13.
KINETIC THEORY
13. Kinetic Theory
Equation of state of a perfect gas
Work done in compressing a gas
Kinetic theory of gases – assumptions
Concept of pressure
Kinetic interpretation of temperature
rms speed of a gas molecules
Degrees of freedom
Law of equi-partition of energy
Applications of specific heat capacities of gases
Concept of mean free path
Avogadro’s number
Perfect (ideal) gas equation
• This equation gives the relation between pressure P, volume V and absolute
temperature T of a gas. This equation is
PV = nRT
where n is the number of moles of the gas and R is the universal gas constant.
• Derivation:
• According to Boyle’s, for a given mass of a gas at constant temperature,
V α 1/P -------(1)
• According to Charles’ law, for a given mass of a gas at constant pressure,
V α T ----------(2)
• From eqn. (1) and (2),
V α T/P
V = R T/P
PV = RT
• For n moles of a gas, PV = nRT
Perfect (ideal) gas equation . . . . . .
• As number of moles,
n = No. of molecules / Avogadro’s number = N / NA
PV = nRT
= (N/NA)RT
= (R/NA)NT
PV = kB NT
where R = 8.31 J mol-1 K-1
KB = Boltzmann’s constant = 1.38 x 10-23 JK-1.
AVOGADRO’S NUMBER(NA):
• It is the number of particles present in one mole of the substance.
NA = 6.0225 x 1023 mole-1.
• n = Ms/M = N/NA
where Ms is the mass of the sample and M is the molar mass.
Assumptions of kinetic theory of an ideal gas
1. All gases consist of molecules. The molecules are rigid, elastic
spheres identical in all respects for a given gas and different for
different gases.
2. The size of a molecule is negligible compared with the average
distance between the molecules.
3. The molecules are in the state of continuous random motion.
4. During the random motion, the molecule collide with one another
and with the walls of the vessel.
5. The collisions are perfectly elastic and there are no forces of
attraction or repulsion between the molecules.
6. Between two collisions a molecule moves in a strait path with a
uniform velocity. The average distance covered by a molecule
between two successive collisions is called mean free path.
7. The collisions are almost instantaneous.
Pressure exerted by an ideal gas
• Consider an ideal gas enclosed in a cubical vessel and the sides of the cube
are parallel to the co-ordinate axes as shown.
• Let n be the number of gas molecules per unit volume and m be the mass of
each molecule.
• A molecule moving with velocity (vx, vy, vz) hits the planar wall of area
A(perpenducular to x-axis). The velocity after collision is (-v x, vy, vz).
• The change in momentum of the molecule = -2mv x.
The momentum imparted to the wall in each collision = 2mv x
Pressure exerted by an ideal gas . . . . .
Kinetic Interpretation of temperature
• Consider one mole of a gas.
• Density, ρ = M / V
• According to kinetic theory, the pressure exerted by the gas is
• Absolute zero as that temperature at which all molecular motion stops.
Root mean square speed
• It is defined as the square root of the mean of the squares of the speeds
of the individual molecules of a gas.
• If v1, v2, v3, . . . .vn are the speeds of the n gas molecules, then the root
mean square speed for the gas is given by
• Hence for lighter gases, the r.m.s speed is comparatively high, as it
depends inversely upon the square root of its molecular mass.
Degrees of freedom
• The degrees of freedom of a dynamical system are defined as
the total number of co-ordinates or independent quantities required to describe completely the
position and configuration of the system.
or
• The total number of independent ways in which the particles of the system can absorb energy.
• The number of degrees of freedom of the system is f = 3N-k
where N = number of particles in the system,
k = number of independent relations between the particles.
• (a) Degrees of freedom of a monoatomic gas: The molecule of a monoatomic gas like He,
Ne, Ar etc. consists of a single atom. It is capable of translatory motion only. So it has 3
degrees of freedom.
Here N=1, k=0, so f=3x1-0 = 3.
• (b) Degrees of freedom of a diatomic gas: The molecule of a diatomic gas like N2, O2, H2,
CO,etc. has 5 degrees of freedom.
Here N=2, k=1, so f=3x2-1=5.
(3 due to translatory motion + 2 due to rotationa motion)
• At high temperature(5000K), f = 7. (3 due to
translatory +2 due to rotational + 2 due to vibrational)
Degrees of freedom . . . . .
• (c) Degrees of freedom of a triatomic gas:
• (i) In a non-linear molecule like H2O, SO2, etc., the three
atoms are located at the vertices of a triangle.
Here N=3, k=3, so f=3x3-3=6
( 3 due to translatory + 3 due to rotational)
• (ii) In a linear molecule such as CO2, CS2, HCN, etc., the
three atoms are arranged along a straiht line.
f = 3N-k = 3x3-2 = 7
Law of equi-partition of energy and application to specific heat
capacities of gases
• Law of equipartition of energy: It states that in any dynamical system in
thermal equilibrium, the energy is equally distributed amongst its various
degrees of freedom and the energy associated with each degree of freedom
per molecule is (½)kB T.
• Specific heats of gases:
(i) Specific heats of monoatomic gas:
Average energy associated with each degree of freedom per molecule =
(½)kB T
Average energy associated with three degree of freedom per molecule =
(3/2)kB T
The total internal energy of one mole of a monoatomic gas,
U = (3/2)kBT x NA = (3/2) RT
The molar specific heat at constant volume will be
Cv = dU/dT = (3/2) R
Law of equi-partition of energy and application to specific heat
capacities of gases . . . .
• The molar specific heat at constant pressure,
Cp = Cv + R = (3/2)R + R = (5/2) R
Specific heat ratio, γ = Cp/Cv = 5/3 = 1.67
• (ii) (a) Specific heats of diatomic gas:
Degrees of freedom for diatomic molecule f = 5
Total energy per mole, U = 5 (1/2)kBT x NA = (5/2) RT
Cv = dU/dT = (5/2) R
Cp = Cv + R = (7/2) R
γ = 7/5 = 1.4
(b)Specific heats of diatomic gas at higher temperature:
Total energy per mole, U = 7 (1/2)kBT x NA = (7/2) RT
Cv = dU/dT = (7/2) R
Cp = Cv + R = (9/2) R
γ = 9/7 = 1.28
Law of equi-partition of energy and application to specific
heat capacities of gases . . . .
• (iii) Specific heats of triatomic gas:
(a) A non-linear triatomic gas molecule has f = 6.
Total energy per mole, U = 6 (1/2)kBT x NA = 3 RT
Cv = dU/dT = 3 R
C p = Cv + R = 4 R
γ = 4/3 = 1.33
(b) A linear triatomic molecule has f = 7
Total energy per mole, U = 7 (1/2)kBT x NA = (7/2) RT
Cv = dU/dT = (7/2) R
Cp = Cv + R = (9/2) R
γ = 9/7 = 1.28
Mean free path
• The mean free path of a gas molecule is the average distance travelled by the
molecule between two successive collisions.
• If a molecule covers free paths λ1, λ2, . . . ,after successive collisions, then its
Mean free path = λ1+λ2+ . . / Total number of collisions
• Consider each molecule of gas is a sphere of diameter d and all molecules of
the gas except the molecule A are at rest. A will collide with all the molecules
within the volume of cylinder in time ∆t.
Mean free path . . . . .
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