Hydroxyl Radical Quantum Yields from Isopropyl Nitrite Photolysis in Air
Alkyl nitrites photolyze in air to yield alkoxy radicals and NO which, through secondary reactions, generate OH radicals. This photochemistry is important in the atmosphere and in laboratory studies where nitrites are often used as a source of OH. The overall quantum yield for hydroxyl radical forma...
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| Veröffentlicht in: | Environmental science & technology 2010-11, Vol.44 (21), p.8150-8155 |
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| creator | Raff, Jonathan D. Finlayson-Pitts, Barbara J. |
| description | Alkyl nitrites photolyze in air to yield alkoxy radicals and NO which, through secondary reactions, generate OH radicals. This photochemistry is important in the atmosphere and in laboratory studies where nitrites are often used as a source of OH. The overall quantum yield for hydroxyl radical formation from irradiation of isopropyl nitrite (i-C3H7ONO) between 300 and 425 nm in 1 atm air at 296 ± 2 K is reported for the first time. The OH radical was scavenged by reaction with CF3CFCF2 and the formation of CF3CFO and CF2O monitored as a function of time using Fourier transform infrared spectrometry. The quantum yield was found to be 0.54 ± 0.07 (2σ) and is independent of whether or not NO was added (up to 3 × 1014 molecules cm−3) prior to photolysis to increase NO concentrations above those due to the photolysis of the nitrite. Ultraviolet−visible and infrared cross sections of i-C3H7ONO are also reported. These data on the OH quantum yields as well as the UV−visible and infrared cross sections for isopropyl nitrite are critical for quantitatively interpreting the results of laboratory studies where i-C3H7ONO is employed as an OH source as well as for assessing the role of alkyl nitrites in the chemistry of the troposphere. |
| doi_str_mv | 10.1021/es102218d |
| format | Article |
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This photochemistry is important in the atmosphere and in laboratory studies where nitrites are often used as a source of OH. The overall quantum yield for hydroxyl radical formation from irradiation of isopropyl nitrite (i-C3H7ONO) between 300 and 425 nm in 1 atm air at 296 ± 2 K is reported for the first time. The OH radical was scavenged by reaction with CF3CFCF2 and the formation of CF3CFO and CF2O monitored as a function of time using Fourier transform infrared spectrometry. The quantum yield was found to be 0.54 ± 0.07 (2σ) and is independent of whether or not NO was added (up to 3 × 1014 molecules cm−3) prior to photolysis to increase NO concentrations above those due to the photolysis of the nitrite. Ultraviolet−visible and infrared cross sections of i-C3H7ONO are also reported. These data on the OH quantum yields as well as the UV−visible and infrared cross sections for isopropyl nitrite are critical for quantitatively interpreting the results of laboratory studies where i-C3H7ONO is employed as an OH source as well as for assessing the role of alkyl nitrites in the chemistry of the troposphere.</description><identifier>ISSN: 0013-936X</identifier><identifier>EISSN: 1520-5851</identifier><identifier>DOI: 10.1021/es102218d</identifier><identifier>PMID: 20879762</identifier><identifier>CODEN: ESTHAG</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Air Pollutants - analysis ; Air Pollutants - chemical synthesis ; Air pollution ; Applied sciences ; Atmosphere - chemistry ; Environmental Processes ; Exact sciences and technology ; Fourier transforms ; Hydroxyl Radical - analysis ; Hydroxyl Radical - chemical synthesis ; Laboratories ; Mass spectrometry ; Nitric oxide ; Nitrites - chemistry ; Photolysis ; Pollution ; Spectroscopy, Fourier Transform Infrared ; Studies ; Troposphere ; Ultraviolet radiation ; Ultraviolet Rays</subject><ispartof>Environmental science & technology, 2010-11, Vol.44 (21), p.8150-8155</ispartof><rights>Copyright © 2010 American Chemical Society</rights><rights>2015 INIST-CNRS</rights><rights>Copyright American Chemical Society Nov 1, 2010</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a371t-54653d3394fbbd458ee00cb15dab745dea5e61a08966ef177ca9359dd93109723</citedby><cites>FETCH-LOGICAL-a371t-54653d3394fbbd458ee00cb15dab745dea5e61a08966ef177ca9359dd93109723</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/es102218d$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/es102218d$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,777,781,2752,27057,27905,27906,56719,56769</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=23382378$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/20879762$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Raff, Jonathan D.</creatorcontrib><creatorcontrib>Finlayson-Pitts, Barbara J.</creatorcontrib><title>Hydroxyl Radical Quantum Yields from Isopropyl Nitrite Photolysis in Air</title><title>Environmental science & technology</title><addtitle>Environ. Sci. Technol</addtitle><description>Alkyl nitrites photolyze in air to yield alkoxy radicals and NO which, through secondary reactions, generate OH radicals. This photochemistry is important in the atmosphere and in laboratory studies where nitrites are often used as a source of OH. The overall quantum yield for hydroxyl radical formation from irradiation of isopropyl nitrite (i-C3H7ONO) between 300 and 425 nm in 1 atm air at 296 ± 2 K is reported for the first time. The OH radical was scavenged by reaction with CF3CFCF2 and the formation of CF3CFO and CF2O monitored as a function of time using Fourier transform infrared spectrometry. The quantum yield was found to be 0.54 ± 0.07 (2σ) and is independent of whether or not NO was added (up to 3 × 1014 molecules cm−3) prior to photolysis to increase NO concentrations above those due to the photolysis of the nitrite. Ultraviolet−visible and infrared cross sections of i-C3H7ONO are also reported. These data on the OH quantum yields as well as the UV−visible and infrared cross sections for isopropyl nitrite are critical for quantitatively interpreting the results of laboratory studies where i-C3H7ONO is employed as an OH source as well as for assessing the role of alkyl nitrites in the chemistry of the troposphere.</description><subject>Air Pollutants - analysis</subject><subject>Air Pollutants - chemical synthesis</subject><subject>Air pollution</subject><subject>Applied sciences</subject><subject>Atmosphere - chemistry</subject><subject>Environmental Processes</subject><subject>Exact sciences and technology</subject><subject>Fourier transforms</subject><subject>Hydroxyl Radical - analysis</subject><subject>Hydroxyl Radical - chemical synthesis</subject><subject>Laboratories</subject><subject>Mass spectrometry</subject><subject>Nitric oxide</subject><subject>Nitrites - chemistry</subject><subject>Photolysis</subject><subject>Pollution</subject><subject>Spectroscopy, Fourier Transform Infrared</subject><subject>Studies</subject><subject>Troposphere</subject><subject>Ultraviolet radiation</subject><subject>Ultraviolet Rays</subject><issn>0013-936X</issn><issn>1520-5851</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2010</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpl0F1LwzAUBuAgipvTC_-ABEHEi2o-mia5HEPdYPiFgl6VtEkx0jYzacH9eyObG-jVuXk45z0vAMcYXWJE8JUJcRAs9A4YYkZQwgTDu2CIEKaJpNnrAByE8IEQIhSJfTAgSHDJMzIE0-lSe_e1rOGT0rZUNXzsVdv1DXyzptYBVt41cBbcwrtFVHe287Yz8OHdda5eBhugbeHY-kOwV6k6mKP1HIGXm-vnyTSZ39_OJuN5oijHXcLSjFFNqUyrotApE8YgVBaYaVXwlGmjmMmwQkJmmakw56WSlEmtJcVIckJH4Hy1Nwb67E3o8saG0tS1ao3rQx6_SrnEqYzy9I_8cL1vY7hcYIajy1BEFytUeheCN1W-8LZRfpljlP-Um2_KjfZkvbAvGqM38rfNCM7WQIVYZeVVW9qwdZQKQrnYOlWGbaj_B78B-D2L8w</recordid><startdate>20101101</startdate><enddate>20101101</enddate><creator>Raff, Jonathan D.</creator><creator>Finlayson-Pitts, Barbara J.</creator><general>American Chemical Society</general><scope>IQODW</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7QO</scope><scope>7ST</scope><scope>7T7</scope><scope>7U7</scope><scope>8FD</scope><scope>C1K</scope><scope>FR3</scope><scope>P64</scope><scope>SOI</scope><scope>7X8</scope></search><sort><creationdate>20101101</creationdate><title>Hydroxyl Radical Quantum Yields from Isopropyl Nitrite Photolysis in Air</title><author>Raff, Jonathan D. ; Finlayson-Pitts, Barbara J.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a371t-54653d3394fbbd458ee00cb15dab745dea5e61a08966ef177ca9359dd93109723</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2010</creationdate><topic>Air Pollutants - analysis</topic><topic>Air Pollutants - chemical synthesis</topic><topic>Air pollution</topic><topic>Applied sciences</topic><topic>Atmosphere - chemistry</topic><topic>Environmental Processes</topic><topic>Exact sciences and technology</topic><topic>Fourier transforms</topic><topic>Hydroxyl Radical - analysis</topic><topic>Hydroxyl Radical - chemical synthesis</topic><topic>Laboratories</topic><topic>Mass spectrometry</topic><topic>Nitric oxide</topic><topic>Nitrites - chemistry</topic><topic>Photolysis</topic><topic>Pollution</topic><topic>Spectroscopy, Fourier Transform Infrared</topic><topic>Studies</topic><topic>Troposphere</topic><topic>Ultraviolet radiation</topic><topic>Ultraviolet Rays</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Raff, Jonathan D.</creatorcontrib><creatorcontrib>Finlayson-Pitts, Barbara J.</creatorcontrib><collection>Pascal-Francis</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Biotechnology Research Abstracts</collection><collection>Environment Abstracts</collection><collection>Industrial and Applied Microbiology Abstracts (Microbiology A)</collection><collection>Toxicology Abstracts</collection><collection>Technology Research Database</collection><collection>Environmental Sciences and Pollution Management</collection><collection>Engineering Research Database</collection><collection>Biotechnology and BioEngineering Abstracts</collection><collection>Environment Abstracts</collection><collection>MEDLINE - Academic</collection><jtitle>Environmental science & technology</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Raff, Jonathan D.</au><au>Finlayson-Pitts, Barbara J.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Hydroxyl Radical Quantum Yields from Isopropyl Nitrite Photolysis in Air</atitle><jtitle>Environmental science & technology</jtitle><addtitle>Environ. Sci. Technol</addtitle><date>2010-11-01</date><risdate>2010</risdate><volume>44</volume><issue>21</issue><spage>8150</spage><epage>8155</epage><pages>8150-8155</pages><issn>0013-936X</issn><eissn>1520-5851</eissn><coden>ESTHAG</coden><abstract>Alkyl nitrites photolyze in air to yield alkoxy radicals and NO which, through secondary reactions, generate OH radicals. This photochemistry is important in the atmosphere and in laboratory studies where nitrites are often used as a source of OH. The overall quantum yield for hydroxyl radical formation from irradiation of isopropyl nitrite (i-C3H7ONO) between 300 and 425 nm in 1 atm air at 296 ± 2 K is reported for the first time. The OH radical was scavenged by reaction with CF3CFCF2 and the formation of CF3CFO and CF2O monitored as a function of time using Fourier transform infrared spectrometry. The quantum yield was found to be 0.54 ± 0.07 (2σ) and is independent of whether or not NO was added (up to 3 × 1014 molecules cm−3) prior to photolysis to increase NO concentrations above those due to the photolysis of the nitrite. Ultraviolet−visible and infrared cross sections of i-C3H7ONO are also reported. These data on the OH quantum yields as well as the UV−visible and infrared cross sections for isopropyl nitrite are critical for quantitatively interpreting the results of laboratory studies where i-C3H7ONO is employed as an OH source as well as for assessing the role of alkyl nitrites in the chemistry of the troposphere.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>20879762</pmid><doi>10.1021/es102218d</doi><tpages>6</tpages></addata></record> |
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| subjects | Air Pollutants - analysis Air Pollutants - chemical synthesis Air pollution Applied sciences Atmosphere - chemistry Environmental Processes Exact sciences and technology Fourier transforms Hydroxyl Radical - analysis Hydroxyl Radical - chemical synthesis Laboratories Mass spectrometry Nitric oxide Nitrites - chemistry Photolysis Pollution Spectroscopy, Fourier Transform Infrared Studies Troposphere Ultraviolet radiation Ultraviolet Rays |
| title | Hydroxyl Radical Quantum Yields from Isopropyl Nitrite Photolysis in Air |
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