Molecular modulation spectroscopy: recent studies involving peroxy radical reactions

Geert Moortgat; John Crowley; Dieter Bauer

doi:10.1117/12.140218

12 February 1993 Molecular modulation spectroscopy: recent studies involving peroxy radical reactions

Geert Moortgat, John Crowley, Dieter Bauer

Proceedings Volume 1715, Optical Methods in Atmospheric Chemistry; (1993) https://doi.org/10.1117/12.140218
Event: Environmental Sensing '92, 1992, Berlin, Germany

Abstract

The UV absorption spectrum and the self-reaction rate constants of the ethylperoxy (C₂H₅O₂) radical and of two brominated peroxy substitutes, 2-bromo-ethylperoxy (BrCH₂CH₂O₂) and 3-bromo-sec-butylperoxy [(CH₃)BrCHCH(CH₃)O₂], were measured via the molecular modulation technique in conjunction with both single wavelength and diode-array UV spectroscopy. The UV spectrum of the three peroxy radicals shows broad absorption with a (sigma) _max near 4.3 X 10^-18 cm² molecule^-1 at about 240 nm. Analysis of decay profiles of C₂H₅O₂ at 250 nm enabled an overall removal rate, k_obs, of (1.1 +/- 0.1) X 10^-13 cm³ molecule^-1 s^-1 at 298 K to be determined. Between 250 and 330 K, k_obs may be represented by: k_obs (250 - 330 K) equals (1.85 +/- 0.2) X 10^-13 exp -[(147 +/- 30)/T] cm^{3/ molecule(superscript -1} s^-1. Self-reaction rate constants, k_obs, of (6.2 +/- 0.1) X 10^-12 and (9.6 +/- 1.9) X 10^-13 cm³ molecule^-1 s^-1 were obtained at 298 K for (BrCH₂CH₂O₂) and [(CH₃)BrCHCH(CH₃)O₂], respectively.

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Geert Moortgat, John Crowley, and Dieter Bauer "Molecular modulation spectroscopy: recent studies involving peroxy radical reactions", Proc. SPIE 1715, Optical Methods in Atmospheric Chemistry, (12 February 1993); https://doi.org/10.1117/12.140218

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