Chemistry in Non-Aqueous Solvents by B. Trémillon

By B. Trémillon

Arising doubtless from its pre-eminence as a average liquid, water has continuously been thought of by way of chemists because the unique solvent during which very various chemical reactions can occur, either for preparational and for analytical reasons. This explains the very long-standing curiosity proven within the examine of aqueous strategies. during this con­ nection, it has to be under pressure that the idea of Arrhenius and Ostwald (1887-1894) on electrolytic dissociation, used to be initially devised completely for ideas in water and that the 1st precise idea of acidity caused by this can be associated with using this solvent. The newer improvement of various physico-chemical size equipment has made attainable a rise of data during this zone as much as an incredibly complicated measure of systematization. therefore this day we've got on hand either a truly great amount of experimental information, including very subtle equipment of deduction and of quantitative therapy of chemical reactions in answer which permit us to make the fullest use of this knowledge. however, . apparently rather glaring at this time that there are lots of chemical tactics which can't happen in water, and that its use as a solvent imposes 2 advent obstacles. to be able to conquer those boundaries, it was once common that curiosity may be interested in solvents except water and that the recent percentages therefore unfolded might be explored.

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In this model a molten salt is regarded as a form of crystal lattice, made up of two distinct sub-lattices each penetrating the other: on one hand the cation sub-lattice, and on the other hand the anion sub-lattice. The intense Coulomb electrostatic forces operating lead to an alternation of electric charges; a cation must be surrounded by anions and an anion must be surrounded by cations. Random distribution therefore only occurs for cations in the sites of the cation sub-lattice, and on the other hand, for anions in the anion sub-lattice.

Solutions of alkali metals in their halides are a typical example of this; they recall solutions of these metals in liquid ammonia. The laws of conductivity of these solutions lead to deducing the existence of free mobile electrons occupying, according to the previous structural model, sites in the anion sub-lattice of the molten salt (Cubicciotti, 1952; Bronstein and Bredig, 1958). 48 SOLVENTS AND SOLUTES In all other cases, corresponding to the second category of solutions of metals in their molten salts, it is deduced that the atoms of dissolved metal exchange the electrons which they provide with the metallic cations constituting one of the ionic groups present in the solvent, or that they combine with these cations, thus leading to the formation of a metallic cation in an intermediate oxidation state (sub-halide).

For example, the order of increasing solvation force of halide anions in solvents of the first category is I - < Br

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