Joint effect of temperature and structure on catalytic acidolysis of epichlorohydrin
Shved Olena M., Доктор хімічних наук
Vasyl' Stus Donetsk National University
The system "oxirane - organic acid - catalyst of basic nature" was studied using the methods of chemical kinetics, spectroscopy, and correlation analysis, for which the conditions for detecting a unique isoparametric effect were established, and a new method for determining the concentration of aliphatic tertiary amines during the reaction was developed.
Results are summarized from a study of the enthalpy–entropy compensation effect in non-catalytic and pyridine-catalyzed reactions of aryloxiranes with organic acids of various classes. This effect is observed in isoparametric (isokinetic, isoenergetic) reaction series, due to the interaction (nonadditivity) of the joint effects of temperature and structure. Experimental evidence of its physical reality in a number of cross reaction series is considered. The character of activation processes when there is no enthalpy–entropy compensation is discussed.
The method of spectrophotometric determination of quaternary ammonium cation concentration in epichlorohydrin medium is described, which allows to control the current concentration of amine / quaternary ammonium salt and provides information about the behavior of the catalyst during the reaction, which makes it possible to study the reaction mechanism.
Bakhalova Ievheniia A.
Bespal'ko Yuliya M.
Shpanko Ihor Vasylovych
Yutilova Kseniia S.