Pulse radiolysis and Fourier transform infrared study of neopentyl peroxy radicals in the gas phase at 297 K

Timothy Wallington, Jean M. Andino, Alan Potts

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

The ultraviolet absorption spectrum of the neopentyl peroxy radical (CH3)3CCH2O2, 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. Our measured spectrum is in good agreement with previous work. The rate constant for the self reaction is k4 = (1.07 ± 0.22) × 10-12 cm3 molecule-1 s-1. The branching ratio k4a/k4 was measured to be 0.39 ± 0.03. In the presence of 150 torr of O2, neopentoxy radicals produced from reaction (4a) decompose to give HCHO and t-butyl radicals. These findings show that the correct mechanistic interpretation of the distinctly nonsecond order decay of UV absorption in kinetic studies of the self reaction of neopentyl peroxy radicals is that proposed by P. D. Lightfoot et al. Namely, the observed slowly decaying residual absorption is caused by the formation of t-butyl peroxy radicals from the decomposition of neopentoxy radicals.

Original languageEnglish
Pages (from-to)649-663
Number of pages15
JournalInternational Journal of Chemical Kinetics
Volume24
Issue number7
Publication statusPublished - Jul 1992

Fingerprint

Pulse Radiolysis
Radiolysis
Fourier Analysis
radiolysis
Fourier transforms
Gases
vapor phases
Infrared radiation
Kinetics
pulses
Absorption spectra
Rate constants
Decomposition
Wavelength
Molecules
ultraviolet absorption
kinetics
ultraviolet spectra
absorption cross sections
absorption spectra

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

Cite this

Pulse radiolysis and Fourier transform infrared study of neopentyl peroxy radicals in the gas phase at 297 K. / Wallington, Timothy; Andino, Jean M.; Potts, Alan.

In: International Journal of Chemical Kinetics, Vol. 24, No. 7, 07.1992, p. 649-663.

Research output: Contribution to journalArticle

@article{cbd734630dbb4e1bbd6abf9f4d2dac08,
title = "Pulse radiolysis and Fourier transform infrared study of neopentyl peroxy radicals in the gas phase at 297 K",
abstract = "The ultraviolet absorption spectrum of the neopentyl peroxy radical (CH3)3CCH2O2, 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. Our measured spectrum is in good agreement with previous work. The rate constant for the self reaction is k4 = (1.07 ± 0.22) × 10-12 cm3 molecule-1 s-1. The branching ratio k4a/k4 was measured to be 0.39 ± 0.03. In the presence of 150 torr of O2, neopentoxy radicals produced from reaction (4a) decompose to give HCHO and t-butyl radicals. These findings show that the correct mechanistic interpretation of the distinctly nonsecond order decay of UV absorption in kinetic studies of the self reaction of neopentyl peroxy radicals is that proposed by P. D. Lightfoot et al. Namely, the observed slowly decaying residual absorption is caused by the formation of t-butyl peroxy radicals from the decomposition of neopentoxy radicals.",
author = "Timothy Wallington and Andino, {Jean M.} and Alan Potts",
year = "1992",
month = "7",
language = "English",
volume = "24",
pages = "649--663",
journal = "International Journal of Chemical Kinetics",
issn = "0538-8066",
publisher = "John Wiley and Sons Inc.",
number = "7",

}

TY - JOUR

T1 - Pulse radiolysis and Fourier transform infrared study of neopentyl peroxy radicals in the gas phase at 297 K

AU - Wallington, Timothy

AU - Andino, Jean M.

AU - Potts, Alan

PY - 1992/7

Y1 - 1992/7

N2 - The ultraviolet absorption spectrum of the neopentyl peroxy radical (CH3)3CCH2O2, 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. Our measured spectrum is in good agreement with previous work. The rate constant for the self reaction is k4 = (1.07 ± 0.22) × 10-12 cm3 molecule-1 s-1. The branching ratio k4a/k4 was measured to be 0.39 ± 0.03. In the presence of 150 torr of O2, neopentoxy radicals produced from reaction (4a) decompose to give HCHO and t-butyl radicals. These findings show that the correct mechanistic interpretation of the distinctly nonsecond order decay of UV absorption in kinetic studies of the self reaction of neopentyl peroxy radicals is that proposed by P. D. Lightfoot et al. Namely, the observed slowly decaying residual absorption is caused by the formation of t-butyl peroxy radicals from the decomposition of neopentoxy radicals.

AB - The ultraviolet absorption spectrum of the neopentyl peroxy radical (CH3)3CCH2O2, 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. Our measured spectrum is in good agreement with previous work. The rate constant for the self reaction is k4 = (1.07 ± 0.22) × 10-12 cm3 molecule-1 s-1. The branching ratio k4a/k4 was measured to be 0.39 ± 0.03. In the presence of 150 torr of O2, neopentoxy radicals produced from reaction (4a) decompose to give HCHO and t-butyl radicals. These findings show that the correct mechanistic interpretation of the distinctly nonsecond order decay of UV absorption in kinetic studies of the self reaction of neopentyl peroxy radicals is that proposed by P. D. Lightfoot et al. Namely, the observed slowly decaying residual absorption is caused by the formation of t-butyl peroxy radicals from the decomposition of neopentoxy radicals.

UR - http://www.scopus.com/inward/record.url?scp=0026896464&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0026896464&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0026896464

VL - 24

SP - 649

EP - 663

JO - International Journal of Chemical Kinetics

JF - International Journal of Chemical Kinetics

SN - 0538-8066

IS - 7

ER -