Kinetic Molecular Theory

NOTES:
o For the Exam, you should be able to explain why the kinetic-molecular
theory explain the multiple laws.

Postulates the kinetic-molecular theory

o The volume occupied by individual gas particles is negligible compared
with the volume of the container
o Gas particles are in constant, random, straight-line motion except
when they collide with the container walls or each other
Implies that there are neither attractive nor repulsive forces
between the particles
o Energy is exchanged during particle collisions but none is lost through
particle collisions: the total kinetic energy is constant
Distribution of Speeds
o A consequence of the myriad particle collisions, each transferring
energy, is that particle speed is best described as a distribution
o The most probable speed is directly proportional to the absolute
temperature
Molecular-Level Nature of Pressure
How do the individual gas particles (atoms or molecules) exert the force that
leads to pressure?
o Pressure is due to gas particle collisions with the container walls
Boyles Law
o How can Boyles law (V = 1/P) be explained in terms of gas particles?
As volume decreases, pressure increases because the number of
collisions between particles and the container walls per unit time
increases
Charless Law
o How can Charless aw (V = T) be explained in terms of gas particles?
As temperature increases, so does average molecular speed.
Greater average molecular speed means more frequent and
more energetic collisions between particles and the container
walls, leading to an increase in pressure which causes an
increase in volume.
Avogadros Law
o How can Avogadros law (V = n) be explained in terms of gas particles?
Adding more particles means more collisions between particles
and the container walls per unit time. More collisions mean
greater pressure. Greater pressure causes the volume to
increase
Amontons Law
o How can Amontons law (P = T) be explained in terms of gas particles?
As temperature increases so does average molecular speed.
Greater average molecular speed means more frequent and
more energetic collisions between particles and the container
walls, leading to an increase in pressure.
Kinetic Energy, Temperature, and Mass
o Why do equal numbers of particles of two different gasses such as
oxygen and helium exert the same pressure, despite their different
masses?

One important conclusion of the kinetic-molecular theory is that

average gas-particle kinetic energy depends on temperature
EKinetic = 3RT/2Navogadro
o According to classical mechanics, kinetic energy depends on particle
mass and speed
EKinetic = mu2
Thus, if a heavy particle and a light particle have the same
temperature (kinetic energy), the heavy particle must be moving
more slowly.
Daltons law of Partial Pressures
o How can Daltons law of partial pressures (Ptotal = P1 + P2 +) be
explained in terms of gas particles?
Creating a gas mixture increases the number of particles, which
increases the number of collisions between particles and the
container walls, increasing pressure. Since all of the gas
particles are the same temperature (kinetic energy), the
pressure increase only depends on the number of particles (their
pressure), not their identity(mass)
Why do the Gas Laws Work?
o Since the kinetic-molecular theory well describes why the gas laws
work, the postulates of the kinetic-molecular theory must be valid.
o Of particular importance is the implication of the second postulate:
there are neither attractive nor repulsive forces between the particles
o Gases are so similar to one another in their physical behavior because
the forces of attraction and repulsion between the particles can be
ignored
o The forces of attraction and repulsion in a gas sample can be ignored
because the average distance between particles is so great.
Temperature and Speed
o One important conclusion of the kinetic-molecular theory is that
average gas particle kinetic energy depends on temperature,
EKinetic = 3RT/2NAvogadro
o According to classical mechanics, kinetic energy depends on particle
mass and speed
EKinetic = mu2
o Equating these two expression yields
3RT/2NAvogadro = mu2
o Conclusion: Temperature is a measure of molecular level motion
Diffusion and Effusion of gases
o Due to their constant motion and high speeds, gas particles mix rapidly
when they come in contact.
o Diffusion is the mixing of gas molecules by random motion under
conditions where molecules by random motion under conditions where
molecular collisions occur.
o Effusion is the escape of a gas through a pinhole into a vacuum
without molecular collisions.
Rate of Effusion
o According to Grahams law, the rate of effusion of a gas is inversely
proportional to the square root of its mass:
Rate of effusion = 1/m1/2
o When comparing two gases at the same temperature and pressure, the
ratio of their effusion rates is inversely proportional to the ratio of the
square roots of their masses:
Rate1
m21/2
o

------- = ------- Rate2

m11/2
Real Gases
o Gas behavior in accord with the ideal gas law is the ideal case
o Real (i.e. non-ideal) gases dont always perfectly obey the ideal gas
law, although at STP most gases behave ideally
o The main deviations from ideality are:
At high pressures, the volume occupied by the gas particles is
non-negligible.
At high pressures, gas particle attractions are important
o The Van der Waals equation accounts for these deviations:
(P + an2/V)(V-nb) = nRT
B is an empirically determined constant: b = particle size
A s an empirically determined constant; a = size of particle
attraction