Chemistry in Non-Aqueous Solvents by B. Trémillon

By B. Trémillon

Coming up without doubt from its pre-eminence as a traditional liquid, water has regularly been thought of via chemists because the unique solvent during which very diversified chemical reactions can ensue, either for preparational and for analytical reasons. This explains the very long-standing curiosity proven within the learn of aqueous options. during this con­ nection, it has to be under pressure that the speculation of Arrhenius and Ostwald (1887-1894) on electrolytic dissociation, was once initially devised completely for ideas in water and that the 1st real idea of acidity as a result of this can be associated with using this solvent. The newer improvement of various physico-chemical dimension tools has made attainable a rise of information during this region as much as a very complex measure of systematization. hence this present day we have now on hand either a truly great amount of experimental info, including very subtle tools of deduction and of quantitative remedy of chemical reactions in answer which allow us to make the fullest use of this information. however, . apparently particularly glaring at the present that there are lots of chemical procedures which can't occur in water, and that its use as a solvent imposes 2 creation obstacles. which will triumph over those obstacles, it used to be average that curiosity will be interested in solvents except water and that the hot percentages hence spread out may be explored.

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Chemistry in Non-Aqueous Solvents

Bobbing up doubtless from its pre-eminence as a average liquid, water has continually been thought of by means of chemists because the unique solvent during which very diverse chemical reactions can occur, either for preparational and for analytical reasons. This explains the very long-standing curiosity proven within the learn of aqueous ideas.

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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.

Electrostatic Coulomb forces between ions of opposite sign, their magnitude increasing inversely as B, are responsible for this. It is already known, since the Debye-Hiickel theory (l923), that these electrostatic forces, at long distance, are the cause of the divergences between the activity and the concentration of free ions in solution, divergences which increase with the ionic strength. It was by completing this theory that Bjerrum (1926) produced the first justification of the existence of ion-pairs and gave SOLVENTS AND SOLUTES 37 the first theoretical treatment of the subject.

It is only very small or highly 39 SOLVENTS AND SOLUTES charged ions which can exhibit a weak ionic association in concentrated solution. 15 But in a solvent of low dielectric constant (e < about 40) the critical distance dc, inversely proportional to e, becomes greater that the closest approach distance for all electrolytes. As a result the proportion of associ ated ions cannot be neglected. The theory developed by Bjerrum gives an expression from which the value of the association constant may be calculated: K )3 _ 4nN(ZlZ2Ne 2 -ass 1000 eRT f b expy _ --dyy4 2 where: _ b 4nN (ZlZ2Ne 2 - Q( ) 1000 eRT '" )3 (1-6) 40 SOLVENTS AND SOLUTES and 2 1 de (I-7) eRT a a The function Q(b) (a transcendental exponential integral function) can be calculated numerically; there are tables of values in existence which can be used for calculation of Kass.

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