Lecture 37

Last Lecture:
Equations of state. The ideal gas.
Kinetic model of a gas. (Chap. 18 Sec. 1-4)
This Lecture:
Maxwell-Boltzmann distribution.
Van der Waals Equation. (Chap. 18 Sec. 5)

Last time we connected the Macroscopic

and Microscopic pictures of an ideal gas
pV

2
total translational kinetic energy of molecules
3

when combined with the ideal gas law: PV = nRT

we found:

3
1
kT m v 2
2
2
where

Average kinetic energy of one molecule

(for monoatomic ideal gas)

R
1.38 10 23 J/K
NA

Boltzmanns constant

Clicker Question: Molecular speeds

Two separate containers of gas are in thermal equilibrium with each other.
One contains He and the other contains Ar. Which of the following
statements is correct?
1. . v 2 v 2
He
Ar
2
2
2. . v He
v Ar
2
2
3. . v He
v Ar

3
K E kT
2
1
3
2
m v kT
2
2

They have the same average kinetic energy.

The heavier mass must have slower speeds.

Root-mean-square velocities
The key quantity is <v2>
Take the square-root
v rms

mean of squared velocities

back to the units of velocity

v2

1
3
2
mv rms kT
2
2

Example: 3 molecules at 400,500,600 ms-1

average
rms

400 500 600

500 m/s
3

4002 5002 600 2

507 m/s
3

Not the same!

Mean free path

Assume molecules are rigid spheres of radius r. Only one moves, with speed v.
It will collide with another molecule when their centers are at distance 2r.

ie, in dt it collides if there are other molecules with centers inside this cylinder:

dN 2r vdt

2r

vdt

Collision per unit time:

If all molecules are moving, a similar calculation gives

Average time between collisions:

tmean

Average displacement between collisions

(mean free path)

N
V
dN
N
4 r 2v
dt
V

dN
N
4 r 2v
2
dt
V

1
V

dN 4 2r 2vN
dt

vtmean

V
4 2r 2 N

Molecular speeds
Not all molecules have the same speed.
If we have N molecules, the number of molecules with speeds
between v and v + dv is:
dN Nf (v )dv

f (v ) = distribution function (probability density)

f (v )dv

= probability of finding a molecule with speed between v

and v + dv

Maxwell-Boltzmann distribution

higher T

higher speeds are

more probable

m
f (v ) 4

2 kT

3/ 2
2

v e

mv 2 /(2 kT )

Maxwell-Boltzmann
distribution

Distribution = probability density

f (v )dv

v2

v1

= probability of finding a molecule with speed between v and v + dv

f (v )dv probability of finding molecule with speeds between v1 and v 2

= area under the curve

Normalization:

f (v )dv 1

Most probable speed, average speed, rms speed

Most probable speed (where

f(v) is maximum)

2kT
m

v mp

vf (v )dv

f (v )dv
0

vf (v )dv ...

8kT
m

Average speed

v rms

3kT
v f (v )dv ...
m
2

3kT
m

Average squared speed

rms speed

Beyond an ideal gas

We used this picture to derive the

Ideal Gas Equations

But real gases are more complicated

The Van der Waals state equation

The ideal gas equation is the first approximation to the behavior of gases.
Now lets start to correct the idealization of a gas.
Reduce the assumptions by including:
molecule size reduces volume to move
molecular interactions (attraction) reduces pressure

n2
p a 2 V nb nRT
V

n2
p a 2
V

a, b are determined empirically.

Different for each gas

n
V
1

b nRT

V

This model is used for more extreme conditions. If the gas is diluted
(ie, n/V is very small), the corrections are negligible.

pV diagrams
Convenient tool to represent states and transitions from one state to
another (line represents a series of thermal states)
p

Expansion at constant
pressure

states

B
process

(isobaric process)

VB

VA

Example: helium in balloon expanding in the room and warming up

If we treat the helium in the
balloon as an ideal gas, we can
predict T for each state:

TA/B

pVA/B
nR

Clicker Question: Constant volume

This pV diagram can describe:

pB

pA

A. A tightly closed container cooling

down.
B. A pump slowly creates a vacuum
inside a closed container.

A
V

C. Either of the two processes

(isochoric process)
In either case, volume is constant
and pressure is decreasing.
In case A, becauseT decreases.
In case B, because n decreases.

Isothermal curves
For an ideal gas, p

nRT
V

T1 T2 T3 T4

(For constant n, a hyperbola for each T;

Boyles Law )

Each point in a pV diagram

is a possible state (p, V, T )

Isothermal curve = all states with the same T

Clicker Question: Free expansion

A container is divided in two by a thin wall. One side contains an ideal
gas, the other has vacuum. The thin wall is punctured and disintegrates.
Which of the following is the correct pV diagram for this process?
1A
Initial state

B2
Initial state
Final state

Final state

3
C

D4
Initial state

Initial state

Final state
Final state

Final state has larger V, lower p

During the rapid expansion, the gas does NOT uniformly fill V at a uniform p
hence it is not in a thermal state.
hence no states during process
hence this process is not represented by line

1A
Initial state

B2
Initial state
Final state

Final state

3
C

D4
Initial state

Initial state
Final state

Final state

Further beyond the ideal gas

When a real gas is compressed, it eventually becomes a liquid

Decrease volume at constant

temperatureT2:
At point a, vapor begins to condense
into liquid.
Between a and b: Pressure and T remain
constant as volume decreases, more of
vapor converted into liquid.
At point b, all is liquid. A further
decrease in volume will require large
increase in p.

The critical temperature

Critical point for water: 647K and 218 atm

For T >> Tc, ideal gas.

Supercritical fluid

solid

Triple
point

liquid

Critical point

gas

critical temperature

= highest temperature where a

phase transition happens.

pVT diagram: Ideal gas

States are points on

this surface.

pVT diagram: Water

Phase transitions
appear as angles.