*Equation of state of perfect gas, Work

done on compressing a gas. Kinetic theory

of gases-Assumptions, Concept of Pressure-
Expression for pressure exerted by a gas,
Kinetic Energy and Temperature, rms speed
of gas molecules, degrees of freedom..+
Kinetic
Theory of
Gases
Unit X
Salik Hussain
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Introduction:The kinetic theory of gases describes a gas as a large number of small particles
(atoms or molecules), all of which are in constant, random motion. The rapidly moving particles constantly
collide with each other and with the walls of the container. Kinetic theory explains macroscopic properties of
gases, such as pressure, temperature, or volume, by considering their molecular composition and motion.

Thermodynamic state:A given sample of a substance has a number of parameters which can be
physically measured. These parameters specify the thermodynamic stateof the system. These parameters
are inter-related with each other and hence if some parameters are known the rest can be calculated. For
example, if pressure and volume are specified the rest of the parameters can be easily calculated. Thus a
thermodynamic state of a given sample of an ideal gas is completely described if its pressure and its volume
are given.

Equation of state of a Perfect gas:The thermodynamic system has definite values of pressure, volume &
temperature. These variables are not independent of each other, rather they are related to each other in the form of an
equation (, , ) = 0.Such a relation is called the equation of state. For a perfect (ideal) gas , the equation of state is
writes as
= ; where P = Pressure
V = Volume
n= no. of moles of a given gas
R= Universal gas constant (R=8.31J/mol-K)
T= Temperature

Work Done During Expansion and Compression of a gas:
Work is said to be done when the body moves through a certain distance in the direction of the applied force.
Let us consider a gas confined to a cylinder that has a movable piston at one end.
During expansion of the gas, the piston moves outwards and the work is said to be done by the system. [Note that
during expansion, direction of the applied force and motion is in the same direction thus work is taken positive during
expansion as explained later.]
During compression of the gas, the piston moves inward and the work is said to be done on the system. [Note that
during compression, the direction of the applied force and motion is in the opposite direction thus work is taken to be
negative during compression].
The amount of work done is equal to the product of the magnitude of the force and the distance through which the
point of application of force moves.
. . =
Let P be the pressure of gas at any instant. Let A be thecross-sectional area of the piston. Then the force on the
piston due to the gas is . Let the gas push the piston up through an infinitely small distance ,then the work
done is given by:
=
=
= -----------------------()
where

,
The total work done by the gas in expanding from initial volume V
1
to final volume V
2
at constant pressure is given by:
= =

----------------------()
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Equation ()represents the total work done during expansion.
When the work is done on the system i.e. system is being compressed from volume V
2
to volume V
1,
then
=

i.e. Work done on the system (Compression) is taken to be negative.


Kinetic Theory of Gases: This theory is based on certain simplifying assumptions given below. These
assumptions help to keep the mathematical treatment simple. Even though these assumptions arent strictly
valid, yet the model developed on the basis of this theory can be safely applied to all gases.
Postulates or Assumptions of Kinetic Theory of Gases:
The theory for ideal gases makes the following assumptions:
The gas consists of very small particles. This smallness of their size is such that the total volume of the
individual gas molecules added up is negligible compared to the volume of the smallest open ball
containing all the molecules. This is equivalent to stating that the average distance separating the gas
particles is large compared to their size.
These particles have the same mass, i.e. all the particles are identical with regards their shape & size
etc.
The number of molecules is so large that statistical treatment can be applied.
These molecules are in constant, random, and rapid motion and moving in all the possible directions
with all possible velocities.
The rapidly moving particles constantly collide among themselves and with the walls of the container.
All these collisions are perfectly elastic. This means, the molecules are considered to be perfectly
spherical in shape, and elastic in nature.
Except during collisions, the interactions among molecules are negligible. (That is, they exert
no forces on one another.)
The average kinetic energy of the gas particles depends only on the temperature of the system.
The time during collision of molecule with the container's wall is negligible as compared to the time
between successive collisions.
Concept of Pressure:
According to kinetic theory of gases, the molecules of a gas are in perpetual random motion. The molecules
not only collide with one another but also with the walls of the container thus imparting a certain amount of
momentum at regular intervals. According to Newtons second law of motion, the rate of change of
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momentum is proportional to force. Thus the molecules of a gas exert a force on the walls of the container.
Thus the walls of the container experience a steady force. This force per unit area is called as the Pressure of
the gas. In other words, the pressure of a gas is due to the continuous bombardment of the vessel.
Expression for Pressure Exerted by a gas:
(This topic is discussed at the last page)

Degrees of freedom:
A degree of freedom of a system is a formal description of a parameter that contributes to the state of a
physical system. It can also be defined as the minimum number of coordinates required to specify the
position of a particle or system of particles. In mechanics, a point particle can move independently in the
three directions of space. Thus, the momentum of a particle consists of three components, each called
a degree of freedom. A system of N independent particles, therefore, has the total of 3N degrees of freedom.
Gas Laws:
The early gas laws were developed at the end of the 18th century, when scientists began to realize that
relationships between the pressure, volume and temperature of a sample of gas could be obtained which
would hold for all gases. Gases behave in a similar way over a wide variety of conditions because to a good
approximation they all have molecules which are widely spaced, and nowadays the equation of state for an
ideal gas is derived from kinetic theory. The earlier gas laws are now considered as special cases of the ideal
gas equation, with one or more of the variables held constant.
Boyle's law:
Published in 1662, Boyle's law states that, at constant temperature, the product of an ideal gas's pressure and
volume is always constant.
Mathematically,Boyle's law is:

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where P is the pressure (Pa), V the volume (m
3
) of a gas, and k
1
(measured in joules) is the constant from this
equationit is not the same as the constants from the other equations below.
This is known as Boyles law which states: the volume of a given mass of gas is inversely proportional to its
pressure, if the temperature remains constant. Mathematically this is:
where k is just a constant (i.e. NOT Boltzmann's constant)
Charles's law:
Charles's Law, or the law of volumes, was found in 1678. It says that, for an ideal gas at constant pressure, the
volume is directly proportional to the absolute temperature (in kelvin).

Gay-Lussac's law:
Gay-Lussac's law, or the pressure law, was found by Joseph Louis Gay-Lussac in 1809. It states that the
pressure exerted on a container's sides by an ideal gas is proportional to the absolute temperature.


Avogadro's law:
Avogadro's law states that the volume occupied by an ideal gas is proportional to the number of moles (or
molecules) present in the container.

where n is equal to the number of moles of gas (the number of molecules divided by Avogadro's Number).

Combined and ideal gas laws:
The combined gas law or general gas equation is formed by the combination of the three laws, and shows the
relationship between the pressure, volume, and temperature for a fixed mass of gas:

With the addition of Avogadro's law, the combined gas law develops into the ideal gas law:

Where the symbols have their usual meaning.
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These equations are exact only for an ideal gas, which neglects various intermolecular effects. However, the
ideal gas law is a good approximation for most gases under moderate pressure and temperature. This law has
the following important consequences:
1. If temperature and pressure are kept constant, then the volume of the gas is directly proportional to
the number of molecules of gas.
2. If the temperature and volume remain constant, then the pressure of the gas changes is directly
proportional to the number of molecules of gas present.
3. If the number of gas molecules and the temperature remain constant, then the pressure is inversely
proportional to the volume.
4. If the temperature changes and the number of gas molecules are kept constant, then either pressure
or volume (or both) will change in direct proportion to the temperature.
Other gas laws:
Graham's law:Graham found experimentally that the rate of effusion of a gas is inversely proportional to the square
root of the mass of its particles. This formula can be written as:

where:
Rate
1
is the rate of effusion of the first gas (volume or number of moles per unit time).
Rate
2
is the rate of effusion for the second gas.
M
1
is the molar mass of gas 1
M
2
is the molar mass of gas 2.
Dalton's law of partial pressures states that the pressure of a mixture of gases simply is the sum of the partial
pressures of the individual components. Dalton's Law is as follows:
,