due to heat
work done plus the increase in internal energy.
mechanical energies (work) is set up and in the
In the first law, a conversion between heat and
balancing process, internal energy U is defined.
the heat gained by the
When a cold body is placed in contact with a hot body, first law says thatattained. The first law
is
colder body is equal toheat lostby the hotter body when an equilibrium
colder to the hotter body. The
does not specifically say that heat does not flow spontaneously from the covered by first
fact that heat can only pass from a hot body toa colder body and not otherwise is not
law. First law is, therefore, insufficient for the sake of completeness of thermodynamic studies. To
second
cover the directional properties of heat, it is desired to define some law. This is the basis of the
law of thermodynamics.
Significance of the first law. The first law of thermodynamics establishes the relation between
heat and work. According to this law, heat can be produced only by the expenditure of energy in some
form or the other. Hence it follows directly from this law that it is impossible to make a perpetual
motion machine or toderive work without any expenditure of energy.
Application of the first law. From the first law of thermodynamics,
dQ = dU+ P dV ...()
The thermal energy of asystem Uis afunction of any two of P, Vand T. Choosing Tand V,
U=f(T, n ...(2)

OU OU
We have, dU = dT + dV ...3)
oT Jv
Therefore, the first law becomes

dT .(4)
T )v
Dividing by dT, we get
dy
+P ...(5)
dT dT
This equation is true for any process involving any temperature change dT and any volume
change dV.
(a) If Vis
constant, dV = 0 and
d ...(6)
 2.11 Second Law of
thermodynamics
There are two conventional statements of second law of thermodynamics.
(9Clausius statement. I is impossible for self-acting machine, unaided by any exter al
3en', to transfer heat from abody at alower temperature to abody at a higher temperut,r
heat cannot of itself pass from a cold to a
hot body.
Explanation. This statement implies that to convey heat continuously from a cold to a hot bo0y,
t is necessary to supplywork by an outside agent. We know from experience that when two bodies are
in contact, heat energy flows rom the hot body to the cold body. The second law rules out the possibility
OT heat energy flowing from cold to hot body in such a case and so determines the direction of transter
of heat. The direction can be reversed onlyby an expenditure of work. This takes place in a
in which refr1gerator
electrical energy is used to pump heat from the cool interior to the warmer room.
It is impossible to construct a refrigerator that works without the supply of energy.
(in Kelvin-Planck statement. It is impossible to construct a device which, operating in a
cycle, has the sole effect ofextracting heat from a reservoir and performing an equivalent amount of
work.
Explanation. According to this statement, a single reservoir at a single temperature cannot
continuously transfer heat into work.This statement implies that we cannot produce mechanical wotk
by extracting heat from a single reservoir without returning any heat to areservoir at alower temperature
As an example, it is impossible to drive a steamship across the ocean by extracting heat from the
Ocean.

Hence,heat can be converted into work only if abody at a higher temperature and another d
a lower temperature are available.
2.12. Thermodynamic (or Absoluteor Work) scale of temperature
The efficjency of a reversible engine is independent of the working substance and depends
onlv on the two temperatures between which the engine works. Since n =|-0.lo o n
can depend only on the tempera-tures. This led kelvin to suggest a new scale of temperature. If we
equation is
let a. andq, represent these two temperatures, his defining
 ...(8)
2.3 Heatengine
Heat engine is a device which converts heat into work A heat engine, in
three parts. general, consists of
1. A source or high
temperature reservoir at Source
a temperature T, T,
2. Asink or low temperature
reservoir at temperature
3. Aworking substance.
In a cycle of heat engine, the working
substance Working
substance W=Q,-Q.
extracts heat , from source, does some work Wand rejects
remaining heat 2, to sink (Fig. 2.1).
Efficiency of heat engine
n=
Work done (W)
Heat taken from source (2) Sink
=|-_7-5 Tz
Fig. 2.1
This is general expression for the efficiency of heat engine.
2.4 Expression for the efficiency of aCarnot's engine
Carnot's engine consists of the following parts.
(1) Source. A source is a hot body at a constant temperature 7, K. The heat engine can
heat from the source (Fig. 2.2). draw
(2) Sink.The sink is acold body at a constant lower temperature T, K. Any amount of heat
be rejected to the sink. can

(3) Working substance. The working substance isan ideal gas enclosed in a cylinder-piston
arrangement.
26
THERMAL PHYSICs

Pertectly non-conducting stand is also provided so that the working substa0

adiabatic operation.
Piston

Working
Substance Cylinder
(Air)

Conducting
Conducting Insulating Conducting

Source Sink
Stand
T, K T,K

Fig.2.2
2.5 Carnot's cycle as refrigerator Hot

When the Carnot's engine works as arefrigerator, it absorbs

heat , from the sink at temperature T,. Wamount of work is
done on it by some external means and rejects heat O, to the
source at a temperature T, (Fig. 2.4).

Coefficient of performance = W
W

The coeficient of performance Kis defined as the ratio

of the heat taken in from the cold body to the work needed to
run the refrigerator.
Cold
Example 1. Find the efficiency of the Carnot's engine
working between the steam point and the ice point.
Sol. T, = 100°C =373K,T, = 0°C=273K, n =? Fig. 2.4

n=
T -, 373 - 273 a
0.2681 = 26.81%
373

Example 2. Find the efficiency of aCarnot's engine working

Sol. T, = 273 +
between 127C and 27°C.
127 400K, , =273 + 27 =300K, n =?
300
12 400
= 0.25

%efficiency =259%
 29
THERMODYNAMICS
Fxample 3. 4 Carnot's engine is operaled beWeen wo reservoirS al temperatures of 450K
heat fromthe source in each cycle, calculate the
If the engine receives 4200joules of engine and the wol
end 350 ¤
heat rejecdedto the sink in each cycle. Calculute lhe efficiency of the
mOunt of
each Cvcle.
done bv the engine in Q, 4200 J;
T, -350K; Q, -?
Sol. T, 450K;

4200 x 350 = 3267J.

450

350 = 0.2222 =22.22%

n=1 450)
Work done by the engine in each cycle
=0, - , =4200 -3267= 933 J
Example 4. A Carnot's engine whose temperature of the source is 400 Ktakes 840 J of heat
the temperature of the sink? Also
a this temperature and rejects630 J of heat to the sink. What. is
calculate the efficiency of the engine.
Sol. , = 840J, , =630 J, T, =400 K, T,=?
S
400
- 630 = 300 K.
840

300
n=1 =|- = 0.25
400

% efficiency = 25%
Example 5: A Carnot engine whose low temperature reservoir is at 7°C has an eficiency of
50% It is desired to increase the eficiency to 70%. By how many degrees should the temperature oj
Ihe high temperature reservoir be increased?
Sol. I Case. n=50% =0.5; T,=7°C=273 + 7=280K; T,=?

Now,

280
0.5 =| or 7 =560 K

II Case. n'=70% =0.7, T, = 280K, T; =?

n'=|
T
280
or 0.7 =| or T = 933.3 K
T
 THERMAL

30

Increase in temperature
work When temperature
the
-T, =933.3 - 560 =373.3 K input inno source and th
=I ofheat
comverts l/6th the
temperature of the
Example 6. A Carnot engineefficiencyis doubled Find
the sink is reduced by 62°C, the
sink.

Sol. ICase. n= or 7, = 1.27,

' = - ; -62)_,!
IICase. 6

7-7+62 1
Or 3

or 27 =3T,- 186
or 2 x 1.2 T, -3T, - 186 (:T=12 T)
T,=310K = 37°C
T, = 1.2T, =1.2 x 310 =372K =99C.
between 260 K and 300 K receive
Example 7. ACarnot's engine working as a refrigerator amount of heat rejected t
2100J of heat fromthe reservoir at a lower temperature. Calculate the
work done in each cycle ts
Ihe resenvoir at ahigher temperature. Calculate also the amount of
operate the refrigerator.
SoL. T, = 300 K, 1,= 260 K. 2,-2100 J:
300
:2100 = 2423 J
T 260
Hot
Work done = W=9,-9, - 2423 - 2100=323 J.
Example 8. A Carnot srefrigerator takes heat from water at
0°C and discards it to aroom at 27°C. 1kg of water at 0°C is to be
changed into ice at 0°C How many joules of heat are discarded to the
room? What is the work done by the refriger ator in this process? What
is the coefficient ofperformance of the machine? W
SoL. When the Carnot's engine works as a refrigerator, it
absorbs heat , fromn the sink at temperature T, Wamount of work
is done on it by some external means and rejects heat , to the
source at a temperature 7 (Fig 2.5).
Cod
Coefficiet of perfornance =
2- T,-7,
Fig 2.5
Here, T, -300 K, T, = 273K
Heat given out by ikg of water at0°C when tis converted into ice,0. -336 1051

e-(336
273) 10) =3692 10 1
THERMODYNAMICS
() W=(Q,-Q)=(3.692 x 10)-(3.36 x109) =3.32 x104J
(3.36 x 10)
(u) Coefficient of performance = = 10.12
e-e (3.32 x10*)
2,6 Carnot's theorem
Thetheorem consists oftwo parts and can be stated as follows:
() All reversible heat engines working between the same two temperatures have the s