Acid-base reactions solvent classification

Classification of Solvents. Solvent classification helps to identify properties useful in solvent selection for individual applications for example, the study of acid-base reactions, oxidation-reduction reactions, inorganic coordination chemistry, organic nucleophilic displacement reactions, and electrochemistry. 

Solvents can be classified as EPD or EPA according to their chemical constitution and reaction partners [65]. However, not all solvents come under this classification since e.g. aliphatic hydrocarbons possess neither EPD nor EPA properties. An EPD solvent preferably solvates electron-pair acceptor molecules or ions. The reverse is true for EPA solvents. In this respect, most solute/solvent interactions can be classified as generalized Lewis acid/base reactions. A dipolar solvent molecule will always have an electron-rich or basic site, and an electron-poor or acidic site. Gutmann introduced so-called donor numbers, DN, and acceptor numbers, AN, as quantitative measures of the donor and acceptor strengths [65] cf. Section 2.2.6 and Tables 2-3 and 2-4. Due to their coordinating ability, electron-pair donor and acceptor solvents are, in general, good ionizers cf. Section 2.6. 

Solvent classification In acid-base reactions the solvent plays an active or specific role in two ways it may react generally with ions and molecules (solvation), and as indicated above, it has acidic and basic properties that are of active concern. Broadly, solute-solvent interactions are studied by electrical and spectral methods. ... 

An even more general theory of acids and bases was given by the American chemist G. N. Lewis in 1923. In this theory, an acid is an electron acceptor and a base is an electron donor. This is a more general theory than the Br0nsted-Lowry theory, because it allows the acid-base classification to be applied to reactions in which neither H (aq) nor OH (aq) play a role, or even to reactions in which there is no solvent. For example, the following are acid-base reactions in the Lewis theory... 

The classification of solvents has been dealt with in various books on non-aque-ous solvents [25, 26]. In the classification of solvents, it is usual to use some solvent properties as criteria. In order to discuss solvent effects on chemical reactions, it is convenient to use relative permittivities and acid-base properties as the criteria. 

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... 

When one considers the incredible number of chemical reactions that are possible, it becomes apparent why a scheme that systemizes a large number of reactions is so important and useful. Indeed, classification of reaction types is important in all areas of chemistry, and a great deal of inorganic chemistry can be systematized or classified by the broad types of compounds known as acids and bases. Many properties and reactions of substances are understandable, and predictions can often be made about their reactions in terms of acid-base theories. In this chapter, we will describe the most useful acid-base theories and show their applications to inorganic chemistry. However, water is not the only solvent that is important in inorganic chemistry, and a great deal of chemistry has been carried out in other solvents. In fact, the chemistry of nonaqueous solvents is currently a field of a substantial amount of research in inorganic chemistry, so some of the fundamental nonaqueous solvent chemistry will be described in this chapter. 

BrOnsted acid—base properties, Lewis acid—base propeties (EPA—EPD) etc. Such classifications make it possible to select a type of solvent which we believe will fit the reaction. Often our choice is based on assumptions as to the reaction mechanism. 

Solvent effects on acid-base equilibria are naturally most marked when the solvent itself enters into the equilibrium, as is the case for the conventional definition of acid strength by means of the equilibrium A-fSH B4-SH2 (where SH is the solvent). The existence of such an equilibrium implies that the solvent has some basic properties. Similarly, the occurrence of the reaction B + SH A-f S (where S is the anion derived by abstracting a proton from the solvent) implies that the solvent is acidic. The most important factor determining qualitative behaviour in a wide range of solvents is the acidic or basic nature of the solvent, as determined by its chemical nature. In a preliminary classification we can neglect other factors, notably the effect of dielectric constant on the association of ions or the forces between them. 

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