The equilibrium extraction behavior of Sm(III), Eu(III) and Dy(III) from aqueous NaClO4 solutions in the pH range of 4–9 at 0.1 M ionic strength into organic solutions of 1-nitroso-2-naphthol (HA) and 1,10-phenanthroline (Phen) has been studied. The equilibrium concentrations of Eu were assayed through the 344 keV photopeak of the152Eu radiotracer used. The concentrations of Sm and Dy were measured by irradiating one mL portions of the organic extract and analyzing the 104 and 108 keV photopeaks of the short-lived neutron activation products,155Sm and165mDy, respectively. Quantitative extraction of Eu with 5×10–2 M HA alone was obtained in the pH range of 6.7–7.8 with n-butanol, 7.4–8.5 with chloroform, 8.0–8.7 with ethyl acetate, 7.7–8.5 with isoamyl alcohol and 6.1–8.0 with methyl isobutyl ketone (MIBK). But, Eu was extracted only to a maximum of 78% and 83% in the pH range of 8.3–8.9 and 7.4–8.1 with carbon tetrachloride and xylene, respectively. The extraction of Sm and Dy were found quantitative in the pH range of 6.3–7.0 and 6.6–7.1, respectively, with 5×10–2 M HA alone in MIBK solutions. The synergistic extraction of Eu was quantitative in the pH range of 6.6–9.8 with chloroform, 7.8–8.9 with ethyl acetate, 7.7–8.5 with isoamyl alcohol and 6.0–9.6 with MIBK when 1×10–2 M each of HA and Phen were employed. Sm and Dy were quantitatively extracted into MIBK solutions containing 5×10–2 M each of HA and Phen in the pH range 6.0–7.5 and 6.1–7.5, respectively. The distribution ratios of these lanthanides (Ln) were determined as a function of pH, and HA and Phen concentrations. The analysis of the data suggests that these Ln are extracted as LnA3 chelates when HA alone is used. In the presence of HA and Phen, both LnA3(Phen) and LnA3(Phen)2 adducts are formed only in the MIBK system while LnA3(Phen) complexes are the predominant ones in all other solvent systems studied. The extraction constants and the adduct formation constants of these complexes have been calculated.
The extraction behavior of Sm(III), Eu(III) and Dy(III) with 1-nitroso-2-naphthol (HA) and trioctylphosphine oxide (TOPO) in methyl isobutyl ketone (MIBK) from aqueous NaClO4 solutions in the pH range 4–9 at 0.1M ionic strength has been studied. The equilibrium concentrations of Sm and Dy were measured using their short-lived neutron activation products,155Sm and165mDy, respectively. In the case of Eu, the concentrations were assayed through the152,154Eu radiotracer. The distribution ratios of these elements were determined as a function of pH, 1-nitroso-2-naphthol and TOPO concentrations. The extractions of Sm, Eu and Dy were found to be quantitative with MIBK solutions in the pH range 5.9–7.5, 5.6–7.5 and 5.8–7.5, respectively. Quantitative extraction of Eu was also obtained between pH 5.8 and 8.8 with chloroform solutions. The results show that these lanthanides (Ln) are extracted as LnA3 chelates with 1-nitroso-2-naphthol alone, and in the presence of TOPO as LnA3(TOPO) and LnA3(TOPO)2 adducts. The extraction constants and the adduct formation constants of these complexes have been calculated.
A method has been developed for the simultaneous preconcentration of Cd(II), Co(II), Cu(II), Hg(II), Mn(II), Th(IV), U(VI), V(IV) and Zn(II) from 500–1000 ml of water samples by coprecipitation using a combination of 1-(2-thiazolylazo)-2-naphthol, ammonium pyrrolidinedithiocarbamate and ammonium salt of N-nitroso-phenylhydroxylamine. The elemental contents have been measured by neutron activation analysis using different schemes of irradiation, decay and counting periods. Quantitative recoveries of all the above elements have been achieved between pH 6.0 and 7.2. For most of the elements, the enrichment factors are of the order of 104. The precision, expressed in terms of relative standard deviation, and accuracy of measurements are within ±5–10%. The detection limits are in the ppb range. The method has been applied to sea and drinking water samples and biological materials.
The complex formation of Eu(III) by bicarbonate/carbonate ions has been studied at 0.1 M ionic strength and 25°C using synergistic solvent extraction system of 1-nitroso-2-naphthol and 1,10-phenanthroline in chloroform. Concentrations of bicarbonate (5·10–3 to 1·10–1 M) and carbonate (5·10–4 to 1·10–2 M) ions in the aqueous phase have been varied in the pH range of 8.0 to 9.1 to simulate ground and natural water compositions. Under these conditions, the following species have been identified: Eu(HCO3)2+, Eu(HCO3)2+, Eu(CO3)+ and Eu(CO3)2–. Their conditional formation constants (log ) have been calculated as 4.77, 6.74, 6.92 and 10.42, respectively. These values suggest that the carbonate complexes of Eu(III) are highly stable.
A systematic study of separating the actinides from each other in 1 M hydrochloric acid media has been carried out using selective oxidation/reduction processes followed by coprecipitation with neodymium fluoride. We have optimized two such procedures, one with bromate and another with permanganate, for the sequential separation of Am, Pu, Np, and U isotopes. The first procedure involves oxidation of Pu, Np, and U to +6 state in 1 M HCl media at 85° C with 30% NaBrO3 and separation from trivalent Am by collecting the latter on the first NdF3 coprecipitated source. Plutonium is then reduced and converted to +4 oxidation state with 40% NaNO2 at 85°C, while Np and U are kept oxidized with additional bromate in 50–70°C hot solution, thus separating Pu by collection on a second NdF3 source. At this stage, Np present in the filtrate is reduced with hydroxylamine hydrochloride and separated from U by collecting on a third source. Subsequently, U is reduced with 30% TiCl3 and co-precipitated on a final source. The second procedure, which employs KMnO4 in 1 M HCl media at 60–85°C for oxidizing Pu, Np, and U, and separating from Am, produced MnO2 which is collected along with Am on the coprecipitated NdF3. This MnO2 is dissolved on the filter itself with 1 mL of acidified 1.5% H2O2 without any degradation of the -spectra. After evaporating the filtrate to destroy H2O2, Pu, Np, and U are separated by following steps similar to those in the bromate procedure. The recoveries of the actinides with both procedurés are >99%. The decontamination factors are between 103 and 104. The precision and accuracy of measurements, as expressed by the relative standard deviation of replicate analyses, are within 5%. Absolute detection limits for a one-day count on a 600 mm2 detector at 32% counting efficiency and 450 mm2 detector at 27% counting efficiency are about 2.7×10–4 and 3.2×10–4 Bq, respectively. These procedures have been applied to the analysis of actinides in environmental samples.
Authors:R. Subba Rao, P. Sivakumar, R. Natarajan, and P. Vasudeva Rao
The transport of hydrochloric acid across a supported liquid membrane using Aliquat 336 in xylene as a carrier was studied. The effect of carrier concentration (0.1–0.6M) on the transportation of hydrochloric acid with and without phase modifier was investigated. The study indicated that the flux of transportation decreased with increasing carrier concentration in the absence of phase modifier. In the presence of phase modifier, however, the flux increased up to 0.2M carrier concentration and started decreasing afterwards. The transportation behavior of hydrochloric acid with and without phase modifier has been attributed to the tendency of aggregation of the carrier.
The problem of common extension ofcharges (finitely additive measures) is generalised to include group-valued functions defined on a system of sets (u-systems). To eachu-systemU an Abelian groupH(U) is attached. Every Abelian group is isomorphic to one of the formH(U). The groupH(U) is an indicator for extendability of charges fromU to the Boolean algebra generated byU. AllG-valued measures extend if and only if Ext(H(U),G)=0, for instance.
Authors:Nivedila Patnaik, R. Patil, R. Saktivelu, and R. Bhima Rao
In this paper an attempt has been made to characterize the low grade calcareous graphite ore from Shivaganga region, India. By judicious combination of structural, thermal and chemical analytical techniques, the liberation size of graphite as well as estimation of minerals are determined to establish a feasible beneficiation process. This data show a good correlation. The ore consists of graphite, calcite and quartz as major minerals. The d-values and decomposition of calcite are found maximum at two size fractions i.e., +500 and below 90 microns. The TG and chemical analysis data on quantitative minerals estimation confirms that calcite significantly liberates below 90 micron size fraction and accounts for 60% calcite and 10% graphite minerals distribution. The DTA data show that calcite decomposes between 700–850°C and graphite starts combustion at 850°C. In view of this, to achieve calcite free graphite the ore needs to be calcined below 850°C and ground to 80% passing 75 micron size prior to flotation.
A new process for the partitioning of plutonium and uranium during the reprocessing of spent fuel discharged from fast reactor
was optimised using hydroxyurea (HU) as a reductant. Stoichiometric ratio of HU required for the reduction of Pu(IV) was studied.
The effect of concentration of uranium, plutonium and acidity on the distribution ratio (Kd) of Pu in the presence of HU was
studied. The effect of HU in further purification of Pu such as solvent extraction and precipitation of plutonium as oxalate
was also studied. The results of the study indicate that Pu and U can be separated from each other using HU as reductant.