The explanation for the rate enhancing effect of microwave (MW) irradiation is still
the subject of controversy. It is, however, agreed that it may involve the possible role of thermal
effects. In this article, our explanation is presented using the example of the direct esterification
of a cyclic phosphinic acid, modelling the distribution of the local overheatings by exponential
functions for the first time, and taking the effect of the overheatings into consideration by the
Arrhenius equation. One of the explanatory models described well the experimental rate
enhancement observed for the MW-assisted direct esterification of 1-hydroxy-3-methyl-3-
phospholene 1-oxide with butanol.
Keywords: Energetics, modelling, esterification, local overheating effect, microwave, phosphinates.
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