CHAPTER

THERMODYNAMICS
Chapter Objectives
Thermodynamics: Thernal equilibrium, Zeroth Law of Thermodymamics, Conceyt of teniperature, heat, work and iniernal

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energ Firstlatoof thermodyumics, iothermal, isochoric, fsobaric and adiabatie processes

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Secondlowof thermodynumics : reversible nnd irreversible procesnes, Heat engineand refrigerator, Carnot theorem, Carnot
its efficiency.
engineand

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STUDY MATERIAL
For more details,
Concepts Clarified:

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can the code

Thermodynamics: It can be defined as the study of interrelation between heat and otherforms of

energy
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Thermodynamic System : A thermodynamic system can be defined as the collection of large
number of molecules of matter ie., solid, liquid, gas which are arranged such that it possess an
amount of pressure, volume and temperature.
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There are various thermodynamic state variables like Pressure, Volume, Temperature and Internal Temperature etc.
which are the dependant attributes of a thermodynamic system.
in thermodynamics, we study the interaction of heat & energy during the change of one thermodynamic state to
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another and deals with the thermodynamic systems.

Thermal Equilibrium: Equiibrium implies to a state where alldependant variables of a
thermodynamic system ie, Pressure, Volume and Temperature
do not with time.
change
Two connected system come to a Thermal Equilibrium as their temperature becomes same. For more details,
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Zeroth law of Thermodynamics: It is based on thermal equilibrium. As per this law, if there exist an the code

three system A, B and C such that A and C are in thermal equilibrium aiso B and C are in thermal
equilibrium then A and B will also be in thermal equilibrium.

Concept of temperature:
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Temperature is a relative measure of hotness or coldness of the body.

SI Unit Kelvin (K) A
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Commonly Used Unit °C o r °F or °R

Hence, complete relation among °C, °F Kand °R is given as
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0 32 273.15 =-0
100 0 212 32 372.15-273.15 80-0

AbsoluteTemperature Scale:
K
lt is Kelvin scale wherein Ice Point273.15 K, Steam Point =373.15
both have s a m e reading.
At 40 degrees, Celsius scale and Fahrenheit scale
For more details,
Heat, Wark and Internal Energy scan the code
system that exist due to its
nternai Energy(U) can be defined as the energy possessed by any Centre of Mass. The internal
to the Frame of
exist with
ecular KE and PE. This PE and KE molecularrespect motion. The only dependant attribute
of Internal
of the matter exists due to its
Y
tnergy is the Existing State
Mathematically, U= I L
3 n = Number of Moles,f = Degree oíFreedom, R = Universal Gas Constant, T = temperature
T e I n t e r n a l Energy,
wher
e:Adding Work or Heat will affect the Internal Energy of the System directly.
Heat Energy It can be defined as the energy transformed from the systenm or to the system by the proce.
Conduction, Convection and Radiation. This transformation occurs due to the existenceof Temperature Difes
The energy that is transferred from one system to another by force moving its point of erence
direction is called work.
application in its Own
Work doneby the system: Fdx P, Adx =[,4V =

x
Where Ps is the pressure of the piston, net work done can be positive or negative
depending on expansion or contraction respectively. Work and heat are function of
path whereas Internal Energy is the function of state. Heat and Work are independent System
attributes in spite they appear same in most cases. F=PA
Important Terms
State variables: PV, T moles (Extensive or Intensive depending on state)

Equation of State: Equation that connects P (Pressure), V (Volume) and T (temperature) of a gas under certai

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conditions is known as Equation of State.
specific

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A. Boyle's Law: PV =Constant
B. Charle's Law: V/T = Constant

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Which gives, PV nRT

Thermodynamic Process: A process is said to be thermodynamic when the variables of the system changes wit
time. The variable can be Pressure, temperature or Volume. There are various types of Thermodynamic Processesax
follows:
1. Isothermal: The process when only Temperature remains constant throughout.
2. Isochoric: The process when only Volume remains constant throughout.
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3. Isobaric: The process when only Pressure remains constant throughout.
without transfer of heat or mass of substances between a
4. Adiabatic: An adiabatic process occurs
work in
surroundings. Energy is transferred to the surroundings only as an
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thermodynamic system and its

adiabatic process. For more details
Scan the code
Quasi Static Process:
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and thermal changes take place at such a slow

A process under equilibrium in which the mechanical
rate that at every instant the system seems to be under constant equilibrium with the surroundings.
Note: All the processes are considered as Quasi static unless it is defined or given.
PV Indicator Diagram A graph plotted between Pressure and Volume of a gas under P
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Thermodynamic Process. Such a system is known as P-V Diagram.

a Isobaric, b> Isothermal, c > Adiabatic, d - Isochoric,
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Area under P-V diagram gives the value of Work done.

First Law of Thermodynamics:
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For more details

Let AQ = Heat supplied to the system, AW = Work done by the system, AU

=
Change in scan the code

Internal Energy.
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the energy can

of Energy, it states that
First law of Thermodynamics is the law of Conservation another form.
transformed from one form to
never be created nor be destroyed. It can be
AQ = AW+ AU

when heat is added to the system and AQ is negative

when heat moves out ot the
1. AQ is positive
system.
and while contraction, work is negative.
2. During Expansion, work is positive AU is negative when temperature
deceases.
3. AU is
positivewhen temperature increases, whereas is 1st Law considered
Hence the
considered to be performed o n the system.
In chemistry, work done is usualy
AQ+AW =AU.
Application:
on various processes:
how First Law of thermodynamics is applicable
nust

Let's see
Usually the walls of the container mu
with Constant temperature.
A. Isothermal Process: The process and its surroundings.
between gas
perfectly conducting to
allow free exchange of heat
conditions are perfectly ideal.
Process will be slow and both the
Constant or PV Constant. =
T
Equation of State:
=
 IndicatorDiagram P
PV at any point, AU
PA
Slope of
=
0:
V
W-r,av (Temperature remain constant) T

RT
W-4V V
(Using PV = nRT)

W nRTin

First Law of Thermodynamics, Q = W + AU

Q nRTIn ,

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The heat is supplhed
Remarks:All the heat supplied is used entirely to do work against external surrounding.
then the gas expands & if heat is withdrawn then the gas contracts.

Real Life Examples (a) Melting of ice at 0c, (b) Boiling of ice at 100°C

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. Adiabatic Process: When there is no heat exchange with surroundings.
or
any exchange
Conditions: The walls of the container must be perfectly non-conducting in order prevent
to
be rapid so there
or expansion should
heat between the gas and its surroundings. The process of compression

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conditions and are hard to obtain.
is no time for the exchange of heat. These conditions are again ideal

Equation ofState: PV = Constant or TV'= Constant or PT= Constant

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Indicator Diagram: PT
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Slope of Adiabatic Curve

=

******no- **~---
** isotherm
Curve. ....

Graph for Adiabatic Curve is steeper than Isothermal

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AU=RDInR(L-T,) PV-PV
2 Y-1 Y-1
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Work Done by Gas: If gas expands from V, to V2 W=-V V

Hence, PV = Constant»P = Constant/V

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[v Constant 1 L
onstant1- 1-7 v"*
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And we know, P V'=P2 V,= Constant

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-w-y-R%_nR(T-T)
1-y 1-Y
First Law of Thermodynamics: Q AU+W (Substituting the Values)
Under Adiabatic Process, Q = 0.
decreases and vice versa.
fgas expands adiabatically then its temp
Real Life Examples: Sudden burst of Cycle.Tube
A heated or cooled inside a rigid container
Isochoric Process : Volume remins constant. gas being
Constant.
of State: V Constant or P/T
=
Equation =

AUfRAT nR(T,-T)-V-PY nRAT

Y-1
2 Y-1 Y-1
Work, W =0 (as gas does notexpands)
nf RAT
rirst Law of Thermodynamics: Q= AU+ W=
2
 When heat is supplied to abody the temperature increases as per the relation, Q= nCAT =»C=
nAT
Coniy depends on external conditions for gases. Here it is referred as ie, Molar heat capacity at Conath
Volume. nAT stany
Comparing we get, Cy -
D. Isobaric Process: When pressure remains constant. When in one container, the piston is free to move andisn
connected by any agent. iS no
Equation of State:P Constant,V/T = Constant P

IndicatorDiagram:
AU = R A T

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W=PaV=PAT =PV,-PV =nRAT

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First Law of Thermodynamics:
Q aU +w =a4 nRAT=|

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2
Like Cy we can define molar capacity at Constant Pressure

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C, Usingthe above equation: C,-+R sh
Replacingwith C,we get,C, =
C, +R
Like Specific Heat at Constant Volume and Constant Pressure, we can define the molar specific heat for any
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process.
Example:Cadiabatic = 0, Cisothermal

Basically, gas does not possess a unique specific heat., Mainly we have Cp, C
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Specific Heat Capacity at Constant Volume : Amount of heat required to raise the temperature of 1 g of a gas
through 1°C keeping volume constant. It is denoted by C
Specific Heat Capacity at Constant Pressure : Amount of heat required to raise the temperature of 1 g of a gas
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through 1°C keeping pressure constant. It is denoted by Cp

We have the relation as Cp-C, R
Melting Process In any case, first law is always applicable,
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Qm
W 0 (In such change of state from solid to liquid we ignore any expansion or contraction as it is very small)
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First law of Thermodynamics: AU Q-W mL = =

Note: The heat used in this process is used in increasing internal energy of the system.
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Boiling Process
Q mLy=P(V -V,)- Pressure is constant during boiling and equal to atmospheric pressure.
Pt For more details
AU Q-W =
my-P(V2-V) scan the code

Cyclic Process
A cyclic process is the one which returns to initial stage after undergoing a
series of changes.
AU mly=Q
where, W- area under loop, Q = W as per First Law of Thermodynamics.
Note: W is positive if cycle is clockwise and it is negative if the cyclic process is anti-clockwise.

Limitations of First Law of Thermodynamics:

(i) It doesn'tpredict the direction of occurrence.
(ii) Extent of Change cannot be predicted using this law.
Heat Source cannot be predicted using this
law.
(iii)
 Taat Engine: Heat Engine is a device that converts heat energy into mechanical energy
Hea
ieat Source at higher
E l e m e n t s - 1 .

temperatuure
2. Working Substance
3. Heat Sink at lower
temperature
Working: Q, heat trom Heat Source enters the System W
k W is done by the system» Q2 heat is rejected to Heat
Sink.
Applying First Law of Thermodynamics
Energy is always conserved : Q ==W+Q Source or Working Sink or Cold
Reservoir
Thermal Efficiency of a heat engine is defined as the ratio of
Hot Reservoir| Substance
net work done to the net heat absorbed by the system. Usually T
denoted by n.
W

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We get the final equation as n=1-
Note: Efficiency in
ideal case is 1 and the mechanism for conversion of
heat into work varies for different engines.

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Based on heating mode, heat engines are classified majorly into two
External Combustion Engine: External Furnace is used to heat the system within Heat Engine.
is produced internally by burning of fuel to generate heat and same is used
to
Internal Combustion Engine : Heat

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heat the system within Heat Engine.
Refrigerators and Heat Pump:A refrigerator or heat pump is a device used for cooling things.
Elements: 1. Cold Reservoir at temperature T sh
2. A working substance
3. Cold reservoir at temperature T1
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Working mixture.
1. Sudden Expansion of Gas from High to low pressure and convert it to vapour liquid
2. Collection of heat from the region to be cooled converting the cooling fluid into vapour.
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3. Heating of vapour due to the external work done on the working substance of the system.
W
4. Release of heat to the surrounding and bringing it to initial
state.

First Law of Thermodynamics, Q W+ =

Q1 Hot | Cold
Coefficient of Performance : It is defined as the ratio of Quantity Reservoir Q2 Reservoir
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of heat removed per cycle from content of refrigerator (Q) to the T2

this heat.
energy spent per cycle (W) to remove

(Ideally B=o)
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Second Law of Thermodynamics:

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This law can be stated in many ways. Both statements are same, but both had their own signiticance. |For more details,
whose sole result is the absorption of heat from scan the code
A. Kelvin Plank Statement-"No process is possible
conversion of the heat into work".
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a reservoir and the complete sole result is the transfer of heat from a colder
8. Celsius Statement: "No process is possible whose

object to a hotter object".

Note: 100% efficiency in Heat Engine orinfinite
COP (Coefficient of Performance) in Refrigeration
is not possible in real. For more details,
scan the code
Reversible and Irreversible Process: from a n initial state i moves to
is said to be reversible, ifthe system
aReversible f and theAprocess
A.
final stateProcess: processcan be turned back under similar initial state without any changes
universe as well.
will be no changes anywhere in
tO the surrounding. There
ImportantConditions:
Process should be Quasi- Static.
. forces like Friction, Inelasticity etc.
should be free from Dissipative
System but slow expansion ot
a n ideal gas is almost reversible.

Example : No such process exists doesn't satisty any c o n d i t i o n tor Reversible process is called Irreversible
B. Process : A process which
irreversible
Process.
Important Condition
. Process is spontaneous.
2r e s e n c e of Dissipative forces like Friction, Viscosity etc.
Significance of Reversibility: Por more detaila
1. Heat is converted into Mechanical
Energy. scan the eo
2. Second Law of Thermodynamics rules out the possibility of the perfect heat engine with 100%
efficiency.
3. Heat Engine based on ldealised reversible cycle achieves the Highest Possible Eficiency
Carnot Engine
A scientist named as "Sadi Carnot" designed a system based on Ideal
Cycle of operation for a Heat engine called Carnot Cycle. Engine based on
this cycle is called Carnot Engine.
The basic required parts of an Ideal engine are shown as Ideal Cylinder
A. Heat Source : The heat source is maintained Gas
usualiy at higher
temperature T, the working substance draws the required heat from Source at
the source. The Source is an infinite reservoir of heat and
any amount Temp. T,
Insulating8 Sinkat
of heat can be drawn from it, keeping the
LPad Temp.T
Temperature T.at
B. Heat Sink: The heat sink is usually maintained at fixed lower
temperature T2 the working substance rejects th

h
left-out heat to the sink. The Sink is an infinite reservoir of heat and
any amount of heat can be rejected to t
keeping the Temperature at T2

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C.Working Substance:A perfect gas acts as the working substance. It is contained in a cylinder with non-conducting
sides but having a perfectly conducting-base.
Note: Thereis an Insulating pad or stand which is usually used to carry the

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cylinder that isolated the working substance completely from the surroundings.
The main 4 stages of Carnot Cycle are as follows : A(V, P)
A. Isothermal Expansion BV,P)
C. Isothermal Compression
Carnot engine usually follows Carnot
B. Adiabatic Expansion
D. Adiabatic Compression
Cycle as
shown in figure: ita DY,P)cv,?
:
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Consider 1 gm mole of an ideal gas enclosed in the cylinder. Let V,, P, T, be
the
pressure temperature of the gas. The initial state
initial volume, and
gas is represented by the point A on P-V diagram, we shall assume that all the
of the
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four processes are quasi-static and non-dissipative, the two conditions for their MN X
reversibility. Volume (V)
Steps involved in this Cycle:
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A. Isothermal Expansion: The cylinder is at source and

gas expands by slow motion of piston in outward directio
As base is perfectly conducting, process is isothermal.
Now, AU, = 0
am

4 W RT, In =Area ABMKA

Here, 4 Heat absorbed by gas, W,= Work done by gas.

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B. Adiabatic Expansion: The cylinder is removed from source and is placed on insulating pad. This gas can expand
further from B to C i.e., P;V2 to P^V3 This process is adiabatic as the gas is thermally insulated from all sides.
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4-0AU,- Y-1
w,-Kl=-Area
Y-1
of BCNMB
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C. Isother1nal Compression: Now the cylinder is removed from insulating pad at temperature T2 it is placed o
the heat sink. Thepiston is moved slowly such that the gas is compressed until the pressure reaches P, and
volume is V
AU, =0W, =RT,In - =Area of cDLNC

4,-RT,In
where, 4,=heat absorbed in process, W, = workdone by gas.

D. Adiabatic Compression: The cylinder is replaced oninsulating cylinder in order to keep the process in adiabalts
condition. Here the gas is further compressed to Initial state Pi and V.

AU,-
Y-1
W, -

Y-1
- Area DAKLD
Here, 4,-0, W, = Work done by gas.
Analysis:
Totalwork done by engine per cycle,
W+W+W,+W, = W, +W
As, W-RT,In+RT,In

Total Heat Absorbed =q, =RT, In

0, nv
0,=Total Heat
Released =-4, =
RT,in

Area under ABCDA

Wecan see that for heat engine, W= Q-Q
=

Efficiencyof Carnot Engine, n==1-

h
Q ,

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Now Step 2 is adiabatic, Step 4 is also adiabatic.
TV=T,V

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and T,V =T,V

Q T
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lcarnot
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source temperature and

sink temperature.
1. carnot engine -Only depends upon attain.
which is impossible to
when T2 =0, K or T,
o =

2. engine1; Only
carnot mechanical energy unless
there is some difference between
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Heat cannot be converted to

3. If T T2 n ;
=

temperature of source and sink.

be stated as follow:
The statement can
Carnot Theorem: reservoir) and T2 (Cold Reservoir) respectively
two source and sink T,(Hot
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A. No engine can given

work between
than the Carnot Engine.
that can have an efficiency higher Such an Engine is known as Carnot
Substance used in the Engine.
of the Working
B. is
Efficiency independent
Engine.
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Proof of Carnot Theorem Same Source (Hot

-

T,) and
between
R and an Irreversible Engine I, working
1. Let there be a Reversible Engine
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Sink (Cold T) and

i.e., Iacts as Heatengine W
2. Rand I will act like couple in the system
a
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Ractsas Refrigerator. deliver work

the -W
Q, heat from
source

I absorb
3. Working: "Let engine W to the sink in one cycle".
balance Q
-

W, and release the to the source taking Q,

same heat Q, T
such that it returns be done on it. Q-W
.4
K1s arranged
trom the sink and requiring

< n, if R must
work W Q1-Q,to
act as an engine
=

it would give less output

R
Suppose nR Q-W>Q-W.
and
than that of I, W<Wfor a given Q, heat (Q,
-

W) -

(Q1- W) =
W -
W and delivers same

5. In total if we calculate the

value, system extracts
the 1-R
Kelvin Plank Law (Second
law of thermod ynamics)
This is against the
amount of work in one cycle. tor the second statement i.e.,
"Carnot efficiency is
Similar holds good
wrong.
Hence Q, > QR is
assertion

Independent of working substance.

always hold good for

any working substance
TWill