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Reanalysis of data (Bruice and York 1961) for the pH dependences of thecalculated apparent second-order rate constants (k2) for the reaction oftris-(hydroxymethyl)-aminomethane (TRIS) with phenyl esters reveals that the pHprofiles are consistently much better represented as multiphasic, i.e. as aseries of straight lines separated by discontinuities in the form of sharpbreaks or noncontiguities (jumps), than by the continuous function used by theauthors. For p-nitrophenyl acetate, m-nitrophenyl acetate, p-chlorophenylacetate and phenyl acetate, the profiles are best represented as multiphasic inplots of log k2 vs. pH, whereas the profile for p-methylphenyl acetate is onlymultiphasic in a plot of k2 vs. pH. Data for the pseudo-first-order rateconstants (kobs) give multiphasic pH profiles with patterns identical or verysimilar to those for k2. Extensive reanalyses of data for a wide variety ofenzymatic and non-enzymatic reactions show, similarly, that pH profiles are ingeneral better represented as multiphasic than as curvilinear.

Multiphasic pH profiles for the reaction of tris-(hydroxymethyl)-aminomethane with phenyl esters