Реферат: Kinetics of the liquid-phase acetaldehyde chlorination to monochloroacetaldehyde was studied in the medium of water-free carbon tetrachloride containing a catalyst, trichloroacetic acid or hydrogen chloride, The apparent activation energy and reaction orders for all components of the reacting mixture were determined. A mechanistic scheme for the reaction in a nonpolar medium was proposed: A + catalyst <----> I-1 --> I-2(+Cl-2,) --> CH2ClCHO + HCl + catalyst, The mechanism involves three steps: (1) the reaction of acetaldehyde with the catalyst, which yields an intermediate species I-1; (2) the isomerization of I-1 into another intermediate I-2; and (3) the reaction of I-2 with chlorine dissolved in the mixture. Isomerization is a rate-limiting step of the process, and the rate is independent of the chlorine concentration. The kinetic description is presented for the pseudo-steady-state chlorination in the nonpolar medium in the presence of Bronsted acids. The effect of association of catalyst molecules on the apparent rate order (n) with respect to the catalyst (HCl) in homogeneous reactions was analyzed. The value of II varies depending on the dominating catalyst structure and activities of various structures: lip < rt < p, where p is the maximum number of associated monomer molecules. The fractional reaction order with respect to the catalyst in acetaldehyde chlorination results from specific features of equilibria in the steps preceding the limiting step, rather than HCl association.

Библиографическая ссылка: Gorshkov S.V. , Kolbanovskii Y.A. , Lebedeva T.L. , Rozovskii A.Y.
Kinetics and mechanism of acetaldehyde chlorination in a nonpolar solvent: 1. Basic features of the process
Kinetics and Catalysis. 1997. V.38. N6. P.747-753. WOS Scopus РИНЦ CAPlus

Оригинальная версия: Горшков С.В. , Колбановский Ю.А. , Лебедева Т.Л. , Розовский А.Я.
Кинетика и механизм хлорирования ацетальдегида в неполярном растворителе. I. Основные закономерности
Кинетика и катализ. 1997. Т.38. №6. С.817-824. РЖ ВИНИТИ

Даты:

Поступила в редакцию:	29 мая 1996 г.
Опубликована в печати:	1 нояб. 1997 г.

Идентификаторы БД:

Web of science:	WOS:000071180900004
Scopus:	2-s2.0-0642365347
РИНЦ:	13254876
Chemical Abstracts:	1998:18554

Цитирование в БД:

БД	Цитирований
Scopus	2