James Clerk Maxwell and Modern PhysicsGlazebrook, Richard
History
James Clerk Maxwell and Modern Physics
Glazebrook, Richard
Maxwell, James Clerk, 1831-1879; Physics -- History
The theorem in question, from which the result (1) follows as a simple
deduction, has been thus stated by Dr. Larmor.[54]
“There exists a positive function belonging to a group of molecules
which, as they settle themselves into a steady state--on the average
derived from a great number of configurations--maintains a steady
downward trend. The Maxwell-Boltzmann steady state is the one in which
this function has finally attained its minimum value, and is thus a
unique steady state, it still being borne in mind that this is only a
proposition of averages derived from a great number of instances in
which nothing is conserved in encounters, except the energy, and that
exceptional circumstances may exist, comparatively very few in number,
in which the trend is, at any rate, temporarily the other way.”
This theorem, when applied to cases of motion, such as that of a gas at
constant temperature enclosed in a rigid envelope impermeable to heat,
appears to be proved. For such a case, therefore, the Maxwell-Boltzmann
law is the only one possible.
But whether this be so or not, the law first introduced by Maxwell is
one of those possible, and the advance in molecular science due to its
introduction is enormous.
We come now to the second result, the equal partition of the energy
among all the degrees of freedom of each molecule. Lord Kelvin
has pointed out a flaw in Maxwell’s proof, but Boltzmann showed
(_Philosophical Magazine_, March, 1893) how this flaw can easily
be corrected, and it may be said that in all cases in which the
Boltzmann-Maxwell law of the distribution of velocities holds,
Maxwell’s law of the equal partition of energy holds also.
Three cases are considered by Mr. Bryan, in which the law of
distribution fails for rigid molecules: the first is when the molecules
have all, in addition to their velocities of agitation, a common
velocity of translation in a fixed direction; the second is when the
gas has a motion of uniform rotation about a fixed axis; while the
third is when each molecule has an axis of symmetry. In this last case
the forces acting during a collision necessarily pass through the
axis of symmetry, the angular velocity, therefore, of any molecule
about this axis remains constant, the number of molecules having a
given angular velocity will remain the same throughout the motion,
and the part of the kinetic energy which depends on this component of
the motion will remain fixed, and will not come into consideration
when dealing with the equal partition of the energy among the various
degrees of freedom.
Such a molecule has five, and not six, degrees of freedom; three
quantities are needed to determine the position of its centre of
gravity, and two to fix the position of the axis of symmetry.
In this case, then, as Boltzmann points out, in the expression for the
ratio of the specific heats, we must have _n_ equal to 5, and hence
γ = 1 + 2/_n_ = 1 + 2/5 = 1·4
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