The Kinetic Molecular Theory of Gases
Introduction
❒
The
gas laws help us to predict the behavior of gases, but they do not explain what
happens at the molecular level to cause the changes we observe in the
macroscopic world. For example, why does a gas expand on heating?
❒
In the nineteenth century, a number of physicists, notably Ludwig
Boltzmann and James Clerk Maxwell, found
that the physical properties of gases can be explained in terms of the motion
of individual molecules. This molecular movement is a form of energy, which we
define as the capacity to do work or to produce change. In mechanics, work is
defined as force times distance.
❒
Because energy can be measured as work, we can write:
❒
The joule (J) is the SI unit of energy:
Alternatively, energy can be expressed in kilojoules (kJ):
There are many different kinds of energy. Kinetic energy (KE) is
the type of energy expended by a moving object, or energy of motion.
The findings of Maxwell, Boltzmann, and others resulted in a number
of generalizations about gas behavior that have since been known as the kinetic
molecular theory of gases, or simply the kinetic theory of gases.
Assumptions of The Kinetic Molecular Theory of Gases
Central to the kinetic theory are the following assumptions:
(1) A gas is composed of molecules that are separated from each other
by distances far greater than their own dimensions. The molecules can be
considered to be “points”; that is, they possess mass but have negligible
volume.
(2) Gas molecules are in constant motion in random directions, and
they frequently collide with one another. Collisions among molecules are
perfectly elastic. In other words, energy can be transferred from one molecule
to another as a result of a collision. Nevertheless, the total energy of all
the molecules in a system remains the same.
(3) Gas molecules exert neither attractive nor repulsive forces on one
another.
(4) The average kinetic energy of the molecules is proportional to the
temperature of the gas in kelvins. Any two gases at the same temperature will
have the same average kinetic energy. The average kinetic energy of a molecule
is given by:
where m is the mass of the molecule and u is its speed. The
horizontal bar denotes an average value.
❒ The
quantity ū2 is called mean square speed; it is the average of the
square of the speeds of all the molecules:
where N is the number of molecules.
❒ Assumption
4 enables us to write:
where C is the proportionality constant and T is the absolute
temperature.
(5) Gas pressure is the result of collisions between molecules and the
walls of their container. It depends on the frequency of collision per unit
area and on how “hard” the molecules strike the wall.
(6) The theory also provides a molecular interpretation of temperature.
According to Equation:
The absolute temperature of a gas is a measure of the average
kinetic energy of the molecules. In other words, the absolute temperature is an
indication of the random motion of the molecules the higher the temperature,
the more energetic the molecules. Because it is related to the temperature of
the gas sample, random molecular motion is sometimes referred to as thermal
motion.
Application to the Gas Laws
Although the kinetic theory of gases is based on a rather simple
model, the mathematical details involved are very complex. However, on a
qualitative basis, it is possible to use the theory to account for the general
properties of substances in the gaseous state. The following examples illustrate
the range of its utility.
(1) Compressibility of Gases:
Because molecules in the gas phase are separated by large distances
(assumption 1), gases can be compressed easily to occupy less volume.
(2) Boyle’s Law:
The pressure exerted by a gas results from the impact of its
molecules on the walls of the container. The collision rate, or the number of
molecular collisions with the walls per second, is proportional to the number
density (that is, number of molecules per unit volume) of the gas.
Decreasing the volume of a given amount of gas increases its number
density and hence its collision rate. For this reason, the pressure of a gas is
inversely proportional to the volume it occupies; as volume decreases, pressure
increases and vice versa.
(3) Charles’s Law:
Because the average kinetic energy of gas molecules is proportional
to the sample’s absolute temperature (assumption 4), raising the temperature
increases the average kinetic energy.
Consequently, molecules will collide with the walls of the container
more frequently and with greater impact if the gas is heated, and thus the
pressure increases.
The volume of gas will expand until the gas pressure is balanced by
the constant external pressure.
(4) Avogadro’s Law:
We have shown that the pressure of a gas is directly proportional to
both the density and the temperature of the gas. Because the mass of the gas is
directly proportional to the number of moles (n) of the gas, we can represent
density by n/V. Therefore:
For two gases, 1 and 2, we write:
where C is the proportionality constant.
Thus, for two gases under the same conditions of pressure, volume,
and temperature (that is, when P1 = P2 , T1 =
T2 , and V1 = V2 ), it follows that n1 =
n2 , which is a mathematical expression of Avogadro’s law.
(5) Dalton’s Law of Partial Pressures:
If molecules do not attract or repel one another (assumption 3),
then the pressure exerted by one type of molecule is unaffected by the presence
of another gas. Consequently, the total pressure is given by the sum of
individual gas pressures.
Reference: Chemistry / Raymond Chang ,Williams College /(10th edition).
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