Kinetic study of the reactions of the sodium dimer (Na2) with a range of atmospheric species
The reactions of Na(2) with a series of atmospheric constituents were studied using a fast flow tube with detection of Na(2) by laser induced fluorescence at 656.2 nm [Na(2)(A(1)Sigma(+)(u) - X(1)Sigma(+)(g))]. The resulting rate coefficients at 298 K for the reactions of Na(2) with OH, O(2), NO(2),...
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| Veröffentlicht in: | Physical chemistry chemical physics : PCCP 2006-01, Vol.8 (26), p.3104-3115 |
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| container_issue | 26 |
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| container_title | Physical chemistry chemical physics : PCCP |
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| creator | Self, Daniel E Plane, John M C Heard, Dwayne E |
| description | The reactions of Na(2) with a series of atmospheric constituents were studied using a fast flow tube with detection of Na(2) by laser induced fluorescence at 656.2 nm [Na(2)(A(1)Sigma(+)(u) - X(1)Sigma(+)(g))]. The resulting rate coefficients at 298 K for the reactions of Na(2) with OH, O(2), NO(2), NO, O(3), H, H(2) and H(2)O are: (1.01(+0.35)(-0.25)) x 10(-10), (2.95 +/- 0.46) x 10(-11), (1.79(+0.51)(-0.31)) x 10(-10), (1.33 +/- 0.16) x 10(-11), (8.0(+24)(-3.0)) x 10(-11), < or =6 x 10(-12), |
| doi_str_mv | 10.1039/b604305d |
| format | Article |
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The resulting rate coefficients at 298 K for the reactions of Na(2) with OH, O(2), NO(2), NO, O(3), H, H(2) and H(2)O are: (1.01(+0.35)(-0.25)) x 10(-10), (2.95 +/- 0.46) x 10(-11), (1.79(+0.51)(-0.31)) x 10(-10), (1.33 +/- 0.16) x 10(-11), (8.0(+24)(-3.0)) x 10(-11), < or =6 x 10(-12), <or =4 x 10(-15), and <or =3 x 10(-13) cm(3) molecule(-1) s(-1), respectively. The quoted uncertainties include measurement imprecision at the 1sigma level, and systematic errors. The reaction between Na(2) and OH produces chemiluminescence at 589 nm [Na(3(2)P(J) - 3(2)S(1/2))], with a measured branching ratio of (7.6(+15.0)(-3.7)) x 10(-3). The reaction enthalpies are calculated using quantum theory at the Complete Basis Set (CBS-Q) level; all reactions except Na(2) + H(2)O and Na(2) + H(2) are exothermic. The surprisingly slow reaction of Na(2) with OH is explained using trajectory calculations and consideration of the splitting between the covalent and ionic surfaces involved in the reaction, coupled with the Landau-Zener formalism. The small upper limit to the rate coefficient for the strongly exothermic reaction Na(2) + H appears to be a striking example of the light atom anomaly where the reaction is kinematically constrained.</description><identifier>ISSN: 1463-9076</identifier><identifier>EISSN: 1463-9084</identifier><identifier>DOI: 10.1039/b604305d</identifier><identifier>PMID: 16804612</identifier><language>eng</language><publisher>England</publisher><subject>Computer Simulation ; Hydroxides - analysis ; Hydroxides - chemistry ; Kinetics ; Models, Chemical ; Models, Molecular ; Sodium - analysis ; Sodium - chemistry</subject><ispartof>Physical chemistry chemical physics : PCCP, 2006-01, Vol.8 (26), p.3104-3115</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><cites>FETCH-LOGICAL-c262t-e52561248b3fe77d6ba17624110feff13c32c772d7b936e3c856ad45a6c146e13</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,2818,27901,27902</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/16804612$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Self, Daniel E</creatorcontrib><creatorcontrib>Plane, John M C</creatorcontrib><creatorcontrib>Heard, Dwayne E</creatorcontrib><title>Kinetic study of the reactions of the sodium dimer (Na2) with a range of atmospheric species</title><title>Physical chemistry chemical physics : PCCP</title><addtitle>Phys Chem Chem Phys</addtitle><description>The reactions of Na(2) with a series of atmospheric constituents were studied using a fast flow tube with detection of Na(2) by laser induced fluorescence at 656.2 nm [Na(2)(A(1)Sigma(+)(u) - X(1)Sigma(+)(g))]. The resulting rate coefficients at 298 K for the reactions of Na(2) with OH, O(2), NO(2), NO, O(3), H, H(2) and H(2)O are: (1.01(+0.35)(-0.25)) x 10(-10), (2.95 +/- 0.46) x 10(-11), (1.79(+0.51)(-0.31)) x 10(-10), (1.33 +/- 0.16) x 10(-11), (8.0(+24)(-3.0)) x 10(-11), < or =6 x 10(-12), <or =4 x 10(-15), and <or =3 x 10(-13) cm(3) molecule(-1) s(-1), respectively. The quoted uncertainties include measurement imprecision at the 1sigma level, and systematic errors. The reaction between Na(2) and OH produces chemiluminescence at 589 nm [Na(3(2)P(J) - 3(2)S(1/2))], with a measured branching ratio of (7.6(+15.0)(-3.7)) x 10(-3). The reaction enthalpies are calculated using quantum theory at the Complete Basis Set (CBS-Q) level; all reactions except Na(2) + H(2)O and Na(2) + H(2) are exothermic. The surprisingly slow reaction of Na(2) with OH is explained using trajectory calculations and consideration of the splitting between the covalent and ionic surfaces involved in the reaction, coupled with the Landau-Zener formalism. The small upper limit to the rate coefficient for the strongly exothermic reaction Na(2) + H appears to be a striking example of the light atom anomaly where the reaction is kinematically constrained.</description><subject>Computer Simulation</subject><subject>Hydroxides - analysis</subject><subject>Hydroxides - chemistry</subject><subject>Kinetics</subject><subject>Models, Chemical</subject><subject>Models, Molecular</subject><subject>Sodium - analysis</subject><subject>Sodium - chemistry</subject><issn>1463-9076</issn><issn>1463-9084</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2006</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpFkE1LAzEQhoMotlbBXyA5ST2s5muT7VGKX1j0ojdhySazNtLdrEkW6b93S1s9zcvw8DLzIHROyTUlfHZTSSI4ye0BGlMheTYjhTj8y0qO0EmMX4QQmlN-jEZUFkRIysbo49m1kJzBMfV2jX2N0xJwAG2S823cL6K3rm-wdQ0EPH3R7Ar_uLTEGgfdfsIG06nxsVtC2JR1YBzEU3RU61WEs92coPf7u7f5Y7Z4fXia3y4ywyRLGeQsH44RRcVrUMrKSlMlmaCU1FDXlBvOjFLMqmrGJXBT5FJbkWtphg-B8gm63PZ2wX_3EFPZuGhgtdIt-D6WssgLSYkawOkWNMHHGKAuu-AaHdYlJeXGZLk3OaAXu86-asD-gzt1_Beg3WzI</recordid><startdate>20060101</startdate><enddate>20060101</enddate><creator>Self, Daniel E</creator><creator>Plane, John M C</creator><creator>Heard, Dwayne E</creator><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>7X8</scope></search><sort><creationdate>20060101</creationdate><title>Kinetic study of the reactions of the sodium dimer (Na2) with a range of atmospheric species</title><author>Self, Daniel E ; Plane, John M C ; Heard, Dwayne E</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c262t-e52561248b3fe77d6ba17624110feff13c32c772d7b936e3c856ad45a6c146e13</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2006</creationdate><topic>Computer Simulation</topic><topic>Hydroxides - analysis</topic><topic>Hydroxides - chemistry</topic><topic>Kinetics</topic><topic>Models, Chemical</topic><topic>Models, Molecular</topic><topic>Sodium - analysis</topic><topic>Sodium - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Self, Daniel E</creatorcontrib><creatorcontrib>Plane, John M C</creatorcontrib><creatorcontrib>Heard, Dwayne E</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Physical chemistry chemical physics : PCCP</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Self, Daniel E</au><au>Plane, John M C</au><au>Heard, Dwayne E</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Kinetic study of the reactions of the sodium dimer (Na2) with a range of atmospheric species</atitle><jtitle>Physical chemistry chemical physics : PCCP</jtitle><addtitle>Phys Chem Chem Phys</addtitle><date>2006-01-01</date><risdate>2006</risdate><volume>8</volume><issue>26</issue><spage>3104</spage><epage>3115</epage><pages>3104-3115</pages><issn>1463-9076</issn><eissn>1463-9084</eissn><abstract>The reactions of Na(2) with a series of atmospheric constituents were studied using a fast flow tube with detection of Na(2) by laser induced fluorescence at 656.2 nm [Na(2)(A(1)Sigma(+)(u) - X(1)Sigma(+)(g))]. The resulting rate coefficients at 298 K for the reactions of Na(2) with OH, O(2), NO(2), NO, O(3), H, H(2) and H(2)O are: (1.01(+0.35)(-0.25)) x 10(-10), (2.95 +/- 0.46) x 10(-11), (1.79(+0.51)(-0.31)) x 10(-10), (1.33 +/- 0.16) x 10(-11), (8.0(+24)(-3.0)) x 10(-11), < or =6 x 10(-12), <or =4 x 10(-15), and <or =3 x 10(-13) cm(3) molecule(-1) s(-1), respectively. The quoted uncertainties include measurement imprecision at the 1sigma level, and systematic errors. The reaction between Na(2) and OH produces chemiluminescence at 589 nm [Na(3(2)P(J) - 3(2)S(1/2))], with a measured branching ratio of (7.6(+15.0)(-3.7)) x 10(-3). The reaction enthalpies are calculated using quantum theory at the Complete Basis Set (CBS-Q) level; all reactions except Na(2) + H(2)O and Na(2) + H(2) are exothermic. The surprisingly slow reaction of Na(2) with OH is explained using trajectory calculations and consideration of the splitting between the covalent and ionic surfaces involved in the reaction, coupled with the Landau-Zener formalism. The small upper limit to the rate coefficient for the strongly exothermic reaction Na(2) + H appears to be a striking example of the light atom anomaly where the reaction is kinematically constrained.</abstract><cop>England</cop><pmid>16804612</pmid><doi>10.1039/b604305d</doi><tpages>12</tpages></addata></record> |
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| source | Royal Society of Chemistry Journals Archive (1841-2007); MEDLINE; Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Computer Simulation Hydroxides - analysis Hydroxides - chemistry Kinetics Models, Chemical Models, Molecular Sodium - analysis Sodium - chemistry |
| title | Kinetic study of the reactions of the sodium dimer (Na2) with a range of atmospheric species |
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