THE KINETICS OF MECHANISMS OF METHYL 2-BROMOPROPIONATE AND 2-BROMOPROPIONIC ACID PYROLYSES UNDER MAXIMUM INHIBITION

被引：24
|
作者：
CHUCHANI, G
DOMINGUEZ, RM
ROTINOV, A
机构：
[1] Centro de Química, Instituto Venezolano de Investigaciones Científicas (I.V.I.C.), Caracas, 1020-A
来源：
INTERNATIONAL JOURNAL OF CHEMICAL KINETICS | 1991年 / 23卷 / 09期
关键词：
D O I：
10.1002/kin.550230904
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
The kinetics of the gas phase pyrolyses of methyl 2-bromopropionate and 2-bromopropionic acid were studied in a seasoned, static reaction vessel and under maximum inhibition of the free radical suppressor toluene. The working temperature and pressure range was 310-430-degrees-C and 26.5-201.5 torr, respectively. The reactions proved to be homogeneous, unimolecular, and obeys a first-order rate law. The rate coefficients are expressible by the following equations: for methyl 2-bromopropionate, log k1(s-1) = (13.10 +/- 0.34) - (211.4 +/- 4.4)kJ mol-1(2.303RT)-1; for 2-bromopropionic acid, log k1(s-1) = 12.41 +/- 0.29) - (180.3 +/- 3.4)kJ mol-1(2.303RT)-1. The bromoacid yields acetaldehyde, CO and HBr. Because of this result, the mechanisms is believed to proceed via a polar five-membered cyclic transition state.
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页码：779 / 783
页数：5
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