{"created":"2021-03-01T06:14:22.661189+00:00","id":7705,"links":{},"metadata":{"_buckets":{"deposit":"90b7abb0-3cdc-4f6a-8f07-b9b64b5a81f0"},"_deposit":{"id":"7705","owners":[],"pid":{"revision_id":0,"type":"depid","value":"7705"},"status":"published"},"_oai":{"id":"oai:nagoya.repo.nii.ac.jp:00007705","sets":["336:337:338:895"]},"author_link":["21843","21844","21845","21846"],"item_1615768549627":{"attribute_name":"出版タイプ","attribute_value_mlt":[{"subitem_version_resource":"http://purl.org/coar/version/c_970fb48d4fbd8a85","subitem_version_type":"VoR"}]},"item_9_biblio_info_6":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2006","bibliographicIssueDateType":"Issued"},"bibliographicPageEnd":"71","bibliographicPageStart":"51","bibliographicVolumeNumber":"53","bibliographic_titles":[{"bibliographic_title":"The Journal of Earth and Planetary Sciences, Nagoya University","bibliographic_titleLang":"en"}]}]},"item_9_description_4":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"Light REE^3+(aq) is a mixture of two distinguishable species of nonahydrate and octahydrate in equilibrium with respect the hydration change reaction that [REE(H_2O_8]^3+(aq)+H_2O(I)=[REE(H_2O)_9]^3+(aq), and the apparent hydration number of light REE^3+(aq) is changing across the series. Here is discussed nephelauxetic effects of the two REE^3+(aq) series from ΔH^0_γ data for the hydration change reaction and the tetrad effect variations of their hydration enthalpies (ΔH_hyd.) and REE-OH_2 distances. The ΔH^0_γ data combined with those data for solution of REE(ES)_3・9(H_2O) with ES = C_2H_5SO_4^- reported previously, suggest that Racah (E^1 and E^3) parameters for light REE^3+ like Nd^3+ decrease in the following order:[REE(H_2O)_9]^3+(aq)>REE(ES)_3・9(H_2O)> [REE(H_2O)_8]^3+(aq). The average REE^3+-OH_2 distance also decreases in this order. Hence this is a nephelauxetic series that Racah parameters are reduced with decreasing REE^3+-OH_2 distance. The Racah parameters for [REE(H_2O)_9]^3+(aq) series are fairly large and comparable with those of gaseous free REE^3+. No significant tetrad effect is expected in its series variation of (-ΔH_hyd.). By contrast, [REE(H_2O)8]^3+(aq) series has significantly smaller Racah parameters than gaseous free REE^3+, and a convex tetrad effect is expected in the series variation of (-ΔH_hyd.). Since (-ΔH_hyd.). of [REE(H_2O_8)]^3+(aq) in heavy REE series is fitted to a linear function of the reciprocal of observed REE-OH_2 disrance in REECl_3 solution, this relation has been extended to light REE series, and a similar relation for [REE(H_2O)_9]^3+(aq) in light REE series has also been determined from our thermodynamic mixture model and observed REE-OH_2 distances in REECL_3 (REE=La, Pr and Nd) solutions. The reciprocal of REE-OH_2 distance in [REE(H_2O)_8]^3+(aq), when plotted against the atomic number of REE, indicates a small convex tetrad effect whereas such an effect is absent in [REE(H_2O)_9]^3+(aq) , in accordance with their nephelauxetic effects. Interestingly, (-ΔH_hyd.) of [REE(H_2O)_9]^3+(aq) satisfies a linear function of 1/(REE-OH_2), and at the same time, the series variations of both (-ΔH_hyd.) and 1/(REE-OH_2) exhibit small convex tetrad effects when plotted against the atomic number of REE. This is analogous to the relationship between the lattice enthalpy of REEO_1.5(cubic) and REE-O distance. The property of (-ΔH_hyd.) and the lattice enthalpy of REEO_1.5 can be understood from the viewpoints: i) the existence of REE(III) cluster with the equilibrium configuration having the minimum energy by itself, and ii) the classical limit in quantum-chemical energetics where Planck’s constant (h) equals zero. It is emphatically noted that the observed tetrad effects and RSPET can complement the classical ion model with a tactic by which internal structures of the real REE^3+ ions are legitimately introduced into our thermodynamic discussion.","subitem_description_language":"en","subitem_description_type":"Abstract"}]},"item_9_description_5":{"attribute_name":"内容記述","attribute_value_mlt":[{"subitem_description":"国立情報学研究所で電子化したコンテンツを使用している。","subitem_description_language":"ja","subitem_description_type":"Other"}]},"item_9_identifier_60":{"attribute_name":"URI","attribute_value_mlt":[{"subitem_identifier_type":"HDL","subitem_identifier_uri":"http://hdl.handle.net/2237/9423"}]},"item_9_identifier_registration":{"attribute_name":"ID登録","attribute_value_mlt":[{"subitem_identifier_reg_text":"10.18999/joueps.53.51","subitem_identifier_reg_type":"JaLC"}]},"item_9_publisher_32":{"attribute_name":"出版者","attribute_value_mlt":[{"subitem_publisher":"Dept. of Earth and Planetary Sciences, Nagoya University","subitem_publisher_language":"en"}]},"item_9_select_15":{"attribute_name":"著者版フラグ","attribute_value_mlt":[{"subitem_select_item":"publisher"}]},"item_9_source_id_7":{"attribute_name":"ISSN（print）","attribute_value_mlt":[{"subitem_source_identifier":"0919-875X","subitem_source_identifier_type":"PISSN"}]},"item_9_text_14":{"attribute_name":"フォーマット","attribute_value_mlt":[{"subitem_text_value":"application/pdf"}]},"item_access_right":{"attribute_name":"アクセス権","attribute_value_mlt":[{"subitem_access_right":"open access","subitem_access_right_uri":"http://purl.org/coar/access_right/c_abf2"}]},"item_creator":{"attribute_name":"著者","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"KAWABE, Iwao","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"21843","nameIdentifierScheme":"WEKO"}]},{"creatorNames":[{"creatorName":"TAKAHASHI, Takafumi","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"21844","nameIdentifierScheme":"WEKO"}]},{"creatorNames":[{"creatorName":"TANAKA, Kazuya","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"21845","nameIdentifierScheme":"WEKO"}]},{"creatorNames":[{"creatorName":"OHTA, Atsuyuki","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"21846","nameIdentifierScheme":"WEKO"}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2018-02-19"}],"displaytype":"detail","filename":"KJ00004741140.pdf","filesize":[{"value":"1.6 MB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"KJ00004741140.pdf","objectType":"fulltext","url":"https://nagoya.repo.nii.ac.jp/record/7705/files/KJ00004741140.pdf"},"version_id":"10d9539c-835a-4d3b-853c-0e41b0b2a345"}]},"item_language":{"attribute_name":"言語","attribute_value_mlt":[{"subitem_language":"eng"}]},"item_resource_type":{"attribute_name":"資源タイプ","attribute_value_mlt":[{"resourcetype":"departmental bulletin paper","resourceuri":"http://purl.org/coar/resource_type/c_6501"}]},"item_title":"Hydration change reaction of light REE^3+(aq) series-II:Contrasting nephelauxetic effects between hydrated [REE(H_2O)_9]^3+ and [REE(H_2O)_8]^3+ series and the tetrad effects in their hydration enthalpies and REE-OH_2 distances","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"Hydration change reaction of light REE^3+(aq) series-II:Contrasting nephelauxetic effects between hydrated [REE(H_2O)_9]^3+ and [REE(H_2O)_8]^3+ series and the tetrad effects in their hydration enthalpies and REE-OH_2 distances","subitem_title_language":"en"}]},"item_type_id":"9","owner":"1","path":["895"],"pubdate":{"attribute_name":"PubDate","attribute_value":"2008-02-19"},"publish_date":"2008-02-19","publish_status":"0","recid":"7705","relation_version_is_last":true,"title":["Hydration change reaction of light REE^3+(aq) series-II:Contrasting nephelauxetic effects between hydrated [REE(H_2O)_9]^3+ and [REE(H_2O)_8]^3+ series and the tetrad effects in their hydration enthalpies and REE-OH_2 distances"],"weko_creator_id":"1","weko_shared_id":-1},"updated":"2023-01-16T04:53:11.363448+00:00"}