the relations of the specific heats, because the knowledge of
the specific heats of gases at that time was of so uncertain a
character. He attributed most weight to his later determinations
of the mechanical equivalent made by the direct method
of friction of liquids. He showed that the results obtained with
different liquids, water, mercury and sperm oil, were the same,
namely, 782 foot-pounds; and finally repeating the method with
water, using all the precautions and improvements which his experience
had suggested, he obtained the value 772 foot-pounds,
which was accepted universally for many years, and has only
recently required alteration on account of the more exact definition
of the heat unit, and the standard scale of temperature (see
Calorimetry). The great value of Joule’s work for the general
establishment of the principle of the conservation of energy
lay in the variety and completeness of the experimental evidence
he adduced. It was not sufficient to find the relation between
heat and mechanical work or other forms of energy in one
particular case. It was necessary to show that the same relation
held in all cases which could be examined experimentally, and
that the ratio of equivalence of the different forms of energy,
measured in different ways, was independent of the manner in
which the conversion was effected and of the material or working
substance employed.
As the result of Joule’s experiments, we are justified in concluding that heat is a form of energy, and that all its transformations are subject to the general principle of the conservation of energy. As applied to heat, the principle is called the first law of thermodynamics, and may be stated as follows: When heat is transformed into any other kind of energy, or vice versa, the total quantity of energy remains invariable; that is to say, the quantity of heat which disappears is equivalent to the quantity of the other kind of energy produced and vice versa.
The number of units of mechanical work equivalent to one unit of heat is generally called the mechanical equivalent of heat, or Joule’s equivalent, and is denoted by the letter J. Its numerical value depends on the units employed for heat and mechanical energy respectively. The values of the equivalent in terms of the units most commonly employed at the present time are as follows:—
| 777 foot-pounds (Lat. 45°) | are equivalent to | 1 B.Th.U. (℔ deg. Fahr.) |
| 1399 foot-pounds ” | ” ” | 1 ℔ deg. C. |
| 426.3 kilogrammetres | ” ” | 1 kilogram-deg. C. or kilo-calorie. |
| 426.3 grammetres | ” ” | 1 gram-deg. C. or calorie. |
| 4.180 joules | ” ” | 1 gram-deg. C. or calorie. |
The water for the heat units is supposed to be taken at 20° C. or 68° F., and the degree of temperature is supposed to be measured by the hydrogen thermometer. The acceleration of gravity in latitude 45° is taken as 980.7 C.G.S. For details of more recent and accurate methods of determination, the reader should refer to the article Calorimetry, where tables of the variation of the specific heat of water with temperature are also given.
The second law of thermodynamics is a title often used to denote Carnot’s principle or some equivalent mathematical expression. In some cases this title is not conferred on Carnot’s principle itself, but on some axiom from which the principle may be indirectly deduced. These axioms, however, cannot as a rule be directly applied, so that it would appear preferable to take Carnot’s principle itself as the second law. It may be observed that, as a matter of history, Carnot’s principle was established and generally admitted before the principle of the conservation of energy as applied to heat, and that from this point of view the titles, first and second laws, are not particularly appropriate.
20. Combination of Carnot’s Principle with the Mechanical Theory.—A very instructive paper, as showing the state of the science of heat about this time, is that of C. H. A. Holtzmann, “On the Heat and Elasticity of Gases and Vapours” (Mannheim, 1845; Taylor’s Scientific Memoirs, iv. 189). He points out that the theory of Laplace and Poisson does not agree with facts when applied to vapours, and that Clapeyron’s formulae, though probably correct, contain an undetermined function (Carnot’s F′t, Clapeyron’s 1/C) of the temperature. He determines the value of this function to be J/T by assuming, with Séguin and Mayer, that the work done in the isothermal expansion of a gas is a measure of the heat absorbed. From the then accepted value .078 of the difference of the specific heats of air, he finds the numerical value of J to be 374 kilogrammetres per kilo-calorie. Assuming the heat equivalent of the work to remain in the gas, he obtains expressions similar to Clapeyron’s for the total heat and the specific heats. In consequence of this assumption, the formulae he obtained for adiabatic expansion were necessarily wrong, but no data existed at that time for testing them. In applying his formulae to vapours, he obtained an expression for the saturation-pressure of steam, which agreed with the empirical formula of Roche, and satisfied other experimental data on the supposition that the coefficient of expansion of steam was .00423, and its specific heat 1.69—values which are now known to be impossible, but which appeared at the time to give a very satisfactory explanation of the phenomena.
The essay of Hermann Helmholtz, On the Conservation of Force (Berlin, 1847), discusses all the known cases of the transformation of energy, and is justly regarded as one of the chief landmarks in the establishment of the energy-principle. Helmholtz gives an admirable statement of the fundamental principle as applied to heat, but makes no attempt to formulate the correct equations of thermodynamics on the mechanical theory. He points out the fallacy of Holtzmann’s (and Mayer’s) calculation of the equivalent, but admits that it is supported by Joule’s experiments, though he does not seem to appreciate the true value of Joule’s work. He considers that Holtzmann’s formulae are well supported by experiment, and are much preferable to Clapeyron’s, because the value of the undetermined function F′t is found. But he fails to notice that Holtzmann’s equations are fundamentally inconsistent with the conservation of energy, because the heat equivalent of the external work done is supposed to remain in the gas.
That a quantity of heat equivalent to the work performed actually disappears when a gas does work in expansion, was first shown by Joule in the paper on condensation and rarefaction of air (1845) already referred to. At the conclusion of this paper he felt justified by direct experimental evidence in reasserting definitely the hypothesis of Séguin (loc. cit. p. 383) that “the steam while expanding in the cylinder loses heat in quantity exactly proportional to the mechanical force developed, and that on the condensation of the steam the heat thus converted into power is not given back.” He did not see his way to reconcile this conclusion with Clapeyron’s description of Carnot’s cycle. At a later date, in a letter to Professor W. Thomson (Lord Kelvin) (1848), he pointed out that, since, according to his own experiments, the work done in the expansion of a gas at constant temperature is equivalent to the heat absorbed, by equating Carnot’s expressions (given in § 17) for the work done and the heat absorbed, the value of Carnot’s function F′t must be equal to J/T, in order to reconcile his principle with the mechanical theory.
Professor W. Thomson gave an account of Carnot’s theory (Trans. Roy. Soc. Edin., Jan. 1849), in which he recognized the discrepancy between Clapeyron’s statement and Joule’s experiments, but did not see his way out of the difficulty. He therefore adopted Carnot’s principle provisionally, and proceeded to calculate a table of values of Carnot’s function F′t, from the values of the total-heat and vapour-pressure of steam-then recently determined by Regnault (Mémoires de l’Institut de Paris, 1847). In making the calculation, he assumed that the specific volume v of saturated steam at any temperature T and pressure p is that given by the gaseous laws, pv = RT. The results are otherwise correct so far as Regnault’s data are accurate, because the values of the efficiency per degree F′t are not affected by any assumption with regard to the nature of heat. He obtained the values of the efficiency F′t over a finite range from t to 0° C., by adding up the values of F′t for the separate degrees. This latter proceeding is inconsistent with the mechanical theory, but is the
