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Reaction of atomic oxygen with cyclopentadiene
Author(s) -
Nakamura Kazumoto,
Koda Seiichiro
Publication year - 1977
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550090107
Subject(s) - chemistry , oxygen , atomic carbon , carbon monoxide , 2 butene , photochemistry , cyclopentadiene , torr , medicinal chemistry , hydrogen , organic chemistry , catalysis , physics , thermodynamics
The reaction of 1,3‐cyclopentadiene (CPD) with ground‐state atomic oxygen O( 3 P ), produced by mercury photosensitized decomposition of nitrous oxide, was studied. The identified products were carbon monoxide and the following C 4 H 6 isomers: 3‐methylcyclopropene, 1,3‐butadiene, 1,2‐butadiene, and 1‐butyne. The yield of carbon monoxide over oxygen atoms produced (ϕ CO ) was equal to the sum of the yields of C 4 H 6 isomers in any experiment. ϕ CO was 0.43 at the total pressure of 6.5 torr and 0.20 at 500 torr. We did not succeed in detecting any addition products such as C 5 H 6 O isomers. It was found that 3‐methylcyclopropene was produced with excess energy and was partly isomerized to other C 4 H 6 isomers, especially to 1‐butyne. The excess energy was estimated to be about 50 kcal/mol. The rate coefficient of the reaction was obtained relative to those for the reactions of atomic oxygen with trans ‐2‐butene and 1‐butene. The ratios k CPD+O / k trans‐2‐butene+O = 2.34 and k CPD+O / k 1‐butene+O = 11.3 were obtained. Probable reaction mechanisms and intermediates are suggested.