Fundamentals of Physical Chemistry (InCh2004)

Chapter 1
Kinetic Theory of Gases

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1.1. Kinetic molecular 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.
1.2 The Kinetic gas equation
§ It relates the pressure and volume of a gas to the molecular mass
and molecular speed.
�
�� = ��rms2
�
Where, n = number of moles, M = molar mass of the molecule
rms = root mean square speed of the molecules
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 1
rms = 2 2 where, 2 = x2 + y2 + z2
The equation is similar with the ideal gas equation of state:
�� = ���
where R = The universal gas constant = 8.314 JK-1mol-1
§ For the two equations to be equal,
�
��� = ��rms2
�
Therefore, the root mean square speed of the gaseous molecules is given
by
���
rms =
�
1.3 Molecular speeds
1.3.1 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.
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ü It is given by the Maxwell distribution of speeds.
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� 2 −
�
�  = 4�  � 2��
2
2���
Where,  = speed of a molecule, f() = fraction of molecules having a speed
of 

Fig. The distribution of molecular speeds with temperature and molar mass
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If
§ the temperature of the gas is low or
§ the molecular mass of the gas is high
Ø Greater fraction of the molecules will have low speed
If
§ the temperature of the gas is high or
§ The molecular mass of the gas is low
Ø Greater fraction of the molecules will have high speed

1.3.2 Different kinds of speeds

a) Root mean square speed (rms):
§ It is the square root of the mean of the squares of the speeds, .
���
rms = 2 =
�

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§ 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.
Ø The higher the temperature, the higher the root mean square speed of
the molecules
Ø Heavy molecules travel more slowly than light molecules at the same
temperature
b) Mean speed (mean):
��� �
mean = = rms
� ��
c) Most probable speed (mp):
��� �
mp = = rms
� �
d) Mean relative speed(rel):It is the mean speed with which one
molecule approaches another of the same kind.
�
rel = � mean = ���
��
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§ The relative mean speed of two dissimilar molecules of molar
masses MA and MB is given by
��� �� ��
rel = where  =
 �� +��

1.3.3 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
Solution
J = kgm2s-2, MN2 = 28  10-3kgmol-1
��� ��.������2�−2�−1���−1  ����
a) rms = = = ���. ���−1
� ����−3�����−1

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 8�� 88.314���2�−2�−1���−1  298�
b) mean = = = ���. ���−1
� 3.142810−3�����−1

2�� 28.314���2�−2�−1���−1  298�

c) mp = = = ���. ���−1
� 2810−3�����−1

d) rel = 2 mean = 2  474.8��−1 = ���. ���−1

Exercise:
1. Calculate the above speeds for
a) N2 at 350 K
b) H2 at 350 K
2. Determine the relative ratios of the above speeds
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1.4 Molecular collisions
1.4.1 Collision properties
a) Collision frequency (z):
§ The number of collisions a molecule makes per unit time
� �
� = rel = rel
� ��
Where,
= d2 = collision cross section ( d = collision diameter)
N = number of molecules = nNA, V = volume of the container
P = pressure

Cases
1. At constant volume, the collision frequency increases with
increasing temperature
Reason: The relative mean speed increases with increasing
temperature
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 2. At constant temperature, the collision frequency increases with
increasing pressure
Reason: Greater pressure implies greater number density (N/V) of
the molecules
Example:
Calculate the collision frequency for a N2 molecule in a sample at 1
atm and 25oC
Solution
1 atm = 101325 Pa = 101325Jm-3
(N2) = 0.43  10-18m2
� 8�� �
� = rel = 2
�� � ��

88.314���2�−2�−1���−1  298� 101325Jm−3

= �. ����−18�2 � 
3.142810−3�����−1 1.38 10−23JK−1298K
� = ���9�−1

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b) The mean free path ()
§ It is the average distance a molecule travels between collisions
rel ��
= =
� �
Cases:
1.  is inversely proportional to P
2. As T increases
ü P increases
ü T/P remains constant
Ø  is independent of temperature
1.4.2 Collision with a wall or surface
Collision flux (zw):
§ Number of collisions per unit area per unit time
�
�w =
�����
The product of Zw and area yields the collision frequency.
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1.4.3 The rate of effusion:
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.
��
���� �� �������� = �w� =
2����

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1.5 Ideal and real gases
1.5.1 Ideal gases
Ideal Gas: A gas is said to be ideal if
i. The size of the molecules is considered to be negligible
ii. The molecules do not interact with each other.
The Ideal Gas Law
• Boyle’s law: V  1/P (T, n = constant)
• Charles’s law: V  T (P, n = constant)
• Avogadro’s law: V  n (P, T = constant)
Therefore:
��
�∝ ; �� ∝ ��; �� = ����������
�
Let the Constant = R (universal gas constant)
Accordingly,
�� = ��� Ideal gas equation

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Values of R:
R = 8.314 J K-1 mol-1
= 8.2  10-2 dm3atm K-1mol-1
= 8.314 Pa m3 K-1 mol-1
= 8.314  10-2 dm3 bar K-1mol-1
Example: In an industrial process, nitrogen enters a vessel of
constant volume at 100 atm and 300 K.
To what temperature should the gas be heated in order to exert a
pressure of 300 atm?
Solution:

Given: P1 = 100 atm, P2 = 300 atm, T1 = 300 K,V1 = V2, n1 = n2, T2 = ?

�1 �2
=
�1 �2
�2 300���
�2 = �1 = 300� = 900�
�1 100���
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1.5.2 Real gases
Real gas: A gas sample that does not obey the ideal (perfect) gas law
exactly.
Deviation from ideal behavior
§ The deviations are significant at high pressures and low
temperatures.
§ Real gases deviate from the ideal gas law because of molecular
interactions.
Ø Repulsive forces between molecules assist expansion while
attractive forces assist compression.
§ Repulsive forces are short range interactions.
Ø They are significant when the molecules are close to each other,
as under high pressure.
§ Attractive forces are relatively long-range interactions.
Ø They are significant when the molecules are fairly close to each
other.
Ø They are ineffective when the molecules are far apart.
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At low pressures,
Ø the molecules are far apart.
Ø the intermolecular forces have no significant role.
Therefore,
§ A gas sample at low pressure behaves ideally.
At moderate pressures,
§ The attractive forces dominate the repulsive forces.
Ø A gas at moderate pressures is expected to be more compressible
than an ideal gas.
At high pressures,
§ The repulsive forces dominate.
Ø A gas at high pressures is expected to be less compressible.

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Characteristic Features of Gases
The Compression Factor (Z):
��
�=
���
Vom = ideal molar volume, Vm = actual molar volume
��
��� =
�
Therefore,
�
�= �
�� �
��� = ���
§ For a perfect gas, Z = 1 under all conditions.
§ Deviation of Z from 1 is a measure of departure from a perfect
behavior.

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Effect of Pressure on Z
Ø At very low pressure, all gases have Z = 1.
Ø At high pressures, all gases have Z > 1.
Ø At intermediate pressures, most gases have Z < 1.

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Critical Constants
§ When a gas sample is compressed at a certain temperature, its
pressure is expected to rise (Boyle’s law).
§ When the pressure reaches a certain point, it remains constant and
the gas condenses to a liquid, forming a gas – liquid distinct
phases.
§ If the compression takes place at or above a certain temperature
the pressure of the gas increases without condensation.
Critical temperature (T c ): The temperature at which the gas –
liquid interface vanishes
§ The corresponding pressure and molar volume are called critical
pressure (Pc) and critical molar volume (Vc), respectively.
§ Tc, Pc and Vc collectively are called critical constants.
§ The critical constants are characteristic of the type of the gas.

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 Example:
Gas Tc(K) Pc(atm) Vc(cm3mol-1)
CO2 304.2 72.9 94.0
O2 154.8 50.14 78.0
He 5.2 2.26 57.8
Super critical fluid: The single phase that fills the entire volume
when T ≥ Tc .
Ø It is denser than gases under normal condition.
1.5.3 Vander Waal's equation
§ In real gases, the volume available for moving gaseous molecules
is decreased because of the repulsive forces.
Ø The smaller volume is V – nb.
§ The pressure of the gases is decreased because of the attractive
forces among the molecules.
Ø The decrease is proportional to the molar concentration and is
equal to a (n/V)2.
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van der Waals equation
��� � � �� �
�= −� �= −
�−�� � �m−� ���
Vm= V/n = molar volume
a, b are van der Waals coefficients.
ü They are characteristics of a gas.
Units
a = atmdm6mol-2 b = dm3mol-1
Example: Calculate the pressure exerted by one mole of Ar at 100 oC.
(V m = 0.298dm 3 mol -1 , a = 1.337 atmdm 6 mol -2 , b = 3.2 × 10 -2
dm3mol-1)
Solution
�� � 0.082��3������−1�−1373� 1.337�����6���−2
�= − = −
��2 0.298��3���−1−0.032��3���−1 0.298��3���−1
2
�m−�
= 99.929���

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The critical constants are related to the van der Waals coefficients.
At critical constants,
�� �2�
=0 =0
��� �2��2
Using the van der Waals equation,
�� �� 2� �2� 2�� 6�
=− + =0 = − =0
��� ��−� 2 ��3 ���2 ��−� 3 ��4

Using the critical constants,

��� 2� 2� 2
− + =0 ��� = �� − �
��−� 2 ��3 ��3
2��� 6� 3� 3
− =0 ��� = �� − �
��−� 3 ��4 ��4
Using the equations,
2� 2 3� 3
�� − � = �� − �
��3 ��4 22
 �� � ���� �
�� = �� �� = �� = �� = =
���� ���� ��� �
1.5.4. The Principle of Corresponding States
§ Real gases at the same reduced volume (VR) and reduced temperature
(TR) exert the same reduced pressure (PR).
§ The reduced variables are given by;
�� � �
�� = �� = P� =
�� �� ��
�� = ���� � = ���� P = ����
�� �
Using the van der Waals equation, � = −
�m−� ���
����� �
���� = −
����−� ������
Substitution for Pc, Vc and Tc yields
8�
� ��� � 8�R 3
�� 2 = 27��
− , �� = −
27� ��3�−� ��2 3� 2 3�R−1 ��2
Accordingly, if two gases have the same VR and TR values, they will
have the same PR.
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