Kinetic Theory of Gases

Gas:
A state of matter which contains large number of molecules in random motion. Kinetic
theory of gases analyzes the behavior of gas under suitable conditions.

Ideal Gas:
A theoretical gas in which molecules occupy negligible state and do not possess any inter-
particle interaction. Ideal gas obeys ideal gas laws and follows a simplified equation.

Real Gas:
In real gases, molecules occupy space and possess intermolecular interactions.

Postulates of kinetic Theory of Gases

(i) In a gas, the size of molecules is negligible or the average separation between them is large
compared with their dimensions. This means that the volume of the molecules is negligible when
compared with the volume of the container.

(ii) Each molecule is considered to be a hard sphere and collide elastically with the other molecules
and container walls. The pressure that a gas exerts on the walls of its container is a consequence of
the repeated collision of the gas molecules with the walls.

(iii) It is assumed that molecules obey Newton’s Laws of motion but during motion they do not interact
each other except during collision and these are not deformed during collisions thus forces between
molecules are short range forces which only acts during collisions.

(iv) As during motion molecules do not interact, the total energy of a gas can be considering as the
sum of kinetic energies of all of its molecules and hence a gas contain zero potential energy.

(v) During collision the time of contact is negligible compared to the time between two successive
collisions of a gas molecule, which ids called relaxation time.

(vi) As a while molecules move randomly. By “randomly” it means that any molecules can move in any
direction at any speed. The direction of motion of gas molecules change only when it collides with the
other gas molecules or the container wall. This results a random zigzag path of a molecules shown in
figure.

This type of random motion is termed “Brownian Motion”. Also it has been assumed that the
distribution of speed does not change in time, despite the collision between molecules. That is at
any given moment, a certain percentage move at low speed and so on.
 Kinetic Theory of Gases
(vii) The gas under consideration is assumed a pure substance. That is, all of its molecules are
identical.

(viii) Effect of gravity on gas molecules in a container is neglected. That is in a container we assume
throughout its volume density of is same.

(ix) At all temperature and pressures, all gases obey ideal gas law which related the microscope
characteristic of a gas i.e. pressure, volume and temperature. The ideal gas law is stated as,

PV= nRT
Here n are number of moles of a gas and R is universal gas constant.

* Real gases show ideal behavior at low pressure and high temperature.

Various Gas Laws:

Boyle’s Law
Boyle’s gives the relation between pressure of a gas with volume at constant temperature. This law
is given as,
1
P𝛼
𝑉
Or, PV= constant
Alternatively, Boyle’s law may be written as
P1V1= P2V2

*For one mole of ideal gas at STP,

PV=nRT
1×8.314×273
V=
1.013×105
=2.2406×10-2m3
= 22406cm3
=22.4 liter

Charles and Gay-Lussac Law

 Kinetic Theory of Gases
At constant pressure, volume of the gas is directly proportional to the absolute
temperature.

According to Charles’s law,

𝑉1 𝑇1
=
𝑉2 𝑇2
𝑉
= constant
𝑇
Ideal Gas Law
Ideal gas laws at all temperatures and pressures can be applied to real gases. The ideal gas
equation is given as,

PV=nRT
𝑃1 𝑉1 𝑃 𝑉
= 22
𝑇1 𝑇2
Avogadro’s Number and Avogadro Hypothesis
The number of molecule in a mole is known as Avogadro’s number, NA. Although Avogadro was not
able to actually determine the value of NA. Several methods have been devised to measure NA and
the acceptable value found is, NA= 6.023×1023 molecules/mole

Thus in n moles of a gas total number of molecules of the gas are, N = n NA .

or the number of moles of a gas can be given as,
𝑁 𝑚
n= =
𝑁𝐴 𝑀

From gas laws, we have

PV=nRT
𝑁 𝑚
PV= RT= RT
𝑁𝐴 𝑀
PV= NkT
𝑅
Where k= is the Boltzmann’s constant and has the value k= 1.38 × 10-23J/K.
𝑁𝐴

Dalton’s Law of partial Pressures

This law states that the total pressure of a mixture of gases is equal to the sum of the partial
pressures of the gases in the mixture. In a container of volume V if n different gases are taken at a
common temperature independently at pressure P1, P2…Pn, then on mixing all these gases in the
same container at the same temperature, the total pressure of the mixture is given by
PT= P1+P2+……..Pn
 Kinetic Theory of Gases
Different Forms of Ideal Gas Law
PV=nRT
𝑚 𝑚
With n= , PV= RT
𝑀 𝑀
𝑚
or P= RT
𝑉𝑀
𝜌𝑅𝑇
or P=
𝑀
Real Gases and Change of Phase

“A gas will change to liquid phase if its temperature is less then critical temperature if sufficient
pressure is applied on the gas”.

Barometric Relation
Maxwell developed a relation to find atmospheric pressure as a function of height from ground level
(more precisely sea level). The relation is named Barometric Relation.
Let’s consider an atmospheric layer of width dx at a height x above the earth surface as shown in
figure.
According to Pascal’s assumption as we go up in air, pressure decreases thus if just below this
elemental layer if pressure is P and just above it is P-dP, then dP is the pressure difference due to this
small layer of width dx. Thus we can write,
dP= -dx 𝜌 g

Here minus sing indicates that the pressure decreases as altitude increases where 𝜌 is the air density
in the elemental layer at a height dx. According to gas law the pressure at this layer is given as,

𝑅𝑇
P=𝜌
𝑀
 Kinetic Theory of Gases
From both equations
𝑃𝑀
dP= -dx g
𝑅𝑇
or
𝑑𝑃 𝑀𝑔
=- dx
𝑃 𝑅𝑇
Integrating this expression within proper limits, gives
𝑃 ℎ
𝑑𝑃 𝑀𝑔
∫ = ∫ 𝑑𝑥
𝑃 𝑅𝑇
𝑃0 0
𝑃 𝑀𝑔ℎ
or ln = −
𝑃0 𝑅𝑇
[Assuming through the atmosphere temperature T= constant]
or
Mgh
P=P0 exp(- )
RT

Here P0 is the atmospheric pressure on ground-level or sea-level and equation gives the pressure of
atmospheric air at a height h above the earth surface and is called as Barometric formula.

Distribution of Molecular Speeds

The molecules in a gas are assumed to be in random motion, which means that many molecules have
speeds less than the average speed and others have speed greater than the average speed. On the
basis of kinetic theory and experiments, Maxwell plotted a graph of variation of speed with relative
number of molecules as shown in figure. The graph shows how the speed of molecules in a gas are
distributed. This is known as Maxwell distribution of speed. The speed varies from zero up to many
times the average speed, but as can be seen from the graph, most molecules have speed that are not
far from the average,

The exact distribution of speed is described by a distribution function by Maxwell, who defined a
function named probability distribution function f(v), so that, of the N molecules in a gaseous system,
the number dN molecules which have range of speeds between v and v + dv or in the very short
neighborhood of v is given by,

dN = ƒ(v) dv
 Kinetic Theory of Gases
Thus ƒ(v) is the number of molecules per unit range of speeds. As the speeds of molecules vary in a
wide range from zero to infinity, from equation, we can write for total number of molecules as
∞
N= ∫0 ƒ(𝑣)𝑑𝑣
The distribution function ƒ(v) was obtained by statistical analysis and found out as

𝑀𝑣2
2 𝑀 3/2 −
ƒ(v)= 4𝜋Nv [2𝜋𝑅𝑇]𝑒 2𝑅𝑇

Where R is universal gas constant and M is the molar mass, using above equation we can write,
3
𝑀𝑣2
𝑀 2
ƒ(𝑣)𝑑𝑣 = 4𝜋𝑁𝑣 2
𝑒 − 2𝑅𝑇 dv
[2𝜋𝑅𝑇]
Here ƒ(v) dv is the number of molecules that have speeds between v and v + dv and this equation is
called as analytical Maxwell Boltzmann distribution function. Figure shows the function computed for
oxygen, neon and helium gases at 300k temperature. Here we can observe that the peak of curve
represents the speed, the maximum number of molecules have and it is called the most probable
speed is exhibited by large number of molecules of gas at a given temperature.

It can also be seen from figure (a) that more massive molecules have lower most probable speed. For
a given gas the most probable molecular speed becomes greater with increasers in temperature as
shown in figure (b). It can also be seen that more molecules have high speeds and fewer molecule
have lower speeds throughout the range of speeds.
 Kinetic Theory of Gases

Different Speeds For Molecules of Gas

(i) Average velocity

Initially we’ve discussed that all molecules of gas in a container are in Brownian motion, thus due to
randomness the direction of motion of different molecules are random and continuously changing
due to repeated collision randomly. If 𝑣 ⃗⃗⃗⃗1, ⃗⃗⃗⃗
𝑣2 …….𝑣
⃗⃗⃗⃗𝑁 are the instantaneous velocity vectors of all N
molecules of a gas, the average velocity vector of these N molecules can be written as

It is obvious that as all vectors are randomly scattered in space thus their sum i.e. the number of
expression in above equation can be approximated to zero. Thus the average velocity vector of
molecules in a gas is always taken as zero.

(ii) Root-Mean-Square Velocity of Gas Molecules

As the name implies this is the square root of mean of squares of velocities of all the molecules of a
gas is always taken as zero.

and

Mathematically its value can be calculated by using the distribution function and taking the average
of the square of the speed. since ƒ(v) dv is the number of molecules with speed v in the range dv, the
mean square speed can be given as

Integrating the expression in above equation, we finally get

3𝑅𝑇
〈𝑣 2 〉 =
𝑀
So that rms speed can be given as
3𝑅𝑇
vrms=√
𝑀
In most of numeric calculation and analysis of kinetic theory we use rms velocity for gas molecules.
 Kinetic Theory of Gases
(iii) Mean Speed of Gas Molecules

We have discussed that due to randomness average velocity vector of all the molecules of a gas
comes out zero. But it is not same in case of mean or average speed. We obtain the mean speed by
averaging the speed of the molecules. It can be simply defined as

Using distribution function we can calculate the mean speed as

Integrating expression in above equation results

8𝑅𝑇
vmean=√
𝜋𝑀

We can see on comparing both above equation

vmean < vrms
(iv) Most Probable Speed of Gas Molecules

The speed maximum number of molecules have and this is the speed corresponding to which
distribution function has maximum or peak value. Its value can be obtained by differentiating the
distribution function ƒ(v) and setting the derivative equal to zero. The final result obtained is

2𝑅𝑇
vmp= √
𝑀
Comparing above equation we can see
vmp <vmean<vrms