GUEST AUTHOR

John C. Aherne Textbook Errors, 63

Crawford Municipal
Technical Institute
Cork, Ireland
Kinetic Energies of Gas Molecules

The distribution of kinetic energy among That this is so follows in a straightforward manner
molecules of a gas at a given temperature is often dis- from the Maxwell-Boltzmann relation. According to
cussed in connection with the study of the gas laws or of this law, the fraction of molecules (l/n0)dn having
reaction rates. In the more elementary treatment this
discussion is usually qualitative but is commonly il-
lustrated by a graph showing a plot of “fraction of
molecules” versus “energy.”
In some textbooks* the curve representing this rela-
1
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tion has the general characteristics of the curve shown

in Figure 1, i.e., it has points of inflection on both sides
of the maximum. This is incorrect. Figure 1 actually
represents the distribution of molecular speeds. The
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Figure 2. Distribution of kinetic energies.

speeds c (i.e. velocities irrespective of direction) between

c and c + dc is given by2
1 dn
—

TT
“
4ir 'e-mc’/VcTci (1)
n o
dc

This relation is more readily manipulated in its reduced

form, i.e., when the speeds are expressed in terms of the
modal velocity (2fc7T/m)'A. We therefore substitute
c =
c(2kT/mY/r and dc =
(2kT/m)l/idc
Equation (1) then simplifies to
i. —

(2)
n0 dc

In order to find the corresponding relation for the

energy distribution we only need to realize that
proper shape of the curve for the distribution of kinetic E/kT Vsmc */kT c2 E (3)
= = =

energies is shown in Figure 2. It has a point of in- where E is the kinetic energy expressed in units of kT.
flection only on the high energy side of the maximum.
Now dE 2c dc and hence from equation (2) we find
=

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1
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continuation of errors and not the evaluation of individual texts,
the sources of errors discussed will not be cited. In order to be
presented an error must occur in at least two independent recent
standard books.
2 (4)
n0 dE
A plot of the left hand side of equation (4) against E
s
A method which is relatively painless to the beginner for
calculating this distribution has been discussed recently [Aherne,
J. C., Education in Chemistry, London, 1 (3), 157 (1964)]. It
makes use of histograms and of the reduced form of the equation.

Volume 42, Number 12, December 1965 / 655

(or if one wishes to illustrate the effect of temperature, physical reality. The curve approaches the origin
against E) gives the desired graph (Fig. 2). tangentially to the ordinate.
We may now locate the extrema and points of in- On the other hand successive differentiation of equa-
flection of the curve in the usual manner by differentiat- tion (2) with respect to c yields
ing twice with respect to E and by determining the roots
of these derivatives. We find
i0-s(;),A*-I-',+'1 (7>

= 0 for c —
±1, 0

0 for E and
= =
Vs
od for E 0
-ft
—
=

n0 dc3
= 8
\tt/
5c* + l] (8)
and
= 0 for c <•>
±1.51, ±0.47
k ft = 2 E"A- V*-/l (6) Hence the curve has a maximum at the modal speed
-

= 0 for E =
1.207 or -0.207 (MV), has two points of inflection (one at 0.47 MV
and the other at 1.51 MV), and approaches the origin
Thus the curve in Figure 2 has a maximum at E l/2 =
tangentially to the c axis.
(or E 1/JcT) and one point of inflection at E
=
1.207 = Note that the roots for negative values of c have no
(or 1.207kT). However, the second point of inflection physical significance, since we are here considering
occurs at a negative value of E and hence has no speeds, i.e., velocities without directions.

656 / Journal of Chemical Education