Structural properties of the inner coordination sphere of indium chloride complexes in organic and aqueous solutions.
Identifieur interne : 000038 ( Main/Exploration ); précédent : 000037; suivant : 000039Structural properties of the inner coordination sphere of indium chloride complexes in organic and aqueous solutions.
Auteurs : RBID : pubmed:24217005Abstract
The nature of the inner coordination sphere of In(3+) present in both the organic and aqueous solutions during the solvent extraction of In(3+) from an aqueous HCl solution with tri-n-octyl amine (TOA) was investigated by In K-edge XAFS. This information was then used to clarify the details of the extraction properties of indium chloride anion complexes with TOA. In aqueous HCl solution (0.1-10 M), In(3+) exists as octahedral anion complexes, [InCln(H2O)6-n](3-n) (n ≥ 4); the [InCl6](3-) complex is dominant at 10 M HCl. The extraction of In(3+) from HCl solution with TOA was performed using two kinds of diluents: nitrobenzene (NB) or n-dodecane (DD), which contained 20 vol% of 2-ethylhexanol as an additive. The stoichiometric composition of the extracted complexes, which is estimated from the distribution ratios of In(3+), is affected by the diluents and the HCl concentration of the aqueous phase; the apparent values of TOA/In(3+) in the extracted complex are 3 for DD-1 M HCl (diluent-aqueous phase) and DD-5 M HCl, 2 for NB-1 M HCl and NB-5 M HCl, and 1 for NB-10 M HCl. The EXAFS analysis of these extracted complexes shows that the In(3+) has ∼4 Cl(-) at ∼2.336 Å and no H2O in the inner coordination sphere; additionally, the shape of the XANES suggests that their coordination geometry is tetrahedral. Therefore, the same tetrahedral [InCl4](-) complex is formed during the extraction in spite of the variation in the stoichiometric composition (TOA/In(3+) = 1-3) of the extracted complexes.
DOI: 10.1039/c3dt52474d
PubMed: 24217005
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<record><TEI><teiHeader><fileDesc><titleStmt><title xml:lang="en">Structural properties of the inner coordination sphere of indium chloride complexes in organic and aqueous solutions.</title><author><name sortKey="Narita, Hirokazu" uniqKey="Narita H">Hirokazu Narita</name><affiliation wicri:level="1"><nlm:affiliation>Research Institute for Environmental Management Technology, National Institute of Advanced Industrial Science and Technology (AIST), 16-1 Onogawa, Tsukuba, Ibaraki 305-8569, Japan. hirokazu-narita@aist.go.jp.</nlm:affiliation><country xml:lang="fr">Japon</country><wicri:regionArea>Research Institute for Environmental Management Technology, National Institute of Advanced Industrial Science and Technology (AIST), 16-1 Onogawa, Tsukuba, Ibaraki 305-8569</wicri:regionArea></affiliation></author><author><name sortKey="Tanaka, Mikiya" uniqKey="Tanaka M">Mikiya Tanaka</name></author><author><name sortKey="Shiwaku, Hideaki" uniqKey="Shiwaku H">Hideaki Shiwaku</name></author><author><name sortKey="Okamoto, Yoshihiro" uniqKey="Okamoto Y">Yoshihiro Okamoto</name></author><author><name sortKey="Suzuki, Shinichi" uniqKey="Suzuki S">Shinichi Suzuki</name></author><author><name sortKey="Ikeda Ohno, Atsushi" uniqKey="Ikeda Ohno A">Atsushi Ikeda-Ohno</name></author><author><name sortKey="Yaita, Tsuyoshi" uniqKey="Yaita T">Tsuyoshi Yaita</name></author></titleStmt><publicationStmt><date when="2014">2014</date><idno type="doi">10.1039/c3dt52474d</idno><idno type="RBID">pubmed:24217005</idno><idno type="pmid">24217005</idno><idno type="wicri:Area/Main/Corpus">000311</idno><idno type="wicri:Area/Main/Curation">000311</idno><idno type="wicri:Area/Main/Exploration">000038</idno></publicationStmt></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">The nature of the inner coordination sphere of In(3+) present in both the organic and aqueous solutions during the solvent extraction of In(3+) from an aqueous HCl solution with tri-n-octyl amine (TOA) was investigated by In K-edge XAFS. This information was then used to clarify the details of the extraction properties of indium chloride anion complexes with TOA. In aqueous HCl solution (0.1-10 M), In(3+) exists as octahedral anion complexes, [InCln(H2O)6-n](3-n) (n ≥ 4); the [InCl6](3-) complex is dominant at 10 M HCl. The extraction of In(3+) from HCl solution with TOA was performed using two kinds of diluents: nitrobenzene (NB) or n-dodecane (DD), which contained 20 vol% of 2-ethylhexanol as an additive. The stoichiometric composition of the extracted complexes, which is estimated from the distribution ratios of In(3+), is affected by the diluents and the HCl concentration of the aqueous phase; the apparent values of TOA/In(3+) in the extracted complex are 3 for DD-1 M HCl (diluent-aqueous phase) and DD-5 M HCl, 2 for NB-1 M HCl and NB-5 M HCl, and 1 for NB-10 M HCl. The EXAFS analysis of these extracted complexes shows that the In(3+) has ∼4 Cl(-) at ∼2.336 Å and no H2O in the inner coordination sphere; additionally, the shape of the XANES suggests that their coordination geometry is tetrahedral. Therefore, the same tetrahedral [InCl4](-) complex is formed during the extraction in spite of the variation in the stoichiometric composition (TOA/In(3+) = 1-3) of the extracted complexes.</div></front></TEI><pubmed><MedlineCitation Owner="NLM" Status="In-Process"><PMID Version="1">24217005</PMID><DateCreated><Year>2013</Year><Month>12</Month><Day>18</Day></DateCreated><Article PubModel="Print"><Journal><ISSN IssnType="Electronic">1477-9234</ISSN><JournalIssue CitedMedium="Internet"><Volume>43</Volume><Issue>4</Issue><PubDate><Year>2014</Year><Month>Jan</Month><Day>28</Day></PubDate></JournalIssue><Title>Dalton transactions (Cambridge, England : 2003)</Title><ISOAbbreviation>Dalton Trans</ISOAbbreviation></Journal><ArticleTitle>Structural properties of the inner coordination sphere of indium chloride complexes in organic and aqueous solutions.</ArticleTitle><Pagination><MedlinePgn>1630-5</MedlinePgn></Pagination><ELocationID EIdType="doi" ValidYN="Y">10.1039/c3dt52474d</ELocationID><Abstract><AbstractText>The nature of the inner coordination sphere of In(3+) present in both the organic and aqueous solutions during the solvent extraction of In(3+) from an aqueous HCl solution with tri-n-octyl amine (TOA) was investigated by In K-edge XAFS. This information was then used to clarify the details of the extraction properties of indium chloride anion complexes with TOA. In aqueous HCl solution (0.1-10 M), In(3+) exists as octahedral anion complexes, [InCln(H2O)6-n](3-n) (n ≥ 4); the [InCl6](3-) complex is dominant at 10 M HCl. The extraction of In(3+) from HCl solution with TOA was performed using two kinds of diluents: nitrobenzene (NB) or n-dodecane (DD), which contained 20 vol% of 2-ethylhexanol as an additive. The stoichiometric composition of the extracted complexes, which is estimated from the distribution ratios of In(3+), is affected by the diluents and the HCl concentration of the aqueous phase; the apparent values of TOA/In(3+) in the extracted complex are 3 for DD-1 M HCl (diluent-aqueous phase) and DD-5 M HCl, 2 for NB-1 M HCl and NB-5 M HCl, and 1 for NB-10 M HCl. The EXAFS analysis of these extracted complexes shows that the In(3+) has ∼4 Cl(-) at ∼2.336 Å and no H2O in the inner coordination sphere; additionally, the shape of the XANES suggests that their coordination geometry is tetrahedral. Therefore, the same tetrahedral [InCl4](-) complex is formed during the extraction in spite of the variation in the stoichiometric composition (TOA/In(3+) = 1-3) of the extracted complexes.</AbstractText></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Narita</LastName><ForeName>Hirokazu</ForeName><Initials>H</Initials><Affiliation>Research Institute for Environmental Management Technology, National Institute of Advanced Industrial Science and Technology (AIST), 16-1 Onogawa, Tsukuba, Ibaraki 305-8569, Japan. hirokazu-narita@aist.go.jp.</Affiliation></Author><Author ValidYN="Y"><LastName>Tanaka</LastName><ForeName>Mikiya</ForeName><Initials>M</Initials></Author><Author ValidYN="Y"><LastName>Shiwaku</LastName><ForeName>Hideaki</ForeName><Initials>H</Initials></Author><Author ValidYN="Y"><LastName>Okamoto</LastName><ForeName>Yoshihiro</ForeName><Initials>Y</Initials></Author><Author ValidYN="Y"><LastName>Suzuki</LastName><ForeName>Shinichi</ForeName><Initials>S</Initials></Author><Author ValidYN="Y"><LastName>Ikeda-Ohno</LastName><ForeName>Atsushi</ForeName><Initials>A</Initials></Author><Author ValidYN="Y"><LastName>Yaita</LastName><ForeName>Tsuyoshi</ForeName><Initials>T</Initials></Author></AuthorList><Language>eng</Language><PublicationTypeList><PublicationType>Journal Article</PublicationType></PublicationTypeList></Article><MedlineJournalInfo><Country>England</Country><MedlineTA>Dalton Trans</MedlineTA><NlmUniqueID>101176026</NlmUniqueID><ISSNLinking>1477-9226</ISSNLinking></MedlineJournalInfo></MedlineCitation><PubmedData><History><PubMedPubDate PubStatus="entrez"><Year>2013</Year><Month>11</Month><Day>13</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="pubmed"><Year>2013</Year><Month>11</Month><Day>13</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="medline"><Year>2013</Year><Month>11</Month><Day>13</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate></History><PublicationStatus>ppublish</PublicationStatus><ArticleIdList><ArticleId IdType="doi">10.1039/c3dt52474d</ArticleId><ArticleId IdType="pubmed">24217005</ArticleId></ArticleIdList></PubmedData></pubmed></record>Pour manipuler ce document sous Unix (Dilib)
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