Reaction and deactivation of HCl ( v =1, 2) by O atoms
Laser-induced fluorescence, following direct excitation of HCl (v=2), was used to measure the total deactivation rate constant for HCl (v=2) by O(3Pg) atoms as (5.2±0.4) ×10−12 cm3 molecule−1 sec−1. This is partitioned into a reaction rate constant of (1.5±1.2) ×10−12 cm3 molecule−1 sec−1 for HCl (v...
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| Veröffentlicht in: | J. Chem. Phys.; (United States) 1978-01, Vol.68 (2), p.513-521 |
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| creator | Macdonald, R. Glen Moore, C. Bradley |
| description | Laser-induced fluorescence, following direct excitation of HCl (v=2), was used to measure the total deactivation rate constant for HCl (v=2) by O(3Pg) atoms as (5.2±0.4) ×10−12 cm3 molecule−1 sec−1. This is partitioned into a reaction rate constant of (1.5±1.2) ×10−12 cm3 molecule−1 sec−1 for HCl (v=2)+O(3Pg) →OH (v=1, 0)+Cl and a relaxation rate constant for HCl (v=2)+O(3Pg) →HCl (v=1)+O(3Pg) of (3.7±1.2) ×10−12 cm3 molecule−1 sec−1. The total deactivation rate constant for HCl (v=1)+O(3Pg) atoms, including reaction and relaxation, was measured to be (8.9±1.3) ×10−13 cm3 molecule−1 sec−1. All measurements were carried out at 296±2 °K. The vibrationally enhanced chemical reaction rate constant for HCl (v=2) is roughly a factor of 104 greater than the reaction rate constant for HCl (v=0) with O atoms. The reaction appears to occur adiabatically on the lowest triplet potential hypersurface. For HCl (v=2, 1)+O vibrational relaxation is faster than chemical reaction even though the total energy is well above the barrier to reaction. |
| doi_str_mv | 10.1063/1.435760 |
| format | Article |
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Glen ; Moore, C. Bradley</creator><creatorcontrib>Macdonald, R. Glen ; Moore, C. Bradley ; Department of Chemistry, University of California, and Materials and Molecular Research Division of the Lawrence Berkeley Laboratory, Berkeley, California 94720</creatorcontrib><description>Laser-induced fluorescence, following direct excitation of HCl (v=2), was used to measure the total deactivation rate constant for HCl (v=2) by O(3Pg) atoms as (5.2±0.4) ×10−12 cm3 molecule−1 sec−1. This is partitioned into a reaction rate constant of (1.5±1.2) ×10−12 cm3 molecule−1 sec−1 for HCl (v=2)+O(3Pg) →OH (v=1, 0)+Cl and a relaxation rate constant for HCl (v=2)+O(3Pg) →HCl (v=1)+O(3Pg) of (3.7±1.2) ×10−12 cm3 molecule−1 sec−1. The total deactivation rate constant for HCl (v=1)+O(3Pg) atoms, including reaction and relaxation, was measured to be (8.9±1.3) ×10−13 cm3 molecule−1 sec−1. All measurements were carried out at 296±2 °K. The vibrationally enhanced chemical reaction rate constant for HCl (v=2) is roughly a factor of 104 greater than the reaction rate constant for HCl (v=0) with O atoms. The reaction appears to occur adiabatically on the lowest triplet potential hypersurface. For HCl (v=2, 1)+O vibrational relaxation is faster than chemical reaction even though the total energy is well above the barrier to reaction.</description><identifier>ISSN: 0021-9606</identifier><identifier>EISSN: 1089-7690</identifier><identifier>DOI: 10.1063/1.435760</identifier><language>eng</language><publisher>United States</publisher><subject>400201 - Chemical & Physicochemical Properties ; CHEMICAL REACTION KINETICS ; CRYOGENIC FLUIDS ; ELEMENTS ; ENERGY LEVELS ; EXCITED STATES ; FLUIDS ; FLUORESCENCE ; HYDROCHLORIC ACID ; HYDROGEN COMPOUNDS ; INORGANIC ACIDS ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; KINETICS ; LUMINESCENCE ; NONMETALS ; OXYGEN ; REACTION KINETICS ; RELAXATION ; VIBRATIONAL STATES</subject><ispartof>J. Chem. 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Bradley</creatorcontrib><creatorcontrib>Department of Chemistry, University of California, and Materials and Molecular Research Division of the Lawrence Berkeley Laboratory, Berkeley, California 94720</creatorcontrib><title>Reaction and deactivation of HCl ( v =1, 2) by O atoms</title><title>J. Chem. Phys.; (United States)</title><description>Laser-induced fluorescence, following direct excitation of HCl (v=2), was used to measure the total deactivation rate constant for HCl (v=2) by O(3Pg) atoms as (5.2±0.4) ×10−12 cm3 molecule−1 sec−1. This is partitioned into a reaction rate constant of (1.5±1.2) ×10−12 cm3 molecule−1 sec−1 for HCl (v=2)+O(3Pg) →OH (v=1, 0)+Cl and a relaxation rate constant for HCl (v=2)+O(3Pg) →HCl (v=1)+O(3Pg) of (3.7±1.2) ×10−12 cm3 molecule−1 sec−1. The total deactivation rate constant for HCl (v=1)+O(3Pg) atoms, including reaction and relaxation, was measured to be (8.9±1.3) ×10−13 cm3 molecule−1 sec−1. All measurements were carried out at 296±2 °K. The vibrationally enhanced chemical reaction rate constant for HCl (v=2) is roughly a factor of 104 greater than the reaction rate constant for HCl (v=0) with O atoms. The reaction appears to occur adiabatically on the lowest triplet potential hypersurface. For HCl (v=2, 1)+O vibrational relaxation is faster than chemical reaction even though the total energy is well above the barrier to reaction.</description><subject>400201 - Chemical & Physicochemical Properties</subject><subject>CHEMICAL REACTION KINETICS</subject><subject>CRYOGENIC FLUIDS</subject><subject>ELEMENTS</subject><subject>ENERGY LEVELS</subject><subject>EXCITED STATES</subject><subject>FLUIDS</subject><subject>FLUORESCENCE</subject><subject>HYDROCHLORIC ACID</subject><subject>HYDROGEN COMPOUNDS</subject><subject>INORGANIC ACIDS</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>KINETICS</subject><subject>LUMINESCENCE</subject><subject>NONMETALS</subject><subject>OXYGEN</subject><subject>REACTION KINETICS</subject><subject>RELAXATION</subject><subject>VIBRATIONAL STATES</subject><issn>0021-9606</issn><issn>1089-7690</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1978</creationdate><recordtype>article</recordtype><recordid>eNotkE1LAzEURYMoWKvgTwiuKjj15TuzcCGDWqFQEF2HN5kER9qJTEKh_17tuLrcy-EuDiHXDJYMtLhnSymU0XBCZgxsXRldwymZAXBW1Rr0ObnI-QsAmOFyRvRbQF_6NFAcOtodyx6PQ4p01Wzpgu7pA7uj_Ja2B7qhWNIuX5KziNscrv5zTj6en96bVbXevLw2j-vKc8VLFZgO0nMfTRDWxiAggBVoguk8RuRWSy2FaC0PNarYGi8R0aOSinHojJiTm-k35dK77PsS_KdPwxB8cYoroWv1Cy0myI8p5zFE9z32OxwPjoH7k-KYm6SIH1eoUEY</recordid><startdate>19780115</startdate><enddate>19780115</enddate><creator>Macdonald, R. Glen</creator><creator>Moore, C. Bradley</creator><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>19780115</creationdate><title>Reaction and deactivation of HCl ( v =1, 2) by O atoms</title><author>Macdonald, R. Glen ; Moore, C. Bradley</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c252t-e16e4c2cf7e388fe30e083a7e7dcafa28646433b82e9a5fb7c4aaaca545120d73</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1978</creationdate><topic>400201 - Chemical & Physicochemical Properties</topic><topic>CHEMICAL REACTION KINETICS</topic><topic>CRYOGENIC FLUIDS</topic><topic>ELEMENTS</topic><topic>ENERGY LEVELS</topic><topic>EXCITED STATES</topic><topic>FLUIDS</topic><topic>FLUORESCENCE</topic><topic>HYDROCHLORIC ACID</topic><topic>HYDROGEN COMPOUNDS</topic><topic>INORGANIC ACIDS</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>KINETICS</topic><topic>LUMINESCENCE</topic><topic>NONMETALS</topic><topic>OXYGEN</topic><topic>REACTION KINETICS</topic><topic>RELAXATION</topic><topic>VIBRATIONAL STATES</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Macdonald, R. Glen</creatorcontrib><creatorcontrib>Moore, C. Bradley</creatorcontrib><creatorcontrib>Department of Chemistry, University of California, and Materials and Molecular Research Division of the Lawrence Berkeley Laboratory, Berkeley, California 94720</creatorcontrib><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>J. Chem. Phys.; (United States)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Macdonald, R. Glen</au><au>Moore, C. Bradley</au><aucorp>Department of Chemistry, University of California, and Materials and Molecular Research Division of the Lawrence Berkeley Laboratory, Berkeley, California 94720</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Reaction and deactivation of HCl ( v =1, 2) by O atoms</atitle><jtitle>J. Chem. Phys.; (United States)</jtitle><date>1978-01-15</date><risdate>1978</risdate><volume>68</volume><issue>2</issue><spage>513</spage><epage>521</epage><pages>513-521</pages><issn>0021-9606</issn><eissn>1089-7690</eissn><abstract>Laser-induced fluorescence, following direct excitation of HCl (v=2), was used to measure the total deactivation rate constant for HCl (v=2) by O(3Pg) atoms as (5.2±0.4) ×10−12 cm3 molecule−1 sec−1. This is partitioned into a reaction rate constant of (1.5±1.2) ×10−12 cm3 molecule−1 sec−1 for HCl (v=2)+O(3Pg) →OH (v=1, 0)+Cl and a relaxation rate constant for HCl (v=2)+O(3Pg) →HCl (v=1)+O(3Pg) of (3.7±1.2) ×10−12 cm3 molecule−1 sec−1. The total deactivation rate constant for HCl (v=1)+O(3Pg) atoms, including reaction and relaxation, was measured to be (8.9±1.3) ×10−13 cm3 molecule−1 sec−1. All measurements were carried out at 296±2 °K. The vibrationally enhanced chemical reaction rate constant for HCl (v=2) is roughly a factor of 104 greater than the reaction rate constant for HCl (v=0) with O atoms. The reaction appears to occur adiabatically on the lowest triplet potential hypersurface. For HCl (v=2, 1)+O vibrational relaxation is faster than chemical reaction even though the total energy is well above the barrier to reaction.</abstract><cop>United States</cop><doi>10.1063/1.435760</doi><tpages>9</tpages></addata></record> |
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| ispartof | J. Chem. Phys.; (United States), 1978-01, Vol.68 (2), p.513-521 |
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| subjects | 400201 - Chemical & Physicochemical Properties CHEMICAL REACTION KINETICS CRYOGENIC FLUIDS ELEMENTS ENERGY LEVELS EXCITED STATES FLUIDS FLUORESCENCE HYDROCHLORIC ACID HYDROGEN COMPOUNDS INORGANIC ACIDS INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY KINETICS LUMINESCENCE NONMETALS OXYGEN REACTION KINETICS RELAXATION VIBRATIONAL STATES |
| title | Reaction and deactivation of HCl ( v =1, 2) by O atoms |
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