It was found that lead reacts with 18-crown-6 (L) and tungstosilicic acid (H4A) in acidic solutions and a compound with low solubility is formed what was confirmed by radiometric titration methods. Coprecipitation of complexion cation of PbL2+ with similar complexion cations of calcium, strontium and barium was studied. Formation of low soluble salts was utilized for separation of Pb from Ca, Sr and Ba from 1 mol·dm–3 HNO3. The ratio of Pb/Ca, Pb/Sr and Pb/Ba in the precipitation or separation factors Spb/M undoubted depends on the ratio of the stability constants of lead and metals with 18C6 (
M), what can be used for determination of more precise constant stability
The development of a rapid and reproducible method for the separation of plutonium from soil samples is described. Tetravalent plutonium is extracted from 8M HNO3 into 30% Aliquat-336/toluene mixture. Uranium and thorium are removed with nitric and hydrochloric acid washes. Plutonium is backextracted with HCl–H2C2O4 and HCl–HF solutions. Plutonium is coprecipitated with NdF3 and filtrated onto a 0.1–0.2 m membrane filter to prepare a source for -spectrometry. The chemical yields of separation are about 50–60%.
The rate of pertraction of Sr2+ by 18-crown-6 (18-C-6) ether and picric acid in bulk liquid membrane systems containing various surface-active substances depends not only on the concentration of 18-C-6 and picric acid but also on the presence of various surface-active substances.
The selective separation ability of the cyclic crowns, known for liquid-liquid extraction, e.g. alkali metals, is found to be effective for emulsion membrane extraction. 18-C-6, DB-18-C-6, DC-18-C-6 crowns were used as carriers. The co-transport of the ionic pair SrL2+. 2A through the membrane has been studied. Calcium was considered as a main competing ion. Even in the case of 20-fold preconcentration, there have been found conditions under which the pertraction process can reach Sr/Ca separation factors of about 500 and the yield of strontium is high (95–98%). The presence of calcium up to 1000-fold excess has no influence on the yield of strontium (1.10–5M). The calcium content in the isolated emulsion was caused by second emulsification of the outer solution. The influence of potassium on strontium pertraction has been studied and some transport data of Cs and Y have been obtained.
The possibility of simultaneous extraction of palladium and technetium from nitrate solutions was investigated using tri-n-octylamine
(TOA) solutions in carbon tetrachloride as a heavy, non-flammable diluent. Conditions of technetium extraction being essentially
known, the main attention was focussed on the extraction of palladium which was studied in dependence on the concentration
of nitric acid, salts (nitrates, chlorides, nitrites), urea and palladium. A strong decrease of Pd extraction with 10% TOA
in CCl4 has been found above a palladium concentration of 10−4M but in the presence of chlorides and nitrites a satisfactory high distribution can be preserved. Both Tc and Pd extracted
with TOA/CCl4 can be stripped into dilute ammoniacal solutions. An extraction procedure for the simultaneous isolation of Pd (80% yield)
and Tc (99%) from fission product waste solutions (0.20 g Tc and 0.17 g Pd/dm3 0.5–1.0M HNO3) is proposed.
The transport of metal ions (Ca2+, Sr2+, Ba2+, Na+, K+, Cs+) through hollow fiber supported dichlorobenzene liquid membrane has been studied. The transport of cations using 8-crown-6 ether as a carrier and picrate as co-counter ion as well as a pertraction device and capillary isotachophoresis (ITP) measurement of the cation concentration is described.
Authors:V. Mikulaj, P. Rajec, A. Švec, N. Cuong, and V. Ahn
A continuous extraction device for preconcentration of metals with light phase internal recycle has been developed. This system was used for preconcentration of cobalt and uranium from 20–30 dm3 samples with 10.8 dm3/hours feed rate. The emulsion membranes were created of surfactants and LIX 64 N (for cobalt) or di-2ethylhexyl-phosphoric acid (for uranium) as a carrier to control stability and permeability for long time periods. The results from continuous extraction of cobalt and uranium using the device constructed have shown the possibility to reach 100–200-fold preconcentration of metals with high yield (min. 92%).
Authors:P. Rajec, V. Švec, V. Mikulaj, and R. Hanzel
Lead as well as strontium form low solubility compounds of composition (ML2)2A·nH2O, (M=Pb2+, Sr2+), in the presence of 15-crown-5 (L) and tungstosilicic acid (H4A) in acid media as found by radiometric precipitation titration. “Sandwich” structure of crown-ether complexes of lead and
strontium could be expected due to the small size of cavity of 15-crown-5. Coprecipitation of PbL2/su2+ with crown complexes of strontium cation after adding tungstosilicic acid was studied in 0.01 mol·dm−3 HNO3. A significant influence of H+ cation in 1 mol·dm−3 HNO3 on coprecipitation of lead was observed. Formation of HL+ complexes by protonisation of 15-crown-5 competes to the formation of ML22+ complexes (approximately twenty percent of 15-crown-5 are used for creation of HL+ complexes). Formation of low solubility salts was utilised for separation of lead from strontium in 0.01 mol·dm−3 HNO3. The ratio of constant stability of lead and strontium β‘ with 15-crown-5 in 0.01 mol·dm−3 HNO3 was calculated. The separation factor S(Pb/Sr) depends on the ratio of stability constants βPbL2/βSrL2 The precipitation method can be used for separation of metals with high constant stability with crown ethers from solutions
containing other metals in the case of gradual addition of crown.
Authors:P. Rajec, V. Mikulaj, P. Husarčik, and V. Švec
The coprecipitation of radium with strontium or calcium, 18C6 and tungstosilicic acid was studied. It was determined that radium is coprecipitated with Ca and Sr and mixed compounds are fomed. It was also find the yield of Ra depends on the ratio of stability constants of metals present in a solution with 18C6. The stability constant of Ra with 18C6 was determined using a precipitation method.
Authors:V. Mikulaj, P. Rajec, A. Švec, and J. Macková
Transport of strontium through supported hollow fiber dichlorobenzene liquid membranes has been studied. The possible mechanism of strontium transport with 18-crown-6 ether as a carrier and picrate as co-counter-ion as well as the construction of a pertraction device with on-line radiometric detection of strontium using85Sr tracer is described. Preliminary results of strontium pertraction in a recycling and one-pass mode with different concentrations of crown are shown.