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Lecture - 6 - 18-01-2024

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Lecture - 6 - 18-01-2024

Uploaded by

an23ms268
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© © All Rights Reserved
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Download as PDF, TXT or read online on Scribd
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Kinetic Theory of Gases

Developed by Daniel Bernoulli (1738) and subsequent progress was made by Joule, Clausius, Maxwell
and Boltzmann within 1848-1898.

Assumptions:
(1) The gas is composed of very small discrete particles, called molecules. For a gas, the mass of the
molecules are same and different for different gases.

(2) The molecules are moving at random in all directions with variety of speeds. Some are very fast while
others are slow.

(3) Due to random motion, the molecules are executing collision with the walls of the container (wall-
collision) and also with themselves (intermolecular collisions). These collisions are perfectly elastic,
and so there occurs no loss of kinetic energy or momentum of the molecules by these collisions.

(4) The gas molecules are assumed to be point masses, i.e., their size is very small in comparison to the
distance they travel.

(5) There exists no intermolecular attractions especially at low Pr., i.e., one molecule can exert Pr.
independent of the influence of the other molecules.

(6) The pressure exerted by a gas is due to the incessant and uniform wall-collisions of the molecules.
Higher the frequency of the wall-collisions, greater will be the Pr. of the gas. This explains Boyle’s
Law since when Vol. is reduced, wall-collisions becomes more frequent and the Pr. is increased.

(7) Though the molecular speeds are constantly changing due to intermolecular collisions, average
kinetic energy () of the molecules remains fixed at a given temp. This explains Charles Law that
when temp. is increased,  is increased, velocities (as  = ½ mc2) are increased, wall-collisions
becomes more frequent and violent, so Pr. is increased when Vol. is kept constant or Vol. is increased
when Pr. is kept constant. 1
Kinetic Theory of Gases

Concept of Temp. and Kinetic Theory:-


The speed (cRMS) is more fundamental than average speed,c, since it originates spontaneously from the
average kinetic energy of the molecules and it depends on the thermodynamic parameter, temp (T) (Postulate 7).

Kinetic theory of gases can provide a concept of temp. (T). Average kinetic energy () is a measure of temp.
Higher the average kinetic energy of a gas, greater will be its temperature. When the molecules are at rest
(i.e., = 0), the temp. will also be 0 K.
2
Kinetic Theory of Gases
Formulation of Kinetic Equation:-

The postulates of the kinetic theory enable us to calculate the Pr. of a gas in terms of molecular quantities.

Let us take a cube of edge length l containing N molecules of a gas of molecular mass m and RMS speed is c at temp. T
and Pr. P. Let N1 molecules have speed c1, N2 molecules have speed c2, N3 molecules have speed c3, and so on.

Let us concentrate our attention to a single


molecule among N1 that have resultant speed
c1 and the component velocities are u, v, and
w along the X-, Y- and Z-axis, respectively. So,

c12 = u2 + v2 + w2

Molecule will collide walls A and B with the component velocity u and other opposite faces by v and w.

Change of momentum of the molecule along X-direction for a single collision = mu – (–mu) = 2mu.

The number of collisions suffered by the molecule in unit time between the two opposite walls = u/l

So, the rate of change of momentum for the above type collisions =

3
Kinetic Theory of Gases: Formulation of Kinetic Equation

According to the Newton’s 2nd Law of motion, rate of change momentum due to wall-collision is equal
to the force developed on the walls of the gas container. Thus,

These equations are also valid for any shape of the gas container other than cubic one. 4
Kinetic Theory of Gases
Expression of root-mean square speed:-
Let us apply the kinetic equation for 1 mole ideal gas. In that case, mN = mNA = M, the molar mass of the gas.
Ideal gas equation for 1 mole is PV = RT

This shows that RMS speed depends on the molar mass (M) and temp. (T) of the gas.
Expression of average kinetic energy () :-

5
Kinetic Theory of Gases: Deduction of the gas laws from kinetic equation

This equation provides necessary deduction of the gas laws such as Boyle’s law, Charles law, etc.
Deduction of Avogadro’s law is shown here;

So, dividing the equation (1) by the equation (2), we have N1 = N2. It means that equal volumes of all gases at
the same T and P contain equal number of molecules and it is Avogadro’s law.

Deduction of Graham’s law of diffusion (Thomas Graham, Scottish Physical Chemist, 1848):

The rate of diffusion of a gas (rd) is directly proportional to the speed of the gas.

Thus, at given temp. (T), the rate of diffusion is inversely proportional to the square root of molar mass
of the gas and this is Graham’s law of diffusion. 6
What is the difference between root mean square velocity and average velocity?

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