Intermetallic Solid Solutions

IN thermodynamic studies of gas mixtures and liquid solutions, the respective problems have been greatly simplified by the use of two general limiting laws; Dalton's law of partial pressures and Raoult's law. It is generally recognized that these two laws have a common physical and chemical basis which may be stated as follows: The law may be expected to be strictly valid only for systems in which the different molecular species are so nearly the same in their physical and chemical properties that a molecule is unable to recognize whether its neighbor is one of its own kind or not. Positive and negative deviations from both laws are frequently encountered. The occurrence of negative deviations in both gases and liquids is ascribed to attractive forces which, in the more extreme cases, may be so large in magnitude and so highly specific in character as to lead to the formation of definite chemical compounds. Positive deviations in gases develop only at higher pressures where the intermolecular distances are so decreased that factors such as molecular size and shape, which ultimately become concerned with the repulsive forces, come into play. In liquid mixtures, positive deviations are generally considered as due to differences in the symmetrical (nonpolar) fields of force which surround the various molecular species and which are supposed to give rise to a tendency for each species to associate with its own kind and thus to "squeeze out" the other variety. Fundamentally this also involves the existence of repulsive forces between unlike molecules. If the fields of force are unsymmetrical (polar) a tendency towards compound formation results. Stated in more exact terms, strict adherence to the law means that the "activity" (or any adequate measure of this quantity) of a component in a mixture is a linear function of the molecular (or atomic)