Premium
Thermal Behaviour of C 8 H 8 Hydrocarbons Gas‐Phase Thermolysis of Cuneane, a New Example of a High‐Strain Energy Release Process
Author(s) -
Hasseurück Karin,
Martin HansDieter,
Walsh Robin
Publication year - 1988
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19881210225
Subject(s) - chemistry , arrhenius equation , activation energy , thermal decomposition , cyclooctatetraene , reaction rate constant , atmospheric temperature range , decomposition , pyrolysis , kinetics , arrhenius plot , thermodynamics , order of reaction , reaction mechanism , gas phase , analytical chemistry (journal) , organic chemistry , molecule , catalysis , physics , quantum mechanics
The kinetics of thermal decomposition of cuneane 2) ( 1 ) in the gas phase have been investigated in the temperature range 180–220°C. The reaction is a clean first‐order homogeneous process leading to the formation of two C 8 H 8 isomers, viz., semibullvalene 3) ( 2 ) and cyclooctatetraene ( 3 ). The rate constant varies with temperature according to the Arrhenius equation log( k/S −1 ) = (13.82 ± 0.09) – (37.7 ± 0.2 kcal mol −1 )/ RT In10. The Arrhenius parameters are consistent with a biradical mechanism leading to the formation of semibullvalene ( 2 ). The product proportions are pressure‐dependent which strongly suggests that semibullvalene ( 2 ) is initially formed with high vibrational energy content (ca. 74 kcal mol −1 ) and can react further to give cyclooctatetraene ( 3 ).