Solvates classification scheme

This classification has been broadened39,40 by replacing the Brpnsted acid (proton donor) with a Lewis acid (an electron acceptor) and the Brpnsted base with a Lewis base (an electron donor). (A Brpnsted acid is a Lewis acid but not necessarily vice versa.) Solvent-proton interactions are therefore included as one subdivision of this classification, but many solvation reactions of cations with solvents also will be included as reactions of Lewis acid-base systems. This approach still does not solve the problem of fitting specific solvation interactions into the classification scheme. For example, acetonitrile behaves as a good Lewis base toward silver ion, but a poor one toward hydronium ion. The broader scheme also does not specifically take into account hydrogenbonding effects in hydroxylic and other solvents, which affect both the dielectric... 

In light of the variety of behaviour exhibited by solvates, Byrn (1982) has suggested a classification scheme for crystal solvates based on that behaviour, rather than on stability. He proposed that the solvates for which the solvent can be removed from the crystal and added back to the crystal reversibly without greatly changing the X-ray powder diffraction pattern (Section 4.4) would be considered pseudopoly-morphic solvates. Those which undergo a change in structure, as evidenced by a different powder diffraction pattern, would be described as polymorphic solvates. The appellation does not seem to have been adopted by many other workers. 

A simple classification scheme of solids is given in Fig. 7.1. In order to differentiate between the types of solids, we have to consider the Gibbs phase rule, which is discussed in any physical chemistry textbook. The basic question is whether the solid substance consists of only one chemical entity (component) or more than one. Usually the component is one molecular unit, with only covalent bonded atoms. However, a component can also consist of more constituents if their concentration cannot be varied independently. An example of this is a salt. The hydrochloride salt of a base must be regarded as a one-component system as long as the acid and the base are present in a stoichiometric ratio. A deficiency of hydrochloric acid results in a mixture of the salt and the free base, which behave as two completely different substances (i.e. two different systems). Polymorphic forms, the glassy state, or the melt of the base (or the salt) are considered as different phases within such a system (a phase is defined as the portion of a system that itself is homogeneous in composition but physically distinguishable from other phases). When the base (or salt) is dissolved in a solvent, a new system is obtained this is also tme when a solvent is part of the crystal lattice, as in the case of a solvate. Thus, each solvate represents a different multicomponent system of a compound, whereas, polymorphic forms are different phases. The variables in the solvate are the kind of solvate (hydrate. 

Organic liquids are classified in a variety of ways. A common classification scheme is based on the nature of the bonding between molecules during solvation. Three general categories exist protic liquids, nonpolar aprotic liquids, and dipolar aptotic liquids. Protic liquids (e.g., alcohols, carboxylic acids, amines, amides) are those that can provide protons to... 

These types are not all sharply divided, but many compounds may be considered to belong to two or more of these classifications. Although schemes of nomenclature are available for all of these types, the schemes are reasonably satisfactory for only three (solvates, double salts, and iso- and heteropoly acids and salts). This situation is the more regrettable because so large a proportion of the total number of known compounds belongs to the class of higher order compounds and modem research is rapidly enlarging both the number and complexity. 

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