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- Author or Editor: H. Imura x
- Chemistry and Chemical Engineering x
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Abstract
The extraction of La(III), Gd(III), and Lu(III) with 18-crown-6 (18C6) has been studied using pentadecafluorooctanoate (PDFO) as a counter anion. Very high extractability of La(III) was observed in various organic solvents such as benzene, chloroform, 1,2-dichloroethane, and nitrobenzene. The predominant species extracted into benzene was found to be Ln(PDFO)3 (18C6), and the extraction constants (K ex,s1 =[Ln(PDFO)3 (18C6)]org/[Ln3+][PDFO]3[18C6]org) were 1013.12 for La(III), 109.74 for Gd(III), and 109.67 for Lu(III). These values are 1010 times higher than those in the trichloroacetate-18C6 system reported previously. The present PDFO-18C6 system was superior to the picrate- and hexafluoroacetylacetonate-18C6 system for the separation efficiency of light lanthanides(III).
Abstract
Partition coefficients of Cu(acac)2 were determined in eleven organic solvents-0.10M perchlorate systems. Their magnitude was compared with that of the enol form of Hacac and evaluated by a modified equation based on the regular solution theory. The partition coefficient of the copper (II) chelate has been demonstrated to strongly depend on some specific solute-solvent interactions such as direct coordination to the central metal and hydrogen bonding to the ligand molecules. In the case of chloroform, particularly the specific interaction has been elucidated by an association reaction, for which the equilibrium constant has been determined.
Abstract
Substoichiometric isotope dilution analysis for the determination of trace iron has been studied by using synergistic extraction of iron(III) with a substoichiometric amount of 4-isopropyltropolone (Hipt) in the presence of an excess of 3,5-dichlorophenol (DCP) in heptane. Optimum conditions for the substoichiometric extraction of iron(III) in 
g to sub-g levels were examined and the high selectivity for iron(III) toward various metal ions encountered in the analysis of biological materials was confirmed. The present method was applied to a biological reference material (NIES, CRM No.9, sargasso) without any pre-separation and was successfully evaluated. Furthermore, substoichiometric stable isotope dilution mass spectrometry using the present extraction method was also used with the above sample. Applicability and practicability was compared for both substoichiometric methods.
Abstract
The synergistic effect on the extraction of thorium(IV) was found by the combination of 2-thenoyltrifluoroacetone (Htta) and 1,10-phenanthroline (phen) or 4,7-diphenyl-1,10-phenanthroline (dpp) as a neutral bidentate ligand. Especially in the presence of dpp (1·10–3M) in benzene, the distribution ratio of thorium(IV) increased by a factor of about 300. Such synergistic enhancement of the extraction was ascribed to the formation of the adduct complex of Th(tta)4(phen) and Th(tta)4(dpp) in the organic phase. The extraction constant and the adduct formation constant were determined and discussed.
Abstract
The synergic extraction of La(III), Eu(III), and Lu(III) with 2-thenoyltrifluoroacetone (Htta) and triphenylarsine oxide (tpao) in benzene has been studied. The extractability of lanthanoids, Ln(III), is significantly affected by the association of Htta with tpao in the organic phase. The associated species is Htta·tpao and the association constant is determined as 101.63. The intrinsic extraction equilibrium of Ln(III) is analyzed using the free concentration of Htta and tpao. The synergic enhancement is ascribable to the formation of the adduct complexes shown as Ln(tta)3tpao and Ln(tta)3(tpao)2 in the present extraction system. The adduct formation constants determined are very large as expected from the high basicity of tpao.
Abstract
The substoichiometric isotope dilution analysis for manganese(II) in a synergistic extraction system of a chelating agent and a neutral ligand is described. The substoichiometric extarction is based on a substoichiometric amount of 2-thenoyltrifluoroacetone and an excess of 1,10-phenanthroline. The recommended condition and the reproducibility of the present system were examined. The present method was applied for NBS-SRM tomato leaves and NIES-SRM chlorella, and very good results with high accuracy and precision were demonstrated.
Abstract
The substoichiometric isotope dilution analysis for U(VI) in a synergic extraction system of an excess amount of a chelating agent HHFA and a substoichiometric amount of neutral ligand TOPO has been developed. A constant but substoichiometric amout of U(VI) can be precisely extracted, and U down to ppm levels can be accurately determined by the present method. This method was applied to the analysis of a phosphate rock.
Abstract
Extraction behaviour of lanthanoid/III/ has been investigated by using 18-crown-6/CR/ as a neutral microcyclic ligand, trichloroacetate/TCA–/ as an anionic counter ion, and 1,2-dichloroethane as an organic solvent. From the equilibrium studies, the extractable complex such as LnCR3+ was found for La/III/, Ce/III/, Pr/III/, Nd/III/, Sm/III/, and Eu/III/ and also the formation of Ln/CR/ 2 3+ complexes was suggested for Tb/III/, Tm/III/, and Lu/III/. The extractability of lanthanoid/III/ steeply decreased with increase in the atomic number. This order of extractability was a reverse trend compared with that in many other extraction systems reported so far. Very high separation factors especially among light lanthanoid/III/ were observed.
Abstract
Synergistic effect of neutral bidentate ligands, L, such as 1,10-phenanthroline(phen), 2,9-dimethyl-1,10-phenanthroline(dmp), and 2,2
-bipyridine(bpy), and of neutral unidentate ligands TBP and TOPO have been studied in the extraction of Mn(II) labeled with54Mn, using 2-thenoyl-trifluoroacetone(HTTA) in various organic solvents. The following factors play an important role in the synergistic extraction involving bidentate ligands; two-phase partition of bidentate ligands, their protonation and complex formation with Mn(II) in the aqueous phase. The mixed ligand complex, Mn(TTA)2L, is formed in all bidentate ligand systems. The adduct formation constant (
S,1) decreases in the following order; phen (lg
S,1=12.64) > dmp(11.32)> · bpy(8.54) in the cyclohexane system. This order is ascribed to the bacisity and the steric effect of the bidentate ligands. Organic solvents influence both the adduct formation and the partition of the ligands, and
S,1 decreases in the order cyclohexane>carbon tetrachloride>chlorobenzen 
= benzene>chloroform.
Abstract
Preseparation of lanthanoids by substoichiometric precipitation of calcium oxalate and simple radiochemical separation of lanthanoids by lanthanum oxalate have been developed. They were combined with neutron activation analysis of a marine macro-alga (Laminaria religiosa, brown alga) sample. Quantitative recovery of lanthanoids throughout the procedure was examined by radiotracer technique. Eleven lanthanoids, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Er, Yb and Lu, at 0.7–140 ng g–1 were determined with a relative standard deviation of 1–7% (n=3). Concentrations of lanthanoids in the marine macro-alga were compared with land plant and sea water.
