1 inorg. nach Chem.,1973, Vol 38. pp.2813-2524, Pergamon Press. Printed in Great Britain SOLVENT EXTRACTION OF TRIVALENT ACTINIDES AND LANTHANIDES FROM A MIXTURE OF CARBOXYLIC AND AMINOPOLYACETIC ACIDS J.J. FARDY and J. M. PEARSON Chemical Technology Division, Australian Atomic Energy Commission, Private Mail Bag, Suther- land, N.S.W., Australia, 2232 (Received 11 August 1972) Abstract—The purity of di(2-ethylhexy!)phosphoric acid (HDEHP) markedly influenced the separa- tion of cerium from americium in a lactic acid solution containing diethylenetriaminepentaacetic acid (DTPA) but had little influence on separations involving the least extractable rare earths. curopium and promethium. Synergism occurred in the solvent extraction of these elements by mixtures of thenoyltrifluoro- acetone (HTTA) and neutral organophosphates (S) from the same aqueous medium. This effect decreased as S was changed from a phosphine oxide, through phosphonate, to the neutral alkyl phosphates. Tracer studies showed that the composition of each extracting species is given by the general formula M(TTA),S: where M is a trivalent actinide or lanthanide. These species were in- dependent of the diluent used but the extraction coefficients of the metal ions decreased by a factor of 10* from cyclohexane to chloroform. At a constant pH the extraction of americium and cerium ‘was inversely proportional to DTPA concentration in the region 10 *~10-'M. At lower DTPA concentrations the cerium dependence decreased rapidly while the americium increased until at 10-*M. concentration of DTPA the extraction order was reversed. When the DTPA concentration was constant the separation of cerium from americium increased with increasing pH. reaching a constant ‘maximum at pH 2:6 and above. INTRODUCTION THE YIELD of transplutonium elements from the irradiation of plutonium is usually only a few per cent of the target material. Consequently, the atom ratio of fission product lanthanides to the transplutonium elements is approximately 10/1. The The separation of the lanthanide group of elements from the trivalent trans- plutonium elements is difficult due to their similarity in chemical properties but has been achieved, with various degress of success, by complexing the transplutonium elements with chloride[!-4], thiocyanate [5-7] and aminocarboxylic acids[8, 9]. G. R. Choppin and A. Chetham-Strode,J. inorg. nucl. Chem. 18,377 (1960), M.H. Lloydand R. E. Leuze, Nuct. Sei. Engng 11,274 (1961). E. K. Hulet, R. G. Gutmacher and M. S. Coops, J. inorg. nucl. Chem. 17, $50(1961). R. D. Baybarz, B. S. Weaver and H. B. Kinser, Nucl. Sci. Engng 17. 457 (1963). J. S. Coleman, R. H, Penneman, T. K, Kennan, L. E. LaMer, D. E. Armstrong and |. B. Asprey. J. inorg. nucl. Chem. 3,327 1957), 6, S, W. Rabideau, L. B. Asprey, T. K. Kennan and t. W. Newton, Proc. 2nd Int. Conf. Peaceful Uses Atom. Energy, Geneva 1958, Vol. 28, p. 361. United Nations, New York (1938). 7. J. P. Surls and G. R. Choppin.J. inorg. nucl. Chem. 4, 62 (1957). 8. E.J. Wheelwright, F. P. Roberts, L. H. Bray, G. L. Ritter and A. L. Bolt, USAEC Rep. BNWL- SA-1492, 1968. 9. B.S. Weaverand F. A. Kappelmann.J. inorg. nucl. Chem. 30, 263 (1968). 25032514 J.J, FARDY and J. M. PEARSON Peppard et al.[10, 11] obtained overlap in the extraction of these elements when using organophosphorus reagents as extractants in mineral acid systems but Weaver and Kappelmann[9] added a mixture of carboxylic and aminocarboxylic acids and obtained complete separation through preferential complexing of the actinides. This paper examines the carboxylic-aminocarboxylic acid system further using di(2-ethylhexyl)phosphoric acid (HDEHP) and synergistic ex- tractants. The majority of studies was confined to lactic acid solutions containing DTPA, EXPERIMENTAL, Materials All chemicals used in these studies were of reagent grade or the highest purity obtainable from ‘commercial sources, with the exception of those purified as described below. ‘The HDEHP was purchased from Albright and Wilson Ltd. and Koch-Light Laboratories Ltd The former was purified by the method of Peppard et al. [10], .c. heating with 6M hydrochloric acid to destroy pyro esters by hydrolysis, water scrubbing to remove the acid, partitioning with diethyl ether and ethylene glycol, combining the ether extracts and removing the ether by evaporation under re- duced pressure at room temperature. The Koch-Light product was purified by the procedure of ‘Schmitt and Blake[12]. In this method the successive steps were acid hydrolysis, conversion to the sodium salt, extraction of the neutral species with petroleum ether. removal of iron by filtration, re- conversion to the acid form and removal of monoalkyl phosphoric acid with ethylene glycol. The radioactive tracer isotopes “*Am, “Ce, "Eu, "Pm and *'Y were obtained from The Radio- chemical Centre, Amersham, and “Cm from the Oak Ridge National Laboratory Isotope Sales Department, The sodium salt of DL-lactic acid-1-1"C was purchased from Amersham, Apparatus and procedures Equilibrium distribution coefficients, E,°, defined as the ratio of the concentration of the element in the organic phase to the concentration in the aqueous phase. were determined by the following method. Equal volumes of the two phases, contained in one fluid ounce screw-cap glass bottles whose caps were fitted with polythene inserts, were shaken on a constant temperature (25°-+ 0.1°C) shaking machine (Laboratory Thermal Equipment). The phases were separated and the concentration of the tracer in each phase was determined by measuring the gamma activity of a 0-5 ml sample in a well type gamma scintillation counter or by determining the alpha or beta activity of a 0-1 ml sample added to 10 ml of a liquid scintillation medium on a liquid scintillation spectrometer. A ‘minutes was sufficient to reach equilibrium for the extractions with HDEHP but this was extended to ‘overnight for the extractions with other solvents. RESULTS AND DISCUSSION Influence of HDEHP purity Weaver and Kappelman|9] demonstrated that extraction by HDEHP from lactic solutions containing diethylenetriaminepentaacetic acid (DTPA) completely separates the actinides from the lanthanides. However commercial HDEHP can contain varying amounts of monoalky! phosphoric acids, trialkylphosphates and alcoholic impurities. HDEHP from two different sources and purified by two different methods[10, 12] was used in a series of extractions to assess the influence of this parameter on lanthanide-actinide separation. The results are summarised in Table | in which the separation factor is defined as the ratio of the values of E,¢ for the two elements. The separation of promethium and europium from ). F, Peppard, G. W. Mason. J. L. Maier and W. J. Driscoll.J. inorg. nucl. Chem. 4, 326 (1957), . F. Peppard, G. W. Mason and W.J. Driscoll, J. inorg. nucl. Chem. 12, 144 (1959). DF. DF. . J. M. Schmitt and C. A. Blake, USAEC Rep. ORNL-3548, 1964.Solvent extraction of trivalent actinides and lanthanides 2515 Table 1. Extraction of americium and lanthanides from IM lactic acid, 0-0SM DTPA at pH 3-0 by 0-3M HDEHP in cyclohexane HDEHP Separation Factor Source Purification Cefam = Pm/Am — Eu/am Albright and Wilson Nil 1220 404 Albright and Wilson —Pepparderal.(10]_ 21143955 Koch-Li Nil 7 468 Koch-Light Schmittand Blake(12] 162-4 44:2 americium depended little on the purity of the HDEHP extractant. Separations involving the more extractable cerium were affected markedly, the separation factor increasing by a factor of two after purification of the solvent, and the same effect was observed when americium was replaced by curium. Extraction by other solvents Extractions from mixtures of lactic acid and DTPA were examined for other solvents. Studies were restricted to americium and cerium to minimise the number of equilibrations in these sorting tests. Substitution of the neutral alkyl phosphine oxides. amines or chelating extractants for the alkyl phosphoric acid. HDEHP. did not lead to significant extraction of either americium or cerium (Table 2). However, the synergistic combination of a neutral alkyl phosphine oxide (rri-n-octylphosphine oxide, TOPO) and a chelating agent (thenoyltri- fluoroacetone. HTTA) yielded good extractions and a separation factor of approximately forty. While this separation factor was only one quarter of that obtained with the solvent HDEHP, it was far superior to values recorded for other solvent mixtures. Synergism in the solvent extraction system HTTA(neutral organophosphorus ester The extent of this synergic effect was examined by measuring distribution data for 0-2 molar TOPO or HTTA in cylohexane and from mixtures of these ex- ‘Table 2. Extraction of americium and cerium from 1M lactic acid, 0-05M DTPA at pH 3:0 by various solvents in cyclohexane Extraction coefficients Solvents Separation factor Ce Am 03M HDEHP 373 0:38 03M Primene JMT <001 <001 03M Alamine 336 <001 = <001 O-3MAliquat 336 123 087 bat 03M TOPO <001 << 001 03M HTTA < 001 <0-01 01M TOPO/O-IM HTTA 8:56 0-20 416 03M HDEHP/0-1M TOPO 33:30 0-22 150-1 03M HDEHP/0-IMTBP* 30-20 019 159-0 “TBP Tri-n-butyl phosphate2516 J. J. FARDY and J. M. PEARSON tractants and an aqueous phase containing 0-1M lactic acid and 005M DTPA at PH 3-0, The results are summarized in Fig. 1. Extraction coefficients increased by a factor of greater than 10° for americium and 10° for cerium in a cyclohexane solution containing 0-14M HTTA and 0-05M TOPO compared with either 0-2 M HTTA or 0-2 M TOPO alone. However the separation coefficient between these elements had an approximately constant value (40) over the range of HTTA/TOPO mixtures investigated. The solvent mixture, 0-18 M TOPO-0-02M HTTA, was chosen, and the studies extended to include europium and promethium because these two generally give the lowest separation factor from actinides. Yttrium, although not a rare earth was also studied because it is a trivalent element which displayed high ex- traction in earlier studies[9]. Again, the extraction coefficients of europium and Promethium were lower than for cerium as seen in Table 3 and the separation factor between europium and americium fell to 4-3, The extraction pattern was very similar to that exhibited by HDEHP and yttrium was more extractable than cerium. Normally the higher actinides, californium and beyond, extract more readily than americium so that overlap in the extraction of actinides and lan- thanides might be expected in the region of neodymium and californium. extroction coefficient &. ee or HTTA molerity CBO OO 006 00 TOPO molarity Fig. 1. Synergic effects due to HTTA/TOPO. Aqueous phase: IM lactic acid 0-05M DTPA at pH3-0of trivalent actinicles and lanthanides 2517 Table 3. Extraction of some lanthanides and yttrium from 1M lactic acid, 0-SM DTPA. pH 3:0 by 0-18M TOPO-0-2M HTTA in cyclohexane Separation Distribution factor Lanthanide coefficient’ RE/Am Ce 278 Bel Eu o-4i 43 Pm 0-64 67 Y 15-1 236 Influence of pH Changes in the extraction of cerium and americium were examined at constant concentration of extractant, lactic acid and DTPA but at various pH values from 1-8 to 3-5. The separation between these two elements increased with increasing pH and reached a constant maximum at pH values 2-6 and above (Fig. 2). The separation factor was improved when lactic acid was omitted from the solutions but this led to greater difficulty in controlling the pH. Influence of DTPA concentration The results obtained when the DTPA concentration was varied while the pH was maintained constant at 3-0 are summarized in Fig. 3. The extractions of . ° 5 oth io! s o © Am —otPa = DT PAvlectic ° Sis Eas 10° {oj } jj oj 4 1 0 Tie F092 Fa Fe PESO BE a BO pl Fig. 2. Dependence of extraction on pH in the presence and absence of 1 M lactic acid. Aqueous phase: 0-05M DTPA, variable pH. Organic phase: 0:12M TOPO/0-08M HITA.2518 J. J. FARDY and J. M. PEARSON coefficient extroction Bio IF 10 Concentration of DTPA, M oF 0" Fig. 3. Dependence of extraction on the concentration of DTPA, Aqueous pha: lactic acid, variable DTPA concentration, pH 3-0. Organic phase: 0-18M TOPO/0-02M HTTA. Table 4, Extraction of americium and cerium rom various 1M carboxylic acid solutions at pH3-0 Extraction Separation Extractant A coefficient Am factor Ce/Am 018M TOPO-0-02MHTTA — Formic > 10° Acetic > 10° Lactic 140:2 16 ‘Tartaric > 10° Citric 1-25 10 Sulphosalicylic > 10° 018M TOPO-0-02M HTTA —Cirtic-0-0SM DTPA 0-075 10-0 0-12M TOPO-0-08M HTTA. o4 18-2 0-06M TOPO-0-14M HTTA. 30-6 12-0 002M TOPO-0-18M HTTA. 147 7 americium and cerium were inversely proportional to approximately the first power of the DTPA concentration in the region 10~* to 10-'M. However at lower concentrations of DTPA ( < 10-'M) the cerium dependence decreased rapidly while the americium dependence increased until at a concentration of 10-‘M DTPA the order of extraction was reversed.Solvent extraction of trivalent actinides and lanthanides 2519 Influence of concentration of lactic acid The extraction dependencies of americium and cerium as a function of lactic acid concentration were measured at constant DTPA concentration and pH (Fig, 4). The extraction of americium decreased slowly with increasing lactic acid concentration. The inverse relationship for the extraction of cerium was more pronounced, and the effect was greatest at high concentrations of lactic aci (> 0-2M). Consequently, the separation factor for these elements was halved in the region 0-5-1 M compared to the region < 0-1M lactic acid. Extraction coefficients for europium and promethium were remeasured in 0-1 M lactic acid solution containing 0-05 M DTPA and adjusted to pH of 3-0 to determine whether their separation factors relative to americium increased as the lactic acid con- centration was decreased. However, there was no marked change. Extractions from carboxylic acids The extraction of americium and cerium from | M solutions of a number of carboxylic acids, adjusted to pH 3-0, was examined. The extraction coefficients of both elements exceeded 10° except for solutions containing lactic or citric acid. Americium was extracted to a greater extent than cerium from lactic acid solutions while in citric acid solutions the TOPO/HTTA extractant showed no preference (Table 4). Measurements were also made with various mixtures of TOPO and 0! - ~ 10% 2 ob sho 3 a ~ 8 ta, 5 S No 3 2 ol Woo B u “ wl n tot oF 107 10° Concentration of lactic acid, M Fig. 4. Dependence of extraction on the concentration of lactic acid. Aqueous phase: 005M DTPA, variable lactic acid concentration, pH 3-0. Organic phase: 0-18M TOPO/ 002M HTTA,2520 J.J. FARDY and J. M. PEARSON HTTA and citric acid containing DTPA, but separation factors were lower than those obtained in the comparable lactic acid system. Choice of aminopolyacetic acid Earlier studies[9] clearly showed the superiority of DTPA over a number of aminopolyacetic acids, and a spectrophotometric study of the complexing of americium(III) with aminopolyacetic acid by Delle Site and Baybarz(13] further supported this choice. Therefore we chose to limit this study to DTPA. Extraction from other neutral organophosphorus esters Similar synergic effects were obtained when other neutral organophosphorus esters, tributyl phosphine oxide (TBPO), dibutyl butyl phosphonate (DBBP) and TBP were substituted for TOPO. The results revealed little difference between the phosphine oxides but the remaining esters varied in the same order as their expected donor properties, viz. phosphine oxides > phosphonates > phosphates. The influence of diluent The effect of the diluents cyclohexane, hexane, carbon tetrachloride, benzene and chloroform on the partition coefficients of americium and cerium was meas- ured (Table 5) for extraction by 0-18M TOPO-0-02 M HTTA, from I M lactic acid, containing 0-05 M DTPA at pH 3-0 and spiked with tracer "Am or "Ce. Very large changes in the synergic effect ( > 10) occurred in this series of diluents. This is analogous to the effect reported by Healy[14] for a similar extractant mixture in a mineral acid system, 0-01 M hydrochloric acid. Table 5. Effect of diluent on americium and cerium extrac- tion from IM lactic acid, 0-05M DTPA at pH 3-0 by 0:18M TOPO-0-02M HTTA in various diluents Diluent Cyclohexane Hexane CCl, Benzene CHCl, Ee Am 64 55 024 006 =< 10% EgCe 194-2 195312 0-007 Mechanism of extraction Studies of synergism with HTTA in the solvent extraction of metallic species (14, 15] have shown that in hydrochloric acid systems the reaction can be des- cribed by the general equation Mi +XHTTA oy) + YS = MCITA)2S xo) + 2Hin where the subscripts a and o denote the aqueous and organic phase respectively, Sa neutral organophosphate and x and z have a value of 3 and y a value of 2 for 13. A, Delle Site and R. D. Baybarz, J. inorg. nucl. Chem. 31,2201 (1969). 14. T. V. Healy, J. inorg. nucl. Chem. 19, 314 (1961), 15. T. V. Healy,J. inorg. nucl. Chem. 19, 328 (1961).Solvent extraction of trivalent actinides and lanthanides 2821 trivalent rare earths and actinides. However similar studies in a nitric acid medium by Irving and Edgington(16, 17] revealed that the formation of the synergic species, involving a mixed nitrate complex, could be represented by the general equation Min + (x— 1) ATTA) + NOs + YScoy = M(TTA),-; NOjSyo)+ 1) He, Information on the species extracted into the cyclohexane phase of our system was obtained by maintaining constant two of the three variables, HTTA,. TOPO and hydrogen ion concentration, while changing the third. The strong buffering action of the lactic acid prevented an evaluation of the dependence of the extraction coefficient on hydrogen ion concentration. However, at constant hydrogen ion and TOPO concentration a log/log plot of the extraction coefficient of tracer *'Am against HTTA concentration yielded a linear relationship of slope 2-8 (Fig. 5). This indicates a third power dependence of the extraction Constent phosphote ester concn of OO6M ent traction coeffi So Am, & im 1 10? Molority of HTTA in cyclonexane Fig. 5. Am=third power dependence of extraction on HTTA concentration in HTTA/ ‘ester synergistic system. Aqueous phase: 1M lactic acid, 0-0SM DTPA at pH 3-0. 16. H. Irving and D. N. Edgington,J. inorg. nucl. Chem. 18, 158 (1960) 17. H. Irving and D. N. Edgington.J. inorg. nucl. Chem. 20, 314.1961).2522 J. J, FARDY and J. M. PEARSON coefficients on the HTTA ‘concentration. A similar log/log plot for tracer “Ce yielded similar results (Fig. 6). The dependence of E,’ on the HTTA concentra- tion did not alter for either element when TOPO was replaced by TBPO, DBBP. or TBP. However, with TBP, the HTTA dependence was not linear below a concentration of 0-05 molar. The dependence of the americium extraction on the TOPO concentration at constant concentrations of HTTA and hydrogen ion (Fig. 7) was linear, the line having a slope of two. The dependence on the concen- tration of the ester was the same for TBPO, DBBP and TBP, and this relation- ship was not altered when americium was replaced with cerium (Fig. 8). cerium extroction coe sce, 401M TOPO 201M TBO 201M DBEP 801m TEP oF 107 10? Molority of HTTA in cyclohexene Fig. 6. Ce—third power dependence of extraction on HTTA concentration in HTTA/ ester synergistic system. Aqueous phase: 1M lactic acid, 005M DTPA at pH 3-0. Since the HTTA concentration dependence is equivalent to the valence of both extracted cations, no mixed complexes involving nitrate or lactate anions are involved. The small variation in extraction for different lactate concentrations described earlier in this paper supported this conclusion. Thus, the results in- dicated that the species involved in the extraction was M (TTA),(TOPO), where M 1zpresents a trivalent actinide or lanthanide. While the above data show that the extracted metal complex did not contain lactate, further studies were done to determine the extent of carboxylic acid extraction by the synergic combination since it is well known that TOPO extracts2523 Of HE Ofna 2 Va. WS0-0°PIS® 2H" [| -ASeyd Snoanby ‘wa Ww Vd.LC WNSO-0 “PDP ONDe| PY | :28eyd snoanby ‘war -SKs SNSISADUAS 10189/W_LLH Ul Uo!TTs 19909 49189 UO oss omyst@10UA$ 19189/Y,LLLH U! woRENUasUOD 19389 UO uonsenxe Jo a.uspuadap 19m0d puoras—3 °g BLY uonaenxe Jo suepuadap s9mod puosss—wy {By W. “suDxayo|o4> 49459 s4oudsoud Jo Ayss0|0% . auoi2k> ui 19489 94oydsoud jo Ay! 1.01 2.01 e-08 +01 201 £91 +01 tion of trivalent actinides and lanthanides ‘9033 5 e 5 3 3 4819154909 vog04x9 watse9 JINCVol. 35. No.7—M2524 J. J. FARDY and J.-M. PEARSON mineral acids[18]. Initially both alkali titration and '‘C labelled lactic acid were used to follow the extent of acid extraction. Both techniques yielded similar results. In later work the amount of acid extracted was determined only by liquid scintillation counting of the labelled compound. These ate summarized in Fig. 9, 108 mm Acié extracted io L L L 0 2 * . Molarity of lactic acid, Fig. 9. Extraction of lactic acid from aqueous solution by 0-1M TOPO in cyclohexane. The dependence of lactic acid extraction on lactic acid concentration is similar to that displayed by hydrochloric, sulphuric and phosphoric acid but differs from that shown by nitric and perchloric acids[18]. The mole ratio of TOPO to lactic acid in the organic phase was not changed significantly when DTPA was added to the aqueous phase or TTA to the organic phase. Although these studies indicated that the synergistic combination, TOPO/ HTTA, may not separate all the actinides from rare earths in a solution of car- boxylic and aminopolyacetic acid americium and cerium were readily separated from rare earth mixtures. Studies are continuing in this laboratory on the separa- tion of americium from curium in the same system by the oxidation of the ameri- cium to the pentavalent or hexavalent state. 18, J.C. White and W. J. Ross, USAEC Rep. NAS-NS 3102, 1961