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000046729 084__ $$2WoS$$aChemistry, Multidisciplinary
000046729 1001_ $$0P:(DE-HGF)0$$aIonova, G.$$b0
000046729 245__ $$aMechanism of trivalent actinide/lanthanide separation using synergistic mixtures of di (chlorophenyl) dithiophosphinic acid and neutral o-bearing co-extractants
000046729 260__ $$aLondon$$bRSC$$c2001
000046729 300__ $$a491 - 501
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000046729 440_0 $$04599$$aNew Journal of Chemistry$$v25$$x1144-0546
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000046729 520__ $$aThe mechanism of synergistic selective extraction of Am(III) over Eu(III) from aqueous nitric acid solutions using di(chlorophenyl)dithiophosphinic acid [(Cl Phi)(2)PSSH] and neutral O-bearing organophosphorus co-extractants (B) has been investigated. (Cl Phi)(2)PSSH forms weaker complexes with Am(III) than R2PSSH (where R = alkyl group). However, the Am(III)/(Cl Phi)(2)PSSH complexes are stronger than the corresponding Eu(III)/(Cl Phi)(2)PSSH complexes, although the difference is not as large as in the case of the corresponding complexes formed with R2PSSH. The donor properties of co-extractants are also discussed. Chemical shifts in the P-31 NMR spectra of the organophosphorus co-extractants correlate qualitatively with the extractability of Am(III) and Eu(III) in (Cl Phi)(2)PSSH + B synergistic mixtures. The synergistic effect determines the selectivity not only qualitatively but also quantitatively. The high selectivity observed using tri-2-ethylhexyl phosphate (T2EHP) is caused by a synergistic bonding effect for the Am(III) complex and an antagonistic effect for Eu(III).A donor-acceptor mechanism is shown to promote Am(III) extraction for almost all B co-extractants. A contribution of entropy terms for extracted Eu(III) extraction is assumed to be significant. Interatomic distances REu-S in the Eu(III) complexes are calculated.The softness of S-bearing extractants XYPSSH (with X and Y = R, RO or ClC6H4) is discussed from the point of view of the effective charge carried by the S atoms. The hardness of Eu(III) and Am(III) is evaluated.
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000046729 7001_ $$0P:(DE-HGF)0$$aIonov, S.$$b1
000046729 7001_ $$0P:(DE-HGF)0$$aRabbe, C.$$b2
000046729 7001_ $$0P:(DE-HGF)0$$aMadic, C.$$b3
000046729 7001_ $$0P:(DE-HGF)0$$aGuillaumont, R.$$b4
000046729 7001_ $$0P:(DE-Juel1)130383$$aModolo, G.$$b5$$uFZJ
000046729 7001_ $$0P:(DE-HGF)0$$aKrupa, J. C.$$b6
000046729 773__ $$0PERI:(DE-600)1472933-7$$a10.1039/b006745h$$gVol. 25, p. 491 - 501$$n3$$p491 - 501$$q25<491 - 501$$tNew journal of chemistry$$v25$$x1144-0546$$y2001
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