and collision diameter. Liquefaction of gases.

OF GASES
THE KINETIC MOLEcULAR THEORY
behaviour of gases; some basic laws like
well studied about the
n your lower classes you have very
Boyle's law, Charle's law,... and very commonly used the ideal gas equation. based on
the various laws were only empirical generalisations
At the time of their enunciation, gas nineteenth
theoretical background to justify them. In the
experimental observations. There was no
known as Kinetic
Clausius, Maxwell and Boltzmann developed a theory,
however, Krönig,
century, theoretical basis for the various gas laws. Essential
Molecular Theory of Gases, which provided sound
aspectsof this theory have been discussed below.

1,1. POSTULATES OF KINETIC MOLECULAR THEORY

number of minute particles, called molecules. The molecules are so
1. A gas consists of a large
small that their actual volume is a negligible fraction of the total volume (space) occupied by
the gas.
22 The molecules are in a state of continuous rapid motion in all possible directions, colliding
in a random manner with one another and with the walls of the vessel.
3 The molecules of a gas are hard rigid balls (point masses) so that their molecular collisions
are perfectly elastic and there is no net loss of energy when the gas molecules collide with
one another or against the walls of the vessel. The kinetic energy may be transferred from
one molecule to another but it is not converted into any other form of energy such as heat.
There are no attractive forces amongst molecules or amongst molecules and the walls of the
vessel in which the gas is present. The molecules move
independently of one another. In fact,
there are no intermolecular forces of attraction or repulsion the molecules of a
amongst perfect
(idea) gas.
55. The pressure of a gas is due to the bombardment of the molecules on the walls of the vessel
containing the gas.

1
 PHYSICAL CHEMISTRY
2GS)
FOR THE POSTULATES
1.2. JUSTIFICATION
discussed below.
he above postulates appear to be justified by experience, as

1. The first assumption that the volume of molecules themselves in a gas is a negligible fraction of
the total volume occupied by the gas is borne out by the fact that in a gas like oxygen, hydrogen or nitrogen,
at N.T.P., the volume occupied by the molecules themselves is only 0-014 per cent of the total volume
The remaining 99.986 per cent of the volume is merely an empty space.
2. The carbon particles in smoke when observed under an ultra-microscope are seen to be in constant
zig-zag motion. This is an evidence for the second assumption that the molecules of air in motion, impart
continuous kicks to the carbon particles which, therefore, remain in constant zig-zag motuon. You might
have noticed that the small dust particles/fibre-bits, made visible by being illuminated by the light entering
through a chink of the door/window in a comparatively dark room are flying randomly in all the directions.
Their, this random motion is actuated by the bombardment on them of the randomly moving molecules of
the gases present in the air. This shows that the molecules of a gas are always moving randomly in all
possible directions
3. The molecules are in constant motion and, therefore, they collide frequently with one another as
well as with the walls of the containing vessel (Fig. 1(a)). If the collisions are not elastic, the molecules
will lose some energy at each collision and, therefore, they will come to rest ultimately. But this does
not happen. Hence, the collisions are elastic as provided in the third assumption.
4. The experiments have shown that when pressure on a gas is released, it expands readily, i.e., the
molecules move farther away from one another. This indicates that the force of attraction between the
molecules, if any, is negligibly small. This supports the fourth assumption.
5. If a gas is contained in a closed vessel, it is expected that the moving molecules will keep on
hitting the walls of the vessel continuously thus exerting pressure as provided in the fifth assumption.
It may be emphasised that the postulates of the kinetic theory are fully valid only for an ideal gas.
These are only partially valid for real gases.

3 . PRESSURE OF AN IDEAL (OR PERFECT) GAS-KINETIC GAS EQUATION

The pressure of a gas can be evaluated by calculating the momentum transferred on a unit area of the
wall of the vessel by the molecules of the gas. Let the vessel be a cubic vessel with each side equal to l.
Let us consider one single molecule of the gas having velocity v. This velocity can be resolved into
three mutually perpendicular components along the three axes, x, y and z and parallel to the three sides of
the cube, as shown in Fig. 1(b). Let these components be v. V, and v, along the x-axis, y-axis and the
2-axis, respectively. These components are related to the velocity v by the following relation:
(1)

area 2

mvx -mV

g0

Fig. 1(a). Random motion of

gaseous molecules. Fig. 1(b). Resolution Fig. 1(c). Transfer of momentum
of molecular velocity.
to a wall of the vessel.
 3(GS)
THE GASEOUS STATE
vill
Consider the motion of one of the molecules along the r-axis, striking the face A. Its inomentu
be mv. On striking the wall, it will rebound exactly in the opposite direction with the same V

because the collision is completely elastic and there is no loss of energy (Fig. 1(C).
The change of momentum = mv-(-mv,)= 2mv ..2
particle, as a result of the impact, moves say to (refer the left Fig. 1(c), it traverSesa
Since the
distance to the left and then l to the right before it can strike the face A again. In other words, ne
Travelling w1uu a

has to traverse a distance 21 for each successive collision on the same face.
particle
velocity of vz, time required to cover the distance of 2 =

x
..(3)
The number of collisions per second =
Momentum transferred per second to the face A
2
= Momentum transferred per collision x number of collisions

..(4)
2mv,x
of molecule on the two
Consequently total momentum transferred per second due to the impact one

2mV ...5)
opposite faces along the x-axis
molecule on the two opposite
transferred per second due to impact of single
a
Similarly, the momentum

2m and along the z-axis = 2m

faces along the y-axis=
single molecule on all the six faces of the cube
Hence, the momentum transferred per second by a

will be
2P 2mv, 2m (6)

2 , + , +v) ..()
v2 (Eq. 1)
But v2+v2+ v =

The momentum transferred per second on all the walls by one molecule
2mv .8)
momentum transferred per second on all the
walls by N molecules of the
We now sum up the total on the individual velocities
the contribution to the total momentum will depend
gas. According to Eq. 8,
these individual velocities be vi, V2, V3,....V
of the gas molecules. Let the walls by N molecules per second
Total momentum transferred to

the numerator as well as the denominator by N, where N is total number of molecules,

Multiplying
we have

2m ++ ..9)
N

But the summation term V+V2+Vs* is known as the root mean square (rms) velocity
N
which may be denoted as c. Then, evidently,
 PHYSICAL CHEMISTRY-
4(GS)
transferred per second = 2mNc We know,
Total momentum
Force = mass X acceleration

unit of force in S.I. system is newton (N)

But the total monnentum transferred per second is equal . I N = 1 kg x 1 ms = 1 kg ms2
to force F. Hence,
Now pressure = (force per unit area)
F= 2mMVc2
.(10) Area
in S.I. system unit of pressure is pascal (Pa
The pressure, by definition, is force per unit area.
I newton
Hence, 1Pa= 1m2 = lkg ms2
Force 2mNc m m
Pressure =
Area Ix Area i.e. 1 Pa =
1 kg ml s2
Now the total area of the six faces of the cubicai
vessel 6. Hence, Background Infomation
Pressure,
2mNc 2mNc2 mNc Some Units and their Interconversion
P= Ix 62 6 3V
1 Litre
1 decimetre cube =
= 1L
1 dm3
( . P = volume of the cubical vessel = V)
-
1 milli litre = 1 mL
Or PV mNe 1 cubic centimetre = 1 cc
..(11) 1 centimetre cube = 1 cm3
This equation is known as the Kinetic Gas 1 micro litre 1 uL =

Equation. 1 cm3 =1 mL =1 c.c

No doubt this equation has been derived for a
cubical box, however it is applicable to any shape of
the vessel. dm 100
f000 m
Sample Problem 1. Show that for kinetic gas 1000 L
equation that RMS c' of an ideal gas is 1000 dm
independent of pressure at constant
1 cm31 mL
10 cm
temperature.
=
103 L
= 10-3 dm?
Solution: We know by Kinetic gas equation 1 uL = 10L
1 atmosphere = l atm
PV =}mNe'
(Eq. 11) I pascal = 1 Pa
I newton = 1N
or 3PV
c mNN
1 Pa IN/m2 = 1 kg m-l s2
1 bar = 10 Pa
When pressure of an ideal
will change, consequently,
gas changes, volume
101325 bar
1,atm
760 mmHg
..(a) 6cm Hg
nN =
Constant for a given amount of Z60 Tor
For
gas] ESI ar0987 atm
an ideal gas,
1 kilogram =
1 kg
1 gram =
1g
2 1 kg =
1000 g
100 kg 1
=
quintal
1000 kg = 1 ton
 THE GASEOUS STATE 5(GS)
at constant temperature T =
T2 =
T (say). PV = P2 V2
Equation (a) becomes

2
C1 C2
| Thus, for an ideal gas 'c' is independent of pressure.

Sample Problem 2. 3x1023 molecules each of mass 5x 10-3g have been enclosed in a vessel, which
when connected to a barometer reads a pressure of 57 cm Hg. Find the volume of the vessel if
root mean square velocity c of the molecules under the given conditions is 480 m/s.
Solution: We know as per kinetic gas equation,
PV =mNc Eq. 11)

or V = 3P mNc

given m = 5 x10-23 g = 5x10-26 kg

N =3x 10"molecules
P 57
= $7 cm Hg = a t m . = 0.75 atm.
76
0.75 x 1.01325 x10' Pa
= 0.75 x 1.01325 kg ms2

Putting the values in Eq. (a),

v xX10 kg molecule"" x 3 x 10 moleculex(480)ms?

0.75x1.01325 kg m"s

5x48 x 48 x1026+23+2- kg m's-2

0.75x1.01325 kg m's
15159.1 x10- m
=15159.1 x106x10 L (Im? =
10L)
=
15159.1 x10- L =
15.16 L =
15.16 d (: IL =
1 dm)
15.16 L

Practice roblems
1.1 Pressure of 1-01325 kg of a gas enclosed in
of the gas molecules.
a
cylinder of volume 1-2 m3 is 1-00 atm. Find rms

12 Using kinetic gas equation, find c

()
of N2 gas at NIP.
Using Kinetic gas equation, find c of CO2 gas at 2 atm
behaviour of both the pressure and 400 K. (Assume ideal
gases.
 PHYSICAL CHEMISTRY-

6(GS) AND TEMPERATURE

ENERGY
KINETIC
2.
consideration. The number of molecules involved will then be N
is under
one mole of gas
a
Suppose kinetic gas equation (11) may then be written as
number). The
(the Avogadro's
..(12)
PV=mN, =}x4mNe =j*K.E.
and is the (average) kinetic enerey
translationalkinetic energy of one mole of the gas
the
where K.E. is because it has been obtained
from the equation K.E.
molecules. This energy is average, kinetic theory the
of all the
velocity of all the molecules. Now in
an average (rms)
mNcwhere c represents elastic balls, they do not have any other
motion else than
molecules are considered as rigid perfectly translational energy
therefore this K.E. i.e mNAd is the average
translational (in the three directions),
written as E. i.e.,
of one mole of the gas which is simply

Average translational energy i.e.,

K.E, =
mNc =
E (say)
. Eq. 12 becomes

PV E
PV RT (for an ideal gas)
But

RT E
K.E. = RT
..(13)

Since R is a constant.
EcT
...(14)
ideal is proportional to its absoBute temperature.
i.e. Average translational kinetic energy of an gas
the gas.
of the nature, volume (or pressure) of
It may further be seen that this energy is independent arrived at by the
a function of absolute temperature.
This is a very important generalization
It isjust
applicaíon of kinetic theory of gases.
3. DERIVATION OF GAS LAWS

forth by various scientists from time to time can be

All the experimental and empirical gas laws put
as shown below:
easily derived from the kinetic gas equation,
3.1BOYLE'S LAW
Since kinetic energy varies as
We know that molecular velocities increase with rise in temperature.
to
to define temperature in terms of kinetic energy. Thus, according
square of velocity, it is possible
kinetic theory, the absolute temperature T of a gas is proportional to the mean kinetic energy E = mNc

i. Boyle's Law
Ta mN2 Volume ofa given amount of a
gas at constant temperature is
mNc T inversely proportional to its
m N = KT
pressure,i.e., Vc
where K' is proportionality constant
 7(GS)
THE GASEOUS STATE ..(15)

or
K.E. = KT

kinetic gas equation, (Eq. 11)

According to
PV = mNc2

mNe2

or PV K.E
value of KE from Eq. 15,
Putting the ...(16)
PV= KT
R.H.S. becomes constant.
At a constant temperature T, ...(17
PV = constant
Hence
..(18)
V
or

This is Boyle's law.

3.2. CHARLE'S LAw

Charles' Law
Volume ofa given amount of a
As per Eq.16 constant pressure P is
gas at
PV GKT directly proportic.nal
to absolute

temperature T.

i.e., V« T
constant say
=
K"
at constant P, is a
V *"T ..(19)
Vc T
i.e.
This is Charle's Law.

3.3. AVOGADRO'S LAW

written
equation may be
as
kinetic gas
For any two gases, the
and PaV- }mN%e =}x^mM,
PV =zmMf= }xtmNg and V^= V2, it
two gases are the same,
that is, when Pi=P2
and volumes of
the
When pressures
follows that (1/2)mMeG = (1/2)mNz .(20)
the mean molecular kinetic energy of each gas is
also at the same temperature,
If the two gases are
the same, that is,
(1/2m = (1/2)m%c
.
..21)

Dividing Eq. 20 by Eq. 21,

we get
N = N

under the conditions of temperature and pressure

say, equal volumes of all gases
same
Thus, we can
contain equal number of molecules. This is Avogadro's law.
 PHYSICAL CHEMISTRY
8(GS)
GAS EQUATION
3.4.THE IDEAL
Charles's law and Avogadro's law, we find that the volume of a gas depends
Combining Boyle's law,
and number of moles, as follows
on the pressure, temperature
V c 1/P (at constant T and n) (Boyle's law)
V acT (at constant n) (Charles' law)
P and

V acn (at constant Tand P) (Avogadro's law)

i.e.,
Thus, V should be proportional to the product of these three terms,
PV = nRT ..(22)
V acnTIP =
R{nT/P) or
constant.
Where R is proportionality constant, known as ideal gas
But Eq. 22 is the ideal gas equation.

3.5. GRAHAM'S LAW OF DIFFUSION

According to kinetic gas equation
(Eq. 11)
PV mNc?
total of gas/voBume
C
3PV 3P 3P mNIV = mass

V mN = density of the gas (p)

...(23)
i.e. rcc
(r) of a gas, depends upon
the rms velocity of its molecules,
Now of rate of diffusion
.. (24)
rc 3P or r
Vp P will be
diffusion of two gases at the
same temperature T and pressure
And the ratio of the rates of
given by
..(25)
2 VP and pressure are inversely
diffusion of two gases under identical conditions of temperature
Thus rates of of diffusion.
this is Graham's law
root of their densities and
proportional to the square

OF PARTIAL PRESSURES
3.6. DALTON'S LAW
vessel of volume V. Then,
1. are contained in a
molecules, each of m, of a gas
mass
Suppose, Ni will be given by
according to Eq. 11, the pressurepi of the gas
...(a)
Pi NG
3V
molecules of the gas 1.
where is the root mean square velocity of the
c another non-reacting gas B
are contained
in the
each of mass m2, of
Now, supPpose, N2 molecules, at that time. The pressure
P2 or
and there is no other gas present
same vessel at the same tempevature
this gas will similarly be given by
..(b)
P2=
m2N2c
3V
where c2 is the root mean square velocity of the molecules of the gas 2.
 THE GASEOUS STATE 9GS)
If both the gases are present in the same vessel at the same time, the total pressure P will be given
by the pressure exerted by all the molecules, L.e., molecules of both the gases 1. and 2

P m,NG +maN, =
mN /3V + maM2/3V =Pi + P2 ...(26)
3V

i.e. P P1 +P2
Similarly, if three or more gases are present, the total pressure will be given by
P =Pi tP2 + Ps + .(27)
where p1. P2», Ps are he partial pressures ofthe gases 1., 2., 3.. respectively
Thus, when in a vessel two or more non-reacting gases are present, the total pressure of the gases is
equal to the sum of their partial pressures. But this is Dalton's law of partial pressures.

Background Information- Translational Motion -

According to postulate (3) of the kinetic theoryofgases (Sec 1.1), the molecules of a gas are very
tiny point masses. They are moving randomly in all he directions, in straight lines till they collide.
Since they are point masses, they move as one body. This motion is totally external, since they are just
point masses and do not have parts which move with respect to one another (just as we can move our
various body parts). Thus they neither have vibrational nor rotational movement.

The only possible external lateral motion of point mass to move from pt. A to pt. B is called
translatory motion.

Atoms of noble gases like that of He, Ne, Ar and mercury vapours behave like point masses.

A
--<---
Angular Collision
Head on Collision
Translatory motion (retracing the path)

Flg.2. Translatory motion and collisions.

4. THERMAL MOTION OF THE MOLECULES
Translational kinetic energy of I mol of an ideal gas is given by

KE RT (Eq. 13)
Further, since translational kinetic energy * C, it follows that
T or cT
(28)
Thus, the molecular velocity of any gas is proportional to the COMMITTO MEMORY
square root of the absolute temperalure. The molecular motion
R=0.08206 L atm K-l mol-1
is, therefore, often temed as thermal motion of the molecules. =
0.08206 dm atm K-l mol-
At absolute zero (i.e. at T=0), kinetic is
words, thermal motion ceases completely at energy
zero. In other =
0.08314 L bar K-l mol-l
absolute zero.
=8.314 JK-1 mol-l
It readily follows from Eq. 28 that the translational kinetic
energy=1.987» 2 cal K-l mol-l