Kinetics of the unimolecular reaction of CH2OO and the bimolecular reactions with the water monomer, acetaldehyde and acetone under atmospheric conditionsElectronic supplementary information (ESI) available. See DOI: 10.1039/c5cp02224j
Stabilized Criegee Intermediates (sCIs) have been identified as oxidants of atmospheric trace gases such as SO 2 , NO 2 , carboxylic acids or carbonyls. The atmospheric sCI concentrations, and accordingly their importance for trace gas oxidation, are controlled by the rate of the most important loss...
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| container_start_page | 19862 |
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| creator | Berndt, Torsten Kaethner, Ralf Voigtländer, Jens Stratmann, Frank Pfeifle, Mark Reichle, Patrick Sipilä, Mikko Kulmala, Markku Olzmann, Matthias |
| description | Stabilized Criegee Intermediates (sCIs) have been identified as oxidants of atmospheric trace gases such as SO
2
, NO
2
, carboxylic acids or carbonyls. The atmospheric sCI concentrations, and accordingly their importance for trace gas oxidation, are controlled by the rate of the most important loss processes, very likely the unimolecular reactions and the reaction with water vapour (monomer and dimer) ubiquitously present at high concentrations in the troposphere. In this study, the rate coefficients of the unimolecular reaction of the simplest sCI, formaldehyde oxide, CH
2
OO, and its bimolecular reaction with the water monomer have been experimentally determined at
T
= (297 ± 1) K and at atmospheric pressure by using a free-jet flow system. CH
2
OO was produced by the reaction of ozone with C
2
H
4
, and CH
2
OO concentrations were probed indirectly by detecting H
2
SO
4
after titration with SO
2
. Time-resolved experiments yield a rate coefficient of the unimolecular reaction of
k
(uni)
= (0.19 ± 0.07) s
−1
, a value that is supported by quantum-chemical and statistical rate theory calculations as well as by additional measurements performed under CH
2
OO steady-state conditions. A rate coefficient of
k
(CH
2
OO+H
2
O)
= (3.2 ± 1.2) × 10
−16
cm
3
molecule
−1
s
−1
has been determined for sufficiently low H
2
O concentrations ( |
| doi_str_mv | 10.1039/c5cp02224j |
| format | Article |
| fullrecord | <record><control><sourceid>rsc</sourceid><recordid>TN_cdi_rsc_primary_c5cp02224j</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>c5cp02224j</sourcerecordid><originalsourceid>FETCH-rsc_primary_c5cp02224j3</originalsourceid><addsrcrecordid>eNqFkE1Lw0AQhhdRsH5cvAvjTcHWzUer9VojLR5yqPcw3UzIlv0IuxtLf7N_wiSIHhQ9zTDvwzPDMHYR8UnEk_mdmIqGx3Gcbg_YKEpnyXjOH9LDr_5-dsxOvN9yzqNplIzY-4s0FKTwYCsINUFrpLaKRKvQgSMUQVrTh4tlnOeAphywzS-Uh50M9RDvMJADbY3V5G4BBQVUJdX7kgZFP7Cm31Z2HAZtfVOTkwKENaUcbFnnD86abujbplGkyQR0e5Cmsk7jcNh1tl7dAL6hVLhRNIE1ETzlq0f4-ZIzdlSh8nT-WU_Z5XP2uliOnRdF46Tu5MU3nvyfX_2VF01ZJR9txoMh</addsrcrecordid><sourcetype>Enrichment Source</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Kinetics of the unimolecular reaction of CH2OO and the bimolecular reactions with the water monomer, acetaldehyde and acetone under atmospheric conditionsElectronic supplementary information (ESI) available. See DOI: 10.1039/c5cp02224j</title><source>Royal Society Of Chemistry Journals 2008-</source><source>Alma/SFX Local Collection</source><creator>Berndt, Torsten ; Kaethner, Ralf ; Voigtländer, Jens ; Stratmann, Frank ; Pfeifle, Mark ; Reichle, Patrick ; Sipilä, Mikko ; Kulmala, Markku ; Olzmann, Matthias</creator><creatorcontrib>Berndt, Torsten ; Kaethner, Ralf ; Voigtländer, Jens ; Stratmann, Frank ; Pfeifle, Mark ; Reichle, Patrick ; Sipilä, Mikko ; Kulmala, Markku ; Olzmann, Matthias</creatorcontrib><description>Stabilized Criegee Intermediates (sCIs) have been identified as oxidants of atmospheric trace gases such as SO
2
, NO
2
, carboxylic acids or carbonyls. The atmospheric sCI concentrations, and accordingly their importance for trace gas oxidation, are controlled by the rate of the most important loss processes, very likely the unimolecular reactions and the reaction with water vapour (monomer and dimer) ubiquitously present at high concentrations in the troposphere. In this study, the rate coefficients of the unimolecular reaction of the simplest sCI, formaldehyde oxide, CH
2
OO, and its bimolecular reaction with the water monomer have been experimentally determined at
T
= (297 ± 1) K and at atmospheric pressure by using a free-jet flow system. CH
2
OO was produced by the reaction of ozone with C
2
H
4
, and CH
2
OO concentrations were probed indirectly by detecting H
2
SO
4
after titration with SO
2
. Time-resolved experiments yield a rate coefficient of the unimolecular reaction of
k
(uni)
= (0.19 ± 0.07) s
−1
, a value that is supported by quantum-chemical and statistical rate theory calculations as well as by additional measurements performed under CH
2
OO steady-state conditions. A rate coefficient of
k
(CH
2
OO+H
2
O)
= (3.2 ± 1.2) × 10
−16
cm
3
molecule
−1
s
−1
has been determined for sufficiently low H
2
O concentrations (<10
15
molecule cm
−3
) that allow separation from the CH
2
OO reaction with the water dimer. In order to evaluate the accuracy of the experimental approach, the rate coefficients of the reactions with acetaldehyde and acetone were reinvestigated. The obtained rate coefficients
k
(CH
2
OO+acetald)
= (1.7 ± 0.5) × 10
−12
and
k
(CH
2
OO+acetone)
= (3.4 ± 0.9) × 10
−13
cm
3
molecule
−1
s
−1
are in good agreement with literature data.
The rate coefficients of the unimolecular reaction of CH
2
OO and the bimolecular reactions with the water monomer and carbonyls were measured.</description><identifier>ISSN: 1463-9076</identifier><identifier>EISSN: 1463-9084</identifier><identifier>DOI: 10.1039/c5cp02224j</identifier><language>eng</language><creationdate>2015-07</creationdate><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27901,27902</link.rule.ids></links><search><creatorcontrib>Berndt, Torsten</creatorcontrib><creatorcontrib>Kaethner, Ralf</creatorcontrib><creatorcontrib>Voigtländer, Jens</creatorcontrib><creatorcontrib>Stratmann, Frank</creatorcontrib><creatorcontrib>Pfeifle, Mark</creatorcontrib><creatorcontrib>Reichle, Patrick</creatorcontrib><creatorcontrib>Sipilä, Mikko</creatorcontrib><creatorcontrib>Kulmala, Markku</creatorcontrib><creatorcontrib>Olzmann, Matthias</creatorcontrib><title>Kinetics of the unimolecular reaction of CH2OO and the bimolecular reactions with the water monomer, acetaldehyde and acetone under atmospheric conditionsElectronic supplementary information (ESI) available. See DOI: 10.1039/c5cp02224j</title><description>Stabilized Criegee Intermediates (sCIs) have been identified as oxidants of atmospheric trace gases such as SO
2
, NO
2
, carboxylic acids or carbonyls. The atmospheric sCI concentrations, and accordingly their importance for trace gas oxidation, are controlled by the rate of the most important loss processes, very likely the unimolecular reactions and the reaction with water vapour (monomer and dimer) ubiquitously present at high concentrations in the troposphere. In this study, the rate coefficients of the unimolecular reaction of the simplest sCI, formaldehyde oxide, CH
2
OO, and its bimolecular reaction with the water monomer have been experimentally determined at
T
= (297 ± 1) K and at atmospheric pressure by using a free-jet flow system. CH
2
OO was produced by the reaction of ozone with C
2
H
4
, and CH
2
OO concentrations were probed indirectly by detecting H
2
SO
4
after titration with SO
2
. Time-resolved experiments yield a rate coefficient of the unimolecular reaction of
k
(uni)
= (0.19 ± 0.07) s
−1
, a value that is supported by quantum-chemical and statistical rate theory calculations as well as by additional measurements performed under CH
2
OO steady-state conditions. A rate coefficient of
k
(CH
2
OO+H
2
O)
= (3.2 ± 1.2) × 10
−16
cm
3
molecule
−1
s
−1
has been determined for sufficiently low H
2
O concentrations (<10
15
molecule cm
−3
) that allow separation from the CH
2
OO reaction with the water dimer. In order to evaluate the accuracy of the experimental approach, the rate coefficients of the reactions with acetaldehyde and acetone were reinvestigated. The obtained rate coefficients
k
(CH
2
OO+acetald)
= (1.7 ± 0.5) × 10
−12
and
k
(CH
2
OO+acetone)
= (3.4 ± 0.9) × 10
−13
cm
3
molecule
−1
s
−1
are in good agreement with literature data.
The rate coefficients of the unimolecular reaction of CH
2
OO and the bimolecular reactions with the water monomer and carbonyls were measured.</description><issn>1463-9076</issn><issn>1463-9084</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><sourceid/><recordid>eNqFkE1Lw0AQhhdRsH5cvAvjTcHWzUer9VojLR5yqPcw3UzIlv0IuxtLf7N_wiSIHhQ9zTDvwzPDMHYR8UnEk_mdmIqGx3Gcbg_YKEpnyXjOH9LDr_5-dsxOvN9yzqNplIzY-4s0FKTwYCsINUFrpLaKRKvQgSMUQVrTh4tlnOeAphywzS-Uh50M9RDvMJADbY3V5G4BBQVUJdX7kgZFP7Cm31Z2HAZtfVOTkwKENaUcbFnnD86abujbplGkyQR0e5Cmsk7jcNh1tl7dAL6hVLhRNIE1ETzlq0f4-ZIzdlSh8nT-WU_Z5XP2uliOnRdF46Tu5MU3nvyfX_2VF01ZJR9txoMh</recordid><startdate>20150722</startdate><enddate>20150722</enddate><creator>Berndt, Torsten</creator><creator>Kaethner, Ralf</creator><creator>Voigtländer, Jens</creator><creator>Stratmann, Frank</creator><creator>Pfeifle, Mark</creator><creator>Reichle, Patrick</creator><creator>Sipilä, Mikko</creator><creator>Kulmala, Markku</creator><creator>Olzmann, Matthias</creator><scope/></search><sort><creationdate>20150722</creationdate><title>Kinetics of the unimolecular reaction of CH2OO and the bimolecular reactions with the water monomer, acetaldehyde and acetone under atmospheric conditionsElectronic supplementary information (ESI) available. See DOI: 10.1039/c5cp02224j</title><author>Berndt, Torsten ; Kaethner, Ralf ; Voigtländer, Jens ; Stratmann, Frank ; Pfeifle, Mark ; Reichle, Patrick ; Sipilä, Mikko ; Kulmala, Markku ; Olzmann, Matthias</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-rsc_primary_c5cp02224j3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Berndt, Torsten</creatorcontrib><creatorcontrib>Kaethner, Ralf</creatorcontrib><creatorcontrib>Voigtländer, Jens</creatorcontrib><creatorcontrib>Stratmann, Frank</creatorcontrib><creatorcontrib>Pfeifle, Mark</creatorcontrib><creatorcontrib>Reichle, Patrick</creatorcontrib><creatorcontrib>Sipilä, Mikko</creatorcontrib><creatorcontrib>Kulmala, Markku</creatorcontrib><creatorcontrib>Olzmann, Matthias</creatorcontrib></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Berndt, Torsten</au><au>Kaethner, Ralf</au><au>Voigtländer, Jens</au><au>Stratmann, Frank</au><au>Pfeifle, Mark</au><au>Reichle, Patrick</au><au>Sipilä, Mikko</au><au>Kulmala, Markku</au><au>Olzmann, Matthias</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Kinetics of the unimolecular reaction of CH2OO and the bimolecular reactions with the water monomer, acetaldehyde and acetone under atmospheric conditionsElectronic supplementary information (ESI) available. See DOI: 10.1039/c5cp02224j</atitle><date>2015-07-22</date><risdate>2015</risdate><volume>17</volume><issue>3</issue><spage>19862</spage><epage>19873</epage><pages>19862-19873</pages><issn>1463-9076</issn><eissn>1463-9084</eissn><abstract>Stabilized Criegee Intermediates (sCIs) have been identified as oxidants of atmospheric trace gases such as SO
2
, NO
2
, carboxylic acids or carbonyls. The atmospheric sCI concentrations, and accordingly their importance for trace gas oxidation, are controlled by the rate of the most important loss processes, very likely the unimolecular reactions and the reaction with water vapour (monomer and dimer) ubiquitously present at high concentrations in the troposphere. In this study, the rate coefficients of the unimolecular reaction of the simplest sCI, formaldehyde oxide, CH
2
OO, and its bimolecular reaction with the water monomer have been experimentally determined at
T
= (297 ± 1) K and at atmospheric pressure by using a free-jet flow system. CH
2
OO was produced by the reaction of ozone with C
2
H
4
, and CH
2
OO concentrations were probed indirectly by detecting H
2
SO
4
after titration with SO
2
. Time-resolved experiments yield a rate coefficient of the unimolecular reaction of
k
(uni)
= (0.19 ± 0.07) s
−1
, a value that is supported by quantum-chemical and statistical rate theory calculations as well as by additional measurements performed under CH
2
OO steady-state conditions. A rate coefficient of
k
(CH
2
OO+H
2
O)
= (3.2 ± 1.2) × 10
−16
cm
3
molecule
−1
s
−1
has been determined for sufficiently low H
2
O concentrations (<10
15
molecule cm
−3
) that allow separation from the CH
2
OO reaction with the water dimer. In order to evaluate the accuracy of the experimental approach, the rate coefficients of the reactions with acetaldehyde and acetone were reinvestigated. The obtained rate coefficients
k
(CH
2
OO+acetald)
= (1.7 ± 0.5) × 10
−12
and
k
(CH
2
OO+acetone)
= (3.4 ± 0.9) × 10
−13
cm
3
molecule
−1
s
−1
are in good agreement with literature data.
The rate coefficients of the unimolecular reaction of CH
2
OO and the bimolecular reactions with the water monomer and carbonyls were measured.</abstract><doi>10.1039/c5cp02224j</doi><tpages>12</tpages></addata></record> |
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| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| title | Kinetics of the unimolecular reaction of CH2OO and the bimolecular reactions with the water monomer, acetaldehyde and acetone under atmospheric conditionsElectronic supplementary information (ESI) available. See DOI: 10.1039/c5cp02224j |
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