Lecture 35 The Kinetic Theory of Gases

Chapter 11 Monday November 26th

Quick review of 3rd law Basic assumptions behind Kinetic Theory The molecular speed distribution function Molecular flux Gas pressure and the ideal gas law Equipartition of energy (if time) Reading: Note: Chapter 11 (pages 181 - 211) Homework 10 will be due on Fri. Nov. 30th Exam 3 will be on Mon. Dec. 3rd in class I will post practice test and formula sheet Review - Thu. Nov. 29th at 5pm

Statements of the third law

T 0 T 0

lim G = lim H
T 0 T 0

lim G = lim H

The Nernst formulation of the Third Law:

All reactions in a liquid or solid in thermal equilibrium take place with no change of entropy in the neighborhood of absolute zero.

Statements of the third law

T 0 T 0

lim G = lim H
T 0 T 0

lim G = lim H

Plancks statement of the Third Law:

The entropy of a true equilibrium state of a system at absolute zero is zero.

The Tds equations

Specific heat of a solid

Copper

Statements of the third law

T 0 T 0

lim G = lim H
T 0 T 0

lim G = lim H

Another statement of the Third Law is:

It is impossible to reduce the temperature of a system to absolute zero using a finite number of processes.

Adiabatic cooling

B1

B
M

B2 > B1

T3 T2

T1

dU = TdS PdV = TdS MdB = Q MdB

Adiabatic cooling

B1

B2 > B1

T3 T2

T1

dU = TdS PdV = TdS MdB = Q MdB

Equivalence of the 3rd law statements

B1

B2 > B1

0 T3

T2

T1

dU = TdS PdV = TdS MdB = Q MdB

Kinetic Theory - Basic assumptions

1. A macroscopic volume contains a large number of molecules. 2. The separation of molecules is large compared with molecular dimensions and with the range of intermolecular forces. d d

0.0002 to 0.05 eV d

Kinetic Theory - Basic assumptions

3. No forces exist between molecules except those associated with collisions.
We treat these collisions like hard collisions between billiard balls.

4. All collisions are elastic.

In other words, energy and momentum are conserved. Again, the analogy with collisions between billiard balls.

5. The molecules are uniformly distributed within a container. 6. The directions of the velocities are uniformly distributed. This statement characterizes the fact that the motion of molecules is random.

The probability density function

The random motions of the molecules can be characterized by a probability distribution function. Since the velocity directions are uniformly distributed, we can reduce the problem to a speed distribution function which is isotropic. Let f(v)dv be the fractional number of molecules in the speed range from v to v + dv. A probability distribution function has to satisfy the condition

f ( v ) dv = 1
0 2 0

We can then use the distribution function to compute the average behavior of the molecules:

v = vf ( v ) dv
0

v = v 2 f ( v ) dv

vrms = v 2

Exam 2 statistics

f(s)
6 5

s = s f ( s ) = 68
s =0

100

Frequency

4 3 2 1 0

Mean = 68% Median = 67%

100

s f ( s ) ds

20

30

40

50

60

70

80

90 100

Score (%)

Element of area on the wall of the container where molecules exert a pressure due to their change in momentum upon bouncing from the wall.

Molecular Flux # in cylinder = n f (v )dv ( vdt cos dA )

# of molecules n= volume

Molecular Flux

d = v sin d d
2

v v
v
d

Molecular Flux
End result
Number of molecules striking a unit area of the container walls per unit time is called the flux :

1 = nv 4

Gas pressure and the ideal gas law

Assume specular collisions*

Change in momentum:

mv cos ( mv cos ) = 2mv cos

*Bold assumption but more general calculation gives same result.

Gas pressure and the ideal gas law

End result
Pressure related to the momentum transfer to the walls, i.e.

Force dp / dt 1 P= = = nmv 2 dA dA 3
Or,

1 2 1 2 2 PV = Nmv = N mv = NkT 3 3 2
Nk nR, nR R 8314 J kilomole 1 K 1 k= = = N NA 6.02 1023 kilomole 1

where,

k = 1.38 1023 J.K1 (Boltzmanns constant)

Gas pressure and the ideal gas law

Kinetic theory provides a natural interpretation of the absolute temperature of a dilute gas. Namely, the temperature is proportional to the mean kinetic energy (K) of the gas molecules.
The mean kinetic energy is independent of pressure, volume, and the molecular species, i.e. it is the same for all molecules.

1 2 1 2 2 2 PV = Nmv = N mv = N K = NkT 3 3 2 3