Abstract
THE velocity, ν
9 of reactions which exhibit general acid-base catalysis in carboxylate buffers is generally assumed to conform to the equation : 
where the various catalytic constants, k, are differentiated by their subscripts. However, Dawson and Spivey1 reported in 1930 that the quantitative description of the rate of enolization of acetone, as measured by its iodination in acetate buffers, required an additional cross-term k
x[HA][A−]. The experimental result was substantiated in 1953 by Bell and Jones2, who also found similar cross-terms, which may account for up to 20 per cent of ν, for trimethylacetate and glycollate buffers. These data are widely considered to be the sole evidence3,4 for the occurrence in aqueous solution of a catalytic mechanism, which requires the simultaneous presence of an acid and a base in the transition state complex. The process has been variously described3,4 as ‘concerted’, ‘synchronous’, ‘push-pull’, ‘ternary’ (with reference to the hypothetical number of species in the transition state) and ‘bimolecular’ (with reference to the hypothetical number of catalytic molecules).
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References
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ROSSOTTI, F. The Concerted Mechanism in Acid-Base Catalysis. Nature 188, 936–937 (1960). https://doi.org/10.1038/188936a0
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DOI: https://doi.org/10.1038/188936a0
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