Velocity and Energy Distributions in Gases

B. A. Morrow and D. F. Tessier

University of Ottawa, Onawa, Ontario, Canada KIN 984

Physical Chemistry textbooks generally show plots of the

velocity1 distribution function [F(u)] which is derived from
the kinetic theory of ideal gases (see also Fig. A). The velocity
a t the maximum of this curve is easily evaluated by solving
d[F(u)]ldu = 0 to yield the most probable velocity (up) as

where k is the Boltzmann constant, T the temperature, and

m the molecular mass. Many books also derive the kinetic
energy distribution function (Fig. B), F ( E ) , and one can
similarly show that the most probable energy is

We have found that students are frequently puzzled to find

that if E,, is equated to the translational kinetic energy
(l/2mu2),then the velocity at the most probable energy is

. .
a result which differs by 4 from the most probable velocity
itself. The purpose of the present paper is to show how this
apparent inconsistency arises.
The answer lies in the mathematical nature of the problem.
Although we may be considering -loz3 molecules, it is not
reasonable to ask how many molecules will have an exact ve-
locity since exactness implies knowledge to an infinite number
of significant figures. Instead, one seeks an expression which
will give the fraction of molecules (WJN, where N is the total
number of molecules) which have a velocity within a specific
+
range, say from u to u du. The desired relationship is W J N Distribution function olots for H" at 300 K. A. 8v)versus v-B. Am versus E: C.
= F(u)du whereF(u), the velocity distribution function, (see
any Physical Chemistry text for the derivation) is given by

"7".

By a similar argument, the fraction of molecules ( W E I N )
which have kinetic energies from E to E + dE is F(E)dE,
where F ( E ) is the energy distribution function. Because E =
mu2/2, the latter can be derived from eqn. (4) by making the
substitution u = (ZElm)ll%nd du = (2mE)-ll2dE to yield
, ,
Plots of F(u) versus u and of F(E) versus E for Hz at 300 K
are shown in Figures A and B respectively. The area under
these curves at a given u or E and of width du or dE of course
gives dN,,/N or W E I N , respectively. However, because d E
= mudu, a volume element in energy space is not proportional
to a volume element in velocity space. Therefore, whereas an
area at u of width du under curve A correctly gives the fraction
of molecules which have velocities in this interval, the fraction
of molecules which have energies in this same interval is a
function of u and depends on the location of the interval. By
analogy, the volume of water collected at various locations
during a rainstorm in a pail of fixed dimensions will reflect the
fraction of the total number of drops falling at those locations.
But, if the radius of the pail also varies as afunction of location
in the storm, a modified interpretation must be ascribed to
the data.
The reason why u,, and u at Ep differ by 4 can be seen
more clearly if we express F ( E ) as a function of velocity by
substituting mu212 for E in (5) to yield;
(6)
Although the numerical value of F E ( u )is obviously the same
as that of F(E), FE(v)is pot a distribution function2because
dEldu is not a constant. That is, if PE(U)is plotted against
velocity (Fig. C ) , then an area bounded by an interval du
corresponds to
However, as long as du and dl3 are infinitesimal, we can say
that such an area re~resentsthe fraction of molecules ( d N r /
N ) having energies i n the interval dElmu = mudulmu= du.
The fraction of molecules which have uelocities in this same
interval du and at the same velocity u differs by a factor of mu
because m u F ~ ( u ) d u= F(u)du. Therefore, whereas the maxi-
mum in curve C corresponds to the velocity at the most
probable energy (eqn. (311, the most probable velocity itself
is necessarily greater when FE(u)is multiplied by the linearly
increasing function mu.
' Strictly we mean speed, not velocity, smce we are not concerned
with direction.
The FE(v)function is also not normalized.

Volume 59 Number 3 March 1982 193