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Extraction of Thorium and Uranium from Chloride Solutions by Tri-N-Butyl Phosphate and Tri-N-Octyl Phosphine Oxide

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Extraction of Thorium and Uranium from Chloride Solutions by Tri-N-Butyl Phosphate and Tri-N-Octyl Phosphine Oxide Journal of NUCLEAR SCIENCE and TECHNOLOGY, 1, No.5, p.155~462 (1964). 155 Extraction of Thorium and Uranium from Chloride Solutions by Tri-n-Butyl Phosphate and Tri-n-Octyl Phosphine Oxide Kenju WATANABE* Received November 4, 1963 The extraction of thorium and uranium chlorides by TBP and TOPO was studied. The composition of complexes extracted from the chloride solutions of low acid concentration was established by partition study to be UO2Cl2(TOPO)2,UCl4(TOPO)2, ThCl4(TOPO)2 and UCl4(TBP)2. Composition of the thorium complex in the TBP phase free from hydrochloric acid was revealed by infrared study to be ThCl4(TBP)4. The extraction behavior of thorium chloride by TBP was different from that of U(IV) and Pu(IV) chloride, and the composition of the complex was presumed to be HThCl5(TBP)4 in the extraction from concentrated chloride solution containing hydrochloric acid. The extraction of thorium, uranium and drochloric acid. The extraction of Pu by TBP plutonium chlorides by tri-n-butyl phosphate from hydrochloric acid is also discussed. (TBP) or tri-n-octyl phosphine oxide (TOPO) has been studied by many workers. The EXPERIMENTAL distribution of uranyl chloride between TBP and hydrochloric acid was reported by Reilly(1), General techniques used were similar to Irving(2), Larsen(3) and Ishimori(4). Naito pro- those in previous studies(4)(10).Measurements posed the composition of the extracted complex were made at a constant temperature of 25dc. to be UO2Cl2(TBP)2(5). According to Iwase(6), Reagents: TBP was purified by the usual in the extraction of uranium tetrachloride method(10)~(13).TOPO was obtained from East- from hydrochloric acid solution by TBP, the man Organic Chemicals and Dojindo & Co., composition of the species extracted is UCl4• Ltd. The TOPO was purified to remove 3TBP. The extraction behavior of thorium acidic impurities: A xylene solution of TOPO chloride between the aqueous and TBP phases was scrubbed three times with 5 % sodium was investigated by Peppard(7), but the extrac- bicarbonate solution, twice with water, twice tion mechanism still remains uncertain. The with 1M hydrochloric acid and three times extraction behavior of Th between TOPO with water, all in succession. Other reagents and hydrochloric acid solutions was studied used were of A. R. grade. by Ross(8), who determined the extracted Radioactive tracers: The extraction of U species to be ThCl4¥HCl¥3TOPO. He also and Th was studied by the use of 237Uand studied the extraction of several metal ions 231Th prepared by g-ray irradiation of natural including uranyl chloride by TOPO(9). In most U and Th with a linear accelerator(14). of the studies mentioned above, excepting the Thorium-234 milked from 238U(15)was also used one by Naito, the metal ions were extracted as thorium tracer. Plutonium-239 was pre- from fairly concentrated acidic solutions, where pared by neutron irradiation of U in JRR- competitive extraction of the metal chloride l(16)(17). and hydrochloric acid was observed. Uranium(IV) was prepared by reduction The present paper endeavors to elucidate with zinc metal; and Pu(IV) by the addition the extraction mechanism by comparing the of 0.2 M ammonium nitrite. extraction of thorium and uranium chlorides by TBP and TOPO from chloride solutions * Japan Atomic Energy Research Institute, Tokai- with that from solutions containing only hy- mura, Ibaraki Pref. 9 156 J. Nucl. Sci. Tech. Infrared measurement: A Koken DS Type 301 spectrometer equipped with a rock salt prism RESULTS AND DISCUSSION was used in the infrared measurements. The techniques were essentially the same as de- 1. TOPO-Chloride Solution System scribed in the reports(5)(18) by Naito, et al. The measurements of the distribution ratio Determination of thorium in TBP phase: In Kd for Th, U(IV) and (VI) were made by the the infrared study, the concentration of Th extraction from solutions in various concen- in TBP phase was determined as follows: trations of both hydrochloric acid and chloride. Thorium in TBP solution of a known volume The chloride solutions was added with 0.1 M was stripped into aqueous solution and precip- hydrochloric acid to prevent hydrolysis. In itated with oxalic acid. Then the Th oxalate these cases, the concentration of metal ions in was ignited to oxide, and weighed. the aqueous phase was maintained at less than Distribution of U(IV) Distribution of Th between 1% between 1% TOPO- Distribution of U(VI) between TOPO-toluene and Chloride toluene and Chloride 1% TOPO-toluene and Chloride Solutions Solutions Solutions Fig.1 Fig.2 Fig.3 10-4 M. The results obtained are shown in As is shown in Figs. 1, 2 and 3, the Kd Figs.1, 2 and 3. values for Th,U(IV) and (VI) in the extraction In Fig.1, the dotted lines show the results from solutions of low hydrochloric acid con- obtained by the use of TOPO as received, while centration are approximately the same as with TOPO scrubbed with sodium bicarbonate those from the corresponding chloride solutions solution the results are as indicated by the containing 0.1 M hydrochloric acid. In the solid lines. It is likely that the TOPO as region of more concentrated solutions, how- received contains some impurities of acid form ever, the Kd values in the hydrochloric acid seeing that Kd values increase again with system show a maximum, whereas those decreasing acidity in the region of hydrochloric in the chloride solution system do not and acid concentration less than 1 M, while with continue to increase evenly with the chloride TOPO scrubbed with alkali solution Kd con- concentration. The decrease of Kd values in tinues to decrease down to lowest concentra- the region of high acid concentration may be tions. Therefore, in this work, the purified explained as competitive extraction of the TOPO was used to avoid the influence of acidic metal ions and hydrochloric acid, as pointed impurity. out by some investigators(5)(19)~(21). According 10 Vol.1, No.5 (1964) 157 to Naito(5), Kd values for metal ions of same because the complex concentration in the valency extracted in the same extraction organic phase is low. If the measurement is system should have a maximum at nearly the made in the region where little variation of same acid concentration. In fact, in the (fH+) is expected, one can determine ap- extraction by TOPO of thorium and uranium proximately the value of (n-m) from the slope chlorides, both tetravalent, the Kd values for of the curve relating logKd(M) to logCH+. these metal ions assume maximum values at Such curves are reproduced in Fig.4, for the about the same hydrochloric acid concentration case where sodium chloride was added to of 7.5~8 M (Figs.1 and 2), maintain the constant chloride concentration. Mechanism of extraction: In the present From this figure, it is concluded that the systems, the extraction mechanism of metal values of (n-m) are zero for Th, U(IV) and chloride may be expressed by the equation (VI), thus establishing that the complexes of TOPO and these metal ions do not contain hydrogen ion. (1) where M+m indicates a metal ion and S an extracting reagent, while n and m are integers. When the solute concentration in the organic phase is low and it is assumed that the all metal ions in the organic phase contribute to the formation of the complex, the following equation for the distribution ratio, Kd(M) can be derived: (2) where f and C respectively are the activity coefficient and equilibrium concentration of the corresponding term indicated by the suffix, Variation of Kd Values for Th, U(IV) and Cd0 is the initial concentration of the solvent and (VI) with Acid Concentration Aq. soln. NaCl+HCl, [Cl-]=5M in the organic phase. The extraction mecha- Fig.4 nism can be determined by finding the values of n, (n-m) and m. Since the presence Solvent dependence: When the Kd(M) is of hydrochloric acid causes competitive ex- measured while keeping the concentration of traction of metal ion and acid which com- chloride and hydrochloric acid constant, Eq. plicates the analysis of extraction mechanism, (2) becomes the concentration of acid must be kept as low Kd(M)=const.,(f0d)m,(C0d)m.(4) as possible to simplify the analysis. On the If the measurement is made at low solvent other hand, it is known that hydrolysis of concentration, the value of m is obtained by Th begins from about pH2(22)~(24). Bearing plotting logKd(M) vs. logCd0since the variation these facts in mind, an acidity of 0.1 M was of fd0 is small under this condition. The chosen as experimental condition for the solvent dependence curves for Th, U(IV) and chloride solution system. The amount of (VI) are shown in Fig.5. From the slopes of hydrochloric acid extracted into TOPO phase these lines the value of m is determined to be is very small under this condition(25). 2 for all these metal chlorides. Acid dependence: If the Kd is measured at Chloride dependence: In a similar way, one constant concentrations of the TOPO and chlo- can determine the chloride dependence n by ride, Eq.(2) becomes measuring Kd(M) under constant concentration Kd(M)=const.,(fH)n-m,(CH+)n-m(3) of solvent and hydrochloric acid, and varying where it is assumed that (fcomplex) is constant the concentration of chloride. In this case, 11 158 J. Nucl. Sci. Tech. U(IV) and (VI) by TOPO are ThCl4(TOPO)2, UCl4 (TOPO)2 and UO2Cl2(TOPO)2.
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