The separation of americium from lighter lanthanoids has been performedby high-speed countercurrent chromatograph (CCC) equipped with a small coiledcolumn. An extractant having higher affinity for americium, 5,8-diethyl-7-hydroxydodecan-6-oneoxime (LIX 63) was employed as a stationary phase. Americium was chromatographicallyfractionated by gradient elution from large amounts of lighter lanthanoidsthrough a coiled column.
Synergistic effect with a strong donor, trioctyl phosphine oxide (TOPO), has been studied in the extraction of thenoyltrifluoroacetone
(TTA) complexes of uranyl ion. The chemical form of the species extracted was found to be the 1∶1 adduct, UO2A2·S (S∶TOPO), and no evidence was found concerning other mixed complexes. Adduct formation constants determined in twelve inert
solvents vary from lg KS=6.79 in chloroform to 9.58 in n-hexane, while their increasing order is almost the same as that for the adducts with other
phosphine oxides and TBP.
The adsorbability of pertechnetate ion (TcO
) reached 96% for an active carbon at the 0.1 g/50 ml concentration level, increasing with diminution of acid and its salt concentrations, and depending on the type of anions present. With constant anion concentration, TcO
adsorbability rose with decreasing pH in the acidic region, followed in the region around neutrality by a plateau, and in the basic region by an appreciable decline of TcO
adsorbability. In the acidic region, part of once-adsorbed TcO
appeared to be displaced by other anions. Reversibility was noted between the adsorption and desorption of TcO
Sorption of uranium(VI) has been inbestigated using an open-cell plyurethane foam impregnated with 5,8-diethyl-7-hydroxy-6-dodecanone oxime (LIX 63). Above pH 4.5 more than 99% of uranium is sorbed onto the LIX 63 impregnated foam, and uranium can be desorbed with a dilute acid from the foam. The sorption capacity for uranium increases linearly with increasing concentration of impregnated LIX 63. Quantitative removal of uranium from salt solutions was accomplished.
The extraction behavior of Eu(III) has been studied using di(2,4,4-trimethylpentyl)phosphinic acid (DTMPPA, HA) in kerosene. Europium was extracted as Eu(HA2)3 with the extraction constant of 2.0·10–3. This extraction system was applied to the transport of Eu(III) across a DTMPPA liquid membrane supported on porous polytetrafluoroethylene. Europium was quantitatively moved through the liquid membrane containing 0.1M (HA)2 as a mobile carrier from the feed solution of pH above 3 into the product solution of 0.1M HNO3, yielding a concentration factor of ten. The transport rate increased with increasing pH and DTMPPA concentration.
The selective transport of Am across a supported liquid membrane (SLM) has been investigated by using bis (2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex 301) as a mobile carrier. This extractant containing soft donor atoms exhibits strong affinity for actinoids, giving a large separation factor between trivalent Am and Eu. Separation of Am from Eu was achieved by an SLM containing highly purified Cyanex 301. Americium was preferentially transported across the SLM and concentrated in the product solution, while most of Eu remained in the feed solution.
Transport of La, Nd, Eu, Tb, Tm and Lu through a supported liquid membrane (SLM) was investigated by using di(2,4,4-trimethylpentyl)phosphinic acid (DTMPPA) as a mobile carrier. Lanthanoid elements in the feed solution were quantitatively transported and concentrated into the product solution of mild acidity. The transport rates increased with increasing atomic number of lanthanoids in the low pH region of the feed solution. Separation factors evaluated from the transport rates for lanthanoids were close to those from the distribution ratios in liquid-liquid extraction.
The selective transport of yttrium(III) in the presence of iron(III) through a supported liquid membrane (SLM) has been investigated
by using di(2-ethylhexyl)phosphoric acid (DEHPA) as a mobile carrier. Yttrium(III) with fast kinetics was preferentially transported
from the feed solution of dilute acid into the product solution of 1M H2SO4, while most of iron(III) with slow kinetics remained in the feed solution. The effective separation of yttrium(III) from
a large amount of iron(III) was accomplished by the selective transport of yttrium(III) through the SLM.
The extraction equilibria were investigated of the thenoyltrifluoroacetone (TTA) chelate of uranyl ion between aqueous perchlorate
medium and thirteen organic solvents. The extracted species was shown to be UO2A2. The solubility parameter of the chelate was estimated from the partition data and it was confirmed that the relationship
lgPM=n lgPHA+const. holds for the present system. When the extraction constant (Kex) is considered in relation to the distribution coefficients, theKex values are expected to be constant under certain conditions for all of the solvents; the lgKex values were found to be constant (lgKex=−2.85±0.17).
We have compared the 127I Mössbauer spectra of eleven organoantimony compounds with hypervalent bonding, E-Sb-I (E = O, I, N, C ). The charges on iodine atoms fall between -0.54 e for the compound with Sb-I bond length of 2.83 Å and -0.82 e for the compound with 3.34 Å. The negative charges on iodine atoms have been found to increase with the increase in the Sb-I bond lengths. Regarding to the dependence of the kind of E atoms, the negative charges on iodine atoms have been found to decrease with the increase in the electronegativities of E atoms. 121Sb Mössbauer spectra have shown the decrease of the group oxygen electronegativity of hexafluorocumyl alcohol by substituting CF3 for CH3, and this was reflected through O-Sb-I bonding as the increase in the negative charges of iodine atoms in the 127I Mössbauer spectra.