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 amphoteric acid-base behavior of hydrous zirconium oxide (HZO) was investigated by titrating HZO with 0.05M HNO3 and NaOH at constant ionic strength. The sorption of strontium from 0.05M NaNO3 solution was measured as a function of pH. Abrupt increase in sorption was observed at the equilibrium pH of 9. The experimental titration and strontium sorption data on HZO were evaluated using the constant capacitance model (CCM) and diffuse double layer model (DLM). Various model parameters of Surface Complexation Models (SCM) were estimated, numerically, by non-linear regression. Modeling the sorption and speciation of Sr2+ on HZO indicated that the hydrolysis of Sr2+ to lower charged SrOH+ is the pre-requisite for the abrupt sorption behavior at pH 9.
A rapid and high resolution separation of lanthanides by HPLC technique has been developed using Di-(2-ethylhexyl) phosphoric acid (HDEHP) coated reverse phase column and a-hydroxy isobutyric acid as the complexing reagent for elution. A gradient elution technique has been developed for achieving the separation of the entire lanthanide series. Isocratic elution procedure has also been developed for the separation of lighter (La to Gd) as well heavier lanthanides (Lu to Tb). This paper describes the separation methods developed and their application for the determination of lanthanides in a fission product mixture.
Carrier-free 22Na was separated from bulk quantities of magnesium by both ion exchange and extraction chromatographic techniques. An extraction chromatographic procedure based on di-(2-ethylhexyl) phosphoric acid (HDEHP) coated on to an inert support (Amberlite XAD-7) was developed for the first time for separation of sodium from magnesium. The sorption behavior for sodium and magnesium was studied as a function of percentage of HDEHP loaded on to the inert support as well as pH of aqueous phase. These data were used to arrive at the optimum conditions of separation. In addition, carrier free 22Na was also separated from magnesium using ion exchange chromatographic technique.
A systematic study on the extraction of U(VI) from nitric acid medium by tri-n-butylphosphate (TBP) dissolved in a non-traditional diluent namely 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6) ionic liquid (IL) is reported. The results are compared with those obtained using TBP/n-dodecane (DD). The distribution ratio for the extraction of U(VI) from nitric acid by 1.1M TBP/bmimPF6 increases with increasing nitric acid concentration. The U(VI) distribution ratios are comparable in the nitric acid concentration range of 0.01M to 4M, to the ratios measured using 1.1M TBP/DD. In contrast to the extraction behavior of TBP/DD, the D values continued to increase with the increase in the concentration of nitric acid above 4.0M. The stoichiometry of uranyl solvate extracted by 1.1M TBP/IL is similar to that of TBP/DD system, wherein two molecules of TBP are associated with one molecule of uranyl nitrate in the organic phase. Ionic liquid alone also extracts uranium from nitric acid, albeit to a small extent. The exothermic enthalpy accompanying the extraction of U(VI) in TBP/bmimPF6 decreases with increasing nitric acid and with TBP concentrations.
Commercially available polystyrene-divinylbenzene (PS-DVB) resins functionalized with isothiouronium (Tulsion CH-95), phosphinic
acid (Tulsion CH-96) and methylene thiol (Tulsion CH-97) moieties have been used for separating palladium from nitric acid
medium. Extraction of palladium has been studied as a function of time, concentration of nitric acid and palladium. The distribution
coefficients (Kd, ml/g) of palladium on sulfur based resins (Tulsion CH-95 and Tulsion CH-97) are higher (5000-104ml/g in 0.1M nitric acid) than on Tulsion CH-96 resin and decrease with increasing concentration of nitric acid. The initial
rate of extraction of palladium by Tulsion CH-95 and Tulsion CH-97 resins was very rapid and the time required for the establishment
of equilibrium was a function of palladium concentration in the aqueous phase. The rate data could be fitted by a second order
rate equation and the magnitude of rate constant for the extraction of palladium by these resins (~102M-1. min-1) decreased in the order of: Tulsion CH-95 > Tulsion CH-97 > Tulsion CH-96. The extraction isotherms of Tulsion CH-95 were
fitted by Langmuir adsorption model and the coefficients were obtained by regression. The extraction capacity of palladium
on Tulsion CH-95 was found to be ~20 mg/g at 3M nitric acid. Column experiments have been conducted and the data were fitted
using Thomas model. A column utilization of 75% was achieved for the extraction of palladium by Tulsion CH-95 resin.
Imidazolium nitrate anchored on poly(styrene-divinylbenzene) co-polymer, Im-NO3, has been synthesized and evaluated for plutonium purification. The results are compared with those obtained using Dowex
1 × 4 anion exchange resin. The distribution coefficient (Kd) of Pu(IV) increased with increase in concentration of nitric acid, reached a maximum at 8 M, followed by decrease in Kd values. Rapid ion exchange of Pu(IV) followed by the establishment of equilibrium occurred within 100 min of equilibration
and the data was fitted in to first order rate equation. Variation of distribution coefficient of Pu(IV) as a function of
exchange capacity and nitrate ion concentration suggest the involvement of anion exchange mechanism is responsible for extraction.
The apparent ion exchange capacity was 310 mg/g at 8 M nitric acid. The performance of the Im-NO3 under dynamic condition was assessed by column breakthrough experiments. Radiolytic degradation of Im-NO3 resin in presence and absence of nitric acid (8 M) was studied and the results are reported in this paper.
The sorption of Pu from nitric acid solutions containing oxalate/fluoride was studied using an indigenously available macroporous
bifunctional phosphinic acid (MPBPA) resin. Batch experiments were carried out to obtain the distribution data of Pu(IV) with
a view to optimize conditions for its recovery from nitric acid waste solutions containing oxalate or fluoride ions. The measurements
showed high distribution ratio (D) values even in the presence of strong complexing ions, like oxalate and fluoride, indicating the possibility of recovery
of Pu from these types of waste solution. Column studies were carried out using this resin to recover Pu from the oxalate
supernatant waste solution, which showed that up to 99% of Pu could be adsorbed on the resin. Elution of Pu loaded on the
resin was studied using different eluting agents.