E.

Craig Dukes

Physics 1425
General Physics 1

Kinetic Theory of Gases

 The explanation of the behavior of gases in terms of the constituent
atoms and molecules is called the
kinetic theory of gases
Assumptions used in this theory are:
1. A gas consists of very many identical molecules
2. The molecules themselves occupy a negligible fraction of the
total volume of the gas
3. The molecules move about randomly in direction and speed
4. The molecules collide elastically according to Newton’s Laws.

The study of gases involves very many molecules, too many to treat
individually, so we discuss their average behavior. This is called
Statistical Mechanics
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 Let’s see if we can understand the pressure of
a gas in terms of the average kinetic energy
of its constituent molecules.
In the kinetic theory of gases pressure is due
to collisions of molecules with the walls of
the container.
Let’s first look at what happens when one molecule collides with the
right wall. The collision is elastic so the magnitude of its velocity is
unchanged: 1
2 mv 2
x  1
2 mv 
x
2
or vx  vx

The change in momentum is: p  (mv)  2mvx

If I know the time between collisions with the wall then the force can
be determined: p
F
t
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 It takes a time t to travel a distance 2L back
to the same wall:
x 2 L 2L
vx    t 
t t vx
Hence the force this lone molecule exerts on
the right wall is: p 2mvx mvx2
F  
t (2 L vx ) L
To find the total force we need to add all of the contributions of all of
the molecules.
F   v1x  v2 x   vnx    vix
m 2 2 2 m N 2
L L i 1
m 1  N 2
 N vx where vx   vix 
2 2

L N  i 1 
Since all of the gas molecules are moving about randomly:
vx2  v y2  vz2  13 v 2  13 (v 2 ) av
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 Therefore the force on the right wall is:
2
m N m ( v ) av
F  N vx 
2

L L 3

and the pressure is:

F 1 N 1N 2N 1 2 2N
P  m(v ) av 
2
m(v ) av 
2
 mv   K av
A 3 AL 3V 3V 2  av 3 V
PV  23 NK av
But we know for the ideal gas law that: PV  NkT

K av   12 mv 2   32 kT
av

The temperature is a measure of the average kinetic energy of the

molecules in a substance.
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 What is the average speed of air molecules of O2 and N2 at room
temperature (20°C)?

3
2 kT  K av  12 m(v 2 ) av
3kT 3RT
(v ) av  vrms 
2
or vrms 
m M
m(O 2 )  (32.0 g/mol) / (6.022 10 23 molecules/mol)  5.3  1026 kg
m(N 2 )  (28.0 g/mol) / (6.022 10 23 molecules/mol)  4.7  1026 kg
3(1.38 1023 J/K)(293K)
O 2 : vrms  26
 478 m/s (=1,069 mph)
5.3 10 kg
3(1.38 1023 J/K)(293K)
N 2 : vrms  26
 510 m/s
4.7 10 kg

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 The distribution of speeds of 3
1 mv 2
 m  2

molecules of gas was first f (v)  4 N   ve
2 2 kT
obtained by James Clerk  2 kT 
Maxwell.
f (v)dv
is probability that a molecule
has a speed between v and v +
dv. The average speed is:


v
 0
vf (v)dv
N
kT
 1.60
m
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 The distribution of speeds of 3
1 mv 2
 m  2

molecules of gas was first f (v)  4 N   ve
2 2 kT
obtained by James Clerk  2 kT 
Maxwell.

Note: vrms  v av
Try: vi  1, 6, 4, 2, 6,3, 2,5 m/s
1 8
vav   vi  3.6 m/s
8 i 1
vrms  18  vi2  4.1m/s
For an ideal gas they differ by 8%

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 k = 1.38 x 10-23 J/K (Boltzmann Constant)
PV  NkT N = # of molecule or atoms

PV  nRT R = 8.31 J/(mol∙K) (Universal Gas Constant)

n = # of moles of molecule or atoms
NA = 6.022 1023 molecules/mole

Kav   12 mv2   23 kT
av

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 Sometimes we want to know the
most probable or average or root-
mean-square speed:

df (v) 2kT kT
Most probable speed: set  0; v p   1.41
dv m m

Average speed: v
 0
vf (v)dv

8 kT
 1.60
kT
N  m m

3kT kT
Root-mean-square: vrms  (v 2 ) av   1.73
m m
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 What is the room-mean-square What is the escape velocity of
(rms) speed of He? He?
Potential energy! 0 0
3kT Ke  U e  K  U 
vrms  or vrms  1,350 m/s GM e mHe
m
2 mHe vHe  0
1 2

r
2GM e
v  11,182 m/s
re

Although the rms speed of He

is much less than the escape
velocity of He, there is a tail to
the speed distribution, which is
such that eventually all of the
He leaves the atmosphere.
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 For many years the United States produced essentially all of the
He in the world, it being first found in 1903 in Dexter, Kansas when
drilling for natural gas.
Because of a military embargo of He to Germany, German
Zeppelins used highly flammable hydrogen gas.
The US still produces about 75% of the He in the world. There are
concerns that because the supply is finite it may be running out.

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 The simple answer is that the gravitational force
is too small to hold the gases from escaping.
A more nuanced answer takes into account the
fact that the smaller planets have smaller radii

GMm  V
F M  4 3
 3  r
2
r
G  43  r 3 m

r2
 43  G  mr

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 Vapor Pressure

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 If a liquid is placed in an evacuated jar molecules at the surface will
escape producing a vapor or gas. As this continues the gas pressure
above the liquid mounts. This cools the liquid since the most energetic
molecules are the ones that have escaped.

Eventually the number of molecules that strike the liquid surface and
are recaptured equals the number leaving, and equilibrium is
achieved.
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 The pressure of the gas at that point is called the equilibrium vapor
pressure, or more commonly, the vapor pressure.
The vapor pressure only depends on the temperature and substance.

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 If there is no pressure above the liquid, or if the pressure is less than
or equal to the vapor pressure, not only will the molecules at the
surface escape, but everywhere this will happen: the liquid boils.
Note: SR-71 pilots wore pressure
suits as at the high altitudes they
flew the pressure was so little that
their blood would boil at body
temperature.

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 A liquid boils when its saturated vapor pressure is equal to the
external pressure.

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 An open container of water can
evaporate, rather than boil, away. The
fastest molecules are escaping from the
water’s surface, so evaporation is a
cooling process as well.
The inverse process is called
condensation. When the evaporation
and condensation processes are in
equilibrium, the vapor just above the
liquid is said to be saturated, and its
pressure is the saturated vapor pressure.

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 iClicker Question

A. Because it is usually colder at high altitudes,

requiring more time to cook
B. Because the lower pressure at high altitudes
decreases the boiling point
C. Because foods have different chemical
properties at high altitudes
D. None of the above
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 iClicker Question

A. None of the liquid spills out of the top

B. Less heat escapes since it is sealed on all sides
C. The equilibrium vapor pressure is increased raising the
boiling point of water, allowing the food to be cooked more
quickly
D. None of the above
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 When a liquid such as water is in contact with a gas that is not solely
composed of the same element, then the pressure of the water
vapor is what determines whether it is in equilibrium or not. That is,
the pressure the water vapor would have if it alone were the only
gas. We call this the partial pressure.
If the partial pressure is equal to the equilibrium vapor pressure then
no water evaporates and we have 100% humidity.

partial pressure of H 2 O
Relative humidity  100%
equilibrium vapor pressure of H 2 O

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 partial pressure of H 2 O
Relative humidity  100%
equilibrium vapor pressure of H 2 O
If we have 100% humidity the
air is said to be saturated. If
the temperature is lowered
then the equilibrium vapor
pressure is less and water
condenses out of the vapor.
The dew point is the
temperature at which the
relative humidity is 100%.
If the temperature goes below
the dew point, dew fog, or
even rain may occur.
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 The water molecules having higher speed are able to leave a sweat
drop on the skin, resulting in a lower temperature and drawing heat
from the skin. This in turn heats the drop and the process occurs
again.

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 Phases

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 A pressure vs temperature curve is called a phase diagram.

Gas and liquid

phases
indistinguishable
beyond the critical
point

Note that there can be more than one form of the solid and liquid
phases.
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 Water is a bit unusual in that increasing the pressure of ice near 0°C
can make it turn to water.
Carbon-dioxide has no liquid phase at atmospheric pressures and
hence dry ice (solid CO2) sublimates directly to the gaseous phase.
H2O CO2

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 iClicker Question
Two sealed containers, labeled A and B as shown, are at the same
temperature and each contain
the same number of moles of
an ideal monatomic gas. Which
one of the following statements
concerning these containers is
true?
A. The rms speed of the atoms
in the gas is greater in B than in A.
B. The frequency of collisions of the atoms with the walls of container
B is greater than that for container A.
C. The kinetic energy of the atoms in the gas is greater in B than in A.
D. The pressure within container B is less than the pressure inside
container A.
E. The force that an atom exerts on the walls of container B is greater
than in for those in container A.
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 The mean free path can be calculated, given the average speed, the
density of the gas, the size of the molecules, and the relative speed
of the colliding molecules. The result:
1

4 r 2 2  N V 
m

Note that it depends, and reasonably so, on the # density (N/V)

and the area πr2 the molecules present to each other.
For air at 1 atm and 0°C, the mfp = 8 x10-8 m (or about 300 X the
diameter of an air molecule).
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 Midterm 3 Wed, April 19, in rooms 203, 204
• Come to me after class if neither of these times work
• All multiple choice: practice test and formulas on UVaCollab
• Chs. 11-14, 17-18, omitting Sections 12-6,7; 13-11,13
• Show up for midterm promptly
• No internet capable electronics allowed
• Calculators needed
• Pencils needed

Last Name 203 204

6:30-8:00 pm A–L Abazov - Hatter Hector Jr. - Lyon
8:30-10:00 pm M–Z Mace - Stein Stenburg - Zorzi

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 PV  nRT

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 Ideal Gas Law assumes molecules have no size and that there are
no forces between molecules except when in collision. Neither of
these statements is strictly true, particularly at high pressures and
small volumes where the molecules are close to one another.
RT
Volume reduction: P(V  nb)  nRT P
(V n)  b
a
Pressure reduction: P  P 
(V n) 2
Combining the two effects:

 a V  Van der Walls

P 2 
 b   RT equation of state
 (V n)   n 
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  a V 
P  b   RT Note: the constants a
2 
 (V n)   n  and b depend on the
type of gas.

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 Diffusion

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 If we were to drop 5 molecules of something – blood perhaps – in
a bath of perfectly still water they would not remain stationary, but
slowly move away in an erratic fashion, changing direction as they
bump into water molecules. We call this motion a random walk.

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 Another way of describing the process is to say that the blood
diffused through the water. That is, the random walk eventually leads
to the blood molecules being uniformly distributed through the water.
The blood is called the solute and the water is called the solvent.
A substance will always diffuse by this random walk process from a
region of high concentration to one of lower concentration.
C1  C2 dC
J  DA  DA
x dx
J  moles/s or kg/s

Fick’s Law of Diffusion

C1 and C2 are concentrations in
mol/m3 or kg/m3
D – diffusion constant
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 Some textbooks use the spreading of a fragrance from a bottle of
perfume throughout a room as an example of diffusion.
Unfortunately, that process takes place via convection and not
diffusion. The air currents in the room carry the fragrance and even
if the doors and windows were sealed, as well as the heating or air
conditioning, convection would still dominate as the heat generated
by our bodies would produce currents of air.
Indeed, diffusion is rarely the primary means of transport in any
macroscopic situation. However, it is crucial in many microscopic
situations and in particular in the respiratory systems of many
animals.

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 Many insects “breath” through passages called
trachea that have external openings called
spiracles which are located on the sides of the
abdomen.
The smaller trachea deliver oxygen directly to
cells through diffusion. These small pipes (0.2
mm diameter, 1 mm long) are dead-ended and
cannot be actively ventilated.
The amount of oxygen needed to sustain flight is
enormous: up to 6.5 mol/m3 of tissue per
second. In other words, each cubic meter of
muscle consumes the oxygen in a cubic meter of
air every 1.3 s.
All delivered by diffusion.

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 Diffusion is of paramount
importance in delivering oxygen to
the embryo in a bird’s egg. The
shell is formed of calcium
carbonate, and although it appears
solid, it is actually pierced with
thousands of small pores, or tubes,
connecting the inner and outer
surfaces of the shell.
The developing bird needs oxygen
for metabolism and also must
dissipate carbon dioxide. The
liquids inside the shell, however,
must not be allowed to escape.

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 What fraction of a chicken’s egg is pores?

We can use Fick’s law of diffusion to

estimate this quantity.
C1  C2 dC
?
J  DA  DA
x dx
J  mol/s
Shell thickness: 0.46 mm
Shell radius: 2.3 cm
Oxygen needed: 3.1 x 10-7 mol/s

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 We need to find the concentration of oxygen inside and outside of the
egg. Outside:
n P 1.01105 Pa
PV  nRT or    40.2 mol/m3
V RT 8.32 J/mol K 303K

oxygen is 0.209 of the volume of the atmosphere so its concentration

is: nO air
Cair   40.2 mol/m3 0.209  8.4 mol/m 3
V
The concentration of oxygen inside the egg has been measured to be:
nO egg
Cegg   6.6 mol/m3
V
The difference in concentrations is:
C  Cair  Cegg  8.4 mol/m3  6.6 mol/m3  1.8 mol/m 3
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 We can now use Fick’s Law to find the area of the pores:
C1  C2 C
J  DA  DA
x x
3
x 7 0.46  10 m
A J  3.1 10 mol/s
DC 1.8 105 m 2 /s 1.8 mol/m 3
 4.4 106 m 2

The total area of the egg shell is about:

4 r 2  4 (2.3 102 m) 2  6.6 10 3 m 2
The ratio of the pore area to the total area is then:
4.4 103 m3 4
 6.6  10 m 3
or 0.066%
6.6 103 m3

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