Unit 8 Kinetic Theory of Gases

UNIT 8
KINETIC THEORY OF GASES

Structure
8.1 Introduction
8.7 Ideal Gas Equation
Expected Learning Outcomes
Calculation of Average Kinetic
8.2 Recapitulating Gas Laws
Energy
Boyle‟s Law
Calculation of Number Density and
Charles‟ Law Concentration
Gay Lussac‟s law Calculation of Mean Square Speed
Avogadro‟s Law and Root Mean Square Speed

8.3 Equation of State for Ideal 8.8 Distribution of Molecular

Gases Speeds

8.4 Dalton‟s Law of Partial 8.9 Principle of Equipartition of

Pressure Energy

8.5 Kinetic Theory of Gases 8.10 Intermolecular Collisions

Resolution of Molecular Velocities 8.11 Mean Free Path

Mean Square Speed 8.12 Summary

8.6 Derivation of The Expression 8.13 Terminal Questions

for Pressure of A Gas 8.14 Answer

8.1 INTRODUCTION
Chemistry may be defined as the study of matter in terms of its structure,
composition and properties. You know that under ordinary conditions of
pressure and temperature, matter exists in three states, viz., solid, liquid and
gas. For example, at ordinary pressures, H2O can exist as ice, water or steam
depending on the temperature. The behaviour of matter in these three states
is quite different due to the extent of interaction between the constituent
species. The gases behave quite different from solids and liquids in which
these interactions are relatively stronger. The solids and liquids are sometimes
referred to as condensed states. It is important to note that the physical
properties of different gases are generally similar and can be expressed in
terms of simple laws. 7
Block 1 States of Matter

In this and the next unit you would learn about the behaviour of gases from
kinetic theory approach. This approach considers a gas to be a collection of a
large number of identical particles (atoms or molecules), that are in constant,
and random motion. This theory is based on a set of postulates and explains
the macroscopic properties like, pressure, volume and temperature of the gas.

We would begin the unit by recalling different gas laws formulated on the basis
of extensive experimental studies of gases. These laws provide
interrelationships between different properties of gases and can be combined
to formulate an equation of state for ideal gases. Having done so, we would
introduce the kinetic theory of gases in terms of its postulates. These would
then be used to derive an expression for the pressure of the gas in terms of
molecular velocities and collisions between the molecules. This equation is
quite useful in calculating the parameters such as pressure, average kinetic
energy etc. of the gas molecules. The principle of equipartition of energy and
the distribution of molecular speeds and the dependence of molecular speeds
on temperature will also be discussed. Finally, the equations for calculating the
collision number and the mean free path of molecules of a gaseous sample
will be derived. In the next unit, the deviation from ideal behaviour and the
behaviour of real gases shall be taken up for discussion.

Expected Learning Outcomes

After studying this unit, you should be able to:
 state and explain the gas laws;
 derive the ideal gas equation from gas laws;
 calculate one of the unknowns amongst pressure, volume, temperature
or amount of a gas using the ideal gas equation;
 state Dalton‟s law of partial pressures;
 state postulates of kinetic theory of gases and derive the equation
1
pV  m N u 2 ;
3
 explain the distribution of molecular speeds;
 calculate the most probable speed, the average speed and the root
mean square speed of the molecules of a gas;
 state and explain the principle of equipartition of energy;
 derive an expression to calculate the collision number between gas
molecules; and
 define mean free path and calculate the mean free path of molecules in
a gaseous sample.

8.2 RECAPITULATING GAS LAWS

Some of the earliest experimental measurements on pressure, volume and
temperature (p-V-T) were made on air at atmospheric pressure and room
8 temperature. Fortunately, under these conditions air behaves nearly as an
Unit 8 Kinetic Theory of Gases
ideal gas. This helped a lot in the formulation of the gas laws. You would have
studied Boyle‟s law, Charles‟ law and Avogadro‟s law in your previous classes.
These provide quantitative relationship between different properties of gases.
These properties are recognised in terms of four physical quantities viz.,
pressure, temperature, volume and amount of the gas. We shall recapitulate
the gas laws after stating the SI units of pressure, volume and temperature.

Pressure: The SI unit of pressure is pascal (Pa). It is the pressure of one

5
newton per square metre (N m-2), or, in terms of SI base units, it equals one 1 bar = 10 Pa
kilogram per metre per second squared (1 kg m-1s-2).It‟s equivalence with other
units of pressure is as follows:

1 atmosphere = 1 atm = 760 mm Hg = 760 Torr

= 1.0132  105 Pa = 1.0132 bar

Volume: The SI unit of volume is cubic metre or metre cube (m3). Other
equivalent units are given below:

1 m3 = 103 dm3 = 103 L = 106 cm3 = 106 mL

In the above expression „L‟ stands for litre.

Temperature: The SI unit of temperature is kelvin (K). To convert temperature

from Celsius scale into Kelvin scale, 273.15 is to be added to the former e.g.,
25oC would be 298.15 K.

Let us now state and explain the gas laws.

8.2.1 Boyle’s Law

It is a relation between pressure and volume of a gas at a given temperature
formulated by the physicist Robert Boyle in 1662. It states that at constant
temperature T, the volume, V, of a fixed amount of gas varies inversely as its
pressure, p.

1
i.e., V (T , n  constant) …(8.1)
p

or pV  K 1 (T , n  constant) …(8.2)

Here K1 is a constant at a given temperature for a fixed amount of the gas.

This implies that for a given amount of gas at a constant temperature the
product of pressure and volume is a constant. This can be represented as

p1V1 = p2V2. …(8.3)

This type of behaviour of a gas is shown graphically in Fig. 8.1.The p versus V

plot (Fig. 8.1 (a)) at constant temperature is called an isotherm and
resembles a hyperbola. You may note that doubling the pressure reduces the
volume to half.

Alternatively, the graphical representation of Boyle‟s law can be done in terms

of a plot between pressure and 1/V as shown in Fig. 8.1 (b)) which gives a
straight line. 9
Block 1 States of Matter

Fig. 8.1: p-V isotherms: a) variation of the volume of a gas with the pressure
exerted on the gas, at constant temperature and b) p versus 1/V plot for
a gas at constant temperature.

8.2.2 Charles’ Law

It relates the volume and temperature of a gas at constant pressure and was
discovered in 1787 by the French physicists Jacques Charles. The law states
that for a certain amount of gas at a constant pressure, its volume (V) is
directly proportional to its absolute temperature (T).
i.e., V  T ( p, n  constant) …(8.4)

V V1 V 2
or V  K 2T or  constant or  …(8.5)
T T1 T 2

where K2 is constant for a given pressure and amount of gas and it does not
depend on the identity of the gas. The variation of volume with temperature at
different constant pressures is given in Fig. 8.2. For a given pressure the plot
is a straight line and is known as an isobar.

Fig. 8.2: Isobars relating volume of a gas with temperature at different

pressures.

The law implies that if you increase the volume of a certain amount of gas at
constant pressure then it must be accompanied by an increase in the
temperature. Although most gases follow Charles‟s law to a good extent
however they deviate from it at high pressures and low temperatures. You
may also note that all the isobars extrapolate to a constant temperature of -
10 273.15 oC i.e., the absolute zero.
Unit 8 Kinetic Theory of Gases
8.2.3 Gay Lussac’s Law
The Gay-Lussac‟s law (or Amonton's law) relates the pressure of a gas with
its absolute temperature at constant volume. Sometimes this law is called
pressure law and it states that the pressure of a given mass of gas varies
directly with the absolute temperature of the gas when the volume is kept
constant i.e.,
p  T (V , m  constant) or p  K 3T …(8.6)

Thus, if we increase the temperature of a gas keeping the mass and volume of
the gas constant then its pressure would also increase.

8.2.4 Avogadro’s Law

According to Avogadro‟s hypothesis equal volumes of all the gases contain
equal number of molecules under the same conditions of temperature and
pressure. In other words,
Avogadro number is
V  N ( T , p  constant) …(8.7) equal to 6.022  10
23

and has no units.

where N is the number of molecules in a volume V. We know that the number Avogadro constant is
of moles (n) is related to the number of molecules (N) as per the following equal to
6.022  10 mol1.
23
equation,
N
n …(8.8)
NA

Where, NA is Avogadro constant (6.022  1023 mol1). Using Eq. 8.7 and
Eq.8.8, we can write that at constant temperature and pressure,
V  n or V  K  n ( p,T  constant) …(8.9)

This gives us the Avogadro’s law which states that at constant temperature It is important to know
and pressure, the volume of a gas is proportional to the number of moles of the difference
the gas. In other words, equal amount of two gases would occupy same between STP and
volume at the same temperature and pressure. NTP.

The constant of proportionality in Eq. (8.9), K is equal to the volume per mole STP: Standard
of gas and is called molar volume. The molar volumes of all gases for given Temperature and
Pressure and 273.15
values of T and p are approximately equal. The conditions of temperature of 5
5
K and 10 Pa
273.15 K and a pressure of 10 Pa (1 bar) respectively are called standard respectively.
temperature and pressure, often abbreviated as STP. The molar volume of a
gas is approximately 22.71 L at STP. NTP: Normal
Temperature
It is important to know the difference between STP and the earlier term NTP. Pressure are 293.15
The Normal Temperature and Pressure (NTP) are 293.15 K (i.e., 20oC) and K and 1 atm (101.325
1 atm (101.325 kPa). The molar volume of a gas is approximately 22.41 L at kPa) respectively.
NTP. IUPAC recommends the unit of pressure to be Pa and recommends to
use standard pressure of 1 bar (105 Pa) rather than earlier term atm
(101.325 kPa).

Using the above gas laws, we can arrive at the ideal gas equation. Let us see
how? 11
Block 1 States of Matter

8.3 EQUATION OF STATE FOR IDEAL GASES

The three gas laws explained above can be summarised as
1
Boyle‟s law: V  (T , n  constant) …(8.1)
p
Charles law: V  T ( p, n  constant) …(8.4)
Avogadro‟s law: V  n ( p,T  constant) …(8.7)

These laws can be combined to give the combined gas law i.e.,
nT
V …(8.10)
p
This can be rearranged to
pV  nRT …(8.11)

Where, R is the gas constant. Eq. 8.11 is known as the equation of state for
an ideal gas. The state of the gas is its condition at a given instance i.e., under
given set of conditions. A particular state of a gas is described by its pressure,
volume, temperature and the amount. An ideal or a perfect gas is a
hypothetical gas whose pressure-volume-temperature behavior can be
completely accounted for by the ideal gas equation. Knowledge of any three of
its properties is enough to define the state of the gas completely, since the
fourth property can then be determined using Eq. 8.11. However, if in some
case, there are changes in pressure, volume, and temperature, or even in the
amount of gas then we must use a modified form of the ideal gas equation
involving the initial and final conditions. We can write,
pV p 2V 2
R  1 1 (before change) and R (after change) … (8.12)
n1T1 n 2T 2

Equating the two, we get

p1V1 p 2V 2 … (8.13)

n1T1 n 2T 2

For fixed amount of a gas, it becomes

p1V1 p 2V 2 … (8.14)
 ( n  constant)
T1 T2

Let us now discuss the units of the gas constant, R.

From Eq. 8.11 we can write,
pV
R
nT
Substituting the values of p,V, n and T for one mole of a gas at STP, we get
(1 bar ) (22.71 L)

(1 mol) (273.15 K)

Simplifying, we get
L. bar
 0.08314  0.08314 L.bar K -1 mol -1
K.mol

12 = 0.08314 L bar K1 mol1.

Unit 8 Kinetic Theory of Gases
1
The gas constant, R has the dimension of (energy) (amount of substance)
(temperature)1.The values of R in other units are given below:
In SI units,
R = 8.314 J K1mol1 the value of R is
= 8.314  107 erg K1mol1 8.314 J K1mol1, we
will be using this
= 1.987 cal K1mol1
value throughout this
Calculations Using Ideal Gas Equation course.

The ideal gas equation (Eq. 8.11) is useful in calculating any of the unknowns
amongst pressure, volume, temperature or the amount of gases from three of
the other known quantities. Let us illustrate this by taking some examples.

Example 8.1: Calculate the volume occupied by 0.0660 kg of carbon dioxide

gas at a temperature of 300.2 K and a pressure of
9.41  104 Pa assuming ideal behavior for the gas.
Solution: From Eq. (8.11) we have pV  nRT

This can be rearranged as: V  nRT

p

We are given the values of pressure and temperature; R is a constant so we

need to know the number of moles of given sample of carbon dioxide to
calculate the volume.
Mass of carbon dioxide
Number of moles of carbon dioxide ( n ) 
Molar mass of carbon dioxide
0.0660 kg
  1.5 mol
0.044 kg mol 1

Substituting the values of different quantities in the rearranged gas equation, 1J 1kg m 2 s 2

we get 1Pa 1kg m 1 s  2
1.5 mol   ( 8.314 J K 1mol 1 )  (300.2 K )
 0.0398 m 3
V
 1m 3
9.41 10 4 Pa

Thus, carbon dioxide under given set of conditions would occupy a volume of Also 1J  1 Pa
3
1m
0.0398 m3.

Example 8.2: If one mole of nitrogen gas occupied a volume of 25 dm3 at a

temperature of 300 K, calculate its pressure assuming ideal
behavior for the gas.
Solution: From Eq. (8.11) we have pV  nRT

This can be rearranged as: p  nRT

V

We are given the values of n , V and T; R is a constant so we can substitutes

these values and get the value of pressure.
1.0 mol   ( 8.314 J K 1mol 1 )  (300 K )
p  p  9.977 10 4 Pa
3 3 3 -3
25 dm  10 m dm

4
Thus, the pressure of nitrgen gas would be 9.977  10 Pa
13
Block 1 States of Matter

Using the ideas developed above; attempt the following simple questions to
assess your learning.

SAQ 1
Calculate the density of oxygen gas at 273.2 K and 1.013 105Pa, assuming
ideal behavior. (Given: Mm (O2) = 0.032 kg mol-1)
(Hints: (i) Number of moles = Mass/Molar mass
(ii) Density = Mass/Volume

SAQ 2
How many molecules of oxygen are present in 0.0032 kg of the gas?

8.4 DALTON’S LAW OF PARTIAL PRESSURES

We have so far discussed about the behavior of pure gases. However, many a
times we deal with mixtures of gases e.g., air. How can we explain the
pressure-volume-temperature relationship of a sample of air or any other
mixture containing several gases? In such cases, the total gas pressure is
related to partial pressures, that is, the pressures of individual gas
components in the mixture. This law is known as Dalton‟s law of partial
pressures. It states that at constant temperature, the total pressure exerted by
a mixture of non-reactive gases behaving ideally, is the sum of the pressures
exerted by the individual gases occupying the same volume alone. The
individual pressure of a gas in a mixture of gases is called its partial pressure.
The essential condition is that the gases should not react chemically.

Mathematical form of Dalton’s law

Let us consider three ideal gases, A, B and C. Let the pressure of the gases
be pA, pB and pC, respectively when each of them is kept individually at a
temperature T and volume V. Let us now force these gases into a vessel of
volume V at the same temperature. According to Dalton‟s law of partial
pressures, the total pressure (pt) of the mixture of gases is given by
p t  p A  pB  pC …(8.15)

Using Eq. 8.11 for each of the gases, we can write

n RT
pA  A …(8.16)
V
n RT
pB  B …(8.17)
V
n RT
and pC  C …(8.18)
V

Substituting Eq. 8.16 to 8.18, in Eq. 8.15, we get,

RT
p t  ( n A  nB  n C ) …(8.19)
14 V
Unit 8 Kinetic Theory of Gases
Since the total number of moles of the gases is equal to the sum of the
number of moles of each component, i.e. nt = nA + nB + nC. we can write,
n t RT
pt  …(8.20)
V
Dividing Eq. 8.16 to Eq. 8.18 by Eq. 8.20 and rearranging we get, pA RT V
 nA  
n pt V RTn t
p A  A pt …(8.21)
nt n
p A  A  pt
n nt
pB  B pt …(8.22)
nt

n
and pC  C p t …(8.23)
nt
The mole fraction is a
n n n
The terms A , B and C are called the mole fractions of gases A, B and dimensionless
nt nt nt quantity that
C, respectively in the mixture and are represented as xA, xB and xC expresses the ratio of
respectively. the number of moles
of one component to
Thus, the Eq. 8.21 to 8.23 can be rewritten as, the number of moles
pA  x A pt of all components
…(8.24)
present.
pB  x B p t …(8.25)
pA  xC pt …(8.26)
In other words, the partial pressure of a gas in a gaseous mixture is given
by the product of its mole fraction in the mixture and total pressure.

You may remember that in a mixture of gases, the sum of partial pressures of
different gases must equal the total pressure of the gas and the sum of mole
fractions of all the gases must be equal to 1. Let us take an example to see
the application of Dalton‟s law of partial pressures.

Example 3: At 298 K, 0.002 m3 of helium gas at a pressure of 105 Pa is

mixed with 0.003 m3 of neon gas at a pressure of 1.5  105 Pa.
Calculate the following
i) the mole fractions of the gases
ii) total pressure, and
iii) partial pressures of the two gases
Solution: i) In order to compute the mole fractions we need to first know
about the number of moles of the two gases.
From Eq. (8.11) we have pV  nRT
pV
This can be rearranged as: n 
RT

We are given the values of p , V and T; R is a constant so we can substitutes

these values and get the value of number of moles as follows

(1.5  105 Pa)  (0.002 m3 )

n (He)   0.0802 mol 1 Pa = 1 Jm3
(8.314 J K 1 mol1 )  (300 K )
15
Block 1 States of Matter

(1.5  105 Pa)  (0.003 m3 )

n (Ne)   0.1804 mol
(8.314 J K 1 mol1 )  (300 K )

Total number of moles = nt = 0.0802 + 0.1804 = 0.2606

The mole fractions can be calculated as follows
n 0.0802
x (He)  He   0.3077
nt 0.2606

n 0.1804
x (Ne)  Ne   0.6923
nt 0.2606

n t RT
ii) According to Eq. (8.20) p t 
V

Substituting the values we get,

pt 
0.2606 mol   ( 8.314 J mol 1 K 1 )  (298 K )
 1.29  10 5 Pa
3
0.005 m
n
iii) According to Eq. (8.21), the partial pressure is given as p A  A pt
nt
Substituting the values,
0.0802
p He   (1.29  10 5 Pa)  3.96  10 4 Pa
0.2606
0.1804
pNe   (1.29  10 5 Pa)  8.93  10 4 Pa
0.2606

Using the above principles, attempt the following simple questions to assess
your learning

SAQ 3
2.00 mol of nitrogen, 1.00 mol of oxygen and 2.00 mol of methane are kept in
a vessel of volume 0.0600 m3 at 250.2 K. calculate the total pressure of the
mixture of gases and the partial pressure of the individual gases using
Dalton‟s law of partial pressures.

SAQ 4
State the name of the gas present in air which has the highest partial
pressure.

8.5 KINETIC THEORY OF GASES

The gas laws discussed so far were arrived at on the basis of experimental
work. The kinetic theory of gases put forward by Maxwell (1860) and
Boltzmann (1867) provided a theoretical explanation for the properties of
gases. Let us first go through the following basic assumptions of the kinetic
16 theory of gases.
Unit 8 Kinetic Theory of Gases
1) A gas is composed of a very large number of tiny molecules. The gas
molecules are far apart from one another in comparison with their own
dimensions. The gas molecules are considered as small hard spheres.
Their volume is negligible compared to the total volume occupied by the
gas. The molecules can be considered to be “point masses”; that is, they
possess mass but have negligible volume

2) The gas molecules are in a state of constant random and rectilinear

motion, i.e., they move in all possible directions with different speeds.
3) During their motion they collide frequently with each other and with the
walls of the container. These collisions are perfectly elastic, which means
that the total kinetic energy of the molecules before and after the collision
is the same. In other words, we can say that the energy can be
transferred from one molecule to another as a result of a collision but, the
total energy of all the molecules in a system remains the same.
4) There are no intermolecular forces between the molecules, i.e., there are
no forces of attraction or repulsion between them.
5) The pressure exerted by the gas is due to the force exerted on the walls
of the container due to non-stop bombardment of the molecules.
6) The absolute temperature of a gas is proportional to the mean kinetic
energy of the molecules present in it.
We shall use these assumptions in the next section. Let us first discuss some
of the features regarding molecular velocities which will be required for
deriving the equation of state for the gases.

8.5.1 Resolution of Molecular Velocities

Velocity (u) is a vector quantity. The components of u in the x, y and z
directions are ux, uy and uz. The speed u is the magnitude of the vector u and
the latter is represented by the distance OC (Fig. 8.3).

Fig. 8.3: Components of velocity, u in x, y and z directions.

The lengths OA, OD and OE represent the x, y and z components of the

velocity vector i.e., ux, uy and uz. Hence, note that OC = u

OA = DB = ux

OD = AB = uy

OE = BC = uz 17
Block 1 States of Matter

CB is perpendicular to xy plane (shaded). Since OB is in xy plane, BC is

perpendicular to OB. Hence, OBC = 90

2
From the right angled triangle OBC, u2 = OC2 = OB2 + BC2 = OB2+ u z

You can see from the diagram that OD is on y axis. Since DB is parallel to x
axis, DB is perpendicular to OD, i.e., ODB = 90
2 2
In the right angled triangle ODB, OB2 = OD2 + DB2 = u y  u x

 u 2  OB2  u z2  u x2  u y2  u z2 …(8.27)

The velocity component like ux can be positive, negative or zero

(corresponding to motion in the positive x-direction, motion in the negative x-
direction or no motion in the x-direction), but the speed, u by definition must be
positive or zero.

8.5.2 Mean Square Speed

All the molecules of the gas do not move at the same speed. As a result, x
components of the velocities of different molecules are different. This is also
2
true of y components and z components of the velocities. If
The bar in u
u12x , u 22x , u 32x , .....u Nx
2
, are the square of the x components of the velocities for
represents the
average of the u
2 2
the molecules, 1, 2, 3, .... N, then the average of these values, u x , is given by,
values.
( u12x  u 2
2  u 2  .....u 2 )
u x2 
x 3x Nx
…(8.28)
N

2
For u y2 and u z also, the expressions similar to Eq. 8.28 can be written.
Further, similar to Eq. 8.27, the average of the square of the molecular
2
speeds, u 2 , is related to u x2 , u y2 and u z as

u 2  u x2  u y2  u z2 …(8.29)

The quantity u 2 is called the mean square speed. Since the gas molecules
are in random motion, no particular direction is preferred. Secondly, since the
2
quantities u x2 , u y2 and u z are equal. Hence, we can write

u x2  u y2  u z2  u 2 /3 …(8.30)

The above equations will be helpful to you in understanding the derivation

described in the next section.

8.6 DERIVATION OF THE EXPRESSION FOR

PRESSURE OF A GAS
Let us consider a cubical container with side „I‟ filled with N gas molecules,
each with mass „m‟. Let us assume that one of the molecules moves in the x
18 direction with velocity component u1x (Fig. 8.4). It will strike the wall at the yz
Unit 8 Kinetic Theory of Gases
plane (shaded face) with momentum mu1x and will suffer an elastic collision so
that it bounces back with a momentum mu1x.

Fig. 8.4: Schematic representation of the motion of a gas molecule in a cubical

box.

The change in momentum of the molecule in one collision is,

mu1x (mu1x) = 2 mu1x. The molecule will travel back towards the opposite
face and strike it. After bouncing back from there it will again travel towards We consider the
the shaded face and strike it again. Thus, this molecule has to travel a momentum change
along x axis only.
distance of 2l before it collides with the shaded face again. Therefore, the time
required for the next collision can be calculated as follows:

The molecule travels a distance of u1x in one second. Hence, to travel a

2l
distance of 2l, the time required  second. That is, the time interval
u1x
2l
required for each successive collision with the shaded face is second.
u 1x
Hence the number of collisions between the molecule and the shaded face
u
taking place in unit time will be the inverse of the above expression, i.e. 1x .
2l

The change of momentum Change of number of collisions a

in one second (or rate of momentum per molecule undergoes
= 
change of momentum) per molecule per with the shaded face
molecule collision in one second
u 1x
= 2 mu 1x 
2l
mu 12x
=
l

As per Newton‟s second law of motion, we know that force = rate of change of
momentum

mu 12x
Hence force due to collisions by one molecule  …(8.31)
l

Similarly we can derive expressions for the force exerted by second, third …..
Nth molecule over the shaded face. The total force (F) exerted by N molecules
over the shaded face can be calculated as follows:
19
Block 1 States of Matter
m 2
F [ u  u 22 y  u 32z  .......  u Nx
2
] …(8.32)
l 1x

From Eq. (8.28), the term in the bracket is equal to Nu x2 .

Substituting it in Eq. (8.32), we get

m
 Nu x2 …(8.33)
l

Using Eq. 8.32, we can write u x2  u 2 / 3

mN u 2
Substituting it in Eq. (8.32), we get F  … (8.34)
3l
Now, we know that pressure (p) is force per unit area (A). The area of the
shaded face is l2. Therefore, we get

F F mN u 2 mN u 2
 p    …(8.35)
A I2 3l . I 2 3l 3

Since for a cube, volume (V) = l3, we can write that

mN u 2
p …(8.36)
3V
1
 pV  mN u 2 …(8.37)
3
We shall use this equation in the next section for calculating the average
kinetic energy, number density, and concentration etc. of the gas molecules.

8.7 IDEAL GAS EQUATION

Although all the gas laws could be derived from Eq. 8.35, we shall derive the
ideal gas equation only and then proceed to calculate different molecular
parameters. Eq. 8.37 can be rewritten as,
2 1 
pV  N  mu 2  …(8.38)
3 2 
From the kinetic theory of gases (postulate 6) it is known that the absolute
temperature of a gas sample is directly proportional to the mean kinetic energy
of the molecules, i.e.,
1
T mu 2
2
1
or mu 2  K1T …(8.39)
2
Where, K1 is a constant.
Substituting this in Eq. 8.38, we obtain,
2
pV  NK1T …(8.40)
3
This can be written as pV  Nk B T …(8.41)
20
Unit 8 Kinetic Theory of Gases
Where, kB is known as Boltzmann constant, and is equal to 2/3K1. The value of
kB is 1.38  1023 JK1. Eq. 8.41 is the ideal gas equation for N molecules. For R is the gas constant
a gas having n moles, the number of molecules N is given by, for one mole and kB is
the gas constant for
N = n NA …(8.42) one molecule.

where NA is Avogadro constant, and it is equal to the number of molecules (or

species) in one mole of a substance. It is equal to 6.022  1023 mol1. Hence
the equation for n moles of the gas can be written by substituting Eq. 8.42 in
Eq. 8.41.

pV = nNAkBT = nRT …(8.43)

where R is equal to NAkB. Eq. 8.43 is the same as Eq. 8.11 which has been
derived in Sec. 8.3. Let us now calculate some parameters of the gas
molecules by the combined use of Eq. 8.37, 8.39, 8.41 and 8.43.

8.7.1 Calculation of Average Kinetic Energy

1
According to Eq. 8.39 we know that the average kinetic energy ( mu 2 ) is
2
given as
1
mu 2  K1T …(8.39)
2
3
We also know that K 1  k B . Substituting it in Eq. 8.39 we get
2

1 3
Average kinetic energy per molecule  m u 2  k BT …(8.44)
2 2

Similarly, average kinetic energy per mole can be obtained by multiplying the
expression with Avogadro‟s constant, NA and simplifying as given below

1  3 
 ( N A )  m u 2   ( N A )  k BT 
 2   2 

3
 N A k BT
2

3
 RT (R  N A k B ) …(8.45)
2

The energy calculated using this expression is also called the translational
energy; this energy is due to the motion of the molecules in space.

Let us take an example to understand the use of Eq. 8.44 and Eq. 8.45

Example8.4: Calculate the average translational energy i) per molecule and ii)
per mole of a gas at 300 K.

Solution: According to Eq. 8.44, the translational energy per molecule is

given as
21
Block 1 States of Matter
1 3
Translational energy per molecule  m u 2  k BT
2 2
Substituting the value of Boltzmann‟s constant and temperature we get
3
  1.38  10  23 JK 1  300 K
The kinetic energy of 2
a gas is due to 21
random motion of the Simplifying we get Translational energy per molecule  6.21 10 J mol 1
gas molecules. This is
also called thermal ii) Similarly, the translational energy per mole of gas can be obtained by
energy. Temperature using Eq. (8.45). Substituting the value of Boltzmann‟s constant and
is a measure of temperature we get
kinetic (or thermal)
energy. 3
Translational energy per mole   8.314 J K 1mol 1  300 K
2

3 1
Simplifying we get Translational energy per mole  3.74  10 J mol

8.7.2 Calculation of Number Density and Concentration

Number density (no) is defined as the number of molecules of a gas in unit
volume. It can be calculated by rearranging Eq. 8.41 as follows.

N p
Number density of a gas (no)   …(8.46)
V k BT

Similarly, concentration (c), defined as the number of moles of a gas in unit

volume, can be calculated by rearranging Eq. 8.43.

n p
Concentration of a gas (c)   …(8.47)
V RT

Thus, we note that the number density and the concentration of a gas depend
on its pressure and the temperature. It is directly proportional to the pressure
and inversely proportional to the temperature. Let us apply Eq. (8.46) and Eq.
(8.47) to calculate the number density and concentration of a gas at a
temperature of 298.2 K and pressure of 1.013  105 Pa.

Number density (no) of gas molecules at given temperature and pressure can
be obtained by substituting the values of different terms in Eq. 8.46.

p 1.013  10 5 Pa
n0  
k BT 1.38  10  23 J K 1  298.2 K

 2.462  10 25 m 3
Similarly, the concentration (c) of gas molecules at given temperature and
pressure can be obtained by substituting the values of different terms in
Eq. (8.47)

p 1.013  10 5 Pa
   40.86 mol m 3
RT 8.314 J K 1mol 1  298.2 K
22
Unit 8 Kinetic Theory of Gases
Let us take up the calculation of mean square speed and root mean square
speed

8.7.3 Calculation of Mean Square Speed and Root

Mean Square Speed
2
In Subsec 8.6.2, we have defined mean square speed ( u ). The square root
of its value is called root mean square speed and is represented as urms. For For 1 mol, n =1
one mole of the gas, we can write by combining Eq. (8.37) and Eq. (8.43),
N = NA
M u 2  n  1 and 
pV  RT  m  
3  M m  m N  Molar mass  m NA= Mm

3RT
i.e., mean square speed (u 2 )  …(8.48)
Mm

3RT
Root mean square speed  u 2   u rm s  …(8.49)
  Mm

Let us take an example to see the application of Eq. (8.49)

Example 8.5: Calculate the root mean square speed (urms) of methane
molecules at 515 K. (Given Mm (CH4) = 0.016 kg mol-1).

Solution: Substituting the values of different terms in Eq. 8.49 we get

1J 1 kg m 2 s  2
1 1 
3 RT 3  8.314 J K mol  515 K 1 kg 1 kg
u rms  
Mm 0.016 kg mol -1

 8.96  10 2 m s 1  1 m 2 s  2  1 m s 1

Thus, the root mean square speed of methane molecules at 515 K would be

 8.96  10 2 m s 1
Air has average molar
Using the above example answer the following simple question. mass of 0.029 kg
mol1. At room
SAQ 5 temperature (300 K),
urms of air molecules
Calculate the root mean square speed of hydrogen molecules at 500 K. (Molar is 510 ms1.
mass of hydrogen = 0.002 kg mol1)

8.8 DISTRIBUTION OF MOLECULAR SPEEDS

A fundamental assumption of the kinetic theory of gases is that the molecules
of the gas are in random and continuous motion. The molecules, however, do
not move with constant velocity throughout. They travel with changing
velocities due to the large number of collisions. Since velocity is a vector
quantity and the molecules are in random motion, the average velocity is zero.
But the speed of the molecules is not a vector quantity and hence the average
speed is a finite quantity. Since there are a large number of molecules in any
23
Block 1 States of Matter

sample of a gas, there will be different numbers of molecules having different

speeds.

A typical distribution of the speeds of the molecules of nitrogen gas at 273 K is

shown in Fig. 8.5.

Sound waves are

caused by the
oscillations of the air
molecules. Hence,
speed of the sound
waves cannot be
more than the urms of
the air molecules. The
speed of sound in air Fig. 8.5: Distribution of speeds of nitrogen molecules at 273 K.
is 340 ms1 (i.e.,
around two thirds of Here the number of molecules having a particular speed is plotted against
urms of air molecules). speed. The curve is not symmetrical and shows that there are more molecules
with higher speeds than the ones with the lower speeds. Very few molecules
have extremely small or extremely high speeds. The distribution is
characterised by most probable, average and root mean square speeds.
These are defined below:

i) The most probable speed, ump, is that which the largest fraction of
molecules possesses. It corresponds to the maximum in the distribution
curve for speeds (Fig. 8.5).

ii) The average speed u , (also called the mean speed) is defined by the
equation:

1
u (u1  u 2  u3  ......  uN ) …(8.50)
N

Here, u is the average speed of N molecules.

iii) The root mean square speed, urms, is defined by the equation:

1 2
urms  u 2  ( u  u 22  u 32  .....  u N
2
) …(8.51)
N 1

Maxwell and Boltzmann derived an expression for the distribution of molecular

speeds. Using this expression, it is possible to derive the following
relationships between molar mass and the three types of speeds:

2RT
ump  …(8.52)
Mm

8 RT
u …(8.53)
M m

3 RT
urm s  …(8.54)
24 Mm
Unit 8 Kinetic Theory of Gases
Let us calculate the average speed of nitrogen molecules at 298.2 K using
Eq. (8.53). Average speed (u ) of nitrogen molecules at 298.2 can be
obtained by substituting the values of R, T,  and Mm, in Eq. (8.53).

8 RT 8  8.314 J K 1mol 1  298.2 K

 
Mm 3.142  0.028 kg mol 1

u  474.8 m s 1

A change in temperature affects the molecular speed distribution curve. The

distribution curves for nitrogen gas at temperatures of 100, 300 and 700 K are
shown in Fig. 8.6.

Fig. 8.6: Distribution of speeds of nitrogen molecules at three different

temperatures.

From the above curves, it can be seen that at higher temperatures (i) the most
probable speed is higher (ii) the fraction of the molecules possessing the most
probable speed decreases and (iii) the distribution of the molecular speeds
changes such that the spread is broader, compared to the distribution at lower
temperatures. Using the principles discussed above, answer the following
simple question.

SAQ 6
Calculate the ratio ump : u : urms for a gas of molar mass Mm. Does the value
of this ratio depend on temperature?

8.9 PRINCIPLE OF EQUIPARTITION OF ENERGY

In Subsec 8.8.1, we showed that the translational kinetic energy per mole is
3
RT . Likewise we can calculate the contribution to energy arising out of
2
rotation and vibration of molecules. Each mode of motion is called a degree of
freedom. All gaseous molecules have three translational degrees of freedom.
This is so since the translational motion is described by three independent
coordinates. 25
Block 1 States of Matter

Apart from the translational degrees of freedom a linear molecule has two
rotational degrees of freedom since rotation is possible only around the two
axes perpendicular to its molecular axis. A non-linear molecule can rotate
around all the three mutually perpendicular axes and hence has three
rotational degrees of freedom.

A molecule having F atoms (i.e., atomicity is F) has totally 3F degrees of

freedom because 3F coordinates are required to locate their nuclei in space.
That is, the sum of translational, rotational and vibrational degrees of freedom
for a molecule is 3F. The vibrational degrees of freedom for linear and non-
linear molecules can be calculated using the following expression:

Vibrational degreesof freedom   3F  (sumof translational and rotational


of a molecule having F atoms  degrees of freedom)

Hence, a linear molecule has 3F  (3 + 2) = 3F  5 vibrational degrees of

freedom. But a non-linear molecule has 3F  (3 + 3) = 3F  6 vibrational
degrees of freedom. For example, carbon dioxide (F = 3, a linear molecule)
has [(3  3)  5] = 4 vibrational degrees of freedom and water (F = 3, a non-
linear molecule) has [(3  3)  6 = 3] vibrational degrees of freedom.

So far, we have calculated the degrees of freedom for each kind of motion. We
can calculate the energy of molecules due to each kind of motion using the
equipartition theorem of classical physics. This theorem can be stated as
follows:

“The average energy of each different mode of motion of one mole of

1
molecules is RT.”
2

Thus each translational and rotational degree of freedom contributes energy

1
equivalent to RT to the energy of one mole of molecules. But each
2
vibrational degree of freedom must contribute RT to the energy. This is
Molar heat capacity is because vibrational motion has both potential and kinetic energy associated
the quantity of heat 1
with it and each contributes RT to energy.
required to raise the 2
temperature of one
mole of a substance Using this principle, the total energy (U) of the gaseous molecules can be
through one degree calculated. From the values of U at different temperatures, molar heat capacity
kelvin values at constant volume (Cv ) and at constant pressure (C p ) can be
Molar heat capacity = calculated using the following expressions.
Molar mass  specific
 U  … (8.55)
heat Cv   
 T v
C p ,Cv and R have … (8.56)
C p  Cv  R
the same units, viz.,
J K1 mol1. The contribution RT to energy due to each vibrational degree of freedom is
significant only at high temperatures. At room temperature we need to
26 consider the contributions due to translational and rotational degrees of
Unit 8 Kinetic Theory of Gases

freedom only. This is evident from the molar heat capacity values and C p / Cv
ratios of some gases at 298 K given in Table 8.1. Classical physics cannot
explain as to why contributions of vibrational degrees of freedom to heat
capacity values is significant only at high temperatures

This can be explained this using the principles of quantum mechanics, which
you have learnt in BCHCT-131 course. However, this is beyond the scope of
this course.

Table 8.1: C p and Cv values and their ratio at 298 K

Type of the Example Degrees of U* Cv Cp Cp

molecule freedom 1 1 1
J mol J mol K J mol 1 K 1 CV

Monoatomic Helium 3 (translational) 3 3 5 1.66

RT R R
gas 2 2 2
Diatomic gas Carbon 3 (translational) 3 5 7 1.40
RT RT RT
monoxide 2 5 2 2
RT
2 (rotational) 1 2
2 RT
2
1 (vibrational -----
not active at
298 K)
Non-linear Water 3 (translational) 3 3R 4R 1.33
RT
triatomic 2
molecule 3RT
3 (rotational) 1
3  RT
2
3 (vibrational ----
not active at
298 K)

Using the ideas given above, answer the following SAQ.

SAQ 7
The specific heat capacity of a gas at constant volume at 298 K is 692 J kg1
K1 and its molar mass is 0.018 kg mol1. What is the value for C p / Cv ratio
for the gas? (Hint: Cv  specific heat at constant volume  molar mass)

8.10 INTERMOLECULAR COLLISIONS

A cubic meter of nitrogen gas at room temperature and pressure contains
about 2.462  1025 molecules (Subsec. 8.7.2) moving with an average speed
of 474.8 m s1 (Sec. 8.8). In a gas, the molecules are not only in continuous
motion, but also are constantly colliding with one another. Because of
collisions, a molecule changes its direction often and moves in a zigzag way.
The path of such a molecule can be imagined (as shown in Fig. 8.7) to be
within a cylinder. An estimate of the number of collisions taking place in one
27
Block 1 States of Matter

second in unit volume (known as total collision frequency) can be made by

introducing the concept of molecular size. For the sake of simplicity, the gas
molecules are considered to be hard spheres with diameter . Thus, two
molecules will collide with each other („hit‟) if they are within a distance . If the
distance is more than , the two molecules do not collide(„miss‟) Fig. 8.7
depicts the motion of a molecule and indicates the condition under which it hits
or misses another molecule.

Fig. 8.7: The motion of molecule in a cylinder.

Since the average speed of a molecule is u , it covers a distance equal to u in
one second. Due to its zigzag motion, all molecules present in the cylinder
Collision density is an with base equal to2 collide with the moving molecule. The volume covered
important parameter by the molecule in one second is given by Eq. 8.51.
in deciding the
reaction rate. We
shall study this in the
Volume covered by the molecule in one second = base of the cylinder  height
unit on chemical
kinetics.
  2 u …(8.57)

We know that the number of molecules present per unit volume (number
density) is no. The collision frequency for a single molecule (z1(1)) is equal to
the number of collisions a molecule undergoes in one second. It is given by
the product of the volume covered by the molecule in one second and the
number density.

z1 (1)   2 uno …(8.58)

In the derivation of Eq. 8.58, we have assumed that only one molecule moves
and the others are static. In reality, all the molecules are moving. To account
for this fact, the relative average speed u 2 should be used instead of u in
Eq. 8.58. Hence the collision frequency for a single molecule, becomes

z1 (1)  2 2 uno …(8.59)

Eq. 8.59 gives the number of collisions experienced by one molecule in unit
time. The number of collisions experienced by all the molecules in unit time in
unit volume (i.e., total collision frequency, or collision density, Z11) is given by

1 1
Z11  z1 ( 1)no   2 uno2 …(8.60)
2 2
1
The factor has been introduced so that collision between any two molecules
2
is not counted twice. Let us take an example to learn the calculation of
28 collision density
Unit 8 Kinetic Theory of Gases

Example 8.6: Calculate the collision density of nitrogen gas at 298.2 K and
1.013  105 Pa. The collision diameter of nitrogen gas is given as
3.740 1010 m.

Solution: According to Eq. (8.60), to calculate the collision density we need to

know the number density, average speed and collision diameter. We
are given the value of collision diameter and the other two terms
have been already calculated in Subsec. 8.7.2 and Section 8.8
respectively. Let us recall them

Number density n o  2.462  10 25 m 3

Average speed, u  474.8 m s 1

1
According to Eq. (8.60) the collision density Z11   2u no2
2

Substituting the values of different terms, we get

1
  3.142  ( 3.740  10 10 m ) 2  474.8 m s 1  ( 2.462  10 25 m 3 ) 2
2

 Z11  8.945  10 34 m 3 s 1

8.11 MEAN FREE PATH

An important quantity in the kinetic theory of gases is the mean free path, .
This is defined as the mean distance travelled by a gas molecule between two
consecutive collisions. An equation useful in calculating the mean free path
can be derived as follows:

Average distance travelled by a molecule in one second = u

The number of collisions per molecule per second = z1(1)

Mean free path () = Average distance travelled between two consecutive
collisions

u
…(8.61)
z1 (1)

Substituting the value of z1(1) from Eq. (8.59) we get

u

2 2 u n o

1
i.e.,  …(8.62)
2 2 n o

It can be seen that the value of  Is inversely proportional to no and hence it

should be inversely proportional to pressure (Subsec. 8. 7. 2).

The lower value of  at higher pressure is understandable since at higher

pressure, a molecule will undergo larger number of collisions. It may also be
29
Block 1 States of Matter

noted that the mean free path is inversely proportional to  . This means that a
2

larger molecule will have greater chance of collisions. As a matter of fact,

quantity 2 is called the collision cross section of the molecule in the hard
sphere model proposed for gas molecules.

Using the above principles, work out the following SAQ.

SAQ 8
Calculate the mean free path of nitrogen molecule at 298.2 K and
1.013  105 Pa. The collision diameter for the molecule is 3.740  1010 m.

8.12 SUMMARY
In this unit, we have discussed some characteristic features of gases. Laws
governing the behavior of gases at low pressures and high temperatures are
stated and explained. It has been shown how a simple kinetic molecular model
of the gas can he used to derive an equation to calculate the pressure exerted
by a gas. This equation can be used further to derive the ideal gas equation.
This model is useful in showing how the constant collisions between
molecules are responsible for a distribution of the speed of molecules. Further,
this model helps us in deriving expressions for various kinds of speeds. We
have also evolved a method of calculating the collision density and the mean
free path assuming hard sphere model for the molecules.

8.13 TERMINAL QUESTIONS

1. Calculate the molar mass of a gas for which density is 1.25  103 kg m3
at 273.2 K and 1.013  105 Pa.

2. A mixture of 2.00  103kg of H2 and 2.00  103kg of He exerts a

pressure of 1.50105 Pa. What are the partial pressures of H2 and He?

3. Calculate the ratio of mean square speeds of oxygen to nitrogen

molecules at 300 K.

4. Calculate the number density and concentration of oxygen at

1.013  105Pa and 300 K.

5. What is the C p / Cv value of non-rigid diatomic gas?

[Hint: A non-rigid molecule has vibrational degree of freedom too.]

8.14 ANSWERS

Self-Assessment Questions
w
1. pV  nRT  RT
30 Mm
Unit 8 Kinetic Theory of Gases
pM m
Density  w / V 
RT

Substituting the values,

1.013  10 5 Pa  0.032 kg mol 1 1 Pa kg

 1J
8.314 J K 1mol 1  273.2 K
1 kg m 1 s  2 kg

 1.472 kg m 3 . 1 kg m 2 s  2

2. 6.022  1022 molecules.  1 kg m  3

3. Total number of moles (nt)  nN 2  no2  nCH4  5.00 mol.

nt RT
Total pressure ( pt ) 
V

5.00 mol  8.314 JK 1 mol 1  250.2 K

  1.73  10 5 Pa
3
0.0600m

nN 2 2.00
pN 2  pt   1.73  10 5 Pa  6.92  10 4 Pa
nt 5.00

Similarly po2  3.46  10 4 Pa

p CH4  6.92  10 4 Pa

4. Nitrogen

5. Root mean square speed of hydrogen at 500 K

3 RT 3  8.314 J K 1mol 1  500 K

 
Mm 0.002 kg mol 1

 2.50  10 3 ms 1

6. ump : u : urms

2RT 8 RT 3 RT
 : :
Mm M m Mm

RT
Dividing by we get
Mm

8
 2: : 3


Dividing by 2

 1.000 : 1.128 : 1.225

The above ratios do not vary with temperature since temperature term
does not appear in it. 31
Block 1 States of Matter

7. Cv  692 J kg 1 K 1  0.018 kg mol 1

 12.5 J K 1mol 1

Since C p  C v  R

C p  (12.5  8.314)  20.8 J K 1mol 1

Cp
 1.66
Cv

1
8. 
2 2 n o

Using no calculated in Subsec. 8.7.2,

1

1.414  3.142  ( 3.740  10 10 m ) 2  2.462  10 25 m 3

 6.536  10 8 m

Terminal Questions
1. Molar mass of the gas = 28.02 kg mol1.

2. pH2  1.00  105 Pa; pHe  5.00  10 4 Pa

u 2 Oxygen 7
3. 
2 8
u Nitrogen

4. Number density = 2.447 1025 m3;

Concentration = 40.61 mol m3.

5. U = (3 RT / 2) + (2 RT / 2) + (1 RT)

= 7 / 2 RT

9
Cv  7 / 2R and C p  R
2
9
Hence, C p / Cv 
7

32