Speciation of Molybdenum and Tungsten in Molten Chlorides: A Spectroelectrochemical Study
Speciation of tungsten and molybdenum in alkali chloride melts (based on NaCl-2CsCl, NaCl-KCl and 3LiCl-2KCl mixtures) was studied between 450 and 750 oC using electronic absorption spectroscopy. Only W(IV) and W(V) chloro- and oxychlorospecies can be stabilised under conditions studied. Tungsten(IV...
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| creator | Volkovich, Vladimir A. Danilov, Danil A. A. Polovov, Ilya B. Vasin, Boris D. D. Griffiths, Trevor R. R. Aleksandrov, Denis E. Tropin, Oleg A. A. Tsarevskii, Dmitrii V. V. |
| description | Speciation of tungsten and molybdenum in alkali chloride melts (based on NaCl-2CsCl, NaCl-KCl and 3LiCl-2KCl mixtures) was studied between 450 and 750 oC using electronic absorption spectroscopy. Only W(IV) and W(V) chloro- and oxychlorospecies can be stabilised under conditions studied. Tungsten(IV) chloride ions are very sensitive to oxide/hydroxide impurities present in the melt. Anodic dissolution of W metal at anodic current densities in the range of 0.005-0.1 A/cm2 produces only WCl6 2- ions that can be electrochemically oxidised to WCl6 -. Small amounts of oxide ions present in the melt result in a gradual conversion of W(IV) chloro-species into W(IV) oxychloro-species. In the presence of O2 WCl6 2- is oxidised into tungsten(V) species WOCl5 2-. Molybdenum forms Mo(III), (IV) and (V) species. MoCl6 2- complex ions in chloride melts can be obtained by reacting MoO2 with HCl, or by electrochemical oxidation of Mo(III) (MoCl6 3- → MoCl6 2-) on a glassy carbon electrode. |
| doi_str_mv | 10.1149/1.2798697 |
| format | Conference Proceeding |
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A. ; Polovov, Ilya B. ; Vasin, Boris D. D. ; Griffiths, Trevor R. R. ; Aleksandrov, Denis E. ; Tropin, Oleg A. A. ; Tsarevskii, Dmitrii V. V.</creator><creatorcontrib>Volkovich, Vladimir A. ; Danilov, Danil A. A. ; Polovov, Ilya B. ; Vasin, Boris D. D. ; Griffiths, Trevor R. R. ; Aleksandrov, Denis E. ; Tropin, Oleg A. A. ; Tsarevskii, Dmitrii V. V.</creatorcontrib><description>Speciation of tungsten and molybdenum in alkali chloride melts (based on NaCl-2CsCl, NaCl-KCl and 3LiCl-2KCl mixtures) was studied between 450 and 750 oC using electronic absorption spectroscopy. Only W(IV) and W(V) chloro- and oxychlorospecies can be stabilised under conditions studied. Tungsten(IV) chloride ions are very sensitive to oxide/hydroxide impurities present in the melt. Anodic dissolution of W metal at anodic current densities in the range of 0.005-0.1 A/cm2 produces only WCl6 2- ions that can be electrochemically oxidised to WCl6 -. Small amounts of oxide ions present in the melt result in a gradual conversion of W(IV) chloro-species into W(IV) oxychloro-species. In the presence of O2 WCl6 2- is oxidised into tungsten(V) species WOCl5 2-. Molybdenum forms Mo(III), (IV) and (V) species. MoCl6 2- complex ions in chloride melts can be obtained by reacting MoO2 with HCl, or by electrochemical oxidation of Mo(III) (MoCl6 3- → MoCl6 2-) on a glassy carbon electrode.</description><identifier>ISSN: 1938-5862</identifier><identifier>EISSN: 1938-6737</identifier><identifier>DOI: 10.1149/1.2798697</identifier><language>eng</language><ispartof>ECS transactions, 2007, Vol.3 (35), p.555-566</ispartof><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c144t-8e1f7fb768c8ea1fe1a29e3eda1d7185f702aeaf653eae19038037a9d45906543</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27901,27902</link.rule.ids></links><search><creatorcontrib>Volkovich, Vladimir A.</creatorcontrib><creatorcontrib>Danilov, Danil A. A.</creatorcontrib><creatorcontrib>Polovov, Ilya B.</creatorcontrib><creatorcontrib>Vasin, Boris D. 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Small amounts of oxide ions present in the melt result in a gradual conversion of W(IV) chloro-species into W(IV) oxychloro-species. In the presence of O2 WCl6 2- is oxidised into tungsten(V) species WOCl5 2-. Molybdenum forms Mo(III), (IV) and (V) species. MoCl6 2- complex ions in chloride melts can be obtained by reacting MoO2 with HCl, or by electrochemical oxidation of Mo(III) (MoCl6 3- → MoCl6 2-) on a glassy carbon electrode.</description><issn>1938-5862</issn><issn>1938-6737</issn><fulltext>true</fulltext><rsrctype>conference_proceeding</rsrctype><creationdate>2007</creationdate><recordtype>conference_proceeding</recordtype><recordid>eNotkDtPwzAUhS0EEqUw8A-8MqT4xokfbFXESypiaBmYIje-pkGJXdnpkH8PgUzfkc5jOITcAlsBFPoeVrnUSmh5RhagucqE5PJ81qUS-SW5SumbMfEblwvyuT1i05qhDZ4GR99CN-4t-lNPjbd0d_JfaUBPWz9Zk6oOXYitxfRA13QqDzFg94fmgH3bmI5uh5Mdr8mFM13Cm5lL8vH0uKtess3782u13mQNFMWQKQQn3V4K1Sg04BBMrpGjNWAlqNJJlhs0TpQcDYJmXDEujbZFqZkoC74kd_-7TQwpRXT1Mba9iWMNrJ4-qaGeP-E_ks1UwQ</recordid><startdate>20071012</startdate><enddate>20071012</enddate><creator>Volkovich, Vladimir A.</creator><creator>Danilov, Danil A. A.</creator><creator>Polovov, Ilya B.</creator><creator>Vasin, Boris D. D.</creator><creator>Griffiths, Trevor R. R.</creator><creator>Aleksandrov, Denis E.</creator><creator>Tropin, Oleg A. A.</creator><creator>Tsarevskii, Dmitrii V. V.</creator><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20071012</creationdate><title>Speciation of Molybdenum and Tungsten in Molten Chlorides: A Spectroelectrochemical Study</title><author>Volkovich, Vladimir A. ; Danilov, Danil A. A. ; Polovov, Ilya B. ; Vasin, Boris D. D. ; Griffiths, Trevor R. R. ; Aleksandrov, Denis E. ; Tropin, Oleg A. A. ; Tsarevskii, Dmitrii V. V.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c144t-8e1f7fb768c8ea1fe1a29e3eda1d7185f702aeaf653eae19038037a9d45906543</frbrgroupid><rsrctype>conference_proceedings</rsrctype><prefilter>conference_proceedings</prefilter><language>eng</language><creationdate>2007</creationdate><toplevel>online_resources</toplevel><creatorcontrib>Volkovich, Vladimir A.</creatorcontrib><creatorcontrib>Danilov, Danil A. A.</creatorcontrib><creatorcontrib>Polovov, Ilya B.</creatorcontrib><creatorcontrib>Vasin, Boris D. D.</creatorcontrib><creatorcontrib>Griffiths, Trevor R. R.</creatorcontrib><creatorcontrib>Aleksandrov, Denis E.</creatorcontrib><creatorcontrib>Tropin, Oleg A. A.</creatorcontrib><creatorcontrib>Tsarevskii, Dmitrii V. V.</creatorcontrib><collection>CrossRef</collection></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Volkovich, Vladimir A.</au><au>Danilov, Danil A. A.</au><au>Polovov, Ilya B.</au><au>Vasin, Boris D. D.</au><au>Griffiths, Trevor R. R.</au><au>Aleksandrov, Denis E.</au><au>Tropin, Oleg A. A.</au><au>Tsarevskii, Dmitrii V. V.</au><format>book</format><genre>proceeding</genre><ristype>CONF</ristype><atitle>Speciation of Molybdenum and Tungsten in Molten Chlorides: A Spectroelectrochemical Study</atitle><btitle>ECS transactions</btitle><date>2007-10-12</date><risdate>2007</risdate><volume>3</volume><issue>35</issue><spage>555</spage><epage>566</epage><pages>555-566</pages><issn>1938-5862</issn><eissn>1938-6737</eissn><abstract>Speciation of tungsten and molybdenum in alkali chloride melts (based on NaCl-2CsCl, NaCl-KCl and 3LiCl-2KCl mixtures) was studied between 450 and 750 oC using electronic absorption spectroscopy. Only W(IV) and W(V) chloro- and oxychlorospecies can be stabilised under conditions studied. Tungsten(IV) chloride ions are very sensitive to oxide/hydroxide impurities present in the melt. Anodic dissolution of W metal at anodic current densities in the range of 0.005-0.1 A/cm2 produces only WCl6 2- ions that can be electrochemically oxidised to WCl6 -. Small amounts of oxide ions present in the melt result in a gradual conversion of W(IV) chloro-species into W(IV) oxychloro-species. In the presence of O2 WCl6 2- is oxidised into tungsten(V) species WOCl5 2-. Molybdenum forms Mo(III), (IV) and (V) species. MoCl6 2- complex ions in chloride melts can be obtained by reacting MoO2 with HCl, or by electrochemical oxidation of Mo(III) (MoCl6 3- → MoCl6 2-) on a glassy carbon electrode.</abstract><doi>10.1149/1.2798697</doi><tpages>12</tpages></addata></record> |
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| identifier | ISSN: 1938-5862 |
| ispartof | ECS transactions, 2007, Vol.3 (35), p.555-566 |
| issn | 1938-5862 1938-6737 |
| language | eng |
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| source | IOP Publishing Journals; Institute of Physics (IOP) Journals - HEAL-Link |
| title | Speciation of Molybdenum and Tungsten in Molten Chlorides: A Spectroelectrochemical Study |
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