Chemistry in Non-Aqueous Solvents by B. Trémillon

By B. Trémillon

Arising without doubt from its pre-eminence as a usual liquid, water has continuously been thought of through chemists because the unique solvent during which very diversified chemical reactions can happen, either for preparational and for analytical reasons. This explains the very long-standing curiosity proven within the learn of aqueous strategies. during this con­ nection, it needs to be under pressure that the speculation of Arrhenius and Ostwald (1887-1894) on electrolytic dissociation, was once initially devised completely for suggestions in water and that the 1st precise proposal of acidity as a result of this is often associated with using this solvent. The more moderen improvement of diverse physico-chemical dimension equipment has made attainable a rise of information during this sector as much as an exceptionally complex measure of systematization. hence this present day we have now on hand either a truly great amount of experimental facts, including very sophisticated tools of deduction and of quantitative therapy of chemical reactions in resolution which permit us to make the fullest use of this information. however, . it sounds as if fairly obvious at the moment that there are various chemical techniques which can't ensue in water, and that its use as a solvent imposes 2 creation obstacles. with a view to triumph over those barriers, it was once normal that curiosity may be drawn to solvents except water and that the recent chances therefore unfolded could be explored.

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Another conception, developed especially for ions in aqueous solution (Samoilov, 1957), is the consideration of the effect of the solute on the translatory movements due to thermal agitation of the solvent molecules situated in its vicinity. For the molecules of a pure liquid these movements are defined in the following manner: each molecule occupies, for a certain time, a site in the structure (ordered at short distance), in which it vibrates about an equilibrium position; when it possesses sufficient energy 28 SOLVENTS AND SOLUTES (of activation) to pass through the potential barrier, it jumps from this equilibrium site to another free site (a vacancy in the structure) near by, thus making a translatory movement.

To justify fully the simplified formulation, we must note that if the expression of the mass action law applied to a chemical system in the equilibrium state does in theory introduce the activity of the solvent S, this latter can be regarded as practically invariable and very close to unity when the solution is sufficiently diluted; it then disappears also from the expression of the mass action law, which only introduces the activities of substances A, B, and AB (solvated), which amounts to the application of this law to the system formulated as in (1-18).

D G the free enthalpy change corre- 50 SOLVENTS AND SOLUTES sponding to the exchange, within the solvent, of an anion B- in contact with X+ for an anion Y-, so forming an ion pair X+Y-. The following diagram illustrates the exchange process: A+ B- B- ·0 A+ B- A+ BA+ A+G A+ B- + A+ B- A+ n A+ B- A+ B- 0G B- A+ B- A+ B- (1-13) B- A+ B- A+ B- A- B- A+ B- In the case where the only interaction between the X+ and Y- ions consists of electrostatic Coulomb forces, and also for A + and B- ions (considered as rigid spheres in contact), we can calculate Lt G from the energies of attraction of the simple ion-pairs X+B-, A +Y-, X+Y- and A +B -; these energies are inversely proportional to the distances d between the centres of the ions under consideration (sums of ionic radii: respectively dXB ' dAY, dxy and dAB, for the different ion-pairs).

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