Abstract
The paH*–rate profile for the hydrolysis of N-p-nitrobenzylideneaniline was investigated in the paH* range 2·72–10·94, in buffered aqueous methanol solutions (20·0% w/w H2O) at 25° and ionic strength 0·045M. The dependence of rate coefficients on buffer concentration at constant paH*, constant ratio of buffer components at each paH*, and constant ionic strength was also studied in the paH* range 3·02–8·25. The observed rate coefficients show the influence of catalysis, obeying the expression Kobs=Kext+Kcat[HA], in which the straight line parameters show a complex dependence on aH*. Starting from the generally accepted mechanism for these reactions, a steady-state rate equation for specific and general catalysis was developed. An analysis of this rate equation has given not only the entire set of parameters but also the rate-determining steps and the values of some individual rate coefficients. The risk of making erroneous conclusions in the absence of a quantitative study of general catalysis is underlined.
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Schedule a callMore From: Journal of the Chemical Society, Perkin Transactions 2
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