A system of physical chemistry - Index of


A system of physical chemistry - Index of



NaCl, AgCl, KBr, and the triatomic substance PbClg. He supposes

the heat content of the body to be constituted of two parts, one due to

the vibrations of the molecules as a whole, and the other to the vibrations

of the atoms within the molecules. The first part can be obtained

by Debye's method, taking the upper limit of the frequency as deter-

mined by Lindemann's melting-point formula ; the second part can be

determined by Einstein's method, the characteristic frequency being

•determined by Rubens' "residual rays" method. The agreement with

observation is quite good ; details can be found in Vortrdge uber die

Kinetische Theorie dcr Materie und der Elektrizitdt (Teubner). Still

further extensions of Debye's ideas have been made by Born and

Karman and Thirring in papers contained in the Phys. Zeit., 14 (1913).

It was pointed out above that Planck's formula is derived from an

innovation in the treatment of statistical problems, the assumption, in

fact, that the elementary region of the two-dimensional condition diagram

for a system of oscillators is finite in area, and the replacement of

Maxwell's integral by a series. Planck has applied the same idea to the

six-dimensional condition diagram for an ideal monatomic gas, and

arrived at a result which had been already obtained by Nernst, who

bases his derivation of it on his well-known " heat theorem ".^ There

are several ways of wording this theorem, according to the particular

thermodynamic function which one elects to make use of in the state-

ment. As expressed by Planck in his Thermodynamics, it is as follows :

^'The entropy of a condensed system, which is.chemically homogeneous,

is zero at the absolute zero of temperature ". This law removes from the

•expression for the entropy of a body in a definite state that indefiniteness

in value which arises in the usual thermodynamic treatment and

which is due to the entrance into the formula of an undetermined con-

stant on integrating the differential of the entropy. For if clearly the

entropy of a body can be given definitely for one state, it is determinate

for all other states which can be conceivably reached from the former

by a reversible path. So if we can conceive that the body can be led

to the condition of a chemically homogeneous solid or liquid at absolute

zero, by a reversible process, Nernst's heat theorem makes it possible to

calculate its entropy without ambiguity, if sufficient experimental data

are available. By such means it can be shown that the entropy of one

gram-molecule of an ideal gas is given by the equation—

S = C^(i -f log T) - R log/ -fa . . (13)

(absolute units of temperature, pressure, and energy being used), where

the "chemical constant," a, indeterminate on pure thermodynamical

grounds, has, according to Nernst's theorem, the value—

R,„gQ + ^ .... M

in which p% is the vapour pressure of liquid condensed from the gas at

a very low temperature 6, and rg is the heat of vaporisation of the liquid

at absolute zero.

' Nachr. d. Ges. d. Wisseiisch zur Gd'.tingen Math. Phys. Kl. (1906).




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