Classical Mechanics Formula

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.

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Lecture 37

Last time we connected the Macroscopic

when combined with the ideal gas law: PV = nRT

Average kinetic energy of one molecule

Clicker Question: Molecular speeds

They have the same average kinetic energy.

mean of squared velocities

back to the units of velocity

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

400 500 600

4002 5002 600 2

Not the same!

Mean free path

Collision per unit time:

If all molecules are moving, a similar calculation gives

Average displacement between collisions

(mean free path)

f (v ) = distribution function (probability density)

= probability of finding a molecule with speed between v

higher speeds are

Distribution = probability density

= 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

Most probable speed, average speed, rms speed

Most probable speed (where

Average squared speed

Beyond an ideal gas

We used this picture to derive the

But real gases are more complicated

The Van der Waals state equation

a, b are determined empirically.

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

Clicker Question: Constant volume

A. A tightly closed container cooling

C. Either of the two processes

(For constant n, a hyperbola for each T;

Each point in a pV diagram

Isothermal curve = all states with the same T

Clicker Question: Free expansion

Final state has larger V, lower p

Further beyond the ideal gas

Decrease volume at constant

The critical temperature

For T >> Tc, ideal gas.

= highest temperature where a

pVT diagram: Ideal gas

States are points on

pVT diagram: Water

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