Note 26 — Chapter II · THE COMPOSITION OF WATER, HYDROGEN

The law of Gay-Lussac states that all gases in all conditions present one coefficient of expansion 0·00367; that is, when heated from 0° to 100° they expand like air; namely, a thousand volumes of a gas measured at 0° will occupy 1367 volumes at 100°. Regnault, about 1850, showed that Gay-Lussac's law is not entirely correct, and that different gases, and also one and the same gas at different pressures, have not quite the same coefficients of expansion. Thus the expansion of air between 0° and 100° is 0·367 under the ordinary pressure of one atmosphere, and at three atmospheres it is 0·371, the expansion of hydrogen is 0·366, and of carbonic anhydride 0·37. Regnault, however, did not directly determine the change of volume between 0° and 100°, but measured the variation of tension with the change of temperature; but since gases do not entirely follow Mariotte's law, the change of volume cannot be directly judged by the variation of tension. The investigations carried on by myself and Kayander, about 1870, showed the variation of volume on heating from 0° to 100° under a constant pressure. These investigations confirmed Regnault's conclusion that Gay-Lussac's law is not entirely correct, and further showed (1) that the expansion per volume from 0° to 100° under a pressure of one atmosphere, for air = 0·368, for hydrogen = 0·367, for carbonic anhydride = 0·373, for hydrogen bromide = 0·386, &c.; (2) that for gases which are more compressible than should follow from Mariotte's law the expansion by heat increases with the pressure—for example, for air at a pressure of three and a half atmospheres, it equals 0·371, for carbonic anhydride at one atmosphere it equals 0·373, at three atmospheres 0·389, and at eight atmospheres 0·413; (3) that for gases which are less compressible than should follow from Mariotte's law, the expansion by heat decreases with an increase of pressure—for example, for hydrogen at one atmosphere 0·367, at eight atmospheres 0·369, for air at a quarter of an atmosphere 0·370, at one atmosphere 0·368; and hydrogen like air (and all gases) is less compressed at low pressures than should follow from Mariotte's law (see Note 25). Hence, hydrogen, starting from zero to the highest pressures, exhibits a gradually, although only slightly, varying coefficient of expansion, whilst for air and other gases at the atmospheric and higher pressures, the coefficient of expansion increases with the increase of pressure, so long as their compressibility is greater than should follow from Mariotte's law. But when at considerable pressures, this kind of discrepancy passes into the normal (see Note 25), then the coefficient of expansion of all gases decreases with an increase of pressure, as is seen from the researches of Amagat. The difference between the two coefficients of expansion, for a constant pressure and for a constant volume, is explained by these relations. Thus, for example, for air at a pressure of one atmosphere the true coefficient of expansion (the volume varying at constant pressure) = 0·00368 (according to Mendeléeff and Kayander) and the variation of tension (at a constant volume, according to Regnault) = 0·00367.