As regards the molecular volumes of gases it has been shown that simple relations are obtained when quantities represented by their respective molecular weights are compared under identical conditions of temperature and pressure—that is, under circumstances in which equal numbers of molecules form the basis of comparison. The investigation of the molecular volumes of liquids is complicated by the uncertainty as to what constitutes in their case a valid condition of comparison. Kopp’s assumption that a comparable condition was the temperature at which the vapour pressures of the liquids are equal to the mean atmospheric pressure was justified by the fact that the boiling-points of liquids are approximately two thirds of their respective critical temperatures. His conclusions have been confirmed and extended by Lossen, Thorpe, and Schiff. It has been shown that the molecular volume of a liquid—that is, the product of its relative density at the boiling-point into its molecular weight—is in the main an additive function modified by constitutive influences. Definite values have thus been obtained for a number of the elements from a comparison of homologous or similarly constituted compounds; and in certain cases these are found to be practically identical with the values of the elements in the uncombined state.
Considerable light has been gained during the last two decades concerning the nature of _solution_. In its most comprehensive sense solution means the homogeneous mixture of two or more substances: thus the gases which exert no chemical action on each other are mutually soluble; gases, liquids, and solids may be soluble in liquids; and, lastly, solids maybe soluble in solids, forming what are known as _solid solutions_. The mutual solubility of gases was studied by Dalton who enunciated the _law of partial pressures_, which states that the total pressure of a mixture of gases is the sum of the pressures exerted by the individual components. This, like all the so-called gaseous laws, is necessarily not strictly accurate under ordinary conditions, but approximates to truth in proportion as the gases are rarefied. Van ’t Hoff pointed out that the true partial pressures of the components of a gaseous mixture might be experimentally ascertained by the use of a membrane capable of effecting their separation, and on this principle Ramsay measured the partial pressures of a mixture of hydrogen and nitrogen contained in a palladium vessel connected with a manometer. The palladium, at a sufficiently high temperature, is permeable to hydrogen to the exclusion of the nitrogen. The conditions affecting the solubility of gases in liquids were experimentally studied by Dalton and Henry, and what is known as Henry’s law implies that the volume of a gas dissolved by a definite volume of a liquid is independent of the pressure; or, in other words, the density (concentration) of the gas in solution is proportional to that in the space above the liquid. Gases are dissolved by liquids in very different amounts, but nothing definite is known as yet concerning the relation between the nature of the gas and its solubility, although certain broad generalisations are possible. Thus neutral gases—_e.g._, hydrogen and nitrogen—are sparingly soluble, whereas gases which show acidic or basic properties, such as the hydrogen halides, etc., ammonia, etc., are freely soluble. Easily liquefiable gases are also comparatively soluble as noted by Graham.
