Delhi Public School, Sonepat

CLASS-11
SUBJECT-PHYSICS
Chapter: Thermodynamics

Thermodynamics: It is the branch of Physics which deals with the conversion of heat energy
into mechanical energy and vice – versa.

System: A thermodynamic system is an assembly of large number of particles.

Surrounding: Those particles which are having a direct impact on the system are called
surroundings.

A system and its surroundings are separated by Walls.

W The walls are of two types:
types
1. Diethermic Walls and 2. Adiabatic Walls

1. Diethermic Walls: Those walls which allow free exchange of heat between system and
surroundings are called diethermic
dieth walls.
2. Adiabatic Walls: The walls which do not allow exchange of heat between system and
surroundings are called adiabatic walls
walls.

There are three types of Systems:

ystems:
1. Open System: In this system heat and matter are exchanged freely between system and
surroundings.
2. Closed System: In this system only heat is exchanged but not matter with surroundings.
3. Isolated System: In this system no exchange of matter or heat takes place with
surroundings.

Thermodynamic Variables: The variables which determine the state of a system: P, V and T.

Equation of State: An equation which helps us to find the relation between thermodyna
thermodynamic
variable. Example: PV = nRT (Ideal Gas Equation)

Zeroth Law of Thermodynamics: If two systems A and B are separately in thermal equilibrium
with a system C then they both are in thermal equilibrium with each other.

Temperature: Temperaturee is defined as that physical quantity which determines whether two
objects are in thermal equilibrium or not.

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Thermodynamic Processes: Thermodynamic processes are those processes in which
thermodynamic variables like P, V and T change with time. Example: Compression of Gas.

They are of Four types:

1. Isothermal Process: A process which takes place when temperature is maintained
constant throughout is called isothermal process (diethermic walls are required for this
type of process).
2. Isochoric Process: A process which takes place when volume is maintained constant
throughout is called isochoric process.
3. Isobaric Process: A process which takes place when pressure is maintained constant
throughout is called isobaric process.
4. Adiabatic Process: A process which takes place when heat content of the system is
maintained constant throughout and exchange of heat is NOT allowed is called
adiabatic process (adiabatic walls are required for this type of process).

Sign Convention:
(i) Heat Energy: ∆Q = Positive (heat is supplied to the system)
∆Q = Negative (heat is removed / lost from the system)
(ii) Internal Energy: ∆U = Positive (internal energy of the system increases)
∆U = Negative (internal energy of the system decreases)
(iii) Work Done: W = Positive (work is done by the system)
W = Negative (work is done on the system)

Internal Energy: Internal Energy is the energy possessed by the system (gas). It is of two types:
1. Internal Kinetic Energy: It is the energy possessed by molecules due to their constant
random motion.
The speed of the molecules depends upon the temperature. More the temperature more is
the speed and hence more is the kinetic energy. Therefore, Internal Kinetic energy is a
function of temperature.
2. Internal Potential Energy: It is the energy present among molecules of an object
because of their position with respect to each other due to intermolecular forces of
attraction.

In real gases, internal energy is present due to both kinetic and potential energy of atoms but the
absence of attractive force among molecules of ideal gases result in absence of internal potential
energy between the molecules.
Therefore, internal energy for Ideal gas is only Kinetic and is a function of temperature while
for Real gas it is both Kinetic and Potential.

Isothermal Process: The two conditions which are essential for isothermal process are:
1. The walls and base of the container should be diethermic, then they allow heat to
exchange and keep the temperature constant.
On compression the heat of the system should be lost to keep the temperature constant as
compression results in increase of temperature.
On expansion the gas cools down and hence needs to gain heat to keep the temperature constant
as expansion results in decrease of temperature.

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 2. Moreover, the process should be slow to allow exchange of heat.

Equation of Isothermal Process:

Process PV = Constant

Adiabatic Process: The two conditions which are essential for adiabatic process are:
1. The walls and the base of the container should be adiabatic (heat is neither absorbed nor
released).
Temperature changes as during compression temperature increases and during expansion
temperature decreases.
2. The process should be fast so that the system (gas) does not get enough time for exchange
of heat.

Equation of Adiabatic Process:

Process PVγ = Constant
where γ = cp / cv where cp is the specific heat capacity at
constant pressure and cv is the specific heat capacity at constant
volume

The value of γ for monoatomic
ic gas =  = 1.67

γ for diatomic gas = = 1.40



γ for polyatomic gas =  = 1.33

Other Equations: As, PV = RT (n = 1)

P = RT / V
Substituting, PVγ = RTVγ-1 = constant => TVγ-1 = constant

Also, V = RT / P
Substituting, PVγ = P (RT/P)γ = constant => P1-γTγ = constant

Indicator Diagram / PV Diagram

Diagram: Plotting a variation of pressure with volume for various
thermodynamic processes results in a diagram called Indicator diagram. The Slope of such a
diagram or PV curve as it is called depends on the type of process or change i.e. isothermal or
adiabatic.

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To prove Slope of Adiabatic Curve is more than the slope of Isothermal Curve:
Curve

Proof:: The equation of Isothermal process is PV = constant

To find the slope we differentiate the above equation.
PdV + VdP = 0

PdV = - VdP

- P / V = dP / dV = slope --- (i)

The equation of Adiabatic process is  PVγ = constant

To find the slope we differentiate the above equation.
PγVγ-1dV + VγdP = 0

γPVγ-1dV = -VγdP

- γPVγ-1 / Vγ = dP / dV

-γP / V = dP / dV = slope --- (ii)

Therefore slope of adiabatic curve is γ times slope of isothermal curve and has more slope than
isothermal curve. Figure (c) represents expansion while figure (d) represents compression.

Work done in an Isothermal Process:

Process: Let us consider an isothermal process with initial
volume V1, final volume V2, pressure P and temperature T.
The work done W = (Force) . (Displacement)
(

dW = F . dx where, F = force applied by gas during expansion
and dx = displacement of piston

dW = PAdx

dW = PdV --- (i)
Now using ideal gas equation, PV = RT (taking n = 1)

P = RT / V
Putting in equation
uation (i), dW = RT dV / V
To get the total work done, we integrate the above equation, we get

W =   = RT 
  

W = RT [loge V] (from V1 to V2)

W = 2.303 RT [loge V] (from V1 to V2)

W = 2.303 RT [loge V2 - loge V1]

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Wiso = 2.303 RT [loge  ] --- (ii)

For isothermal process, PV = constant

P1V1 = P2V2

P1 / P2 = V2 / V1


Wiso = 2.303 RT [loge  ] --- (iii)

Work done in an Adiabatic Process: Let P1, V1 and T1 be the pressure, volume and temperature
of the system in its initial state and P2, V2 and T2 be the pressure, volume and temperature of the
system in its final state.
If expansion takes place, V2 > V1 and the work done by the system will be positive.
If compression takes place, V2 < V1 and the work done by the system will be negative.
Now, work done during expansion of gas in adiabatic change = W =   =  
For adiabatic change, PVγ = constant = K

P = K / Vγ
 

W =   =  

 


W=K     

 

W=K  (from V1 to V2)
 



W=       --- (i)
 

We know that in adiabatic change P1V1γ = P2V2γ = K


Also, W= !    ! 
 

    

W= P V $   P V $ 
 


W= [P2V2 – P1V1]
 
For an ideal gas, PV = RT (for n = 1)


W= %&'  &' (
 
)

Wadi = [T2 – T1]
 *

If T2 > T1; W = negative as γ > 1 => 1 – γ = negative

Negative work means work is done on the system. Hence compression leads to increase in
temperature.
When gas is allowed to expand temperature of gas falls and T2 < T1 => W = positive and work is
done by the system.
+
Heat absorbed or released can be related to work using Joule’s constant: H= where J = 4.18
,

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Work can be also found by the area under the PV diagram or indicator diagram.

First Law of Thermodynamics: The first law of thermodynamics states that if heat is supplied
to a system capable of doing work, then some of the heat supplied increases the internal energy
of the system and rest of the heat is used to do work.
dQ = dU + dW where dQ = heat provided,
dU = change in internal energy and
dW = work done
dQ is taken positive when heat is gained by the system and negative when heat is lost by the
system, dU is taken positive when internal energy of the system increase and negative when
internal energy of the system decreases and dW is taken positive when work is done by the
system and negative when work is done on the system.

Applications of First Law of Thermodynamics: MAYER’S RELATION 

To prove: Cp – Cv = R
Proof: Let us supply heat to a system containing gas at constant volume, dQ = dU + dW, where
dW = PdV
If the volume is kept constant, dV = 0

dW = PdV = 0

dQ = dU --- (i)
Also, dQ = mcvdT where, m = mass of the gas in the system, cv = specific heat capacity at
constant volume and dT = difference in temperature.
In moles, dQ = nCvdT where, n = number of moles and Cv = molar specific heat capacity.
If n = 1, dQ = Cv dT --- (ii)
Equating (i) and (ii) we get, dU = CvdT --- (iii)

Let us supply heat to a system containing gas at constant pressure, dQ = dU + dW

where, dW = PdV

dQ = dU + PdV --- (iv)
Also, dQ = m cp dT
In moles, dQ = n Cp dT where, n = number of moles
If n = 1, dQ = Cp dT --- (v)
Equating equation (iii), (iv) and (v);
Cp dT = Cv dT + PdV

(Cp – Cv) dT = PdV
-.

Cp – Cv = P --- (vi)
-/
Using ideal gas equation, PV = nRT where we take n = 1 we get,
PV=RT
Differentiating both sides with respect to temperature,
0 02 01
P 01 + V 01 = R 01
-.

P =R as dP / dT = 0 (at constant pressure)
-/
Putting the value in equation (vi) we get,
Cp – Cv = R
)
In terms of mass, cp – cv = r where, r = where M is molecular mass of the gas.
3

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Limitations of First Law of Thermodynamics:
1. This law does not tell us in which direction will the change in internal energy occur.
2. It does not tell us about the extent of change which takes place in the system.
3. It does not give us any information about the heat being absorbed or released from hotter
body to cooler one.

Cyclic and Non Cyclic Process:

Cyclic Process
A process in which series of changes takes
place in such a manner that the system returns
to its original state (P1, V1, T1).
Non Cyclic Process
A process in which series of changes takes place in
such a manner that the system reaches a new state and
does not return to its original state i.e. (P1, V1, T1) is
initial state and (P2, V2, T2) is the final state.
Graph:

Graph:

Reversible and Irreversible Process:

Reversible Process
A process in which series of changes takes place in
such a manner that the system reaches or return to the
original state via the same intermediate stages is
called reversible process.
In this process, the process proceeds in both directions
with equal ease.
Graph:
Irreversible Process
A process in which series of changes takes place
in such a manner that the system cannot reach or
return to the original state is called irreversible
process.
Graph:

Work done during a Cyclic Process: We know that work done by the system is considered
positive while work done on the system is considered negative.

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Area under graph ACB = work done during expansion = W1
Area under graph ADB = work done during compression = W2
Total work done = W1 – W2 = area within ACDBA
= area within the closed loop gives work done in cyclic process

Heat Engine:: A device which converts heat energy into mechanical energy is called a heat
engine.
It has 3 parts:
1. Source:: It is a reservoir of heat maintained at a high temperature
T1 having infinite thermal capacity i.e. no matter how much heat is
removed from the reservoir the temperature will remain T1.
2. Working Substance:: It is a gas which absorbs heat and does the
work i.e. it converts heat energy into mechanical energy.
3. Sink:: It is a reservoir of heat maintained at a low temperature T2
having infinite thermal capacity i.e. no matter how much heat is
provided the temperature will not rise above T2.
The process involved is cyclic as the working substance reaches the same
state. In a cyclic process the change in the internal energy dU = 0. Hence
1st law becomes dQ = dW.

Efficiency (η): Efficiency is defined as the ratio of output received to input provided. As per the
schematic representation of heat engine the efficiency of a heat engine can be denoted by the
following formula:

456756 89:;
89:; 09=?
Efficiency (η) =
<=756 >?@6 7:9AB0?0
7:9AB0?0

C  CE

η=
C

D

η=1–
D

Carnott’s Cycle for a Heat Engine:

Engine Carnott
devised an ideal cycle for a heat engine and called it
the Carnott’s Heat Engine.
Construction  A source at a high temperature, a
working substance which is an ideal gas taken in a
cylinder fit with a frictionless piston. The cylinder
has insulated piston and walls but the base of the
cylinder is conducting. Along with these it needs a
sink maintained at a low temperature and insulating
pads which is actually an insulating stand on which
the cylinder can be kept.
Working  There are four processes involved in
the cycle:
1. Isothermal Expansion

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 2. Adiabatic Expansion
3. Isothermal Compression
4. Adiabatic
iabatic Compression

The process starts with Isothermal Expansion.

Expansion The
gas absorbs heat from the source and expands. Let the
initial state of the gas be (P1, V1, T1). Due to
isothermal expansion its state becomes (P2, V2, T1) due
to absorption of Q1 amount of heat. It is seen P1 > P2
and V1 < V2.
Work done during isothermal expansion = area under
P-V graph AB.
.

W1 = Q1 = 2.303RT1 log10 .  --- (i)


This is followed by Adiabatic Expansion.

Expansion Due to
this process the gas changes its state from (P2, V2,
T1) to (P3, V3, T2). There is a decrease in
temperature i.e. T2 < T1.
Work done during adiabatic expansion = area under
graph BC.
)

W2 = (T2 – T1) --- (ii)
 *

After adiabatic expansion, Isothermal

Compression follows. The state of the gas changes
from (P3, V3, T2) to (P4, V4, T2) due to release of Q2
amount of heat from the system. It is seen P4 > P3
and V4 < V3.
Work done during isothermal compression = area under graph DC


W3 = Q2 = - 2.303 RT2 log10 G 
H
.I

W3 = 2.303 RT2 log10 .  --- (iii)
J

The above process is followed by Adiabatic Compression,, the state of the gas changes from
(P4, V4, T2) to (P1, V1, T1). There is an increase in temperature from T2 to T1.
Work done during adiabatic compression = area under graph AD
F

W4 = - (T1 – T2)
 
)

W4 =  *
(T2 – T1) --- (iv)
Net work done = W = W1 + W2 - W3 - W4 = area inside the closed loop ABCD
 F  F

W = 2.303RT1 log10  E  + (T2 – T1) - 2.303 RT2 log10  H  - (T2 – T1)
   G  
. .I

W = 2.303 R [T1 log10   - T2 log10  ] = Q1 – Q2 --- (v)
. .J
Now, equation for isothermal expansion is P1V1 = P2V2
Equation for adiabatic expansion is P2V2γ = P3V3γ

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Equation for isothermal compression is P3V3 = P4V4
Equation for adiabatic compression is P4V4γ = P1V1γ
Multiplying all the four equations: P1V1P2V2γP3V3P4V4γ = P2V2P3V3γP4V4P1V1γ

V1 (1 - γ) V3 (1 – γ) = V2 (1 – γ) V4 (1 – γ)

V1 V3 = V2 V4
.I .

= --- (vi)
.J .

+ C  CE CE
Now, Efficiency of Carnott’s Cycle = η = = =1– --- (vii)
C C C

Q
CE .L F1E MNOP  H 
QG
Also, = Q {from equation (i) and (iii)}
C .L F1 MNOP  E 
Q
CE 1E

= {from equation (vi)}
C 1

/

η=1-
/

D /
Discussion of Carnott’s Cycle: η=1– =1–
D /

1. If T1 and T2 are finite such that T1 > T2, then η < 1, i.e. η < 100%. This means that even
after using ideal conditions Carnott’s engine could not provide 100% efficiency.

2. If T2 = 0 kelvin and T1 = ∞, the η = 1, i.e. 100%. Obtaining these temperatures from a

system having infinite thermal capacity is impossible. Hence η ≠ 100%.

3. If T1 = T2, η = 0. Therefore, no work is done if the source and sink are at the same
temperature as heat flow does not take place.

4. If Q2 = 0, then η = 1 i.e. 100%. Now, it is not possible for any machine to take energy
from a source and do the work without energy from a source and without rejecting any
energy to the surroundings. Therefore, η = 100%

Carnott’s Theorem: Carnott’s theorem states that a heat engine working between two fixed /
finite temperatures (T1 and T2) cannot be more efficient than a Carnott’s heat engine working
between the same two temperatures.

Second Law of Thermodynamics: CLAUSSIUS STATEMENT 

“It is impossible for a self acting machine unaided by an external agent to
transfer heat from a body at lower temperature to higher temperature.

Heat Pump / Refrigerator: A refrigerator or a heat pump consists of:

1. Source: Surroundings (at higher temperature, T1)
2. Sink: Fruits and Vegetables (at lower temperature, T2)
3. Working Substance: Frayon gas (HFC – 134a)
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Efficiency of a Refrigerator:
Efficiency of a refrigerator is
measured in terms of coefficient of
performance (β).
456756 R>?@6 @ST9:S?0U
β=
<=756 R89:; 09=?U
The refrigerator undergoes a cyclic
process. Hence dU = 0

dQ = dW

dQ = Q2 – Q1

dW = - W

- W = Q2 – Q1

W = Q1 – Q2
D

β=
D  D
Dividing the numerator and denominator by Q1, we get
VE
V
β= V
 E
V
CE 1E
As we have proved earlier that, =
C 1
/
/

β= /
 
/

Numerical Problems 
Q1. Calculate the efficiency of a Carnott’s engine working between steam point and ice point.
Ans. Given: T1 = 373 K (steam point) and T2 = 273 K (ice point); η=?
D /
Now, η = 1 – =1–
D /
 LL

η = 1 -  =  = 0.26 = 26%

Q2. A Carnott’s engine intakes steam at 200°C and after doing work exhausts it to sink at 100°C.
Calculate the percentage of heat utilized in doing work.
Ans. Given: T1 = 200°C = 473 K and T2 = 100°C = 373 K

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 C  CE
Percentage of heat used to do work = × 100 = η × 100
C
1E

Percentage of heat used to do work = 1 – ×100
1
 LL

Percentage of heat used to do work = 1 -  × 100 =  × 100 = 21.14%

******************************************************************************

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