LECTURE 3 - KINETIC MODEL OF GASES

3.1 KINETIC-MOLECULAR THEORY OF IDEAL GASES

The ideal gas equation
PV = nRT
describes how gases behave.
• A gas expands when heated at constant pressure
• The pressure increases when a gas is compressed at constant temperature

THE KINETIC MOLECULAR THEORY ("the theory of moving molecules"; Rudolf Clausius, 1857)
1. Gases consist of large numbers of molecules (or atoms, in the case of the noble gases) that are
in continuous, random motion
2. The volume of all the molecules of the gas is negligible compared to the total volume in which the gas
is contained
3. Attractive and repulsive forces between gas molecules is negligible
4. The average kinetic energy of the molecules does not change with time (as long as the temperature of
the gas remains constant). Energy can be transferred between molecules during collisions (but the
collisions are perfectly elastic)
5. The average kinetic energy of the molecules is proportional to absolute temperature. At any given
temperature, the molecules of all gases have the same average kinetic energy. In other words, if I
have two gas samples, both at the same temperature, then the average kinetic energy for the
collection of gas molecules in one sample is equal to the average kinetic energy for the collection of
gas molecules in the other sample.
Pressure
• The pressure of a gas is causes by collisions of the molecules with the walls of the container.
• The magnitude of the pressure is related to how hard and how often the molecules strike the wall
• The "hardness" of the impact of the molecules with the wall will be related to the velocity of the
molecules times the mass of the molecules

Absolute Temperature
• The absolute temperature is a measure of the average kinetic energy of its molecules
• If two different gases are at the same temperature, their molecules have the same average kinetic
energy
• If the temperature of a gas is doubled, the average kinetic energy of its molecules is doubled

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Application of the Molecular Kinetic Theory to the Gas Laws

Effect of a volume increase at a constant temperature

• Constant temperature means that the average kinetic energy of the gas molecules remains constant
• This means that the rms speed of the molecules, u, remains unchanged
• If the rms speed remains unchanged, but the volume increases, this means that there will be fewer
collisions with the container walls over a given time
• Therefore, the pressure will decrease (Boyle's law)

Effect of a Temperature Increase at Constant Volume

• An increase in temperature means an increase in the average kinetic energy of the gas molecules,
thus an increase in u
• There will be more collisions per unit time, furthermore, the momentum of each collision increases
(molecules strike the wall harder)
• Therefore, there will be an increase in pressure
• If we allow the volume to change to maintain constant pressure, the volume will increase with
increasing temperature (Charles's law)

3.2 THE KINETIC-MOLECULAR THEORY OF IDEAL GASES

An experimental study of the behavior of the gas, such as that carried out by Boyle, cannot determine
the nature of the gas or why the gas obeys particular laws. In order to understand gases, one could first
propose some hypothesis about the nature of gases. Such hypotheses are often referred to as constituting a
“model” for a gas. The properties of the gas that are deduced from this model are then compared to the
experimental properties of the gas. The validity of the model is reflected in its ability to predict the behavior
of gases.
We will simply state three postulates of the kinetic-molecular model, and show how this model leads
to the ideal gas laws. This model of an idealized gas will be seen to fit the behavior of many real gases.
1. The gas is assumed to be composed of individual particles (atoms or molecules) whose actual
dimensions are small in comparison to the distances between them.
2. These particles are in constant motion and therefore have kinetic energy.
3. Neither attractive nor repulsive forces exist between the particles.

In order to see how this model predicts the observed

behavior quantitatively, we must arrive at an equation
relating the pressure and volume of a gas to the important
characteristics of the gas, namely the number of the particles
present, their mass, and the velocity with which they move.
We will first focus our attention on a single molecule of mass
m confined in an otherwise empty container of volume V. The
particle traverses the container with velocity u (a vector
quantity indicating both speed and direction). Because of the
particle’s X-component of velocity (i.e., the component 𝑢𝑥 as
shown in Figure 1.7) the molecule will traverse the container
of length x in the X-direction, collide with the wall YZ, and
then rebound. In the impact the molecule exerts a force 𝐹𝑤 on
the wall. This force is exactly counterbalanced by the force F
exerted on the molecule by the wall. The force F is equal to Figure 1.7 Container showing coordinates and
the change of momentum p of the molecule in the given velocity components for gas particle of mass m
direction per unit time, in agreement with Newton’s second
law of motion,
𝑑𝑝 𝑑(𝑚𝑢) 𝑑𝑢
𝐹= = 𝑚𝑎 = =𝑚
𝑑𝑡 𝑑𝑡 𝑑𝑡

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 The molecule’s momentum in the X-direction when it strikes the wall is 𝑚𝑢𝑥 . Since we assume that
the collision is perfectly elastic, the molecule bounces off the wall with a velocity −𝑢𝑥 in the opposite
direction.
The change in velocity of the molecule on each collision is
∆𝑢𝑥 = [−𝑢𝑥 (𝑎𝑓𝑡𝑒𝑟 𝑐𝑜𝑙𝑙𝑖𝑠𝑖𝑜𝑛)] − [𝑢𝑥 (𝑏𝑒𝑓𝑜𝑟𝑒 𝑐𝑜𝑙𝑙𝑖𝑠𝑖𝑜𝑛)]
= −2𝑢𝑥
The corresponding change of momentum is −2𝑚𝑢𝑥 . Since each collision with this wall occurs only
after the molecule travels a distance of 2x (i.e., round trip), the number of collisions a molecule makes in unit
time by 2x. The result is
𝑢𝑥
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑐𝑜𝑙𝑙𝑖𝑠𝑖𝑜𝑛 𝑖𝑛 𝑢𝑛𝑖𝑡 𝑡𝑖𝑚𝑒 =
2𝑥
The change of momentum per unit time is thus
𝑑𝑢 𝑢𝑥 𝑚𝑢𝑥2
𝐹=𝑚 = (−2𝑢𝑥 𝑚) ( ) = −
𝑑𝑡 2𝑥 𝑥
The force Fw exerted on the wall by the particle is exactly equal in magnitude to this but with
opposite sign:
𝑚𝑢𝑥2
𝐹𝑤 = −𝐹 =
𝑥
Since the pressure is force per unit area and the area A is yz, we may write the pressure in the X-
direction, Px, as
𝐹𝑤 𝐹𝑤
𝑃𝑥 = =
𝐴 𝑦𝑧
𝒎𝒖𝟐𝒙 𝒎𝒖𝟐𝒙
= =
𝒙𝒚𝒛 𝑽
Since xyz = V is the volume of the container.

3.3 The Pressure of a Gas Derived from Kinetic Theory

So far we have considered only one molecule that has been assumed to travel at constant velocity.
For an assembly of N molecules there will be a distribution of molecular velocities, since even if the molecules
all began with the same velocity, collisions would occur altering the original velocity. If we define 𝑢𝑖2 as the
square of the velocity component in the X-direction of molecule i and take the average of this molecules
rather than the sum over 𝑢𝑖2 , we have
𝑢12 + 𝑢22 + 𝑢32 + ⋯ + 𝑢𝑁 2 ∑𝑁 2
𝑖=1 𝑢𝑖
̅̅̅
𝑢𝑥2 = =
𝑁 𝑁
where ̅̅̅
𝑢𝑥2 is the mean of the squares of the normal component of the velocity in the X-direction. The
pressure should therefore be written as
𝑵𝒎𝒖 ̅̅̅𝟐𝒙̅
𝑷𝒙 =
𝑽
This is the equation for the pressure of a one-dimensional gas. For the components of velocity in the
Y-direction and in the Z-direction, we would obtain expressions similar as the above but now involving ̅̅̅ 𝑢𝑦2
and 𝑢̅̅̅𝑧2 , respectively. It is more convenient to write these expressions in terms of the magnitude of the
velocity u rather than in the terms of the squares of the velocity components. The word speed is used for the
magnitude of the velocity; speed is defined as the positive square root of 𝑢2 and is related to the velocity
components by the Pythagorean theorem:
|𝑢| = √𝑢2 = √𝑢𝑥2 + 𝑢𝑦2 + 𝑢𝑧2

If we average over all molecules, we obtain

̅̅̅
𝑢2 = ̅̅̅
𝑢𝑥2 + ̅̅̅
𝑢𝑦2 + ̅̅̅
𝑢𝑧2
Since there is no reason for one direction to be favored over the others, the mean of the 𝑢𝑥2 values will
be the same as the mean 𝑢𝑦2 values and the mean of 𝑢𝑧2 values. Hence, the sum of the means is equal to ̅̅̅ 𝑢2 and
̅̅̅
2
each mean is equal to 1/3𝑢 , that is,
1 2
̅̅̅
𝑢𝑥2 = ̅̅̅
𝑢𝑦2 = ̅̅̅
𝑢𝑧2 = ̅̅̅
𝑢
3

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 Substituting into Px, gives the final expression for the pressure on any wall:
𝑵𝒎𝒖 ̅̅̅𝟐̅ 𝟏
𝑷= 𝒐𝒓 𝑷𝑽 = 𝑵𝒎𝒖 ̅̅̅𝟐̅
𝟑𝑽 𝟑
This is the fundamental equation as derived from the simple kinetic theory of gases. We see that it is
in the form of Boyle’s law and is consistent with Charles’ law if 𝑚𝑢 ̅̅̅2 is directly proportional to the absolute
temperature. In order to make this relation exact, we substitute nRT for PV:
𝟏 ̅̅̅𝟐̅
𝒏𝑹𝑻 = 𝑵𝒎𝒖
𝟑
Or
𝟏 ̅̅̅𝟐̅ = 𝑹𝑻 ̅̅̅𝟐̅ = 𝟑𝑹𝑻
𝑳𝒎𝒖 𝒐𝒓 𝒖
𝟑 𝑴
Since N/n is equal to the Avogadro constant L, and mL=M, the molar mass

3.4 KINETIC ENERGY AND TEMPERATURE

We have seen how the kinetic molecular theory of gases may be used to explain the experimental
form of two gas laws. It can also shed light on the nature of kinetic energy. In order to determine the exact
relation between ̅𝒖̅̅𝟐̅ and T, the mechanical variable u must be related to temperature, which is not a
mechanical variable. For our purpose of determining the relation between kinetic energy and temperature,
the equation may be converted into another useful form by recognizing that the average kinetic energy ̅∈̅̅𝑘̅ per
molecule is
1 ̅̅̅𝟐̅
̅∈̅̅𝑘̅= 𝑚𝒖
2
Substitution of this expression gives
1 2
𝑃𝑉 = 𝑁 ∙ 2 ̅∈̅̅𝑘̅= 𝑁 ̅∈̅̅𝑘̅
3 3
Thus, at constant pressure, the volume of a gas is proportional to the number of gas molecules and
the average kinetic energy of the molecules. Since
𝑁 = 𝑛𝐿
Substitution yields
2
𝑃𝑉 = 𝑛𝐿 ̅∈̅̅𝑘̅
3
Since 𝐿 ̅∈̅̅𝑘̅ is the total kinetic energy 𝐸𝑘 per mole of gas,
2
𝑃𝑉 = 𝑛𝐸𝑘
3
The connection between 𝐸𝑘 and the temperature is provided by the empirical ideal gas law, PV= nRT.
By equating the right hand sides of the last two equations we obtain
2 𝟑
𝑛𝐸 = 𝑛𝑅𝑇 𝑜𝑟 𝑬𝒌 = 𝑹𝑻
3 𝑘 𝟐
The average kinetic energy per molecule ̅∈̅̅𝑘̅ is obtained by dividing both sides by the Avogadro
constant L:
𝟑
̅̅̅
∈ 𝒌 = 𝒌𝑩 𝑻
𝟐
Where 𝑘𝐵 = 𝑅𝐿. Named after the Austrian physicist Ludwig Edward Boltzmann (1844-1906), the
Boltzmann constant 𝑘𝐵 is the gas constant per molecule. Thus the average kinetic energy of the molecules is
proportional to the absolute temperature. Since ̅̅̅ ∈𝒌 is independent of the kind of substance, the average
molecular kinetic energy of all substances is the same at a fixed temperature.
𝑘𝐵 = 1.380622 𝑥 10−23 𝐽/𝐾
An interesting aspect of this fact is seen when we consider a number of different gases all at the same
̅̅̅̅
𝑁𝑚𝑢 2
temperature and pressure. Then equation 𝑃 = may be written as
3𝑉
𝑁1 𝑚1 ̅̅̅
𝑢12 𝑁2 𝑚2 ̅̅̅
𝑢22 𝑁𝑖 𝑚𝑖 ̅̅̅
𝑢𝑖2
= =⋯=
3𝑉1 3𝑉2 3𝑉𝑖
Or
𝑁1 𝑁2 𝑁𝑖
= =⋯=
3𝑉1 3𝑉2 3𝑉𝑖

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 Thus 𝑵𝟏 = 𝑵𝟐 = ⋯ = 𝑵𝒊 when the volumes are equal. In other words, equal volumes of gases at the
same pressure and temperature contain equal numbers of molecules. This is just a statement of Avogadro’s
hypothesis 𝑉 ∝ 𝑛 𝑜𝑟 𝑉 = 𝐶 𝑚 𝑛 (𝑣𝑎𝑙𝑖𝑑 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑃 𝑎𝑛𝑑 𝑇)

3.5 MOLECULAR COLLISIONS

̅̅̅̅
𝑁𝑚𝑢 2 3
The ability to relate pressure and temperature to molecular quantities 𝑃 = and ̅∈̅̅𝑘̅= 𝑘𝐵 𝑇 is a
3𝑉 2
major accomplishment of the kinetic theory of gases. We now apply the kinetic theory to the investigation of
the collisions of molecules in order to have a clearer understanding of the interactions in a gas. We will be
interested in three aspects of molecular interaction: the number of collisions experienced by a molecule per
unit time, the total number of collisions in a unit volume per unit time, and how far the molecules travel
between collisions
In this development we consider that the molecules behave as a rigid sphere in elastic collisions and
that there are two kinds of molecules, A and B, with diameters d A and dB. Suppose that a molecule of A travels
with an average speed of ̅̅̅
𝑢𝐴 in a container that contains both A and B molecules. We will first assume that the
molecules of B are stationary and later remove this restriction. As shown in the figure, a collision will occur
each time the distance between the center of a molecule A and that of molecule B becomes equal to 𝑑𝐴𝐵 =
(𝑑𝐴 + 𝑑𝐵 )/2, where 𝑑𝐴𝐵 is called the collision diameter. A convenient way to visualize this is to construct
around the center of A an imaginary sphere of radius 𝑑𝐴𝐵 , which is the sum of the two radii. In unit time this
2
imaginary sphere, represented by the dashed circle in Figure 1.8 will sweep out a volume of 𝜋𝑑𝐴𝐵 𝑢𝐴 If the
̅̅̅.
center of a B molecule is in this volume, there will be a collision. If 𝑁𝐵 is the total number of B molecule in the
system, the number per unit volume is 𝑁𝐵 /𝑉, and the number of centers of B molecules in the volume swept
2
out is 𝜋𝑑𝐴𝐵 𝑢𝐴 𝐵 /𝑉. This number is the number 𝑍𝐴 of collision experienced by the one molecule of A in unit
̅̅̅𝑁
time:
2
𝜋𝑑𝐴𝐵 𝑢𝐴 𝐵
̅̅̅𝑁
𝑍𝐴 = 𝑆𝐼 𝑢𝑛𝑖𝑡 ∶ 𝑠 −1
𝑉
Collision Frequency. This number is known as the collision frequency. If there is a total of 𝑁𝐴 /𝑉
molecules of A per unit volume in addition to the B molecules, the total number 𝑍𝐴𝐵 of A-B collisions per unit
volume per unit time is 𝑍𝐴 multiplied by 𝑁𝐴 /𝑉:
2
𝜋𝑑𝐴𝐵 𝑢𝐴 𝐴 𝑁𝐵
̅̅̅𝑁
𝑍𝐴𝐵 = (𝑆𝐼 𝑢𝑛𝑖𝑡: 𝑚−3 𝑠 −1 )
𝑉2
This quantity, the number of collisions divided by volume and by time, is known as the collision
density, often called the collision number.
If only A molecules are present, we are concerned with the collision density 𝑍𝐴𝐴 for the collisions of A
molecules with one another. The expression for this resembles that for 𝑍𝐴𝐵 , but a factor ½ has to be
introduced:
1 2
𝑢𝐴 𝐴2
𝜋𝑑𝐴 ̅̅̅𝑁
𝑍𝐴𝐴 = 2 (𝑆𝐼 𝑢𝑛𝑖𝑡: 𝑚−3 𝑠 −1 )
𝑉2
The reason for the factor ½ is the otherwise we would count each collision twice. For example, we
would count a collision of A1 with A2 and A2 with A1 as two separate collisions instead of one.
An error in this treatment of collisions is that we have only considered the average speed 𝑢̅𝐴 of the A
molecules. More correctly, we should consider the relative speeds 𝑢̅𝐴𝐵 or 𝑢̅𝐴𝐴 of the molecules.
When we have a mixture containing two kinds of molecules A and B of different masses, the 𝑢̅𝐴 and
1
𝑢̅𝐵 values are different. The average relative speed 𝑢̅𝐴𝐵 is equal to (𝑢̅2𝐴 + 𝑢̅2 𝐵 )2 , and we modify 𝑍𝐴 =
2 ̅̅̅̅𝑁 2 ̅̅̅̅𝑁
𝜋𝑑𝐴𝐵 𝑢𝐴 𝐵 𝜋𝑑𝐴𝐵 𝑢 𝐴 𝐴 𝑁𝐵
and 𝑍𝐴𝐵 = by replacing 𝑢̅𝐴 by 𝑢̅𝐴𝐵 :
𝑉 𝑉2
1
2
𝜋𝑑𝐴𝐵 (𝑢̅2𝐴 + 𝑢̅2 𝐵 )2 𝑁𝐵
𝑍𝐴 = (𝑆𝑖 𝑢𝑛𝑖𝑡 ∶ 𝑠 −1 )
𝑉
𝟏
𝝅𝒅𝟐𝑨𝑩 (𝒖
̅𝟐 𝑨 + 𝒖
̅ 𝟐 𝑩 )𝟐 𝑵𝑨 𝑵𝑩
𝒁𝑨𝑩 = (𝑺𝑰 𝒖𝒏𝒊𝒕: 𝒎−𝟑 𝒔−𝟏 )
𝑽𝟐
If we have only A molecules, the average relative speed of two molecules is
𝑢̅𝐴𝐴 = √2𝑢̅𝐴

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 1 2 ̅̅̅̅𝑁2
𝜋𝑑𝐴 𝑢𝐴 𝐴
We must therefore replace 𝑢̅𝐴 in 𝑍𝐴𝐴 = 2 by 𝑢̅𝐴𝐴 or √2𝑢̅𝐴 , and we obtain for the collision
𝑉2
density the more correct expression
√𝟐𝝅𝒅𝟐𝑨 ̅̅̅̅𝑵
𝒖𝑨 𝟐𝑨
𝒁𝑨𝑨 = (𝑺𝑰 𝒖𝒏𝒊𝒕: 𝒎−𝟑 𝒔−𝟏 )
𝟐𝑽𝟐
The corresponding expression for 𝑍𝐴 , the number of collisions of 1 molecule of A in 1s, when only A
molecules are present, is
√𝟐𝝅𝒅𝟐𝑨 ̅̅̅̅𝑵
𝒖𝑨 𝑨
𝒁𝑨 = (𝑺𝑰 𝒖𝒏𝒊𝒕: 𝒔−𝟏 )
𝑽

EXAMPLE
Nitrogen and Oxygen are held in a 1.00m3 container maintained at 300K at a partial pressures of
𝑃𝑁2 = 80 𝑘𝑃𝑎 𝑎𝑛𝑑 𝑃𝑂2 = 21 𝑘𝑃𝑎. If the collision diameters are
𝑑𝑁2 = 3.74 𝑥 10−10 𝑚 𝑎𝑛𝑑 𝑑𝑂2 = 3.57 𝑥 10−10 𝑚
Calculate𝑍𝐴 , the average number of collisions experienced in unit time by one molecule of nitrogen
and by one molecule of oxygen. Also calculate 𝑍𝐴𝐵 , the average number of collisions per unit volume per unit
time. Do this last calculation both at 300K and 3000K on the assumption that the value for d and N do not
1
change. At 300K, (𝑢̅2 𝑁 + 𝑢̅2 𝑂2 )2 is 625 m/s ; at 3000K, it is 2062 m/s.
2

Solution
The values of 𝑁𝑁2 and 𝑁𝑂2 are calculated from the ideal gas law:
𝑁𝑅𝑇
𝑃𝑉 = 𝑛𝑅𝑇 =
𝐿
For N2
𝐿𝑃𝑉
𝑁𝑁2 =
𝑅𝑇
6.022 𝑥 1023 𝑚𝑜𝑙 −1 𝑥 80 000 𝑃𝑎 𝑥 1𝑚3
𝑁𝑁2 =
8.314 𝐽 𝐾 −1 𝑚𝑜𝑙 −1 𝑥 300𝐾
= 1.93 𝑥 1025 𝑎𝑡 300𝐾
For O2
𝑁𝑂2 = 5.07 𝑥 1024 𝑎𝑡 300𝐾
The total number of collisions with unlike molecules is given by
1
2
𝜋𝑑𝐴𝐵 (𝑢̅2 𝐴 + 𝑢̅2 𝐵 )2 𝑁𝐵
𝑍𝐴 =
𝑉
2
3.74 + 3.57 𝑚
𝑍𝑁2 = 𝜋 [( ) 𝑥 10−10 𝑚] 𝑥 625 𝑥 5.07 𝑥 1024 𝑥 1𝑚3
2 𝑠
= 1.33 𝑥 109 𝑠 −1
625𝑚
𝑍𝑂2 = 𝜋[3.66 𝑥 10−10 𝑚]2 𝑥 𝑥 1.93 𝑥 1025 𝑥 1𝑚3
𝑠
= 5.08 𝑥 109 𝑠 −1
We have for the total number of collisions per cubic metre per second using,

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 1
2
𝜋𝑑𝐴𝐵 (𝑢̅2𝐴 + 𝑢̅2 𝐵 )2 𝑁𝐴 𝑁𝐵
𝑍𝐴𝐵 =
𝑉2
−10 )2 (625)(1.93
𝑍𝑁2,𝑂2 = 𝜋(3.66 𝑥 10 𝑥 1025 )(5.07 𝑥 1024 )
= 𝟐. 𝟓𝟕 𝒙 𝟏𝟎𝟑𝟒 𝒎−𝟑 𝒔−𝟏
𝟑𝟒 −𝟑 −𝟏
At 3000K, 𝒁𝑵𝟐 ,𝑶𝟐 = 𝟖. 𝟒𝟗 𝒙 𝟏𝟎 𝒎 𝒔 .

3.6 MEAN FREE PATH

A concept of particular significance in the treatment of certain properties is the mean free path λ.
This is the average distance that a molecule travels between two successive collisions. We have seen that for a
√𝟐𝝅𝒅𝟐
𝑨 ̅̅̅̅𝑵
𝒖𝑨 𝑨
single gas the number of collisions that a molecule makes in unit time, 𝑍𝐴 , is . In unit time the
𝑽
molecule has traveled, on the average, a distance of 𝑢̅𝐴 . The mean free path is therefore
𝒅𝒊𝒔𝒕𝒂𝒏𝒄𝒆 𝒕𝒓𝒂𝒗𝒆𝒍𝒆𝒅 𝒊𝒏 𝒖𝒏𝒊𝒕 𝒕𝒊𝒎𝒆 ̅𝑨
𝒖
𝛌= =
𝒏𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒄𝒐𝒍𝒍𝒊𝒔𝒊𝒐𝒏𝒔 𝒊𝒏 𝒖𝒏𝒊𝒕 𝒕𝒊𝒎𝒆 √𝟐𝝅𝒅𝑨 ̅̅̅̅𝑵 𝟐
𝒖𝑨 𝑨 /𝑽
𝑽
=
√𝟐𝝅𝒅𝟐𝑨 𝑵𝑨
The magnitude of the dA’s is obviously very important to the kinetic theory of gases, since it is the
only molecular property that we need to know in order to calculate collision numbers and the mean free path.
_________________________________________________________________________________________________________________________

EXAMPLE
Molecular oxygen has a collision diameter of 3.57 𝑥 10−10 m. Calculate λ for oxygen at 300K and
101.325 kPa.

Solution:
Since PV = nRT = (N/L)RT,
λ may be written as
𝑽
𝛌=
√𝟐𝝅𝒅𝟐𝑨 𝑵𝑨
8.3145 (𝐽 𝐾 −1 𝑚𝑜𝑙 −1 )𝑥 300𝐾
=
√2𝜋[3.57 𝑥 10−10 (𝑚)]2 𝑥 6.022 𝑥 1023 (𝑚𝑜𝑙)−1 𝑥 101325 𝑃𝑎
= 𝟕. 𝟐𝟐 𝒙 𝟏𝟎−𝟖 𝒎

3.7 MAXWELL DISTRIBUTION OF MOLECULAR SPEEDS AND TRANSLATIONAL ENERGIES

Maxwell’s famous equation for the distribution of molecular speeds in gases, developed in the early
1860s, inspired Boltzmann to produce a more general equation that dealt with energies of any kind.

The Distribution of Speeds

In his derivation of the distribution of molecular speeds, Maxwell paid no attention to the mechanics
of collisions between molecules. Instead he based his arguments on the probability theory, such as the theory
of errors that had been given by Pierre-Simon Laplace (1749-1827). It is interesting to note that although
Maxwell had obtained an important result, he himself was not convinced that his work was of real
significance. The reason for his doubt was that he had not been able to explain the specific heats of gases on
the basis of his kinetic theory; we now realize that those results require the quantum theory for their
explanation.
The treatment we will describe is essentially that given in 1860 by Maxwell. The speed u of a
molecule can be resolve into its three components along the X, Y, and Z axes. If 𝑢𝑥 is the component along the
1
X axis, the corresponding kinetic energy is 𝑚𝑢𝑥2 where m is the mass of the molecule. We can then ask: what
2

RVM Lecture Manual: Physical Chemistry 1 21

 is the probability 𝑑𝑃𝑥 that the molecule has a speed component along
the X axis between 𝑢𝑥 and 𝑢𝑥 + 𝑑𝑢𝑥 ? We must, of course, consider a
range of speeds, since otherwise the probability is zero. This probability
is proportional to the range 𝑑𝑢𝑥 , and Maxwell deduced on the basis of
2
probability theory that it is proportional to 𝑒 −𝛽𝜖𝑥 , or 𝑒 −𝑚𝑢𝑥𝛽/2 , where 𝛽
is constant. We can therefore write
2
𝑑𝑃𝑥 = 𝐵𝑒 −𝑚𝑢𝑥𝛽/2 𝑑𝑢𝑥
Where B is the proportionality constant. We also have similar
expressions for the other components:
2 2
𝑑𝑃𝑦 = 𝐵𝑒 −𝑚𝑢𝑦𝛽/2 𝑑𝑢𝑦 𝑎𝑛𝑑 𝑑𝑃𝑧 = 𝐵𝑒 −𝑚𝑢𝑧 𝛽/2 𝑑𝑢𝑧
The product of these three expressions is
2 2 2
𝑑𝑃𝑥 𝑑𝑃𝑦 𝑑𝑃𝑧 = 𝐵3 𝑒 −𝑚𝑢𝑥𝛽/2 𝑒 −𝑚𝑢𝑦 𝛽/2 𝑒 −𝑚𝑢𝑧 𝛽/2 𝑑𝑢𝑥 𝑑𝑢𝑦 𝑑𝑢𝑧
Since 𝑢2 = 𝑢𝑥2 + 𝑢𝑦2 + 𝑢𝑧2 , where u is the speed,
2
𝑑𝑃𝑥 𝑑𝑃𝑦 𝑑𝑃𝑧 = 𝐵3 𝑒 −𝑚𝑢 𝛽/2 𝑑𝑢𝑥 𝑑𝑢𝑦 𝑑𝑢𝑧
This expression is the probability that the three components of
speed have values between 𝑢𝑥 and 𝑢𝑥 + 𝑑𝑢𝑥 , 𝑢𝑦 and 𝑢𝑦 + 𝑑𝑢𝑦 , and 𝑢𝑧
and 𝑢𝑧 + 𝑑𝑢𝑧 . However, what we are really interested in is the
probability that the actual speed of the molecule lies between
𝑢 𝑎𝑛𝑑 𝑢 + 𝑑𝑢, and this can be achieved by a variety of combinations of the three components of speed. We
cannot construct a speed diagram, shown in Figure 1.10, with the exponents 𝑢𝑥 , 𝑢𝑦 , 𝑎𝑛𝑑 𝑢𝑧 as the three axes.
We then construct a spherical shell, of radius u and thickness du. What we want is the probability that
systems lie within the shell, but the product 𝑑𝑃𝑥 𝑑𝑃𝑦 𝑑𝑃𝑧 has only given us the probability that they lie within
the small cube shown in diagram. The volume of this cube is 𝑑𝑢𝑥 𝑑𝑢𝑦 𝑑𝑢𝑧 , and the volume of the spherical
shell is 4𝜋𝑢2 𝑑𝑢. In order to obtain the probability dP that the speed lies between 𝑢 𝑎𝑛𝑑 𝑢 + 𝑑𝑢, we must
therefore replace 𝑑𝑢𝑥 𝑑𝑢𝑦 𝑑𝑢𝑧 by 4𝜋𝑢2 𝑑𝑢:
𝑚𝑢2 𝛽
𝑑𝑃 = 4𝜋𝐵3 𝑒 − 2 𝑑𝑢
The fraction dN/N of the N molecules that have speeds between 𝑢 𝑎𝑛𝑑 𝑢 + 𝑑𝑢 is given by the ratio of
this expression to its value integrated form u=0 to 𝑢 = ∞, since that is the range of possible speeds. Thus
𝑚𝑢2 𝛽
𝑑𝑁 4𝜋𝐵3 𝑒 − 2 𝑑𝑢
= 𝑚𝑢2 𝛽
𝑁 ∞
4𝜋𝐵3 ∫0 𝑒 − 2 𝑑𝑢
The integral in the denominator is a standard one, and when we evaluate it, we obtain
𝑑𝑁 𝛽𝑚 3/2 2
= 4𝜋 ( ) 𝑒 −𝑚𝑢 𝛽/2 𝑢2 𝑑𝑢
𝑁 2𝜋
We now consider what the mean-square speed is on the basis of this treatment. The point of doing
this is that we already know the mean-square speed from kinetic theory. Thus, we have
3𝑅𝑇
̅̅̅
𝑢2 =
𝐿𝑚
This quantity is obtained from the previous equation above by multiplying u 2 by the fraction dN/N
and integrating:
∞
𝑑𝑁 𝛽𝑚 3/2 ∞ 2
̅̅̅
𝑢2 = ∫ 𝑢2 = 4𝜋 ( ) ∫ 𝑒 −𝑚𝑢 𝛽/2 𝑢2 𝑑𝑢
0 𝑁 2𝜋 0
The integral is again a standard one, and evaluating it leads to
3
̅̅̅
𝑢2 =
𝑚𝛽
̅̅̅ 3𝑅𝑇 3
Comparison of the expressions in 𝑢 = 2 and ̅̅̅
𝑢2 = then gives the important result that
𝐿𝑚 𝑚𝛽
𝐿 1
𝛽= =
𝑅𝑇 𝑘𝐵 𝑇

RVM Lecture Manual: Physical Chemistry 1 22

 Where R/L has been written as 𝑘𝐵 , which is called the
Boltzmann constant. Equation
𝑚𝑢2 𝛽
−
𝑑𝑁 4𝜋𝐵3 𝑒 2 𝑑𝑢
= 𝑚𝑢2 𝛽
may thus be written as
𝑁 ∞ −
4𝜋𝐵3 ∫0 𝑒 2 𝑑𝑢
𝟑 𝟐
𝒅𝑵 𝒎 𝒎𝒖
𝟐 −
= 𝟒𝝅 ( ) 𝒆 𝟐𝒌𝑩 𝑻 𝒖𝟐 𝒅𝒖
𝑵 𝟐𝝅𝒌𝑩 𝑻
This is usually known as the Maxwell distribution law.
Figure 1.11 shows a plot of (1/N)(dN/du) for oxygen gas at
two temperatures. Near the origin the curves are parabolic because
of the dominance of the u2 term in the equation, but at higher speeds
the exponential term is more important. Note that the curve
becomes much flatter as the temperature is raised. Indicated on the
curve for 300K are the root mean square speed √̅̅̅ 𝑢2 , the average
speed 𝑢̅ , and the most probable speed 𝑢𝑚𝑝 . The mean-square speed is Figure 1.11. The Maxwell
given in equation 𝑢 ̅̅̅2 = 3 , and insertion of 1 for 𝛽 gives the distribution of molecular speeds
𝑚𝛽 𝑘𝐵 𝑇 for oxygen at 300K and 1500 K.
expression in Table 1.3; the root-mean-square speed is its square Note that the areas below the two
root. The mean speed or average speed is given by curves are identical since the total
∞
𝑑𝑁 number of molecules is fixed.
𝑢̅ = ∫ 𝑢
0 𝑁
3 𝑚𝑢2
𝑑𝑁 𝑚 2 −
Insertion of = 4𝜋 ( ) 𝑒 2𝑘𝐵 𝑇 𝑢2 𝑑𝑢 and integration leads to the expression in Table 1.3. The
𝑁 2𝜋𝑘𝐵 𝑇
most probable is the speed at the maximum of the curve and is obtained by differentiating (1/N)(dN/du)
with respect to u and setting the result equal to zero. The resulting expression for this quantity is also given in
Table 1.3

TABLE 1.3 QUANTITIES RELATING TO THE MAXWELL DISTRIBUTION OF MOLECULAR SPEEDS

̅̅̅ 3𝑘𝐵 𝑇
MEAN-SQUARE SPEED 𝑢2 =
𝑚
3𝑘𝐵 𝑇
SQUARE ROOT OF THE MEAN-SQUARE SPEED √̅̅̅
𝑢2 = √
𝑚

8𝑘𝐵 𝑇
AVERAGE SPEED 𝑢̅ = √
𝜋𝑚

2𝑘𝐵 𝑇
MOST PROBABLE SPEED 𝑢𝑚𝑝 = √
𝑚
3
AVERAGE TRANSLATIONAL ENERGY 𝜖̅ = 𝑘𝐵 𝑇
2

3.8 THE DISTRIBUTION OF TRANSLATIONAL ENERGY

3 𝑚𝑢2
𝑑𝑁 𝑚 2 −
We can convert = 4𝜋 ( ) 𝑒 2𝑘𝐵 𝑇 𝑢2 𝑑𝑢 into an equation for the energy distribution. We start
𝑁 2𝜋𝑘𝐵 𝑇
with
1
∈= 𝑚𝑢2
2
And differentiation gives
1
𝑑∈ 2∈ 2 1
= 𝑚𝑢 = 𝑚 ( ) = (2 ∈ 𝑚)2
𝑑𝑢 𝑚
3 𝑚𝑢2
− 1
𝑑𝑁 𝑚 2
We can therefore replace du in = 4𝜋 ( ) 𝑒 2𝑘𝐵 𝑇 𝑢2 𝑑𝑢 by 𝑑 ∈/(2 ∈ 𝑚)2 and u2 by (2 ∈/𝑚) ,
𝑁 2𝜋𝑘𝐵 𝑇
and we obtain

RVM Lecture Manual: Physical Chemistry 1 23

 3
𝑑𝑁 𝑚 𝜖 2𝜖
2 −
= 4𝜋 ( ) 𝑒 𝑘𝐵𝑇 1 𝑑𝜖
𝑁 2𝜋𝑘𝐵 𝑇
𝑚(2𝜖𝑚)2
𝟐𝝅 𝝐 𝟏
−
= 𝒆 𝒌𝑩 𝑻 𝝐𝟐 𝒅𝝐
𝟑
(𝝅𝒌𝑩 𝑻)𝟐
This is often known as the Maxwell-Boltzmann distribution Law

EXERCISES:

1. By what factor are the root-mean-square speeds changed if a gas is heated from 300 K to 400 K?
2. Calculate the mean free path of Ar at 20 °C and 1.00 bar. The collision diameter d = 3.84 × 10–10 m. In
interstellar space it is estimated that atomic hydrogen exists at a concentration of one particle per cubic
meter. If the collision diameter is 2.5 × 10–10 m, calculate the mean free path λ. The temperature of
interstellar space is 2.7 K.
3. What is the mean speed, K, of N2 molecules in air at 25°C?
4. The best laboratory vacuum pump can generate a vacuum of about 1 nTorr. At 25°C and assuming that air
consists of N2 molecules with a collision diameter of 395 pm, calculate (a) the mean speed of the
molecules, (b) the mean free path, (c) the collision frequency in the gas.
5. At what pressure does the mean free path of argon at 25°C become comparable to the diameters of the
atoms themselves?
6. At an altitude of 15 km the temperature is 217 K and the pressure 12.1 kPa. What is the mean free path of
N2 molecules? (σ =0.43 nm2.)
Use the Maxwell distribution of speeds to estimate the fraction of CO2 molecules at 300 K that have
speeds in the range 200 to 250 m/s.
7. Hydrogen gas has a molecular collision diameter of 0.258 nm. Calculate the mean free path of hydrogen at
298.15 K and (a) 133.32 Pa, (b)101.325 kPa, and (c) 1.0 x 108 Pa.
8. The speed that a body of any mass must have to escape from the earth is 1.07 x 10 4 m/s. At what
temperature would the average speed of (a) an H2 molecule, and (b) an O2 molecule be equal to this
escape speed?

RVM Lecture Manual: Physical Chemistry 1 24