Kinetic-Molecular Theory

The ideal gas equation

pV = nRT
Has been presented as a compliation of empirical observation, i.e. the
historically significant Gas Laws, but does The Ideal Gas equation have some
deeper, more fundamental meaning?

The Kinetic-Molecular Theory

1. Gases consist of large numbers of molecules (or atoms, in the case of the
noble gases) that are in continuous, random motion. Usually there is a
great distance between each other, so the molecules travel in straight
lines between abrupt collisions at the walls and between each other.
These collisions randomize the motion of the molecules. Most of the
collisions between molecules are binary, in that only two molecules are
involved.
2. The volume of the molecules of the gas is negligible compared to the
total volume in which the gas is contained. A common bond length
between atoms is about 10-10 m or 1 Angstrom. Small molecules are
therefore on the order of 10 Angstroms in diameter, or less than 10-24
Liters in Molecular Volume, quite tiny indeed! Remember, however that
there can be a great many molecules in the sample of gas, perhaps on the
order of a mole, or 6 x 1023. So that when concentrations of molecules
exceed about 1 mol/liter, then the approximation that the volume of ALL
the molecules in the container is much less than the volume of the
container itself, fails. In the case of an ideal gas, we will assume that
molecules are point masses, i.e., the volume of a mole of gas molecules
(as if they were at rest) is zero, so molecular and container volumes
never become comparable.
3. Attractive forces between gas molecules are negligible. We know that if
these forces were significant, the molecules would stick together. This
happens when it rains and gaseous water molecules stick together to
form a liquid. Water vapor is a condensible gas, and this shows us that
gas molecules are sticky, but at a high enough temperature they form
only a permanent gas, because their stickiness can be considered
negligible. We will assume that in an ideal gas, molecular attractive
forces are not just small, but identically zero.
Consequences:

• The average kinetic energy of the molecules does not change with time.
The molecules bounce and bounce but, on average, do not slow down as
long as the temperature of the gas remains constant. Energy can be
transferred between molecules during collisions but not lost because the
collisions are perfectly elastic (not sticky)
• The average kinetic energy of the molecules is proportional to absolute
temperature (A result of Thermodynamics). At a given temperature the
molecules of all species of gas, no matter what size shape or weight,
have the same average kinetic energy.

The Molecular picture of Pressure

• The pressure of a gas is manifested at the boundary of the vessel it is

confined in, and is caused by collisions (momentum transfer) of the
molecules of the gas with the walls of the container.
• The magnitude of the pressure is related to how hard and how often the
molecules strike the wall. Check out this simulation of molecules in
motion in a gas.

Absolute Temperature

• The absolute temperature of a gas is a measure of the average kinetic

energy of its' molecules
• If two different gases are at the same temperature, their molecules have
the same average kinetic energy
• If the absolute temperature of a gas is doubled, the average kinetic
energy of its molecules is doubled.
• If the temperature approaches absolute zero, the kinetic energy of the
molecules approach zero and they 'stop'

Molecular Speed, Averaging, and The Maxwell-Boltzmann Speed

Distribution

• Although the molecules in a sample of gas have an average kinetic

energy (and therefore an average speed) the individual molecules move
at various speeds, i.e. they exhibit a DISTRIBUTION of speeds; Some
 move fast, others relatively slowly. Collisions change individual
molecular speeds but the distribution of speeds remains the same.
• At the same temperature, lighter gases move, on average, faster than
heavier gases.

The following graph shows the Distribution of Speeds for Gases, i.e.the fraction of the
sample of gas molecules that have a given speed is shown by the height of the curve
above the speed axis. There are no molecules exactly at rest.

• At higher temperatures at greater fraction of the molecules are moving at

higher speeds. This is important for activated chemical processes,
reactions.
• The average kinetic energy, ε, is related to the root mean square (rms)
speed u

Where does this number lie on our Graph of the speed distribution? To find
out, the root mean square 'average' of the distribution must be taken (defined)
in a specific way. It is defined exactly how it sounds. First your square all the
speeds, then average those numbers, and take the square root of that average.
The mean of a distribution is just the average of all the numbers in the
distribtion. The most probable value of a distribution is also exactly what it
sounds like, the speed of that the largest fraction of molecules are travelling. In
general, the mean, the root mean square and the most probable value in a
distribution are all different.

A Note on Distributions a simple numerical example:

Suppose we have four molecules in our gas sample. Their speeds are 3.0, 4.5,
5.2 and 8.3 m/s.

• The mean (simple average) speed is:

• The root mean square speed is:

The rms speed as well as the entire distribution of speeds of gas molecules are a
function of temperature. Below, the blue line is a cold gas and the red line is a
hot gas. Note that the rms speed, u as well as the entire speed distribution
changes with temperature for a given gas.
The rms speed for a given speed distribution (which is determined by the
temperature and molecular weight of the gas) is greater in magnitude than the most
probable speed or the mean speed.
Trick question: What is the mean velocity of the molecules in a gas at any temperature?

Gas Laws and Kinetic Theory

• At constant temperature, the average kinetic energy of the gas molecules

remains constant
• Therefore, the rms speed of the molecules, u, also remains unchanged
• If the rms speed remains unchanged, but the volume increases, there will
be fewer collisions with the container walls over a a given time:
Therefore, the pressure will decrease (Boyle's law)

• An increase in temperature means an increase in the average kinetic

energy of the gas molecules, thus an increase in u
• At constant volume, the greater speed will mean more collisions per unit
time and an increase in pressure
• If, instead, we allow the volume to change to maintain constant pressure,
the volume must increase with increasing temperature to maintain
constant pressure (i.e. the number and strength of 'hits' per wall), which
is just Charles's law
The Ideal Gas Equation of State follows directly from the Kinetic Theory of
Gases. Here is a Pseudo-Derivation

Molecular Effusion and Diffusion

Kinetic-molecular theory states that the average kinetic energy of a mole of
molecules is proportional to absolute temperature, and the proportionality
constant is R, the universal gas constant

(1/2)Mu2 = (3/2)R T = Molar Kinetic (translational)

Energy of the gas
• At a given temperature, all gases have the same average kinetic energy
and for a three dimensional gas this value is (3/2)RT. (what is the molar
kinetic energy of a two dimesional gas trapped in the surface of a metal?)
• The rms velocity, u, in m/s, is simply

where M is the molar mass in kg/mole, R is the gas constant in J/K.mole, and T
is the absolute temperature in K.

Numerical Example:

Calculate the rms speed, u, of an N2 molecule at room temperature (25°C) Be

careful of your UNITS!

T = (25+273)K = 298K
M = 28 g/mol = 0.028 kg/mol
R = 8.314 J/mol K = 8.314 kg m2/s2 mol K
u = 515 m/s

Note: this is equal to 1,150 miles/hour!

Effusion

The escape of a gas through a tiny pore or pinhole in its container is called
EFFUSION.
The effusion rate, r, has been found to be inversely proportional to the square
root of its molar mass: (Why?)

Thus, comparison of the effusion rates of two gases with different masses will
follow the relation:

This effect was observed in the 19th century by Graham and is sometimes called
GRAHAM's LAW

A note on Rates and Times

The effusion time (the time it takes for a certain amount of gas to escape a
vessel) is inversely proportional to the effusion rate (the amount of gas effusing
from the hole per unit time). Be careful that you understand whether it is a rate
or a time that you are calculating.

Gas may effuse, but for this to happen a molecule must pass through a pore or
pinhole and escape to the outside. In effect, a molecule must 'collide' with an
escape hole. The number of such collisions will be linearly proportional to the
average speed of the molecules in the gas and thus the effusion rate. The
effusion time should be inversely proportional to the average speed of the
molecules or proportional to the square root of the ratio of the molecular
masses..
The ratio of effusion rates, ri, for two gases labelled by i, is proportional to the
ratio of the RMS speeds of the gases, ui

Diffusion

Similarly to effusion, the process of diffusion is the spontaneous intermingling

(mixing) of dissimilar gases (fluids) that are initially spatially separated. If you
put a drop of ink in a glass of water and you see the ink gradually spread out to
fill the glass, this is diffusion

• The relative rates of diffusion of two gases is also determined by the

ratio of their average (rms) speeds

• The speed of molecules is quite high, but the rates of diffusion are
slower than molecular speeds due to molecular collisions
• At the density of the atmosphere at sea level, each gas molecule
experiences collisions at a rate of about 1010 (i.e. 10 billion) times per
second
• Due to these collisions, the direction of a molecule of gas in the
atmosphere is constantly changing, and the diffusion rate is much
reduced from the instantaneous speed of the molecule

The average distance traveled by a molecule between

collisions with another molecule is called the mean free
path
• The higher the density of gas, the smaller the mean free path (more
likelyhood of a collision). The larger the molecules, the smaller the mean
free path. The mean free path depends on the number density of the gas
molecules and their size --- and nothing else
• At sea level the mean free path of atmospheric gases is about 60 nm
• At 100 km altitude, the atmosphere is less dense than where we live at
the surface of the earth, and the mean free path is about 0.1 m (about 1
million times longer than at sea level)