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The nuclear magnetic resonance technique of preferential solvation analysis developed by Frankel, Stengle, and Langford is applied to determination of the composition of the solvation shell about trans-[Cr(NH 3 ) 2 (NCS) 4 ] −  in acetone–water mixtures. The composition of the solvation shell is correlated with the rate of acid hydrolysis of the chromium complex. It emerges that the solvolysis reaction is second order with respect to the solvolytically reactive solvent, water. The mechanistic implications of the rate law are considered as is the significance of analysis of preferential solvation for the determination of kinetic order of solvolytic reactions.

Kinetic order with respect to solvent: Acid hydrolysis and preferential solvation of the Reineckate ion