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dc.contributor.author
Blanco, Maria Belen
dc.contributor.author
Bejan, Iustinian
dc.contributor.author
Barnes, Ian
dc.contributor.author
Wiesen, Peter
dc.contributor.author
Teruel, Mariano Andres
dc.date.available
2019-03-26T19:44:38Z
dc.date.issued
2009-08
dc.identifier.citation
Blanco, Maria Belen; Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Teruel, Mariano Andres; The Cl-initiated oxidation of CH3C(O)OCH=CH2, CH3C(O)OCH2CH=CH2, and CH2=CHC(O)O(CH2)3CH3 in the troposphere; Springer Heidelberg; Environmental Science and Pollution Research; 16; 6; 8-2009; 641-648
dc.identifier.issn
0944-1344
dc.identifier.uri
http://hdl.handle.net/11336/72576
dc.description.abstract
Background, aim, and scope Unsaturated esters are emitted to the atmosphere from biogenic and anthropogenic sources, including those from the polymer industry. Little information exists concerning the atmospheric degradation of unsaturated esters, which are mainly initiated by OH radicals. Limited information is available on the degradation of alkenes by Cl atoms and almost no data exists for the reactions of unsaturated esters with Cl atoms. This data is necessary to assess the impact of such reactions in maritime environments where, under circumstances, OH radical- and Cl atom-initiated oxidation of the compounds can be important. Rate coefficients for the reactions of chlorine atoms with vinyl acetate, allyl acetate, and n-butyl acrylate have been determined at 298 ± 3 K and atmospheric pressure. The kinetic data have been used in combination with that for structurally similar compounds to infer the kinetic contributions from the possible reaction channels to the overall reaction rate. Materials and methods The decay of the organics was followed using in situ Fourier transform infrared spectroscopy and the rate coefficients were determined using a relative kinetic method and different hydrocarbon reference compounds. Results The following room temperature rate coefficients (in cm3 molecule-1 s-1) were obtained: k1 (Cl+CH3C(O)OCH=CH2) = (2.68±0.91) × 10-10, k2 (Cl+CH3C(O)OCH2CH=CH2)=(1.30±0.45) × 10-10, and k3 (Cl+CH2=CHC(O)O(CH2)3CH3)=(2.50±0.78) × 10-10, where the uncertainties are a combination of the 2σ statistical errors from linear regression analyses and a contribution to cover uncertainties in the rate coefficients of the reference hydrocarbons. Discussion This is the first kinetic study of the title reactions under atmospheric conditions. The kinetic data were analyzed in terms of reactivity trends and used to estimate the atmospheric lifetimes of the esters and assess their potential importance in the marine atmosphere. Conclusions Although reaction with OH radicals is the major atmospheric sink for the unsaturated esters studied, reaction with Cl atoms can compete in the early morning hours in coastal areas where the Cl concentration can reach peak values as high as 1 × 105 atoms cm-3. The calculated residence times show that the chemistry of unsaturated esters will impact air quality locally near their emission sources. Recommendations and perspectives The reactions need to be studied over the range of temperatures and pressures generally encountered in the marine atmosphere. In addition, product studies should also be performed as a function of temperature since this will allow degradation mechanisms to be derived, which are representative for the wide range of conditions occurring in marine environments. Inclusion of the kinetic and product data in tropospheric numerical models will allow an assessment of potential environmental impacts of the esters for different marine pollution scenarios. © Springer-Verlag 2008.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
Springer Heidelberg
dc.rights
info:eu-repo/semantics/restrictedAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
Chlorine Atoms
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Environmental Chamber
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Rate Coefficients
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Tropospheric Chemistry
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Unsaturated Esters
dc.subject.classification
Meteorología y Ciencias Atmosféricas
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Ciencias de la Tierra y relacionadas con el Medio Ambiente
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CIENCIAS NATURALES Y EXACTAS
dc.title
The Cl-initiated oxidation of CH3C(O)OCH=CH2, CH3C(O)OCH2CH=CH2, and CH2=CHC(O)O(CH2)3CH3 in the troposphere
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2019-03-18T14:42:34Z
dc.journal.volume
16
dc.journal.number
6
dc.journal.pagination
641-648
dc.journal.pais
Alemania
dc.journal.ciudad
Heidelberg
dc.description.fil
Fil: Blanco, Maria Belen. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
dc.description.fil
Fil: Bejan, Iustinian. Bergische Universität Wuppertal; Alemania. University of Iasi; Rumania
dc.description.fil
Fil: Barnes, Ian. Bergische Universität Wuppertal; Alemania
dc.description.fil
Fil: Wiesen, Peter. Bergische Universität Wuppertal; Alemania
dc.description.fil
Fil: Teruel, Mariano Andres. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
dc.journal.title
Environmental Science and Pollution Research
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/https://dx.doi.org/10.1007/s11356-008-0096-y
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://link.springer.com/article/10.1007/s11356-008-0096-y
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