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By B. Trémillon

Arising without doubt from its pre-eminence as a usual liquid, water has continually been thought of through chemists because the unique solvent within which very diverse chemical reactions can occur, either for preparational and for analytical reasons. This explains the very long-standing curiosity proven within the research of aqueous options. during this con­ nection, it needs to be under pressure that the idea of Arrhenius and Ostwald (1887-1894) on electrolytic dissociation, was once initially devised completely for suggestions in water and that the 1st real idea of acidity as a result of this is often associated with using this solvent. The newer improvement of diverse physico-chemical dimension equipment has made attainable a rise of information during this zone as much as an exceptionally complicated measure of systematization. therefore this day we now have on hand either a truly great amount of experimental info, including very sophisticated equipment of deduction and of quantitative therapy of chemical reactions in resolution which permit us to make the fullest use of this knowledge. however, . apparently relatively glaring at the moment that there are many chemical strategies which can't ensue in water, and that its use as a solvent imposes 2 creation barriers. so as to conquer those barriers, it was once common that curiosity might be drawn to solvents except water and that the recent probabilities hence unfolded may be explored.

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Group in molten hydroxides are solvated Ni 2+ or Zn 2+ ions (solvated by the solvent anions). The preceding structural ionic model is ultimately applied to these complex groups. Let us consider for example the case of the Cu + ion dissolved in molten mixtures of aluminium chloride and sodium chloride. In a mixture where the molar proportion of AICl 3 is slightly greater than that of NaCI, the solvent consists of a sub-lattice of Na + cations and a sub-lattice of AICI; anions, including a small proportion of AI 2 CI; anions (corresponding to AICl 3 in excess in comparison with Na +AICli); in this mixture, the Cu + ion remains free and inserts itself in the sub-lattice of the Na + cations.

This naturally amounts to attributing to the solute, contrary to the cases of molecular solvents, an electric charge different from the true over-all charge carried by the solvated material; but this is no inconvenience except when we are concerned with properties where the charge of the material is relevant (electromigration in particular). CHAPTER II ACIDITY AND PROTOL YSIS PHENOMENA The concept of 'acidity' has for a very long time occupied a very special place in solution chemistry. By 1786, Guyton de Morveau had already written "to hold the definition of acids is to hold the key to chemistry".

S,'s. () .... cPo. Po. , Q:l ::s Po. , Po. 7 Values quoted in Chemical Reactions in Solvents and Melts, by G. Charlot and B. TremiIIon, Tremillon, pub. Pergamon Press, 1969 (translated from French). 1 ~~ III ~ 36 SOLVENTS AND SOLUTES fraction of a salt in a sufficiently concentrated solution remains practically negligible in comparison with the part present in the form of ion-pairs. For B going from 10 to about 40, the proportion of free ions ceases to be negligible, but there still is formation of ion-pairs, except in very dilute solution.

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