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Near-ultraviolet absorption cross sections of nitrophenols and their potential influence on tropospheric oxidation capacity.

Authors
  • Chen, Jun
  • Wenger, John C
  • Venables, Dean S
Type
Published Article
Journal
The Journal of Physical Chemistry A
Publisher
American Chemical Society
Publication Date
Nov 10, 2011
Volume
115
Issue
44
Pages
12235–12242
Identifiers
DOI: 10.1021/jp206929r
PMID: 21958133
Source
Medline
License
Unknown

Abstract

Nitrophenols and methylnitrophenols have been identified as photolytic precursors of nitrous acid, HONO, but their gas-phase absorption has not previously been reported. In this study, the absorption cross sections of 2-nitrophenol, 3-methyl-2-nitrophenol, and 4-methyl-2-nitrophenol were measured from 320 to 450 nm using incoherent broad-band cavity-enhanced absorption spectroscopy (IBBCEAS). The benzaldehyde absorption spectrum was measured to validate the approach and was in good agreement with literature spectra. The nitrophenol absorption cross sections are large (ca. 10(-17) cm(2) molecule(-1)) and blue-shifted about 20 nm compared to previously measured solution spectra. Besides forming HONO, nitrophenol absorption influences other photochemistry by reducing the available actinic flux. The magnitudes of both effects are evaluated as a function of solar zenith angle, and nitrophenol absorption is shown to lower the photolysis rates of O(3) and NO(2).

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