Abstract
The principles of ‘thermokinetic’ experiments have been described, whereby the initial rates of chemical reaction in solution are determined by following the temperature rise in an adiabatic system; data are obtained within the first few seconds of mixing, and at rates of the order of one measurement s–1. The procedure has been applied to the base-catalysed condensation reaction of acetone to form diacetone alcohol, an exceptionally difficult reaction to follow because of the small extent to which the reaction proceeds. At 26 °C, the equilibrium constant for the base-catalysed ionisation of acetone has been established as having a value of 1.2(9) l mol–1 while the rate constant for the ionic dimerisation has the value 2.5(2)× 10–3 mol l–1 s–1.
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