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Chapter-6

Gases

Part-3

9 October 2002

Chemistry Research: Some History

George B. Kistiakowsky

Dudley R. Herschbach

Kinetic-Molecular Theory

How does a gas behave at the molecular scale?

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

Molecular collisions & pressure

• 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

Root mean square speed,(u2)1/2

which is ∝ u2, it is the average of the square of speed that is

important:

u2 = (u12 + u22 + … uN2)/N

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

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

PV = (1/3)NAmu2

3RT = NAmu2

but NAm = molar mass, M

urms = (3RT/M)1/2

Temperature

How does temperature affect the average kinetic

energy of gas molecules?

urms = (3RT/M)1/2

Solve for T

T = (M/3R)u2

Effusion of a Gas

Effusion

is defined as the escape of gas molecules from a container via a

tiny orifice into vacuum.

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.

Graham’s Law:

The rates of effusion of two different gases are inversely

proportional to the square roots of their molar masses.

Diffusion

What is diffusion?

Diffusion of a gas corresponds to gradual mixing of two or

more gases due to random molecular motions of the gas

molecules.

gases?

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).

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