The Physicochemical Properties of Solvents and Their Relevance to Electrochemistry

The Physicochemical Properties of Solvents and Their Relevance to Electrochemistry. The solvent properties of electrochemical importance include the following protic character (acid-base properties), anodic and cathodic voltage limits (related to redox properties and protic character), mutual solubility of the solute and solvent, and physicochemical properties of the solvent (dielectric constant and polarity, donor or solvating properties, liquid range, viscosity, and spectroscopic properties). Practical factors also enter into the choice and include the availability and cost of the solvent, ease of purification, toxicity, and general ease of handling. 

Protic character. The protic character of the solvent is an important consideration because electrochemical intermediates (particularly radical anions) frequently react rapidly with protons. The classification of solvents into protic or aptotic solvents is somewhat arbitrary. A simple classification1 is that protic solvents (such as hydrogen fluoride, water, methanol, formamide, and ammonia) are strong hydrogen-bond donors, exchange protons rapidly, and in- 

A classification of solvents can be developed on the basis of the stability of the radial anion produced by reduction of aromatic hydrocarbons, such as naphthalene and anthracene. The solvent reactions of such anions have been widely studied2 and have generally been found to go by a sequence of reactions in either a protic solvent or in the presence of a proton donor in an aprotic solvent 3 

The reversible one-electron transfer to form an anion radical (R ) is followed by an irreversible chemical protonation to form /f H, which is subsequently reduced itself (the reduction potential of the species / H, has been shown to be more positive3 than that of the parent, R) and then undergoes another irreversible protonation reaction. In a protic solvent, the reactions proceed rapidly to the final product, / H2. In a rigorously purified aprotic solvent, the intermediate anion radical R , has an appreciable lifetime and reacts only slowly, principally with adventitious impurities in the solvent. Thus, the stability of aromatic anion radicals can be taken as a measure of the protic character of a solvent. 

More recently, it has been suggested that the mechanism of reduction of aromatic hydrocarbons proceeds via the reaction of Eq. (7.3b) rather than that of Eq. (7.3a),4 but this will have no effect on a classification that is based on the stability of the radical anion produced in the reaction of Eq. (7.1). 

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