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Kinetics of gas‐phase decomposition of oxetan and oxetan‐2,2‐ d 2
Author(s) -
Zalotai L.,
Hunyadizoltán Zs.,
Bérces T.,
Márta F.
Publication year - 1983
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.550150602
Subject(s) - chemistry , decomposition , arrhenius equation , kinetic energy , gas phase , thermodynamics , activation energy , organic chemistry , physics , quantum mechanics
The pressure dependence of the first‐order rate coefficient of oxetan and oxetan‐2,2‐ d 2 decomposition has been studied in the pressure range from about 7 kPa down to 0.01 kPa at various temperatures between 673 and 758 K. Experimental data were analyzed using RRKM theory. Interpretation of the fall‐off curves lends support to the high‐pressure Arrhenius parameters A = 10 15.42 s −1 and E A = 259.5 kJ/mol derived from measurements made in the pressure‐independent range. Decomposition of oxetan is found to occur via biradical intermediates. Data for the kinetic isotope effect were used to derive kinetic parameters for the ring‐opening elementary steps in oxetan and oxetan‐ d 2 decomposition.