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Lanthanide tetrad effects : Extension of Jorgensen's theory and its new developments

Research Project

Project/Area Number 21654081
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeSingle-year Grants
Research Field Geochemistry/Astrochemistry
Research InstitutionNagoya University

Principal Investigator

KAWABE Iwao  名古屋大学, 環境学研究科, 教授 (40127890)

Project Period (FY) 2009 – 2011
Project Status Completed (Fiscal Year 2011)
Budget Amount *help
¥3,310,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥210,000)
Fiscal Year 2011: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000)
Fiscal Year 2010: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 2009: ¥1,900,000 (Direct Cost: ¥1,900,000)
Keywords地殻・マントル物質 / 地球化学 / 希土類元素化学 / ランタニド化学 / 四組効果 / 希土類元素 / ヨルゲンセン-川邊式 / REE分配係数 / 希土類元素鉱物 / ランタニド / ランタニド四組効果 / ヨルゲンセン理論 / 電子雲拡大効果 / ランタニド・キレート錯体 / ヨルゲンセン・川邊の式 / ランタニドの熱力学 / 熱力学量
Research Abstract

As a case study of thermodynamic data for aqueous Ln(III)-chelate complex formations, those data for Ln(III)-DTPA and Ln-EDTA complex formations have been examined in view of the Jorgensen-Kawabe(JK) equation for the lanthanide tetrad effect. Ln-chelate formations represent such reactions that ligands of H-2O of aqua Ln(III) ions are replaced by(DTPA+H-2O) or(EDTA+H-2O), where. H and. S show similar tetrad effects, but the tetrad effects are cancelled almost totally in. G through. G=. H-T. S. Previous studies overlooked this mechanism, and led to misunderstanding.
As an experimental study, REE(Ln+Y) partition coefficients for the pair of BaSO4/aqueous solution have been determined in the temperature range of 10~ 200. C. The tetrad effects of△H and△S for REE partitioning reaction have been shown. Using the Gibbs-Helmholtz equation and JK equation, the tetrad effects have been analyzed.
REE abundance patterns of rare-earth minerals(kimuraite and lanthanite) normalized by chondrite, indicate the tetrad effects. We confirmed that the tetrad effects can be well reproduced by JK equation. This is the first demonstration in REE geochemistry that REE compositions of REE minerals can be fitted to the simple theoretical equation.
In order help graduate students and young researchers understand the theoretical base of Jorgensen-Kawabe equation, the three textbooks on Statistical Mechanics, Physics on Electricity and Magnetism, Quantum Mechanics have been prepared and registered them in Repository of NU Library for their open uses. Jorgensen-Kawabe equation itself and the results of the present study are discussed and cited in another textbook"REE Chemistry and Geochemistry", which is now in preparation.

Report

(4 results)
  • 2011 Annual Research Report   Final Research Report ( PDF )
  • 2010 Annual Research Report
  • 2009 Annual Research Report
  • Research Products

    (11 results)

All 2011 2010 2009 Other

All Presentation (8 results) Remarks (3 results)

  • [Presentation] BaSO-4/水溶液系におけるREE分配係数の温度変化(10~200℃):固相REE^<3+>の結合状態変化と分配反応ΔH-rとΔS-rの四組効果2011

    • Author(s)
      川邊岩夫,奥村友幸
    • Organizer
      日本地球化学会年会
    • Place of Presentation
      北海道大学札幌キャンパス
    • Year and Date
      2011-09-16
    • Related Report
      2011 Final Research Report
  • [Presentation] Reexamination of natural kimuraite and synthetic experiment of kimuraite2011

    • Author(s)
      Jiao Wenfang, Kawabe, I., and Kato, T.
    • Organizer
      日本地球化学会年会
    • Place of Presentation
      北海道大学札幌キャンパス
    • Year and Date
      2011-09-16
    • Related Report
      2011 Final Research Report
  • [Presentation] BaSO_4/水溶液系におけるREE分配係数の温度変化(10~200℃):固相REE^<3+>の結合状態変化と分配反応ΔH_rとΔS_rの四組効果2011

    • Author(s)
      川邊岩夫, 奥村友幸
    • Organizer
      日本地球化学会
    • Place of Presentation
      北海道大学札幌キャンパス
    • Year and Date
      2011-09-16
    • Related Report
      2011 Annual Research Report
  • [Presentation] Reexamination of natural kimuraite and synthetic experiment of kimuraite2011

    • Author(s)
      Jiao Wenfang, Kawabe, I., Kato, T.
    • Organizer
      日本地球化学会
    • Place of Presentation
      北海道大学札幌キャンパス
    • Year and Date
      2011-09-16
    • Related Report
      2011 Annual Research Report
  • [Presentation] ランタニド・二水素化物系列の標準生成エンタルピー:Jorgensen-Kawabe式から推定するRacahパラメーター2010

    • Author(s)
      川邊岩夫
    • Organizer
      日本地球化学会年会
    • Place of Presentation
      立正大学熊谷キャンパス
    • Year and Date
      2010-09-09
    • Related Report
      2011 Final Research Report
  • [Presentation] ランタニド・二水素化物系列の標準生成エンタルピー:Jorgensen-Kawabe式から推定するRacahパラメーター2010

    • Author(s)
      川邊岩夫
    • Organizer
      日本地球化学会
    • Place of Presentation
      立正大学熊谷キャンパス
    • Year and Date
      2010-09-08
    • Related Report
      2010 Annual Research Report
  • [Presentation] ランタニド(III)酸化物系列のエンタルピ-温度変化とJorgensen-Kawabe式の新展開2009

    • Author(s)
      川邊岩夫・平原靖大
    • Organizer
      日本地球化学会年会
    • Place of Presentation
      広島大学
    • Year and Date
      2009-09-17
    • Related Report
      2011 Final Research Report
  • [Presentation] ランタニド(III)酸化物系列のエンタルピー温度変化とJorgensen-Kawabe式の新展開 : 熱膨張で増大するRacahパラメーター2009

    • Author(s)
      川邊岩夫・平原靖大
    • Organizer
      日本地球化学会年会
    • Place of Presentation
      広島大学
    • Year and Date
      2009-09-17
    • Related Report
      2009 Annual Research Report
  • [Remarks] 川邊岩夫,物質科学を学ぶための電磁気学の基礎事項

    • URL

      http://ir.nul.nagoya-u.ac.jp/jspui/handle/2237/16107

    • Related Report
      2011 Final Research Report
  • [Remarks] 川邊岩夫,量子力学の基礎事項

    • URL

      http://ir.nul.nagoya-u.ac.jp/jspui/handle/2237/16108

    • Related Report
      2011 Final Research Report
  • [Remarks] 川邊岩夫,量子力学の基礎事項

    • URL

      http://ir.nul.nagoya-u.ac.jp/jspui/handle/2237/16109

    • Related Report
      2011 Final Research Report

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Published: 2009-04-01   Modified: 2016-04-21  

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