collide

perfectly
ibriumheamotion
t travelsandnegligible
a In temperature
high At
of on the Gases
Phenomena
elastic
each
Transport
state gas kineic
mean
free
molecules
by other.
spheres
sporting theory
patroom
hper At
give of
about of
tenperaluse,
rise gases,
omentum, .e., J0'm.
to
viscosity, but it
INTRODUCTION is
When finite assuned
an particle B
the aur SIZe. particle A
nducivity
and molecule gas that
Due
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and
quilibrium, RelationD.
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ofK)" "Transport
TemperaturePhenomena
Pressure . "
. Influence . .
iffusion, about Temperature
Hydrogen
Diffusion
Self
. K. Viscosity
n" Variation Introduction
Expression Mean "
Effect Relation
motion, of Thermal
Largest
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when 10" the Between on Collision
random on
Conductivity
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tries al Effect n EffectTemperatureMean (2)"
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 Phenomena in Gases Ö3
HAPTER 3:Transport
3.1 Molecular Collisions
According to kinetic theory of gases, the molecules are of finite size. During the random mou
of gas molecules in all possible directions and with all possible velocities, they collide win ea
other. Between two successive collisions, a molecule moves with aconstant speed, along a sualg
line as shown in Fig. 3.1. These collisions are known as molecular collisions.

3.2 Mean Free Path (0)

At a given temperature, the molecules suffer continuous collisions with one another. Between
any two collisions, the molecule travels freely a certain distance in a straight line. This distance 1S
known as free path. Thus, the path covered by a gas molecule between any two consecutive colislons
in astraight line is called the free path. The direction of the molecule is changed after every collision.
After a number of collisions, the total path appears to be zig-zag and free path is not constant as
shown in Fig. 3.1. Therefore, a term mean free path is used and is defined as the average distance
travelled by a gas molecule between two successive collisions. It is denoted by 2. If the total distance
travelled after Ncollisions is S, then mean free path (^) is given by
S

Fig. 3.1
successive colli
Mean free time (t): The average time taken by a gas molecule between two
sions is called mean free time (t) and is given by
T =

molecule.
where Cis the average velocity of a gas
3.3 Sphere of Influence
is assumed that all
Inthe kinetic theory for an ideal gas, it
elastic spheres
the gas mnolecules are identical and perfectly
doing so, they
noving randomly in all possible directions. InFor the sake of
other. blc
are continuously colliding against eachthatthe molecule under
Simplicity of calculations, it is assumed A

Consideration say A, is in motion, all other molecules are at rest

molecule. Taking Sphere of
Fig. (3.2). Let o be the diameter of each gas draw a sphere of Influence
centre, if we
ue centre of molecule A as a with all those molecules
Tadius o, then molecule A will collide called Fig. 3.2
Such a sphere is
WhOse centres lie within this sphere.
sphere of influence'.
 Physics
heat, Thermodynamics and Statistical
84

3.4 Collision Cross-section

influence, we get a
If we take a cross--section along the diameter of a sphere of
section. The area =T » is called the collision cross-section as shown by dotted lines in
the effective area which determines the probability that a molecule of diameter
g will
col iFisigon32.Crog
another molecule of the same diameter. colide n
Expression)
0 EXpression for Mean Free Path (Clausius' of
identical perfectly elasticspheres, each
Suppose
assumed the molecules
that the molecules doof not
a gas all force
exertareany diameter
0.tik
on each other. To simplify the calculations, we furhe
assume that (1) only the molecule under consideration is in motion while all other molecules are at
The sphere of influence ofthe molecule has a radius oi.e. equal to the diameter of the molecule rest,2
Collision
Fig33.
Cross-Section

Fig3.3
Let c be the average velocity of molecule A and n be the number of molecules per unit volum.,
then in one second, A will collide with all the molecules whose centres lie within a cylinder of radius
G and length c.
No. of molecules in the cylinder
= T cn
No. of collisions made by molecule A in 1 second
= L cn

1Collision takes place in seconds.

TU Cn
The time interval between two successive collisions

2 seconds
N Cn
Distance travelled between two successive collisions
= speed x time
= CX

Mean free path,

Tn
This is Clausius' expression for the mean free path.
 CHAPTER 3: Transport Phenomena in Gases 85
Maxwell'sFormula
The above expression (3.1) is not exact because it is based on the assumption that only one
moleculeunder consideration is in motion while all other are at rest. If the motion of all the molecules
and the Maxwell's law of distribution of molecular velocities is applied, which
takeninto account
is
must holdin steady state, the corrected formula for mean free path is
1
=
..3.2)
V2 Tuo'n
This is Maxwell's formula for the mean free path.
C
TE2 and nae known, the molecular diametero can be calculated. Collision frequency is f =where
molecule.
cis average velocity of the gas
36 Variationof with Tenmperature and Pressure
Consider lmole of an ideal gas.Then
PV = RT
Dividing both sides by N, the Avogadro'snumber, we have,
PV RT
N N

P=
The pressure P of a gas is given by ..3.3)
P= nkT
and k= R the Boltzmann's constant.
N
Where, n= Vthe no. of molecules per unit volume N

P
Equation (3.3) gives, n =
kT
Substituting for n in equation (3.2), the mean free path
1

kT ..3.4)
or

absolute temperature (T) and inversely as the

Ihus, the mean free path varies directly as the
pressure.

3.7 Transport Phenomena

kinetic theory of gases., the molecules of a gas are in a state of thermal agitation.
cCording to the (thermal
therefore, attains a steady state or equilibrium state by transporting momentum, heat
gas, conductivity
another layer, giving rise to the viscosity,
5Y)and mass from one laver of a gas to
and diffusion respectively and the phenomena is called transport phenomena.
The transport phenomena occur only in the non-equilibrium state of a gas.
3.8 Viscosity: Transport of Momentum
have different velocities. This willresultinthe
The different layers of a non-equilibrium gas. may
case, the layer moVing
fasteron of the different layers with respect to one another. In such a
equilibriumstate. Thus, the
bringabout an
faster will impart momentum to the layer moving slower to
transport of momentum gives rise to the phenomenon of viscosity.
86 Heat, Thermodynamics and Statistical Physics
Consider a gas flowing over a horizontal surface OX from left to right. The velocity of
contact with the surface OX is Zero and goes on increasing along 0Z at a uniform rate dv the layex
velocity gradient (Fig 3.4).
known
as
dz

V+ dv
dz
F

N B

dz

Fig 3.4
Let us consider a layer AB moving with a drift
molecules in this layer have the same drift velocity.velocity V, situated at a distance Z from O. All the
and below AB respectively at a distance equal to Consider two more layers EF and CD just above
the mean free path of the molecules, so that the
molecules moving vertically up or down do not suffer any
layers. collision while moving between the two
The velocity of the gas in the layer EF = V+ dy
dz
and the velocity of the gas in the layer CD = V- 2
dz
Due to thermal agitation, the gas
molecules are moving in all directions, thus, the average num
ber of molecules along any one (+ ve or- ve) axis
will be 61 th of the total number of molecules in the
gas.
Let n be number of molecules per unit volume,
m be the mass of each gas molecule,
c be the average
velocity of a molecule at a given temperature of the
Number of molecules passing downwards gas, then
from EF to CD per unit area of the AB
nc
in one second
6
Eorward momentum lost per unit area per second by the
layer EF
6
Similarly, the number of molecules passing upwards from CDto EF per unit area of the layerA8
in one second is also
=
nc
6
 CHAPTER 3: Transport Phenomena in Gases
87
Forward momentum gained per unit area per second by the
layer Dr

dz
Net momentum lost by the layer EF per
unit area per second

-
mnc dv
3 dz
The layer CD below AB gains the same amount of momentum. Hence, the layer EF above AB
tends to accelerate its motion and the layer CD below AB tends to retard its
mnotion.
The backward dragging force per unit area = gain or loss of momentum per unit area per
second.
1
y
F =;mnc A,dz ...3.5)

This must be equal to the viscous or tangential force acting per unit area of the layer AB,
n being the coeficient of viscosity of the gas.
d 3 mnc dz
1
Or
3
mnc

or ...(3.6)
where p = mn, the density of the gas
t
3.9 Effect of Temperature on n
The density (p) of the gas decreases with increase in temperature but , the mean free path
increases in the same proportion so that pâ remains constant. Since the average molecular speed c is
directly proportional to the square root of its absolute temperature (coc VT), the coefficient of vis
cosity (n) willalso be proportional to /r .
Therefore,
...3.7)
In other words, the coefficient of viscosity of a gas increases with increase in temperature.

3.10 Effect of Pressure on n

, the mean free path decreases in
The density (p) ofa gas increases with increase in pressure butaverage molecular speed c is inde
e same proportion, so that p' remains constant. Moreover, the
pendent of pressure. Thus, using relation

n, the coefficient of viscosity is independent of pressure.

3.I1 ThermalConductivity: Transport of Thermal Energy

carry kinetic
The different layers of a gas may have different temperatures. The molecules will
about an
energy (heat) from regions of higher temperature to the region of lower temperature to bring
88
Heat, Thermodynamics and Statistical Physics
equilibrium state., Thus, the transport of thermal energy (thermal) gives rise to the
thermal conductivity.
Consider a fixed
ture gradient
mass of a gas at rest as shown in Fig. 3.5.
Suppose there is a

along 0Z. Inthe steady state, the temperature of each horizontal

ounifhoernmomeNTeomnpera
d: layer paralel to

A B

dz

Fig. 3.5
OX is constant. Let 0 be the
temperature of layer AB. The temperature of the layer EF which is at a
distance (the mean free path) above AB is and the layer CD at the distance below AB
will be This means the gas above the layer AB is at
AB. Hence, molecules of gas coming from higher temperature than the gas below
EF and passing downward across AB
than the molecules coming from CD and
passing upward across AB. Thus, thepossesses
molecules below AB is continuously increasing average
more K.E.
and that of molecules above AB is energy of
creasing, tillthe equilibrium is reached. continuously de
Number of molecules crossing unit area of the layer AB
where n is the number of gas molecules per upward or downward per second nC6
unit volume and c is the average
If m is the mass of each gas molecular velocity.
molecule, then the mass of gas crossing unit area
or downward per second = mnc of layer AB upwau
6
If C.be the specific heat of the gas at constant volume,then
Heat energy carried by the molecules in
direction per second crossing unit area of the layer AB in the downward

mass x specific heat x

mnc xcy temperature
Similarly, heat energy carried by the
direction per second molecules crossing in unit area of the layer upward
AB inthe
mne yCy
6
 CHAPTER 3: Transport Phenomena in Gases 89
Net transfer of heat energy per unit area of layer AB in the downward direction per second
mnc
xC, xe+ de mnc
x Cy
6 6

mC y do 1 de
6 Cy x2^ d
Since mn =p, the density of the gas,
de
..(3.8)
The coefficient of thermal conductivity (K) of the gas is defined as the quantity of heat that flows
per unit area per second per unit temperature gradient.
Q = K ..(3.9)
dz
Equating equation (3.8) and (3.9),
K de dÝ
dz
1
OI,
K=pcCy ...(3.10)

3.12 Relation between n and K

The coefficient of viscosity of a gas is given by
n = 13 pca
and, the coefficient of thermal conductivity is

K = pcÀ CG
K= 1 Cy ..3.11)
is true only if
The relation is, however, does not hold good withthe experimental values since it
translation.
all the heat supplied is converted into kinetic energy of
According to Chapman and Enskog, the corrected value is
K = e Cy

where g = 1
4
(9y-5), where Yis ratio oftwo specific heats of the gas.
1 ..3.12)
K=epc Cy
3.13 Effect of Temperature on K
The coefficient of thermal conductivity (K) is given by equation (3.10) as

K = pc Cy
= ;mnc. Cy (": p=mn)

1 1
K = mnc. C, X
90
Heat, Thermodynamics and Statistical Physics
mc Cy
K=
3V2no?
But CoT
Ko«T
Thus, the coefficient of conductivity of a gas is directly proportional tothe
its absolute temperature. In thermal square rooto
other words, coefficient of thermal conductivity increases with
in the temperature.
increas
3.14 Effect of Pressure on K
In the relation, K=[n C all the quantities [, n and Cy are independent of pressure. Hence th
coefficient of conductivity K is also independent of pressure.
3.15 Largest Thermal Conductivity of Hydrogen
The coefficient of thermal conductivityof a gas is given by
K =

1
Substituting for =

V2 nOn
we have, K =
1mcCy
(': p= mn)

If M is the molecular weight and N, the

Avogadro's number, then m = YN and C, its molu
specific heat, then

K=

1 Cy
In this relation, N is constant, being
3v2 No ..(3.14)
Avogadro's number. For a diatomic gas, the value of gram
molecular specific heat Cyis the same for all gases being equal to R,
diameters (G) for all gases 2 Assuming equal molecuu
K«c
But c =average speed of the molecules
|8kT
VTm
Where K is Boltzmann's constant.

Vm
Thus, coefficient of thermnal conductivity (K) is inversely proportional to the square rootoft*}
the gas,
mass of the molecule of
As the mass of molecule of hydrogen is the least among diatomic gases, the thernal condat
(K) of hydrogen gas will be greatest at a given temperature.
 CHAPTER 3: Transport Phenomena in Gases 91

3.16Self Diffusion: Transport of Mass

The phenomenon of self diffusion is due to the transport of mass from aregion of higher concen
tration to a region of lower concentration to bring about an cquilibrium.
Consider agas having aconcentration gradient dz
along 0Z. Let nbe the concentration of layer
AB.
Consider two more layers EF and CD above and below that of AB at a distance equal to the
mean free path of the molecules of the gas, so that the molecules moving vertically upward or down
wand do not collide between these two layers (Fig. 3.6).

E F

A B

C
D (h-)

-X

Fig 3.6

Concentration at the layer EF = n+ dn

dz

and concentration at the layer CD =n-1 dn

dz
Therefore, the number of molecules coming from layer EF and crossing AB downward per unit
area per second

and number of molecules coming from layer CD and crossing AB upward per unit area per second

Net number of molecules crossing per unit area per second of layer AB in downward
direc
tion

dn
=
dz
92 Heat, Thermodvnamics andStatistical Physics
The coefficient of diffusion is defined as the ratio ofthe number of molecules crossing per u
One second to the rate of change of concentration with distance.

3
dn
Coefficient of diffusion D =
dn
dz

D= c
3.17 Effect ofTemperature and Pressure
KT
We have from eq.34
8kT
and C =

1 kT 8*T
D =
3 J26p V m

...3.16)

This shows that the coefficient of self diffusion is directly proportional to T and inversey
proportional to the pressureP.

3.18 Relation Between n and D

From the relations for
1
n= pc
and D =

we have D = ..(3.17)
Thisrelation between D andm does not agree wellwith the experimental values for a A
gas. m
detailed analysis yields the relation
D'=

where f is a numerical factor whose value is nearly 1.4.

The values of Table 3.1 the density (p), average speed (C), molecular diameter (o), meanfreeput
(2), coefficient of viscosity (n), coefficient of viscosity (K) at N.TP. and specific heat capacityst ot
stant volume (Cy) for some gases are given in the following table. All the quantities are in SI units.
 CHAPTER 3: Transport Phenomena in Gases 93

TABLE 3.1

Gas K C
m kg/m m/s m Ns/m W/mk J/kgk
2.18 x 10-10 0.179 1202.1 28.5 x10 18.6 x 10 1415 x 104
Helium 3157
2.47 x 10-0 0.090 1699.9 18.3 x10 8.35 x 10 1684 x 10
Hydrogen 10142

Nitrogen 3.5 x 100 1.25 454.4 9.44 x 10 16.7 × 10 243 x 104 741

Oxygen 3.39 x 100 1.429 424.99,95 x 10 19.2 x 10 244 x 10 652

Carbon dioxide 4.18 x 10-0 1.977 362.4 6.3 x 10 14.3 x 1o 145 x 104 640

Air 1.293 18.325 x10 241 x 10 708

NUMERICAL EXAMPLES
EXAMPLE 3.1
Theviscosity of a gas at NTP was found to be 1.66 x10 dynes/cm per unit velocity
gradient. The rm.sS. velocity of the molecules is 4.5 x 10' cm/s. The density of gas is 1.25 grams
per litre. (Nagpur 2009, 2001, Madurai 2003)
Calculate (i) mean free path of the molecules of the gas,
(ü) frequency of collision.
(iüi) molecular diameter of the gas molecules.
SoLUTION. Here F= 1.66 x104 units
c= 4.5 x104
p = 1.25 x 10 g/cc

() =
3n
pc
3x1.66x104
1.25x 10x4.5x10
A = 9x 10 cm
(i) Frequency of collision = number of collisions per second
r.m.s. Velocity
Mean free path
N = C

4.5x10
9x10-6
N= 5x 10
(i) Avogadro's number = 6.023 x 10
6.023 x 1023
Number of molecules per cC = n= 22400
94 Heat, Thermodvnamics and Statistical Physics
According to Maxwell's relation
1 1
V2.no'n 1.44 x r n

1.44 x TXnX

6.023 x 1023
1.444x3,142
x x| 22400 x9x10
Þ = 3 x 10 cm
ExAMPLE 3.2
The diameter of nitrogen molecule is 3.2 x 10" m. The number of molecules at 0°C and )
atm. pressure is 2.69 × 10 per m. Calculate mean free path for nitrogen molecules.
(Nagpur 2004)
SoLUTION. The mean free path is given by

= J1 'n

= V2x3.14x (3.2 x10-10x2.69x1025

1 X10-5
122.32
= 0.008175 x 10 m
EXAMPLE 3.3
Find the coefficient of viscosity of nitrogen at N.T.P. from the following data:
p=1.25 kg/m, G=454.4 m/s, A=9.44 x 10 m (Nagpur 2005)
SoLUTION. The mean free path is given by
=
3n
pc

Coefficient of viscosity,n p
3

9.44x10 x1.25x 454.4

3
= 1787 x 10 Nm
per unit velocity
ExAMPLE 3.4 gradient
Calculate the molecular diameter of Nirogen molecules ifn = 2,7x 102 molecules per
and mean free path n for nitrogen is 8 x 10 n
(Nagpur 2007, 2004)
SoLUTON. The mean free path is given by
1

TOn
 CHAPTER 3: Transport Phenomena in Gases 95

= J2x3.14 x8x10x2.71025
1
95.918x10!7 959.18 x10!6
G =0.03229 x 10 m
EXAMPLE 3.5
In an experiment, the viscosity of the gas was found to be 2.25 x 10* CGS units. The rm.s.
velocity of the molecules is 4.5 x 10* cm/s. The densityof the gas is l gram per litre. Calculate
the mean free path of the molecules. (Bangalore 2001)
SOLUTION. Here n = 2.25 x 10 CGS units
C= 4.5 × 10* cm/s
p = 1g/litre
p = 10 glcc
3n
and
pc
3×2.25x10
=

10x4.5x10*
A = 15 x 10 cm
EXAMPLE 3.6
Calculate the mean free path of agas molecule, giventhat the molecular diameter is
2x 10 cm and the number ofmolecule per cc is 3 x 10". (Purvanchal 2005, Kuvempa Uni. 2005),
SoLUTION.
1
=

1.44x3.14x(2×10x3x10o
= 2.12 x10 Cm
[Note: The mean free path is less than the wavelength of light in the visible spectrum.]
EXAMPLE 3.7
Calculate the mean free path of gas molecules in a chamber of 10" mm of mercury pressure,
assuming the molecular diameter to be 2A°,One gram molecule of thegas occupies 22.4 liters at
N.IP. Take the temperature of the chamber to be 273 K. (Calcutta 2002)
SoLUTION. At 760 mm Hg pressure and 273 Ktemperature, the number of molecules in 22.4
litres ofa gas is
= 6.023 x 10
Therefore, the number of molecules per cm' in the chamber at 10® mm of pressure and 273 K
temperature
6.023 ×10x10 x10-!
n =
22400×760×10
n = 3.538 x 10 molecules/cm
G =2Å =2x 10 cm
96
Heat,Thermodynamics and Statistical Physics
Mean free path= =
J2no'n

144x3.14x(2x10x3x 538×10o
= 1.97 x 10* cm
EXAMPLE 3.8
Calculate the mean free path of nitrogen molecule at 27°C temperature and one
pressure, The molecular diameter of nitrogen is 3.5 x 10 Cm. atmospheric
SoLUTION. One atmospheric pressure =76 cm height of mercury
P=76x 10 x 13.6 × 10° x9.8
P =1.013 x 10 Nm
Temperature, T =273+ 27=300 K
Boltzmann's constant, k = 1.38× 10 Jk
Molecular diameter, G = 3.5 x 10 cm
= 35 x 100 m
kT
Mean free path, 2=
V2Po
kT
V2 nPo
1.38× 1023 x 300
1.414x3.14 x1.013x10 × (3.5x100)'
= 7.5 x10 Im
EXAMPLE 3.9
The diameter of the molecule of agas is 2 x 1
J/K. Calculate the mean free path at NTP. cm and Boltzmann's constant is l.38 x 10
SOLUTION. Here d = 2x 10* cm =2 x 10-10 m (Garhwal 2000)
k = 1.38 x 10 JK
ILet n be the number of the molecules per cubic meter.
PV = RT
PV = NkT
n =

At NTP n = 0.76x 13.6× 10 ×9.8

1.38 x 1o-23 X 273
n = 2.688 x 1025
Mean free path =
1
V2 Trd'n 3.14x
= 2.094 ×10 m (2x10-0,x2.688 x 10 x1.41
 CHAPTER 3: Transport Phenomena in Gases 97
EXAMPLE 3.10
Eor ovgen at standard conditions, calculate (a) Collision frequency of the molecules, and (b)
the mean free path. Given at standard conditions for oxygen,
() the nunber of molecules per cubic metre = 3 x 10
(ii) Diameter of oygen molecule = 3.6 x 10l0 m (Pune 2001)
SOLUTION.
Here k = 1.38 x 103
32
and m = =5.31 x 10° kg
6.023 x1026
Average speed of oxygen molecule at 0°C (273 K)
8 kT

8x1.38>x10x273
3.14x5.31x1026
V= 426 m/s
Also d = 3.6 x 10-10 m
n =3x 10 molecules/m
(a) Collision frequency (number of collisions per second)
= Td vn
= 3.14 (3.6 x 10yx426 x3 10
= 5.2 x 10
(b) Mean free path
1 1
=

V2 d n 3.14x(3.6× 100y' x3x10 xl414

=5.792 × 10 m.
EXAMPLE 3.11 sa

The molecular diameter of an ideal gas is 2 x 10 mat a temperature of 20°Cand pressure

Iatmosphere. Calculate the
(a) mean free path
(b) collision frequency
Velocity of molecules at
20°C = 51l m/s,
Take I atmospheric pressure
= 1.01 x 10 Nhm
SoLUTION.
(a) Here T= 293 K
Asthe gas is ideal, the
equation
PV =Nk T can be applied
P 1.01x 10
n = N kT
(1.38x10)x 293
n = 2.5 x 10° molecules/m
98 " Heat, Thermodynamics and Statistical Physics
mean free path
1
2 =
1414x d'n
=

1.414x r(2x10 x(2.5x10)

=2.25 x 10 m
(b) collision frequency
511
f = A225x10
f =2.27 x 10 per second
EXAMPLE 3.12
Calculatethenumber of collisions per second of a molecule of agas having mean o
1.876 × 10 m. Take average speed of the molecule as 51l n/s.
SoLUTION. Mean free path = 1.876 x 10 m (Madras 200%
V = 511 m/s
Collision frequency,
511
=2.72 x 10 per second
1.876 x 10
EXAMPLE 3.13
Calculate the radius of an oxygen molecule if its coefficient of thermal conductivity
K = 24x 10 Jhm-s-K at 0°C
and C, = 20.9 x 10 Jkilo-mole-K,
Boltzmann's constant k = 1.38 x 10 JIK
and mass of an oxygen mnolecule
m = 5.31 x 1026 (Rajasthan 200)
kg
SoLUTION. K =
mC C,
s(/2)no
3 kT
But
mc =r C=
m

=
mC Cå
3x1.414x3.142 xK
3kTm) C,
3x1.414×3.142 x K
23x1.38 x1023 X273x 5.31x 102671/2 x 20.9x10
3x1.414×3.142 x24x10
Or G = 3.036 x 10 m
ExAMPLE3.14
The averagespeed ofFmolecules of a gas is 4.5 x 10 m/s. The density of gas is 1.25kghn'
frequencyG
the coefficient of viscosily of gas is 1.66 x 10 Ns/m, Find mean free path and. 2005/%)
(Nagpur
collision.
SOLUTION. Given: n = 1.66 x 1015 Ns/m
p =1.25 kg/m
 CHAPTER 3: Transport Phenomena in Gases 99

C = 4.5 x 10

3n 3x1.66x105
Mean free path, =
pc 1.25 x4.5 x 10
=8.85 x 10 m
Frequency of colision,
c 4.5x102

= 5.085 × 10 collisions/s
EXAMPLE 3.15
Calculate the frequency of sound at which the wavelength of sound wave omeseaual to the
becomes
mean free path in oxygen at 0°C and l.0atmospheric pressure. Take diameterof oxygen molecule
as 3 x 1O° cin. (Calcutta 2000)
SOLUTION. The mean free path is given by

V2 (no n)y
At 0°C and 1 atmospheric pressure means at N.T.P.,
6x1023
n.= and G=3x 108 cm,
22400
1
=

1.414x3.14x (3×10y x(6x10* /22400)

22400
* 1414x3.14 >x9x 10lb x6x1023
= 9.37x 10° cm.
This wavelength, as per given problem, represents the wavelength of sound waves. Therefore,
the frequency, corresponding tothis wavelength will be
V 332 × 100cm/sec
V=
9.37x10 cm
= 3.54 x 10 Hertz
EXAMPLE 3.16
Calculate the diameter of a molecule of benzene, if n = 2.79 × 10 molecules per c.c. and
mean free path for benzene 2.2 x 10 cm. (Nagpur 2008)
SoLUTON. The mean free path is given by
1

V2(rÀn)
1
1.414x3.14x 2.2x 10 x2.79x109
 100
Heat, Thermodynamics and Statistical Physics
=36.2404 x 10-l6
2.725 x 10!4
10
Molecular dianeter, Þ = 6.02 x cm.

EXAMPLE 3.17
The mean free path of molecules of a certain gas at presSure p andtemperature Tis 2 ×lg
cm. Deduce the mean free path under the following condittons:
() pressure p x 10,temperature 1.
(i) pressure p/2, temperature 2T.
Also calculate the probability that under condition, pressure p and temperature T; molecules
would taverse 6 x 10 cn. without collision.

SOLUTION. The mean free path at pressure pand temperature T1s given by

kT
A=
(2)ro'p
() The mean free path at pressure p × 10 and temperature T will be
kT
(v2)no pxi0
Dividing equation (i) by equation (i), we get
= 10 Or A, = 10°= 10° x 2x 10 cm
Ay = 20 cm. ..)
(ii) The mean free path at pressure p/2 and temperature 2 T will be
k.2T 4kT

V2no' (p/2) N2n¡ p

Dividing eqn. (iii) by eqn. (), we get
= 4 or ,=4=4x2x 10
...)
Ay =8x 10 cm.
where B
Let the probability that a molecule will collide in traversing a distance dx be udx,after traversing
Then the fraction of molecules colliding with adistance dx
some constant related to À.
a distance x will be
dN = - u dx
N
indicatesthe
molecules which traverse freely a distance x. Negative sign
where Nis the number of increase in distance.
decrease of probability with
Integrating (iv), we get
log, N = -pi+c where C is a constant of integration.
by boundary conditions.
and is evaluated x = 0, N= N,
At log, N, = C
Substituting,
loge N=-x+ log. No
 CHAPTER 3: Transport Phenomena in Gases 101

loge = - r

N
N ..(v)
The required probability is given by
P= e ...(vi)
Todeduce the ratiou and 2, from equation (v), which gives
dN = N,e-pd)
dN
P(1, + dx>x>x) = ue d:
No

Substituting in eqn. (vi), we get, the required probability as

P= eyA
Here 2 = 2x10 cm, and I =6x 10 cm.
Probability, P= 6x102 x10
P=e-3

EXERCISE-I|
3.1 Define the terms
(i) mean free path,
(Nagpur 2007, 2005, Bangalore 2002, 2004, Agra 2003, Mysore 2004, Kamraj 2003,
Calcutta 2005, M.S. Uni. Tamil Nadu 2007, Kuvempa 2005, Agra 2006, 2004)
(i) mean free time of agas molecule (Nagpur 2007, 2006/s)
3.2 Explain the term sphere of influence and collision cross-section. (Nagpur 2007, 2004, 05)
3,3 Derive the Clausius expression for mean free path (a) on the basis of kinetic theory of gases.
(M.S. Uni. Tamil Nadu 2007, Patna 2004, Kanpur 2002, Nagpur Uni. 2007)
1
3.4 Obtain Maxwell's expression for mean free path = where o is the molecular diameter
V2 Ton
and n is the number of molecules per unit volume, on the bais of kinetic theory of gases.
(Nagpur 2007, 2004, 2003, 2001, Ranchi 2005, Bangalore 2002, 2005,
Mysore 2005, Purvanchal 2005, 2003)
3.5 Explain the variation of mean free path (.) with temperature and pressure. (Bangalore 2002)
3.6 What are transport phenomena? Explain in brief the viscosity, conductivity and self diffusion on the
basis of kinetic theory of gases. (Agra 2006, Nagpur 2009, 2004, 05, Ranchi 2005, Patna 2004)
Dl Derive an expression for the viscosity (n) ofa gas in terms of mean free path of its molecules. Show
that it is independent of pressure but depends upon the temperature of the gas. Discuss the effect of
pressure and temperature on coefficient of viscosity.
(Nagpur 2009, 2007, 2005/w, 2005/s, Ranchi 2005, Osmania 2005, Alagappa 2004, Patna 2004,
2000, 2002, Agra 2002, Delhi 2000,Kanpur 2001, Bangalore 2000, Calcutta 2005,
Purvanchal 2006, 2002, M.S. Uni. Tamil Nadu 2007)
102 Heat, Thermodynamics and Statistical Physics
kinetic theorv
of gases. Shoy
3.8 Derive an expression for thermal conductivity (K) of a gas on the basis of diatomic:
largest among all
that coefficient of thermal l conductivity of hydrogen should be
(Madras 2004, 05, Ranchi 2005, Alagappa 2004, Agra 2006, 2000, Meerut 2002 molecules,.
Nagpur 2009, 2006, M.S. Uni. Tamil Nadu
conductivity
3.9 Obtain the relation between coefficient of viscosity(n) and coefficient thermal (K). Why
the experimental values do not folow this relationship. (Nagpur 2006
3.10 Derive the relation for coefficient of self-diffusion Dand show that it is directly proportional to
(Calcutta 2004, Garhwal 2001, 02.,
and inversely proportional to the pressure.
J.M Obtain the relation between coefficient of viscosity and coefficient of diffusion. Meerut 201
3.12 Explain the efect of temperature and pressure on coefficient of viscosity.
(Nagpur 2008, 2004, Purwanchal 20A
3.13 What is the effect of temperature and pressure on thermal conductivity? (Nagpur 2008,
2006, 2004)
3.14 Discuss the effect of temperature and pressure on mean free path. (Garhwal 2002)
3.15 What is meant by the mean free path of the molecules of a gas. Obtain an expression for it and show
that it is inversely proportional, to the pressure and directly proportional to the absolute temperature
of the gas. (Agra 2002, Nagpur 2009, Rohilkhand 200)
3.16 Write notes on
() Transport phenomenon (Patna 2005, Nagpur Uni. 2008, Purvanchal 207
(ü) Relation between thermal and electrical conductivities (Patna 204)
(iüi) Mean free path (^). (Agra 2006, Kanpur 2000, Rohilkhand 2000, 2002)
(iv) Frequency of collision.
(Agra 2001)
(v) Degrees of freedom (Kumaun 19)
3.17 Calculate the diameter of a molecule of a gas if the number of molecules per cm" in a gas is 3 x
mean free path is 2 x 10* cm. 19* and
[Ans. 7.28 × 10 cm] (Utkal 2003)
3.18 The diameter of the molecules of a gas is 3 x 100 m. Find the
mean free path 2 at S.T.P.
[Ans. 1.03 x 10 m] (Garhwal 2000, Purvanchal 204)
3.19 Calculate the radius of an oxygen molecule if its coefficient of viscosity at 0°C is
Given: mass of an oxygen molecule =5.31 x 10kg. Boltzmann 19.2 × 10°N-sm:
constantk=1.38 x 10 joule/degre.
3.20 Calculate the mean free path of argon molecules at 25°C and 1 atm. [Ans. 1.5 R] Purvanchal 2006)
= 1.38 x 10 Joule/K. pressure. Given o=2.56 A° andk
[Ans. 1.4 x 10 metre
3.21 The density of nitrogen at N.TP. is 1.25 kg/m and its
units. Determine mean free path of a molecule of a gas. coefficient of viscosity is 1.66 x 10 M.k.
3.22 The mean free path of molecules of a gas at [Ans. 8.084 x 10° m
free path if pressure P and temperature Tis 2. What will be the me
() the pressure in kept constant and the
(ii) the temperature is kept temperature is doubled
constant and the pressure is doubled
rHint : the mean free path will be
doubled in the first case and will be halved in the
3.23 The mean free path of the molecules of a gas is 2 x 10 second cas)
metre at pressure Temperature 200 K.
p and
Calculate its value of ()p, 400 K, (ii) 2p, 200K. (i)
2P, 400 K
[Ans.(i) 4x 10 m(ii) 1Tis
3.24 The mean free path of a gas molecule at pressure p and temperature × 10
5.2x 10°(iii)
mnetre. 10'mete
8 x What willbe
metre

the mean free path at (i) a pressure 2p and T

temperature 4 pressure p/2 and temperature 27.
[Ans. (i) 0.15 x 10, m(ü) 4.8 x 10° m] (Nagpur 2001, Bangalore 2001)
 CHAPTER 3: Transport Phenomena in Gases " 103
3.25 Determine the temperature at which mean free path of
10 m. Given: the radius of oxygen at 1 atmospheric pressure is 9,95 x
oxygen molecule is 1.695 >x 10 m.
3.26 A cross-section for collision of slow
neutrons in hydrogen is about 20 x 10* cm,
[Ans. 100°C]
free path of such neutrons in hydrogen at What is the mean
ur constant k= 1.38 x 10 Jk.
N.T.P.? Normal pressure is 10 N/m and Boltzmann

rut 2 [Hint : n= P , collision cross-section = ¡ = 20 x 10 cmn

kT
[Ans. 13.4 m]
3.27 Calculate the root mean square velocity of oxygen molecules at
1.43 kg.n 27°C. Density of oxygen at N.T.P. is
3.28 Calculate the diameter of molecule of benzene if n=2.79 x 10 [Ans. 4.835 × 10 ms]
Afor benzene is 2.2 x 10 cm. molecules per c.c. and mean free path
3.29 Calculate the mean
1025Path
free of a gas molecule of diamneter 3.2 A. [Ans, 6.06 x 10 cm)
volume is 2.5 x Im.
The number of molecules per unit
3.30 The viscosity of a gas (oxygen) at a temperature of 16°C is 169 [Ans. 8.79 x 10° m)
the molecules of the gas. Avogadro's number = 6.02 x micropoise. Calculate the diameter of
10. Molecular weight of oxygen = 32 and
Boltzmann'sconstant K = 1.38 x 10 J/K. [Ans. 3.97 x 10-0 m]
3.31 Calculate the fraction of molecules which will be
travelling
mean free path. Calculate the distance after which only oneundeflected after traversing 0.693 times the
undeflected.
percent of the incident molecules remain
(Calcutta 2003)
OBJECTIVE QUESTIONS
3.1 Viscosity of a gas is due to transport of
(a) momentum (b) energy
(C) mass (d) none of these
3.2 Out of the following which has the highest thermal
conductivity at the same temperature
(a) oxygen (b) helium
(c) hydrogen (d) carbon dioxide
3.3 In diffusion, the transport of the following occurs:
(a) momentum (b) energy
(C) mass (d) none of these
3.4 At very low temperatures, the coefficient of viscosity of a gas
(a) decreases with decrease of prcssure.
(6) increases with inercase of pressure.
(c) is independent of pressure.
the
me
(d) is equal to precssure.
3.5 The mean free path of a gas molecule is inersely proportional to (Kanpur 2001)
(a) square of the diameter of the molecule.
(6) square root of the diameter of the molecule.
(c) molecular diamneter.
ase
(d) fourth power of the molecular diameter.
S.6 The mean free path of molecules of a certain gas at pressure p and temperature Tis 2 x 10° m. The
mean free path at pressure p x 10 and temperature T is
(a) 2x 10 m (b) 2x 10 m
(c) 2 x 104 m (d) 2x 10 m (Rohilkhand 2003)
3.7 The molecular density in a gas is n and the diameter of its molecule is d, then the mean free path of
molecule is (Kanpur 2002)
1
(a) (b) TUnd
nd²
(c) (d)
V2 Tnd? 3/2 Tnd
104 Heat, Thermodynamics and Statistical Physics
3.8 Viscosityof a gas is directly proportional to:
(a) Temperature (b) Density of gas (Garhwal 2
(c) VT
J. The mean free path of gas at pressure p and temperature 1 1S
(a) kT
(b)
p
(Grahwal 20%02
(C (d) 1

ANSWERS
3.1 (a) 3,2 (c) 3.3 (c) 3.4 (c)
3.5 (a) 3.6 (a) 3.7 (c) 3.8 (b)
3.9 (a)