Revision Notes

Class 11 Physics
Chapter 12 – Thermodynamics

1. THERMODYNAMICS
It deals with the study of interactions between heat and other forms of energy.
Thermodynamic System:
A collection of large numbers of molecules of matter (solid, liquid or gas) that
are arranged in a manner such that these possess particular values of pressure,
volume and temperature forms a thermodynamic system.
The parameters like pressure, volume, temperature, internal energy, etc.,
which determine the state or condition of a system are termed thermodynamic
state variables.
In thermodynamics, we consider the thermodynamic systems as a whole and
learn the interaction of heat and energy during the change of one
thermodynamic state to another.
1.1 Thermal Equilibrium
The term ‘equilibrium’ in thermodynamics refers to the state when all the
macroscopic variables expressing the system ( P, V, T , mass etc.,) do not
change with time.
● Two systems when in contact with each other are said to be in thermal
equilibrium when their temperatures become the same.
● Zeroth law of thermodynamics states that when the thermodynamics
systems A and B are separately in thermal equilibrium with a third
thermodynamic system C, then the systems A and B are also in thermal
equilibrium with each other.
1.2 Heat, Work and Internal Energy
Internal Energy refers to the energy possessed by any system because of its
molecular kinetic energy and molecular potential energy. Both these
energies are considered with respect to center of mass frame.
Internal energy is dependent entirely on the state and thus, it is a state
variable. In the case of real gases, internal energy is only by virtue of their
molecular motion whereas for ideal gases, it is mathematically given by
nfRT
U
2
where,
n is the number of moles
f is the degree of freedom

Class XI Physics www.vedantu.com 1

 R is the universal gas constant
T is the temperature in kelvin
Internal Energy can be altered either by providing heat energy or by
performing some work.
Heat Energy refers to the energy transformed to or from the system due to
the difference in temperatures by conduction, convection or radiation.
The energy that gets transferred from one system to another by force
moving its point of application in its own direction is termed work.

Mathematically, work done by the system is given by

W   Fdx   Ps Adx   PdV
where Ps is the pressure of the system on the piston.
This work done by the system is positive when the system is expanding and
it is negative when the system is contracting.
● Work and heat are path functions while internal energy is a state
function.
● Heat and work are two different terminologies even though they might
look similar.

1.3 Important Thermodynamics Terms

State Variables: P, V, T, moles
State variables can be extensive or intensive.
Equation of State: The equation that relates the pressure (P) , the volume
(V) and absolute temperature (T) of a gas is known as the equation of
state.
PV  constant (Boyle’s Law)
V
 constant (Charles’ Law)
T
 PV  nRT
Thermodynamic Process: A thermodynamic process happens when a few
changes occur in the state of a thermodynamic system, i.e., the

Class XI Physics www.vedantu.com 2

 thermodynamic parameters of the system get altered with time.
Thermodynamic process can be isothermal, adiabatic, isobaric or isochoric.
Quasi Static Process: A thermodynamic process that is infinitely slow is
termed quasi-static process.
● In a quasi static process, the system undergoes change with slow speed
such that at every instant, the system is in both thermal and mechanical
equilibrium with the surroundings.
● Quasi-static process is an ideal process. We generally consider all the
processes to be quasi static unless mentioned differently.

Indicator P-V Diagram: A graph between pressure and volume of a gas

under thermodynamic operation is known as a P-V diagram.

With respect to the diagram;

a  Isobaric
b  Isothermal
c  Adiabatic
d  Isochoric
Also, the area under the P-V diagram provides us the work done by a gas.

1.4 First Law of Thermodynamics

Suppose that
Q  Heat supplied to the system by the surroundings
W  Work done by the system on the surroundings
U  Change in internal energy of the system.
First law of thermodynamics suggests that energy can neither be created
nor be destroyed. It can only be transformed from one form to another.
Mathematically,
Q  U  W
Sign Conventions:
● When heat gets supplied to the system, then Q is taken positive and
when heat gets withdrawn from the system, Q is negative.

Class XI Physics www.vedantu.com 3

 ● When a gas expands, work done by the gas is taken positive whereas
when a gas contracts, work is taken negative.
● U is taken positive when temperature increases while U is taken
negative when temperature decreases.

It is to be noted here that we always take work done by the system. In

chemistry, work done on the system is considered. Hence there is another
perspective to the first law of thermodynamics in chemistry.
Mathematically, this can be expressed as
Q  W  U
where Q and U have the same meanings but W stands for the work
done on the system.

1.5 Application of the First of Law of Thermodynamics

Here, we observe how the first law of thermodynamics is applied to
different thermodynamic processes.
1.5.1 Isothermal Process
Description: A thermodynamic process in which the temperature remains
constant.
Condition: The walls of the container should be perfectly conductive to
allow free exchange of heat between the gas and its surroundings.
The process of compression or expansion must be slow in order to provide
time for exchange of heat.
Both these conditions are considered perfectly ideal.
Equation of State: T  Constant or Pv  Constant
Indicator Diagram:

P
Slope of P  V at any point is equal to 
.
V
Change in internal energy, U  0 (Temperature remains constant)
Work done is given by
v2

W   Pg dV
v1

Class XI Physics www.vedantu.com 4

 v2
 nRT 
W   dV [Using PV  nRT ]
v1  V 
v 
 W  nRT ln  2 
 v1 
First Law of Thermodynamics:
Q  U  W
v 
 Q  nRT ln  2 
 v1 
Remarks: All the heat supplied is utilized entirely to do work against
external surroundings. When heat is supplied, then the gas expands
whereas when heat is withdrawn, then the gas contracts.
Practical Examples:
Melting of ice at 0C .
Boiling of H 2O at 100C .

1.5.2 Adiabatic Process

Description: A thermodynamic process in which there is no heat
exchange with surroundings.
Conditions: The walls of the container should be perfectly non-
conducting in order to prevent any exchange of heat between the gas and
its surroundings.
The process of compression or expansion must be rapid so that there is no
time for the exchange of heat.
These conditions are ideal conditions and are difficult to achieve.
Equation of State:
PVr  constant
 TVr 1  constant
r
 PT  constant
1 r

Indicator Diagram

Class XI Physics www.vedantu.com 5

 P
Slope of adiabatic curve  r
V
As given in the graph, the adiabatic curve is steeper than the isothermal
curve. Change in internal energy,
nfRT nR  T2  T1  P2 V2  P1V1
U    .
2 r 1 r 1
Work done by the gas when it adiabatically expands from V1 to V2 is
given by
v2
dV
W  r
v1
V
v2
dV
 W  constant 
v1
Vr
 PV r  constant 
 
  P  constant 
 Vr 
v2
 V  r 1 
 W  constant   
 1  r  v1
constant  1 1 
W  r 1  r 1 
1  r  V2 V1 
Also, it is known that
P1V1r  P2V2r  constant
1  P2 V2 P1V1 
W   
1  r  V2r 1 V1r 1 
P2 V2  P1V1 nR  T1  T2 
W 
1 r r 1
First Law of Thermodynamics
Q  U  W
Substituting the values
We get Q  0 , as expected
Remarks: When gas expands adiabatically, then its temp decreases and
vice versa.
Practical Examples:
Propagation of sound waves in the form of compression and rarefaction.
Spontaneous bursting of a cycle tube.

Class XI Physics www.vedantu.com 6

 1.5.3 Isochoric Process
Description: A thermodynamic process in which the volume remains
constant.
Condition: A gas being heated or cooled inside a rigid container.
P
Equation of State: V  constant or  constant
T
Indicator Diagram:

Change in internal energy is given by

nfRT nR  T2  T1 
U  
2 r 1
P V  P V nRT
 U  2 2 1 1 
r 1 r 1
Work done is given by W  0 since the gas does not expand.

First Law of thermodynamics

Q  U  W
nfRT
Q 
2
Remarks: As we have learnt that when heat is supplied to any process, its
temperature increases according to relation:
Q  nCT
Q
C
nT
Now, this C is dependent on external conditions for gases.
Q
Here, it is referred to as i.e., Molar heat capacity at constant
nT v
volume.
Mathematically, it can be derived as
fR
Cv 
2

Class XI Physics www.vedantu.com 7

 1.5.4 Isobaric Process
Description: A thermodynamic process in which the pressure remains
constant.
Condition: When in a container, the piston can move freely and it is not
connected by any agent.
Equation of State:
V
P  constant or  constant
T
Indicator Diagram:

nfRT
Change in internal energy, U  is the same as always.
2
Work done is given by
W   PdV  PV
(since pressure is constant)
 W  PV2  PV  nRT
First Law of Thermodynamics
Q  U  W
nfRT
Q  +nRT
2
 fR 
 Q    R  T
2 
Remarks: Just like CV , we may define molar heat capacity at constant
Q
pressure as CP  .
nT P
Mathematically, it can be derived as:
fR
CP  R
2
fR
Replacing by CV , we get CP  CV  R , which is known as Mayer’s
2
relation.

Class XI Physics www.vedantu.com 8

 Notes:
● Just like molar specific heat at constant pressure and molar specific heat
at constant volume, we may define molar specific heat for any process.
For example:
Cadiabatic  0
Cisothermal  
Basically, gases do not possess unique specific heats though we have
CP and CV mainly.
Specific Heat at Constant Volume: It refers to the amount of heat
needed to raise the temperature of 1g of a gas through 1C , when its
volume is kept constant. It is denoted by c V .
Specific Heat at Constant Pressure: It refers to the amount of heat
needed to raise the temperature of 1g of a gas through 1C keeping its
pressure constant. It is denoted by c P .
● Here, it is to be noted that CP ,CV refer to molar heat capacity while
c P , c V refer to specific heat capacity.
● CV  McV and CP  McP where M stands for the molar mass of any
sample.
C  CV R
 cP  cV  P 
M M

1.5.5 Melting Process

In any case, the first law is always applicable.
During the melting process,
Internal energy, Q  mL f , as studied earlier and where L f is the latent
heat of fusion.
Work done, W  0 .
(In the change of state from solid to liquid, we do not consider any
expansion or contraction as it is very small)
With respect to the first law of thermodynamics,
U  Q  W
 U  mL f
Remark: The heat provided during melting is utilized in increasing the
internal energy of any substance.

1.5.6 Boiling Process

During the boiling process,
Internal energy, Q  mL V , where L V is the latent heat of vaporization.

Class XI Physics www.vedantu.com 9

 Work done, W  P  V2 – V1  .
(Pressure is constant during boiling and it is equal to atmospheric pressure)
With respect to the first law of thermodynamics,
U  Q  W
 U  mLf  P  V2  V1 

1.5.7 Cyclic Process

A cyclic process refers to the process wherein the system returns to its
initial stage after undergoing a series of changes.
Example Indicator Diagram

Here, change in internal energy, U  mL V  0 .

Work done, W  Area under the loop.
 Q  W according to the first law of thermodynamics.
Also, W is positive when the cycle is clockwise whereas it is negative
when the cyclic is anti-clockwise.

1.6 Limitations of the First Law of Thermodynamics

● The first law does not provide the direction in which the change can
occur.
● The first law provides no idea on the extent of change.
● The first law of thermodynamics provides no information about the
source of heat. i.e., whether it is a hot or a cold body.

1.7 Heat Engines

Heat engine is a device which converts heat energy into mechanical energy.
Key Elements
● A source of heat at higher temperature
● A working substance
● A sink of heat at lower temperature
Working
● The working substance follows a cycle consisting of several processes.

Class XI Physics www.vedantu.com 10

 ● In some processes, it absorbs a total amount of heat Q1 from the source
at temperature T1 .
● In some other processes, it rejects a total amount of heat Q 2 to the sink
at a lower temperature T2 .
● The work done by the system in a cycle gets transferred to the
environment with the help of an arrangement.
Schematic Diagram

First Law of Thermodynamics

Since energy is always conserved,
Q1  W  Q 2
Thermal Efficiency of a heat engine refers to the ratio of net work done per
cycle by the engine to the total amount of heat absorbed per cycle by the
working substance from the source. It is represented by  . Mathematically,
W

Q1
Substituting for Q1 , we get
Q
  1 2
Q1
Ideally, engines must have efficiency   1.
Remarks: The mechanism of conversion of heat into work varies for various
heat engines:
● The system which gets heated by an external furnace similar to a steam
engine. These engines are called external combustion engines.
● The system wherein heat is produced by burning the fuel inside the
main body of the engine. These engines are called internal combustion
engines.

1.8 Refrigerator and Heat Pumps

A refrigerator or heat pump is a device utilized for cooling things.
Key Elements

Class XI Physics www.vedantu.com 11

 ● A cold reservoir at temperature T2
● A working substance
● A hot reservoir at temperature T1
Working
● The working substance follows a cycle consisting of several processes.
● A sudden expansion of the gas from high to low pressure cools it and
converts it into a vapor-liquid mixture.
● Absorption by the cold fluid of heat from the region to be cooled
converts it into vapor.
● The vapor gets heated up due to external work done on the working
substance.
● The heat gets released by the vapor to the surroundings bringing it to
the initial state and completing the cycle.
Schematic Diagram

First Law of Thermodynamics

Q2  W  Q1
Coefficient of performance of refrigerator () refers to the ratio of quantity of
heat removed per cycle from contents of the refrigerator  Q2  to the energy
spent per cycle (W) to remove this heat. Mathematically,
Q
 2
W
Substituting for W , we get
Q2

Q1  Q2
Ideally, heat pumps must have    .

1.9 Second Law of Thermodynamics

There are a lot of ways in which this law can be stated.
Even though all the statements are the same with respect to their contents, the
following two are the most significant.

Class XI Physics www.vedantu.com 12

Kelvin Planck Statement: No process is possible whose sole result is the
absorption of heat from a reservoir and the complete conversion of the heat
into work.
Clausius Statement: No process is possible whose sole result is the transfer
of heat from a colder object to a hotter object.
Significance: 100% efficiency in heat engines or infinite CoP in refrigerators
is not possible.

1.10 Reversible and Irreversible Process

Reversible Process: A thermodynamic process taking a system from initial
state i to final state f is considered reversible if the process can be reversed
back such that both the system and the surroundings return to their original
states with no other change anywhere else in the universe.
Conditions for reversibility:
1. Process must proceed at an extremely slow rate, i.e., process is quasi
static so that the system is in equilibrium with surroundings at every
stage.
2. The system must be free from dissipative forces like friction,
inelasticity, viscosity, etc.
Examples: No process can be considered perfectly reversible though a slow
expansion of an ideal gas is approximately reversible.
Irreversible Process: A process that does not satisfy any of the conditions of
a reversible process is known as an irreversible process.
Causes:
● Spontaneous process
● Presence of friction, viscosity and other dissipative forces
Significance of Reversibility:
● Major concern of thermodynamics is the efficiency with which the heat
is converted into mechanical energy.
● Second law of thermodynamics opts out the possibility of a perfect heat
engine with 100% efficiency.
● It is found that heat engines based on idealized reversible processes
attain the highest possible efficiency.

2.11 Carnot Engine

Sadi Carnot devised an ideal cycle of operation for a heat engine termed the
Carnot cycle.
The engine used for realizing this ideal cycle is known as the Carnot heat
engine.
Construction

Class XI Physics www.vedantu.com 13

The essential sections of an ideal heat engine or Carnot heat engine are shown
in the diagram below.

i. Source of heat: The source is maintained at a fixed higher temperature

T1 , from which the working substance takes heat. The source is
supposed to possess infinite thermal capacity and as such any amount of
heat can be taken from it without altering its temperature.
ii. Sink of heat: The sink is maintained at a fixed lower temperature T2 , to
which any amount of heat can be emitted by the working substance. It
has also infinite thermal capacity and as such its temperature remains
constant at T2 , even when any amount of heat is emitted to it.
iii. Working substance: A perfect gas plays the role of a working
substance. It is contained in a cylinder with non-conducting sides but
having a perfectly conducting-base. This cylinder is fixed with a
perfectly non-conducting and frictionless piston.
Apart from these essential parts, there is also a perfectly insulating
stand or pad on which the cylinder can be positioned. It provides
complete isolation to the working substance from the surroundings so
that the gas can undergo adiabatic changes.

Working

The Carnot cycle consists of the following four stages:

1. Isothermal expansion
2. Adiabatic expansion
3. Isothermal compression
4. Adiabatic compression

The cycle is carried out by making use of the Carnot engine as detailed below:

Class XI Physics www.vedantu.com 14

Consider one gram mole of an ideal gas enclosed in the cylinder. Let V1 , P1
and T1 be the initial volume, pressure and temperature of the gas respectively.
The initial state of the gas is demonstrated by point A in the above P-V
diagram. We may assume that all the four processes are quasi-static and non-
dissipative in nature, which are the two conditions for reversibility.
Steps
1. Isothermal Expansion:
The cylinder is positioned on the source and the gas is allowed to
expand from A(V1 ,P1 ) to B(V2 ,P2 ) by the slow outward motion of the
piston. As the base is perfectly conducting, the process is isothermal.
Now,
U1  0 ;
V 
 Q1  W1  RT1 ln  2   Area ABMKA
 V1 
where,
Q1  Heat absorbed by gas in this process
W1  Work done by gas in this process

2. Adiabatic Expansion:
The cylinder is now removed from the source and is positioned on the
perfectly insulating pad. The gas is allowed to expand further from
B(P2 ,V2 ) to C(P3 ,V3 ) . As the gas is thermally insulated from all sides,
the process is adiabatic.
Here,
Q2  0 ;
R  T2  T1 
 U 2  W2   Area BCNMB
r 1

Class XI Physics www.vedantu.com 15

 3. Isothermal Compression:
The cylinder is now removed from the insulating pad and is positioned
on the sink at a temperature T2 . The piston is moved slowly so that the
gas is compressed until the pressure is P4 and the volume is V4 .
Here,
U 3  0
V 
W3  Q3  RT2 ln  4   Area CDLNC
 V3 
where,
Q3  Heat absorbed in this porcess
W3  Work done by gas in this process

4. Adiabatic Compression:
The cylinder is again positioned on the insulating pad such that the
process remains adiabatic. Here, the gas is further compressed to its
initial pressure and volume. i.e., P1 and V1 .
Here,
Q4  0 ;
R  T1  T2 
W4  U 4    Area DAKLD
r 1

Analysis:

Total work done by the engine per cycle is derived as:

W  W1  W2  W3  W4
 W  W1  W3
V  V 
 W  RT1 ln  2   RT2 ln  4 
 V1   V3 
V 
Q1  Total heat abosrbed  RT1 ln  2 
 V1 
V 
Q2  Total heat released   RT2 ln  4 
 V3 
Clearly, it is seen that for a heat engine,
W  Q1  Q 2  Area under ABCDA

Class XI Physics www.vedantu.com 16

Efficiency of Carnot Engine

Mathematically, efficiency of a Carnot engine is given by

W Q
 1 2
Q1 Q1

Now, considering all the adiabatic processes, we have

T1V2r 1  T2V3r 1 and T1V1r 1  T2V4r 1
V V
 2 3
V1 V4
Clearly,
Q T
 1 1
Q2 T2
T
 Carnot  1  2
T1

Division
● Carnot is dependent only on source temperature and sink temperature.
● Carnot  1 only when T2  0 K or T1   , which is not possible to
achieve.
● If T2  T1    0 , heat cannot be converted to mechanical energy
unless there is an equal difference between the temperature of the
source as well as the sink.

1.12 Carnot Theorem

Statement
a) Working between two given temperatures, T1 of hot reservoir (the
source) and T2 of the cold reservoir (the sink), no engine can have
efficiency more than that of the Carnot engine.
b) The efficiency of the Carnot engine is not dependent on the nature of
the working substance.

Proof

Step - 1: Consider a reversible engine R and an irreversible engine I working

between the source (hot reservoir at T1 ) and sink (cold reservoir at T2 ).

Class XI Physics www.vedantu.com 17

Step - 2: Pair up two engines in such a manner that I act like heat engine and
R acts like a refrigerator.
Step - 3: Suppose that the engine I absorbs Q1 heat from the source; deliver a
work W1 and release the balance Q1  W1 to the sink in a single cycle.

Step - 4: Setup R such that it returns the same heat to the source, taking Q 2
from the sink and requiring a work W  Q1  Q2 to be done on it.
Step - 5: Suppose R  I i.e., When R were to act as an engine, it would
give less work output than that of I .
 W  W1 for a given Q1 and Q1  W  Q1  W1
Step - 6: In totality, the I-R system extracts heat
 r1  W    Q1  W1   W1  W and delivers the same amount of work in a
single cycle without any change in source or anywhere else. This contradicts
the second law of thermodynamics. (Kelvin - Planck statement)
Clearly, the assumption q1  q R is incorrect.
A similar argument can be set up for the second statement of the Carnot
theorem, i.e., Carnot efficiency is independent of the working substance.
Q T
Thus, 1  1 will always hold true for any working substance used in a
Q 2 T2
Carnot engine.

2. KINETIC THEORY OF GASES

In this topic, we would discuss the behavior of gases and how different state
variables like P, V, T, moles, U are connected with each other.

2.1 Molecular Nature of Matter

Similar to the atomic theory given by Delton, atoms are treated as the
smallest constituents of elements. All the atoms of an element are identical
while atoms of different elements are different.
In solids: Atoms are tightly packed; interatomic spacing is of the order of
o
A ; interatomic force of attraction is strong.

Class XI Physics www.vedantu.com 18

 In liquids: Atoms are not as tightly packed as in solids; interatomic
o
spacing is of the order of 2A ; the interatomic force of attraction is
relatively weaker.
In Gases: Atoms are free to move anywhere; interatomic spacing is of the
o
order of 10A ; interatomic forces are much weaker in gases than both in
solids and liquids.
In this chapter, we would be concentrating more on gases.

2.2 Molecular Nature of Matter

2.2.1 Ideal Gas

Ideal gas refers to a gas that strictly obeys all the gas laws (such as
Boyle’s law, Charles’ law, Gay Lussac’s law, etc.).
Characteristics
● The size of the molecule of an ideal gas is considered to be zero.
● There would be no force of attraction or repulsion amongst the
molecules of an ideal gas.

2.2.2 Real Gas

All gases are considered as real gases.
All real gases showcase the ideal gas behavior at low pressures and high
temperatures, when they cannot be liquified.

2.2.3 Ideal Gas Laws

Avogadro Hypothesis: This hypothesis suggests that Equal volumes of
all gas under identical conditions of pressure and temperature would
contain an equal number of molecules.
Perfect Gas Equation: Perfect gas equation is given by
PV  nRT
where,
n  Number of moles
r  Universal Gas constant  N A k B
N A  Avogadro number
k B  Boltzmann constant
R  8.314 J/mol K
Boyle’s Law: When the temperature of a provided mass of gas is kept
constant, its pressure varies inversely with the volume of gas.
Mathematically,
PV  constant

Class XI Physics www.vedantu.com 19

 Charles Law: When pressure of a provided mass is kept constant,
volume of the gas varies directly with the temperature of the gas.
Mathematically,
VT
Dalton’s Law of Partial Pressures: The total pressure of a mixture of
ideal gases is considered as the sum of partial pressures exerted by the
individual gases in that mixture. Mathematically,
P – V   n1  n 2  n 3  ... RT
RT
 P   n1  n 2  n 3  ...
V
 P  P1  P2  ......
n RT
where P1  1 is the partial pressure related with the gas having n 1
V
moles.
Deviation of Real Gas from Ideal Gas

Class XI Physics www.vedantu.com 20

2.3 Kinetic Theory Postulates
a) A gas consists of a very large number of molecules (of the order of
Avogadro’s number, 1023 ), which are perfect elastic spheres. For a
given gas, they are identical in all respects but for different gases, they
are different.
b) The molecules of a gas are in a state of incessant random motion. They
move in all directions with different speeds, (of the order of 500 m/s )
and obey Newton’s laws of motion.
c) The size of the gas molecules is very small as compared to the distance
o
between them. If the typical size of molecule is 2A , average distance
o
between the molecules is  20A . Thus, the volume occupied by the
molecules is negligible when compared to the volume of the gas.
d) The molecules do not exert any force of attraction or repulsion on each
other except during collision.
e) The collisions of the molecules with themselves and with the walls of
the vessel are perfectly elastic. Also, that momentum and the kinetic
energy of the molecules are conserved during collisions through their
individual velocities change.
f) There is no concentration of the molecules at any point inside the
container i.e., molecular density is uniform throughout the gas.
g) A molecule moves along a straight line between two successive
collisions and the average straight distance covered between two
successive collisions is termed the mean free path of the molecules.
h) The collisions are almost instantaneous, i.e., the time of collision of two
molecules is negligible as compared to the time interval between two
successive collisions.

Class XI Physics www.vedantu.com 21

2.4 Pressure of an Ideal Gas and its expression
Pressure exerted by the gas is because of continuous bombardment of gas
molecules against the walls of the container.
Expression:
Suppose that a gas is enclosed in a cube of side 1 . Consider the axes to be
parallel to the sides of the cube, as shown in figure. A molecule with velocity
 vx , v y , vz  hits the planar wall parallel to yz  plane of area A   l2  . As the
collision is elastic, the molecule rebounds with the same velocity; its y and z
components of velocity do not change in the collision but the x-component
reverses with respect to its sign. That is, the velocity after collision is
 v x , v y , vz  . The change in momentum of the molecule is given by
mv x   mv x   2mv x . Considering the principle of conservation of
momentum, the momentum imparted to the wall in the collision  2mv x .
To calculate the force (and pressure) on the wall, we are to calculate
momentum imparted to the wall per unit time, when it is within the distance
v x t from the wall. That is, the total number of molecules within the volume
1
Av x t which can hit the wall in time T is Av x tn ; where n is the
2
number of molecules per unit volume. Clearly, the total momentum
transferred to the wall by these molecules in time t is given by
1 
Q   2mv x   nAv x t 
2 
Q
The force on the wall refers to the rate of momentum transfer and pressure
t
refers to the force per unit area:
Q
P  nmv 2x
 At 
In fact, all molecules in a gas do not have the same velocity; there is a
distribution in velocities. The above equation therefore, stands for pressure
due to the group of molecules with speed v x in the x  direction and n stands
for the number density of that group of molecules. The total pressure is
obtained by summing over the contribution due to all groups:
P  nmvx2
where vx2 is the average of v2x .
Now the gas is isotropic, i.e., there is no preferred direction of velocity of the
molecules in the vessel. Clearly, by symmetry,

Class XI Physics www.vedantu.com 22

 1 1
vx2  vy2  vz2     vx2  v y2  vz2   v 2
3 3
2
Where, v is the speed and v denotes the mean of the squared speed. Thus,
1
P    nmv 2
3
1 1 M  1
 P  mnv 2    v 2  v 2
3 3 V  3
M  Total mass of gas molecules
V  Total volume of gas molecules
  Total density of the gas molecules

2.4.1 Relation between Pressure and KE of Gas Molecules

1 M  1
It is known that P    v 2  v 2
3 V  3
Clearly,
2
P  E , where E is the mean kinetic energy of gas molecules
3
Thus, pressure exerted by an ideal gas is numerically equal to two third
of mean kinetic energy of gas molecules.

2.4.2 Average KE per molecule of the Gas

It is known that
1 M 
P    v2
3 V 
1
 PV  Mv 2
3
Relating this with the Ideal gas equation;
1
nRT  Mv 2
3
1
 nRT  Nmv 2
3
3nRT 1
  mv 2
2N 2
Also, N  nN A
3RT 1 3
  mv 2  k BT  R  Nk B 
2N A 2 2

Class XI Physics www.vedantu.com 23

 Clearly, the average kinetic energy of translation per molecule of the gas
3
is k BT .
2

2.5 Kinetic Interpretation of Temperature

From the above expressions, it can easily be seen that kinetic energy of one
molecule is only dependent upon its temperature. Clearly, kinetic energy
would cease when the temperature of the gas molecule becomes absolute
zero.
Thus, absolute zero of a temperature is defined as the temperature at which
the root mean square velocity of the gas molecule reduces to zero.

2.6 Derivation of Gas Laws from Kinetic Theory

2.6.1 Boyle’s Law
2
It is known that PV  NK
3
where K is the average kinetic energy of translation per gas molecule at
constant temperature.
K is constant for a provided mass of the gas. N is also constant. Thus,
PV  constant for a provided mass of gas at constant temperature, which
is known as the Boyle’s Law.

2.6.2 Charles’ Law

2
It is known that PV  NK
3
For a provided mass of gas, N is constant.
3
As K  k BT  K  T and thus, PV  T , which is nothing but Charles'
2
law.

2.6.3 Constant Volume Law

2
It is known that PV  NK
3
For a provided mass of gas, N is constant.
3
As K  k BT  K  T
2
Clearly, PV  T
Now, when V is constant, P  T , which is nothing but the constant
volume law.

Class XI Physics www.vedantu.com 24

 2.6.4 Ideal Gas Equation
2 3
Since PV  NK and K  k BT
3 2
2 3 
 PV  N  k BT  or PV  Nk BT
3 2 
which is nothing but the ideal gas equation.

2.6.5 Avogadro’s Law

Consider two gases 1 and 2 . We may write:
2 2
P1V1  N1K1;P2V2  N 2K 2
3 3
Suppose their pressures, volumes and temperatures are the same, then
P1  P2 ;V1  V2 ;K1  K2
Clearly, N1  N 2
Thus, equal volumes of all ideal gases existing under the same
conditions of temperature and pressure contain equal number of
molecules, which is Avogadro’s Law or hypothesis.
PV
Alternatively, since PV  Nk BT  N 
k BT
Now, when P,V, and T are constants, N also turns out to be constant.

2.6.6 Graham’s Law of Diffusion

The rate (r) of diffusion of a gas through a porous pot or into another
gas is evaluated by the rms speed of its molecules, i.e.,
r  v rms
3P 3P 1
However, as v rms  r r
  
Thus, if r1 and r2 are the rates of diffusion of two gases of densities
1 and 2 respectively, then,
r1 1

r2 2
Clearly, the rates of diffusion of two gases are inversely proportional to
the square roots of their densities, which is nothing but Graham’s law of
diffusion.

2.6.7 Dalton’s Law of Partial Pressures

Class XI Physics www.vedantu.com 25

 The kinetic theory of gases talks about the gas pressure as a cause of the
bombardment of the walls of the containing vessel by molecules. In a
mixture of ideal gases, we might therefore expect the total pressure P to
be the sum of the partial pressures  P1 ,P2 ,.... due to each gas, i.e.,
2 N1 2 N2
P  P1  P2  ...  K1  K 2  ...
3 V1 3 V2
2 N N 
 P   1 K1  2 K 2  ... 
3  V1 V2 
In equilibrium, the average kinetic energy of the molecules of various
gases will be equal, i.e.,
3
K1  K 2  K  k BT
2
Thus,
2 3 
 P   n1  n 2  ...  k BT    n1  n 2  ... k BT
3 2 
N N
Where, n1  1 ;n 2  2 ,.....
V1 V2
This represents the Dalton’s Law of partial pressures which suggests that
the resultant pressure exerted by a mixture of gases or vapors which do
not interact in any way is equal to the sum of their individual (i.e.,
partial) pressures.
The following figure demonstrates a model explaining kinetic theory of
gases. It is constructed in accordance with theory on one hand and real
experimental observations on the other hand.

Class XI Physics www.vedantu.com 26

 The above piece of information is tempting but false. Even though the
equation in box IV is useful, it does not suggest anything new, since it
results from combining equations in boxes II and III.

2.7 Internal Energy

As already learnt in thermodynamics, internal Energy of any substance is the
combination of potential energies and kinetic energies of all molecules inside
a provided gas.
● For real gases,
Internal energy  P.E of molecules  K.E of molecules
● For an ideal gas
Internal energy  K.E of molecules
Here, potential energy of molecules is zero as considered in kinetic
theory postulates. There is no interaction between the molecules and
thus, its interactional energy is zero.

2.8 Degree of Freedom

The number of degrees of freedom of a dynamical system refers to the total
number of co-ordinates or independent quantities required to describe
completely the position and configuration of a system.
Examples:
● A particle traveling in straight line, say along X  axis needs only x
coordinate to define itself. It has only one degree of freedom.
● A particle in a plane, needs 2 co-ordinates, hence has 2 degrees of
freedom.
Generally, when
A  number of particles in the system
R  number of independent relations among the particles
N  number of degrees of freedom of the system
 N  3A – R

2.8.1 Monoatomic Gases

The molecules of a monatomic gas (like neon, argon, helium, etc.)
consist only of one atom
A  1; R  0  N  3
Here, for translational motion, there are 3 degrees of freedom.

2.8.2 Diatomic Gases

The molecules of a diatomic gas consist of two atoms.
A  2;

Class XI Physics www.vedantu.com 27

 If the distance between the two molecules is assumed fixed, then R  1.
N5
Here, there are 5 degrees of freedom, which is a combination of 3
translational energies and 2 rotational energies.

When vibrational motion is also considered, then (only at very high

temperatures);
N  7 , in which 3 accounts for translational, 2 for rotational and 2 for
vibrational energy.

2.8.3 Triatomic Gas

The molecules of a triatomic gas consist of three atoms.
Case: Linear

Here,
A  3;R  2  N  7
Case: Non-Linear

Class XI Physics www.vedantu.com 28

 Here,
A  3;R  2  N  6
Here again, vibrational energy is ignored.

2.8.4 Polyatomic Gas

A polyatomic gas has 3 translational and 3 rotational degrees of
freedom. Apart from them, when there are V vibrational modes, then
there would be an additional 2V vibrational degrees of freedom. Thus,
total degrees of freedom is given by
N  3  3  2V  6  2V

2.9 Law of Equipartition of Energy

Statement: For any dynamical system in thermal equilibrium, the total
energy is distributed equally amongst all the degrees of freedom, and the
energy associated with each molecule per degree of freedom is equal to
1
k BT , where k B is Boltzmann constant and T is the temperature of the
2
system.
k T
Application: U  f  B  , where f  total degrees of freedom.
 2 
This law is very helpful in computing the total internal energy of any system,
be it monoatomic, diatomic or any polyatomic. Once the internal energy is
known, we can easily predict Cv and CP for such systems.
Remark: In case vibrational motion is also there in any system, say for a
diatomic molecule, then there must be energy due to vibration as well, given
by
2
1  dy  1 2
E v  m    ky
2  dt  2
where,
dy
 Vibrational velocity
dt
ky 2
 Energy due to configuration
2
Now, according to the law of equipartition,
1
Energy per degree of freedom  k BT .
2

Class XI Physics www.vedantu.com 29

 1 1
 TE  k BT  k BT  k BT is the total energy for one complete vibrational
2 2
mode.

2.10 Specific Heat Capacity

With the information from the law of equipartition, we can predict the heat
capacity of various gases.

2.10.1 Monoatomic Gas

Here, degrees of freedom  3
Average energy of a molecule at temperature T is given by
1 
E  3  k BT 
2 
Energy for one mole  E  N A
3
 U   k B NA  T
2
3
 U  RT
2
In thermodynamics, we have learnt that
Q U
CV   [ W  0 for constant V ]
T V T
3R
 CV 
2
5R C 5
 CP  and r  P 
2 CV 3

2.10.2 Diatomic Gases

When there is no vibration;
Degrees of freedom  5
5
Average energy for one mole  RT
2
U 5
 CV   R
T 2
7R
 CP 
2
C 7
r P 
CV 5

Class XI Physics www.vedantu.com 30

 On the other hand, when vibration is present;
There is only one mode of vibration between 2 molecules.
Clearly, the degrees of freedom  7 .
7
 U  RT
2
7R
 CV 
2
9R
 CP 
2
9
r
7

2.10.3 Polyatomic Gases

Here, the degrees of freedom
 3 for translational;
 3 for rotational;
 2V for vibrational
 N  6  2V
Where, V  Number of vibrational modes
RT
 U  (6  2V)K
2
 CV  (3  V)R
 CP  (4  V)R
4V
r
3 V

2.10.4 Specific heat capacity of solids

● In solids, there is very little difference between heat capacity at
constant pressure or at constant volume. Thus, we do not
differentiate between CP and CV for solids.
Q U
C 
T T
(As solids hardly expand)
Now, in solids, the atoms are arranged in array structures and they
are not free to move independently like the atoms in gases. Clearly,
the atoms in solids do not possess any translational or rotational
degree of freedom.

Class XI Physics www.vedantu.com 31

 However, the molecules do possess vibrational motion along the 3
mutually perpendicular directions.
Thus, for 1 mole of a solid, there are N A number of atoms and the
 1 
energy associated with every molecule  3  2  k BT   3k BT .
 2 
 U  3RT for one mole
Q U
C   3R
T T
● The above equation is known as the law of Dulong and Petit.
● At low temperatures, the vibrational mode might not be that active
and thus, heat capacity is low at low temperatures for solids.

2.10.5 Specific heat capacity of Water

Consider water like a solid.
Water has three atoms, 2 of hydrogen and one of oxygen.
The total degrees of freedom for every atom  3  2  6 .
Thus, the total degrees of freedom for every water molecule  3  2  18 .
 1 
 18  RT 
Q U  2 
C  
T T T
 C  9R

2.11 Maxwell Law of Distribution of Molecules

Assumptions of Maxwell Distribution
● Molecules of all velocities between 0 to  are present.
● Velocity of one molecule continuously changes, though the fraction of
molecules in one range of velocities is constant.
Result
3
mV 2
 M  2  2k BT
2
N  4N   Ve
 2 k B 
T
Where,

Class XI Physics www.vedantu.com 32

 dN
N
dV
dV  change in speed
dN  Total number of molecules with speeds between V and V+dV

With respect to this, we define three types of speeds for molecules of gas.
1
1 
1
Vrms   V 
2
   V 2dN(V) 
2 2

N 
3RT
 Vrms 
M
Where, M  Molecular mass of gas
Similarly,
1 8RT
Vav  V   VdN 
N M
dN
However, VMP is velocity at which  0.
dV
Physically, VMP refers to the velocity possessed by the maximum
number of molecules.
Remarks: Vrms  Vav  VMP

2.12 Mean Free Path

The path traversed by a molecule between two successive collisions with
another molecule is termed the free path. Mathematically,
Total distance travelled by a molecule
l
Number of collisions it makes with other molecules

Expression:
Mean Free Path

Class XI Physics www.vedantu.com 33

Consider spherical molecules of a gas of diameter d . Concentrate on a single
molecule with the average speed  v  . It would suffer collision with any
molecule that comes within a distance d between the centers. In a time t , it
sweeps a volume d 2  v  t , wherein any other molecule would collide
with it (as shown in figure). If n is the number of molecules per unit volume,
the molecule suffers nd 2  v  t collisions in time t . Therefore, the rate
of collisions is nd 2  v  or the time between two successive collisions is on
the average.
1

 n  v  d 2 
The average distance between two successive collisions, termed the mean free
path 1 is given by
1
1  v   
 nd 2 
In this derivation, we considered the other molecules to be at rest. But in fact,
all molecules are moving and the collision rate is computed by the average
relative velocity of the molecules. Clearly, we need to replace  v  by
 vr  in the above expression for a more exact treatment as follows:
1
1
 2nd 2 
Result
1
1
 2nd 2 
Remark: Mean free path is dependent inversely on the number density and
size of a molecule.

Class XI Physics www.vedantu.com 34

2.13 Brownian Motion
The irregular movement of suspended particles like tiny dust particles or
pollen grains in a liquid is termed Brownian motion.

Class XI Physics www.vedantu.com 35