Yu-KEUNG SZE and DONALD E. IRISH. Can. J. Chem. 53,427 (1975). Rarnan spectroscopy has been employed to follow the relatively slow rate of hydrolysis of acetonitrile, catalyzed by rnercury(I1). Rarnan lines at 2275 and 2305 crn-' are characteristic of CH3CN bound to HgZ+, and are distinct from lines of bulk solvent. The intensities of these new lines decrease with time. From the intensities, concentrations of bound acetonitrile, [CH3CNIB were calculated for a time span of 400 min. The data fit a second order rate law: Rate = k[CH3CN], [HzO]. The specific rate constant, k, obtained from four sets of data for the system Hg(C104)2-CH,CN-HZ0 equals 1.05 t 0.06 x mol-' 1 min-' at 25 "C. The energy of activation is 18.9 kcal rnol-I. In the proposed mechanism water molecules attack acetonitrile molecules which are bound to HgZ+ and form a mercury(I1)-acetarnide complex. Raman lines characteristic of this species are observed. This species slowly converts to mercury(I1) arnmine complexes and acetic acid. Anions which coordinate with HgZ+ more strongly than CH3CN, such as nitrate or acetate, slow or prevent the hydrolysis reaction.
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