Carnot's Reflections on the Motive Power of Fire
When Carnot began working on his book, steam engines had achieved widely recognized economic and industrial importance, but there had been no real scientific study of them. Newcomen had invented the first piston-operated steam engine over a century before, in 1712; some 50 years after that, James Watt made his celebrated improvements, which were responsible for greatly increasing the efficiency and practicality of steam engines. Compound engines (engines with more than one stage of expansion) had already been invented, and there was even a crude form of internal-combustion engine, with which Carnot was familiar and which he described in some detail in his book. Although there existed some intuitive understanding of the workings of engines, scientific theory for their operation was almost nonexistent. In 1824 the principle of conservation of energy was still poorly developed and controversial, and an exact formulation of the first law of thermodynamicswas still more than a decade away; the mechanical equivalence of heat would not be formulated for another two decades. The prevalent theory of heat was the caloric theory, which regarded heat as a sort of weightless and invisible fluid that flowed when out of equilibrium.
Engineers in Carnot's time had tried, by means such as highly pressurized steam and the use of fluids, to improve the efficiency of engines. In these early stages of engine development, the efficiency of a typical engine — the useful work it was able to do when a given quantity of fuelwas burned — was only 3%.
The Carnot Cycle
Carnot sought to answer two questions about the operation of heat engines: "Is the work available from a heat source potentially unbounded?" and "Can heat engines in principle be improved by replacing the steam with some other working fluid or gas?" He attempted to answer these in a memoir, published as a popular work in 1824 when he was only 28 years old. It was entitled Réflexions sur la Puissance Motrice du Feu ("Reflections on the Motive Power of Fire"). The book was plainly intended to cover a rather wide range of topics about heat engines in a rather popular fashion; equations were kept to a minimum and called for little more than simple algebra and arithmetic, except occasionally in the footnotes, where he indulged in a few arguments involving some calculus. He discussed the relative merits of air and steam as working fluids, the merits of various aspects of steam engine design, and even included some ideas of his own regarding possible improvements of the practical nature. The most important part of the book was devoted to an abstract presentation of an idealized engine that could be used to understand and clarify the fundamental principles that are generally applied to all heat engines, independent of their design.
Perhaps the most important contribution Carnot made to thermodynamics was his abstraction of the essential features of the steam engine, as they were known in his day, into a more general and idealized heat engine. This resulted in a model thermodynamic system upon which exact calculations could be made, and avoided the complications introduced by many of the crude features of the contemporary steam engine. By idealizing the engine, he could arrive at clear and indisputable answers to his original two questions.
He showed that the efficiency of this idealized engine is a function only of the two temperatures of the reservoirs between which it operates. He did not, however, give the exact form of the function, which was later shown to be (T1−T2)⁄T1, where T1 is the absolute temperature of the hotter reservoir. (Note: This equation probably came from Kelvin.) No thermal engine operating any other cycle can be more efficient, given the same operating temperatures.
The Carnot cycle is the most efficient possible engine, not only because of the (trivial) absence of friction and other incidental wasteful processes; the main reason is that it assumes no conduction of heat between parts of the engine at different temperatures. Carnot knew that the conduction of heat between bodies at different temperatures is a wasteful and irreversible process, which must be eliminated if the heat engine is to achieve maximum efficiency.
Regarding the second point, he also was quite certain that the maximum efficiency attainable did not depend upon the exact nature of theworking fluid. He stated this for emphasis as a general proposition: "The motive power of heat is independent of the agents employed to realize it; its quantity is fixed solely by the temperatures of the bodies between which the transfer of caloric takes place." For his "motive power of heat", we would today say "the efficiency of a reversible heat engine," and rather than "transfer of caloric" we would say "the reversible transfer of heat." He knew intuitively that his engine would have the maximum efficiency, but was unable to state what that efficiency would be.
He concluded:
The production of motive power is therefore due in steam engines not to actual consumption of caloric but to its transportation from a warm body to a cold body.—Carnot 1960, p. 7
and
In the fall of caloric, motive power evidently increases with the difference of temperature between the warm and cold bodies, but we do not know whether it is proportional to this difference.—Carnot 1960, p. 15
The Second Law of Thermodynamics
In Carnot's idealized model, the caloric heat converted into work could be recovered by reversing the motion of the cycle, a concept subsequently known as thermodynamic reversibility. Nevertheless, Carnot further postulated that some caloric is lost and not converted into mechanical work. Hence, a real heat engine could not realize the Carnot cycle's reversibility and would consequently be less efficient.
Though formulated in terms of caloric, rather than entropy, this was an early rendition of the second law of thermodynamics.
