construction. But they possess one obvious defect from a theoretical
point of view, namely, that the subdivision of the temperature
scale depends on the expansion of the particular liquid
selected as the standard. A liquid such as water, which, when continuously
heated at a uniform rate from its freezing-point, first
contracts and then expands, at a rapidly increasing rate, would
obviously be unsuitable. But there is no a priori reason why other
liquids should not behave to some extent in a similar way. As
a matter of fact, it was soon observed that thermometers carefully
constructed with different liquids, such as alcohol, oil and
mercury, did not agree precisely in their indications at points of
the scale intermediate between the fixed points, and diverged
even more widely outside these limits. Another possible method,
proposed in 1694 by Carlo Renaldeni (1615–1698), professor
of mathematics and philosophy at Pisa, would be to determine
the intermediate points of the scale by observing the temperatures
of mixtures of ice-cold and boiling water in varying proportions.
On this method, the temperature of 50° C. would be defined
as that obtained by mixing equal weights of water at 0° C. and
100° C.; 20° C., that obtained by mixing 80 parts of water at
0° C. with 20 parts of water at 100° C. and so on. Each degree
rise of temperature in a mass of water would then represent
the addition of the same quantity of heat. The scale thus
obtained would, as a matter of fact, agree very closely with that
of a mercury thermometer, but the method would be very
difficult to put in practice, and would still have the disadvantage
of depending on the properties of a particular liquid, namely,
water, which is known to behave in an anomalous manner in
other respects. At a later date, the researches of Gay-Lussac
(1802) and Regnault (1847) showed that the laws of the expansion
of gases are much simpler than those of liquids. Whereas the
expansion of alcohol between 0° C. and 100° C. is nearly seven
times as great as that of mercury, all gases (excluding easily
condensible vapours) expand equally, or so nearly equally that
the differences between them cannot be detected without the
most refined observations. This equality of expansion affords
a strong a priori argument for selecting the scale given by the
expansion of a gas as the standard scale of temperature, but there
are still stronger theoretical grounds for this choice, which will
be indicated in discussing the absolute scale (§ 21). Among
liquids mercury is found to agree most nearly with the gas scale,
and is generally employed in thermometers for scientific purposes
on account of its high boiling-point and for other reasons.
The differences of the mercurial scale from the gas scale having
been carefully determined, the mercury thermometer can be
used as a secondary standard to replace the gas thermometer
within certain limits, as the gas thermometer would be very
troublesome to employ directly in ordinary investigations.
For certain purposes, and especially at temperatures beyond
the range of mercury thermometers, electrical thermometers,
also standardized by reference to the gas thermometer, have
been very generally employed in recent years, while for still
higher temperatures beyond the range of the gas thermometer,
thermometers based on the recently established laws of radiation
are the only instruments available. For a further discussion of
the theory and practice of the measurement of temperature,
the reader is referred to the article Thermometry.
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
