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Rh employed, and have different properties from air, but the efficiency is found to vary with compression in the same manner as for air. For this reason a committee of the Institution of Civil Engineers in 1905 recommended the adoption of the air-standard for estimating the effects of varying the compression ratio, and defined the relative efficiency of an internal combustion engine as the ratio of its observed efficiency to that of a perfect air-engine with the same compression.

24. Effect of Dissociation, and Increase of Specific Heat.—One of the most important effects of heat is the decomposition or dissociation of compound molecules. Just as the molecules of a vapour combine with evolution of heat to form the more complicated molecules of the liquid, and as the liquid molecules require the addition of heat to effect their separation into molecules of vapour; so in the case of molecules of different kinds which combine with evolution of heat, the reversal of the process can be effected either by the agency of heat, or indirectly by supplying the requisite amount of energy by electrical or other methods. Just as the latent heat of vaporization diminishes with rise of temperature, and the pressure of the dissociated vapour molecules increases, so in the case of compound molecules in general the heat of combination diminishes with rise of temperature, and the pressure of the products of dissociation increases. There is evidence that the compound carbon dioxide, CO2, is partly dissociated into carbon monoxide and oxygen at high temperatures, and that the proportion dissociated increases with rise of temperature. There is a very close analogy between these phenomena and the vaporization of a liquid. The laws which govern dissociation are the same fundamental laws of thermodynamics, but the relations involved are necessarily more complex on account of the presence of different kinds of molecules, and present special difficulties for accurate investigation in the case where dissociation does not begin to be appreciable until a high temperature is reached. It is easy, however, to see that the general effect of dissociation must be to diminish the available temperature of combustion, and all experiments go to show that in ordinary combustible mixtures the rise of temperature actually attained is much less than that calculated as in § 22, on the assumption that the whole heat of combustion is developed and communicated to products of constant specific heat. The defect of temperature observed can be represented by supposing that the specific heat of the products of combustion increases with rise of temperature. This is the case for CO2 even at ordinary temperatures, according to Regnault, and probably also for air and steam at higher temperatures. Increase of specific heat is a necessary accompaniment of dissociation, and from some points of view may be regarded as merely another way of stating the facts. It is the most convenient method to adopt in the case of products of combustion consisting of a mixture of CO2 and steam with a large excess of inert gases, because the relations of equilibrium of dissociated molecules of so many different kinds would be too complex to permit of any other method of expression. It appears from the researches of Dugald Clerk, H. le Chatelier and others that the apparent specific heat of the products of combustion in a gas-engine may be taken as approximately .34 to .33 in place of .24 at working temperatures between 1000° C. and 1700° C., and that the ratio of the specific heats is about 1.29 in place of 1.41. This limits the availability of the heat of combustion by reducing the rise of temperature actually obtainable in combustion at constant volume by 30 or 40%, and also by reducing the range of temperature ′ / ″ for a given ratio of expansions r from r.41 to r.29. The formula given in § 21 is no longer quite exact, because the ratio of the specific heats of the mixture during compression is not the same as that of the products of combustion during expansion. But since the work done depends principally on the expansion curve, the ratio of the range of temperature in expansion (′ − ″) to the maximum temperature ′ will still give a very good approximation to the possible efficiency. Taking r = 5, as before, for the compression ratio, the possible efficiency is reduced from 48% to 38%, if = 1.29 instead of 1.41. A large gas-engine of the present day with r = 5 may actually realize as much as 34% indicated efficiency, which is 90% of the maximum possible, showing how perfectly all avoidable heat losses have been minimized.

It is often urged that the gas-engine is relatively less efficient than the steam-engine, because, although it has a much higher absolute efficiency, it does not utilize so large a fraction of its temperature range, reckoning that of the steam-engine from the temperature of the boiler to that of the condenser, and that of the gas-engine from the maximum temperature of combustion to that of the air. This is not quite fair, and has given rise to the mistaken notion that “there is an immense margin for improvement in the gas-engine,” which is not the case if the practical limitations of volume are rightly considered. If expansion could be carried out in accordance with Carnot’s principle of maximum efficiency, down to the lower limit of temperature 0, with rejection of heat at 0 during compression to the original volume V0, it would no doubt be possible to obtain an ideal efficiency of nearly 80%. But this would be quite impracticable, as it would require expansion to about 100 times v0, or 500 times the compression volume. Some advantage no doubt might be obtained by carrying the expansion beyond the original volume. This has been done, but is not found to be worth the extra complication. A more practical method, which has been applied by Diesel for liquid fuel, is to introduce the fuel at the end of compression, and adjust the supply in such a manner as to give combustion at nearly constant pressure. This makes it possible to employ higher compression, with a corresponding increase in the ratio of expansion and the theoretical efficiency. With a compression ratio of 14, an indicated efficiency of 40% has been obtained In this way, but owing to additional complications the brake efficiency was only 31%, which is hardly any improvement on the brake efficiency of 30% obtained with the ordinary type of gas-engine. Although Carnot’s principle makes it possible to calculate in every case what the limiting possible efficiency would be for any kind of cycle if all heat losses were abolished, it is very necessary, in applying the principle to practical cases, to take account of the possibility of avoiding the heat losses which are supposed to be absent, and of other practical limitations in the working of the actual engine. An immense amount of time and ingenuity has been wasted in striving to realize impossible margins of ideal efficiency, which a close study of the practical conditions would have shown to be illusory. As Carnot remarks at the conclusion of his essay: “Economy of fuel is only one of the conditions a heat-engine must satisfy; in many cases it is only secondary, and must often give way to considerations of safety, strength and wearing qualities of the machine, of smallness of space occupied, or of expense in erecting. To know how to appreciate justly in each case the considerations of convenience and economy, to be able to distinguish the essential from the accessory, to balance all fairly, and finally to arrive at the best result by the simplest means, such must be the principal talent of the man called on to direct and co-ordinate the work of his fellows for the attainment of a useful object of any kind.”

25. Modes of Transference.—There are three principal modes of transference of heat, namely (1) convection, (2) conduction, and (3) radiation.

(1) In convection, heat is carried or conveyed by the motion of heated masses of matter. The most familiar illustrations of this method of transference are the heating of buildings by the circulation of steam or hot water, or the equalization of temperature of a mass of unequally heated liquid or gas by convection currents, produced by natural changes of density or by artificial stirring. (2) In conduction, heat is transferred by contact between contiguous particles of matter and is passed on from one particle to the next without visible relative motion of the parts of the body. A familiar illustration of conduction is the passage of heat through the metal plates of a boiler from the fire to the water inside, or the transference of heat from a soldering bolt to the solder and the metal with which it is placed in contact.