CHAPTER 2

KINETIC THEORY
OF AN IDEAL
GAS
2.1. KINETIC THEORY OF AN IDEAL GAS

Microscopic model for a gas

Consider a volume V containing
N molecules
Assumptions:

•N is large, particles are

identical.

•Molecules interact only by

elastic collisions with the
other molecules and with the
walls  kinetic energy is
conserved in a collision.
• Molecules move with random
velocities: every direction equally
probable a distribution of speeds
from 0 to  (Maxwell-Boltzmann
distribution).
GOAL: relate temperature and pressure to the
motion of the molecules

Maxwell-Boltzmann distribution
Probability

Speed
The Joule model

•Joule (1840) used the existing

molecular theory of matter and
Newtonian mechanics to model
dynamically molecular activity
in gases.
•According to his model, the
vast number of molecules of a
given system has only
translational motion along
free paths in the x, y, z
directions of the rectangular
cartesian co-ordinates, and
possess no intermolecular
cohesive forces or
gravitational forces.

•Such a model is more suitable

for monatomic gases at low
• The system is assumed to
consist of a large enough
number of molecules (a basic
assumption of the kinetic
theory of gases) so that the
velocity of molecules in any
direction can be statistically
approximated by a root mean
square value (V) of the
instantaneous velocity and can
be assumed to be the same in
all directions (v).
ROOT MEAN SQUARE VELOCITY
RMS Velocity = V

V  (v ) 2
m
Consider a cubic enclosure of side
L containing a large number of
molecules N, each of mass m. We
see:

* (1/3)xN molecules travel in each

of the x, y, x directions, of
which (1/2)x(1/3)xN travel in the
positive and (1/2)x(1/3)xN in the
negative sense.
•The time taken for each
molecule to reach a cube face
is L/V (maximum time).

•Over this time all molecules

(1/2)x(1/3)xN have reached the
same cube face.

•Therefore the number of

molecules reaching each
face/unit time is
•Change of momentum/molecule:
m.V – (–m.V) = 2.m.V

m v

x
•Total time rate of change of
momentum /cube face:

(1/2) x (1/3) x N x (V/L) x

2.m.V = 1/(3L) x m.N.V2 = the
force on the face.
•1/(3L) x m.N.V2 = P.A (pressure
x area) = P.L2

* Therefore: (1/3) x m.N.V2 =

P.L3
* Total mass: m.N
* Density:  = m.N/L3
* P = (1/3) x  x V2
(2.2)
* Let:  – the molar mass
(kg/kmol)
v – specific volume
(m3/kmol)
n – number of kmol
P. v = (1/3) x .V2 (2.3)
•In the case of closed system, if
the product P.v is constant for a
given quantity (n) of a certain
gas (), V2 is also constant.

•That means for a gas conforming to

the Boyle-Mariotte law, the
temperature depends on the RMS of
the translational velocity along
the free paths.
•The perfect gas laws &
processes in the light of
JOULE’s kinetic theory

Law of Charles and Gay-

Lussac

Consider a closed system

containing N molecules,
each of mass m. We have:
P.L3 = (1/3) x m.N.V2 =
(2/3) N.(m.V2/2)
(2.4)
(L3 is the volume of the
Recall
P.L3 = (1/3) x m.N.V2 = (2/3) N.(m.V2/2)

If P is constant, the volume is

directly proportional to
(m.V2/2), or say, temperature
is related to the molecular
kinetic energy.
The Law of CHARLES & GAY-LUSSAC:
The volume of a gas under
constant pressure expands when
raised from the freezing point
to the boiling point by the same
fraction of itself, whatever be
the nature of the gas.
Compression in which (1/2).mV2
remains constant (isothermal) –
Boyle’s law
Consider a piston-cylinder
assembly (A: area of the piston,
L: distance):
- State 1: Volume = A.L
P.A.L = (2/3) x N.(m.V2/2)
- State 2: Volume = A.L/2 (the
distance is halved, the volume is
halved)
• If RMS velocity is constant 
(m.V2/2) = constant

• Thus, halving the volume doubles

the pressure, i.e. Boyle’s law.
 2.2. EQUIPARTITION THEOREM

• It is important to realize that the

average translational kinetic energy
is the sum of three average values:

<(1/2)mV2>=
<(1/2)mVx2>+<(1/2)mVY2>+<(1/2)mVZ2>
• If the particle were a diatomic
molecule, such as N2 and O2, there
is also a rotational kinetic
energy, with an average value
given by:

<(1/2)Iω12>+<(1/2)Iω22>

There are two terms because there

are two possible axes of rotation
normal to the molecular bond.
• Where:
I – Moment of inertia
ω – Angular speed (radians/sec.)
•The surprising
consequence of
statistical mechanics is
that………..
EACH of the “QUADRATIC TERMS”
(e.g. <(1/2)mVx2> and <(1/2)Iω12>)
has the SAME THERMAL-AVERAGE
VALUE.

This fact is known as the

“EQUIPARTITION THEOREM”.
The EQUIPARTITION THEOREM is
the classical basis for
defining a temperature in
terms of the microscopic
motions of the particles……
Sometimes it is stated as:
“Each quadratic degree of
freedom of the system has
exactly the same thermal-average
energy”.
• We empirically define an absolute
temperature T such that each of the
quadratic terms has a thermal-average
energy given by:

<energy per quadratic term> = (1/2)kT

Where:
k – Boltzmann constant = 1.381 x 10-23
J/K
• From this equation:
<energy per quadratic term> =
(1/2)kT

• We can get the following results:

- Average thermal energy of the
monatomic particle: (3/2)kT
- Average thermal energy of the
diatomic molecule: (5/2)kT
• Therefore:
- Total thermal energy of monatomic
gas:
U = (3/2)NkT = (3/2)nRT
- Total thermal energy of diatomic
gas:
U = (5/2)NkT = (5/2)nRT
Where:
R = Universal Gas Constant =
Ideal Gas Constant =
8.314J/(mol-K)
R = NAk
(NA – Avogadro’s Constant = 6.02 x
23
2.3. EQUIPARTITION APPLIED TO A SOLID

• Let us consider the heat

capacity of a solid material.

• In this case, the vibrational

modes look like a collection of
masses bonded together by
springs, analoguos to atomic
bonds.
• Because the vibrational modes have
both kinetic and potential energy
components, each contributing
(1/2)kT, the Equipartition Theorem
applied to solids says:

“In the classical limit, each

normal mode of vibration in a
solid has an average thermal
energy of kT”.
• Because there are 3N vibrational
modes in a solid containing N
atoms, the internal energy and
heat capacity at constant volume
are,

U = 3NkT = 3nRT and CV = 3Nk

And the molar specific heat is,
cv = 3R = 25J/(mol-K)
• Question:
Does it mean that all solids, no
matter what their constituents
or bond strengths, have the same
heat capacity?
• Answer:
Well, almost all.

(Read page 24, Elements of

Thermal Physics)
• EXERCISE 1

1. From kinetic theory we have U =

(3/2)NkT for the ideal monatomic
gas. Determine the change in
entropy S2 – S1 for the ideal gas
as its energy increases from U1 to
U2 at constant volume (Let, dS =
dU/T).

What is the functional form of

entropy for an ideal monatomic
gas?
SOLUTION

• dS/dU = 1/T = (3/2)Nk/U

dS = (3/2)NkdU/U
Integrating:
S2 – S1= (3/2)Nk[ln(U2) – ln(U1)]
S = (3/2)Nkln(U) for an ideal
monatomic gas
EXERCISE 2

2. If you drop a 1kg block of

aluminum from a height of 1meter
and assume that all the center-
of-mass kinetic energy of the
block is converted into heat as
it strikes the floor, what is
the rise in temperature of the
block? (Aluminum has a molar
mass of 12g).
SOLUTION

• mgh = mcvmT.
• Remember: cv = 3R = 25J/(mol-K)
• cvm = 25J/(mol-K)/12(g/mol)
=2.0833J/(g-K)
• T =
1kgx9.81(m/s2)x1m/[1kgx2.0833J/(g
-K)]
T = 0.0047088K (Not
much)
 EXERCISE 3
• a. Plot a few points of the function
x1/2e-x as a function of x and
indicate where the peak and average
energies are. This is a function
describing the distribution of
kinetic energies of an ideal gas,
(E/kT)1/2e-E/kT, at temperature T.
b. Estimate the probability that the
particle will have an energy E
between 0.5kT and 1kT
• Given:
x = .1, .25, .5, 1.0, 1.5, 2.0, 3.0
 SOLUTION
peak at x = .5
average at x = 1.5

x .1 .25 .5 1.0 1.5 2.0 3.0

x1/2e-x .286 .389 .428 .368 .273 .191 .086

• Let’s replace x by E/kT.
• The area in the rectangle
(E/kT=0.5 to 1) is about ¼ the
total area under the curve.
Therefore the probability is about
25%.
HOME WORK

Briefly discuss the following terminologies:

• Maxwell-Boltzmann distribution
• The JOULE model
• Root mean square velocity
• The Boyle-Mariotte law
• Law of Charles and Gay-Lussac
• Equipartition Theorem
• Translational kinetic energy
• Rotational kinetic energy
• Quadratic term
• Boltzmann Constant k = 1.381 x 10-
23 J/K

• Avogadro’s Constant NA = 6.02 x

1023 (molecules/mole)
• Average thermal energy
• The internal energy of an ideal
gas
• Average thermal energy of the
monatomic particle
• Average thermal energy of the