13.

KINETIC THEORY
OF GASES AND
THERMODYNAMICS

KINETIC THEORY OF GASES (KTG)

1. INTRODUCTION
The kinetic theory of gases describes a gas as a large number of small particles (atoms or molecules), all of which
are in constant, random motion. The rapidly moving particles constantly collide with each other and with the walls
of the container. Kinetic theory explains macroscopic properties of gases, such as pressure, temperature, viscosity,
thermal conductivity and volume, by considering their molecular composition and motion. The theory postulates
that gas pressure is due to the impact of molecules or atoms moving at different velocities on the walls of a
container.
But here we will only find the dependency of pressure on velocity and of velocity on temperature.

2. ASSUMPTIONS OF KTG
(a) The collisions b/w gas molecules or between a molecule and the container are completely elastic.
(b) Mass of gas molecules is negligible. So, the effect of gravity and gravitational force on each other can be
neglected.
(c) Volume of molecules is considered to be negligible.
(d) Collision b/w molecules is governed by Newton’s Law of Motion (i.e. Net force = Change in momentum per
unit time)
(e) Interaction force b/w particles is negligible. (That is, they exert no forces on one another.)
(f) Molecules are considered to be in constant, random, and rapid motion. So, average velocity of particles in all
the 3-directions will be zero i.e. <vx> = <vy>=<vz>=0.

MASTERJEE CONCEPTS

These assumptions must always be kept in mind throughout the chapter.

Vaibhav Gupta (JEE 2009 AIR 54)
1 3 . 2 | Kinetic Theor y of Gases and Thermodynamics

3. PRESSURE OF AN IDEAL GAS

Applying Newton’s Laws to an ideal gas under the assumptions of kinetic theory allows the determination of the
average force on container walls. This treatment assumes that the collisions with the walls are perfectly elastic.

Force of molecular Before

Perfectly
collision with wall vx
elastic
 For N identical
Ft = p = 2mvx After collision
with wall molecules :
vx
l
vx
vx
2L
The time for a ‘’round trip’ is t =
vx L
2
2mvx mv x
So the average force is F = =
2L L l
For N molecules :
vx

Figure 13.1

An overbar indicates an average quantity. In the expression for the average force per molecule
m  v1x
2 2
+ v 2x 2
+ v 3x 2 
+  vNx
for N molecules. F =  
L

v2 + v2 + v2 +  v2 
but this can be related to the average: v 2x = 
1x 2x 3x Nx 

It is important to note that it is the average of the square of the velocity which is used, and that this is distinctly
different from the square of the average velocity. The average of the square of the velocity is referred as square of
root mean square speed.

mNv 2x
i.e. Vrms = v 2 ; and for N molecules: F =
L

And, since the molecular motion is random according to KTG, so v=

2
x
2
v=
y v 2z

MASTERJEE CONCEPTS

Why are the RMS velocities the same in all the directions? Practically, if we use some pressure measuring
device and use it from all directions, we would get the same value of pressure which indicates that RMS
velocities must be same in all directions because it is directly proportional to RMS velocity.
Chinmay S Purandare (JEE 2012 AIR 698)

Thus, v 2 = v 2x + v 2y + v 2z = 3v 2x ;

mNv 2
Now, average force from N molecules can be re-written as Faverage =
3L
Favg mNv 2 mNv 2 N
Then the pressure in a container can be expressed=
as P= = = mv 2
A 3LA 3V 3V
 P hysi cs | 13.3

1 2 P
P= ρv ρ: density of gas molecules in the container; Therefore,Vrms
Vrms = 3
3 ρ

2N  1 2 
Expressed in terms of average molecular kinetic energy: P =  mv 
3V  2 

4. KINETIC INTERPRETATION OF TEMPERATURE

The expression for gas pressure developed from kinetic theory relates pressure and volume to the average molecular
kinetic energy. Comparison with the ideal gas law leads to an expression for temperature sometimes referred to as
the kinetic temperature.
PV = nRT
2 1  2 N 1 2 
And we know from above that: PV = N  mv 2  ; Thus, T =  mv 
3  2  3 nR  2 
3
∴ Kinetic energy per mole of gas = RT ;
2
As R = Boltzmann’s constant x Avogadro number; R = kNA

1 2  3
Thus, Average molecular kinetic energy is:
= KEavg = mv  kT
 2  2
3RT
Therefore, Vrms = ; Where Mm is the molecular weight of the gas.
Mm

MASTERJEE CONCEPTS

3RT
In Vrms = , M is the molecular weight in Kg.
M
The temperature at which molecular speed becomes zero is called absolute zero i.e. 0 kelvin
Vaibhav Krishnan (JEE 2009 AIR 22)

Illustration 1: A tank used for filling helium balloons has a volume of 0.3m³ and contains 2.0 mol of helium gas at
20.0°C. Assuming that the helium behaves like an ideal gas.
(a) What is the total translational kinetic energy of the molecules of the gas?
(b) What is the average kinetic energy per molecule? (JEE MAIN)

Sol: Formula for total kinetic energy and kinetic energy per molecule is used.
3
(a) Using (KE)Trans = nRT
2
3
With n = 2.0 mol and T = 293 K, we find that (KE)Trans = (2.0)(8.31)(293) = 7.3 x 10³ J
2
3
(b) The average kinetic energy per molecule is kT.
2
 1 3 . 4 | Kinetic Theor y of Gases and Thermodynamics

1 2
or=
2
mv
1 2
=
2
mv rms
3
2
3
2
( )
kT = 1.38x10−23 (293) = 6.07x10−21 J

Illustration 2: In a circle model of a rotation diatomic molecule of chlorine (Cl2), the two Cl atoms are 2.0 x 10-10 m
apart and rotate about their centre of mass with angular speed ω = 2.0 x 1012 rad/s. What is the rotational kinetic
energy of one molecule of Cl2, which has a molar mass of 70.0 g/mol? (JEE ADVANCED)
1 2
Sol: Rotational kinetic energy of each molecule= Iω
2 m  m
Movement of inertia, I = 2 (mr²) = 2mr²
Cl Cl
70x10−3 2.0x10−10
Here m = 5.81x10−26 kg and
= = r = 1.0x10 −10 m
2x6.02x1023 2 r r
Figure 13.2
∴ I = 2(5.81) x10−26 (1.0 x10−10 )2 =1.16 x 10-45 kg-m²

1 2 1
∴ KR= Iω = x(1.16 x10−45 ) x(2.0 x1012 )2 = 2.32x10−21 J
2 2
1 1
Note: At T = 300 K, rotational K.E, should
= be equal to kT = x(1.38 x10−23 ) x(300) 2.07 x10−21 J
2 2

5. TYPES OF SPEED
There are generally three types of speed defined which are physically important:

5.1 Root Mean Square (RMS) Speed vrms

It is the square root of the average of the square of velocities v 2 i.e. v rms = v 2

As has been derived in the previous section, the value of vrms can be derived from the following formula:

3kT 3RT 3P
v rms
= = =
m M ρ

5.2 Mean/Average Speed vav

v1 + v 2 +  + vN
It is the mean of the speeds of all the particles i.e. v av =
N

8kT 8RT 8P
From the Maxwellian speed distribution law, we can show that
= v av = =
πm πm πρ

5.3 Most Probable Speed vmps

It is the mode of the speeds. That is, the speed which is possessed by most of the molecules of a gas at a given
temperature T.

2kT 2RT 2P
v mp
= = =
m M ρ
 P hysi cs | 13.5

MASTERJEE CONCEPTS

The above quantities are easy to derive by some basic knowledge of calculus. However, only knowing
them is also fine and observe that
1. Vmps: Vrms: Vav:: 1: 1.224: 1.28
2. Vmps =<Vrms =< Vavg
Nivvedan (JEE 2009 AIR 113)

Illustration 3: Consider an 1100 particles gas system with speeds distribution as follows:
1000 particles each with speed 100 m/s; 2000 particles each with speed 200 m/s
4000 particles each with speed 300 m/s; 3000 particles each with speed 400 m/s and 1000 particles each with
speed 500 m/s Find the average speed, and rms speed. (JEE MAIN)

 n1v1 + n2 v 2 + n3 v 3 ......  nv12 + n2 v 22 + n3 v 32 .........

Sol:  Vavg =  and Vrms
 n1 + n2 + n3 + .......  n1 + n2 + n3 + ...........

(1000)(100) + (2000)(200) + (4000)(300) + (3000)(400) + (1000)(500)

The average speed is: v av = = 309 m/s
1100

(1000)(100)2 + (2000)(200)2 + (4000)(300)2 + (3000)(400)2 + (1000)(500)2

The rms speed is: v rms = = 328 m/s
1100

v rms 3
Note: Here ≠ as values and gas molecules are arbitrarily taken.
v av 8/π

Illustration 4: Find the rms speed of hydrogen molecules at room temperature (=300 K). (JEE MAIN)
Sol: Formula based

3RT 3x8.31x300
Mass of 1 mole of hydrogen gas = 2g = 2 x 10-3kg ⇒ v rms = = =1.93x10³m/s
M 2x10 −3

Illustration 5: Find the temperature at which oxygen molecules would have the same rms speed as of hydrogen
molecules at 300 K. (JEE ADVANCED)
Sol: Compare the Vrms of oxygen and hydrogen.

3RT 3R(300)  Mo 
If T be the corresponding temperature = = ⇒ T (300)
=   4800K
Mo MH  MH 
1 3 . 6 | Kinetic Theor y of Gases and Thermodynamics

THERMODYNAMICS
1. INTRODUCTION
You would have certainly noticed the whistle of the process cooker in the kitchen. Have you ever thought of reason
for that? How small amount of water form large volume of vapours. Think of James Watt and his observation that
red to invention of steam engine !

2. GAS LAWS

2.1 Boyle’s Law

The Pressure-Volume Law (by Robert Boyle (1627-1691).
Boyle’s law or the pressure-volume law states that the volume of a given amount of gas varies inversely with the
applied pressure when the temperature and mass are kept constant.
1
V∝ ; i.e. PV = C; Therefore, P1V1 = P2 V2
P
When pressure goes up, volume goes down and vice-versa.

2.2 Charles’ Law

The Temperature-Volume Law (by Jacques Charles (1746 - 1823).
This law states that the volume of a given amount of gas held at constant pressure is directly proportional to the
Kelvin temperature.
v ∝ T; i.e. V / T = C; Therefore, V1 / T1 = V2 / T2
As the volume goes up, the temperature also goes up, and vice-versa.

2.3 Gay-Lussac’s Law

The Pressure Temperature Law (by Joseph Gay-Lussac (1778-1850).
This law states that the pressure of a given amount of gas held at constant volume is directly proportional to the
Kelvin temperature.
P∝T; i.e. P/T = C; Therefore, P1 / T1 = P2 / T2

2.4 Avogadro’s Law

The Volume Amount Law ( Amedeo Avogadro (1776-1856).
Gives the relationship between volume and amount when pressure and temperature are held constant. Remember
amount is measured in moles. Also, since volume is one of the variables, that means the container holding the gas
is flexible in some way and can expand or contract. If the amount of gas in a container is increased, the volume
increases. If the amount of gas in a container is decreased, the volume decreases.
v ∝ n; i.e. V/n = C; Therefore, V1 / n1 = V2 / n2

The combined gas law: The volume of a given amount of gas is proportional to the ratio of its Kelvin temperature
and its pressure.
T
V∝ ; i.e. PV/T = C Therefore, P1 / V=
1 T=
1 P2 V2 / T2
P
 P hysi cs | 13.7

As the pressure goes up, the temperature also goes up, and vice-versa.

The ideal gas law: On combining all the previous laws we get: PV = nRT
Where n: the number of moles and R: constant called the universal gas constant≈ 0.0821 L-atm / mol-K.

MASTERJEE CONCEPTS

For solving problems, it is not advisable to individually think over each and every case. Just remember
this overall equation. PV = nRT
Nitin Chandrol (JEE 2012 AIR 134)

Illustration 6: An air bubble starts rising from the bottom of a lake. Its diameter is 3.6 mm at the bottom and 4 mm
at the surface. The depth of the lake is 250 cm and the temperature at the surface is 40°C. What is the temperature
at the bottom of the lake? Given atmospheric pressure = 76 cm of Hg and g = 980 cm/s². (JEE MAIN)
P1V1 P2 V2
Sol: Amount of air is constant, hence = applicable.
T1 T2
4 3 4
At the bottom of the lake, volume of the bubble V1 = πr = π(0.18)3 cm3
3 1 3
Pressure on the bubble; P1 = atmospheric pressure + pressure due to a column on 250 cm of water = 76 x 13.6 x
980 + 250 x 1 x 980 = (76 x 13.6 +250) 980 dyne/cm²
4 3 4
At the surface of the lake, volume of the bubble V2 = πr = π(0.2)3 cm3
3 2 3
Pressure on the bubble; P2 = atmospheric pressure = (76 x 13.6 x 980) dyne/cm²
T2 = 273 + 40°C = 313° K
4 4
(76 x13.6 + 250)980 x   π(0.18)3 (76 x13.6) x 980   π(0.2)3
PV P V
Now 1 1 = 2 2 or 3 = 3
T1 T2 T1 313

or T1 = 283.37 K; ∴ T1 = 283.37 – 273 = 10.37°C

Illustration 7: P-V diagram of n moles of an ideal gas is as shown in figure. Find the maximum temperature
between A and B. (JEE ADVANCED)

dT d2 T
Sol: Find
= 0, < 0 for Tmax in T/V relation.
dV dV 2
Procedure: For given number of moles of a gas, T ∝ PV

Although (PV)A = (PV)B or TA = TB, still it is not an isothermal process. Because in isothermal process P-V graph is a
rectangular hyperbola while it is a straight line. So, to see the behaviour of temperature first we will find either T-V
equation or T-P equation and from that equation we can judge how the temperature varies. From the graph first
we will write P-V equation, then we will convert it either in T-V equation or in T-P equation.
From the graph the P-V equation can be written as,
P  P 
−  0  V + 3P0
P= (y = -mx + c) or −  0  V 2 + 3P0 V
PV =
V  V 
 0  0
 1 3 . 8 | Kinetic Theor y of Gases and Thermodynamics

P
P  2 1  P  2
= 3P0 V −  0
or nRT  V (as PV = nRT) or
= T 3P0 V −  0  V 
V nR   V0
A
 0    2P0
This is the required T-V equation. This is quadratic in V. Hence T-V graph is a parabola.
P0 B
Now, to find maximum or minimum value of T we can substitute.
V
dT  2P  3 V0 2V0
= 0 or 3P0 −  0 0 ; or
 V = V= V
dV V 2 0 Figure 13.3
 0 
d2 T 3
Further is negative at V = V
dV 2 2 0
3
Hence, T is maximum at V = V and this maximum value is,
2 0
  3V   P   3V  
2
9P V
1 
=Tmax (3P0 )  0  −  0   0   ; or Tmax = 0 0
nR  2 V  2  4nR
    0    Tmax

Thus, T-V graph is as shown in figure A B

TA-TB
2P0 V0 9P0 V0 P0 V0
T=
A T=
B
and Tmax = = 2.25 V
nR 4nR nR V0 2V0
Figure 13.4

3. DEGREE OF FREEDOM (f )
Each independent mode by which a system can absorb energy (Kinetic + Potential) is called a degree of freedom.
It is the number of independent motions possible or number of independent coordinates to specify the dynamic
position of a body. A molecule can have translational K.E, rotational K.E and vibrational energy (potential, kinetic).
(a) Monatomic Gas: It has 3 degrees of freedom, since it can have translational motion in any direction in space.
It can rotate but due to its small moment of inertia, rotational energy is neglected. f = 3
(b) Diatomic gas and linear polyatomic gas: It has 5 degrees of freedom (3 translational + 2 Rotational). Since,
the moment of inertia about the axis joining the atoms is negligible, thus, it only has two rotational degrees
of freedom. In all, f = 5.
At high temperature, its degree of freedom increases by 2 due to the vibrational energy (1 kinetic + 1 potential
vibrational energy). Thus f = 7 at high temperature.
(c) Non-linear Polyatomic gas: It has 6 degrees of freedom (3 translational + 3 rotational). The one rotational
degree of freedom which was neglected above, can’t be neglected over here. Since, the moment of inertia
about any of the three axes is not tending to zero i.e. f = 6.
At high temperature, its degree of freedom increases by 2 due to Vibrational energy
(1 kinetic + 1 potential) Thus, f = 8.
(d) Solid: Solids don’t have any translational or rotational degrees of freedom. But at high temperature, it can
vibrate along 3 axes. Thus it has 2 degrees of freedom per axis (i.e. potential + kinetic vibrational energy).
Thus, at high temperature, solids have 6 degrees of freedom. i.e. f = 6
 P hysi cs | 13.9

MASTERJEE CONCEPTS

fmix = (n1f1 + n2f2+……………) / (n1+n2+……………) is the equation for effective ‘f’ for a mixture of gases.
•• Degrees of freedom of a diatomic and polyatomic gas depend on temperature and there is no
clear cut demarcation line above which vibrational energy becomes significant. Moreover, this
temperature varies from gas to gas. On the other hand for a monatomic gas, there is no such
confusion. Degree of freedom here is 3 at all temperatures. Unless and until stated in the question
you can take f = 3 for a monatomic gas, f = 5 for a diatomic gas and f = 6 for a non-linear
polyatomic gas.
•• When a diatomic or polyatomic gas dissociates into atoms it behaves as a monatomic gas, whose
degrees of freedom are changed accordingly.
B Rajiv Reddy (JEE 2012 AIR 11)

4. INTERNAL ENERGY (U)

(a) In thermodynamics, the internal energy is the total energy contained by a thermodynamic system. It is the
energy needed to create the system but excludes any energy due to external force fields (e.g. Internal energy
does not include the energy due to the motion of the system as a whole. It further excludes any kinetic
or potential energy the body may have because of its location in external gravitational, electrostatic, or
electromagnetic fields.).
(b) Internal energy has two major components, kinetic energy (Ukin) and potential energy(Upot). The kinetic energy
is due to the motion of the system’s particles (translations, rotations, vibrations), and the potential energy is
associated with the static rest mass energy of the constituents of matter. U = Upot + Ukin
(c) The internal energy of a system can be changed by heating the system or by doing work on it.
(d) It is an extensive quantity. The internal energy is a state function of a system, because its value depends only
on the current state of the system and not on the path taken or process undergone to arrive at this state
(e) The SI unit of energy is the joule (J).

5. LAW OF EQUIPARTITION OF ENERGY

According to the law of equipartition of energy, the total energy of a molecule is equally distributed on the average
1
among all the degrees of freedom. For an ideal gas at absolute temperature T, the energy is: kT per molecule per
2
1
degree of freedom. k = Boltzmann’s constant ; RT per mole, R = gas constant.
2
f
Thus, if f be the number of degrees of freedom, the internal energy of n moles of the gas will be nRT . Thus,
2
f
U = nRT
2

6. MOLAR HEAT CAPACITIES (C)

(a) The amount of heat needed to raise the temperature of one mole of a substance by one degree Celsius. i.e.
∆Q
C= ⇒ ∆Q = nC∆T
n∆T
(i) S.I. unit is J/mol K
(ii) The value of C depends on the process through which its temperature is raised.
 1 3 . 1 0 | Kinetic Theor y of Gases and Thermodynamics

(b) Molar heat Capacity at constant Pressure CP : The amount of heat needed to raise the temperature of one
mole of a substance by one degree Celsius at constant pressure.
(c) Molar heat Capacity at constant Volume CV : The amount of heat needed to raise the temperature of one
mole of a substance by one degree Celsius at constant volume.
CP
=(i) γ Ratio
= of CP to C v ; γ is also referred to as the adiabatic constant.
Cv

MASTERJEE CONCEPTS

You Can Write:

CVmix
= (n1Cv1 + n2Cv 2 + ) / (n1 + n2 + )
CPmix
= (n1CP1 + n2CP2 + ) / (n1 + n2 + )
fmix = (n1f1 + n2 f2 + ) / (n1 + n2 + )
But γmix ≠ (n1γ1 + n2 γ 2 + ) / (n1 + n2 + )
1 2 / fmix (you will see it later that γ = 1 + 2/f) = CPmix / C vmix
γmix =+
Anand K (JEE 2011 AIR 47)

7. ZEROTH LAW OF THERMODYNAMICS

If two bodies A and B are in thermal equilibrium and A and C are also in thermal equilibrium, then B and C are also
in thermal equilibrium.

8. FIRST LAW OF THERMODYNAMICS

It is based on the law of conservation of energy. It states that
Heat supplied to the gas = Increment in internal energy + work done by the gas.
∆Q = ∆U + ∆W
In differential form, dQ = dU + dW
We will be using the following sign convention:
(a) For heat transfer: ∆Q is +ve for heat supplied;
∆Q is -ve for heat rejected
(b) For Work Done: ∆W=+ve for work done by gas (in expansion of gas)
∆W=-ve for work done on the gas (in contraction of gas)
We know:
n
Internal energy: Earlier we have seen that U= fRT
2
n
Thus, change in internal energy ∆U= fR∆T
2
n
or in differential from, dU = fRdT
2
Note: Change in Internal Energy is path independent whereas work done or heat energy released are path
dependent. Internal Energy depends only on initial and final state of the system.
 P hysi cs | 13.11

Illustration 8: Calculate the change in internal energy of 3.0 mol of helium gas when its temperature is increased
by 2.0 K. (JEE MAIN)

Sol: Formulas based : f degree of freedom for monoatomic gas is 3.

Helium is a monatomic gas. Internal energy of n moles of the gas is,
3 3
U = nRT ; U
∴ ∆= nR( ∆ T)
2 2
3
Substituting the
= values, ∆U  =  (3)(8.31)(2.0) 74.8 J
2
Heat transfer: From molar heat capacity, we saw that ∆Q = nC∆T or in differential form, dQ = nCdT
Work done: dW = PdV
For a finite change in volume from Vi to Vf, this equation is then integrated between Vi to Vf to find the net work.
v
W=
∫ dw =
∫ v f PdV
i
Now, there are two methods of finding work done by a gas.
P
Method 1: This is used when the P-V equation is known to us. Suppose P as a function of V
1
v
is known to us. P = f(V) then work done can be found by, W = ∫ v f f(V)dV
i
A B
Method 2: Since, work done is the integration of pressure w.r.t volume. So, it is clear that
work represents the area under P-V graph. But, always take care of the sign of the work done.
2
If the volume increases or in case of cyclic process if it is clockwise then +ve work is done by
the gas or vice versa.
Figure 13.5

Illustration 9: A certain amount of an ideal gas passes from state A to B first by means of process 1, then by means
of process 2. In which of the process is the amount of heat absorbed by the gas greater?  (JEE MAIN)

Sol: ∆V is state function, remains constant. Hence work done directly P P

proportional to heat obserbed.
1
Q=
1 W1 + ∆U1 and Q=
2 W2 + ∆U2
A B A B
U is a state function. Hence, ∆U depends only on the initial and final W1
W2
positions. Therefore, ∆U1 = ∆U2 . But W1 > W2 as the area under 1 is
v v
greater than area under 2. Hence, Q1 > Q 2
Figure 13.6

9. REVERSIBLE AND IRREVERSIBLE PROCESS

9.1 Reversible Process

A process in which the system and surroundings can be restored to the initial state from the final state without
producing any change in the thermodynamic properties of the universe.
E.g. an infinitesimal compression of a gas in a cylinder assuming frictionless surfaces.

9.2 Irreversible Process

In irreversible processes, the system is not in equilibrium throughout the process. The initial state can’t be obtained
from the final state without producing changes in the universe.
E.g. heat transfer through a finite temperature difference.
1 3 . 1 2 | Kinetic Theor y of Gases and Thermodynamics

10. DIFFERENT THERMODYNAMIC PROCESSES

10.1 Isochoric Process (V = Constant)

CV is the molar heat capacity for constant volume.
Since ∆V =0 . Therefore, ∆W =
0;
P
f f
= n R∆T and
We know that, nC v ∆T = n R∆T
2 2
By 1st Law of Thermodynamics: ∆Q = ∆U + ∆W ; ∆Q =∆U + 0 ;
V=constant
f f
= n R∆T ; Therefore, ∆Q =
Thus nC v ∆T ∆U ⇒ C v = R;
2 2
So in isochoric process we have ∆Q =∆U =nC v ∆T ; ∆W =
0 T(in K)
Note: Since, ∆U is an extrinsic property(property that is not inherent). So, Figure 13.7
∆U= nC v ∆T can be used for any process.

10.2 Isobaric Process (P = Constant)

Here ∆P =0 ; CP is the molar heat capacity for this process.
Thus, dQ = mCP dT V
P=constant
Since, dU is an extrinsic property, Thus, dU = nC v dT
We know PV = nRT ; ⇒ PdV + VdP = nRdT ⇒ PdV = nRdT [∵ dP = 0]
And dW = PdV = nRdT
So, by using the 1st law of thermodynamics.
T(in K)
nRdT; ⇒ CP = CV + R
We get , dQ= dU + dW; ⇒ nCP dT = nCV dT + nRdt
Thus, for the process, we have, ∆W= P(Vf − Vi )= nR(Tf − Ti ) ; ∆Q = nCP ∆T ; ∆U= nC v ∆T Figure 13.8

Note: We have seen, from above two process that,

f
CV = R and C=
P CV + R  … (i)
2
f 
Thus, C=P  + 1 R  …by (i)
 2 
f 
 + 1 R
CP 2  ; ⇒ γ = 1 + 2 Thus, C= R / ( γ − 1) And C = γR / ( γ − 1)
We know, γ = ; ⇒ γ = V P
CV f f
 R
2
Thus, for different degrees of freedom (i.e. for different gases) we have:

Types of Gas Degrees of freedom Total Energy CP CV γ

3 5 3
Monatomic 3 RT R R 1.67
2 2 2

Diatomic 5
5 7 5 1.4
RT R R
2 2 2
Polyatomic( ≥ 3 ) 6 3RT 4R 3R 1.33
 P hysi cs | 13.13

Illustration 10: A cylindrical vessel of 28cm diameter contains 20g of nitrogen compressed by a piston supporting
a weight of 75kg. The temperature of the gas is 17°C. What work will the gas do, if it is heated to a temperature of
250°C? What amount of heat should be supplied? To what distance will the weight be raised? The process should
be assumed to be isobaric; the heating of the vessel and the external pressure are negligible. (JEE ADVANCED)

Sol: Use isobaric process equations .

m R∆T m 20
∆W (work done) = ∫ PdV = P∆V = P × = R∆T ∴ ∆W
= × 8.3(250 − 17)
= 1381J
M P M 28
7 20
Q n Cp ∆=
∆= T nR ∆T = 3.5 × × 8.3 × (250 − 17) = 4834.7J
2 28

∆V nR∆T 1
h
= = ×
A P A

 mg 
P  P0 +
= 
 A 

20 × 8.3 × (250 − 17)

⇒ h= ⇒ h 0.2
= = m 20 cm
5 22 2 −4
28 × 75 × 9.8 + (10 × × 14 × 10 )
7

10.3 Isothermal Process (T = Constant)

∆T =0 ; ∆U= nCV ∆T= 0 ; ⇒ ∆W =∆Q ;

nRT P
We know, PV = nRT; ⇒ P = ;
V
Vf
nRT Vf Vf
∴∆W
= ∫= V
dv nRTlnV
=  nRTln
Vi
T=constant
V Vi
i

Slope of P-V graph: PV=nRT; ⇒ (dP)V+P(dV)= nRdT

V
Since, dT =0;
Figure 13.9
Thus, (dP)V+P(dV)=0 ; ⇒ dP/dV=- P/V
So, in an isothermal process we have: ∆U =0
Vf Pi P
∆Q =∆W =nRTln =nRTln ; Slope (isothermal) = −
Vi Pf V
And C (molar heat capacity) tends to infinity since even when temperature change is zero, heat transfer is non-zero.

Illustration 11: Three moles of an ideal gas being initially at a temperature T0 = 273K were isothermally expanded
η =5.0 time its initial volume and then isochorically heated so that the pressure in the final state became equal to
that in the initial state. The total amount of heat transferred to the gas during the process equals Q = 80 kJ. Find
the ratio γ =CP / CV for this gas. (JEE ADVANCED)

Sol: Try draw the process on P/V graph, during isothermal process, the change in internal energy is zero while in
R
isochoric process work dne is zero. Take C v = and proceed to find y.
y −1
Procedure:
(1) Find heat expression (Q1) given in isothermal process
(2) Find heat expression (Q2) given in isochoric process
 1 3 . 1 4 | Kinetic Theor y of Gases and Thermodynamics

(3) Find total heat expression (Q=Q1+Q2)

(4) Put the value of Q given in question in the expression obtained above
In Isothermal process, the heat transferred to the gas is given by

2 / V1 ) nRT0 ln η 
Q1 nRT0 ln(V=
= … (i)
=∴ η (V
=2 / V1 ) (P1 / P2 )
In isochoric process, Q2 =∆ U (W=0)
∴ Q=
2 T n{R / ( γ − 1)}∆T 
nC v ∆= … (ii)

P2 T0 P 
Now = or T = T0  1  = ηT0  … (iii)
P1 T  P2 

∴ ∆ T = η T0 − T0 = (η − l)T0
Substituting the value of ∆T from equation (iii) in equation (ii), we get

 R   R 
=Q2 n  (η − 1) T0 ; ∴
= Q nRT0 ln η + n   (n − 1) T0
 γ − 1  γ − 1

Q  η − 1 η −1 η −1
or − ln η = ; or γ −1 = ∴ γ=1 +
nRT0  γ −1 Q Q
− ln η − ln η
nRT0 nRT0

(5 − 1)
Substituting given values, we get γ = 1 + ; Solving, we get γ =1.4
80x102
− ln5
3x8.3x273

10.4 Adiabatic Process (∆Q = 0)

For adiabatic process: ∆Q =
0 ; ∆U = −∆W
1monotomic
nCV dT = −Pdv  … (i) P 2diatomic
By equation of gas: PV = nRT ; ⇒ Pdv + Vdp =
nRdT ; 3polytomic
Pdv + Vdp
∴ ndT = 3 g=1.33
R 2
1 g=1.4
 Pdv + Vdp 
∴ Substituting in (i) we get: C v   = −Pdv g=1.67
 R 
V
C d −dp
⇒ (C v + R)Pdv = ; ⇒ P V
− C v Vdp = CV + R CP  ;
= Adiabatic expansion of mono, dia
CV V P
and polyatomic gases
dV dP
⇒γ =− Figure 13.10
V P
On integrating both sides we get,

dv P dp V P
⇒ γ∫ ∫ = −Pf ∫ ; ⇒ γ ln f =ln i
V i P Vi Pf
γ
Pi  Vf 
⇒ =   ; (say)
Pf  Vi 
∴ PV γ =
Const
 P hysi cs | 13.15

The relation found above can be written in many different ways using ideal gas equation (PV=nRT)
TV γ−1 = constant ; T γP1−γ = constant
Vf Vf
k k
; ∴= ∫=
Pdv ∫ dv
γ
PV = Const = K ⇒ P = ∆W
V γ
Vi Vγ Vi

KVf1−γ − KVi1−γ (Pf Vf γ ) Vf1−γ − (PV γ

i i ) Vi
1−γ
= =
1− γ 1− γ

Pf Vf − PV
i i nR
∆W
⇒= = (T − T )
1− γ 1− γ f i

Slope of P-V graph:

We know, PV γ = constant
P
dp d  cons tant  P P
=   = −γ   ; Thus, (Slope)adiabatic = −γ  
dV dV  V γ
 V
  V Isothermal
Because γ >1, the isothermal curve is not as steep as that for the
adiabatic expansion.
Adiabatic
So, in adiabatic process we have: ∆Q =
0
V
Pf Vf − PV nR Adiabatic and isothermal expansion
=W = i i
(T − T ) ; ∆U = −∆W
1− γ 1− γ f i of an idea gas

P Figure 13.11

(Slope)adiabatic = −γ  
V
And C (molar heat capacity) is zero, since even when temperature change is not zero, heat transfer is zero.

Illustration 12: An ideal monatomic gas at 300K expands adiabatically to twice its volume. What is the final
temperature? (JEE MAIN)

Sol: Adiabatic process PV γ = constant or TV γ−1 = constant.

5
For an ideal monatomic gas, γ =
3
In an adiabatic process, TV γ−1 = cons tant ; ∴ Tf Vf γ−1 =
Ti Viγ−1
γ−1 5
−1
V   1 3
or = Ti  i 
Tf = (300)
=   189K
 Vf  2

Illustration 13: An ideal gas having initial pressure P, volume V and temperature T is allowed to expand adiabatically
until its volume becomes 5.66 V while its temperature falls to T/2.
(a) How many degrees of freedom do the gas molecules have?
(b) Obtain the work done by the gas during the expansion as a function of the initial pressure P and volume V.
 (JEE ADVANCED)
γ−1
T1 V 
Sol: Apply T1V1γ−1 = T2 V2 γ−1 and hence =  2 
T2  V1 

nR  T  nRT nRT PV
=ω  = − T = =
1− γ  2  2( γ − 1) 2 × 0.4 0.8
1 3 . 1 6 | Kinetic Theor y of Gases and Thermodynamics

(a) For adiabatic change,

γ−1 1
TV = T'(V')γ−
= ; T' T=
/ 2, V' 5.66V
γ−1 γ−1 γ−1
TV = (T/ 2) x(5.66 V) ; (5.66) = 2
It shows that the gas is diatomic for which the gas molecules have five degrees of freedom.
(b) Work done by the gas during adiabatic expansion, W, is given by,

PV − P'V' P'V' PV PVT'

= W ; As
= = , P'
γ −1 T T V'T
1 1 P 1  P  PV
P'
= x xP
= ;∴ W=  PV − x5.66V  = = 1.25PV.
2 5.66 11.32 0.4  11.32  0.8

10.5 Cyclic Process

In a cyclic process, the thermodynamic process ends at the initial state. A
Since, initial and final states are same, there, P
B
∴ ∆Q = ∆W ; ∴ ∆Q = ∆W = Area enclosed by the curve.

Sign of ∆W is ‘+’ if process is clockwise and ‘-‘ if process is anti-clockwise. V

Figure 13.12
10.6 Polytropic Process
For a process: PVx = constant where x ≠ 1, also called a polytropic process.

R R R
∆W = (Pf Vf − PV
i i ) / 1 − x = nR ∆ T/ 1 − x ; C=Cv + = +
1− x γ − 1 1− x
dP P
Slope of P-V diagram (also known as Indicator diagram) at any point is = −x
dV V

11. FREE EXPANSION

In a free expansion, the gas is allowed to expand into a vacuum. This happens quickly, so there is no heat transferred.
No work is done, because the gas does not displace anything. According to the First Law, this means that: ∆U = 0
There is no change in internal energy, so the temperature stays the same.
On a PV diagram all you can do is plot the end-points. The process follows a path on the diagram that is not well-
defined because the temperature is constant. The connection between the initial and final states is: PiVi = PfVf
Thus, ∆W=0; ∆Q=0; ∆U=0; T=const. ; thus, PV = constant

Illustration 14: An insulated container is divided into two equal portions. One portion contains an ideal gas at
pressure P and temperature T, while the other portion is a perfect vacuum. If a hole is opened between the two
portions, find the change in internal energy and temperature of the gas?  (JEE ADVANCED)

Sol: No opposing force, hence work done is zero. As the system is thermally insulated, ∆Q =
0
Further as here the gas is expanding against vacuum (surroundings) the process is called free expansion and for it,
∆W= ∫ Pdv = 0 [as for vacuum P = 0]
So in accordance with first law of thermodynamics, i.e. ∆Q = ∆U + ∆W , we have 0 =∆U + 0,
i.e. ∆U =0 or U = constant
 P hysi cs | 13.17

So in this problem internal energy of the gas remains constant, i.e. ∆U = 0 . Now as for an ideal gas=
U 3 / 2 µRT ,
i.e. U ∝ T ; so temperature of the gas will also remain constant, i.e. ∆T =0

MASTERJEE CONCEPTS
(a) A non-conducting container with no external source of heat energy will always undergo any change
adiabatically.
(b) A conducting (finitely conducting) container with no external source of heat energy will undergo
change:
(i) Isothermally if the process is slow
(ii) Adiabatically if the process is fast
(c) An infinitely conducting container with no external source of heat energy will always undergo any
change isothermally.
Yashwanth Sandupatla (JEE 2012 AIR 821)

1
Illustration 15: A gas undergoes a process such that P ∝ If the molar heat capacity for this process is
T
C= 33.24 J/mol-K, find the degree of freedom of the molecules of the gas.  (JEE ADVANCED)
Q
Sol: Heat capacity = amount of heat required for per unit change of temperature. C =
∆T
1
As P ∝ or PT = constant .… (i)
T
We have for one mole an ideal gas PV=RT .… (ii)
From Eqs. (i) and (iii)
P²V = constant or PV1/2 = K (say)  … (iii)
From first law of thermodynamics, ∆Q =∆U + W or C∆T = CV ∆T + W
W
or =
C CV +  … (iv)
∆T
Vf
1/2 Pf Vf − PV R(Tf − Ti ) RT W
Here, ∆W
= ∫ PdV
= K ∫ V −= dv ; = i i
= ;∴ 2R
=
Vf
1 − (1/ 2) 1/ 2 1/ 2 ∆T

R
Substituting in Eq. (iv), we have C = C v + 2R = + 2R
γ −1

 1   1 
Substituting the values, 33.24
= R 2  8.31
+= + 2
 γ − 1   γ − 1 
2 2 2
Solving this we get γ =1.5 ; Now, γ = 1+ or degree of freedom =F = = 4
F γ − 1 1.5 − 1

R R
Alternate Solution: In process PVx =constant, molar heat capacity is given by=C +
γ − 1 1− x

1 R R R
The given process is PV1/2 = constant or x = ; ∴ C = + = + 2R
2 γ −1 1 γ −1
1−
2
Now, we may proceed in the similar manner.
1 3 . 1 8 | Kinetic Theor y of Gases and Thermodynamics

Illustration 16: An ideal gas expands isothermally along AB and does 700 J of work. P
A
(a) How much heat does the gas exchange along AB?
B
(b) The gas then expands adiabatically along BC and does 400 J of work. When the gas
returns to A along CA, it exhausts 100J of heat to its surroundings. How much work is done C
on the gas along this path? (JEE MAIN)
V
Sol: Apply Q =∆U + W for the forces AB, BC & then CA separately. Remember ∆U is a state Figure 13.13
function.
(a) AB is an isothermal process. Hence, 0 and
∆UAB = Q
= AB W
=AB 700J
(b) BC is an adiabatic process. Hence, QBC = 0 ; WBC = 400J (given)
∴ ∆UBC = − WBC =
−400J
ABC is a cyclic process and internal energy is a state function. Therefore, ( ∆U)whole cycle = 0 = ∆UAB + ∆UBC + ∆UCA
and from first law of thermodynamics, Q AB + QBC + Q CA = WAB + WBC + WCA
Substituting the values, 700 + 0 − 100
= 700 + 400 + ∆WCA
∴ ∆WCA =
−500J
Negative sign implies that work is done on the gas.

12. HEAT ENGINE & EFFICIENCY

Heat Engine is a device which converts the input W
heat energy into mechanical energy by using a
cyclic process.
T1 T2
It absorbs a quantity of heat Q1 from a source Hot Q1 Working Cold
and performs an amount of work W and returns (Source) substance (Source)
to the initial state after rejecting some heat Q2
to a sink. The working substance which is gas
or liquid undergoes a cyclic thermodynamic Figure 13.14
process. The source is at a higher temperature
than the sink.
The efficiency η , of a heat engine is given by

 Work done by the working subs tance 

 
=(an ideal gas in our case) during a cycle  W
η
 Heat supplied to the gas during the cycle  Q
1
 
 
From conservation of energy. Q=
1 W + Q2

W Q1 − Q 2 Q Heat released
η= = = 1− 2 ; Thus, ∴ Efficiency(η) = 1 −
Q1 Q1 Q1 Heat absorbed

Illustration 17: The P-V diagram of 0.2 mol of a diatomic ideal gas is shown in figure. Process BC is adiabatic. The
value of γ for this gas is 1.4. (JEE ADVANCED)
(a) Find the pressure and volume at points A, B and C.
(b) Calculate ∆Q , ∆W and ∆U for each of the three processes.
 P hysi cs | 13.19

(c) Find the thermal efficiency of the cycle. P

Take 1 atm = 1.0x105 N/m². B
600 K

Sol: Try to start from A where PA and TA are known.

(a) PA = PC = 1 atm = 1.01 x 105 N/m²
A
1.0 atm C
Process AB is an isochoric process. 300 K
V
PB TB
∴ P ∝ T or = ;
PA TA Figure 13.15

 TB   600 
∴ PB =
=  PA   (1atm) 2atm = 2.02 x 10 N/m²
5
T
 A  300 
nRT
From ideal gas equation V =
P
nRTA (0.2)(8.31)(300)
∴ V=
=
A V=
B ≈ 5.0x10−3 m3 ; = 5 litre
PA (1.01x105 )

nRTC (0.2)(8.31)(455)
VC
= = = 7.6x10−3 m3 ≈ 7.6 litre
PC 5
(1.01x10 )

A 1 atm 5 lt
B 2 atm 5 lt
C 1 atm 7.6 lt

(b) Process AB is an isochoric process. Hence, ∆WAB =

0
5  5
∆Q AB =∆UAB =nC v ∆T =n  2=
R  (TB − TA ) (0.2)   (8.31)(600 − 300) ≈ 1246 J
  2
Process BC is an adiabatic process. Hence, ∆QBC =
0
∴ ∆WBC = −∆UBC
5  5
∆UBC= nC v ∆T==
nCV (TC − TB ) (0.2)  R=
 (455 − 600) (0.2)   (8.31)( −145) J ≈ −602J
2  2
∴ ∆WBC =
−UBC =
602J

Process CA is an isobaric process. Hence,

7  7
∆Q CA= nCP ∆T==
n  R  (TA − TC ) (0.2)   (8.31)(300 − 455)
2  2

12.1 Types of Heat Engine

(a) External combustion engine: In which heat is produced by burning the fuel in a chamber outside the
main body (working substance) of the engine. Steam engine is an external combustion engine. The thermal
efficiency of a steam engine varies from 10 to 20%.
(b) Internal combustion engine: In which heat is produced by burning the fuel inside the main body of the
engine. Petrol engine and diesel engines are internal combustion engine. Here, we will just discuss about only
one heat engine i.e. Carnot engine.
1 3 . 2 0 | Kinetic Theor y of Gases and Thermodynamics

12.2 Carnot Engine

(T1)
Carnot Cycle is the most efficient heat engine which undergoes a cycle of A Q1


two isothermal and two adiabatic processes. It absorbs heat Q1 by expanding
isothermally at T1 along AB and then expands adiabatically along BC to Isothermal (T )
1
temperature T2. It is compressed isothermally at T2 rejecting heat Q2 along B

adiabatic
Pressure
CD and is compressed adiabatically along DA. Its efficiency η is given by:
T2 adiabatic
η = 1−
T1
(T2) D
C (T2)
Isothermal
Q2


Volume
Derivation of efficiency in Carnot engine: Figure 13.16

qin

I isothermal
P IV adiabatic T1=T2=T3 (High temperature)

II adiabatic

III isothermal
T3=T4=T1 (Low temperature)
qout

V
Figure 13.17: P-V diagram of the carnot cycle

MASTERJEE CONCEPTS

Try to prove that carnot engine is the most efficient one among all engines working in the same
temperature range. You will come across a nice use of the second law of thermodynamics!
GV Abhinav (JEE 2012 AIR 329)

Work, heat, ∆ U. and, ∆ H(ncp∆T) in the P-V diagram of the Carnot Cycle.

Process w q ∆U ∆H

V  V 
I −nRTh ln  2  nRTh ln  2  0 0
 V1   V1 

II −nC v (Tl − Th ) 0 nC v (Tl − Th ) nCp (Tl − Th )

V  V 
III −nRTl ln  4  nRTl ln  4  0 0
V V
 3   3 
 P hysi cs | 13.21

Process w q ∆U ∆H

IV −nC v (Th − Tl ) 0 nC v (Th − Tl ) nCp (Th − Tl )

V  V  V  V 
Cycle −nRTh ln  2  − nRTl ln  4  nRTh ln  2  + nRTl ln  4  0 0
V V
 V1   3   V1   3 

The efficiency of the Carnot engine is defined as the ratio of the energy output to the energy input.

V  V 
nRTh ln  2  + nRTl  4 
V  V 
Net work done by heat engine − Wsys  1   3 
Efficiency = = =
Heat absorbed by heat engine qh  V2 
nRTh ln  
 V1 
C /R C /R
 T2  V V3 T  V V4
Since processes II (2-3) and IV (4-1) are adiabatic.
=   = ,and  1 
 T3  V2  T4  V1

V3 V2
and since T1 = T2 and T3 = T4. =
V4 V1

V   V2 
nRThln  2  − nRTln
l 
 V 
 V1   1; Th − Tl
Therefore Efficiency = Efficiency= = 1 − Tl / Th
 V2  Th
nRThln  
 V1 

MASTERJEE CONCEPTS

•• By the second law of thermodynamics we can say that, it is impossible to construct an engine,
operating in a cycle, which will extract heat from a source and convert the whole of it into work. It
implies that it is impossible to make heat flow from a colder body to a hotter body without the help
of an external agency or an engine from outside.
•• That efficiency of Carnot engine is maximum (not 100%) for given temperatures T1 and T2. But still
Carnot is not a practical engine because many ideal situations have been assumed while designing
this engine which can practically not be obtained.
Anurag Saraf (JEE 2011 AIR 226)

Illustration 18: Carnot’s engine takes in a thousand kilo calories of heat from a reservoir at 827°C and exhausts it
to a sink at 27°C. How much work does it perform? What is the efficiency of the engine? (JEE MAIN)

Q1 − Q 2 Q2 T2 Q2 T2
Sol: η = = 1− and for cannot cycle η = 1 − , hence =
Q1 Q1 T1 Q1 T1

Given, Q1 = 106 Cal T1 = (827 + 273) = 1100K and T2 =(27 + 273) =300K

Q2 T2 T2  300  6
as, = ∴ Q2
= = Q   (10 ) = 2.72 x 10 cal
5
Q1 T1 T1 1  1100 
 1 3 . 2 2 | Kinetic Theor y of Gases and Thermodynamics

 T   300 
Efficiency of the cycle, η= 1 − 2  x100 or η= 1 −  x100 = 72.72%
 T1   1100 

PROBLEM-SOLVING TACTICS

(a) Most of the problems of Tmax, Pmax and Vmax are solved by differentiating. Sometimes the graph will be given
and sometimes, the equation will be given. For problems of finding Pmax , you will require either the P-V or
P-T equation.
(b) From the sections of thermodynamic, graphical questions are usually asked so one must have a thorough
understanding of PV diagrams at least. It is generally advised to convert other graphs namely TV and PT graph
to PV graph before solving to visualize it easily. Also in many cases we can directly get asked quantities like
work done because it involves integration of area under the PV graph.
(c) Silly mistakes must be avoided because there is not much variety in problems and not so much to think.
Remember the following points:-
(i) Be very careful in signs of Q and W while solving questions of thermodynamics.
(ii) Be careful in noting the type of gas used in question whether it is monatomic or diatomic.
(iii) Be careful with units of given quantities and asked quantities.
(iv) You can list more from your personal experience.
(d) It would be helpful to note keywords in a question (like noting down slow and fast changes because slow
changes imply reversible change whereas fast change imply irreversible change).
(e) It is always helpful to make a separate list of known quantities and asked quantities and then think of a way,
a link between them.
(f) Questions are mostly based on various reversible or irreversible processes which have their own set of
formulae. And no more processes can be found other than these. Hence, these concepts must be strong and
you should know the algorithm of each one thoroughly.

FORMULAE SHEET

Kinetic Theory of Gases

1
=PV = nMm Vrms2 nRT
3
1 3
=
Kinetic energy per mole of gas = E = Mm Vrms2 RT
2 2
3kT 3RT 3P
Vrms
= = =
m M ρ
 P hysi cs | 13.23

8kT 8RT 8P
Vav
= = = M is the molar mass in kilogram per mole.
πm πM πρ

2kT 2RT 2P
Vmp
= = =
m M ρ

8
Vrms : Vav : Vmps :: 3 : : 2 ; Vmps : Vrms : Vav ::1 : 1.224 : 1.28
π
The mean free path of a gas molecule is the average distance between two successive collisions. It is represented by λ.

kT σ =Diameter of themolecule
λ= Here,
2πd ρ 2 k = Boltzmann'scons tant

Thermodynamics
(a) Boyle’s law: According to this law, for a given mas of a gas the volume P
of a gas at constant temperature (called isothermal process) is inversely
proportional to its pressure, i.e., T=constant
1
V∝ (T= constant) or PV = constant
P
V

Figure 13.18

(b) Charle’s law: According to this law, for a given mass of a gas, the volume of V
a gas at constant pressure (called isobaric process) is directly proportional P=constant
to its absolute temperature, i.e.,
V
V∝T (P= constant) or = cons tant
T
T(in K)

Figure 13.19

(c) Gay Lussac’s law or Pressure law: According to this law, for a given P
mass of a gas the pressure of a gas at constant volume (called isochoric
process) is directly proportional to its absolute temperature, i.e.,
P V=constant
P∝T (V= constant) or = cons tant
T
T(in K)

Figure 13.20

(d) Avogadro’s law: According to this law, at same temperature and pressure
equal volumes of all gases contain equal number of molecules.

Ideal gas equation

PM
PV = nRT OR ρ=
RT
Degree of freedom of monoatomic f = 3 (all translational)
gas
1 3 . 2 4 | Kinetic Theor y of Gases and Thermodynamics

Degree of freedom of a diatomic f = 5 (3 translational + 2 rotational) at room temperatures and f = 7

and linear polyatomic gas
(3 translational + 2 rotational + 2 vibrational) at high temperatures.
Degree of freedom of nonlinear f = 6 (3 translational + 3 rotational) at room temperatures and f = 8
polyatomic gas
(3 translational + 3 rotational + 2 vibrational) at high temperatures.
Degree of freedom of solid An atom in a solid has no degrees of freedom for translational and rotational
motion. At high temperatures due to vibration along 3 axes it has 3 x 2 = 6 degrees
of freedom. f = 6 (all vibrational) at high temperatures.

∆Q
C= or ∆Q = nC∆T
n∆T

For a gas the value of C depends on the process through which its temperature is raised.

Types of gas Degrees of freedom Total energy CP CV γ

3 5 3
Monoatomic 3 RT R R 1.67
2 2 2

5 7 5
Diatomic 5 RT R R 1.4
2 2 2

Polyatomic( ≥ 3 ) 6 3RT 4R 3R 1.33

mic 5/3 = 1.67

o n oato
CP f+2 m
Ratio of specific heat :-  = diatomic 7/5 = 1.4
=
CV f polya
tomi
c 4/3 = 1.33

Note: C of a gas depends on the process of that gas, which can be infinite in types.
2 R γR
and f= ; Cv = ; CP =
γ −1 γ −1 γ −1

Often the first law must be used in its differential form, which is dU = dQ – dW
This can also be written as dQ = dU + dW
∆ Q is +ve for heat supplied
∆ Q is -ve for heat rejected

1. ∆ W = +ve for work done by the gas (in expansion of gas)

∆ W = -ve for work done on the gas (in contraction of gas)
f
2. For change in internal energy of the gas, apply ∆U= nC v ∆T or in differential form, dU = nCvdt = nRdT
2
3. For heat transfer, apply Q
= nC∆T
or in differential form dQ = nCdT
dW = PdV
Vf
W= ∫ dW = ∫ PdV = Area under P-V curve
Vi
 P hysi cs | 13.25

Isothermal Q=W 0 V   Pi 
nRT ln  f  = nRT ln  
 Vi   Pf 

PV
i i − Pf Vf nR∆T
Adiabatic 0 nCV ∆T = −∆U=
γ −1 γ −1

Isobaric nCP ∆T nCV ∆T P(Vf − Vi )

Q = ∆U
Isochoric nCV ∆T 0
= nCV ∆T

P P
(Slope)isothermal = − (Slope)adiabatic = −γ  
V V

 Work done by the working subs tance 

   
(an ideal gas in our case) during a cycle  WTotal Q − ve
η=  × 100= × 100= 1 −  × 100
 Heat supplied to the gas during the cycle  Q + ve Q + ve
   
 
T
For Carnot Engine: η = 1 − 2
T1

Solved Examples

JEE Main/Boards 10 −3 × 250

=
N× 300
760 × 22400 23
6 ×10 × 273
Example 1: An electric bulb of volume 250cm³ was
sealed off during manufacture at the pressure of
10−3 × 250 × 6 × 1023 × 273
10-3mm of Hg at 27°C. Find the number of air molecules N= = 8.02 x1015 mole
in the bulb. 760 × 22400 × 300

N R
Sol:=
PV = RT N= T NkT Example 2: One gram-mole of oxygen at 27°C and one
A A
atmospheric pressure is enclosed in a vessel.
Let N be the number of air molecules in the bulb.
(a) Assuming the molecules to be moving with Vrms , find
V1 =250cm³, P1 = 10-3mm of Hg,
the number of collisions per second which molecules
T1 = 273 + 27 = 300°K make with one square meter area of the vessel wall.
As P1V1 = Nk T where k is constant, then (b) The vessel is next thermally insulated and moved
with a constant speed ν0 . It is then suddenly stopped.
10-3x 250 = N.k.300  … (i)
The process results in a rise of the temperature of the
At N.T.P., one mole of air occupies a volume of 22.4 litre,
gas by 1°C. Calculate the speed ν0 .
=V0 22400
= cm3 ,P0 = 760mmof
760 mm ofHg,
Hg,
P 3NAkT
T = 273° K and N0 = 6 × 1023 molecules Sol: Formula based: n = & Vrms = . Recall
kT Mn
∴760 × 22400 = 6x1023 × k × 273  … (ii)
the assumption of KTG. Kinetic energy changed to
Dividing equation (i) by equation (ii), we get internal energy.