Rates of reaction of alkyl radicals with ozone
The rate constants for a series of alkyl radicals reacting with ozone have been measured at 298 K and 2 torr by using a photoionization mass spectrometer. The radical (R) + ozone rate constants (in units of 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/) are 2.53 +/- 0.54 for CH/sub 3/, 25.3 +/- 5...
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| Veröffentlicht in: | J. Phys. Chem.; (United States) 1984-06, Vol.88 (12), p.2595-2599 |
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| container_title | J. Phys. Chem.; (United States) |
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| creator | Paltenghi, R Ogryzlo, E. A Bayes, Kyle D |
| description | The rate constants for a series of alkyl radicals reacting with ozone have been measured at 298 K and 2 torr by using a photoionization mass spectrometer. The radical (R) + ozone rate constants (in units of 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/) are 2.53 +/- 0.54 for CH/sub 3/, 25.3 +/- 5.8 for C/sub 2/H/sub 5/, 24.4 +/- 5.9 for 1-C/sub 3/H/sub 7/, 46.5 +/- 10.6 for 2-C/sub 3/H/sub 7/, and 54.5 +/- 11.4 for t-C/sub 4/H/sub 9/. As was observed for the R + O/sub 2/ reactions the R + O/sub 3/ reactions show a trend of increasing rate constant k/sub 1/ with decreasing ionization potential (IP) of the radical. When log (k/sub 1/) vs. IP(R) - EA(O/sub 2/ or O/sub 3/) is plotted, where EA represents electron affinity, the two families of rate constants are brought into close proximity. In addition, rate constants for fluorescence quenching of substituted benzenes by O/sub 2/ are cited which extend the log (k) vs. IP-EA plot to lower ionization potential. Adiabatic channel model calculations have been done by using a long-range potential resulting from the perturbation between the R/sup +/ + O/sub 3//sup -/ and R + O/sub 3/ surfaces. These calculations give good agreement with the experimental cross sections and they predict rate constants faster than those derived from the classical harpoon model at low IP-EA. |
| doi_str_mv | 10.1021/j150656a034 |
| format | Article |
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A ; Bayes, Kyle D</creator><creatorcontrib>Paltenghi, R ; Ogryzlo, E. A ; Bayes, Kyle D ; Univ. of California, Los Angeles</creatorcontrib><description>The rate constants for a series of alkyl radicals reacting with ozone have been measured at 298 K and 2 torr by using a photoionization mass spectrometer. The radical (R) + ozone rate constants (in units of 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/) are 2.53 +/- 0.54 for CH/sub 3/, 25.3 +/- 5.8 for C/sub 2/H/sub 5/, 24.4 +/- 5.9 for 1-C/sub 3/H/sub 7/, 46.5 +/- 10.6 for 2-C/sub 3/H/sub 7/, and 54.5 +/- 11.4 for t-C/sub 4/H/sub 9/. As was observed for the R + O/sub 2/ reactions the R + O/sub 3/ reactions show a trend of increasing rate constant k/sub 1/ with decreasing ionization potential (IP) of the radical. When log (k/sub 1/) vs. IP(R) - EA(O/sub 2/ or O/sub 3/) is plotted, where EA represents electron affinity, the two families of rate constants are brought into close proximity. In addition, rate constants for fluorescence quenching of substituted benzenes by O/sub 2/ are cited which extend the log (k) vs. IP-EA plot to lower ionization potential. Adiabatic channel model calculations have been done by using a long-range potential resulting from the perturbation between the R/sup +/ + O/sub 3//sup -/ and R + O/sub 3/ surfaces. These calculations give good agreement with the experimental cross sections and they predict rate constants faster than those derived from the classical harpoon model at low IP-EA.</description><identifier>ISSN: 0022-3654</identifier><identifier>EISSN: 1541-5740</identifier><identifier>DOI: 10.1021/j150656a034</identifier><identifier>CODEN: JPCHAX</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>ALKYL RADICALS ; CHEMICAL REACTIONS ; Chemistry ; DATA ; Exact sciences and technology ; EXPERIMENTAL DATA ; Free radicals chemistry ; INFORMATION ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; KINETICS ; NUMERICAL DATA ; Organic chemistry ; OZONE ; RADICALS 400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987) ; REACTION KINETICS ; Reactivity and mechanisms</subject><ispartof>J. Phys. Chem.; (United States), 1984-06, Vol.88 (12), p.2595-2599</ispartof><rights>1984 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a357t-6783e2f2b42fb9f72bf2a417f7725ce854d9d7cb61b3da608023e4c06b4e08393</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/j150656a034$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/j150656a034$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,881,2752,27053,27901,27902,56713,56763</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=9628691$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/biblio/6916630$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Paltenghi, R</creatorcontrib><creatorcontrib>Ogryzlo, E. A</creatorcontrib><creatorcontrib>Bayes, Kyle D</creatorcontrib><creatorcontrib>Univ. of California, Los Angeles</creatorcontrib><title>Rates of reaction of alkyl radicals with ozone</title><title>J. Phys. Chem.; (United States)</title><addtitle>J. Phys. Chem</addtitle><description>The rate constants for a series of alkyl radicals reacting with ozone have been measured at 298 K and 2 torr by using a photoionization mass spectrometer. The radical (R) + ozone rate constants (in units of 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/) are 2.53 +/- 0.54 for CH/sub 3/, 25.3 +/- 5.8 for C/sub 2/H/sub 5/, 24.4 +/- 5.9 for 1-C/sub 3/H/sub 7/, 46.5 +/- 10.6 for 2-C/sub 3/H/sub 7/, and 54.5 +/- 11.4 for t-C/sub 4/H/sub 9/. As was observed for the R + O/sub 2/ reactions the R + O/sub 3/ reactions show a trend of increasing rate constant k/sub 1/ with decreasing ionization potential (IP) of the radical. When log (k/sub 1/) vs. IP(R) - EA(O/sub 2/ or O/sub 3/) is plotted, where EA represents electron affinity, the two families of rate constants are brought into close proximity. In addition, rate constants for fluorescence quenching of substituted benzenes by O/sub 2/ are cited which extend the log (k) vs. IP-EA plot to lower ionization potential. Adiabatic channel model calculations have been done by using a long-range potential resulting from the perturbation between the R/sup +/ + O/sub 3//sup -/ and R + O/sub 3/ surfaces. These calculations give good agreement with the experimental cross sections and they predict rate constants faster than those derived from the classical harpoon model at low IP-EA.</description><subject>ALKYL RADICALS</subject><subject>CHEMICAL REACTIONS</subject><subject>Chemistry</subject><subject>DATA</subject><subject>Exact sciences and technology</subject><subject>EXPERIMENTAL DATA</subject><subject>Free radicals chemistry</subject><subject>INFORMATION</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>KINETICS</subject><subject>NUMERICAL DATA</subject><subject>Organic chemistry</subject><subject>OZONE</subject><subject>RADICALS 400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)</subject><subject>REACTION KINETICS</subject><subject>Reactivity and mechanisms</subject><issn>0022-3654</issn><issn>1541-5740</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1984</creationdate><recordtype>article</recordtype><recordid>eNpt0MtKAzEUBuAgCtbqyhcYRHAhU3PPzFLqFQraWsFdyKQJTVsnJYlofXpTRooLVwnJdw7n_ACcIjhAEKOrBWKQM64goXughxhFJRMU7oMehBiXhDN6CI5iXEAIESGoBwYTlUwsvC2CUTo5327varXcrIqgZk6rVSw-XZoX_tu35hgc2PxiTn7PPni9u50OH8rR0_3j8HpUKsJEKrmoiMEWNxTbprYCNxYrioQVAjNtKkZn9UzohqOGzBSHFcTEUA15Qw2sSE364Kzr62NyMmqXjJ5r37ZGJ8lrxDmBGV12SAcfYzBWroN7V2EjEZTbPOSfPLI-7_RaxbyVDarVLu5Kao6r3DizsmMuJvO1-1ZhKbkggsnp84uk47cbPhlTSbK_6LzSUS78R2hzLv8O8AP2aXg9</recordid><startdate>19840601</startdate><enddate>19840601</enddate><creator>Paltenghi, R</creator><creator>Ogryzlo, E. A</creator><creator>Bayes, Kyle D</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>19840601</creationdate><title>Rates of reaction of alkyl radicals with ozone</title><author>Paltenghi, R ; Ogryzlo, E. A ; Bayes, Kyle D</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a357t-6783e2f2b42fb9f72bf2a417f7725ce854d9d7cb61b3da608023e4c06b4e08393</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1984</creationdate><topic>ALKYL RADICALS</topic><topic>CHEMICAL REACTIONS</topic><topic>Chemistry</topic><topic>DATA</topic><topic>Exact sciences and technology</topic><topic>EXPERIMENTAL DATA</topic><topic>Free radicals chemistry</topic><topic>INFORMATION</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>KINETICS</topic><topic>NUMERICAL DATA</topic><topic>Organic chemistry</topic><topic>OZONE</topic><topic>RADICALS 400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)</topic><topic>REACTION KINETICS</topic><topic>Reactivity and mechanisms</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Paltenghi, R</creatorcontrib><creatorcontrib>Ogryzlo, E. A</creatorcontrib><creatorcontrib>Bayes, Kyle D</creatorcontrib><creatorcontrib>Univ. of California, Los Angeles</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>J. Phys. Chem.; (United States)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Paltenghi, R</au><au>Ogryzlo, E. A</au><au>Bayes, Kyle D</au><aucorp>Univ. of California, Los Angeles</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Rates of reaction of alkyl radicals with ozone</atitle><jtitle>J. Phys. Chem.; (United States)</jtitle><addtitle>J. Phys. Chem</addtitle><date>1984-06-01</date><risdate>1984</risdate><volume>88</volume><issue>12</issue><spage>2595</spage><epage>2599</epage><pages>2595-2599</pages><issn>0022-3654</issn><eissn>1541-5740</eissn><coden>JPCHAX</coden><abstract>The rate constants for a series of alkyl radicals reacting with ozone have been measured at 298 K and 2 torr by using a photoionization mass spectrometer. The radical (R) + ozone rate constants (in units of 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/) are 2.53 +/- 0.54 for CH/sub 3/, 25.3 +/- 5.8 for C/sub 2/H/sub 5/, 24.4 +/- 5.9 for 1-C/sub 3/H/sub 7/, 46.5 +/- 10.6 for 2-C/sub 3/H/sub 7/, and 54.5 +/- 11.4 for t-C/sub 4/H/sub 9/. As was observed for the R + O/sub 2/ reactions the R + O/sub 3/ reactions show a trend of increasing rate constant k/sub 1/ with decreasing ionization potential (IP) of the radical. When log (k/sub 1/) vs. IP(R) - EA(O/sub 2/ or O/sub 3/) is plotted, where EA represents electron affinity, the two families of rate constants are brought into close proximity. In addition, rate constants for fluorescence quenching of substituted benzenes by O/sub 2/ are cited which extend the log (k) vs. IP-EA plot to lower ionization potential. Adiabatic channel model calculations have been done by using a long-range potential resulting from the perturbation between the R/sup +/ + O/sub 3//sup -/ and R + O/sub 3/ surfaces. These calculations give good agreement with the experimental cross sections and they predict rate constants faster than those derived from the classical harpoon model at low IP-EA.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/j150656a034</doi><tpages>5</tpages></addata></record> |
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| source | American Chemical Society Journals |
| subjects | ALKYL RADICALS CHEMICAL REACTIONS Chemistry DATA Exact sciences and technology EXPERIMENTAL DATA Free radicals chemistry INFORMATION INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY KINETICS NUMERICAL DATA Organic chemistry OZONE RADICALS 400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987) REACTION KINETICS Reactivity and mechanisms |
| title | Rates of reaction of alkyl radicals with ozone |
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