IPUC PPC Kinetic Theory

KINETIC THEORY (5 hours)

Equation of state of a perfect gas - Kinetic theory of an ideal gas: Derivation of - Kinetic interpretation of
temperature: Mention of expression for average kinetic energy of a molecule in terms of absolute temperature -
Definition of rms speed of gas molecules.
Degrees of freedom - Law of equipartition of energy: Statement and applicationto specific heat capacities of
monatomic, diatomic and polyatomic gases -Concept of mean free path, Numerical Problems.

1. BASIC POSTULATE OF KINETIC THEORY OF GASES

a) Every gas consists of extremely small particles known as molecules. The molecules
of a given as are all identical but are different than those another gas.
(b) The molecules of a gas are identical, spherical, rigid and perfectly elastic point
masses.
(c) The size is negligible in comparision to inter molecular distance (10-9 m)
Assumptions regarding motion :
(a) Molecules of a gas keep on moving randomly in all possible direction with all
possible velocities.
(b) The speed of gas molecules lie between zero and infinity (very high speed).
Assumptions regarding collision:
(a) The gas molecules keep on colliding among themselves as well as with the walls of
containing vessel. These collision are perfectly elastic. (ie., the total energy before
collision = total energy after the collisions.)
(b) Molecules move in a straight line with constant speeds during successive collisions.
(c) The distance covered by the molecules between two successive collisions is known
as free path and mean of all free paths is known as mean free path.
(d) The time spent is a collision between two molecules is negligible in comparision of
time between two successive collisions.
Assumptions regarding force:
(a) No attractive or repulsive force acts between gas molecules.
(b) Gravitational attraction among the molecules is ineffective due to extremely small
masses and very high speed of molecules
2. Gas laws
Boyle's Law
According to it for a given mass of an ideal gas at constant
temperature, the volume of a gas is inversely proportional to its
pressure, ie.,
1
V if m* and T = Constant

Charle's Law:
According to it for a given mass of an ideal gas at constant pressure,
volume of a gas is directly proportional to its absolute temperature, ie.,
V T if m and P = Constant

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Gay-Lussac's Law:
According to it, for a given mass of an ideal gas at constant volume, pressure of a gas is
directly proportional to its absolute temperature, ie.,
P T if m and V = constant
Avogadro's Law :
According to it, at same temperature and pressure equal volumes of all gases contain
equal number of molecules, ie., N1 N2 if P,V and T are same

Dalton's Partial Pressure Mixture Law :

Pressure and temperature for ideal gas

CALCULATION OF PRESSURE OF GAS

1. Consider a gas enclosed in a cube of side L. and m be the mass of tne
molecules.Take the axes to be parallel to the sides of the cube, as shown
in Fig.
2. Consider a molecule moving with velocity V in any direction
V = Vx i + Vy j + Vzk
3. This molecule hits the planar wall parallel to yz plane of area A (=
L2with velocity Vx . Since the collision is elastic, the molecule rebounds
with the same velocity;
(a) Momentum before collision = m Vx
(b) Momentum after collision = -m Vx
change in momentum of the molecule = -m Vx -m Vx = -2m Vx
4. By the law of conservation of momentum change in momentum of the wall = equal in
magnitude but opposite in direction to that of molecule P = 2m Vx

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5. The distance travelled parallel to the x-direction = L. Thus, the time between two
2
successive collisions with the shaded wall is =
6. The momentum imparted per unit time to the wall by this molecule is
2
= = 2 2m =

2
If n is the total number of molecules in the sample,The total force on the wall = F,=
8. Assuming average velocity in all direction to be equal, we have
1 1
2 =2 = 2 = 3 (2 +2 + 2 )= 3 ( 2 )
2
where v is the speed and v2 denotes the mean of the squared speed. Thus F,= 3

9. Pressure on the wall =
2 2
Pressure =2 = =
33 3

Pressure per unit volume P =
Kinetic Interpretation of Temperature
Consider a gas molecule of mass m moving with average velocity V

The square root of v2 is known as root mean square (rms) speed and is denoted by vrm

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DEGREE OF FREEDOM (f):

The mean degree of freedom refers to the number of possible independent ways in
which a system can have energy.
For example
(a) Block has one degree of freedom, because it is confined to move in a straight line
and has only one transistional degree of freedom.
(b) The projectile has two degrees of freedom becomes it is confined to move in a pane
and so it has two translational degrees of freedom.
(c) The sphere has two degrees of freedom one rotational and another translational.

Degree of freedom of gas molecules:

A gas molecule can have following types of energies:
(i) Translational KE (ii) Rotational KE (iii) Vibrational energy (potential + kinetic)
Degree of freedom of monoatomic gas:
A monoatomic gas molecule (like He) consists of a single atom. It can have translational
motion in any direction in space. Thus, it has 3 translational
degrees of freedom.
f = 3 (all traslational)
Degree of freedom of a diatomic and linear polyatomic gas
f = 5 (3 translational + 2 rotational ) at room temperatures
f = 7 (3 translational + 2 rotational + 2 vibrational ) at high temperatures
Degree of freedom of nonlinear polyatomic gas
A nonlinear polyatomic molecule (such as NH3) can rotate about any of
three coordinate axes.
f = 6 (3 translational + 3 rotational) at room temperatures
f = 8 (3 translational + 3 rotational + 2 vibrational) at high temperatures
So we will take
f = 6 for a nonlinear triatomic or polyatomic gas
f = 7 for a linear triatomic or polyatomic gas
Law of equipartition of energy
In equilibrium, the total energy is equally distributed in all possible energy modes,
1
with each mode having an average energy equal to 2kBT.
Accordingly, each translational and rotational degree of freedom of a molecule
1
contributes 2kBT. to the energy
1
while each vibrational frequency contributes 2 2kBT. = kBT. , since a vibrational
mode has both kinetic and potential energy modes.

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SPECIFIC HEATS OF GASES

Monatomic Gases
The molecule of a monatomic gas has only three translational degrees of freedom.
1
each mode having an average energy equal to 2kBT.
1 1 1
Thus, the average energy of a molecule at temperature T is Et= 2m2 +2m2 + 2m2
1 1 1 3
= 2kBT+2kBT+2kBT =2kBT
3
Thus, the average energy of a molecule at temperature T is 2kBT..
3 3
The total internal energy of one mole of such a gas is U= =
2 2
3
The molar specific heat at constant volume, Cv, is= = 2
3 5
For an ideal gas, Cp Cv = R Cp =R+ 2 =2
5
where Cp is the molar specific heat at constant pressure. Thus, = 2
5
The ratio of specific heats = =3

Diatomic Gases
A diatomic molecule treated as a rigid rotator like a dumbbell has 5 degrees of
freedom
1
3 translational and 2 rotational. Each mode having an average energy equal to 2kBT.
Thus, the average energy of a molecule at temperature T is
1 1 1 1 1
Et= 2m2 +2m2 + 2m2 +2 2 +2 2
1 1 1 1 1 5
= 2kBT+2kBT+2kBT +2kBT +2kBT =2kBT
5
Thus, the average energy of a molecule at temperature T is is =2kBT
5 5
The total internal energy of one mole of such a gas is U= =
2 2
5
The molar specific heats are then given by Cv= (rigid diatomic) = 2

5 7
For an ideal gas, Cp Cv = R Cp =R+ 2 =2
7
where Cp is the molar specific heat at constant pressure. Thus, = 2
7
(rigid diatomic) = =5

if the diatomic molecule is not rigid but has additional vibration energy

Poly atomic gases

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NOTE
Suppose gas molecules has n degrees of freedom
1 1
The internal energy of one mole of the gas = U = kBT x Na = RT
2 2
1
() ( )
As Cv = Cv = = 2
= R
2

As Cp = R + Cv Cp = 2 R + R =(2 + 1)R

( + 1)
As =
= 2
=( + )

2

Specific heat capacity of solids

We can use the law of equipartition of energy to determine specific heats of solids. Consider
asolid of N atoms, each vibrating about its mean position.
1
An oscillation in one dimension has average energy of 2 x 2kBT = kBT .
In three dimension the average energy is 3 kBT .
For one mole of solid N=NA and total energy is U=3 kBT N A =3RT
Now constant pressure

Q = U+PV = U, since for a solid V is negligible. Hence C= = = 3R
Specific Heat Capacity of Water
We treat water like a solid. For each atom average energy is 3kBT. Water molecule has three
atoms, two hydrogen and one oxygen. So it has U = 3 x 3 kBT NA = 9 RT
and C = Q/ T = U / T = 9R
MEAN FREE PATH
consider molecules of gas are spheres of diameter d. Focus on a single
molecule with the average speed <v>. It will suffer collision with any molecule
that comes within a distance d between the centres. In time t, it sweeps a
volume d2 <v> t where in any other molecule will collide with it If n is the
number of molecules per unit volume, the molecule suffers nd2 <v> t
collisions in time t. Thus the rate of collisions is nd2 <v> or the time between
two successive collisions is on the average, = 1/(n <v> d2 )
The average distance between two successive collisions, called the mean free
path l, is
l = <v> = 1/(nd2)
A more exact treatment gives l = 1/(2nd2)

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