Experimental and theoretical studies on extraction of actinides and lanthanides by alicyclic H-phosphonates

被引：15

作者：

Annam, Suresh ^{[1
]}

Gopakumar, Gopinadhanpillai ^{[2
]}

Rao, C. V. S. Brahmmananda ^{[2
]}

Sivaraman, N. ^{[2
]}

Sivaramakrishna, Akella ^{[1
]}

Vijayakrishna, Kari ^{[1
]}

机构：

[1] VIT Univ, Sch Adv Sci, Dept Chem, Vellore 632014, Tamil Nadu, India

[2] Indira Gandhi Ctr Atom Res IGCAR, Chem Grp, Kalpakkam 603102, Tamil Nadu, India

来源：

RADIOCHIMICA ACTA | 2017年 / 105卷 / 04期

关键词：

H-phosphonates; dialkyl H-phosphonate; actinides; lanthanides; liquid-liquid extraction; DFT calculations; DENSITY-FUNCTIONAL METHODS; BASIS-SETS; SOLVENT-EXTRACTION; PERFORMANCE; RESOLUTION; PHOSPHATE; BEHAVIOR; VALENCE; THORIUM;

D O I：

10.1515/ract-2016-2749

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Three different alicyclic substituents H-phosphonates, namely, dicyclopentyl H-phosphonate, dicyclohexyl H-phosphonate and dimenthyl H-phosphonate were synthesized and used for liquid-liquid extraction of actinide elements (U, Am and Th) and lanthanide (Gd) in n-dodecane from nitric acid medium. The physicochemical properties of the extractants, such as density, viscosity, solubility were determined. At lower acidities, these H-phosphonates exhibit higher distribution values and the extraction following cation exchange mechanism through P-OH group of tri-coordinated phosphite form. At higher acidities (2N), the extraction is primarily via solvation mechanism through P=O group of penta-coordinated phosphonate form. Amongst the three H-phosphonates, examined dimenthyl H-phosphonate showed the best results for the actinide extraction. Density functional theory (DFT) calculations were applied to understand the electronic structure of the ligands and the metal complexes. The calculated large complexation energy of UO2(NO3)(2)(.)2DMnHP is in agreement with the observed trend in experimental distribution ratio data.

引用

页码：329 / 339

页数：11

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