Kinetics of hydrolysis of 1-benzoyl-1,2,4-triazole in aqueous solution as a function of temperature near the temperature of maximum density, and the isochoric controversy

Abstract

At temperatures above and below the temperature of maximum density, TMD, for water at ambient pressure, pairs of temperatures exist at which the molar volumes of water are equal. First-order rate constants for the pH-independent hydrolysis of 1-benzoyl-1,2,4-triazole in aqueous solution at pairs of such isochoric temperatures show no unique features. Taken together with previously published kinetic data for the hydrolysis of a range of simple organic solutes in both water and D 2 O near their respective TMDs, we conclude that special significance in the context of rates of chemical reactions in aqueous solutions should not be attached to the isochoric condition.

The science that’s never been cited

“…In 2003, Buurma and colleagues published a paper about 'the isochoric controversy' -an argument about whether it would be useful to stop a solvent from contracting or expanding during a reaction, as usually occurs when temperatures change 11 . In theory, this technically challenging experiment might offer insight into how solvents influence chemical reaction rates.…”