
%0 Journal Article
%A Adam, KR 
%A Lauder, I 
%A Stimson, VR 
%T Kinetics and Mechanisms of the Acid-catalysed Hydrolysis of Tertiary Butyl Acetate
%J Australian Journal of Chemistry
%D 1962/09/01
%V 15
%N 3
%P 467-479
%K 
%R https://doi.org/10.1071/CH9620467
%U https://www.publish.csiro.au/paper/CH9620467 
%X The kinetics of the acid-catalysed hydrolysis of tertiary butyl acetate in water, in aqueous acetone, and in aqueous dioxan, over a range of temperature have been studied. The Arrhenius equation is not obeyed. In 40% water-60% acetone the energy of activation varies from 26-29 kcal mole-1 for temperatures 48-97 °C. This is due presumably to simultaneous hydrolyses via the AAL1 and the AAC2 mechanisms. By combination of oxygen-18 tracer results and kinetic results the rate constants for reactions by these mechanisms in water have been separated. The observed percentage of alkyl-oxygen fission in water varies from 85 at 25 °C to 97 at 60 °C. Rate constants for reactions by the AAL1 and the AAC2 mechanisms are expressed by the equations :      k (sec-1 l mole-1) = 10l6.l exp (-27500/RT), and     k (sec-1 l mole-1) = 107.9 exp (-l73OO/RT),respectively.   However, the parameters of the latter equation may contain considerable errors because the extent of reaction by the AAC2 mechanism is small.   In water and in 80% water-20% acetone, tertiary butyl acetate undergoes an uncatalysed solvolytic reaction, involving presumably the BAL1 mechanism. The variation of the rate of this reaction with temperature is expressed by the equation,       k (sec-1) = 1012.3 exp (-26800/RT). 
