Mechanistic studies of saponification of some mono-and di-esters of carboxylic acids through iso-kinetic relationships (DELTAH~(not=) vs.DELTAS~(not=)) in protic and aprotic solvent systems

摘要

The mechanism of saponification of structurally related and industrially important mono-and diesters in protic and aprotic solvent systems have been investigated.Time ratio method and Swain's standard data for series first order reactions have been utilized for the evaluation of rate data and thermodynamic parameters viz.DELTAE~(not=),-DELTAH~(not=),DELTAG~(not=),DELTAS~(not=) and logA for the steps which involve the competitive and consecutive saponification reactions.Further,the enthalpy-entropy correlations are used to establish the plausible mechanism of saponification process for the esters.Comparative study of the slopes of linear plots (DELTAH~(not=) vs.DELTAS~(not=)) reveal that dilaurates undergo faster saponification process than distearates and oleostearates irrespective of any solvent sytems.The experimental plots (DELTAH~(not=) vs.DELTAS~(not=)) support a faster saponification process of mono esters than diesters in all the protic and aprotic solvent systems studied.