Chapter 3

KINETIC THEORY OF GASES AND

RADIATION

Omitted topics: 3.2,3.3,3.4,3.8

 Introduction: The study of behavior of gas based on
simplified molecular or particle description of a gas.

• The gas which obeys the gas laws with out any
deviation are considered ideal.
• Boyles law:
• Pα 1/v at constant temperature(T)
• Charles law:
• Vα T at constant pressure (P)
• Gay - Lussac‘s law :
• Pα T at constant volume( V)
• PV α T or P 1 V1/ T 1 = P2 V2 /T 2
• For a fixed mass of gas
• No. of moles = mass(M)/molecular mass(Mo) = N/NA=n
• PV α n T ⇒ PV = n RT
• Ideal gas equation :
PV = n RT
• The gases which follow this equation with out any
deviation are considered ideal .
• In ideal gases the inter atomic or inter molecular
interaction is absent.
• But real gas atoms and molecule interact with each
other , hence they don’t show ideal behavior .
• Real gases exhibit ideal behavior at low density when
the temperature is high and pressure is low.
• To study the macroscopic behavior of gases we
consider the gas ideal.
 Pressure exerted by ideal gas using KTG
• Consider a fixed mass of perfect gas enclosed in
a cube having each side of length l
• Let m = mass of each molecule
• N= no. of molecules of the gas
• Total mass of the gas M= N m
• Area of the face of cube = l 2
l
• Volume of the cube V = l 3
• Density ⍴ = M/V = N m /l 3
• Let C 1 , C 2 , C 3 ……….C N be the velocities of
the molecules
• Each velocity can be resolved into three components.
• Let be the component of velocity C 1. u 1 , v 1 , w 1
W1
• C 1 = U 1 i + V1 j + W1 k
• U 1 similarly U 2 , V 2 , W 2 are the component
•V 1 of velocity of C 2
• U N , V N , W N are the component of velocity C N
Q
2 2 2 2 z Q’
• C 1 = U 1 + V1 + W 1
• C 22 = U 22 + V 22 + W 22 P’ P

• C N 2 = U N2 + V N 2 + W N2
• Consider a molecule of mass m R’ R
moves with velocity C 1 moving
x x axis S’ S
towards the wall PQRS. y
• It moves with velocity U 1 along x axis.
• Before collision momentum = m U 1 (P=MV)
• Momentum after collision = - m U 1
• Change in momentum = m U 1 – ( -m U1 ) = 2 m U 1
• Time interval between successive collision
• t = distance / speed = 2 l /U 1
• The force F 1 exerted on the wall
• = change in momentum/ time = 2 m U 1/(2l/U 1)
• =mU12/l
• Similarly F 2 = m U2 2/l
• F 3 = m U3 2/l
• F N = m U N 2/l
• Resultant force F x = F 1 + F 2+……..+ FN
• Fx = m U 1 2/l +m U 2 2/l +……….+m UN 2/l
•
• F x = m/l ( U 12 + U22 +………….+UN2)
• Similarly
• F y = m/l (V12 + V22 +………..+V N 2)
• F z = m/l ( W 12 + W22+ ……..+WN2)
• P x = F x/A = F x/l2 = m/l3( U 12 + U22 +………….+UN2)
• P y = F y /A = m/l3(V12 + V22 +………..+V N 2)
• P z = F z /A = m/l3 (W 12 + W22+ ……..+WN2)
• Net pressure = P x + P y + P z
• We know P x = P y = P z = P
• P x + P y + P z = 3P
• P = (P x + P y + P z) /3
• =1/3 (m/l3)[ ( U 12 + U22 +………….+UN2)+(V12 + V22
+………..+V N 2)+ (W 12 + W22+ ……..+WN2)]
• P=
• 1/3(m/l3)[(U12+V12+W12)+(U22+V22+W22)+…..(UN2+VN2
+WN2)]
• P= 1/3 (m/l3) ( C12+C22+……….+CN2)
• = 1/3 (m/l3) N C RMS 2
• = 1/3 Nm/V C RMS2
• = 1/3 (M/V) CRMS2
• P = 1/3 ⍴ C RMS2 [ ⍴ = M/V ]
•

2
P = 1/3 ⍴ C RMS
• Show that the root mean square speed C RMS is
directly proportional to the square root of
absolute temperature?
• We know P = 1/3 ⍴ C 2 RMS
• P = 1/3 (M/V) C2RMS
• PV= 1/3 M C2RMS [ PV =n R T ]
• n RT = 1/3 M C2RMS
• (M/Mo)RT= 1/3 M C2RMS [ n= M/Mo ]
• 3RT/Mo = C2RMS
• C RMS =√3RT/Mo

• Hence C RMS α √T
 Show that the average kinetic energy of gas molecule is
directly proportional to its absolute temperature?

• P = 1/3 ⍴ C2RMS
• P = 1/3 (M/V)C2RMS
• PV = 1/3 M C2RMS
• 3PV = Nm C2RMS
• 3/2 PV = N ½ m C 2RMS [ energy of each molecule = ½ mC2RMS ]
• 3/2 PV= E [energy of gas = N × energy of each molecule]
• E = 3/2 PV
• = 3/2 n R T
• = 3/2 (N/No ) R T
• = 3/2 ( R/No ) N T [ E/N = average Kinetic energy ]
• = N ( 3/2 k B T)
• E/N = 3/2 k B T
• Average kinetic energy = 3/2 k B T hence K.E Avg α T
numerical
 Maxwell s distribution
• For a gas due to collisions of the molecules the speed
and direction of the molecules change.
• At a given temperature the root mean square speed of
the molecule remain constant.
• Maxwell gave the mathematical relation for
distribution of speeds in a gas containing large number
of molecules.
• let n v = no. of molecules having velocity v
• Here the shaded area n v d v
represent the no. of molecules
having velocities between v and
v+dv
Specific heat capacity and Mayers relation
• The specific heat capacity of a substance is the amount
of energy required to raise the temperature of 1 kg of
substance by 1 o C.
• c= Δ E /m Δθ
• Δ E = m c Δθ
• Where Δ E = change in thermal energy (J)
• m= mass of substance ( kg)
• Δθ = change in temperature (o C)
• c= specific heat capacity ( J / kg o C )
• Molar specific heat : It is defined as the quantity of heat
required to raise the temperature of 1 mole of
substance by 1 K or 1 o C .
• The heat can be supplied to gases keeping the pressure
constant or by keeping the volume constant.
• Hence the molar specific heat for gases are of two type
• C p = molar specific heat at constant pressure
• C v = molar specific heat at constant volume
• Relation between C p and C v ( Mayer s relation)
• Consider one mole of ideal gas enclosed inside a
cylinder provided with friction less piston.
• Let P , V and T are the pressure volume and
temperature of the gas.
• If the gas is heated so that the temperature rises by dT,
but the volume remain constant.
• Then no work is done (d W = P d V )
• The heat supplied d Q 1 is used to increase the internal
energy ( d E )
• d Q 1 = d E +d W ⇒ d Q 1 = d E = C v d
T………………(1)
• where C v = molar specific heat at constant volume
• If the gas is heated through same temperature at
constant pressure , increasing the volume by d V .
• Then work is done as well as internal energy is
increased.
• d Q 2 = d E + d W ⇒ Cpd T = C v d T + P d
V………from(1)
• Cpd T = C v d T + P d V
• ⇒ Cpd T - C v d T = P d V ∴ for 1 mole of gas
• ⇒ ( C p - C v )d T = R d T PdV=RdT
⇒ Cp - C v = R
Cp–Cv=R/J Cp - C v = R
Where J = joules equivalent of heat
• C p = M o S p and C v = M o S v
• where S p and S v are principal specific heat at constant
pressure and constant volume.
• M o = molar mass
• Sp–Sv=R/MoJ
Specific heat ratio : It is the ratio of specific heat at
constant pressure(C p ) to the specific heat at constant
volume (C v ).
• It is denoted by γ = C p / C v
 Specific heat capacities of gases
and their ratio for different gases
• Mono atomic gas :
• The molecule of mono atomic gas has only three
translational degree of freedom.
• The average energy of a molecule at a temperature T is
3/2 K B T
• Total internal energy of the gas
• U = 3/2 K B T N A =3/2 RT
• we know d U = C v d T ⇒ C v = d U /d T
• C v = 3/ 2 R T / T = 3 / 2 R
• C p = C v + R = 3/ 2 R + R = 5 / 2 R
• γ =Cp/Cv =5/3
• Diatomic gas :
• A diatomic molecule is considered as a rigid rotator ,
has five degrees of freedom like dumbbell.
• Using law of equipartition of energy of a mole of
diatomic gas is
• U = 5/2 K B T N A = 5/2 R T
• C v = d U / d T = 5/2 R
• Cp=Cv+R=5/2R+R=7/2R
• specific heat ratio
• γ=Cp/Cv=7/5
• If the diatomic molecule is non rigid it has additional
vibrational mode .
• U = (5/2 K B T + K B T ) N A = 7/2 R T
• C v = 7/2 R and C p = 9/ 2 R and γ = 9 / 7
• Poly atomic gas :
• A poly atomic gas has three translational , three
rotational and a certain number (f) of vibrational
modes.
• By law of equipartition of energy , one mole of such gas
has
• U = ( 3/2 K B T + 3 / 2 K B T + f K B T ) N A
• C v= ( 3 + f ) R
• Cp= (4+f)R

• ∴ γ = C p / Cv = 4 + f / 3 + f
 Absorption , Reflection and
Transmission of Heat Radiation
• Heat can be transferred by conduction, convection and
radiation .
• Conduction and convection require material medium
but radiation does not require any medium.
• Radiation refers to continuous emission of energy
from the surface of any body which is at higher
temperature than surrounding in the form of electro
magnetic waves.
• Radiation takes place in free space and through
material medium.
 Interaction of thermal radiation and matter
• When thermal radiation fall on the surface an object ,
some part of energy is absorbed , some part is
transmitted and some part gets reflected .
Qr
Q
• Let Q unit of radiant heat
Incident on the surface of body.
Q r = reflected heat energy
Q a = absorbed heat energy
Q t = transmitted heat energy Qa

From the principle of conservation of

Energy : Q = Q r + Q a + Q t Qt
• Q=Qr+Qa+Qt
• ⇒ Q / Q = Q r /Q + Q a /Q + Q t /Q a+r+t=1
• ⇒ 1 = r+a+t
• Coefficient of absorption or absorptive power or
absorptivity (a):
• It is the ratio of quantity of radiant energy absorbed by
the body to the quantity of radiant energy incident on it.
∴ a = Q a /Q
• Coefficient of reflection or reflectivity (r):
• It is the ratio of quantity of radiant energy reflected by
the body to the quantity of radiant energy incident on it.
∴ r = Q r /Q
• Coefficient of transmission or transmissivity (t):
• It is the ratio of quantity of radiant energy transmitted
by the body to the quantity of radiant energy incident on
it. ∴ t = Q t /Q
• If r = 0 and a = 0 , then t = 1 , which means all the incident
radiation transmitted through the object. The object is perfect
transmitter and is completely transparent to the radiation.
• The substance through which the radiation can pass called
diathermanous substance.
• A diathermanous substance neither good absorber nor good
reflector. Example : glass, quartz , sodium chloride , hydrogen,
oxygen, dry air.
• If t = 0 , a + r = 1 , the object does not transmit any radiation . It is
said to be opaque to the radiation. This type of substance called
Athermanous substance.
• Example: water , wood , iron, copper , moist air , benzene etc.
• If t= 0 and a = 0 , then r = 1, all the incident energy is reflected by
object . It is a perfect reflector . A good reflector is a poor absorber
and poor transmitter.
• If r = 0 , and t = 0 , then a = 1 , all the incident energy absorbed by
the body . Such an object is called perfectly black body.
• Note : The value of a , r , t depends upon the
wavelength of incident radiation , in addition to the
material of the object on which it is incident.
• Hence it is possible the object may be athermanous or
diathermanous for certain wavelength , but is a good
absorber for certain other wavelengths.
• Perfectly black body :
• A body , which absorbs the entire radiant energy
incident on it , is called ideal or perfect Black body.
Thus for a perfectly black body a = 1 .
• Any surface that absorbs all the energy that incident on
it and does not reflect any energy , therefore appear
black( unless its temperature is very high or self
luminous) .
Ferry s black body
 Explain Ferry s perfectly black body ?
• i) it is a double walled hollow metallic sphere having a small
aperture through which heat can enter .
• ii) The space between the walls is evacuated.
• iii) The inner surface has a small conical projection in front of
aperture.
• iv) it s interior is coated with lamp black .
• v) The hole is directed towards the source of radiation.
• vi) Any heat which is incident along the axis of the sphere is not
allowed to be reflected back by providing a conical projection
exactly in front of opening.
• vii) The cone scatter the radiation as it undergoes multiple
reflection and it continues till the entire heat entering the sphere
is absorbed (nearly 96%).
• viii) The effective area of perfectly black body , is the area of
aperture.
• In this way the perfectly black body can be realized in practice.
 Emission of Heat Radiation
• The amount of heat (Q)radiated by a body depends
upon :
• The Absolute temperature of the body (T).
• The nature of the body – material, nature of surface –
polished or not etc.
• Surface area of the body (A)
• Time duration for which the body emits radiation (t)
• Q α A and Q α t
• Hence Q α A t
• Q = R A t where R is the radiant power or
• emissive power.
• R = Q / A t = Heat radiated per unit area per unit
time. Or Power emitted per unit area
• Dimension of emissive power are [ L 0 M 1 T -3 ]
• SI unit J m -2 s -1 or W / m 2

Coefficient emission or Emissivity ( e ) :

The coefficient of emission or emissivity of a given body is the
ratio of emissive power of a body (R) to the emissive power of
the black body (R B)at the same temperature.

∴ e = R/RB

For a perfectly Black body e = 1

For a perfect Reflector e = 0
For Ordinary body 0 < e < 1

Note : Emissivity is larger for rough surfaces and smaller for

•
smooth and polished surface .
 Kirchhoff s law of heat radiation and its
theoretical proof
• Kirchhoff s law of radiation states that the coefficient of
absorption of a body is equal to its coefficient of
emission at any given temperature.
• ∴ a=e
• But coefficient of emission e = R / R B
• ∴ a = R / R B or R / a = R B

• Theoretical proof ( Through experiment ) :

• i) Consider an ordinary body O and a perfectly Black
body B suspended in a constant temperature
enclosure.
• ii) The bodies O and B radiate heat to the enclosure
and enclosure also radiate heat to the bodies , After
some time , the temperature of both the bodies will
become same as that of temperature of enclosure.
• iii ) Let
• a = coefficient of absorption
• of body O
O B
• e =coefficient of emission
• of body O
• R = emissive power of body O
• R B = emissive power of body B
• Q = amount of heat radiation incident on each body
• per unit area per unit time.
• For ordinary body O :
• i) The radiant energy absorbed per unit time per unit area by an
ordinary body O = a Q
• ii) The radiant energy emitted per unit area by ordinary body O =
R
• iii) As the temperature of the body O remain constant , i.e. at
thermal equilibrium
• ∴ R = a Q ……………………………..( i )
• For Black Body B :
• i) The radiant energy absorbed per unit time per unit area by an
Black body B = Q
• ii) The radiant energy emitted per unit area by Black body
• B =RB
• iii) As the temperature of the Black body B remain constant , i.e.
at thermal equilibrium
• ∴ R B = Q ……………………………( ii )
• Dividing equation (i) by (ii) we get
• R/RB= aQ/Q
• ⇒R/RB=a
• But R / R B = e = coefficient of emission
• ∴ e=a
• ∴ a=e
• i.e. coefficient of absorption = coefficient of emission
• Hence Kirchhoff s law is proved .
• Application :
• Good absorber is a good emitter .
• A person with black skin experience more heat and
more cold compared to a person of white skin.
• Days are hot and nights are cold in desert.
 Spectral distribution of black body
radiations

• The study of spectrum of black body radiation in terms

of wavelength was carried by Lummer and
Pringsheim maintaining the Black body at different
temperatures.
• The intensity of radiation corresponding to different
wavelengths was measured at different fixed
temperatures of the source.
• A graph of the variation of intensity of radiation (R λ )
with the wavelength λ at different constant
temperature was plotted. R λ

λ
• The following conclusion can be drawn from the graph
(curves)
• i) At each temperature , the black body emits continuous heat
radiation spectrum.
• ii) The energy associated with the radiation of a particular
wavelength increases with increase in temperature of black body.

• iii ) At a given temperature of the black body , the amount of

energy associated with radiation initially increases with
wavelength and after becoming maximum corresponding to a
wavelength λ max , it decreases .
The wavelength λ max is called wavelength of maximum emission .

• iv) The area under each curve represents the total energy emitted
by the perfect black body per second per unit area over the
complete wavelength range at that temperature.

• v) The energy distribution is not uniform. The peak of the curve

shifts towards the left – shorter wavelengths , i.e. the value of
λ max decreases with increase in temperature.
 Wien s Displacement Law
• Wien s displacement law states that the wavelength for
which the emissive power of the black body is maximum
is inversely proportional to the temperature of black
body .
• This law is called displacement law because as the
temperature increases the maximum intensity of
radiation emitted by it gets shifted or displaced
towards the shorter wavelength side.
• λ max α 1 / T
• ∴ λ max = b ( 1/ T )
• ∴ λ max ( T ) = b
• where b is called Wien s constant
• b = 2.898 × 10 – 3 m K
 Stefan – Boltzmann Law of Radiation

• According to this law , “ The rate of emission of radiant

energy per unit area or the power radiated per unit
area of a perfect black body is directly proportional to
the fourth power of its absolute temperature.
• RB α T4
• or R B = σ T 4
• Where σ is Stefan s constant .
σ = 5.67 × 10 – 8 J m -2 K -4 and dimension [ L0M1T-3K-4]
Hence the power radiated by Black body depends only
on temperature.
• if Q is the amount of radiant energy emitted in time t by a perfect
black body of surface area A at temperature T , then Q / A t = σ T 4
•
• For a body which is not black body , the energy radiated per unit
area per unit time is still proportional the fourth power of
temperature but is less than that of black body .
• For ordinary body R = e σ T 4
• Let T 0 = absolute temperature of surrounding .
• Then Energy radiated by black body at temperature T per unit
area per unit time = σ T 4
• The energy absorbed from surrounding per unit area per unit
time = σ T0 4
• ∴ The net energy loss by perfect black body per unit area per unit
time = σ T 4 - σ T 0 4 = σ (T 4 - T 04 )
• For an ordinary body , net loss in energy per unit area per unit time
= e σ (T 4 – T0 4 )
• If T < T 0 , then net gain in thermal energy of body per unit area
per unit time is e σ (T 04 – T 4 )