4. Change of State.—Among the most important effects of heat is that of changing the state of a substance from solid to liquid, or from liquid to vapour. With very few exceptions, all substances, whether simple or compound, are known to be capable of existing in each of the three states under suitable conditions of temperature and pressure. The transition of any substance, from the state of liquid to that of solid or vapour under the ordinary atmospheric pressure, takes place at fixed temperatures, the freezing and boiling-points, which are very sharply defined for pure crystalline substances, and serve in fact as fixed points of the thermometric scale. A change of state cannot, however, be effected in any case without the addition or subtraction of a certain definite quantity of heat. If a piece of ice below the freezing-point is gradually heated at a uniform rate, its temperature may be observed to rise regularly till the freezing-point is reached. At this point it begins to melt, and its temperature ceases to rise. The melting takes a considerable time, during the whole of which heat is being continuously supplied without producing any rise of temperature, although if the same quantity of heat were supplied to an equal mass of water, the temperature of the water would be raised nearly 80° C. Heat thus absorbed in producing a change of state without rise of temperature is called “Latent Heat,” a term introduced by Joseph Black, who was one of the first to study the subject of change of state from the point of view of heat absorbed, and who in many cases actually adopted the comparatively rough method described above of estimating quantities of heat by observing the time required to produce a given change when the substance was receiving heat at a steady rate from its surroundings. For every change of state a definite quantity of heat is required, without which the change cannot take place. Heat must be added to melt a solid, or to vaporize a solid or a liquid, and conversely, heat must be subtracted to reverse the change, i.e. to condense a vapour or freeze a liquid. The quantity required for any given change depends on the nature of the substance and the change considered, and varies to some extent with the conditions (as to pressure, &c.) under which the change is made, but is always the same for the same change under the same conditions. A rough measurement of the latent heat of steam was made as early as 1764 by James Watt, who found that steam at 212° F., when passed from a kettle into a jar of cold water, was capable of raising nearly six times its weight of water to the boiling point. He gives the volume of the steam as about 1800 times that of an equal weight of water.
The phenomena which accompany change of state, and the physical laws by which such changes are governed, are discussed in a series of special articles dealing with particular cases. The articles on [Fusion] and [Alloys] deal with the change from the solid to the liquid state, and the analogous case of solution is discussed in the article on [Solution]. The articles on [Condensation of Gases], [Liquid Gases] and [Vaporization] deal with the theory of the change of state from liquid to vapour, and with the important applications of liquid gases to other researches. The methods of measuring the latent heat of fusion or vaporization are described in the article [Calorimetry], and need not be further discussed here except as an introduction to the history of the evolution of knowledge with regard to the nature of heat.
5. Calorimetry by Latent Heat.—In principle, the simplest and most direct method of measuring quantities of heat consists in observing the effects produced in melting a solid or vaporizing a liquid. It was, in fact, by the fusion of ice that quantities of heat were first measured. If a hot body is placed in a cavity in a block of ice at 0° C., and is covered by a closely fitting slab of ice, the quantity of ice melted will be directly proportional to the quantity of heat lost by the body in cooling to 0° C. None of the heat can possibly escape through the ice, and conversely no heat can possibly get in from outside. The body must cool exactly to 0° C., and every fraction of the heat it loses must melt an equivalent quantity of ice. Apart from heat lost in transferring the heated body to the ice block, the method is theoretically perfect. The only difficulty consists in the practical measurement of the quantity of ice melted. Black estimated this quantity by mopping out the cavity with a sponge before and after the operation. But there is a variable film of water adhering to the walls of the cavity, which gives trouble in accurate work. In 1780 Laplace and Lavoisier used a double-walled metallic vessel containing broken ice, which was in many respects more convenient than the block, but aggravated the difficulty of the film of water adhering to the ice. In spite of this practical difficulty, the quantity of heat required to melt unit weight of ice was for a long time taken as the unit of heat. This unit possesses the great advantage that it is independent of the scale of temperature adopted. At a much later date R. Bunsen (Phil. Mag., 1871), adopting a suggestion of Sir John Herschel’s, devised an ice-calorimeter suitable for measuring small quantities of heat, in which the difficulty of the water film was overcome by measuring the change in volume due to the melting of the ice. The volume of unit mass of ice is approximately 1.0920 times that of unit mass of water, so that the diminution of volume is 0.092 a cubic centimetre for each gramme of ice melted. The method requires careful attention to details of manipulation, which are more fully discussed in the article on [Calorimetry].
For measuring large quantities of heat, such as those produced by the combustion of fuel in a boiler, the most convenient method is the evaporation of water, which is commonly employed by engineers for the purpose. The natural unit in this case is the quantity of heat required to evaporate unit mass of water at the boiling point under atmospheric pressure. In boilers working at a higher pressure, or supplied with water at a lower temperature, appropriate corrections are applied to deduce the quantity evaporated in terms of this unit.
For laboratory work on a small scale the converse method of condensation has been successfully applied by John Joly, in whose steam-calorimeter the quantity of heat required to raise the temperature of a body from the atmospheric temperature to that of steam condensing at atmospheric pressure is observed by weighing the mass of steam condensed on it. (See [Calorimetry].)
6. Thermometric Calorimetry.—For the majority of purposes the most convenient and the most readily applicable method of measuring quantities of heat, is to observe the rise of temperature produced in a known mass of water contained in a suitable vessel or calorimeter. This method was employed from a very early date by Count Rumford and other investigators, and was brought to a high pitch of perfection by Regnault in his extensive calorimetric researches (Mémoires de l’Institut de Paris, 1847); but it is only within comparatively recent years that it has really been placed on a satisfactory basis by the accurate definition of the units involved. The theoretical objections to the method, as compared with latent heat calorimetry, are that some heat is necessarily lost by the calorimeter when its temperature is raised above that of the surroundings, and that some heat is used in heating the vessel containing the water. These are small corrections, which can be estimated with considerable accuracy in practice. A more serious difficulty, which has impaired the value of much careful work by this method, is that the quantity of heat required to raise the temperature of a given mass of water 1° C. depends on the temperature at which the water is taken, and also on the scale of the thermometer employed. It is for this reason, in many cases, impossible to say, at the present time, what was the precise value, within ½ or even 1% of the heat unit, in terms of which many of the older results, such as those of Regnault, were expressed. For many purposes this would not be a serious matter, but for work of scientific precision such a limitation of accuracy would constitute a very serious bar to progress. The unit generally adopted for scientific purposes is the quantity of heat required to raise 1 gram (or kilogram) of water 1° C., and is called the calorie (or kilo-calorie). English engineers usually state results in terms of the British Thermal Unit (B.Th.U.), which is the quantity of heat required to raise 1 ℔ of water 1° F.
7. Watt’s Indicator Diagram; Work of Expansion.—The rapid development of the steam-engine (q.v.) in England during the latter part of the 18th century had a marked effect on the progress of the science of heat. In the first steam-engines the working cylinder served both as boiler and condenser, a very wasteful method, as most of the heat was transferred directly from the fire to the condensing water without useful effect. The first improvement (about 1700) was to use a separate boiler, but the greater part of the steam supplied was still wasted in reheating the cylinder, which had been cooled by the injection of cold water to condense the steam after the previous stroke. In 1769 James Watt showed how to avoid this waste by using a separate condenser and keeping the cylinder as hot as possible. In his earlier engines the steam at full boiler pressure was allowed to raise the piston through nearly the whole of its stroke. Connexion with the boiler was then cut off, and the steam at full pressure was discharged into the condenser. Here again there was unnecessary waste, as the steam was still capable of doing useful work. He subsequently introduced “expansive working,” which effected still further economy. The connexion with the boiler was cut off when a fraction only, say ¼, of the stroke had been completed, the remainder of the stroke being effected by the expansion of the steam already in the cylinder with continually diminishing pressure. By the end of the stroke, when connexion was made to the condenser, the pressure was so reduced that there was comparatively little waste from this cause. Watt also devised an instrument called an indicator (see [Steam Engine]), in which a pencil, moved up and down vertically by the steam pressure, recorded the pressure in the cylinder at every point of the stroke on a sheet of paper moving horizontally in time with the stroke of the piston. The diagram thus obtained made it possible to study what was happening inside the cylinder, and to deduce the work done by the steam in each stroke. The method of the indicator diagram has since proved of great utility in physics in studying the properties of gases and vapours. The work done, or the useful effect obtained from an engine or any kind of machine, is measured by the product of the resistance overcome and the distance through which it is overcome. The result is generally expressed in terms of the equivalent weight raised through a certain height against the force of gravity.[1] If, for instance, the pressure on a piston is 50 ℔ per sq. in., and the area of the piston is 100 sq. in., the force on the piston is 5000 ℔ weight. If the stroke of the piston is 1 ft., the work done per stroke is capable of raising a weight of 5000 ℔ through a height of 1 ft., or 50 ℔ through a height of 100 ft. and so on.
| Fig. 3.—Watt’s Indicator Diagram. Patent of 1782. |
Fig. 3 represents an imaginary indicator diagram for a steam-engine, taken from one of Watt’s patents. Steam is admitted to the cylinder when the piston is at the beginning of its stroke, at S. ST represents the length of the stroke or the limit of horizontal movement of the paper on which the diagram is drawn. The indicating pencil rises to the point A, representing the absolute pressure of 60 ℔ per sq. in. As the piston moves outwards the pencil traces the horizontal line AB, the pressure remaining constant till the point B is reached, at which connexion to the boiler is cut off. The work done so far is represented by the area of the rectangle ABSF, namely AS × SF, multiplied by the area of the piston in sq. in. The result is in foot-pounds if the fraction of the stroke SF is taken in feet. After cut-off at B the steam expands under diminishing pressure, and the pencil falls gradually from B to C, following the steam pressure until the exhaust valve opens at the end of the stroke. The pressure then falls rapidly to that of the condenser, which for an ideal case may be taken as zero, following Watt. The work done during expansion is found by dividing the remainder of the stroke FT into a number of equal parts (say 8, Watt takes 20) and measuring the pressure at the points 1, 2, 3, 4, &c., corresponding to the middle of each. We thus obtain a number of small rectangles, the sum of which is evidently very nearly equal to the whole area BCTF under the expansion curve, or to the remainder of the stroke FT multiplied by the average or mean value of the pressure. The whole work done in the forward stroke is represented by the area ABCTSA, or by the average value of the pressure P over the whole stroke multiplied by the stroke L. This area must be multiplied by the area of the piston A in sq. in. as before, to get the work done per stroke in foot-pounds, which is PLA. If the engine repeats this cycle N times per minute, the work done per minute is PLAN foot-pounds, which is reduced to horse-power by dividing by 33,000. If the steam is ejected by the piston at atmospheric pressure (15 ℔ per sq. in.) instead of being condensed at zero pressure, the area CDST under the atmospheric line CD, representing work done against back-pressure on the return stroke must be subtracted. If the engine repeats the same cycle or series of operations continuously, the indicator diagram will be a closed curve, and the nett work done per cycle will be represented by the included area, whatever the form of the curve.
8. Thermal Efficiency.—The thermal efficiency of an engine is the ratio of the work done by the engine to the heat supplied to it. According to Watt’s observations, confirmed later by Clément and Désormes, the total heat required to produce 1 ℔ of saturated steam at any temperature from water at 0° C. was approximately 650 times the quantity of heat required to raise 1 ℔ of water 1° C. Since 1 ℔ of steam represented on this assumption a certain quantity of heat, the efficiency could be measured naturally in foot-pounds of work obtainable per ℔ of steam, or conversely in pounds of steam consumed per horse-power-hour.