[33] J. pr. Chem. 1858, 73, 391.
[34] Ber. 1907, 40, 3118.
[35] Zeitsch. physikal. Chem. 1898, 25, 568.
It appears unlikely that any one explanation can cover all these interesting facts; there are in each case peculiar factors to be taken into account. In 1841, Regnault,[36] considering the case of the oxides observed by Berzelius, inferred that the development of light and heat denoted that the bodies possessed a lower specific heat after the change than before. The experimental difficulties encountered in attempting to dry the oxides prevented him from confirming this view. He measured the specific heats of the minerals calcite and aragonite (CaCO₃), and of the two allotropic modifications of phosphorus, but could observe no appreciable differences. H. Rose ([vide supra]) showed by experiment that considerable heat was evolved on the glowing of gadolinite, with a decrease of about one-fourteenth in the specific heat. In the case of samarskite there was, however, no appreciable evolution of heat, nor could he determine any difference in the specific heats before and after glowing.
[36] Pogg. Ann. 1841, 53, 249.
Probably the only inference that can be safely drawn is that in most cases the change is due to some molecular re-arrangement. The evolution of water, helium, etc., in some cases, may possibly be due to intramolecular change, but on the one hand the current view at present is that the helium is mechanically held in radio-active minerals, and on the other hand it is not known that the water evolved is water of constitution; in an intermolecular change at fairly high temperature, these might be evolved without disruption of the true mineral molecules. The question of the energy involved, and consequently of the specific heats, appears to depend on factors peculiar to each case, of which at present no accurate conception can be formed; and the change in specific gravity is probably bound up with these. The loss of solubility in acids is a factor not always connected with glowing, as it is frequently observed in the laboratory after ignition of compounds, but here again no adequate explanation is forthcoming.
The possibility of chemical change in one or two cases, however, must not be ignored. Thus ammonium magnesium phosphate, NH₄MgPO₄, on heating glows, and is converted to magnesium pyrophosphate, according to the equation:
2NH₄MgPO₄ = Mg₂P₂O₇ + H₂O + 2NH₃
A case possibly analogous to this is that of the mineral [sipylite] (q.v.), R´´´₂Cb₂O₈, with ‘basic water’ (i.e. R´´´ partially replaced by H). Before the blowpipe this decrepitates with loss of water, and glows brilliantly. The specific gravity after the change does not appear to have been determined. Mallet explains the glow as due to a change to the pyrocolumbate.
Similar explanations may possibly hold in the cases of allanite and risörite, but it must be remembered that we are really ignorant of the part played by the water in these minerals.