Maxwell-Boltzmann Distribution for Ideal Gases

The Maxwell-Boltzmann distribution curves show the distribution of translational speeds (or kinetic energies)
for an ideal gas at two or more temperatures. On the x-axis is the speeds (energies) and on the y-axis is the
probability or the fraction of molecules having that speed (energy). Maxwell-Boltzmann curves are actually
probability distributions commonly used to determine the speeds of molecules. The reason for this
statistical treatment is a direct result of the infinitesemal size of atoms and molecules. Because of their size
and the Heisenberg uncertainty principle, it is not possible to know the true speed of every gas molecule in a
sample.
In any gas, the molecules are moving haphazardly and bouncing off each other and the walls of the container.
All of these collisions are assumed to be elastic meaning that no energy is lost from the system. At any given
time, the energy each molecule has is going to be spread out (distributed) with some molecules having more
or less than others. Also, there are very few molecules with the high energies and there is no maximum energy
for a molecule.
Shown in the graph below are two distribution curves for oxygen, one at 30 K and the other at 60 K. Notice that
each curve has a prominent peak which corresponds to the most probable speed of a molecule. The area under
each curve is the same and the area equals the number of molecules in the sample.

When the temperature is lowered, there is less energy available so the gas molecules have weaker collisions
and move at speeds that do not vary as much from each other. When a gas becomes cooler, not only does its
peak shift to the left but its peak also becomes higher and more narrow. When the temperature is increased,
the curve becomes stretched out resulting in a lower peak. However, because the number of molecules
remain constant, the area under the curve remains the same. There is more energy available which results in
many more energetic collisions. When the curve for higher temperature levels out, (the right-hand region of
both curves, it is above that of the lower temperature creating more surface area.
The speed distribution for the molecules of an ideal gas is given by:
f(v) = 4(MM/(2RT))3/2v2e(-MMvv/2RT)

where f(v) is the probability or frequency of a molecule being at a particular speed, MM is the molar mass of
the gas in kg/mol, R is the gas constant, 8.31 Jmol -1K-1, v is the speed of the gas molecules in m/s, and T is the
kelvin temperature.
There are three characteristic speeds associated with gas molecules as shown in the graph above. The first is
the most probable speed given by:
vmps = (2RT/MM)1/2
The vmps corresponds to the maximum (peak) on the distribution curve and is the speed at which the greatest
number of molecules are moving.
The mean speed is simply the average of all the speeds. This is the speed which half of the molecules have a
higher speed and the other half a lower speed. The mean speed is given by:
vave = (8RT/(MM))1/2
The vave is always greater than the vmps due to the skewness of the distribution.
The third speed is the root mean square speed which is the square root of the sum of the v ave squared and is
given by:
vrms = (3RT/MM)1/2
The vrms is always greater than either the vmps or the vave.

inetic energies)
he y-axis is the
s are actually

se of their size
s molecule in a

of the container.
m. At any given
es having more
maximum energy

60 K. Notice that
le. The area under

eaker collisions
not only does its
re is increased,
molecules
which results in
hand region of

molar mass of
m/s, and T is the

bove. The first is

ch the greatest

olecules have a

squared and is

Maxwell-Boltzmann Distribution for Ideal Gases

Speed

Frac or % Frac or %

Speed

(m/s)
0

(1)
(2)
0.00E+00 0.00E+00

(m/s)
4.43E+00

50

2.47E-03 9.46E-04

4.65E+00

32.63

333 1.53E-05

6.10E-03
6.16E-03
3.56E-03
1.32E-03
3.24E-04
5.49E-05
6.47E-06
5.36E-07
3.14E-08
1.31E-09
3.90E-11
8.31E-13
1.27E-14
1.39E-16
1.10E-18
6.23E-21
2.55E-23
7.53E-26
1.60E-28
2.46E-31
2.74E-34
2.20E-37
1.27E-40
5.34E-44
1.62E-47
3.56E-51
5.65E-55
6.49E-59
5.40E-63
3.25E-67
1.42E-71
4.49E-76
1.03E-80
1.70E-85
2.04E-90
1.78E-95
###
5.11E-106
1.69E-111

4.85E+00
5.05E+00
5.24E+00
5.42E+00

33.49
33.72
33.87
33.87

363
393
423
453

4.43E+00
4.65E+00
4.85E+00
5.05E+00
5.24E+00
5.42E+00

1.6E-005
1.5E-005
1.5E-005
1.4E-005
1.4E-005
1.3E-005

100
150
200
250
300
350
400
450
500
550
600
650
700
750
800
850
900
950
1000
1050
1100
1150
1200
1250
1300
1350
1400
1450
1500
1550
1600
1650
1700
1750
1800
1850
1900
1950
2000

2.97E-03
4.48E-03
4.55E-03
3.45E-03
2.06E-03
9.87E-04
3.87E-04
1.25E-04
3.37E-05
7.58E-06
1.43E-06
2.26E-07
3.00E-08
3.37E-09
3.19E-10
2.55E-11
1.73E-12
9.92E-14
4.82E-15
1.98E-16
6.93E-18
2.05E-19
5.16E-21
1.10E-22
1.99E-24
3.07E-26
4.01E-28
4.45E-30
4.20E-32
3.37E-34
2.30E-36
1.33E-38
6.56E-41
2.75E-43
9.79E-46
2.97E-48
7.65E-51
1.68E-53
3.13E-56

Frac or %
(1)
T
31.68

303 1.61E-05
1.47E-05
1.41E-05
1.36E-05
1.32E-05

257
257
257
257
257
257

0.000018
0.000016
0.000014
0.000012

These values ar
coded to match
graph.

0.00001
0.000008
0.000006
0.000004
0.000002
0
4.00E+00

4.50E+00

5.00E+00

50E+00

MM1

32.00 g/mol

MM2

32.00 g/mol
8.314 J/molK

T2

vmps1
vmps2
vave1
vave2

30 K
60 K

F ractio n o f M o le cu le s

R
T1

f(v) = 4(MM/(2RT))3/2v2e(-MMvv/2RT)

The values in red can

be modified.
Fraction of M olecules vs Spe ed

125 m/s
7.00E-03
177 m/s
6.00E-03
5.00E-03

141 m/s
4.00E-03
199 m/s
3.00E-03

vrms1
vrms2
These values are color
coded to match the
graph.

5.00E+00

5.50E+00

153 m/s
2.00E-03
216 m/s
1.00E-03
0.00E+00
0

100

200

300

Spe e d (m/s)

400

500

500