In recording, with the aid of the two quantities, energy and entropy,
the relations which translate analytically the two principles, we
obtain two relations between the coefficients which occur in a given
phenomenon; but it may be easier and also more suggestive to employ
various functions of these quantities. In a memoir, of which some
extracts appeared as early as 1869, a modest scholar, M. Massieu,
indicated in particular a remarkable function which he termed a
characteristic function, and by the employment of which calculations
are simplified in certain cases.
In the same way J.W. Gibbs, in 1875 and 1878, then Helmholtz in 1882,
and, in France, M. Duhem, from the year 1886 onward, have published
works, at first ill understood, of which the renown was, however,
considerable in the sequel, and in which they made use of analogous
functions under the names of available energy, free energy, or
internal thermodynamic potential. The magnitude thus designated,
attaching, as a consequence of the two principles, to all states of
the system, is perfectly determined when the temperature and other
normal variables are known. It allows us, by calculations often very
easy, to fix the conditions necessary and sufficient for the
maintenance of the system in equilibrium by foreign bodies taken at
the same temperature as itself.
One may hope to constitute in this way, as M. Duhem in a long and
remarkable series of operations has specially endeavoured to do, a
sort of general mechanics which will enable questions of statics to be
treated with accuracy, and all the conditions of equilibrium of the
system, including the calorific properties, to be determined. Thus,
ordinary statics teaches us that a liquid with its vapour on the top
forms a system in equilibrium, if we apply to the two fluids a
pressure depending on temperature alone. Thermodynamics will furnish
us, in addition, with the expression of the heat of vaporization and
of, the specific heats of the two saturated fluids.
This new study has given us also most valuable information on
compressible fluids and on the theory of elastic equilibrium. Added to
certain hypotheses on electric or magnetic phenomena, it gives a
coherent whole from which can be deduced the conditions of electric or
magnetic equilibrium; and it illuminates with a brilliant light the
calorific laws of electrolytic phenomena.
Public-domain text, read in full here on John Shaqi.
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