correct method on the assumption that the heat given up to the
condenser is equal to that taken from the source. The values he
obtained for F′t agreed very well with those previously given by
Carnot and Clapeyron, and showed that this function diminishes
with rise of temperature roughly in the inverse ratio of T, as
suggested by Joule.
R. J. E. Clausius (Pogg. Ann., 1850, 79, p. 369) and W. J. M. Rankine (Trans. Roy. Soc. Edin., 1850) were the first to develop the correct equations of thermodynamics on the mechanical theory. When heat was supplied to a body to change its temperature or state, part remained in the body as intrinsic heat energy E, but part was converted into external work of expansion W and ceased to exist as heat. The part remaining in the body was always the same for the same change of state, however performed, as required by Carnot’s fundamental axiom, but the part corresponding to the external work was necessarily different for different values of the work done. Thus in any cycle in which the body was exactly restored to its initial state, the heat remaining in the body would always be the same, or as Carnot puts it, the quantities of heat absorbed and given out in its diverse transformations are exactly “compensated,” so far as the body is concerned. But the quantities of heat absorbed and given out are not necessarily equal. On the contrary, they differ by the equivalent of the external work done in the cycle. Applying this principle to the case of steam, Clausius deduced a fact previously unknown, that the specific heat of steam maintained in a state of saturation is negative, which was also deduced by Rankine (loc. cit.) about the same time. In applying the principle to gases Clausius assumes (with Mayer and Holtzmann) that the heat absorbed by a gas in isothermal expansion is equivalent to the work done, but he does not appear to be acquainted with Joule’s experiment, and the reasons he adduces in support of this assumption are not conclusive. This being admitted, he deduces from the energy principle alone the propositions already given by Carnot with reference to gases, and shows in addition that the specific heat of a perfect gas must be independent of the density. In the second part of his paper he introduces Carnot’s principle, which he quotes as follows: “The performance of work is equivalent to a transference of heat from a hot to a cold body without the quantity of heat being thereby diminished.” This is not Carnot’s way of stating his principle (see § 15), but has the effect of exaggerating the importance of Clapeyron’s unnecessary assumption. By equating the expressions given by Carnot for the work done and the heat absorbed in the expansion of a gas, he deduces (following Holtzmann) the value J/T for Carnot’s function F′t (which Clapeyron denotes by 1/C). He shows that this assumption gives values of Carnot’s function which agree fairly well with those calculated by Clapeyron and Thomson, and that it leads to values of the mechanical equivalent not differing greatly from those of Joule. Substituting the value J/T for C in the analytical expressions given by Clapeyron for the latent heat of expansion and vaporization, these relations are immediately reduced to their modern form (see Thermodynamics, § 4). Being unacquainted with Carnot’s original work, but recognizing the invalidity of Clapeyron’s description of Carnot’s cycle, Clausius substituted a proof consistent with the mechanical theory, which he based on the axiom that “heat cannot of itself pass from cold to hot.” The proof on this basis involves the application of the energy principle, which does not appear to be necessary, and the axiom to which final appeal is made does not appear more convincing than Carnot’s. Strange to say, Clausius did not in this paper give the expression for the efficiency in a Carnot cycle of finite range (Carnot’s Ft) which follows immediately from the value J/T assumed for the efficiency F′t of a cycle of infinitesimal range at the temperature t C or T Abs.
Rankine did not make the same assumption as Clausius explicitly, but applied the mechanical theory of heat to the development of his hypothesis of molecular vortices, and deduced from it a number of results similar to those obtained by Clausius. Unfortunately the paper (loc. cit.) was not published till some time later, but in a summary given in the Phil. Mag. (July 1851) the principal results were detailed. Assuming the value of Joule’s equivalent, Rankine deduced the value 0.2404 for the specific heat of air at constant pressure, in place of 0.267 as found by Delaroche and Bérard. The subsequent verification of this value by Regnault (Comptes rendus, 1853) afforded strong confirmation of the accuracy of Joule’s work. In a note appended to the abstract in the Phil. Mag. Rankine states that he has succeeded in proving that the maximum efficiency of an engine working in a Carnot cycle of finite range t1 to t0 is of the form (t1 − t0) / (t1 − k), where k is a constant, the same for all substances. This is correct if t represents temperature Centigrade, and k = −273.
Professor W. Thomson (Lord Kelvin) in a paper “On the Dynamical Theory of Heat” (Trans. Roy. Soc. Edin., 1851, first published in the Phil. Mag., 1852) gave a very clear statement of the position of the theory at that time. He showed that the value F′t = J/T, assumed for Carnot’s function by Clausius without any experimental justification, rested solely on the evidence of Joule’s experiment, and might possibly not be true at all temperatures. Assuming the value J/T with this reservation, he gave as the expression for the efficiency over a finite range t1 to t0 C., or T1 to T0 Abs., the result,
| W/H = (t1 − t0) / (t1 + 273) = (T1 − T0) / T1 | (4) |
which, he observed, agrees in form with that found by Rankine.
21. The Absolute Scale of Temperature.—Since Carnot’s function is the same for all substances at the same temperature, and is a function of the temperature only, it supplies a means of measuring temperature independently of the properties of any particular substance. This proposal was first made by Lord Kelvin (Phil. Mag., 1848), who suggested that the degree of temperature should be chosen so that the efficiency of a perfect engine at any point of the scale should be the same, or that Carnot’s function F′t should be constant. This would give the simplest expression for the efficiency on the caloric theory, but the scale so obtained, when the values of Carnot’s function were calculated from Regnault’s observations on steam, was found to differ considerably from the scale of the mercury or air-thermometer. At a later date, when it became clear that the value of Carnot’s function was very nearly proportional to the reciprocal of the temperature T measured from the absolute zero of the gas thermometer, he proposed a simpler method (Phil. Trans., 1854), namely, to define absolute temperature θ as proportional to the reciprocal of Carnot’s function. On this definition of absolute temperature, the expression (θ1 − θ0) / θ1 for the efficiency of a Carnot cycle with limits θ1 and θ0 would be exact, and it became a most important problem to determine how far the temperature T by gas thermometer differed from the absolute temperature θ. With this object he devised a very delicate method, known as the “porous plug experiment” (see Thermodynamics) of testing the deviation of the gas thermometer from the absolute scale. The experiments were carried out in conjunction with Joule, and finally resulted in showing (Phil. Trans., 1862, “On the Thermal Effects of Fluids in Motion”) that the deviations of the air thermometer from the absolute scale as above defined are almost negligible, and that in the case of the gas hydrogen the deviations are so small that a thermometer containing this gas may be taken for all practical purposes as agreeing exactly with the absolute scale at all ordinary temperatures. For this reason the hydrogen thermometer has since been generally adopted as the standard.
22. Availability of Heat of Combustion.—Taking the value 1.13 kilogrammetres per kilo-calorie for 1° C. fall of temperature at 100° C., Carnot attempted to estimate the possible performance of a steam-engine receiving heat at 160° C. and rejecting it at 40° C. Assuming the performance to be simply proportional to the temperature fall, the work done for 120° fall would be 134 kilogrammetres per kilo-calorie. To make an accurate calculation required a knowledge of the variation of the function F′t with temperature. Taking the accurate formula of § 20, the work obtainable is 118 kilogrammetres per kilo-calorie, which is
