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CALORIMETRY

method. Callendar has, however, devised a continuous method of mixture, which appears to be peculiarly adapted to the purpose, and promises to give more certain results. In any case it may be remarked that formulae such as those of Jamin, Henrichsen, Baumgartner, Winkelmann or Dieterici, which give far more rapid rates of increase than that of Regnault, cannot possibly be reconciled with his observations, or with those of Reynolds and Moorby, or Callendar and Barnes, and are certainly inapplicable above 100° C.

§ 16. On the Choice of the Thermal Unit.—So much uncertainty still prevails on this fundamental point that it cannot be passed over without reference. There are three possible kinds of unit, depending on the three fundamental methods already given: (1) the thermometric unit, or the thermal capacity of unit mass of a standard substance under given conditions of temperature and pressure on the scale of a standard thermometer. (2) The latent-heat unit, or the quantity of heat required to melt or vaporize unit mass of a standard substance under given conditions. This unit has the advantage of being independent of thermometry, but the applicability of these methods is limited to special cases, and the relation of the units to other units is difficult to determine. (3) The absolute or mechanical unit, the quantity of heat equivalent to a given quantity of mechanical or electrical energy. This can be very accurately realized, but is not so convenient as (1) for ordinary purposes.

In any case it is necessary to define a thermometric unit of class (1). The standard substance must be a liquid. Water is always selected, although some less volatile liquid, such as aniline or mercury, would possess many advantages. With regard to the scale of temperature, there is very general agreement that the absolute scale as realized by the hydrogen or helium thermometer should be adopted as the ultimate standard of reference. But as the hydrogen thermometer is not directly available for the majority of experiments, it is necessary to use a secondary standard for the practical definition of the unit. The electrical resistance thermometer of platinum presents very great advantages for this purpose over the mercury thermometer in point of reproducibility, accuracy and adaptability to the practical conditions of experiment. The conditions of use of a mercury thermometer in a calorimetric experiment are necessarily different from those under which its corrections are determined, and this difference must inevitably give rise to constant errors in practical work. The primary consideration in the definition of a unit is to select that method which permits the highest order of accuracy in comparison and verification. For this reason the definition of the thermal unit will in the end probably be referred to a scale of temperature defined in terms of a standard platinum thermometer.

There is more diversity of opinion with regard to the question of the standard temperature. Many authors, adopting Regnault's formula, have selected 0° C. as the standard temperature, but this cannot be practically realized in the case of water, and his formula is certainly erroneous at low temperatures. A favourite temperature to select is 4° C., the temperature of maximum density, since at this point the specific heat at constant volume is the same as that at constant pressure But this is really of no consequence, since the specific heat at constant volume cannot be practically realized. The specific heat at 4° could be accurately determined at the mean over the range 0° to 8° keeping the jacket at 0° C. But the change appears to be rather rapid near 0°, the temperature is inconveniently low for ordinary calorimetric work, and the unit at 4° would be so much larger than the specific heat at ordinary temperatures that nearly all experiments would require reduction. The natural point to select would be that of minimum specific heat, but if this occurs at 40° C. it would be inconveniently high for practical realization except by the continuous electrical method. It was proposed by a committee of the British Association to select the temperature at which the specific heat was 4.200 joules, leaving the exact temperature to be subsequently determined. It was supposed at the time, from the original reduction of Rowland's experiments, that this would be nearly at 10° C., but it now appears that it may be as low is 5° C., which would be inconvenient. This is really only an absolute unit in disguise, and evades the essential point, which is the selection of a standard temperature for the water thermometric unit. A similar objection applies to selecting the temperature at which the specific heat is equal to its mean value between 0° and 100°. The mean calorie cannot be accurately realized in practice in any simple manner, and is therefore unsuitable as a standard of comparison. Its relation to the calorie at any given temperature, such as 15° or 20°, cannot be determined with the same degree of accuracy as the ratio of the specific heat at 15° to that at 20°, if the scale of temperature is given. The most practical unit is the calorie at 15° or 20° or some temperature in the range of ordinary practice. The temperature most generally favoured is 15°, but 20° would be more suitable for accurate work. These units differ only by 11 parts in 10,000 according to Callendar and Barnes, or by 13 in 10,000 according to Rowland and Griffiths, so that the difference between them is of no great importance for ordinary purposes. But for purposes of definition it would be necessary to take the mean value of the specific heat over a given range of temperature, preferably at least 10°, rather than the specific heat at a point which necessitates reference to some formula of reduction for the rate of variation. The specific heat at 15° would be determined with reference to the mean over the range 10° to 20°, and that at 20° from the range 15° to 25°. There can be no doubt that the range 10° to 20° is too low for the accurate thermal regulation of the conditions of the experiment. The range 15° to 25° would be much more convenient from this point of view, and a mean temperature of 20° is probably nearest the average of accurate calorimetric work. For instance 20° is the mean of the range of the experiments of Griffiths and of Rowland, and is close to that of Schuster and Gannon. It is readily attainable at any time in a modern laboratory with adequate heating arrangements, and is probably on the whole the most suitable temperature to select.

§ 17. Specific Heat of Gases.—In the case of solids and liquids under ordinary conditions of pressure, the external work of expansion is so small that it may generally be neglected; but with gases or vapours, or with liquids near the critical point, the external work becomes so large that it is essential to specify the conditions under which the specific heat is measured. The most important cases are, the specific heats (1) at constant volume; (2) at constant pressure; (3) at saturation pressure in the case of a liquid or vapour. In consequence of the small thermal capacity of gases and vapours per unit volume at ordinary pressures, the difficulties of direct measurement are almost insuperable except in case (2). Thus the direct experimental evidence is somewhat meagre and conflicting, but the question of the relation of the specific heats of gases is one of great interest in connexion with the kinetic theory and the constitution of the molecule. The well-known experiments of Regnault and Wiedemann on the specific heat of gases at constant pressure agree in showing that the molecular specific heat, or the thermal capacity of the molecular weight in grammes, is approximately independent of the temperature and pressure in case of the more stable diatomic gases, such as H2, O2, N2, CO, &c., and has nearly the same value for each gas. They also indicate that it is much larger, and increases considerably with rise of temperature, in the case of more condensible vapours, such as Cl2, Br2, or more complicated molecules, such as CO2, N2O, NH3, C2H4. The direct determination of the specific heat at constant volume is extremely difficult, but has been successfully attempted by Joly with his steam calorimeter, in the case of air and CO2. Employing pressures between 7 and 27 atmospheres, he found that the specific heat of air between 10° and 100° C. increased very slightly with increase of density, but that of CO2 increased nearly 3% between 7 and 21 atmospheres. The following formulae represent his results for the specific heat s at constant volume in terms of the density d in gms. per c.c.:—


Air, s = 0.1715 + 0.028d,
CO2, s = 0.165 + 0.213d + 0.34d2.

§ 18. Ratio of Specific Heats.—According to the elementary kinetic theory of an ideal gas, the molecules of which are so small and so far apart that their mutual actions may be neglected, the kinetic energy of translation of the molecules is proportional to the absolute temperature, and is equal to 32 of pv, the product of the pressure and the volume, per unit mass. The expansion per degree at constant pressure is v/θ = R/p. The external work of expansion per degree is equal to R, being the product of the pressure and the expansion, and represents the difference of the specific heats S—s, at constant pressure and volume, assuming as above that the internal work of expansion is negligible. If the molecules are supposed to be like smooth, hard, elastic spheres, incapable of receiving any other kind of energy except that of translation, the specific heat at constant volume would be the increase per degree of the kinetic energy namely 3pv/2θ − 3R/2, that at constant pressure would be 5R/2, and the ratio of the specific heats would be 53 or 1.666. This appears to be actually the case for monatomic gases such as mercury vapour (Kundt and Warburg, 1876), argon and helium (Ramsay, 1896). For diatomic or compound gases Clerk Maxwell supposed that the molecule would also possess energy of rotation, and endeavoured to prove that in this case the energy would be equally divided between the six degrees of freedom, three of translation and three of rotation, if the molecule were regarded as a rigid body incapable of vibration-energy. In this case we should have s = 3R, S = 4R, S/s = 43 = 1.333. In 1879 Maxwell considered it one of the greatest difficulties which the kinetic theory had yet encountered, that in spite of the many other degrees of freedom of vibration revealed by the spectroscope, the experimental value of the ratio