Diphosphine dioxides as extraction reagents for the extraction of the actinides. The anomalous aryl strengthening effect (in Russian)
A cycle of investigations of the extraction of mineral acids, actinides, and lanthanides by diphosphine dioxides of various structures in generalized. It was found that in the extraction of acids (HNO/sub 3/, HClO/sub 4/) monodentately coordinated to the dioxides, the laws previously established, relating the extraction capacity to the structure of the compounds, are fulfilled. In the extraction of the actinides and lanthanides(III, IV, VI), accompanied by bidentate coordination, an effect of anomalous aryl strengthening of the complexes is detected: when electronegative aryl groups are introduced into the methylenediphosphine molecule, the basicity of the dioxide is decreased, while the strength of the complexes, contrary to the established principles, increases substantially. It was found that as a result of the anomaly, the extraction of the actinides(III, IV, VI) is increased by a factor of 150 on two aryl groups and by a factor of 2 x 10/sup 4/ on four aryl groups. The anomalous effect arises when a six-membered ring is closed, is maintained when the anion is replaced (by Cl/sup -/ or ClO/sub 4//sup 2 -/), and is especially great in perchloric acid medium but disappears when the bridge is lengthened, the distance of the aryl groups from the phosphorus is increased by a CH/sub 2/ group, and when the aryls are replaced by groups with the same electronegativity but a different nature, for example, Cl(CH/sub 2/)/sub 2/. The cause of the effect is the transmission of electron density from the phenyl groups into the basic ring of the complex, an increase in the principle solvate number, and possibly aromatization of the ring.
- OSTI ID:
- 6950414
- Journal Information:
- Sov. Radiochem. (Engl. Transl.); (United States), Journal Name: Sov. Radiochem. (Engl. Transl.); (United States) Vol. 28:3; ISSN SVRDA
- Country of Publication:
- United States
- Language:
- Russian
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ACTINIDES
ARYL RADICALS
BINDING ENERGY
CHEMICAL BONDS
COMPARATIVE EVALUATIONS
COMPLEXES
COMPLEXOMETRY
ELECTRONEGATIVITY
ELECTRONS
ELEMENTARY PARTICLES
ELEMENTS
ENERGY
EXTRACTION
FERMIONS
HYDROGEN COMPOUNDS
INORGANIC ACIDS
LEPTONS
MATERIALS TESTING
METALS
MOLECULAR STRUCTURE
NITRIC ACID
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
ORGANIC SOLVENTS
PH VALUE
PHOSPHINIC ACIDS
RADICALS
RARE EARTHS
SEPARATION PROCESSES
SOLVENT EXTRACTION
SOLVENT PROPERTIES
SOLVENTS
STRUCTURAL CHEMICAL ANALYSIS
TESTING
VALENCE