Laser Flash Photolysis of Benzophenone in Polymer Films
With a nanosecond laser we studied flash photolysis of benzophenone (BP) dissolved in four different polymer films. We measured kinetics of decay of a triplet state of benzophenone 3BP as well as kinetics of decay of benzophenone ketyl free radicals BPH•. Polymer matrices have plenty of reactive C–H...
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| Veröffentlicht in: | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2011-10, Vol.115 (40), p.10996-11000 |
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| container_title | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory |
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| creator | Levin, Peter P Khudyakov, Igor V |
| description | With a nanosecond laser we studied flash photolysis of benzophenone (BP) dissolved in four different polymer films. We measured kinetics of decay of a triplet state of benzophenone 3BP as well as kinetics of decay of benzophenone ketyl free radicals BPH•. Polymer matrices have plenty of reactive C–H bonds, and the hydrogen abstraction by 3BP leads to a formation of geminate pair which either recombines into molecular products or dissociates. Decay kinetics of 3BP is well described by dispersive kinetics and in particular by the kinetic law suggested in Albery W. J. ; et al. J. Am. Chem. Soc. 1985, 107, 1854 . We observed a broader distribution of rate constants in hard films. It was observed that the decay kinetics of transients radicals in the “hard” polymers is quite satisfactory described by the same law for dispersive kinetics. Kinetics of radicals decay in “soft” polymers is satisfactorily described as a diffusion- enhanced reaction. Effect of a hardness of polymer matrix on the measured kinetic parameters is discussed. |
| doi_str_mv | 10.1021/jp2072183 |
| format | Article |
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We measured kinetics of decay of a triplet state of benzophenone 3BP as well as kinetics of decay of benzophenone ketyl free radicals BPH•. Polymer matrices have plenty of reactive C–H bonds, and the hydrogen abstraction by 3BP leads to a formation of geminate pair which either recombines into molecular products or dissociates. Decay kinetics of 3BP is well described by dispersive kinetics and in particular by the kinetic law suggested in Albery W. J. ; et al. J. Am. Chem. Soc. 1985, 107, 1854 . We observed a broader distribution of rate constants in hard films. It was observed that the decay kinetics of transients radicals in the “hard” polymers is quite satisfactory described by the same law for dispersive kinetics. Kinetics of radicals decay in “soft” polymers is satisfactorily described as a diffusion- enhanced reaction. Effect of a hardness of polymer matrix on the measured kinetic parameters is discussed.</description><identifier>ISSN: 1089-5639</identifier><identifier>EISSN: 1520-5215</identifier><identifier>DOI: 10.1021/jp2072183</identifier><identifier>PMID: 21919502</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>A: Kinetics, Spectroscopy ; Benzophenones - chemistry ; Decomposition ; Flash photolysis ; Free radicals ; Hardness ; Kinetics ; Lasers ; Membranes, Artificial ; Photolysis ; Polymeric films ; Polymers - chemistry ; Radicals ; Reaction kinetics</subject><ispartof>The journal of physical chemistry. 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A, Molecules, spectroscopy, kinetics, environment, & general theory</title><addtitle>J. Phys. Chem. A</addtitle><description>With a nanosecond laser we studied flash photolysis of benzophenone (BP) dissolved in four different polymer films. We measured kinetics of decay of a triplet state of benzophenone 3BP as well as kinetics of decay of benzophenone ketyl free radicals BPH•. Polymer matrices have plenty of reactive C–H bonds, and the hydrogen abstraction by 3BP leads to a formation of geminate pair which either recombines into molecular products or dissociates. Decay kinetics of 3BP is well described by dispersive kinetics and in particular by the kinetic law suggested in Albery W. J. ; et al. J. Am. Chem. Soc. 1985, 107, 1854 . We observed a broader distribution of rate constants in hard films. It was observed that the decay kinetics of transients radicals in the “hard” polymers is quite satisfactory described by the same law for dispersive kinetics. Kinetics of radicals decay in “soft” polymers is satisfactorily described as a diffusion- enhanced reaction. Effect of a hardness of polymer matrix on the measured kinetic parameters is discussed.</description><subject>A: Kinetics, Spectroscopy</subject><subject>Benzophenones - chemistry</subject><subject>Decomposition</subject><subject>Flash photolysis</subject><subject>Free radicals</subject><subject>Hardness</subject><subject>Kinetics</subject><subject>Lasers</subject><subject>Membranes, Artificial</subject><subject>Photolysis</subject><subject>Polymeric films</subject><subject>Polymers - chemistry</subject><subject>Radicals</subject><subject>Reaction kinetics</subject><issn>1089-5639</issn><issn>1520-5215</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2011</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNp9kL1OwzAURi0EoiUw8AIoCwKGgK8d_2SEigJSJTrAbDmuo6ZK4mA3Q3l6XLV0Qkz3St_RGQ5Cl4DvARN4WPUECwKSHqExMIIzRoAdxx_LImOcFiN0FsIKYwyU5KdoRKCAgmEyRmKmg_XptNFhmc6Xbu2aTahD6qr0yXbfrl_aznU2rbt0Hqd2y9ZNG87RSaWbYC_2N0Gf0-ePyWs2e395mzzOMk1zsc6EzQ3LJTeGFFxao4XhGBg3wmhZVoICCE7jhqEwrLS5JFyWmPMKFhzTkiboZuftvfsabFirtg7GNo3urBuCklFLo1FG8vZfEgSjDMi2QYLudqjxLgRvK9X7utV-owCrbVF1KBrZq712KFu7OJC_CSNwvQO0CWrlBt_FHn-IfgCYD3l-</recordid><startdate>20111013</startdate><enddate>20111013</enddate><creator>Levin, Peter P</creator><creator>Khudyakov, Igor V</creator><general>American Chemical Society</general><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>7SP</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><scope>7X8</scope></search><sort><creationdate>20111013</creationdate><title>Laser Flash Photolysis of Benzophenone in Polymer Films</title><author>Levin, Peter P ; Khudyakov, Igor V</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a347t-7e4c5486cc2968eca7c60156c7ca8bf7311763296019c5be48268b066f1d603b3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2011</creationdate><topic>A: Kinetics, Spectroscopy</topic><topic>Benzophenones - chemistry</topic><topic>Decomposition</topic><topic>Flash photolysis</topic><topic>Free radicals</topic><topic>Hardness</topic><topic>Kinetics</topic><topic>Lasers</topic><topic>Membranes, Artificial</topic><topic>Photolysis</topic><topic>Polymeric films</topic><topic>Polymers - chemistry</topic><topic>Radicals</topic><topic>Reaction kinetics</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Levin, Peter P</creatorcontrib><creatorcontrib>Khudyakov, Igor V</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Electronics & Communications Abstracts</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>MEDLINE - Academic</collection><jtitle>The journal of physical chemistry. 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Polymer matrices have plenty of reactive C–H bonds, and the hydrogen abstraction by 3BP leads to a formation of geminate pair which either recombines into molecular products or dissociates. Decay kinetics of 3BP is well described by dispersive kinetics and in particular by the kinetic law suggested in Albery W. J. ; et al. J. Am. Chem. Soc. 1985, 107, 1854 . We observed a broader distribution of rate constants in hard films. It was observed that the decay kinetics of transients radicals in the “hard” polymers is quite satisfactory described by the same law for dispersive kinetics. Kinetics of radicals decay in “soft” polymers is satisfactorily described as a diffusion- enhanced reaction. Effect of a hardness of polymer matrix on the measured kinetic parameters is discussed.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>21919502</pmid><doi>10.1021/jp2072183</doi><tpages>5</tpages></addata></record> |
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| subjects | A: Kinetics, Spectroscopy Benzophenones - chemistry Decomposition Flash photolysis Free radicals Hardness Kinetics Lasers Membranes, Artificial Photolysis Polymeric films Polymers - chemistry Radicals Reaction kinetics |
| title | Laser Flash Photolysis of Benzophenone in Polymer Films |
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