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Tropospheric Photolysis Rates of the Acetaldehyde Isotopologues CD3CHO and CD3CDO Relative to CH3CHO Measured at the European Photoreactor Facility.

Heimdal Nilsson, Elna LU ; Heimdal, Jimmy; Bache-Andreassen, Lihn; Johnson, Matthew S and Nielsen, Claus J (2015) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 119(11). p.2562-2567
Abstract
Acetaldehyde is a hazardous pollutant found in indoor and ambient air. Acetaldehyde photolysis is pressure- and wavelength-dependent with three distinct product channels. In this study, the photolysis rates of CH3CHO, CD3CDO, and CD3CHO are studied in natural tropospheric conditions using long path FTIR spectroscopy, at the European Photoreactor Facility (EUPHORE) in Valencia, Spain. The average relative photolysis rate as an average of four experiments for the fully deuterated isotopologue is jCH3CHO/jCD3CDO = 1.75 ± 0.04, and as a result of a single experiment jCH3CHO/jCD3CHO = 1.10 ± 0.10. These results, combined with our previous determination of jCH3CHO/jCH3CDO = 1.26 ± 0.03, provide mechanistic insight into the photodissociation... (More)
Acetaldehyde is a hazardous pollutant found in indoor and ambient air. Acetaldehyde photolysis is pressure- and wavelength-dependent with three distinct product channels. In this study, the photolysis rates of CH3CHO, CD3CDO, and CD3CHO are studied in natural tropospheric conditions using long path FTIR spectroscopy, at the European Photoreactor Facility (EUPHORE) in Valencia, Spain. The average relative photolysis rate as an average of four experiments for the fully deuterated isotopologue is jCH3CHO/jCD3CDO = 1.75 ± 0.04, and as a result of a single experiment jCH3CHO/jCD3CHO = 1.10 ± 0.10. These results, combined with our previous determination of jCH3CHO/jCH3CDO = 1.26 ± 0.03, provide mechanistic insight into the photodissociation dynamics of the photoexcited species. Despite the extensive isotopic scrambling in photoexcited acetaldehyde that has recently been reported, the position of the substitution has a clear effect on the relative photolysis rates. (Less)
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Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
volume
119
issue
11
pages
2562 - 2567
publisher
The American Chemical Society
external identifiers
  • pmid:25654214
  • wos:000351557300041
  • scopus:84925067775
ISSN
1520-5215
DOI
10.1021/jp509050d
language
English
LU publication?
yes
id
13711654-9b8e-41f0-8588-b29b1010d53f (old id 5145378)
date added to LUP
2015-03-09 14:30:38
date last changed
2017-01-01 03:33:50
@article{13711654-9b8e-41f0-8588-b29b1010d53f,
  abstract     = {Acetaldehyde is a hazardous pollutant found in indoor and ambient air. Acetaldehyde photolysis is pressure- and wavelength-dependent with three distinct product channels. In this study, the photolysis rates of CH3CHO, CD3CDO, and CD3CHO are studied in natural tropospheric conditions using long path FTIR spectroscopy, at the European Photoreactor Facility (EUPHORE) in Valencia, Spain. The average relative photolysis rate as an average of four experiments for the fully deuterated isotopologue is jCH3CHO/jCD3CDO = 1.75 ± 0.04, and as a result of a single experiment jCH3CHO/jCD3CHO = 1.10 ± 0.10. These results, combined with our previous determination of jCH3CHO/jCH3CDO = 1.26 ± 0.03, provide mechanistic insight into the photodissociation dynamics of the photoexcited species. Despite the extensive isotopic scrambling in photoexcited acetaldehyde that has recently been reported, the position of the substitution has a clear effect on the relative photolysis rates.},
  author       = {Heimdal Nilsson, Elna and Heimdal, Jimmy and Bache-Andreassen, Lihn and Johnson, Matthew S and Nielsen, Claus J},
  issn         = {1520-5215},
  language     = {eng},
  number       = {11},
  pages        = {2562--2567},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory},
  title        = {Tropospheric Photolysis Rates of the Acetaldehyde Isotopologues CD3CHO and CD3CDO Relative to CH3CHO Measured at the European Photoreactor Facility.},
  url          = {http://dx.doi.org/10.1021/jp509050d},
  volume       = {119},
  year         = {2015},
}