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Chemistry 5


9 October 2002
Chemistry Research: Some History

George B. Kistiakowsky

Dudley R. Herschbach
Kinetic-Molecular Theory
ƒ How does a gas behave at the molecular scale?

ƒ Key Observations/Assumptions
• Structure
Gas consists of large number of molecules or atoms whose size
is negligible relative to volume
• Motion
Gas molecules are in constant random motion, and travel in
straight-line trajectories between collisions.
• Forces
Gas molecules do not influence one another; assume attractive
and repulsive forces are negligible except during collisions.
• Collisions
Gas molecules collide with each other and container walls.
Individual molecules gain/lose energy during collisions,
although total energy is conserved; collisions are elastic.
• Energy
The average kinetic energy of gas molecules is proportional to
the absolute temperature. At a given temperature, all gases have
the same average kinetic energy (but not speed).
Origin of Pressure
ƒ Molecular collisions & pressure

ƒ Since P = F/A, what are forces of collisions?

• kinetic energy:
Like any moving object, gas molecules have a translational
kinetic energy, ek:
ek = ½mu2
where m is mass and u is speed.
• frequency of collisions:
The number of collisions/second or frequency will affect total
pressure. The collision frequency is related to speed of
molecules and number per unit volume:
collision freqency = u(N/V)
• impact force
The momentum transfer that occurs when a gas molecule
collides with the wall is called an impulse, and is directly
proportional to mass and velocity of molecules:
impulse ∝ mu
Pressure: Molecular Theory
ƒ Root mean square speed,(u2)1/2

Since we are deriving properties based on kinetic energy,

which is ∝ u2, it is the average of the square of speed that is
u2 = (u12 + u22 + … uN2)/N

ƒ Putting all together:

The pressure, P, is then going to be the product of the impulse
and collision frequency terms for three dimensions

P = (impulse)x(collision frequency)

P = 1/3 (N/V)mu2
Molecular Speeds
ƒ How do properties of ideal gas molecules affect
properties such a speed?
Assume we have a mole of gas, then
PV = nRT = RT and N = NA

Substitute into expression for pressure, and solve for u:

PV = (1/3)NAmu2
3RT = NAmu2
but NAm = molar mass, M
urms = (3RT/M)1/2

Note: R = 8.314 J/mol-K, where J = kg(m/s)2

ƒ Distributions vs. Mass

ƒ How does temperature affect the average kinetic
energy of gas molecules?

urms = (3RT/M)1/2
Solve for T
T = (M/3R)u2

That is, temperature and kinetic energy are directly related.

ƒ Distributions vs. Temperature

Effusion of a Gas
ƒ Effusion
is defined as the escape of gas molecules from a container via a
tiny orifice into vacuum.
ƒ Demonstration--Observations
• Large and small metal balls are given an average
kinetic energy by shaking.
• We see that the rate of small balls exiting the
orifice is greater than that of the larger ball, which
are traveling more slowly.

ƒ Graham’s Law:
The rates of effusion of two different gases are inversely
proportional to the square roots of their molar masses.
ƒ What is diffusion?
Diffusion of a gas corresponds to gradual mixing of two or
more gases due to random molecular motions of the gas

ƒ What can we say about diffusion of different

Diffusion rates of gases will depend on the molecular mass of
the gas molecules.
However, we cannot simply apply Graham’s law to diffusion
since molecules of diffusing gas undergo collision during the
process such that their average diffusion rate is much lower
than speed (in absence of collisions).