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Rate Coefficients of C1 and C2 Criegee Intermediate Reactions with Formic and Acetic Acid Near the Collision Limit: Direct Kinetics Measurements and Atmospheric Implications**

Rate coefficients are directly determined for the reactions of the Criegee intermediates (CI) CH(2)OO and CH(3)CHOO with the two simplest carboxylic acids, formic acid (HCOOH) and acetic acid (CH(3)COOH), employing two complementary techniques: multiplexed photoionization mass spectrometry and cavit...

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Autores principales: Welz, Oliver, Eskola, Arkke J, Sheps, Leonid, Rotavera, Brandon, Savee, John D, Scheer, Adam M, Osborn, David L, Lowe, Douglas, Murray Booth, A, Xiao, Ping, Anwar H Khan, M, Percival, Carl J, Shallcross, Dudley E, Taatjes, Craig A
Formato: Online Artículo Texto
Lenguaje:English
Publicado: WILEY-VCH Verlag 2014
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4499262/
https://www.ncbi.nlm.nih.gov/pubmed/24668781
http://dx.doi.org/10.1002/anie.201400964
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author Welz, Oliver
Eskola, Arkke J
Sheps, Leonid
Rotavera, Brandon
Savee, John D
Scheer, Adam M
Osborn, David L
Lowe, Douglas
Murray Booth, A
Xiao, Ping
Anwar H Khan, M
Percival, Carl J
Shallcross, Dudley E
Taatjes, Craig A
author_facet Welz, Oliver
Eskola, Arkke J
Sheps, Leonid
Rotavera, Brandon
Savee, John D
Scheer, Adam M
Osborn, David L
Lowe, Douglas
Murray Booth, A
Xiao, Ping
Anwar H Khan, M
Percival, Carl J
Shallcross, Dudley E
Taatjes, Craig A
author_sort Welz, Oliver
collection PubMed
description Rate coefficients are directly determined for the reactions of the Criegee intermediates (CI) CH(2)OO and CH(3)CHOO with the two simplest carboxylic acids, formic acid (HCOOH) and acetic acid (CH(3)COOH), employing two complementary techniques: multiplexed photoionization mass spectrometry and cavity-enhanced broadband ultraviolet absorption spectroscopy. The measured rate coefficients are in excess of 1×10(−10) cm(3) s(−1), several orders of magnitude larger than those suggested from many previous alkene ozonolysis experiments and assumed in atmospheric modeling studies. These results suggest that the reaction with carboxylic acids is a substantially more important loss process for CIs than is presently assumed. Implementing these rate coefficients in global atmospheric models shows that reactions between CI and organic acids make a substantial contribution to removal of these acids in terrestrial equatorial areas and in other regions where high CI concentrations occur such as high northern latitudes, and implies that sources of acids in these areas are larger than previously recognized.
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spelling pubmed-44992622015-07-16 Rate Coefficients of C1 and C2 Criegee Intermediate Reactions with Formic and Acetic Acid Near the Collision Limit: Direct Kinetics Measurements and Atmospheric Implications** Welz, Oliver Eskola, Arkke J Sheps, Leonid Rotavera, Brandon Savee, John D Scheer, Adam M Osborn, David L Lowe, Douglas Murray Booth, A Xiao, Ping Anwar H Khan, M Percival, Carl J Shallcross, Dudley E Taatjes, Craig A Angew Chem Int Ed Engl Communications Rate coefficients are directly determined for the reactions of the Criegee intermediates (CI) CH(2)OO and CH(3)CHOO with the two simplest carboxylic acids, formic acid (HCOOH) and acetic acid (CH(3)COOH), employing two complementary techniques: multiplexed photoionization mass spectrometry and cavity-enhanced broadband ultraviolet absorption spectroscopy. The measured rate coefficients are in excess of 1×10(−10) cm(3) s(−1), several orders of magnitude larger than those suggested from many previous alkene ozonolysis experiments and assumed in atmospheric modeling studies. These results suggest that the reaction with carboxylic acids is a substantially more important loss process for CIs than is presently assumed. Implementing these rate coefficients in global atmospheric models shows that reactions between CI and organic acids make a substantial contribution to removal of these acids in terrestrial equatorial areas and in other regions where high CI concentrations occur such as high northern latitudes, and implies that sources of acids in these areas are larger than previously recognized. WILEY-VCH Verlag 2014-04-25 2014-03-25 /pmc/articles/PMC4499262/ /pubmed/24668781 http://dx.doi.org/10.1002/anie.201400964 Text en © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. http://creativecommons.org/licenses/by/3.0/ This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Communications
Welz, Oliver
Eskola, Arkke J
Sheps, Leonid
Rotavera, Brandon
Savee, John D
Scheer, Adam M
Osborn, David L
Lowe, Douglas
Murray Booth, A
Xiao, Ping
Anwar H Khan, M
Percival, Carl J
Shallcross, Dudley E
Taatjes, Craig A
Rate Coefficients of C1 and C2 Criegee Intermediate Reactions with Formic and Acetic Acid Near the Collision Limit: Direct Kinetics Measurements and Atmospheric Implications**
title Rate Coefficients of C1 and C2 Criegee Intermediate Reactions with Formic and Acetic Acid Near the Collision Limit: Direct Kinetics Measurements and Atmospheric Implications**
title_full Rate Coefficients of C1 and C2 Criegee Intermediate Reactions with Formic and Acetic Acid Near the Collision Limit: Direct Kinetics Measurements and Atmospheric Implications**
title_fullStr Rate Coefficients of C1 and C2 Criegee Intermediate Reactions with Formic and Acetic Acid Near the Collision Limit: Direct Kinetics Measurements and Atmospheric Implications**
title_full_unstemmed Rate Coefficients of C1 and C2 Criegee Intermediate Reactions with Formic and Acetic Acid Near the Collision Limit: Direct Kinetics Measurements and Atmospheric Implications**
title_short Rate Coefficients of C1 and C2 Criegee Intermediate Reactions with Formic and Acetic Acid Near the Collision Limit: Direct Kinetics Measurements and Atmospheric Implications**
title_sort rate coefficients of c1 and c2 criegee intermediate reactions with formic and acetic acid near the collision limit: direct kinetics measurements and atmospheric implications**
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4499262/
https://www.ncbi.nlm.nih.gov/pubmed/24668781
http://dx.doi.org/10.1002/anie.201400964
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