Derivation of PV=nRT, The Equation of Ideal Gas

According to the kinetic theory of gas,

- Gases are composed of very small molecules and their number of molecules is very large.
- These molecules are elastic.
- They are negligible size compare to their container.
- Their thermal motions are random.
To begin, lets visualize a rectangular box with length L, areas of ends A
1
and A
2
. There is a
single molecule with speed v
x
traveling left and right to the end of the box by colliding with the
end walls.

3D Demonstration of Ideal Gas
The time between collisions with the wall is the distance of travel between wall collisions
divided by the speed.
1.
The frequency of collisions with the wall in collisions per second is
2.
According to Newton, force is the time rate of change of the momentum
3.
The momentum change is equal to the momentum after collision minus the momentum before
collision. Since we consider the momentum after collision to be mv, the momentum before
collision should be in opposite direction and therefore equal to -mv.
4.
According to equation #3, force is the change in momentum divided by change in time .
To get an equation of average force in term of particle velocity , we take change in
momemtum multiply by the frequency from equation #2.
5.
The pressure, P, exerted by a single molecule is the average force per unit area, A. Also V=AL
which is the volume of the rectangular box.
6.
Lets say that we have N molecules of gas traveling on the x-axis. The pressure will be
7.
To simplify the situation we will take the mean square speed of N number of molecules instead
of summing up individual molecules. Therefore, equation #7 will become
8.
Earlier we are trying to simplify the situation by only considering that a molecule with mass m is
traveling on the x axis. However, the real world is much more complicated than that. To make a
more accurate derivation we need to account all 3 possible components of the particles speed,
v
x
, v
y
and v
z
.
9.
Since there are a large number of molecules we can assume that there are equal numbers of
molecules moving in each of co-ordinate directions.
10.
Because the molecules are free to move in three dimensions, they will hit the walls in one of the
three dimensions one third as often. Our final pressure equation becomes
11.
However to simplify the equation further, we define the temperature, T, as a measure of thermal
motion of gas particles because temperature is much easier to measure than the speed of the
particle. The only energy involve in this model is kinetic energy and this kinetic enery is
proportional to the temperature T.
12.
To combine the equation #11 and #12 we solve kinetic energy equation #12 for mv
2
.
13.
Since the temperature can be obtained easily with simple daily measurement like a thermometer,
we will now replace the result of kinetic equation #13 with with a constant R times the
temperature, T. Again, since T is proportional to the kinentic energy it is logical to say that T
times k is equal to the kinetic energy E. k, however, will currently remains unknown.
14.
Combining equation #14 with #11, we get:
15.
Because a molecule is too small and therefore impractical we will take the number of molecules,
N and divide it by the Avogadros number, N
A
= 6.0221 x 10
23
/mol to get n (the number of
moles)
16.
Since N is divided by N
a,
k must be multiply by N
a
to preserve the original equation. Therefore,
the constant R is created.
17.
Now we can achieve the final equation by replacing N (number of melecules) with n (number of
moles) and k with R.
17.
Calculation of R & k
According to numerous tests and observations, one mole of gas is a 22.4 liter vessel at 273K
exerts a pressure of 1.00 atmosphere (atm). From the ideal gas equation above:
A.
B.
C.


The Significance of pV=nRT
The Kinetic Theory of Gases and the Ideal Gas Equation

ASSUME:
Gases are composed of
- Numerous
- Elastic molecules
- of Negligible Size compared to Bulk Container
- whose Thermal Motion is 'Random'
Consider a rectangular box length l, area of ends A, with a single molecule travelling
left and right the length of the box by virtue of collisions with the end walls.

The time between collisions with the left wall is the distance of travel between wall
collisions divided by the speed (magnitude of the velocity) of the particle, u.

The frequency of collisions with that wall in collisions per second is

According to Newton, force is the time rate of change of the momentum

The momentum change upon collision is the momentum after the collision minus the
momentum before the collision To hit the left wall the initial velocity must have been
-u, so:

The average force on the left end wall is the force per collision times the frequency of
colllsions

The pressure, p, (not to be confused with momentum, ) exerted by this single
molecule constrained to move in one horizontal direction (one dimension) is the
average force per unit area

where V =A
.
l is the volume of the rectangular box.
The pressure exerted by N molecules moving in the same way as a single molecule is
simply

where <u
2
> is the mean square speed
*
of the molecules in the box
(If the elastic molecules collide but still remain travelling only in the left-right
dimension the pressure is unaffected by that collision)
If the molecues are free to move in three dimensions, they will hit walls in one of the
three dimensions one third as often. The pressure then of a gas sample of N molecules
in 3-D is

We define the Temperature, T, as a measure of the thermal (random) motion of the
gas particles. The only kind of motion this model of a gas can have is kinetic energy.
This energy is

Thus, we can replace m<u
2
>/3 ( = (2/3)E
kinetic
) with a constant (call it R ) times the
temperature, T

Here n = N/N
A
is the number of moles of gas molecules and N
A
is Avogadro's number.
The empirical observation that one mole of gas in a 22.4 liter vessel at 273K exerts a
pressure of 1.00 atmosphere allows the determination of the constant, R

The kinetic energy for n=1 mol of gas particles at temperature T is


Comparison of eqns (8) and (10) give the relation

So, from equations (12) and (13), the total kinetic energy of a mole of gas is

The root mean square velocity, (<u
2
>)
1/2
, a measure of the average speed of the
molecules may be directly derived from the ideal gas constant, the molecular weight
of the gas and the temperature


Note that R is in units of energy per mole per kelvin and M=N
A
m is the mass of one
mole of molecules (the molecular mass)

The gas constant, R, must be expressed in appropriate units for the correct
determination of numerical values. In the ideal gas equation of state, pV=nRT, the
logical chioce of units is (latmmol
-1
K
-1
). But latm is a non-standard unit of work or
energy, so for equation (15) we convert the units of R to obtain

*
Note: The average force exerted by a single molecule is associated with a time
average and is denoted with an overbar. The mean square speed is associated with an
ensemble average and is denoted by 'pointy braces', < >. The average over molecules
in the sample (or ensemble) is an important part of chemistry since there are so many
molecules (10
23
) in every macroscopic object.