Activation of Hydrogen Peroxide by Acetonitrile in the Oxidation of Thioethers: Reaction Kinetics and Mechanism
The kinetics of oxidation of diethyl sulfide (Et 2 S) with hydrogen peroxide (H 2 O 2 ) in aqueous solutions of acetonitrile (MeCN) was studied using a kinetic distribution method. It was found that the order of the reaction with respect to the substrate depends on pH and changes from the first at p...
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| Veröffentlicht in: | Kinetics and catalysis 2021-05, Vol.62 (3), p.342-349 |
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| container_title | Kinetics and catalysis |
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| creator | Liubymova, A. K. Bezbozhnaya, T. V. Lobachev, V. L. |
| description | The kinetics of oxidation of diethyl sulfide (Et
2
S) with hydrogen peroxide (H
2
O
2
) in aqueous solutions of acetonitrile (MeCN) was studied using a kinetic distribution method. It was found that the order of the reaction with respect to the substrate depends on pH and changes from the first at pH 8.06 to nearly zero at pH 11.02. The initial rates of Et
2
S consumption increase with pH and linearly depend on the concentrations of the hydroperoxide anion (HOO
–
) and MeCN. It was assumed that the reaction involves the nonequilibrium formation of peroxyimidate in the slow stage of the interaction of HOO
–
with MeCN followed by the rapid oxidation of Et
2
S. |
| doi_str_mv | 10.1134/S002315842103006X |
| format | Article |
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2
S) with hydrogen peroxide (H
2
O
2
) in aqueous solutions of acetonitrile (MeCN) was studied using a kinetic distribution method. It was found that the order of the reaction with respect to the substrate depends on pH and changes from the first at pH 8.06 to nearly zero at pH 11.02. The initial rates of Et
2
S consumption increase with pH and linearly depend on the concentrations of the hydroperoxide anion (HOO
–
) and MeCN. It was assumed that the reaction involves the nonequilibrium formation of peroxyimidate in the slow stage of the interaction of HOO
–
with MeCN followed by the rapid oxidation of Et
2
S.</description><identifier>ISSN: 0023-1584</identifier><identifier>EISSN: 1608-3210</identifier><identifier>DOI: 10.1134/S002315842103006X</identifier><language>eng</language><publisher>Moscow: Pleiades Publishing</publisher><subject>Acetonitrile ; Aqueous solutions ; Catalysis ; Chemistry ; Chemistry and Materials Science ; Hydrogen peroxide ; Oxidation ; Physical Chemistry ; Reaction kinetics ; Substrates</subject><ispartof>Kinetics and catalysis, 2021-05, Vol.62 (3), p.342-349</ispartof><rights>Pleiades Publishing, Ltd. 2021. ISSN 0023-1584, Kinetics and Catalysis, 2021, Vol. 62, No. 3, pp. 342–349. © Pleiades Publishing, Ltd., 2021. Russian Text © The Author(s), 2021, published in Kinetika i Kataliz, 2021, Vol. 62, No. 3, pp. 296–304.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c353t-23cf90a4ba1aad6eec56f19449f704960a32c93a453bbdf41a811975ba566b713</citedby><cites>FETCH-LOGICAL-c353t-23cf90a4ba1aad6eec56f19449f704960a32c93a453bbdf41a811975ba566b713</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://link.springer.com/content/pdf/10.1134/S002315842103006X$$EPDF$$P50$$Gspringer$$H</linktopdf><linktohtml>$$Uhttps://link.springer.com/10.1134/S002315842103006X$$EHTML$$P50$$Gspringer$$H</linktohtml><link.rule.ids>314,780,784,27923,27924,41487,42556,51318</link.rule.ids></links><search><creatorcontrib>Liubymova, A. K.</creatorcontrib><creatorcontrib>Bezbozhnaya, T. V.</creatorcontrib><creatorcontrib>Lobachev, V. L.</creatorcontrib><title>Activation of Hydrogen Peroxide by Acetonitrile in the Oxidation of Thioethers: Reaction Kinetics and Mechanism</title><title>Kinetics and catalysis</title><addtitle>Kinet Catal</addtitle><description>The kinetics of oxidation of diethyl sulfide (Et
2
S) with hydrogen peroxide (H
2
O
2
) in aqueous solutions of acetonitrile (MeCN) was studied using a kinetic distribution method. It was found that the order of the reaction with respect to the substrate depends on pH and changes from the first at pH 8.06 to nearly zero at pH 11.02. The initial rates of Et
2
S consumption increase with pH and linearly depend on the concentrations of the hydroperoxide anion (HOO
–
) and MeCN. It was assumed that the reaction involves the nonequilibrium formation of peroxyimidate in the slow stage of the interaction of HOO
–
with MeCN followed by the rapid oxidation of Et
2
S.</description><subject>Acetonitrile</subject><subject>Aqueous solutions</subject><subject>Catalysis</subject><subject>Chemistry</subject><subject>Chemistry and Materials Science</subject><subject>Hydrogen peroxide</subject><subject>Oxidation</subject><subject>Physical Chemistry</subject><subject>Reaction kinetics</subject><subject>Substrates</subject><issn>0023-1584</issn><issn>1608-3210</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNp1kE9LAzEUxIMoWKsfwFvA82qy-dONt1K0FSsVreBtyWbftiltUpNU7Ld3a0UP4unBzPzmwSB0TsklpYxfPROSMyoKnlPCCJGvB6hDJSky1gqHqLOzs51_jE5iXBBCOOWqg3zfJPuuk_UO-waPtnXwM3D4EYL_sDXgaov7BpJ3NgW7BGwdTnPAk9b8oaZz66FVQ7zGT6DNl35vHSRrItauxg9g5trZuDpFR41eRjj7vl30cnszHYyy8WR4N-iPM8MES1nOTKOI5pWmWtcSwAjZUMW5anqEK0k0y41imgtWVXXDqS4oVT1RaSFl1aOsiy72vevg3zYQU7nwm-Dal2UumFJEKFm0KbpPmeBjDNCU62BXOmxLSsrdruWfXVsm3zOxzboZhN_m_6FPSeV6Yw</recordid><startdate>20210501</startdate><enddate>20210501</enddate><creator>Liubymova, A. K.</creator><creator>Bezbozhnaya, T. V.</creator><creator>Lobachev, V. L.</creator><general>Pleiades Publishing</general><general>Springer Nature B.V</general><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20210501</creationdate><title>Activation of Hydrogen Peroxide by Acetonitrile in the Oxidation of Thioethers: Reaction Kinetics and Mechanism</title><author>Liubymova, A. K. ; Bezbozhnaya, T. V. ; Lobachev, V. L.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c353t-23cf90a4ba1aad6eec56f19449f704960a32c93a453bbdf41a811975ba566b713</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>Acetonitrile</topic><topic>Aqueous solutions</topic><topic>Catalysis</topic><topic>Chemistry</topic><topic>Chemistry and Materials Science</topic><topic>Hydrogen peroxide</topic><topic>Oxidation</topic><topic>Physical Chemistry</topic><topic>Reaction kinetics</topic><topic>Substrates</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Liubymova, A. K.</creatorcontrib><creatorcontrib>Bezbozhnaya, T. V.</creatorcontrib><creatorcontrib>Lobachev, V. L.</creatorcontrib><collection>CrossRef</collection><jtitle>Kinetics and catalysis</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Liubymova, A. K.</au><au>Bezbozhnaya, T. V.</au><au>Lobachev, V. L.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Activation of Hydrogen Peroxide by Acetonitrile in the Oxidation of Thioethers: Reaction Kinetics and Mechanism</atitle><jtitle>Kinetics and catalysis</jtitle><stitle>Kinet Catal</stitle><date>2021-05-01</date><risdate>2021</risdate><volume>62</volume><issue>3</issue><spage>342</spage><epage>349</epage><pages>342-349</pages><issn>0023-1584</issn><eissn>1608-3210</eissn><abstract>The kinetics of oxidation of diethyl sulfide (Et
2
S) with hydrogen peroxide (H
2
O
2
) in aqueous solutions of acetonitrile (MeCN) was studied using a kinetic distribution method. It was found that the order of the reaction with respect to the substrate depends on pH and changes from the first at pH 8.06 to nearly zero at pH 11.02. The initial rates of Et
2
S consumption increase with pH and linearly depend on the concentrations of the hydroperoxide anion (HOO
–
) and MeCN. It was assumed that the reaction involves the nonequilibrium formation of peroxyimidate in the slow stage of the interaction of HOO
–
with MeCN followed by the rapid oxidation of Et
2
S.</abstract><cop>Moscow</cop><pub>Pleiades Publishing</pub><doi>10.1134/S002315842103006X</doi><tpages>8</tpages></addata></record> |
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| ispartof | Kinetics and catalysis, 2021-05, Vol.62 (3), p.342-349 |
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| language | eng |
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| source | SpringerLink Journals - AutoHoldings |
| subjects | Acetonitrile Aqueous solutions Catalysis Chemistry Chemistry and Materials Science Hydrogen peroxide Oxidation Physical Chemistry Reaction kinetics Substrates |
| title | Activation of Hydrogen Peroxide by Acetonitrile in the Oxidation of Thioethers: Reaction Kinetics and Mechanism |
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