A system of physical chemistry - Index of


A system of physical chemistry - Index of


however, in this connection to show that while the principle of partitionequi-

is partially true, in the form given by Boltzmann it is not

sufficiently comprehensive. It might be thought that a sufficient ex-

planation of the observed increase in atomic heat with rise in temperature

lies in the


of new degrees of freedom coming into

existence. We cannot, however, imagine a " fractional "

degree of

freedom. It must either exist definitely, or not at all. One would

expect, therefore,


that the atomic heat should rise by steps as the

rises. All observations, however, have shown that the increase

in atomic heat is a perfectly conti?iuous function of the temperature.

Leaving the problem of specific or atomic heats, let us turn to

another important problem, namely, that of thermal radiation ; for it

was through investigation carried out in this field that the modifications

of the principle of equipartition were eventually introduced, which in

the hands of Planck and Einstein have permitted a satisfactory explanation

to be given of the discrepancies hitherto existing between theory

and experiment, not only in the domain of radiation itself, but likewise

in that of the heat content of solids. Whether these modified views

form the ultimate solution of the problem, it is at present impossible to

say. They represent, at any rate, a fundamental stage in the development

of the subject.

Application of [Classical] Statistical Mechanics to Radiation.

We are here concerned with temperature radiation only. A definition

of this term has already been given toj;ether with a short account

of the radiation laws in Chap. XIV. of Vol. II.

In studving the question of radiation, that is of the exchange of

radiant eneigy between matter and ether, it is necessary, of course, to

limit our consideration to the equilibrium state. If an enclosed material

system is maintained at a temperature T, the interior of the system

contains energy constantly radiated to and from the boundary. When

these energy exchanges arrive at equilibrium each cubic centimetre of

the system contains energy in what we may call the undulatory form.

The problem is how to calculate the most probable distribution of the

energy between the various wave-lengths not only for the single temperature

T but for any temperature ; for the equilibrium state may be

defined as that for which the distribution of energy (at the given temperature)

between the various is wave-lengths the most probable. To

work out this statistical problem we must know something about the

number of degrees of freedom possessed by the matter and by the ether

(present throughout the matter) respectively. It will now be shown

that absolutely different results are arrived at, according as to whether

we regard the ether as continuous [i.e. structureless) or it regard as

having a structure. Let us first consider the ether as continuous. In

this case the ether is a medium capable of vibrating in an infinite number

of ways the wave-lengths propagated throughout it having all possible

values between o and 00 . This is the same thing as saying that the

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