Cited by 58Atmospheric chemistry and aerosolsAdvanced Combustion Engine TechnologiesAtmospheric Ozone and Climate

Atmospheric chemistry of alcohols

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Grosjean, Daniel·1997·Journal of the Brazilian Chemical Society

Abstract

The atmospheric chemistry of alcohols, which are widely used as motor vehicle fuels (e.g. ethanol in Brazil) and as industrial solvents, has been reviewed with focus on kinetic data and on reaction mechanisms. Oxidation of alcohols in the atmosphere involves their reaction with the hydroxyl radical (OH). Alcohol-OH reaction rate constants are presented for 33 saturated alcohols including monofunctional and difunctional compounds. The corresponding atmospheric half-lives are one week for methanol and t-butyl alcohol, 2.5 days for ethanol, and 8-15 h for other alcohols. Laboratory studies of alcohol-OH reaction products are described and reaction mechanisms are outlined. Major products are formaldehyde from methanol, acetaldehyde from ethanol, acetone from 2-propanol, 2-butanone and acetaldehyde from 2-butanol and acetone and formaldehyde from t-butyl alcohol. The reaction of OH with alcohols involves H-atom abstraction from C-H bonds; H-atom abstraction from the O-H bond is negligible. The alkyl radicals (R) and a-hydroxyalkyl radicals thus formed react with oxygen. This reaction involves addition for alkyl radicals (R + O2 RO2) and H-atom abstraction for a-hydroxyalkyl radicals (e.g. ethanol + OH CH3CHOH, CH3CHOH + O2 HO2 + CH3CHO). The reaction sequence ethanol acetaldehyde peroxyacetyl nitrate (PAN, CH3C(O)OONO2) is described and is relevant to urban air pollution in Brazil. Recommendation is made to carry out additional product studies in order to develop a better understanding of the atmospheric chemistry of alcohols and of their role in on urban and regional air quality.

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Authors
Grosjean, D.
Corresponding author
Grosjean, Daniel
Venue
Journal of the Brazilian Chemical Society
Published
1997
Volume
8
Issue
5
Pages
433-442
ISSN
0103-5053 (ISSN-L)
OpenAlex
W1984607640
Cited by
58
References
1
Citations by year
2025: 1 · 2024: 1 · 2023: 3 · 2022: 1 · 2021: 4 · 2020: 3 · 2019: 5 · 2018: 4 · 2017: 3 · 2016: 2 · 2015: 1 · 2014: 1 · 2013: 4 · 2012: 5
FWCI
0.79
Type
journal article
Language
en
Open access
Licence
cc-by-nc
Locations
  • Journal of the Brazilian Chemical Society (publishedVersion, cc-by-nc)
  • LA Referencia (Red Federada de Repositorios Institucionales de Publicaciones Científicas) (publishedVersion, other-oa)
  • Americanae (AECID Library) (submittedVersion, other-oa)
Topics
  • Physical Sciences › Earth and Planetary Sciences › Atmospheric Science › Atmospheric chemistry and aerosols
  • Physical Sciences › Chemical Engineering › Fluid Flow and Transfer Processes › Advanced Combustion Engine Technologies
  • Physical Sciences › Earth and Planetary Sciences › Atmospheric Science › Atmospheric Ozone and Climate
Keywords
alcohol oxidation, hydroxyl radicals, rate constants, reaction mechanism, H-atom abstraction, formaldehyde, acetaldehyde, acetone, peroxyacetyl nitrate, urban air pollution, ethanol, methanol, tert-butanol, industrial solvents, air quality

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