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Photochemistry of carbon monoxide and methanol in water and nitric acid hydrate ices: A NEXAFS study

Laffon, C.; Lasne, J.; Bournel, F.; Schulte, Karina LU ; Lacombe, S. and Parent, Ph. (2010) In Physical Chemistry Chemical Physics 12(36). p.10865-10870
Abstract
Soft X-ray induced chemistry of H2O, CO and CH3OH and the effects of the water and nitric acid hydrate (HNO3 center dot 1.65H(2)O) matrix on the photochemistry of CO and CH3OH have been investigated using NEXAFS spectroscopy. For pure H2O, CO and CH3OH ices, we show that the destruction rates are strongly limited by back reactions, leading to strikingly high survival rates of these molecules upon the harsh irradiation conditions to which they are submitted. We also evidence the interplay between the photochemical reactions of CO and CH3OH and those of the matrix. The OH and O radicals released by the photolysis of H2O and HNO3 react with the CO and CH3OH and their fragments, considerably reducing the survival rates compared to pure CO and... (More)
Soft X-ray induced chemistry of H2O, CO and CH3OH and the effects of the water and nitric acid hydrate (HNO3 center dot 1.65H(2)O) matrix on the photochemistry of CO and CH3OH have been investigated using NEXAFS spectroscopy. For pure H2O, CO and CH3OH ices, we show that the destruction rates are strongly limited by back reactions, leading to strikingly high survival rates of these molecules upon the harsh irradiation conditions to which they are submitted. We also evidence the interplay between the photochemical reactions of CO and CH3OH and those of the matrix. The OH and O radicals released by the photolysis of H2O and HNO3 react with the CO and CH3OH and their fragments, considerably reducing the survival rates compared to pure CO and pure CH3OH ices, especially in presence of nitric acid, and dramatically enhancing the formation of CO2 at the expense of CO. Because NEXAFS spectroscopy allows identifying which reactions are important among those possible, it emerges a simple picture of the photochemical routes of CO and CH3OH in the H2O and HNO3/H2O environments. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Physical Chemistry Chemical Physics
volume
12
issue
36
pages
10865 - 10870
publisher
Royal Society of Chemistry
external identifiers
  • wos:000281613300028
  • scopus:77956334716
ISSN
1463-9084
DOI
10.1039/c0cp00229a
language
English
LU publication?
yes
id
d7c1f6d2-08a6-4cd3-9d25-0f32afe479e5 (old id 1697328)
date added to LUP
2010-10-25 11:01:18
date last changed
2018-05-29 09:28:28
@article{d7c1f6d2-08a6-4cd3-9d25-0f32afe479e5,
  abstract     = {Soft X-ray induced chemistry of H2O, CO and CH3OH and the effects of the water and nitric acid hydrate (HNO3 center dot 1.65H(2)O) matrix on the photochemistry of CO and CH3OH have been investigated using NEXAFS spectroscopy. For pure H2O, CO and CH3OH ices, we show that the destruction rates are strongly limited by back reactions, leading to strikingly high survival rates of these molecules upon the harsh irradiation conditions to which they are submitted. We also evidence the interplay between the photochemical reactions of CO and CH3OH and those of the matrix. The OH and O radicals released by the photolysis of H2O and HNO3 react with the CO and CH3OH and their fragments, considerably reducing the survival rates compared to pure CO and pure CH3OH ices, especially in presence of nitric acid, and dramatically enhancing the formation of CO2 at the expense of CO. Because NEXAFS spectroscopy allows identifying which reactions are important among those possible, it emerges a simple picture of the photochemical routes of CO and CH3OH in the H2O and HNO3/H2O environments.},
  author       = {Laffon, C. and Lasne, J. and Bournel, F. and Schulte, Karina and Lacombe, S. and Parent, Ph.},
  issn         = {1463-9084},
  language     = {eng},
  number       = {36},
  pages        = {10865--10870},
  publisher    = {Royal Society of Chemistry},
  series       = {Physical Chemistry Chemical Physics},
  title        = {Photochemistry of carbon monoxide and methanol in water and nitric acid hydrate ices: A NEXAFS study},
  url          = {http://dx.doi.org/10.1039/c0cp00229a},
  volume       = {12},
  year         = {2010},
}