Abstract
The cadmium(II)-chloride and cadmium(II)-bromide association equilibria in highly concentrated solutions of ammonium nitrate in dimethyl sulphoxide in the concentration range 1.0 ≤ R DMSO (≡ n DMSO/ n NH 4NO 3 ) ≤ 5.3 at 345.4 K have been investigated by means of potentiometric measurements, using silver/silver chloride and silver/silver bromide electrodes. The equilibrium constants K 1 (=β 11) and β 21 for the formation of the species CdCl + and CdCl 2 and CdBr + and CdBr 2, respectively, have been determined. The dependence of K 1 on the composition of the NH 4NO 3+DMSO melt is found to be in qualitative agreement with the quasi-lattice model for competitive association and solvation equilibria in highly concentrated solutions of ionic salts in molecular solvents, as originally developed by J. Braunstein. The present results for K 1 are compared with literature data obtained in the aqueous melts NH 4NO 3+H 2O, and the dependence of K 1 on the melt composition in the various cases is discussed in the light of Ahrland's concept of “a”- and “b”-acceptor characters of cadmium(II) in water and in DMSO.
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