The role of temperature on the distribution of Am3+ and UO22+ was investigated in the extraction systems involving TBP and DOSO as the neutral oxodonors and picrate as the organophilic
counter anion. The inner-sphere water molecules and their substitution by the oxodonor molecules appeared to influence the
extraction constants of these metal ions. The conditional extraction constants for Am3+ were found to be larger (about 3 order of magnitude) than those for UO22+. From the thermodynamics data it appeared that both TBP as well as DOSO bind Am3+ ion through outer-sphere coordination. In presence of 1M NaCl, though the interaction with TBP remains unaltered DOSO tend
to form an inner-sphere complex. On the other hand, UO22+ forms inner-sphere complexes with DOSO and outer-sphere complex with TBP in the absence of salt. In the presence of 1M NaCl,
both TBP and DOSO form inner-sphere complexes. The effect of ionic strength on metal ion extraction was also investigated.
The extraction behavior of Am3+ and UO22+ is investigated employing chloroform solution of 18-crown-6 as the organic phase and picrate solution at pH 3.0 as the aqueous
phase. In contrast to the commonly observed behavior, the extraction of Am3+ is preferred to that of UO22+. This unusual separation behavior is investigated as a function of several variable parameters such as crown ether concentration,
picric acid concentration, inert electrolyte concentration, nature of diluent etc. Thermodynamic parameters are also evaluated.
With increasing global nuclear activities, there is a growing interest in understanding the migration behavior of transuranic elements in the terrestrial environment. The laboratory investigations on the adsorption behavior of AM(III) (10–7M) in aqueous solutions showed that there was not adsorption of Am(III) on glass or polyethylene vials from aqueous solutions at pH<3. The rate of adsorption was found to be inversely related to the (H+) in the pH range 4–7. It was also found to be strongly influenced by stirring/shaking as well as by the presence of particulate matter in the aqueous phase. The presence of particulate matter (>0.6 m) in the aqueous solutions significantly inhibits the adsorption rate. Attempts to fit the kinetic data (collected on filtered [particle size >0.6 m] or unfiltered distilled water at pH 6) to the reversible or irreversible first order rate equation did not successfully indicate the complexity of the adsorption process. The presence of 20mg/liter of humic acid at pH 6.3 completely inhibits the adsorption of Am on glass surfaces.
Authors:C. Pawaskar, P. Mohapatra, and V. Manchanda
The extraction behavior of several metal ions viz., Am3+, Eu3+, UO22+, Th4+, Sr2+ and Cs+ was investigated from sulphate medium employing phosphotungstic acid (PTA) and polyethylene glycol (PEG). The influence of
various parameters such as pH, PTA concentration, PEG concentration and salt concentration was studied. The order of extraction
followed the trend: Am3+>Eu3+>>Th4+>UO22+>Sr2+>Cs+ which deviate significantly from the reported order with conventional solvents. The relatively poor extraction of UO22+, Sr2+ and Cs+ was ascribed to their lack of interaction with the phosphotungstate anion. The separation behaviour of Am3+ vis-a-vis Eu3+ was also investigated under different experimental conditions.
Authors:P. Pathak, R. Veeraraghavan, and V. Manchanda
The distribution behavior of uranium and thorium has been investigated in a biphasic system of different aqueous nitric acid
concentrations and a solution of tris(2-ethylhexyl) phosphate (TEHP) inn-dodecane at 25°C. The effect of different uranium and thorium concentrations in the aqueous phase on the extraction of these
metal ions is evaluated. These results indicate that TEHP is a better choice than tri-n-butyl phosphate (TBP) for the separation of233U from the irradiated thorium matrix.
Studies on the individual potentiometric determination of uranium and plutonium in a single aliquot have been initiated recently
in our laboratory. It was required to adapt the reported procedures (for the precise determination of uranium and plutonium
individually when present together in a sample) at various stages to make them suitable for the successive application of
the procedures to the same aliquot. Two alternative schemes are proposed in the present work. In the first, plutonium is determined
by HClO4 oxidation followed by the determination of total uranium and plutonium by Zn(Hg) reduction. In the second, plutonium is determined
by AgO oxidation following the determination of total uranium and plutonium by Zn(Hg) reduction. Amount of uranium is computed
in both cases from the difference of two determinations. Precision for the assay of plutonium and uranium was found to be
±0.25% and ±0.35%, respectively, at milligram levels.
Authors:J. Shukla, V. Manchanda, and M. Subramanian
A rapid method for the synergistic extraction and spectrophotometric determination of plutonium(VI) in milligram amounts using
a mixture of thenoyltrifluoroacetone (TTA) and tributyl phosphate (TBP) in benzene has been developed. Quantitative extraction
is obtained from aqueous solutions of pH=2 affording separation from many commonly occurring impurities, viz., thorium, fission
products and cladding materials. The precision and accuracy of the method has been found to be∼1%. The study of the solid
product isolated from the extraction system indicates the stoichiometry of the extracted species as PuO2(TTA)2 TBP.
Authors:A. Bhattacharyya, P. Mohapatra, and V. Manchanda
Separation of trivalent actinides (An(III)) and lanthanides (Ln(III)) is a challenging task in the nuclear fuel cycle due
to their similar charge and chemical behaviour. Some soft donor ligands show selectivity for An(III) over Ln(III) due to the
formation of stronger covalent bonds with the former. The extraction behaviour of Am(III) and Eu(III) is studied in the present
work with a mixture of Cyanex-301 (bis(2,4,4-trimethylpentyl)di-thiophosphinic acid) with several various ‘N’, ‘O’ or ‘S’ donor neutral ligands. Comparison of the
data was done with that of the oxygen donor analogue of Cyanex-301, i.e. Cyanex-272 (bis(2,4,4-trimethylpentyl)phosphinic acid). Effect of the organic diluent on the extraction behaviour of Am(III) using Cyanex-301
in presence of ‘N’ donor synergists was also studied. Ab initio molecular orbital calculations were carried out using GAMESS
software and charges on the donor atoms were calculated which helped in understanding the co-ordination chemistry of the ligands
and explained the separation behaviour.
Authors:P. Mohapatra, R. Veeraraghavan, and V. Manchanda
The extraction behavior of Th(IV) from dilute nitric as well as perchloric acid medium using 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone
(PMBP) and its mixture with tri-n-octyl phosphine oxide (TOPO) was investigated. The species of the type Th(X)(PMBP)3·(HPMBP) and Th(X)(PMBP)3·(TOPO) were extracted for the binary and ternary extraction systems, respectively, where X=NO3− or ClO4−. The presence of 1.25·10−5M Th carrier in the aqueous phase resulted in the extracted species of the type of Th(PMBP)4 and Th(PMBP)4·(TOPO), respectively. The extraction constant (logkex) for the binary species Th(PMBP)4 was found to be 6.89±0.01 while the overall extraction constant (logK) for the ternary species Th(PMBP)4·(TOPO) was calculated to be 13.17±0.06.
Authors:G. Rama Rao, V. Manchanda, and P. Natarajan
Present work summairzes a method for the estimation of uranium in the presence of plutonium involving the reduction of uranium to U/IV/ and plutonium to Pu/III/ by Zn/Hg/ followed by the selective oxidation of Pu/III/to Pu/IV/with HNO3 catalyzed by molybdate in the presence of large sulphate concenration [5M H2SO4+1.5M /NH4/2SO4]. The oxidation of U/IV/ by K2Cr2O7 is then carried out in the presence of excess of Fe/III/ and Al/NO3/3 to a sharp potentiometric end point. R.S.D. obtained for 20 determinations of uranium /3–6 mg/ was 0.3% in the presence of 0.35 mg of plutonium. Larger quantity for plutonium was found to interfere.