THE NATURE OF HEAT 12. In the early days of the science it was natural to ascribe the manifestations of heat to the action of a subtle imponderable fluid called "caloric," with the power of pene trating, expanding and dissolving bodies, or dissipating them in vapour. The fluid was imponderable, because the most careful experiments failed to show that heat produced any increase in weight. The opposite property of levitation was often ascribed to heat, but it was shown by more cautious investigators that the apparent loss of weight due to heating was to be attributed to evaporation or to upward air currents. The fundamental idea of an imaginary fluid to represent heat was useful as helping the mind to a conception of something remaining invariable in quan tity through many transformations, but in some respects the analogy was misleading, and tended greatly to retard the progress of science. The caloric theory was very simple in its application to the majority of calorimetric experiments, and gave a fair account of the elementary phenomena of change of state, but it encountered serious difficulties in explaining the production of heat by friction, or the changes of temperature accompanying the compression or expansion of a gas.
The' explanation which the calorists offered of the production of heat by friction or compression was that some of the latent caloric was squeezed or ground out of the bodies concerned and became "sensible." In the case of heat developed by friction, they supposed that the abraded portions of the material were capable of holding a smaller quantity of heat, or had less "capacity for heat," than the original material. From a logical point of view, this was a perfectly tenable hypothesis, and one difficult to refute. It was easy to account in this way for the heat produced in boring cannon and similar operations, where the amount of abraded ma terial was large. To refute this explanation, Rumford (Phil. Trans., 1798) made his celebrated experiments with a blunt borer in one of which he succeeded in boiling by friction 26.51b. of cold water in 22 hours, with the production of only 4,145 grains of metallic powder. He then showed by experiment that the metallic powder required the same amount of heat to raise its temperature I °, as an equal weight of the original metal, or that its "capacity for heat" (in this sense) was unaltered by reducing it to powder; and he argued that "in any case so small a quantity of powder could not possibly account for all the heat generated, that the supply of heat appeared to be inexhaustible, and that heat could not be a material substance, but must be something of the nature of motion." Unfortunately Rumford's argument was not quite conclusive. The supporters of the caloric theory appear, whether consciously or unconsciously, to have used the phrase "capacity for heat" in two entirely distinct senses without any clear definition of the difference. The phrase "capacity for heat" might very naturally denote the total quantity of heat contained in a body, which we have no means of measuring, but it was generally used to signify the quantity of heat required to raise the temperature of a body one degree, which is quite a different thing, and has no necessary relation to the total heat. In proving that the powder and the solid metal required the same quantity of heat to raise the tem perature of equal masses of either one degree, Rumford did not prove that they contained equal quantities of heat, which was the real point at issue in this instance. The metal tin actually changes into powder below a certain temperature, and in so doing evolves a measurable quantity of heat. A mixture of the gases oxygen and hydrogen, in the proportions in which they combine to form water, evolves when burnt sufficient heat to raise more than 3o times its weight of water from the freezing to the boiling point; and the mixture of gases may, in this sense, be said to contain so much more heat than the water, although its capacity for heat in the ordinary sense is only about half that of the water produced. To complete the refutation of the calorists' explana tion of the heat produced by friction, it would have been neces sary for Rumford to show that the powder when reconverted into the same state as the solid metal did not absorb a quantity of heat equivalent to that evolved in the grinding; in other words that the heat produced by friction was not simply that due to the change of state of the metal from solid to powder.
Shortly afterwards, in i 799, Davy (see Sir H. Davy's Collected Works, 1839) described an experiment in which he melted ice by rubbing two blocks together. This experiment afforded a very direct refutation of the calorists' view, because it was a well known fact that ice required to have a quantity of heat added to it to convert it into water, so that the water produced by the friction contained more heat than the ice. In stating as the con clusion to be drawn from this experiment that "friction conse quently does not diminish the capacity of bodies for heat," Davy apparently uses the phrase capacity for heat in the sense of total heat contained in a body, because in a later section of the same essay he definitely gives the phrase this meaning, and uses the term "capability of temperature" to denote what we now term capacity for heat.
The delay in the overthrow of the caloric theory, and in the acceptance of the view that heat is a mode of motion, was no doubt partly due to some fundamental confusion of ideas in the use of the term "capacity for heat" and similar phrases. A still greater obstacle lay in the comparative vagueness of the motion or vibration theory. Davy speaks of heat as being "repulsive motion," and distinguishes it from light, which is "projective motion"; though heat is certainly not a substance— according to Davy in the essay under discussion—and may not even be treated as an imponderable fluid, light as certainly is a material substance, and is capable of forming chemical com pounds with ordinary matter, such as oxygen gas, which is not a simple substance, but a compound, termed phosoxygen, of light and oxygen.
Accepting the conclusions of Davy and Rumford that heat is not a material substance but a mode of motion, there still remains the question, what definite conception is to be attached to a quantity of heat? What do we mean by a quantity of vibratory motion, how is the quantity of motion to be estimated, and why should it remain invariable in many transformations? The idea that heat was a "mode of motion" was applicable as a qualitative explanation of many of the effects of heat, but it lacked the quantitative precision of a scientific statement, and could not be applied to the calculation and prediction of definite results. The state of science at the time of Rumford's and Davy's experi ments did not admit of a more exact generalization. The way was paved in the first instance by a more complete study of the laws of gases, to which Laplace, Dalton, Gay-Lussac, Dulong and many others contributed both on the experimental and theoretical side. Although the development proceeded simultaneously along many parallel lines, it is interesting and instructive to take the investigation of the properties of gases, and to endeavour to trace the steps by which the true theory was finally attained.