OXIDATIVE DECARBOXYLATION OF CYCLOHEXANE MONOCARBOXYLIC ACID AS A DEGENERATE BRANCHING CHAIN-REACTION .1. KINETICS

被引：5

作者：

NEMES, I ^{[1
]}

HEBERGER, K ^{[1
]}

KESZLER, A ^{[1
]}

VASVARI, G ^{[1
]}

GAL, D ^{[1
]}

COTARCA, L ^{[1
]}

DELOGU, P ^{[1
]}

机构：

[1] RIC CHIM SCPA,RICE FRUIULI,I-33050 TORVISCOSA,ITALY

来源：

BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 1994年 / 98卷 / 01期

关键词：

CHEMICAL KINETICS; ELEMENTARY REACTIONS; RADICALS; OXIDATION; DECARBOXYLATION;

D O I：

10.1002/bbpc.19940980111

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：

Kinetics of product accumulation during the oxidative decarboxylation of cyclohexane monocarboxylic acid has been followed by GCMS, inhibitor and chemiluminescence methods. Results indicate that in the degenerate branching chain process selective (peroxy) radicals abstract predominantly tertiary hydrogen atoms from the substrate while non-selective (eg. hydroxyl, alkoxy) radicals attack also secondary hydrogen atoms. The rate constant of the chain propagation was found to be k(p) = 7.5 x 10(6) exp (-57.6 kJ mol-1/RT) 1 mol-1 s-1. Furthermore it has been established, that the oxidative decarboxylation proceeds via two parallel pathways: one resulting in cyclohexanone, while the other avoiding the formation of the latter.

引用

页码：75 / 81

页数：7

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[4]

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