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Proceedings Paper

Molecular modulation spectroscopy: recent studies involving peroxy radical reactions
Author(s): Geert Moortgat; John Crowley; Dieter Bauer
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Paper 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, kobs, of (1.1 +/- 0.1) X 10-13 cm3 molecule-1 s-1 at 298 K to be determined. Between 250 and 330 K, kobs may be represented by: kobs (250 - 330 K) equals (1.85 +/- 0.2) X 10-13 exp -[(147 +/- 30)/T] cm3/ molecule(superscript -1 s-1. Self-reaction rate constants, kobs, 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.

Paper Details

Date Published: 12 February 1993
PDF: 14 pages
Proc. SPIE 1715, Optical Methods in Atmospheric Chemistry, (12 February 1993); doi: 10.1117/12.140218
Show Author Affiliations
Geert Moortgat, Max-Planck-Institut fuer Chemie (Germany)
John Crowley, Max-Planck-Institut fuer Chemie (Germany)
Dieter Bauer, Max-Planck-Institut fuer Chemie (Germany)


Published in SPIE Proceedings Vol. 1715:
Optical Methods in Atmospheric Chemistry

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