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Pulse radiolysis and fourier transform infrared study of neopentyl peroxy radicals in the gas phase at 297 K
Author(s) -
Wallington Timothy J.,
Andino Jean M.,
Potts Alan R.,
Nielsen Ole J.
Publication year - 1992
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.550240705
Subject(s) - chemistry , radical , radiolysis , kinetics , reaction rate constant , photochemistry , absorption (acoustics) , gas phase , absorption cross section , infrared , absorption spectroscopy , analytical chemistry (journal) , organic chemistry , cross section (physics) , physics , quantum mechanics , acoustics , optics
The ultraviolet absorption spectrum of the neopentyl peroxy radical (CH 3 ) 3 CCH 2 O 2 , and the kinetics and products of its self reaction have been studied in the gas phase at 298 K. Absorption cross sections were quantified over the wavelength range 230–290 nm. The measured cross section at 250 nm was;\documentclass{article}\pagestyle{empty}\begin{document}$$ \sigma ({\rm CH}_3)_3 {\rm CCH}_2 {\rm O}_{2(250\,{\rm nm})} = (5.4 \pm 1.2) \times 10^{-18} {\rm cm\, molecule}^{-1} $$\end{document} Errors represent statistical (2σ) together with our estimate of potential systematic errors(15%). The kinetics of the decay of the UV absorption following the generation of the neopentyl peroxy radicals was complicated by the rapid decomposition of the (CH 3 ) 3 CCH 2 O radicals formed in channel (4a).By measuring the yield of t ‐butyl peroxy radicals, the branching ratio k 4 a /( k 4 a + k 4 b ) was determined to be 0.39 ± 0.03. The rate constant for the self reaction of neopentyl peroxy radicals was k 4 = (1.07 ± 0.22) × 10 −12 cm 3 molecule −1 s −1 . Quoted errors represent 2σ. These results are discussed with respect to the available literature data. © John Wiley & Sons, Inc.