Catalysis of deuterium transfer between liquid chloroform and water by anion-exchange resins
Anion-exchange resins in the hydroxide form have been successfully utilized for catalysis of deuterium transfer between water and liquid chloroform under stirred three-phase slurry conditions. In-solution rate constants for CDCl 3 H 2O exchange obtained at 15–35 °C with liquid chloroform and 0.10 mo...
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| Veröffentlicht in: | J. Catal.; (United States) 1985, Vol.93 (2), p.209-215 |
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| creator | Symons, E.Allan Bonnett, J.Douglas |
| description | Anion-exchange resins in the hydroxide form have been successfully utilized for catalysis of deuterium transfer between water and liquid chloroform under stirred three-phase slurry conditions. In-solution rate constants for
CDCl
3
H
2O
exchange obtained at 15–35 °C with
liquid chloroform and 0.10 mol/liter NaOH solution under stirred conditions are in good agreement with literature data measured in the absence of bulk chloroform. At 25 °C the resins tested, Rexyn 201(OH) and Ionac ASB-1P(OH), are ~25× more effective per mole of
−OH present than NaOH when they are used as whole beads. A further improvement is observed if the beads are crushed, but the latter state would be less suitable for commercial-scale application. The solubility of chloroform in the aqueous phase under isotope-exchange conditions was required to calculate the in-solution rate constants for exchange. A method was developed to obtain chloroform solubilities in 0.10 mol/liter NaOH solution and aqueous resin slurries; equilibrated solution samples were treated with 1 mol/liter NaOH to hydrolyze the dissolved CHCl
3 to chloride ion, which was then analyzed by specific ion electrode. |
| doi_str_mv | 10.1016/0021-9517(85)90168-X |
| format | Article |
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CDCl
3
H
2O
exchange obtained at 15–35 °C with
liquid chloroform and 0.10 mol/liter NaOH solution under stirred conditions are in good agreement with literature data measured in the absence of bulk chloroform. At 25 °C the resins tested, Rexyn 201(OH) and Ionac ASB-1P(OH), are ~25× more effective per mole of
−OH present than NaOH when they are used as whole beads. A further improvement is observed if the beads are crushed, but the latter state would be less suitable for commercial-scale application. The solubility of chloroform in the aqueous phase under isotope-exchange conditions was required to calculate the in-solution rate constants for exchange. A method was developed to obtain chloroform solubilities in 0.10 mol/liter NaOH solution and aqueous resin slurries; equilibrated solution samples were treated with 1 mol/liter NaOH to hydrolyze the dissolved CHCl
3 to chloride ion, which was then analyzed by specific ion electrode.</description><identifier>ISSN: 0021-9517</identifier><identifier>EISSN: 1090-2694</identifier><identifier>DOI: 10.1016/0021-9517(85)90168-X</identifier><identifier>CODEN: JCTLA5</identifier><language>eng</language><publisher>Amsterdam: Elsevier Inc</publisher><subject>400202 - Isotope Effects, Isotope Exchange, & Isotope Separation ; CATALYSIS ; Catalysts: preparations and properties ; Catalytic reactions ; Chemistry ; CHLORINATED ALIPHATIC HYDROCARBONS ; CHLOROFORM ; DATA ; DEUTERIUM ; ELEMENTS ; Exact sciences and technology ; EXPERIMENTAL DATA ; General and physical chemistry ; General. Nomenclature, chemical documentation, computer chemistry ; HALOGENATED ALIPHATIC HYDROCARBONS ; HYDROGEN ; HYDROGEN COMPOUNDS ; HYDROGEN ISOTOPES ; INFORMATION ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; ION EXCHANGE MATERIALS ; ISOTOPES ; ISOTOPIC EXCHANGE ; LIGHT NUCLEI ; MATERIALS ; NONMETALS ; NUCLEI ; NUMERICAL DATA ; ODD-ODD NUCLEI ; ORGANIC CHLORINE COMPOUNDS ; ORGANIC COMPOUNDS ; ORGANIC HALOGEN COMPOUNDS ; OXYGEN COMPOUNDS ; STABLE ISOTOPES ; Theory of reactions, general kinetics ; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry ; WATER</subject><ispartof>J. Catal.; (United States), 1985, Vol.93 (2), p.209-215</ispartof><rights>1985</rights><rights>1986 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://dx.doi.org/10.1016/0021-9517(85)90168-X$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>314,780,784,885,3550,4024,27923,27924,27925,45995</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=8465437$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/biblio/6082837$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Symons, E.Allan</creatorcontrib><creatorcontrib>Bonnett, J.Douglas</creatorcontrib><creatorcontrib>Atomic Energy of Canada Ltd., Chalk River, Ontario</creatorcontrib><title>Catalysis of deuterium transfer between liquid chloroform and water by anion-exchange resins</title><title>J. Catal.; (United States)</title><description>Anion-exchange resins in the hydroxide form have been successfully utilized for catalysis of deuterium transfer between water and liquid chloroform under stirred three-phase slurry conditions. In-solution rate constants for
CDCl
3
H
2O
exchange obtained at 15–35 °C with
liquid chloroform and 0.10 mol/liter NaOH solution under stirred conditions are in good agreement with literature data measured in the absence of bulk chloroform. At 25 °C the resins tested, Rexyn 201(OH) and Ionac ASB-1P(OH), are ~25× more effective per mole of
−OH present than NaOH when they are used as whole beads. A further improvement is observed if the beads are crushed, but the latter state would be less suitable for commercial-scale application. The solubility of chloroform in the aqueous phase under isotope-exchange conditions was required to calculate the in-solution rate constants for exchange. A method was developed to obtain chloroform solubilities in 0.10 mol/liter NaOH solution and aqueous resin slurries; equilibrated solution samples were treated with 1 mol/liter NaOH to hydrolyze the dissolved CHCl
3 to chloride ion, which was then analyzed by specific ion electrode.</description><subject>400202 - Isotope Effects, Isotope Exchange, & Isotope Separation</subject><subject>CATALYSIS</subject><subject>Catalysts: preparations and properties</subject><subject>Catalytic reactions</subject><subject>Chemistry</subject><subject>CHLORINATED ALIPHATIC HYDROCARBONS</subject><subject>CHLOROFORM</subject><subject>DATA</subject><subject>DEUTERIUM</subject><subject>ELEMENTS</subject><subject>Exact sciences and technology</subject><subject>EXPERIMENTAL DATA</subject><subject>General and physical chemistry</subject><subject>General. Nomenclature, chemical documentation, computer chemistry</subject><subject>HALOGENATED ALIPHATIC HYDROCARBONS</subject><subject>HYDROGEN</subject><subject>HYDROGEN COMPOUNDS</subject><subject>HYDROGEN ISOTOPES</subject><subject>INFORMATION</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>ION EXCHANGE MATERIALS</subject><subject>ISOTOPES</subject><subject>ISOTOPIC EXCHANGE</subject><subject>LIGHT NUCLEI</subject><subject>MATERIALS</subject><subject>NONMETALS</subject><subject>NUCLEI</subject><subject>NUMERICAL DATA</subject><subject>ODD-ODD NUCLEI</subject><subject>ORGANIC CHLORINE COMPOUNDS</subject><subject>ORGANIC COMPOUNDS</subject><subject>ORGANIC HALOGEN COMPOUNDS</subject><subject>OXYGEN COMPOUNDS</subject><subject>STABLE ISOTOPES</subject><subject>Theory of reactions, general kinetics</subject><subject>Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry</subject><subject>WATER</subject><issn>0021-9517</issn><issn>1090-2694</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1985</creationdate><recordtype>article</recordtype><recordid>eNo9kE1LAzEQhoMoWKv_wEMQD3pYTXY32eQiSPELCl4UehBCmp3YyDapSWrtv3fXiqdhhoeXdx6ETim5ooTya0JKWkhGmwvBLmV_EcVsD40okaQouaz30egfOURHKX0QQiljYoTeJjrrbptcwsHiFtYZolsvcY7aJwsRzyFvADzu3OfatdgsuhCDDXGJtW_xRueB2faLC76Ab7PQ_h1whOR8OkYHVncJTv7mGL3e371MHovp88PT5HZaQMl5LioN1jDRNKXpy7dSzltOZD2XbV8SiK2NqCXRZUO5NsQ0rCbaWmPnVX9nvKzG6GyXG1J2KhmXwSxM8B5MVpyIUlRND53voJVORne2f9C4pFbRLXXcKlFzVv9iNzsM-sJfDuKQB95A6-IQ1wanKFGDdzVIVYNUJZj69a5m1Q9ek3dN</recordid><startdate>1985</startdate><enddate>1985</enddate><creator>Symons, E.Allan</creator><creator>Bonnett, J.Douglas</creator><general>Elsevier Inc</general><general>Elsevier</general><scope>IQODW</scope><scope>OTOTI</scope></search><sort><creationdate>1985</creationdate><title>Catalysis of deuterium transfer between liquid chloroform and water by anion-exchange resins</title><author>Symons, E.Allan ; Bonnett, J.Douglas</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-e266t-3aefc58772c901d99bd6094b9d115e0f4c8490a2716ac0c7540affcfb38495623</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1985</creationdate><topic>400202 - Isotope Effects, Isotope Exchange, & Isotope Separation</topic><topic>CATALYSIS</topic><topic>Catalysts: preparations and properties</topic><topic>Catalytic reactions</topic><topic>Chemistry</topic><topic>CHLORINATED ALIPHATIC HYDROCARBONS</topic><topic>CHLOROFORM</topic><topic>DATA</topic><topic>DEUTERIUM</topic><topic>ELEMENTS</topic><topic>Exact sciences and technology</topic><topic>EXPERIMENTAL DATA</topic><topic>General and physical chemistry</topic><topic>General. Nomenclature, chemical documentation, computer chemistry</topic><topic>HALOGENATED ALIPHATIC HYDROCARBONS</topic><topic>HYDROGEN</topic><topic>HYDROGEN COMPOUNDS</topic><topic>HYDROGEN ISOTOPES</topic><topic>INFORMATION</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>ION EXCHANGE MATERIALS</topic><topic>ISOTOPES</topic><topic>ISOTOPIC EXCHANGE</topic><topic>LIGHT NUCLEI</topic><topic>MATERIALS</topic><topic>NONMETALS</topic><topic>NUCLEI</topic><topic>NUMERICAL DATA</topic><topic>ODD-ODD NUCLEI</topic><topic>ORGANIC CHLORINE COMPOUNDS</topic><topic>ORGANIC COMPOUNDS</topic><topic>ORGANIC HALOGEN COMPOUNDS</topic><topic>OXYGEN COMPOUNDS</topic><topic>STABLE ISOTOPES</topic><topic>Theory of reactions, general kinetics</topic><topic>Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry</topic><topic>WATER</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Symons, E.Allan</creatorcontrib><creatorcontrib>Bonnett, J.Douglas</creatorcontrib><creatorcontrib>Atomic Energy of Canada Ltd., Chalk River, Ontario</creatorcontrib><collection>Pascal-Francis</collection><collection>OSTI.GOV</collection><jtitle>J. Catal.; (United States)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Symons, E.Allan</au><au>Bonnett, J.Douglas</au><aucorp>Atomic Energy of Canada Ltd., Chalk River, Ontario</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Catalysis of deuterium transfer between liquid chloroform and water by anion-exchange resins</atitle><jtitle>J. Catal.; (United States)</jtitle><date>1985</date><risdate>1985</risdate><volume>93</volume><issue>2</issue><spage>209</spage><epage>215</epage><pages>209-215</pages><issn>0021-9517</issn><eissn>1090-2694</eissn><coden>JCTLA5</coden><abstract>Anion-exchange resins in the hydroxide form have been successfully utilized for catalysis of deuterium transfer between water and liquid chloroform under stirred three-phase slurry conditions. In-solution rate constants for
CDCl
3
H
2O
exchange obtained at 15–35 °C with
liquid chloroform and 0.10 mol/liter NaOH solution under stirred conditions are in good agreement with literature data measured in the absence of bulk chloroform. At 25 °C the resins tested, Rexyn 201(OH) and Ionac ASB-1P(OH), are ~25× more effective per mole of
−OH present than NaOH when they are used as whole beads. A further improvement is observed if the beads are crushed, but the latter state would be less suitable for commercial-scale application. The solubility of chloroform in the aqueous phase under isotope-exchange conditions was required to calculate the in-solution rate constants for exchange. A method was developed to obtain chloroform solubilities in 0.10 mol/liter NaOH solution and aqueous resin slurries; equilibrated solution samples were treated with 1 mol/liter NaOH to hydrolyze the dissolved CHCl
3 to chloride ion, which was then analyzed by specific ion electrode.</abstract><cop>Amsterdam</cop><pub>Elsevier Inc</pub><doi>10.1016/0021-9517(85)90168-X</doi><tpages>7</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0021-9517 |
| ispartof | J. Catal.; (United States), 1985, Vol.93 (2), p.209-215 |
| issn | 0021-9517 1090-2694 |
| language | eng |
| recordid | cdi_pascalfrancis_primary_8465437 |
| source | Elsevier ScienceDirect Journals Complete |
| subjects | 400202 - Isotope Effects, Isotope Exchange, & Isotope Separation CATALYSIS Catalysts: preparations and properties Catalytic reactions Chemistry CHLORINATED ALIPHATIC HYDROCARBONS CHLOROFORM DATA DEUTERIUM ELEMENTS Exact sciences and technology EXPERIMENTAL DATA General and physical chemistry General. Nomenclature, chemical documentation, computer chemistry HALOGENATED ALIPHATIC HYDROCARBONS HYDROGEN HYDROGEN COMPOUNDS HYDROGEN ISOTOPES INFORMATION INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ION EXCHANGE MATERIALS ISOTOPES ISOTOPIC EXCHANGE LIGHT NUCLEI MATERIALS NONMETALS NUCLEI NUMERICAL DATA ODD-ODD NUCLEI ORGANIC CHLORINE COMPOUNDS ORGANIC COMPOUNDS ORGANIC HALOGEN COMPOUNDS OXYGEN COMPOUNDS STABLE ISOTOPES Theory of reactions, general kinetics Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry WATER |
| title | Catalysis of deuterium transfer between liquid chloroform and water by anion-exchange resins |
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