The rate of hydrolysis of
trimethyl phosphate (tmp) has been measured at 90.5�
as a function of solvent composition in water-dimethyl sulphoxide
and water-ethylene glycol mixtures. The rate constant of the
"spontaneous" hydrolysis decreases with decreasing water content; an
acid-catalysed reaction, whose rate constant increases with decreasing water
content, becomes dominant at low water concentrations. Solvent isotope effects
in D2O have been measured for both the spontaneous and acid-catalysed
reactions, and are close to unity in each case. Salt effects have also been
studied In aqueous sodium nitrate and perchlorate solutions, and are found to
be small. Reaction mechanisms are discussed in the light of the results
obtained.
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