Unit 2

Kinetic Theory of Gases

1
2.1. Postulates of the Kinetic Theory of Gases

1. A gas consists of molecules of mass m in ceaseless random

motion, with a wide range of molecular speeds.
2. The size of the molecules is negligible, when compared with the
average distance travelled between collisions.
3. The molecules interact only through brief, infrequent, and elastic
collisions.
Elastic collision: A collision in which the total translational
kinetic energy of the molecules is conserved.

The Kinetic gas equation

 It relates the pressure and volume of a gas to the molecular mass and
molecular speed.
2
 Consider a particle of mass m travelling with a component of
velocity x collides with the wall and is reflected to opposite
direction.
 Its linear momentum changes from mx before the collision to −m x
after the collision.
 The x-component of momentum therefore changes by 2mx on each
collision.
 The total change of momentum is the product of the change in
momentum of each molecule multiplied by the number of molecules
that reach the wall during the interval.
 A molecule with velocity component x travels a distance x Δt
along the x-axis in an interval Δt
 All the molecules within a distance x Δt of the wall strike it if they
are travelling towards it.
 If the wall has area A, then all the particles in a volume A × x Δt
reach the wall if they are travelling towards it.
3
 The number density of particles is nNA/V,
 It follows that the number of molecules in the volume Ax Δt is
(nNA/V) × Ax Δt.
 At any instant, half the particles are moving to the right and half are
moving to the left.
 Therefore, the average number of collisions with the wall during the
interval Δt is ½nNAAx Δt/V.
 The total momentum change in the interval is the product of the
average number of collisions and the change in momentum on each
collision, 2mx :
𝑛𝑁A𝐴x∆𝑡 𝑛𝑚𝑁Ax2𝐴∆𝑡 𝑛𝑀𝐴x2∆𝑡
𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚 𝑐𝑕𝑎𝑛𝑔𝑒 = × 2𝑚x= =
2𝑉 𝑉 𝑉
 Rate of change of momentum = change of momentum divided by
the interval Δt during which it occurs
Therefore,
𝑛𝑀𝐴x2
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑐𝑕𝑎𝑛𝑔𝑒 𝑜𝑓 𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚 =
𝑉
4
 From the Newton’s second law, Rate of change of momentum =
Force
𝑛𝑀𝐴x2
 The pressure is this force divided by the area (A) on which
𝑉
the impacts occur.
𝑛𝑀x2
𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 =
𝑉
 All the molecules do not travel with the same velocity
 The detected pressure, p, is the average (denoted 〈…〉) of the quan-
tity just calculated:
𝑛𝑀 x2
𝑃=
𝑉
2 = x2 + y2 + z2
The average values of x2, y2, z2 are all the same.
Hence,
1 2
x = 
2
3
5
root-mean-square speed (rms): It is the square root of the mean of
the squares of the speeds, , of the molecules. Therefore,
𝑟𝑚𝑠 = 2 ½
x2 = 13 2 = 132rms
Substitution and rearrangement yields,
𝑷𝑽 = 𝟏𝟑𝒏𝑴2rms The kinetic gas equation

 If the root mean square speed of the molecules depends only on the
temperature, then at constant temperature,
PV = constant
2.2 Distribution of Molecular speeds

 The speed of individual molecules of a gas span a wide range.

 The distribution of molecular speeds is a function of both the
temperature and molar mass of the gas.
6 It is given by the Maxwell distribution of speeds.
 𝑀
3
;
𝑀 2
𝑚
3
;
𝑚  2

𝑒 𝑒
2 2 2 2
𝑓() = 4𝜋 2𝑅𝑇 or 𝑓() = 4𝜋 2𝑘𝑇
2𝜋𝑅𝑇 2𝜋𝑘𝑇

Where,  = root mean square speed of a molecule, f() = fraction of

molecules having a speed , M = molar mass, m = mass of one
molecule, k = Boltzmann constant

Fig. The distribution of molecular speeds with temperature and molar mass

Note: The most probable speed (corresponding to the peak of the

distribution) increases with increasing temperature and with
decreasing molar mass; simultaneously, the distribution becomes
7 broader.
 Greater fraction of the molecules will have low speed if
 the temperature of the gas is low or
 the molecular mass of the gas is high
 Greater fraction of the molecules will have high speed If
 the temperature of the gas is high or
 The molecular mass of the gas is low
 Because of the decaying exponential function, the fraction of
molecules with very high speeds is very small
 Because of M/2RT in the exponential term,
 when M is large, the exponential factor goes most rapidly towards
zero
 As a result, heavy molecules are unlikely to be found with very
high speeds.

8
 When T is high, the exponential factor falls towards zero relatively slowly
as  increases.
 greater fraction of the molecules will have high speeds at high
temperatures than at low temperatures
 A factor 2 (the term before the e) goes to zero as  goes to zero
 The fraction of molecules with very low speeds will also be very small
whatever is their mass.
Different kinds of speeds:
a) Root mean square speed (rms):
∞ n
 The average value of n is calculated as n = 0
𝑓  𝑑
 Integration with n = 2 results in the mean square speed of the
molecules,  n  at a temperature T.
2 = 3𝑅𝑇
𝑀
Hence, the root mean square speed of the molecule is
½
𝟑𝑹𝑻
𝒓𝒎𝒔 =
𝑴
9
 The root mean square speed of the molecules of a gas is proportional to
the square root of the temperature and inversely proportional to the
square root of the molar mass.
 The higher the temperature, the higher the root mean square speed of the
molecules.
 Heavy molecules travel more slowly than light molecules at the same
temperature.
N.B. Substituting the expression for rms into kinetic gas equation yields PV
= nRT.
 This confirms that the kinetic model can be regarded as a model of a
perfect gas.
b) Mean speed ( mean )
It is calculated by multiplying each speed by the fraction of
molecules that have that speed, and then adding all the products
together.
8𝑅𝑇 ½
mean = 𝜋𝑀
10
c) Most probable speed (mp)
2𝑅𝑇 ½ 2 ½
mp = 𝑀
= 3
rms
d) Relative mean speed (rel)
 It is the mean speed with which one molecule approaches another of the
same kind.
rel = 2½ mean
For the relative speed of two dissimilar molecules of masses mA and mB,
𝟖𝒌𝑻 ½ 𝑚A𝑚B
rel = where, 𝜇 =
𝝅𝝁 𝑚A:𝑚B

Fig.
11 A summary of the conclusions that can be deduced from the Maxwell
distribution for molecules of molar mass M at a temperature T
Calculation of molecular speeds
Example: For N2 molecules at 25oC in air, calculate the
a) root mean square speed
b) mean speed
c) most probable speed
d) relative mean speed

Solutions
3𝑅𝑇 ½
a) rms =
𝑀

½
3 × 8.314𝑘𝑔𝑚2𝑠−2𝐾−1𝑚𝑜𝑙−1 × 298 𝐾
rms = = 515.2𝑚𝑠−1
28 × 10−3𝑘𝑔𝑚𝑜𝑙−1

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 b)
½ 2 −2 −1 −1 ½
mean = 8𝑅𝑇
𝜋𝑀
= 8×8.314𝑘𝑔𝑚 𝑠 𝐾 𝑚𝑜𝑙 ×298𝐾
3.14×28×10−3𝑘𝑔𝑚𝑜𝑙−1
= 474.8 𝑚𝑠−1

½ 2 −2 −1 −1 ½
c) mp = 2𝑅𝑇
𝑀
= 2×8.314𝑘𝑔𝑚 𝑠 𝐾 𝑚𝑜𝑙 ×298 𝐾
28×10−3𝑘𝑔𝑚𝑜𝑙−1
= 420.7𝑚𝑠−1

d) rel = 2½ mean = 2½ × 474.8𝑚𝑠−1 = 671.4𝑚𝑠−1

Exercise:
1. Calculate the above speeds for
a) N2 at 350 K
b) H2 at 350 K
2. Calculate the relative speed between H2 and N2 at 350 K
3. Determine the relative ratios of the above speeds

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2.3 Molecular collisions

a) Collision frequency (z):

 The number of collisions a molecule makes per unit time
 Consider one molecule of a gas travelling through the stationary
gas with a mean relative speed rel for a time ∆t.
 It sweeps out a ‘collision tube’ of cross-sectional area σ = πd2,
length rel ∆t and therefore of volume σ rel ∆t.

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 The number of stationary molecules with centers inside the collision
tube (= number of collisions) = V  number density of the
𝑁
molecules(N/V) = rel𝑡
𝑉
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑐𝑜𝑙𝑙𝑖𝑠𝑖𝑜𝑛𝑠
𝑧=
∆𝑡
𝑵
𝒛= 𝝈rel
𝑽

Another expression:

𝑁 𝑛𝑁A 𝑛𝑁A𝑃 𝑁A𝑃 𝑁A 𝑃 𝑃

= = = = =
𝑉 𝑉 𝑛𝑅𝑇 𝑅𝑇 𝑘𝑁A𝑇 𝑘𝑇

Therefore,

𝑷𝝈𝒓𝒆𝒍
𝒛=
𝒌𝑻
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Cases

1. At constant volume, the collision frequency increases with

increasing temperature
Reason: The relative mean speed increases with increasing
temperature
2. At constant temperature, the collision frequency increases with
increasing pressure
Reason: Greater pressure implies greater number density (N/V) of
the molecules
Note: At constant T, rel is constant

Example:
Calculate the collision frequency for a N2 molecule in a sample at 1
atm and 25oC
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Solution
1 atm = 101325 pa = 101325Jm-3
(N2) = 0.45  10-18m2
𝜎𝑃𝒓𝒆𝒍 𝜎𝑃 8𝑅𝑇 0.45  10−18 𝑚2  101325 𝐽𝑚−3 8 8.314 𝐽𝐾−1𝑚𝑜𝑙−1  298𝐾
𝑧= = 2 =  2
𝑇 𝑇 𝜋𝑀 1.38  10−23𝐽𝐾−1 298𝐾 3.14  28  10−3𝑘𝑔𝑚𝑜𝑙−1

= 7.4  109 s-1

b) The mean free path ()
 It is the average distance a molecule travels between collisions
 If a molecule collides with a frequency z, it spends a time 1/z in
1
free flight between collisions, and therefore travels a distance 
𝑧 rel
Hence,
𝒓𝒆𝒍
=
𝒛
Substitution for z yields,
𝒌𝑻
=
17
𝝈𝑷
Cases:
1.  is inversely proportional to P
2. As T increases
 P increases (keeping V constant)
 T/P remains constant
  is independent of temperature
Note: In a container of fixed volume, the distance between collisions is
determined by the number of molecules present in the given volume, not
by the speed at which they travel.
2.4. Collision with a wall or surface
Collision flux (zw):
 Number of collisions per unit area per unit time
𝑃 𝑁 𝑘𝑇 ½ 1𝑛
𝑍w = or 𝑍w = = 
2𝜋𝑚𝑘𝑇 𝑉 2𝜋𝑚 4 𝑉 mean

 The product of Zw and area yields the collision frequency.

N.B . Zw  P, Zw  1/m½, Zw  T½ (since T  P, T/T½ = T½)
18
Rate of effusion:
Effusion is the escape of gaseous molecules through a small hole
into an evacuated space
Graham's law of effusion:
 The rate of effusion of a gas is inversely proportional to the square
root of the molar mass.
 When a gas at a pressure p and temperature T is separated from a
vacuum by a small hole,
 The rate of escape of its molecules is equal to the rate at which
they strike the area of the hole

Where, R = kNA, M = mNA , Ao = hole area

 If a gas is enclosed in a cavity with a small hole, then the rate of
loss of its mass from the container is proportional to its pressure
and inversely proportional to the square root of its molar mass.
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Example

 Caesium (m.p. 29°C, b.p. 686°C) was introduced into a container

and heated to 500°C. The vapor pressure of liquid caesium was 11
kPa. Calculate the mass loss if a hole of diameter 0.50 mm is
opened for 100 s. (M = 132.9 g mol-1)
Solution:
𝑃
m = ZwAomt ∆𝑚 = 𝐴 𝑀𝑡
2𝜋𝑀𝑅𝑇 𝑜
P = 11103Pa = 11103 kgm-1s-2, M = 132.9 10-3 kg mol-1, t = 100s
Ao = r2 = 3.14(0.2510-3m)2= 1.9610-7m2
(2MRT)½ = (2 3.14 132.9 10-3kgmol-1 8.314kgm2s-2 K-1mol-1  773K) ½
= 73.24 kgmol-1ms-1
m = 39110-6 kg = 391mg

20
2.5. Transport phenomena

 If a gas is not uniform with respect to composition, temperature,

and velocity, transport processes occurs until the gas does become
uniform.

Diffusion: The transport of matter in the absence of bulk flow.

Thermal conduction: The transport of heat from regions of high
temperature to regions of low temperature without convection.
Viscous flow: The transfer of momentum from a region of higher
velocity to a region of lower velocity

 In each case the rate of flow is proportional to the rate of change

of a property with distance, gradient.
21
 The rate of migration of a property is measured by its flux, J.
 It is the quantity of that property passing per unit area per unit time.
 If matter is flowing (as in diffusion), we speak of a matter flux
 If the property is energy (as in thermal conduction), then we speak of the
energy flux

a) Flux of Matter:
Consider the diffusion of a gas along the z-axis in a container.
The flux is proportional to the first derivative of the concentration:
𝑁
𝑑
𝑉
𝐽 (matter) = −𝐷
𝑑𝑧

D is the diffusion coefficient

𝟏
𝑫 = mean unit: m2s-1
22
𝟐
Significance of the expression:
1. The mean free path, , decreases as the pressure is increased.
 D decreases with increasing pressure and
 the gas molecules diffuse more slowly.

2. The mean speed increases with temperature.

 D increases with temperature.
 molecules in a hot sample diffuse more quickly than those in a
cool sample (for a given concentration gradient).

3.  increases when the collision cross-section of the molecules

decreases
 D is greater for small molecules than for large molecules.

23
b) Flux of Energy
 The transport of heat is due to a gradient in temperature.
 The rate of thermal conduction (the flux of the energy associated
with thermal motion) is proportional to the temperature gradient:
𝑑𝑇
𝐽 𝑒𝑛𝑒𝑟𝑔𝑦 = −
𝑑𝑧
 is coefficient of thermal conductivity
1
 = mean𝐶V,m[A]
3
CV,m = molar heat capacity at constant volume, [A] = molar
concentration of carrier particles
Unit of : JK-1m-1s-1
Significance of the expression:
1.  decreases as P (concentration) increases.
  is independent of P.
2.  increases with increasing CV,m.
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c) Viscosity ()
 Viscosity is a measure of a fluid's resistance to flow.
𝟏 𝑵
 = mean𝒎
𝟑 𝑽
Other forms:
𝑷𝑴𝑫
 = 𝑴𝑫[𝑨] =
𝑹𝑻
Where [A] is molar concentration of the gas molecules
Unit: Poise (P) 1P = 0.1kgm-1s-1

1.   1/p and [A]  p

Hence,  of a gas is independent of p

2.   mean  T1/2
Hence, , of a gas increases with temperature.
25
Examples
Calculate the flux of energy arising from a temperature gradient of
2.5 K m-1 in a sample of argon in which the mean temperature is
273 K. (Cv,m = 12.472 Jmol-1K-1, At Wt. = 39.95,  = 0.36 nm2)
Solution
𝑑𝑇 1  𝑘𝑇
𝐽 𝑒𝑛𝑒𝑟𝑔𝑦 = − ,  = mean𝐶V,m[A],  mean = ,
𝑑𝑧 3 𝑧 2𝑃
8𝑅𝑇 ½
mean =
𝜋𝑀
½
2𝐶V, m 𝑅𝑇 𝑑𝑇
𝐽=−
3𝑁A 𝜋𝑀 𝑑𝑧

2×12.472𝐽𝐾−1𝑚𝑜𝑙−1 8.314𝐽𝐾−1𝑚𝑜𝑙−1×273𝐾 ½
𝐽= − −18 23 −3 −1 × −2.5𝐾𝑚−1
3×0.36×10 ×6.02×10 3.14×39.95×10 kgmol

= 1.3  10-2 Jm-2s-1

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 In a double-glazed window, the panes of glass are separated by 5.0
cm. What is the rate of transfer of heat by conduction from the
warm room (25°C) to the cold exterior (-10°C) through a window
of area 1.0 m2? (Assume the space between glasses is filled with
air . (air) = 0.24110-3JK-1cm-1s-1)

 Solution
𝑑𝑇 −3 −1 −1 −1
−10 − 25
𝐽 = − = − 0.241 × 10 𝐽𝐾 𝑐𝑚 𝑠 × 𝐾
𝑑𝑧 5𝑐𝑚
J = 1.6910-3 Jcm-2s-1
Hence ,
Rate of energy transfer and energy loss is = JA = 1.6910-3 Jcm-2s-
1(100cm m-1)2 = 16.9 Js-1

27