{"created":"2021-03-01T06:25:37.750264+00:00","id":18233,"links":{},"metadata":{"_buckets":{"deposit":"4bd6cc10-b439-4667-af9d-e5a0d0ef9198"},"_deposit":{"id":"18233","owners":[],"pid":{"revision_id":0,"type":"depid","value":"18233"},"status":"published"},"_oai":{"id":"oai:nagoya.repo.nii.ac.jp:00018233","sets":["488:1524:1624"]},"author_link":["53173"],"control_number":"18233","item_17_biblio_info_6":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2014-06-16","bibliographicIssueDateType":"Issued"}}]},"item_17_description_4":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"The logarithmic formation constants (logK) for aqueous lanthanide(III)-EDTA complexes show a Gd-break and subtle tetrad effect, but the ΔSr and ΔHr data indicate step-like changes in the middle Ln. UV-Vis spectra of Eu3+ for Eu-EDTA solution suggest the hydration change occurring across the middle Ln-EDTA series. This is supported by the recent studies of luminescence kinetics on the inner-sphere waters of Eu-EDTA and Tb-EDTA, and by the lanthanide-induced 17O NMR shifts of Ln-EDTA. Such spectroscopic studies allow to re-examine the long-lasting controversy of the Gd-break and tetrad effect of logK(Ln-EDTA). Here is proposed a thermodynamic model to elucidate it from the viewpoints: i) hydration changes of Ln-EDTA and light Ln3+ (aq) series, ii) the nephelauxetic effect due to the coordination change of Ln3+ of Ln-EDTA, and iii) the improved equation of Jφrgensen theory applicable to ΔHr and ΔGr. This model satisfies the spectroscopic constraints on the hydration states of Ln-EDTA series: Three and two water molecules exist in the inner spheres of light Ln(La~Nd)-EDTA and heavy Ln(Dy~Lu)-EDTA series, respectively. Each middle Ln(Sm~Tb)-EDTA is a mixture of the two hydrate species, and their abundances are given by the equilibrium of hydration change reaction: [Ln ⋅ EDTA⋅ (H2O)3 ]− (aq ) = [Ln ⋅ EDTA⋅ (H2O)2 ]− (aq ) + H2O(l ). The ΔHr, ΔSr and ΔGr data for Ln-EDTA formation, when corrected for hydration changes in Ln-EDTA and light Ln3+ (aq) series, can be fitted by the improved equation of Jφrgensen theory, and the thermodynamic parameters for the formation of two Ln-EDTA series from octahydrate Ln3+ (aq) have been evaluated. The hydration change of middle Ln-EDTA series explains the apparent Gd-break of logK(Ln-EDTA). The nephelauxetic effect by the change in coordination number for Ln3+ (ΔCN) is evident in ΔH values for the three reactions: (a) [Ln ⋅ EDTA⋅ (H2O)3 ]− (aq ) formation from Ln(oct, aq ) 3+ (ΔCN=+1), (b) [Ln ⋅ EDTA⋅ (H2O)2 ]− (aq ) formation from Ln(oct, aq) 3+ (ΔCN=0), and (c) the hydration change reaction of Ln-EDTA given as (b)-(a) (ΔCN=−1). The relative Racah E1 parameter values for Nd3+, ΔE1(Nd3+), from the tetrad effects of ΔH for (a), (b) and (c), are +(39±14) cm-1, −(19±7) cm-1, and −(58±18) cm-1, respectively. The ΔHr values for (a) with ΔCN=+1 show a large convex tetrad effect, and the ΔSr values also exhibit a similar tetrad effect. Therefore, their tetrad effects are significantly cancelled in ΔGr. This is a reason why the subtle tetrad-like variation of logK(Ln-EDTA) is asymmetrical between light and heavy Ln, along with the hydration change effects of middle Ln-EDTA and light Ln3+ (aq) series cancelled partly within the light Ln.","subitem_description_language":"en","subitem_description_type":"Abstract"}]},"item_17_identifier_60":{"attribute_name":"URI","attribute_value_mlt":[{"subitem_identifier_type":"HDL","subitem_identifier_uri":"http://hdl.handle.net/2237/20317"}]},"item_17_select_15":{"attribute_name":"著者版フラグ","attribute_value_mlt":[{"subitem_select_item":"author"}]},"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":"53173","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":"2018-02-21"}],"displaytype":"detail","filename":"EDTA-rev-13.pdf","filesize":[{"value":"3.9 MB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"EDTA-rev-13.pdf","objectType":"fulltext","url":"https://nagoya.repo.nii.ac.jp/record/18233/files/EDTA-rev-13.pdf"},"version_id":"0c8d988f-ee3e-4a7e-b983-bff4d0fb4300"},{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2018-02-21"}],"displaytype":"detail","filename":"EDTA-rev-Figs_13.pdf","filesize":[{"value":"817.8 kB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"EDTA-rev-Figs_13.pdf","objectType":"dataset","url":"https://nagoya.repo.nii.ac.jp/record/18233/files/EDTA-rev-Figs_13.pdf"},"version_id":"277c0256-1325-4911-8bbf-0d1a7e01547d"},{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2018-02-21"}],"displaytype":"detail","filename":"EDTA-Tab_1-3_13.pdf","filesize":[{"value":"219.4 kB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"EDTA-Tab_1-3_13.pdf","objectType":"dataset","url":"https://nagoya.repo.nii.ac.jp/record/18233/files/EDTA-Tab_1-3_13.pdf"},"version_id":"ce447d45-350f-4d8f-a18d-1c50f2ac2cf5"},{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2018-02-21"}],"displaytype":"detail","filename":"EDTA-Tab_4-7_13.pdf","filesize":[{"value":"289.4 kB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"EDTA-Tab_4-7_13.pdf","objectType":"dataset","url":"https://nagoya.repo.nii.ac.jp/record/18233/files/EDTA-Tab_4-7_13.pdf"},"version_id":"f0cab37a-463f-4ace-b8ca-d4c830ab022a"}]},"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":"other","resourceuri":"http://purl.org/coar/resource_type/c_1843"}]},"item_title":"A puzzle of Gd-break and tetrad effect of aqueous lanthanide(III)-EDTA complex formation: Different Racah parameters between two lanthanide-EDTA complex series with distinct hydration states","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"A puzzle of Gd-break and tetrad effect of aqueous lanthanide(III)-EDTA complex formation: Different Racah parameters between two lanthanide-EDTA complex series with distinct hydration states","subitem_title_language":"en"}]},"item_type_id":"17","owner":"1","path":["1624"],"pubdate":{"attribute_name":"PubDate","attribute_value":"2014-06-16"},"publish_date":"2014-06-16","publish_status":"0","recid":"18233","relation_version_is_last":true,"title":["A puzzle of Gd-break and tetrad effect of aqueous lanthanide(III)-EDTA complex formation: Different Racah parameters between two lanthanide-EDTA complex series with distinct hydration states"],"weko_creator_id":"1","weko_shared_id":3},"updated":"2023-01-16T05:05:27.099508+00:00"}