IUPAC-NIST Solubility Data Series. 87. Rare Earth Metal Chlorides in Water and Aqueous Systems

IUPAC-NIST Solubility Data Series. 87. Rare Earth Metal Chlorides in Water and Aqueous Systems. Part 1. Scandium Group „Sc, Y, La…

Tomasz Mioduskia… Institute of Nuclear Chemistry and Technology, Warsaw, Poland

Cezary Gumińskib… Department of Chemistry, University of Warsaw, Warsaw, Poland

Dewen Zengc… College of Chemistry and Chemical Engineering, Hunan University, Hunan, People’s Republic of China

͑Received 12 May 2008; revised manuscript received 20 May 2008; accepted 20 May 2008; published online 15 October 2008͒

This volume presents solubility data for rare earth metal chlorides in water and in ternary and quaternary aqueous systems. The material is divided into three parts: scandium group ͑Sc, Y, La͒, light lanthanide ͑Ce-Eu͒, and heavy lanthanide ͑Gd-Lu͒ chlorides; this part covers the scandium group. Compilations of all available experimental data are introduced for each rare earth metal chloride with a corresponding critical evaluation. Every such evaluation contains a tabulated collection of all solubility results in ͑ ͒ water, a scheme of the water-rich part of the equilibrium Y, La, Ln Cl3 –H2O phase diagram, solubility equation͑s͒, a selection of suggested solubility data, and a discussion of the multicomponent systems. Because the ternary and quaternary systems were almost never studied more than once, no critical evaluations or systematic comparisons of such data were possible. Only simple chlorides ͑no complexes͒ are treated as the input substances in this work. The literature ͑including a thorough coverage of papers in Chinese and Russian͒ has been covered through the middle of 2007. © 2008 American Institute of Physics. ͓DOI: 10.1063/1.2956740͔

Key words: aqueous solution; lanthanum chloride; phase diagram; scandium chloride; solubility; yttrium chloride.

CONTENTS 3.1. Critical Evaluation of the Solubility of YCl3 in Aqueous Solutions...... 1773 3.2. Data for the YCl3 –H2O System...... 1776 1. Preface...... 1766 3.3. YCl3–Inorganic Salt–H2O Systems...... 1781 ͑ ͒ 1.1. Scope of the Volume...... 1766 3.3.1. YCl3 –MCl–H2O M=H,K 1.2. Nature of the Equilibrium Solid Phases.... 1766 Systems...... 1781 ͑ ͒ 1.3. Solubility as a Function of Temperature. . . 1767 3.3.2. YCl3 –MCl2 –H2O M=Mg,Cd 1.4. Quality of the Solubility Results...... 1767 Systems...... 1784 ͑ 1.5. Solubility as a Function of REM Atomic 3.3.3. YCl3 –MCl3 –H2O M=La, Ce, Pr, Number...... 1768 Nd, Eu, Gd, Ho͒ Systems...... 1785 1.6. Acknowledgments and History of the 3.3.4. YCl3 –YF3 –H2O System...... 1789 Project...... 1768 3.4. YCl3–Organic Compound–H2O Systems... 1790 1.7. References for the Preface...... 1769 3.5. Quaternary Systems...... 1792 2. Solubility of Scandium Chloride...... 1769 4. Solubility of Lanthanum Chloride...... 1794 2.1. Critical Evaluation of the Solubility of 4.1. Critical Evaluation of the Solubility of ScCl3 in Aqueous Solutions...... 1769 LaCl3 in Aqueous Solutions...... 1794 2.2. Data for ScCl3 in Aqueous Systems...... 1770 4.2. Data for the LaCl3 –H2O System...... 1803 3. Solubility of Yttrium Chloride...... 1773 4.3. LaCl3–Inorganic Salt–H2O Systems...... 1809 4.3.1. LaCl3 –MCl–H2O ͒ ͑ ͒ a Deceased. M=H,NH4 ,Li,Na,K,Rb,Cs ͒ b Electronic mail: [email protected]. Systems...... 1809 ͒ c Electronic mail: dewenគ[email protected]. 4.3.2. LaCl3 –MCl2 –H2O © 2008 American Institute of Physics.

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͑M=Mg,Ca,Sr,Ba,Cd͒ Systems. . . 1819 pounds ͑materials for glass and ceramic dyeing, lumines- 4.3.3. LaCl3 –MCl3 –H2O cence and laser technique, corrosion inhibition, hydrogen ͑M=Ce,Eu,Yb,Sm,Nd͒ Systems... 1822 storage, and nuclear fuel reprocessing͒. Also, organic chem- ͑ ͒ 4.3.4. LaCl3 –LaA3 –H2O A=F,Br,NO3 ists found a spectacularly high number of reactions catalyzed Systems...... 1825 by REM chlorides. Potentially, medical chemists are looking 4.4. LaCl3–Organic Compound–H2O Systems.. 1827 to apply these compounds as imaging agents in computer 4.4.1. LaCl3–Amine hydrochloride–H2O tomography and the prevention of renal stones. Also, knowl- Systems...... 1827 edge about the solubility in multicomponent systems as well 4.4.2. LaCl3–Hydrazine as the related equilibrium phase diagrams is essential for the hydrochloride–H2O Systems...... 1834 identification of complex compounds of REM chlorides with 4.4.3. LaCl3–Ketone–H2O Systems...... 1835 other salts and many organic compounds. This may likewise 4.4.4. LaCl3–Acetic acid–H2O System.... 1835 improve the extraction and refining of REM compounds. Re- 4.4.5. LaCl3–Amide–H2O Systems...... 1836 cently, several papers related to the solubilities of REM chlo- ͑ ͒ 4.4.6. LaCl3–Urea thiourea –H2O rides in binary, ternary, and quaternary aqueous systems have Systems...... 1838 been published each year. Some selected solubility data of 4.4.7. LaCl3 –N-heterocycle–H2O REM chlorides in aqueous systems were previously Systems...... 1841 collected,1–3 but no systematic evaluation of all relevant re- 4.4.8. LaCl3–Amino acids–H2O Systems. . 1845 sults was carried out. This work attempts to systematize the 4.5. Quaternary Systems...... 1846 immense experimental material acquired in this field. We 5. Cumulative References...... 1851 hope that the present volume will serve as a useful guide for research and technology that involves REMCl3. List of Tables This volume continues the evaluation series of solubilities of REM salts in water ͑nitrates,4 sulfates,5 ethylsulfates,6 7 8͒ 1. The experimental solubility data of ScCl3 in iodates, and other halides and REM halides in non- 9 water at two temperatures...... 1769 aqueous solvents. These projects have been connected with 2. Experimental values of solubility of YCl3 in activity of the IUPAC Solubility Data Commission and Sub- H2O as a function of temperature...... 1773 committee. This volume will be published in three parts: 3. Recommended ͑R͒, tentative ͑T͒, and doubtful Part 1 ͑this paper͒: Scandium group ͑Sc, Y, La͒ ͑ ͒ ͑ ͒ D solubilities of YCl3 in H2O at selected Part 2: Light lanthanides Ce–Eu temperatures...... 1775 Part 3: Heavy lanthanides ͑Gd–Lu͒ 4. Experimental solubilities reported for the LaCl –H O system as a function of 3 2 1.2. Nature of the Equilibrium Solid Phases temperature...... 1796 5. Recommended ͑R͒, tentative ͑T͒, and doubtful Solubility and phase diagrams are mutually connected. ͑ ͒ D solubilities of LaCl3 in H2O at selected Phase diagrams aid in understanding and interpretation of the temperatures...... 1800 solubility results, therefore their schematic sketches are included in every critical evaluation, except the ScCl3 –H2O List of Figures phase diagram because the corresponding data for this system are contradictory so far. It is common knowledge that

1. Selected solubility data for REMCl3, ordered the equilibrium solid phases in REMCl3 –H2O systems near according to atomic number of REM,at273 room temperature have constant hydrate numbers r of the ͑squares͒, 298 ͑circles͒, and 333 ͑triangles͒ K... 1768 chlorides: seven for La, Ce, and Pr and six for Sc, Y, and 2. Water-rich part of the YCl3 –H2O equilibrium Nd-Lu, as found by the method of Schreinemakers and phase diagram...... 1774 chemical analysis and well confirmed by some crystallo- ¯ 3. Water-rich part of the LaCl3 –H2O equilibrium graphic studies. The isotypic heptahydrates are triclinic, P1 phase diagram...... 1795 space group and isotypic hexahydrates are monoclinic, P2/n space group.3 The heptahydrate structure is based on the ͓ ͑ ͒ ͔+ 1. Preface nine-coordinate complex REMCl2 H2O 7 which forms dimeric ͓͑H O͒ REMCl REM͑H O͒ ͔4+ units. The hexahy- 1.1. Scope of the Volume 2 7 2 2 7 drate structure contains eight-coordinate species ͑ ͒ ͓ ͑ ͒ ͔+ A rather traditional generic term rare earth metal REM is REMCl2 H2O 6 . convenient for the title because it comprises the title ele- Below 273 K, the hydration number in REMCl3 ·rH2O ments: scandium, yttrium, lanthanum, and all lanthanides. may be, depending on the system, 8, 9, 10, or even 15, as Their chlorides seem to be the most common salts of REMs. established in exhaustive thermal analysis studies by In recent decades, we observe increasing applications of Sokolova.10 Unfortunately, only a monoclinic structure and these compounds in technology and science. They are used cell parameters for YbCl3 ·9H2O were identified by x-ray for the production of pure REMs, their alloys, and other com- diffraction. Therefore, it would be very useful to confirm the

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1767 results of Sokolova in another laboratory. At temperatures be used only in very narrow temperature ranges. Therefore, higher than 380 K the isotypic REMCl3 ·3H2O hydrates may we tried to use the advanced form of the solubility equation, be formed, and they were structurally investigated by Reuter applied for salts within the IUPAC solubility evaluation et al.11 who found orthorhombic structure, Pnma space projects,15 to describe more adequately the liquidus: group. The structure consists of ͓REMCl / Cl͑H O͒ ͔ chains, ␯ ␯ ͑␯ ͒ 4 2 2 3 ln͕x ͑1−x͒r͑␯ + r͒ +rr−r͓1+͑␯ −1͒x͔− +r ͖ where two REM3+ ions are connected via two Cl− ions. A comparison of the phase diagram shapes of the water- = A + BT−1 + C ln T + DT, ͑3͒ rich parts of the REMCl –H O systems showed quite 3 2 where ␯ is the number of ions produced upon salt dissocia- smooth changes in their invariant points and temperature tion and r is the number of water molecules in the equilib- ranges of stability of the equilibrium solid phases through the rium solid phase. The constants A, B, C, and D are derived REM series. Such regularities allowed predicting12 of the from a fitting procedure when a minimum of four solubility PmCl –H O, HoCl –H O, and TmCl –H O phase dia- 3 2 3 2 3 2 results at various temperatures as well as v and r are known. grams which were earlier not experimentally investigated. Due to the many parameters used and significant scatter of An extension of the phase diagrams to higher temperatures the solubility data from various laboratories for a selected and more salt-rich parts is complicated by the hydrolysis system, application of Eq. ͑3͒ quite frequently resulted in reaction with the formation of oxychlorides ͑or hydroxychlo- unexplained convexities on the solubility curves. In such rides͒ according to the scheme situations, we used the truncated form of Eq. ͑3͒, without the ͑ ͒ REMCl3 +H2O REMOCl + 2HCl. 1 fourth term DT, to obtain monotonic dependencies of the solubility on temperature. Teixeira da Silva13 calculated the stability diagram of Equations ͑2͒ and ͑3͒ are valid between the eutectic and LaCl ·7H O, LaCl , LaOCl, and La O phases depending on 3 2 3 2 3 peritectic or between two peritectic points when the hydra- the temperature and vapor pressures of H O and HCl; it fa- 2 tion number in the equilibrium solid phase is constant. It cilitates estimation of the extent of reaction ͑1͒ at equilib- would be possible to establish the hydration number in the rium conditions. Rafalski and Jonak14 investigated kinetics solid phase in the course of the fitting procedure using Eq. of the hydrolysis reaction ͑1͒ of several REMCl and found 3 ͑3͒, but the solubility results should be then sufficiently pre- that the content of the oxychlorides formed during 3 min of cise and minimally scattered. dehydration was never higher than 1.5 mass % at temperatures lower than 450 K and pressure between 0.01 and 0.04 MPa. This means that solubility determinations and 1.4. Quality of the Solubility Results thermal analysis at temperatures higher than 400 K should Except for the results from the laboratory of Spedding and be performed relatively fast; this condition may be practi- co-workers, who carried out the most careful and multifac- cally satisfied only for the latter method of experiments. eted determinations, the precision and accuracy achieved in other laboratories were rarely better than 1%. There are several reasons why the solubility data for REMCl are seldom 1.3. Solubility as a Function of Temperature 3 precise. The equilibria between the crystal hydrates and the The solubility values are represented in phase diagrams by saturated solutions are very slow and times of days are the liquidus lines. In the binary REMCl3 –H2O systems, the needed to obtain constant results from the subsequent solu- liquiduses are known from eutectic points, much below bility determinations. Harkot16,17 investigated the rate of 273 K, to more than 370 K and even up to 653 K, as in the polythermal crystallization of LaCl3 ·7H2O and found that case of YCl3. This group of salts may be classified as quite the crystallization process was also complicated in the liquid well soluble. There are some general features of the solubil- phase by complex chemical and structural transformations of ity data of REMCl3 in water when temperature is changed. polycondensated forms of the salt. A possibility of formation ϳ Typically, a content of 0.05 mole fraction of REMCl3 in of two crystal hydrates increases if additionally a crystalliza- mixtures with H2O decreases the melting eutectic tempera- tion occurs near a peritectic temperature. ture to the range 209–231 K. Above the eutectic points, the Solubilities of REMCl3 are pH sensitive. The saturated solubilities increase moderately with temperature. Increases solutions of the pure stoichiometric salts ͑1:3͒ are acidic, of the solubility are quite insignificant near room tempera- 1ϽpHϽ2.18 An increase in pH leads to the formation of ture. Unexpectedly, large increases of the solubility have re- hydroxychlorides which, according to Ref. 19, should be less cently been observed above 370 K when temperatures of the soluble than pure REMCl3. A decrease in pH by addition of ͑ ͒ peritectic or congruent decomposition of REMCl3 ·6H2Oor HCl made also a regular decrease in REMCl3 solubility that REMCl3 ·7H2O phases are approached. The strongly bent was observed for many systems investigated. Instead, addi- shapes of the liquiduses require use of an extended form of tion of acetic acid made quite marginal changes in the solu- ͑ the solubility equation because the familiar, linear equation bilities of REMCl3; the recalculated molal concentrations in other words, the molar ratio of the salt to water͒ were prac- ln x = A + BT−1 ͑2͒ tically constant up to 60 mass % of acetic acid, suggesting ͑ where x is the salt solubility expressed in mole fraction, T that an unchanged hydrate of REMCl3 would exist in the the absolute temperature in K, and A and B constants͒ could saturated solutions independently of the acetic acid concen-

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elements form the heptahydrates as the equilibrium solid phases. For NdCl3, the heptahydrate is the solid phase at 273 K whereas the hexahydrate is the equilibrium solid phase at 298 and 333 K; however, the solubility of NdCl3 is higher than that of PrCl3 at 273 and 298 K but not that at 333 K when a significant relative decrease in the solubility of NdCl3 is observed. In the case of the rest of REMCl3, which form hexahydrates at 298 and 333 K, parabolalike dependencies of the solubility versus atomic number ͑or decreasing ionic radius of REM͒ are observed. The shape of the analogous dependence at 273 K is similar, however, between Er and Lu the octahydrates or nonahydrates are formed as the equilibrium solid phases. A minimum of the solubility was observed for Tb at all the three temperatures. Because the three dependencies shown in Fig. 1 are almost parallel, the temperature dependencies of the solubility for any individual REMCl3 should be quite similar. The solubility values for YCl3, which should be near those FIG. 1. Selected solubility data for REMCl3, ordered according to atomic 4 5 ͑ ͒ ͑ ͒ ͑ ͒ for HoCl3, as was observed for the nitrates, sulfates, and number of REM,at273 squares , 298 circles , and 333 triangles K. 6 ethylsulfates, are atypically close to the values for YbCl3. The solubility values determined for ScCl3 at 273 and 298 K tration. Complexation of REM ions by Cl ions in the solu- are strongly scattered and significantly higher than those for tions of REMCl3, according to the discussion of Oakes the rest of REMCl ; they do not show any smooth depen- 20 3 et al., seems to be negligible. Thus, one may conclude that dence of the solubility, therefore no quantitative conclusions the use of only very pure salts of proper stoichiometry guar- related to this system may be drawn. Due to the much higher antees reliable and precise solubility determinations. ionic potential of Sc, its compounds may display atypical Sometimes the solubility data were only graphically pre- physicochemical properties. sented. When they were found to be important, the results were read out from the figures by the compilers. The precision of such a procedure was always indicated in the data sheets under the heading “Estimated Error.” The suggested 1.6. Acknowledgments and History of the Project solubilities at different temperatures, tabulated in the “Criti- The evaluators and compilers gratefully acknowledge the cal Evaluations,” belong to various classes of precision. If encouraging help of the IUPAC Commission V.8. and later there is agreement of at least two independent studies within Subcommittee on Solubility and Equilibrium Data. The experimental errors, the solubility values are assigned to the project was initiated in the early 1980s by Mioduski during “Recommended” category. The “Tentative” values were sug- the catalytic chairmanship of A. S. Kertes and continued dur- gested if one reliable result was reported or if the mean value ing the chairmanships of J. W. Lorimer, M. Salomon, D. of at least two studies was outside their error limits. In the Shaw, and H. Gamsjaeger. Advice and suggestions of M. tabulation, four, three, and two significant figures of the se- Salomon and J. W. Lorimer were very fruitful. The first out- lected solubility values are assigned for precision that is bet- line of the volume was ready in 1989. The sudden death of ter than Ϯ0.1%, Ϯ1%, and Ϯ10%, respectively. Mioduski in 2000 stopped the project for several years, al- Most of the solubility data were reported in the literature though Mioduski had gathered more than half of the material in mass % and seldom in terms of molality. For the sake of for this volume. In 2004 Gumiński started to complete the uniformity, all essential data were converted from mass % literature from the past two decades ͑and sometimes earlier͒, into mol kg−1 ͑molal units͒ using the IUPAC 2005 standard supplement and rearrange the critical evaluations and data atomic masses. Critical evaluations also contain results of the sheets, check numerical data, and retype the whole material saturating concentrations for the binary REMCl –H O sys- 3 2 into electronic form. Realization of the final stage of the tems expressed in mole fractions because the phase diagrams volume preparation was made possible by Zeng, who found were plotted in such units. many papers in Chinese, translated them, calculated solubility equations, plotted the phase diagram figures, and im- 1.5. Solubility as a Function of REM Atomic proved the Critical Evaluations. Therefore, Gumiński is very Number thankful to H. Gamsjaeger and W. Voigt for the successful Dependence of the solubility of REMCl3 on REM atomic involvement of Zeng in the project. The authors of this vol- number is presented in Fig. 1. The selected solubility data at ume also acknowledge the important inputs of J. A. Rard, K. 273, 298, and 333 K are used for its construction. A. Gschneider, J. E. Powell, V. Valyashko, M. Skripkin, H. One may easily observe that the solubility at the three U. Borgstedt, G. Brunisholz, J. C. G. Buenzli, L. Niinisto, G. temperatures is almost constant for La, Ce, and Pr; these R. Choppin, J. Burges, J. Kijowski, T. Moeller, J. M.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1769

Haschke, Z. X. Tang, Y. Sh. Chen, Y. L. Xu, and K. L. TABLE 1. The experimental solubility data of ScCl3 in water at two Loening, who provided the authors with reprints of hardly temperatures available papers and reports. / / −1 T K x1 m1 mol kg Equilibrium solid phase References 1.7. References for the Preface 273 Ͼ0.040 Ͼ2.3 Nothing specified 21 0.083 1 5.03 ScCl3 ·9H2O 22 1H. Stephen and T. Stephen, Solubilities of Inorganic and 0.067 2 4.0 ScCl3 ·9H2O 23 ͑ ͒ ϳ a ϳ a Organic Compounds Pergamon, Oxford, 1979 . 298 0.14 9 ScCl3 ·6H2O 24 2 J. Burgess and J. Kijowski, Adv. Inorg. Chem. Radiochem. 0.101 6.22 ScCl3 ·9H2O 24 24,57͑1981͒. 298.2 0.064 56 3.8307 ScCl3 ·6H2O 25 3 ͑ ͒ Gmelins Handbook Springer-Verlag, Berlin, 1982 , Vol. 39, acalculated by the evaluators from the graphically extrapolated data of Ref. Pt. C4a. 24 4S. Siekierski, T. Mioduski and M. Salomon, IUPAC Solubil- ͑ ͒ ity Data Series Pergamon, Oxford, 1983 , Vol. 13. 21–23 24 5 ͑ ͒ ͑ ͒ termined by Fischer et al. at 273 K, Samodelov at T. Mioduski, Chem. Anal. Warsaw 43, 457 1998 . 25 6T. Mioduski, J. Radioanal. Nucl. Chem. Lett. 128, 351 298 K, and Suzuki et al. at 298.2 K. Table 1 summarizes ͑1988͒. their results. 7H. Miyamoto, Current Topics Sol. Chem. 1,81͑1994͒. The lower solubility limit that could be estimated from the 8T. Mioduski ͑unpublished͒. determination of Ref. 21 seems to be relatively far from satu- 9 ration, and this value may be rejected. In the subsequent T. Mioduski and M. Salomon, IUPAC Solubility Data Series 22,23 ͑Pergamon, Oxford, 1985͒, Vol. 22. publications by Fischer et al., two solubility values were 10N. P. Sokolova, Radiokhimiya 30, 435 ͑1988͒. reported for nonahydrate as the equilibrium solid phase at 11G. Reuter, H. Fink, and H. J. Seifert, Z. Anorg. Chem. 620, 273 K. The experimental result in Ref. 22 was higher than 665 ͑1994͒. the one in Ref. 23 which was obtained from a smoothing 12C. Gumiński, Arch. Metall. Mater. 51, 617 ͑2006͒. procedure. This difference was not commented on by the 13 authors. The still higher solubility value was reported by F. Teixeira da Silva, Trans. Inst. Min. Metall., Sect. C 114, 24 24 C70 ͑2005͒. Samodelov at 298 K. These results, expressed in mass % 14W. Rafalski and K. Jonak, Przem. Chem. 48, 735 ͑1969͒. and molar concentrations of ScCl3, were inconsistent by 15J. W. Lorimer and R. Cohen-Adad, in The Experimental 0.5%. Molalities in the corresponding data sheet were calcu- Determination of Solubilities, edited by G. T. Hefter and R. lated by the compilers using the solubility data expressed in P. T. Tomkins ͑Wiley, Chichester, 2003͒,p.19. mass % ScCl3. Moreover, the experimental solubility result −1 16J. Harkot, Pol. J. Chem. 63, 337 ͑1989͒. of 6.22 mol kg is slightly higher than the theoretical com- −1 ͑ 17J. Harkot, Pol. J. Chem. 64,53͑1990͒. position of the nonahydrate of 6.17 mol kg the solubility ͒ 18F. H. Spedding, J. A. Rard, and V. Saeger, J. Chem. Eng. of ScCl3 in its own crystallization water , invalidating the ͑ ͒ experimental result of Ref. 24. The situation was not clarified Data 19, 373 1974 . 25 19L. G. Sillen and A. Martell, The Chemical Society, Special in the precise determination of Suzuki et al., who found a Publication No. 17, 1964; The Chemical Society, Special significantly lower solubility of ScCl3 at 298.2 K and speci- ͓ ͔ fied ScCl3 ·6H2O 20662-14-0 as the equilibrium solid Publication No. 25, 1971. 21–24 20C. S. Oakes, J. A. Rard, and D. G. Archer, J. Chem. Eng. phase. The previous measurements were not commented Data 49, 313 ͑2004͒. on in Ref. 25. All authors equilibrated the solutions with crystals for 1–2 d which, by comparison to the lanthanide chloride-water systems, seems to be too short a period. 2. Solubility of Scandium Chloride Therefore, at present, it is impossible to suggest the most probable solubility value which should be equal to or higher 2.1. Critical Evaluation of the Solubility of ScCl3 in −1 than 3.83 and equal to or lower than 6.17 mol kg ScCl3 Aqueous Solutions between 273 and 298 K. Also, the solute entity does not clarify the confusing situ- Components: Evaluators: ation. ScCl3 ·9H2O was found as the equilibrium solid phase ͑ ͒ 22–24,26 1 Scandium chloride; ScCl3; T. Mioduski, Institute of at 273 and 298 K in several works. Unexpectedly, ͓10361-84-9͔ Chemistry and Nuclear ͑ ͒ ͓ ͔ ScCl3 ·6H2O was reported as the solute at 298 K by Ref. 25. 2 Water; H2O; 7732-18-5 Technology, Warsaw, Poland and C. Gumiński, Department of In addition to the equilibrium solid analysis in Refs. 22–24, 26 Chemistry, University of Warsaw, Lim et al. claimed that ScCl3 ·7H2O is the “maximally” Poland hydrated salt at room temperature and determined its crystal November 2007 ͑ ͒ structure as monoclinic which is typical of LnCl3 ·6H2O . The single crystals in Ref. 26 were deposited from concen- The ScCl3 –H2O system was not intensively studied and trated aqueous solutions, being slightly acidified to avoid hy- results of the corresponding investigations are frequently drolysis. ͑ controversial. The solubility of ScCl3 in water has been de- Hygroscopic ScCl3 ·6H2O most frequently recrystallized

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1770 MIODUSKI, GUMIŃSKI, AND ZENG from concentrated HCl solutions͒ was the starting substance 33S. V. Aleksandrovskii, Zh. Prikl. Khim. ͑S. Peterburg͒ 70, 27–33 for several dehydration studies. The results differed 1761 ͑1997͒. greatly with respect to the temperature and nature of the 34K. H. Schröder, Thesis, Univ. of Münster, Germany, 1955, ͓ ͔ intermediate products. ScCl3 ·5H2O 114364-35-1 was as quoted in Ref. 3. found in the investigations of Refs. 31 and 32, ScCl ·4H O 35 3 2 Aldrich 2007–2008 Handbook of Fine Chemicals ͑Sigma- ͓ ͔ ͓ ͔ 64618-80-0 in Refs. 32 and 33, ScCl3 ·3H2O 114364-36-2 ͒ ͓ ͔ Aldrich, St. Louis, 2007 , p. 2170. in Ref. 28, ScCl3 ·2H2O 114364-37-3 in Ref. 33, and ScCl3 ·1.5H2O in Ref. 30. Further heating resulted in the formation of ScOCl,27–29,31,33,34 which was finally decom- posed to Sc2O3 above 830 K. Melting of ScCl3 ·6H2O was found at 333,27,31 343–353,28 346,33 341,34 and 336–339 K,35 pointing to relatively good agreement in this 2.2. Data for ScCl3 in Aqueous Systems matter. However, taking into account all these experimental observations, no even provisional ScCl –H O phase diagram 3 2 Components: Original Measurements: may be constructed at present. ͑ ͒ 21 1 Scandium chloride; ScCl3; W. Fischer, J. Wernet, and M. Addition of HCl to the ScCl3 solution caused a systematic ͓10361-84-9͔ Zambusch-Pfisterer, Z. Anorg. ͑ ͒ ͑ ͒ ͑ ͒ decrease in the ScCl3 solubility at 273 K Refs. 22 and 23 as 2 Hydrochloric acid; HCl; Chem. 258, 157 1949 . well as at 298 K;24 the solubility increased again at higher ͓7647-01-0͔ ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 HCl concentrations, but this effect was stronger at 273 K. ͑ ͒ 4 Diethyl ether; C4H10O; The authors of Refs. 22 and 23 observed that ScCl3 ·9H2O ͓60-29-7͔ −1 ͑ ͒ ͓ ͔ was the solute up to 10 mol kg HCl, whereas Ref. 24 found 5 Ethanol; C2H6O; 64-17-5 it up to only 2.1 mol dm−3; above these HCl concentrations, Variables: Prepared by: both authors found the hexahydrate as the equilibrium solid Solvents T. Mioduski and C. Gumiński phase. Temperature: 273 K or room Summarizing these observations, it is impossible at present to suggest any quantitative solubility values of ScCl3 Experimental Values as well as an unquestionable composition of the equilibrium solid phase at a selected temperature. The only statement that Solubility of ScCl3 in water and aqueous mixed solvents at 0 °C or room temperature may be made at present is that ScCl3 is a well soluble salt, its hexahydrate melts at about 340 K and dehydrates gradually. / 3 gSc2O3 100 cm Further studies on this system are strongly advised. / −3a Solvent of saturated solution c1 mol dm Ͼ Ͼ References H2O 16 2.3 40 % HCl Ͼ1.5 Ͼ0.22 21 W. Fischer, J. Wernet, and M. Zumbusch-Pfisterer, Z. An- 40 % HCl+diethyl ether ͑1:1͒ Ͼ4 Ͼ0.6 org. Chem. 258, 157 ͑1949͒. 43 % HCl in 95 % ethanolb 1.25b 0.18b 22W. Fischer and G. Buhler, Z. Anorg. Chem. 285, 156 a ͑1956͒. calculated by the compilers from Sc2O3 content used by the authors as the 23W. Fischer, H. Bauer, I. Dillo, T. Molaug, J. Nier, H. Ro- starting material for the experiments bat room temperature hrer, and K. Trovaag, Z. Anorg. Chem. 357, 177 ͑1968͒. 24 ͑ ͒ A. P. Samodelov, Zh. Neorg. Khim. 10, 1735 1965 . The equilibrium solid phases were not specified. 25Y. Suzuki, R. Yoshino, H. Saitoh, K. Fukushi, and Y. Sone- The authors observed that the degree of ScCl coprecipi- hara, J. Alloys Compd. 180, 383 ͑1992͒. 3 tation with NaCl, NH Cl, or MgCl was very low. 26K. C. Lim, B. W. Skelton, and A. H. White, Aust. J. Chem. 4 2 53, 875 ͑2000͒. Auxiliary Information 27W. W. Wendlandt, J. Inorg. Nucl. Chem. 5,118͑1957͒. Method/Apparatus/Procedure: 28F. Petru and F. Kutek, Collect. Czech. Chem. Commun. 25, ͑ ͒ The solvents were saturated with HCl gas in a glass apparatus. Filtrates of 1143 1960 . the saturated and nonsaturated solutions were analyzed gravimetrically for 29 F. Petru, J. Hradilova, and B. Hajek, Collect. Czech. Chem. Sc content after its precipitation as Sc2O3. Commun. 33, 2720 ͑1968͒. Source and Purity of Materials: 30W. Crookes, Phil. Trans. R. Soc. London, Ser. A 209,15 The materials used were of reagent-grade purity. ͑1908͒. 31I. V. Arkhangelskii, L. N. Komissarova, V. M. Shatskii, and Estimated Error: N. P. Shepelev, Zh. Neorg. Khim. 17, 310 ͑1972͒. Nothing specified. 32G. A. Melson, D. J. Olszanski, and A. K. Rahimi, Spectro- chim. Acta, Part A 33, 301 ͑1977͒.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1771

Smoothed values of solubility of ScCl3 in water and aqueous solutions of Components: Original Measurements: HCl at 0 °C ͑ ͒ 22 1 Scandium chloride; ScCl3; W. Fischer and G. Buhler, Z. ͓10361-84-9͔ Anorg. Chem. 285,156͑1956͒. / –1 a m2 m1 g-equivalent kg m1 Equilibrium solid phase ͑2͒ Hydrochloric acid; HCl; ͓ ͔ 7647-01-0 14 5.2 1.7 ScCl3 ·6H2O ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 15.2 11.8 3.9 ScCl3 ·6H2O

Variables: Prepared by: acalculated by the compilers Concentration of HCl: T. Mioduski and C. Gumiński 0–30.2 mass % Auxiliary Information One temperature: 273 K Method/Apparatus/Procedure:

Isothermal method was used. A hydrate of ScCl3 was equilibrated with the Experimental Values solvents by mixing for 1–3 d at the selected temperature. The saturated ͑ ͒ solutions were filtered through glass wool. Sc was precipitated as Sc OH 3 Solubility of ScCl in water and HCl solutions at 0 °C 3 with NH3 and determined gravimetrically as Sc2O3. This total chloride content was found from a potentiometric titration. The composition of the a a b Equilibration time/d 100w2 m2 100w1 m1 n equilibrium solid was graphically determined by the dry residue method of Schreinemakers. 3c 0 0 43.2 5.03 6.2 3d 0.3 0.47 41.3 4.67 6.8 Source and Purity of Materials: d 2 2.1 0.99 39.9 4.45 6.4 Sc2O3 was purified from Zr, Hf, Fe, Al, and Ln and finally contained d 2 4.8 2.1 32.1 3.36 9.6 0.1% ZrO2. It was further transferred into ScCl3, probably in a form of 3d 8.2 3.8 32.7 3.66 6.7 hydrate. 2c 12.2 5.6 28.3 3.14 5.8 d Estimated Error: 2 14.2 6.2 23.2 2.45 9.1 Ϯ͑ ͒ ͑ c Solubility: nothing specified; 2–7 % as estimated by the compilers 3 18.2 8.4 22.0 2.43 6.2 ͒ d from the data scatter on a graphical presentation of all results . 2 19.7 8.8 18.9 2.03 8.9 Temperature: nothing specified. 3d 22.5 10.3 18.0 2.00 5.9 1c 23.4 10.8 17.2 1.91 6.5 2c 24.6 11.4 16.1 1.79 6.2 d Components: Original Measurements: 3 24.9 11.6 16.4 1.85 6.2 ͑ ͒ 24 c 1 Scandium chloride; ScCl3; A.P. Samodelov, Zh. Neorg. 2 25.5 11.9 15.7 1.76 6.4 ͓ ͔ 10 ͑ ͒ d 10361-84-9 Khim. ,1735 1965 . 3 28.3 13.6 14.8 1.72 6.1 ͑2͒ Hydrochloric acid; HCl; 2 30.2 16.1 18.5 2.38 6.1 ͓7647-01-0͔ ͑ ͒ ͓ ͔ 2 28.8 16.7 23.8 3.32 5.7 3 Water; H2O; 7732-18-5 3 28.3 16.4 24.3 3.39 6.0 3 28.0 16.1 24.3 3.37 6.2 Variables: Prepared by: 3 27.6 15.9 24.7 3.42 5.9 Concentration of HCl: T. Mioduski and C. Gumiński 0–18.2 mass % 3 25.8 15.2 27.7 3.94 6.2 One temperature: 298 K acalculated by the compilers b number of water molecules in the equilibrium solid formula ScCl3 ·nH2O cequilibrium approached from supersaturation by precipitation of the solid Experimental Values excess after the solution was cooled to 0 °C d equilibrium approached from undersaturation by addition of the solid solute Solubility of ScCl3 in H2O and HCl solutions at 25 °C to HCl solution ␳/ −3 a b kg dm 100w2 c2 100w1 c1 m1 Equilibrium solid The authors stated that ScCl3 ·6H2O and ScCl3 ·9H2O are the equilibrium solid phases at HCl concentrations higher 1.420 0 0 48.50 4.65 6.22 A and lower than 23 mass %, respectively; the solute 1.415 0.01 0.04 48.10 4.54 6.13 A ScCl ·9H O was experimentally identified in only three of a 1.417 0.20 0.06 47.10 4.45 5.91 A 3 2 1.413 0.46 0.18 46.20 4.36 5.72 A total of ten tests performed. 1.408 0.80 0.34 44.30 4.16 5.33 A Based on the experimental data presented above, the au- 1.403 1.28 0.50 44.80 4.20 5.49 A thors of Ref. 23 reported smoothed values of ScCl3 solubility 1.398 2.10 0.81 39.70 3.69 4.51 A in HCl solutions at 0 °C. 1.396 2.20 0.82 42.80 3.98 5.14 A 1.393 2.58 1.00 40.70 3.78 4.74 A Smoothed values of solubility of ScCl in water and aqueous solutions of 3 1.391 2.85 1.10 40.80 3.78 4.78 A HCl at 0 °C 1.387 3.32 1.28 38.60 3.57 4.39 A / –1 a 1.390 3.11 1.20 40.20 3.72 4.69 A m2 m1 g-equivalent kg m1 Equilibrium solid phase 1.385 4.00 1.54 38.00 3.51 4.33 A

0 12.1 4.0 ScCl3 ·9H2O 1.382 4.31 1.58 38.80 3.58 4.51 A

5 8.0 2.7 ScCl3 ·9H2O 1.381 4.93 1.91 37.50 3.45 4.30 A c 10 6.0 2.0 ScCl3 ·9H2O 1.380 5.07 1.94 38.70 5.56 4.55 A

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1772 MIODUSKI, GUMIŃSKI, AND ZENG

Solubility of ScCl3 in H2O and HCl solutions at 25 °C Source and Purity of Materials: ͑ ͒ ScCl3 was prepared by chlorination of Sc2O3 99% pure , purified by ␳/ −3 a b kg dm 100w2 c2 100w1 c1 m1 Equilibrium solid thiocyanate extraction with ether, and mixed with wood charcoal at 1273–1373 K. 1.372 5.36 2.05 37.60 3.45 4.36 A Gaseous HCl was obtained by a “conventional method” to saturate the 1.370 5.54 2.12 37.60 3.44 4.37 A solutions. 1.368 5.67 2.17 37.30 3.42 4.32 B Water purity was not specified. 1.367 5.92 2.26 36.80 3.36 4.25 B 1.367 6.43 2.40 36.00 3.28 4.13 B Estimated Error: 1.364 6.60 2.50 35.60 3.24 4.07 B Solubility: nothing specified; Ϯ͑1–3͒% ͑as estimated by the compilers ͒ 1.355 7.45 2.80 34.30 3.10 3.89 B from the scatter of the results on their graphical presentation . Ϯ 1.354 7.50 2.82 33.20 3.00 3.70 B Temperature: precision of 0.05 K. 1.363 7.62 2.87 33.45 3.02 3.75 B 1.350 8.00 3.00 33.30 3.00 3.75 B 1.345 8.46 3.16 32.00 2.86 3.55 B Components: Original Measurements: ͑ ͒ 25 1.341 8.87 3.30 32.00 2.86 3.58 B 1 Scandium chloride; ScCl3; Y. Suzuki, R. Yoshino, H. 1.338 9.15 3.40 30.50 2.72 3.34 B ͓10361-84-9͔ Saitoh, K. Fukushi, and Y. ͑ ͒ ͓ ͔ 1.335 9.45 3.51 30.95 2.85 3.43 B 2 Water; H2O; 7732-18-5 Sonehara, J. Alloys Compd. 180, 383 ͑1992͒. 1.333 9.60 3.56 30.20 2.68 3.31 B 1.331 9.64 3.64 30.00 2.66 3.28 B Variables: Prepared by: 1.331 9.92 3.66 31.50 2.81 3.55 B One temperature: 298.2 K C. Gumiński 1.328 10.13 3.74 30.80 2.72 3.45 B 1.323 10.65 3.92 29.70 2.62 3.29 B 1.320 10.90 4.00 29.55 2.60 3.28 B Experimental Values 1.316 11.22 4.10 29.20 2.56 3.24 B Solubility of ScCl3 in H2O at 25.0 °C was found to be 1.312 11.42 4.30 29.10 2.55 3.23 B −1 1.309 12.10 4.40 28.40 2.48 3.15 B 3.8307 mol kg . The equilibrium solid phase was stated as 1.306 12.40 4.50 28.70 2.50 3.22 B ScCl3 ·6H2O but no analysis of this phase was reported. 1.305 13.80 5.00 27.60 2.40 3.11 B Auxiliary Information 1.302 14.40 5.20 26.60 2.31 2.98 B 1.300 15.22 5.50 26.00 2.25 2.92 B Method/Apparatus/Procedure: 1.302 15.90 5.75 25.80 2.24 2.92 B Isopiestic measurements in isothermal conditions were performed. A 1.303 16.30 5.90 26.20 2.28 3.01 B stainless steel chamber contained six Pt cups placed in a Cu block. The 1.305 16.55 6.00 26.42 2.30 3.06 B cups contained either reference or sample solutions. The chamber was 1.311 17.30 6.30 26.80 2.34 3.17 B thermostated. A Pt gauze was added to each cup to promote equilibration. 1.317 18.60 6.52 27.50 2.41 3.37 B The chamber was slowly evacuated and then gently rotated. The molalities 1.320 18.00 6.60 27.50 2.42 3.33 B at equilibrium were obtained from the weight of stock solution in a cup 1.323 18.20 6.70 29.20 2.78 3.70 B and the weight of solution in a cup after equilibration. The equilibrium periods ranged from 1 to 2 d and was accepted to be when the acalculated by the compilers concentration of two samples of each solution agreed to within Ϯ0.15%. b The concentrations of ScCl and CaCl ͑used as the reference͒ were A=ScCl3 ·9H2O; B=ScCl3 ·6H2O 3 2 cmisprinted value; the correct result should be 3.56 mol dm−3 determined gravimetrically. Source and Purity of Materials: Extrapolation of the solubility results to zero HCl concen- ͑ ͒ The solutions of ScCl3 were prepared from HCl solution reagent grade ͑ ͒ tration, when ScCl3 ·6H2O would be the solute, points to and Sc2O3 99.9+ % . ϳ ScCl3 solubility in water of 58 mass % as metastable solu- Source of H2O was not specified. tion. CaCl2 was of reagent grade; probably recrystallized.

Auxiliary Information Estimated Error: Solubility: precision of better than Ϯ0.15%. Method/Apparatus/Procedure: Temperature: precision of Ϯ0.1 K. Equilibrium was reached from above ͑by increasing HCl concentration in ͒ ScCl3 solution that made precipitation of ScCl3 hydrate excess or from ͑ ͒ below by addition of ScCl3 into HCl solution . 8–10 h was found to be sufﬁcient time to reach equilibrium, but the solutions were agitated for another 20–25 h. HCl was added in gaseous form into the system. The

ScCl3 content was determined gravimetrically and spectrographically, but no details were reported. The HCl content was found by titration with alkali hydroxide solution after addition of dry NaF to precipitate

ScF3 ·3NaF in the solution and to avoid hydrolysis. The composition of the solid phases was determined by the residue method of Schreinemakers and chemical analysis. Then Sc was precipitated with NH3 and the ͑ ͒ resulting Sc OH 3 ignited and weighed as Sc2O3. The content of Cl was determined gravimetrically as AgCl.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1773

3. Solubility of Yttrium Chloride TABLE 2. Experimental values of solubility of YCl3 in H2O as a function of temperature 3.1. Critical Evaluation of the Solubility of YCl3 in / Aqueous Solutions T K m1 x1 Equilibrium solid phase References ͑ ͒ 231 2.4 0.042 H2O s +YCl3 ·15H2O 60

Components: Evaluators: 250 3.0 0.051 YCl3 ·15H2O+YCl3 ·9H2O 60 ͑ ͒ 1 Yttrium chloride; YCl3; T. Mioduski, Institute of Nuclear 263 3.69 0.062 8 YCl3 ·9H2O 57 ͓ ͔ 10361-92-9 Chemistry and Technology, 273 3.6 0.060 YCl3 ·9H2O+YCl3 ·8H2O 60 ͑ ͒ ͓ ͔ 2 Water; H2O; 7732-18-5 Warsaw, Poland; 3.76 0.063 5 Nothing specified 36 C. Gumiński, Department of 3.84 0.064 7 YCl3 ·6H2O 38 Chemistry, University of Warsaw, 3.86 0.065 0 YCl3 ·6H2O 23 Poland; 3.91 0.065 8 YCl ·6H O 55 D. Zeng, College of Chemistry 3 2 273.150 3.5976 0.060 84 Nothing specified 51 and Chemical Engineering, 275.7 3.6 0.061 YCl ·8H O+YCl ·6H O 60 Hunan University, People’s 3 2 3 2 Republic of China 283 4.000 0.067 2 YCl3 ·6H2O 37 July, 2007 3.93 0.066 1 YCl3 ·6H2O 55 289 3.88 0.065 4 Nothing specified 36

293 4.037 0.067 8 YCl3 ·6H2O 37 Data for the solubility of YCl3 in water and aqueous so- 298 4.03 0.067 7 YCl3 ·6H2O 38 lutions have been reported in many papers.21,23,36–64 The 4.047 0.068 0 YCl3 ·6H2O 39 and 42 ͑ ͒ solubility values were mainly determined by analytical meth- 3.99 0.067 0 YCl3 ·6H2O probably 40 and 56 21,23,36–51,53–58,62–64 ods at isothermal conditions. Thermal 3.94 0.066 3 Nothing specified 41 60 61 analysis, visual observation of last crystal dissolution, 4.204 0.070 3 YCl3 ·6H2O 43 isopiestic,52,58,59 and vapor-pressure measurements61 were 3.91 0.065 8 Nothing specified 44 also used. Many studies dealt with ternary and even quater- 3.96 0.066 6 YCl3 ·6H2O 50 3.94 0.066 3 YCl ·6H O 54 and 55 nary systems containing YCl , and the solubility in pure wa- 3 2 3 3.906 0.065 74 YCl ·6H O 63 ter was then given mostly as one point in a phase diagram. In 3 2 3.842 0.064 73 YCl3 ·6H2O 62 several studies devoted to ternary systems and performed in 4.06 0.068 1 YCl3 ·6H2O 58 the same laboratory, probably one solubility determination in 298.15 3.9367 0.066 223 YCl3 ·6H2O 59 water was performed and that result was further repeated; 298.150 3.9478 0.066 37 Nothing specified 51 and 52 however, several times the corresponding values were 298.2 3.86 0.065 0 YCl3 ·6H2O 36 303 4.078 0.068 4 YCl ·6H O 37 slightly different. All solubility results for the YCl3 –H2O 3 2 system are summarized in Table 2. 3.85 0.064 8 YCl3 ·6H2O 47 The experiments at low60 and high temperatures61 en- 3.94 0.066 2 YCl3 ·6H2O 48 3.96 0.066 6 YCl ·6H O 48 and 49 riched our knowledge of the whole YCl –H O system; how- 3 2 3 2 4.02 0.067 5 YCl ·6H O 55 ever, the results obtained at low temperatures60 show only 3 2 313 4.140 0.069 4 YCl3 ·6H2O 37 qualitative agreement with the majority of the solubility data 318 3.93 0.066 1 Nothing specified 36 and there are some reservations about the interpretation of 323 4.202 0.070 3 YCl3 ·6H2O 37 the results obtained in Ref. 60, as is pointed out in the cor- 4.236 0.070 8 YCl3 ·6H2O 39 responding data sheet. Doubtless, YCl3 ·15H2O, 3.96 0.066 6 YCl3 ·6H2O 45 ͓ ͔ 4.22 0.070 6 YCl ·6H O 55 YCl3 ·9H2O, YCl3 ·8H2O, and YCl3 ·6H2O 10025-94-2 3 2 equilibrium solid phases were found to be stable up to their 333 4.20 0.070 3 YCl3 ·6H2O 38 peritectic decompositions at 250, 273, 276 ͑as reported in 3.96 0.066 6 Nothing specified 36 348 4.07 0.068 3 YCl ·6H O 45 Ref. 60͒, and 426 K ͑as reported in Ref. 10͒, respectively; 3 2 353 4.00 0.067 2 Nothing specified 36 see the schematic phase diagram of the YCl3 –H2O system in 373 4.21 0.070 5 YCl3 ·6H2O 45 Fig. 2. The thermal arrests observed in Ref. 60 at ϳ221 K, 425 4.9 0.081 YCl3 ·6H2O 61 placed between YCl3 ·15H2O and YCl3 ·9H2O compounds, 452 7.1 0.113 YCl3 ·6H2O 61 ͑ ͒ were unexplained and might reflect either a decomposition 458 9.5 0.146 YCl3 ·6H2O+YCl3 ? 61 ͑ ͒ temperature of another intermediate phase formed between 523 11.4 0.170 YCl3 ? 61 628 15.4 0.217 YCl ͑?͒ 61 YCl3 ·15H2O and YCl3 ·9H2O or a metastable eutectic reac- 3 ͑ ͒ 653 17.2 0.236 YCl3 ? 61 tion. The eutectic point at 0.042 mole fraction YCl3 and 231 K seems to be more probable than that at 0.051 mole fraction YCl3 and 221 K. The inflection on the liquidus between 276 and 300 K ity results above 276 K. Concerning the high-temperature should not be attributed to any defined thermodynamic ef- part of the diagram, the authors of Ref. 61 found a liquidus fect, but rather results from fitting of the experimental data which was relatively flat at first and with a high slope above because the solubility values obtained from thermal 458 K. Without further decisive experiments in this range, analysis60 below 276 K are distinctly lower than the solubil- we are not able to designate the character of the reaction at

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1774 MIODUSKI, GUMIŃSKI, AND ZENG

ity of YCl3 in water is relatively high, but its increase with temperature is relatively small up to about 373 K and be- comes significant between 373 K and the peritectic ͑or con- gruent͒ melting point at 458 K.61 This would suggest that the system in this temperature range displays a tendency to im- ͑ ͒ miscibility or YCl3 ·6H2O by similarity to LaCl3 ·7H2O melts congruently and forms a eutectic between YCl3 ·6H2O and YCl3 ·2H2O at a temperature slightly lower than 458 K as is reflected in the phase diagram in Fig. 2. Unexpectedly, further increase in temperature above 458 K leads again to a relatively small increase in the solubility, similar to that observed near room temperature. Although some authors51,52,59 claimed to reach the precision of Ϯ0.1%, the whole scatter of the solubility data at selected temperatures is between 5% and 8%. It is very char- acteristic that except for the scattered results of Ref. 36, other data,37–39,45,55 differing in absolute values, show quite similar slopes of the dependencies of the logarithm of the solubility versus reciprocal temperature. Concerning the method of analysis of the saturated solutions, it was observed that the FIG. 2. Water-rich part of the YCl3 –H2O equilibrium phase diagram. ͑ ͒ precipitation of Y2O3 Refs. 37 and 38 gave higher results of the analysis than the titration of Y ions with ethylenedi- ͑ ͒ 45,55 458 K: peritectic or congruent melting. The authors of Ref. amine tetraacetic acid EDTA solution. 61 suggested that above 458 K the equilibrium solid phase There are too few reliable solubility results to propose solubility equations when YCl ·15H O, YCl ·9H O, and was anhydrous YCl3; this statement also needs confirmation 3 2 3 2 in a future experiment because, according to several papers, YCl3 ·8H2O are the equilibrium solid phases. Therefore, we concentrated on finding the proper equation between 276 and the dehydration of YCl3 ·6H2O, upon heating or action of a drying agent, was found to be a stepwise process with the 458 K when the equilibrium solute is YCl3 ·6H2O, as well as 65 above 458 K when the equilibrium solid phase is probably formation of YCl3 ·5.5H2O, YCl3 ·5H2O ͓ ͔ 65,66 ͓ ͔ 66 YCl ·2H O. For construction of the solubility equations, we 114364-34-0 , YCl3 ·4H2O 114364-33-9 , 3 2 ͓ ͔ 65–68 65 used the selected solubility values and the general form of YCl3 ·3H2O 114364-32-8 , YCl3 ·2.5H2O, ͓ ͔ 66–69 the solubility equation expressed by Eq. ͑3͒ ͑see Sec. 1.3͒. YCl3 ·2H2O 114364-31-7 , YCl3 ·H2O ͓ ͔ 65–71 65–67,69,71 Based on least-squares fitting, the following solubility equa- 13470-35-4 , and finally dehydrated YCl3. The authors of Ref. 72 negated, after x-ray diffraction investigations were obtained: tions, the existence of YCl3 ·3H2O in the YCl3 –H2O system. ͕ 4͑ ͒6͑ ͒4+6 −6͓ ͑ ͒ ͔−͑4+6͖͒ ln x1 1−x1 4+6 6 1+ 4−1 x1 Formation of YCl3 ·5.5H2O, YCl3 ·5H2O, YCl3 ·4H2O, and −1 YCl3 ·2.5H2O seems to be unlikely in the opinion of the = 797.150 − 22 972.8T − 137.273 ln T − 0.205 35T, evaluators. YOCl was identified as the final product of ther- ͑4͒ mogravimetric experiments in Refs. 65, 71, 73, and 74. Fur- 65,74 ther thermolysis of YOCl led to the formation of Y2O3. for YCl3 ·6H2O equilibrium solid phase between 276 and The melting point of YCl3 ·6H2O was determined by 458 K, where x1 is the solubility of YCl3 in water expressed many investigators: 426 K,10 434–436 K,37 458 K,53 in mole fraction and T the absolute temperature in K, and 458Ϯ2K,61 429–433 K,70 463 K,74 433 K,75 76 77 ͕ 4͑ ͒2͑ ͒4+2 −2͓ ͑ ͒ ͔−͑4+2͖͒ 424.2–425.0 K, and 458 K. The significant differences ln x1 1−x1 4+2 2 1+ 4−1 x1 may be explained either by the determinations being per- = 217.8634 − 9956.3T−1 − 34.619 ln T + 0.0331T, ͑5͒ formed in different experimental conditions ͑closed or open ͒ vessels, various heating rates , by the melting temperature for YCl3 ·2H2O equilibrium solid phase between 458 and being very sensitive to the purity of YCl3 ·6H2O used, or by 653 K, assuming that such solid phase is in equilibrium in another reaction in the range of 424–463 K. this temperature range. The following solubility data, deviat- The solubility results obtained with the hexahydrate as the ing by more than 3% from the mean values, were not taken equilibrium solute at temperatures below 276 K are treated, into account in the fitting procedure: Refs. 23, 36, 38, and 55 according to the phase diagram studies of Ref. 60, as corre- at 273 K, Ref. 37 at 283 K, Ref. 37 at 293 K, Refs. 38, 39, sponding to a metastable equilibrium, and they are excluded 43, 58, and 62 at 298 K, Refs. 37 and 47 at 303 K, and all from the further evaluation. Thus, the solubility data between data from Refs. 36 and 45 at higher temperatures. The se- the peritectics at 276 and 458 K with the hexahydrate as the lected solubility values are collected in Table 3. equilibrium solid will be further assessed; however, a selec- The solubility of YCl3 in HCl solutions was measured in tion of recommended values is still problematic. The solubil- seven papers.21,23,37,42,45,63,64 There is no doubt that addition

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1775

͑ ͒ ͑ ͒ ͑ ͒ TABLE 3. Recommended R , tentative T , and doubtful D solubilities of YCl3 in H2O at selected temperatures

/ / −1 T K m1 mol kg x1 Equilibrium type Equilibrium solid phase ϳ ϳ ϳ ͑ ͒ ͑ ͒ 231 2.5 0.042 D Eutectic H2O s +YCl3 ·15H2O ϳ ϳ ϳ ͑ ͒ 250 3.0 0.051 D Peritectic YCl3 ·15H2O+YCl3 ·9H2O ͑ ͒ 273 3.6 0.061 R Peritectic YCl3 ·9H2O+YCl3 ·8H2O ϳ ϳ ϳ ͑ ͒ 276 3.7 0.062 D Peritectic YCl3 ·8H2O+YCl3 ·6H2O ͑ ͒ 298.2 3.94 0.0663 R YCl3 ·6H2O ͑ ͒ 323 4.1 0.068 T YCl3 ·6H2O ͑ ͒ 373 4.3 0.071 T YCl3 ·6H2O ͑ ͒ 423 4.9 0.08 T YCl3 ·6H2O ͑ ͒ ͑ ͒ ͑ ͒ 458 9.5 0.14 D Peritectic or congruent YCl3 ·6H2O+YCl3 ·2H2O D ͑ ͒ YCl3 ·6H2O melting ͑ ͒ ͑ ͒ 523 at 1.3 MPa 11 0.17 T YCl3 ·2H2O D Ͼ ͑ ͒ ͑ ͒ 623 at 1.3 MPa 15 0.21 T YCl3 ·2H2O D

͑ of HCl to aqueous solution decreases the YCl3 solubility. A The quaternary systems YCl3 –CeCl3 –EuCl3 –H2O Refs. ͒ ͑ ͒ precise comparison of the data is rather difficult because of 46 and 54 and YCl3 –EuCl3 –HoCl3 –H2O Ref. 78 at the different experimental temperatures and different expres- 298 K were also investigated. Solid phases in the first system sions of HCl content. The data of Ref. 37 show concentra- were dominated by solid solutions. In the second system, a ͑ ͒ tions almost twice as high as the interpolated data of Refs. succession of solid solutions Y,Eu,Ho Cl3 ·6H2O was de- 23, 42, and 45; the latter three papers show concordant re- termined. Reference 78 is not compiled because the results sults. There is quite good agreement between the results of were not presented in numerical form and were condensed in Ref. 42 and single points of Refs. 63 and 64 at 298 K. It is hardly readable figures. Wang et al.64 measured solubilities unexpected that, at the highest HCl concentration of in the YCl3 –CsCl–HCl–H2O system at 298 K and observed 45 45 mass % and temperature of 373 K, no partial dehydra- crystallization of two double salts, YCl3 ·4CsCl·10H2O and tion of hexahydrate was seen. 2YCl3 ·3CsCl·14H2O, which released water gradually at el- Solubility in the ternary YCl3 –LnCl3 –H2O systems at evated temperatures, forming finally anhydrous compounds 54 40,41,50 54 54 44 298 K was studied for La, Ce, Pr, Nd, Eu, of the same salt stoichiometries. Qiao et al.63 observed the 54,57 58 Gd, and Ho. All lanthanide chlorides showed similar formation of the same stable double salts in the quaternary solubilities in a molal scale. According to these results, the CdCl2 –YCl3 –HCl–H2O as well as in the ternary heptahydrates of LaCl , CeCl , and PrCl , do not form solid 3 3 3 CdCl2 –YCl3 –H2O system. solutions with YCl hexahydrate of different structures, but 3 YCl3 solubility was also investigated in solutions contain- at high YCl3 contents La, Ce, or Pr form a series of solid ing organic substances. The authors of Ref. 21 observed 20 ͑ ͒ solutions of the Y,Ln Cl3 ·6H2O type, thus adopting the times lower YCl3 solubility in 40 mass % HCl dissolved in a structure of YCl3 hexahydrate. The YCl3 –NdCl3 –H2O sys- 1:1 mixture of diethyl ether and water, but 4 times higher tem contained a continuous series of solid solutions solubility was observed in 43 mass % HCl dissolved in ͑ ͒ Y,Nd Cl3 ·6H2O as the equilibrium solid phase. Hydrated 95 mass % ethanol; both values are compared to the solubil- chlorides of Eu and Gd co-crystallized with YCl3 ·6H2O; at ity of YCl3 in aqueous 40 mass % HCl solution at 273 K low YCl3 concentrations, the corresponding solid solutions ͑ ϫ −3 −1͒ 1.1 10 mol kg . The ternary systems of YCl3 –H2O based on EuCl3 ·6H2O or GdCl3 ·6H2O and at high YCl3 with urea,47 acetamide,48 thiourea,49 and selenourea49 were concentrations on YCl3 ·6H2O, a solid miscibility break in investigated at 303 K and with ␤-phenylalanine62 at 298 K. between was attributed to a significant difference in the ionic Analysis of the equilibrium solid phases in these systems radii of Gd or Eu and Y. For similar radii, such as for Y and pointed to adduct formation between YCl and urea, aceta- Ho in the YCl –HoCl –H O system, the solid phase was 3 3 3 2 mide, or ␤-phenylalanine but not with thiourea and sele- reported to be a continuous solid solution ͑Y,Ho͒Cl ·6H O 3 2 nourea; the latter systems were of a simple eutonic type. in the whole composition range. In the YCl3 –YF3 –H2O 53 system, formation of YCl3 ·4YF3 ·9H2O was observed. ͑ ͒ ͑ ͒ References Neither KCl Ref. 39 nor MgCl2 Ref. 56 formed double 10 ͑ ͒ salts or solid solutions with YCl3 hexahydrate in the corre- N. P. Sokolova, Radiokhimiya 30, 435 1988 . sponding ternary systems at 298 K; the systems were found 21W. Fischer, J. Wernet, and M. Zumbusch-Pfisterer, Z. An- 63 ͑ ͒ to be of eutonic type. In the CdCl2 –YCl3 –H2O system, the org. Chem. 258, 157 1949 . authors found the formation of two double salts, 23W. Fischer, H. Bauer, I. Dillo, T. Molaug, J. Nier, H. Ro- ͑ ͒ 4CdCl2 ·YCl3 ·13H2O and 5CdCl2 ·2YCl3 ·26H2O, as well as hrer, and K. Trovaag, Z. Anorg. Chem. 357, 177 1968 . 36 a metastable 8CdCl2 ·YCl3 ·15H2O. M. C. Crew, H. E. Steinert, and B. S. Hopkins, J. Phys.

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Chem. 29,34͑1925͒. 58A. A. Sorokina and N. G. Yudina, Izv. Sibir. Otd. Akad. 37M. D. Williams, H. C. Fogg, and C. James, J. Am. Chem. Nauk SSSR, Ser. Khim. Nauk ͑5͒,51͑1981͒. Soc. 47, 297 ͑1925͒. 59J. A. Rard and F. H. Spedding, J. Chem. Eng. Data 27, 454 38J. E. Powell, US Atomic Energy Commission Report No. ͑1982͒. IS-15, 1959. 60N. P. Sokolova, Zh. Neorg. Khim. 28, 782 ͑1983͒. 39Z. N. Shevtsova and I. Vei-Tszyuan, Zh. Neorg. Khim. 8, 61M. A. Urusova and V. M. Valyashko, Zh. Neorg. Khim. 38, 1749 ͑1963͒. 1074 ͑1993͒. 40A. V. Nikolaev, A. A. Sorokina, and V. G. Tsubanov, Dokl. 62F. Ren, Sh. L. Gao, G. H. Chu, and I. Zh. Shiq, Yingyong Akad. Nauk SSSR 172, 1333 ͑1967͒. Huaxue ͑Chin. J. Appl. Chem.͒ 17, 203 ͑2000͒. 41A. V. Nikolaev, A. A. Sorokina, A. Ya. Vilenskaya, and V. 63Zh. P. Qiao, L. H. Zhuo, and H. Wang, Wuji Huaxue Xue- G. Tsubanov, Izv. Sibir. Otd. Akad. Nauk SSSR, Ser. Khim. bao 20, 929 ͑2004͒. Nauk ͑6͒,5͑1967͒. 64H. Wang, J. X. Duan, X. Q. Ran, and Sh. Y. Gao, Chin. J. 42Z. N. Shevtsova, L. S. Nam, and B. G. Korshunov, Zh. Chem. 22, 1128 ͑2004͒. 65 Neorg. Khim. 13, 1682 ͑1968͒. L. Ya. Markovskii, E. Ya. Pesina, Yu. A. Omelchenko, and 43V. S. Petelina, N. I. Nikurashina, and G. V. Illarionova, Yu. D. Kondrashev, Zh. Neorg. Khim. 14,14͑1969͒. 66 Issledovaniya v Oblasti Khimii Redkozemelnykh Elemen- N. V. Baryshnikov, A. V. Polonskii, and A. I. Khokhlov, Zh. tov, Saratovskii Universitet, Saratov 3,48͑1971͒. Neorg. Khim. 20, 3177 ͑1975͒; A. V. Polonskii, N. V. Bary- 44A. V. Nikolaev and A. A. Sorokina, Izv. Sibir. Otd. Akad. shnikov, and L. A. Voskresenskaya, ibid. 21, 317 ͑1976͒. 67 Nauk SSSR, Ser. Khim. Nauk ͑4͒,61͑1971͒. J. M. Wang, Zh. Zh. Guo, Y. Sh. Chen, Sh. F. Huang, and 45 A. N. Zelikman, N. V. Baryshnikov, and A.I. Khokhlov, C. Y. Wang, Xibei Daxue Xuebao ͑J. Northwest Univ., Zh. Neorg. Khim. 16, 2023 ͑1971͒. Supplement͒ 20,49͑1990͒. 68 46A. V. Nikolaev, A. A. Sorokina, and N. G. Yudina, Izv. V. V. Hong and J. Sundström, Thermochim. Acta 307,37 Sibir. Otd. Akad. Nauk SSSR, Ser. Khim. Nauk no 5,28 ͑1997͒. 69 ͑1972͒. G. Haeseler and F. Matthes, J. Less-Common Met. 9, 133 47G. A. Ashimkulova, K. Sulaimankulov, Sh. T. Turdaliev, ͑1965͒. 70 and K. Nogoev, Zh. Neorg. Khim. 18, 2011 ͑1973͒. C. Matignon, Ann. Chim. Phys. 8, 433 ͑1906͒. 71 48G. A. Ashimkulova, Geterogennye Ravnovesiya v Siste- M. Z. Su and P. G. Li, Huaxue Tongbao 4,34͑1979͒. 72 makh Neorganicheskikh i Organicheskikh Soedinenii ͑Ilim, H. J. Seifert and S. Funke, Thermochim. Acta 320,1 Frunze, 1974͒,p.21. ͑1998͒. 49 73 ͑ ͒ G. A. Ashimkulova, K. Nogoev, and K. Sulaimankulov, Zh. W. W. Wendlandt, J. Inorg. Nucl. Chem. 9, 136 1959 . 74 Neorg. Khim. 19, 2588 ͑1974͒. L. G. Sokolova, A. V. Lapitskaya, A. F. Bolshakov, S. B. 50A. V. Nikolaev, L. G. Kosobudskaya, and A. A. Sorokina, Pirkes, and B. V. Abalduyev, Zh. Neorg. Khim. 26, 1736 ͑ ͒ Izv. Sibir. Otd. Akad. Nauk SSSR, Ser. Khim. Nauk ͑5͒,53 1981 ; B. V. Abalduev, A. F. Bolshakov, L. G. Sokolova, ͑1975͒. A. V. Lapitskaya, and S. B. Pirkes, Issledovaniya v Oblasti 51 ͑ F. H. Spedding, V. W. Saeger, K. A. Gray, P. K. Boneau, M. Khimii Redkozemelnykh Elementov Saratovskii Univer- ͒ A. Brown, C. W. DeKock, J. L. Baker, L. E. Shiers, H. O. sitet, Saratov, 1975 ,p.47. 75 Weber, and A. Habenschuss, J. Chem. Eng. Data 20,72 W. W. Wendlandt and R. G. Sewell, Texas J. Sci. 8, 231 ͑ ͒ ͑1975͒. 1961 . 76 52F. H. Spedding, H. O. Weber, V. W. Saeger, H. H. Yu. G. Sakharova and T. A. Ezhova, Zh. Neorg. Khim. 21 ͑ ͒ ͑ ͒ Petheram, J. A. Rard, and A. Habenschuss, J. Chem. Eng. 551 1976 ; Russ. J. Inorg. Chem. 21, 296 1976 . 77 Data 21, 341 ͑1976͒. W. W. Wendlandt and J. L. Bear, Anal. Chim. Acta 21, 439 53 ͑ ͒ N. Levina, G. Dadabaeva, D. D. Ikrami, and A. S. 1959 . 78 Paramzin, Dep. VINITI Report No. N-478-77, 1977. A. V. Nikolaev, A. A. Sorokina, and N. G. Yudina, Izv. 54 ͑ ͒ A. V. Nikolaev, A. A. Sorokina, V. N. Lubkova, and N. G. Sibir. Otd. Akad. Nauk SSSR, Ser. Khim. Nauk 6 ,116 ͑ ͒ Yudina, Osnovy Vzaimodeistviya Solei Redkozemelnykh El- 1983 . ementov v Vode ͑Nauka, Novosibirsk, 1977͒, pp. 36, 45, 46, 53, 72, 79, and 161. 55A. V. Nikolaev, A. A. Sorokina, N. P. Sokolova, G. S. 3.2. Data for the YCl3 –H2O System Kotlyar-Shapirov, N. P. Anoshina, L. I. Bagryantseva and A. P. Olovyanishnikova, Izv. Sibir. Otd. Akad Nauk SSSR, Components: Original Measurements: ͑ ͒ 36 Ser. Khim. Nauk ͑4͒,84͑1977͒. 1 Yttrium chloride; YCl3; M.C. Crew, H.E. Steinert, and ͓ ͔ 56A. V. Nikolaev, A. A. Sorokina, P. A. Stabnikov, N. P. 10361-92-9 B.S. Hopkins, J. Phys. Chem. 29, ͑2͒ Water; H O; ͓7732-18-5͔ 34 ͑1925͒. Sokolova and G. S. Kotlyar-Shapirov, Izv. Sibir. Otd. Akad. 2 Nauk SSSR, Ser. Khim. Nauk ͑6͒,44͑1977͒. Variables: Prepared by: 57N. P. Sokolova, I. I. Yakovlev, and I. N. Komissarova, Izv. Temperature: 273–353 K T. Mioduski and C. Gumiński Sibir. Otd. Akad. Nauk SSSR, Ser. Khim. Nauk ͑6͒,45 ͑1980͒.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1777

Experimental Values Experimental Values

Solubility of YCl3 in water at various temperatures Solubility of YCl3 in water at various temperatures

/ / a a / ͑ ͒ a t °C g YCl3 100 g H2O 100w1 m1 t °C 100w Y2O3 100w1 m1

0 74.3 42.6 3.81 10 25.37 43.85 4.000 72.7 42.1 3.72 20 25.50 44.08 4.037 16 76.5 43.4 3.92 30 25.64 44.33 4.078 75.1 42.9 3.85 40 25.86 44.70 4.140 25.1 75.4 43.0 3.86 50 26.07 45.07 4.202 75.3 43.0 3.86 a 45 77.0 43.5 3.94 calculated by the compilers 76.3 43.3 3.91 60 77.0 43.5 3.94 The authors used YCl3 ·6H2O for the solubility tests, and 77.6 43.7 3.97 they assumed that the equilibrium solid has the same for- 80 78.1 43.9 4.00 mula. No analysis of the solute after the tests was reported. 78.1 43.9 4.00 The melting point of YCl3 ·6H2O was found to be acalculated by the compilers 161–163 °C.

−3a The authors tested that the degree of hydration of the sol- Solubility of YCl3 in aqueous HCl solution of density of 1.1051 g cm ute was not changed between 298 and 353 K, and it may be at various temperatures assumed that the equilibrium solid was YCl3 ·6H2O. At / ͑ ͒ t °C 100w Y2O3 100w1 lower temperatures, the equilibrium solid could be nona- or 10 14.09 24.35 octahydrate of YCl3, but 5 h of equilibration seems to be insufficient time in the opinion of the compilers. 15 14.12 24.41 20 14.25 24.63 Auxiliary Information 30 14.74 25.48 40 15.34 26.52 Method/Apparatus/Procedure: 50 15.94 27.55 The isothermal method was used. Both solute and solvent contained in an Erlenmeyer flask were immersed in a thermostat and vigorously shaken at athis density, if measured at 293 K, corresponds to an aqueous solution intervals. The degree of saturation was controlled periodically and containing ϳ21 mass % HCl equilibration of 5 h was found to be sufficient. At higher temperatures, the saturation point was reached by cooling the supersaturated solution from Auxiliary Information higher temperature. Duplicate samples were drawn off for analysis. The amount of Y was precipitated with oxalic acid. The precipitate was Method/Apparatus/Procedure: filtered, washed, dried, and ignited to the oxide. The factor of 2.9043 was The isothermal method was used. Samples were placed in bottles and used for converting the oxide to the chloride. brought to a temperature either above or below the experimental temperature. They were sealed, placed in a thermostat, and rotated for 9 h Source and Purity of Materials: or more. About 1 cm3 of the saturated solution was withdrawn, diluted to An initial source of Y contained traces of Ho and Er. It was purified by 150 cm3, and precipitated with oxalic acid. The mixture was allowed to precipitation as oxalate and twice as hydroxide ͑in the compilers’ opinion, stand for 12 h or precipitated with oxalic acid. The mixture was allowed ͒ ͑ ͒ the separation may not be effective .YOH 3 was converted to Y2O3, to stand for 12 h or more; then the precipitate was washed, ignited to dissolved in HCl, and the solution evaporated to crystallization. The Y2O3, and weighed. The analyses were made in duplicate; the samples crystals were filtered off, centrifuged, washed, and centrifuged again. were taken from the same bottle. Freshly distilled conductivity water, protected from air, was used. All other reagents were carefully purified. Source and Purity of Materials: The solute was prepared by dissolving highly purified Y2O3 in HCl, Estimated Error: evaporating the solution to the point of crystallization, cooling in ice, and Solubility: precision of Ϯ1.5%. saturating with HCl. The crystals were filtered, washed with saturated HCl Temperature: no better than Ϯ0.1 K ͑by the compilers͒. solution, and recrystallized when necessary. The crystals were dried in vacuum over H2SO4 and NaOH.

Estimated Error: Components: Original Measurements: Nothing speciﬁed; no estimation possible. ͑ ͒ 37 1 Yttrium chloride; YCl3; M.D. Williams, H.C. Fogg, ͓10361-92-9͔ and C. James, J. Am. Chem. Soc. ͑2͒ Hydrochloric acid; HCl; 47,297͑1925͒. ͓7647-01-0͔ Components: Original Measurements: ͑ ͒ ͓ ͔ ͑ ͒ 38 3 Water; H2O; 7732-18-5 1 Yttrium chloride; YCl3; J.E. Powell, US Atomic Energy ͓10361-92-9͔ Commission Report No. IS-15, ͑ ͒ ͓ ͔ Variables: Prepared by: 2 Water; H2O; 7732-18-5 1959. ϳ Solvent: H2Oor 21 mass % T. Mioduski, M. Salomon, and C. HCl Gumiński Variables: Prepared by: Temperature: 283–323 K Temperature: 273–333 K T. Mioduski and C. Gumiński

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1778 MIODUSKI, GUMIŃSKI, AND ZENG

Experimental Values be deduced from another paper from the same laboratory ͓V.S. Petelina, R.V. Mertslin, N.I. Nikurashkina and L.K. Se- Solubility of YCl3 in water at various temperatures dova, Issledovaniya v Oblasti Khimii Redkozemelnykh El- / / a t °C g YCl3 ·H2O 100 g H2O m1 ementov ͑Saratovskii Universitet, Saratov, 1969͒,p.85͔. 0 199 3.84 Auxiliary Information 25 217 4.03 Method/Apparatus/Procedure: 60 233 4.20 The isothermal method was used. The metals in the saturated solutions acalculated by the compilers were determined gravimetrically as oxides by the oxalate method. Source and Purity of Materials: The equilibrium solid phase was reported to be Oxides of the metals ͑of unknown purity͒ were dissolved in HCl ͑1:1͒ YCl3 ·6H2O for all temperatures; this was assured by seeding solutions. The solutions were evaporated until crystallization. The products the supersaturated solutions with YCl3 ·6H2O crystals. How- were dried in a desiccator and analyzed for the metal contents by the oxalate method. ever, the equilibrium solid phase seems to be YCl3 ·9H2Oor YCl3 ·8H2O at 273 K as shown on the equilibrium diagram. Estimated Error: Nothing speciﬁed. Auxiliary Information

Method/Apparatus/Procedure: Components: Original Measurements: Saturated solutions were heated with an excess of YCl3 ·6H2O until the ͑ ͒ 51 salt was completely dissolved and then cooled to the desired temperature. 1 Yttrium chloride; YCl3; F.H. Spedding, V.W. Saeger, ͓ ͔ Small crystals of YCl3 ·6H2O were added to the supersaturated solutions, 10361-92-9 or other rare earth K.A. Gray, P.K. Boneau, M.A. which were further equilibrated isothermally for 24–28 h. Aliquots of the chlorides Brown, C.W. DeKock, J.L. ͑ ͒ ͓ ͔ saturated solutions were analyzed gravimetrically as the oxide for Y 2 Water; H2O; 7732-18-5 Baker, L.E. Shiers, H.O. Weber, content. The salt was ﬁrst evaporated to dryness and HNO3 was added and A. Habenschuss, J. Chem. ͑ ͒ and heated gradually to yield ﬁnally Y2O3, as reported by Powell and Eng. Data 20,72 1975 . Burkholder ͓J. Inorg. Nucl. Chem. 14,65͑1960͔͒. Variables: Prepared by: Source and Purity of Materials: Rare earth chloride T. Mioduski and C. Gumiński ͓ About 99.9% pure Y2O3 was obtained by ion exchange method J.E. Temperature: 273.15 and Powell and F.H. Spedding, Chem. Eng. Prog., Symp. Ser. 55, 101 ͑1959͔͒. 298.15 K It was dissolved in a slight excess of aqueous HCl solution. The resulting moist salt was recrystallized several times before use. Experimental Values Estimated Error:

Nothing speciﬁed Solubility of rare earth chlorides at 25.000 °C and of YCl3 at 0.000 °C

/ −1 ␳/ −3 Salt m1 mol kg gcm Components: Original Measurements: YCl at 0.000 °C 3.5976 1.515 51 ͑1͒ Yttrium chloride; YCl ; 43V.S. Petelina, N.I. Nikurashina, 3 3 YCl at 25.000 °C 3.9478 1.543 79 ͓10361-92-9͔ or and G.V. Illarionova, 3 ͓ ͔ a ͑2͒ Lanthanum chloride; LaCl ; Issledovaniya v Oblasti Khimii LaCl3 10099-58-8 3.8959 1.694 33 3 ͓ ͔ b ͓10099-58-8͔ Redkozemelnykh Elementov, PrCl3 10361-79-2 3.8910; 3.8940 1.716 26 ͑ ͒ ͓ ͔ NdCl ͓10024-93-8͔ 3.9292a 1.737 94 3 Water; H2O; 7732-18-5 Saratovskii Universitet, Saratov 3 ͓ ͔ a 3,48͑1971͒. SmCl3 10361-82-7 3.6401 1.714 41 ͓ ͔ b EuCl3 10025-76-0 3.5889; 3.5864 1.708 75 Variables: Prepared by: ͓ ͔ a GdCl3 10138-52-0 3.5906 1.722 91 Salt: YCl3 or LaCl3 T. Mioduski and C. Gumiński ͓ ͔ b TbCl3 10042-88-3 3.5713; 3.5727 1.723 49 One temperature: 298 K ͓ ͔ c DyCl3 10025-74-8 3.6310 1.745 09 ͓ ͔ b HoCl3 10138-62-2 3.6942; 3.6965 1.766 94 Experimental Values ͓ ͔ a ErCl3 10138-41-7 3.7821 1.793 89 ͓ ͔ b Solubility of YCl3 in water at 25 °C was reported to be TmCl3 13537-18-3 3.8773; 3.8794 1.821 48 −1 ͓ ͔ a 45.08 mass % or 4.204 mol kg ͑as recalculated by the YbCl3 10361-91-8 4.0028 1.861 37 ͓ ͔ b compilers͒. The equilibrium solid phase was found to be LuCl3 10099-66-8 4.1165; 4.1202 1.892 91 YCl ·6H O. 3 2 aas reported in this paper as well as in Ref. 18 Solubility of LaCl3 in water at 25 °C was reported to be bas reported in Ref. 18 −1 46.26 mass % or 3.510 mol kg ͑as recalculated by the cthis value was quoted from Ref. 18 because the original value reported compilers͒. The equilibrium solid phase was found to be ͑3.3610 mol kg−1͒ seems to be an obvious misprint LaCl3 ·8H2O. It seems that these data contain two typo- graphical errors: the solubility should be 49.26 mass % Equilibrium solid phases were not speciﬁed −1 ͑ ͒ LaCl3 or 3.958 mol kg as recalculated by the compilers and the solid phase formula should be LaCl3 ·7H2O as may

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1779

Auxiliary Information Source and Purity of Materials: Initial rare earth oxides were purified by ion exchange and were probably Method/Apparatus/Procedure: 99.85+% pure ͓F.H. Spedding, M.J. Pikal, and B.O. Ayers, J. Phys. Chem. The saturated solutions were prepared by concentrating samples of the 70,2440͑1966͔͒. Excesses of oxides were dissolved in HCl solutions and corresponding stock solutions followed by 3 week equilibration in a the resulting solutions were filtered. The stock solutions were adjusted to 18 constant-temperature bath. The saturated solutions were analyzed by the the equivalence pH ͑ϳ2͒. Chemical analyses for chlorides by AgCl oxide, sulfate, and EDTA titration methods for cations and gravimetrically gravimetric method and for the metal ions by the oxalate or sulfate as AgCl precipitate for chlorides. The densities were carefully measured methods confirmed precisely the salts’ stoichiometry. with a Sprengel-Ostwald pycnometer. The temperature was controlled with Water was purified by distillation from alkaline permanganate solution. a Pt resistance thermometer calibrated by the NBS. Estimated Error: Source and Purity of Materials: Solubility: precision of Ϯ͑0.05–0.1͒%. Initial rare earth oxides were purified by ion exchange and were probably Temperature: precision of Ϯ0.01 K. 99.85+% pure ͓F.H. Spedding, M.J. Pikal, and B.O. Ayers, J. Phys. Chem. 70, 2440 ͑1966͔͒. Excesses of oxides were dissolved in HCl solutions and the resulting solutions were filtered. The stock solutions were adjusted to the equivalence pH ͑ϳ2͒. Components: Original Measurements: ͑ ͒ 55 Water was purified by distillation from alkaline permanganate solution. 1 Yttrium chloride; YCl3; A.V. Nikolaev, A.A. Sorokina, ͓10361-92-9͔ N.P. Sokolova, G.S. ͑ ͒ ͓ ͔ Estimated Error: 2 Water; H2O; 7732-18-5 Kotlyar-Shapirov, N.P. Anoshina, Solubility: precision of Ϯ͑0.05–0.1͒%. L.I. Bagryantseva, and A.P. Temperature: accuracy of Ϯ0.005 K. Olovyanishnikova, Izv. Sibir. Otd. Akad. Nauk SSSR, Ser. Khim. Nauk ͑4͒,84͑1977͒.

Components: Original Measurements: Variables: Prepared by: ͑ ͒ 52 1 Yttrium chloride; YCl3; F.H. Spedding, H.O. Weber, Temperature: 273–323 K T. Mioduski and C. Gumiński ͓10361-92-9͔ or other rare earth V.W. Saeger, H.H. Petheram, J.A. chlorides Rard, and A. Habenschuss, J. ͑ ͒ ͓ ͔ ͑ ͒ Experimental Values 2 Water; H2O; 7732-18-5 Chem. Eng. Data 21, 341 1976 .

Variables: Prepared by: Solubility of YCl3 in water at various temperatures Rare earth metal chloride T. Mioduski, M. Salomon, and C. / / / −1a / −3a ␳/ −3 One temperature: 298.15 K Gumiński t °C 100w1 mass % m1 mol kg c1 mol dm gcm

0 43.3 3.91 — — Experimental Values 10 43.4 3.93 3.44 1.545 25 43.5 3.94 3.44 1.544 Solubilities of rare earth metal chlorides at 25.00 °C 30 44.0 4.02 3.48 1.5468 50 45.2 4.22 3.61 1.559 / –1 Salt m1 mol kg acalculated by the compilers YCl3 3.9478 ͓ ͔ LaCl3 10099-58-8 3.8944 The equilibrium solid phase was reported to be PrCl ͓10361-79-2͔ 3.8969 −3 3 YCl3 ·6H2O and its density was 2.054 g cm . ͓ ͔ NdCl3 10024-93-8 3.9307 ͓ ͔ SmCl3 10361-82-7 3.6414 Auxiliary Information EuCl ͓10025-76-0͔ 3.5839 3 Method/Apparatus/Procedure: GdCl ͓10138-52-0͔ 3.5898 3 Solutions and crystals were isothermally equilibrated with continuous TbCl ͓10042-88-3͔ 3.5733 3 agitation for 3–10 d ͑at low temperatures for 6–8 d͒ in a thermostat. DyCl ͓10025-74-8͔ 3.6302 3 Saturated solutions were analyzed for Y content by titration with EDTA ͓ ͔ HoCl3 10138-62-2 3.6987 solution. The solubility results were mean values of five to ten ͓ ͔ ErCl3 10138-41-7 3.7840 independent examinations. Densities were measured with a pycnometer. ͓ ͔ TmCl3 13537-18-3 3.8814 The density of the hydrated salt was measured with the use of dry ͓ ͔ YbCl3 10361-91-8 4.0018 toluene. ͓ ͔ LuCl3 10099-66-8 4.1239 Source and Purity of Materials: ͑ ͒ Hexahydrate of YCl3 was prepared by dissolving Y2O3 99.9+% pure in The equilibrium solid phases were not specified. HCl solution of special purity. The resulting salt hydrate was recrystallized twice from HCl solution and finally from water. The salt Auxiliary Information crystals were dried at temperatures below 30 °C. The product was analyzed for Y and Cl contents. The water of hydration was calculated by Method/Apparatus/Procedure: difference. The method of isopiestic equilibration was applied. Cups containing both Estimated Error: solution and solute crystals were added to equilibration chambers. Solubility: nothing specified. Duplicate samples were equilibrated for at least 1 week before the precise Ϯ weighing of saturated solutions was started and measurements were made Temperature: stabilities of 0.1 and 1Kat0°C. −3 at 3–4 d intervals for 2 weeks. Density: precision of Ϯ0.003 g cm .

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1780 MIODUSKI, GUMIŃSKI, AND ZENG

There are several reservations related to the interpretation Components: Original Measurements: ͑ ͒ 59 of the experimental results. The meaning of the description 1 Yttrium chloride; YCl3; J.A. Rard and F.H. Spedding, J. ͓10361-92-9͔ Chem. Eng. Data 27, 454 ͑1982͒. “͑metastable͒” is not explained in the text of the paper. The ͑2͒ Water; H O; ͓7732-18-5͔ 2 authors presented the YCl3 –H2O phase diagram with two Variables: Prepared by: alternative eutectic points either at −42 or at −52.5 °C. The One temperature: 298.15 K C. Gumiński eutectic at −52.5 °C seems to be a metastable phenomenon. The third, fourth, and ﬁfth reactions in the table ͑reﬂecting Experimental Values data from a table of the paper͒ seem to be in error and the Solubility of YCl3 in H2O at 25.00 °C was determined to correct equations should be written as, respectively: be 3.9367Ϯ0.0035 mol kg−1 ͑or 0.066 223 mole fraction melt+YCl3 ·9H2O=YCl3 ·15H2O, YCl , as calculated by the compiler͒. 3 melt+YCl ·8H O=YCl ·9H O, The authors stated that the equilibrium solid phase was 3 2 3 2 melt+YCl3 ·6H2O=YCl3 ·8H2O, presumably YCl3 ·6H2O. They observed that YCl3 showed only a slight tendency to supersaturation under isothermal The composition of the solid phases and that of the eutec- conditions. tic point at −42 °C were determined from arrest times of the thermal analysis. The eutectic point at −52.5 °C was postu- Auxiliary Information lated on the presence of unexplained thermal arrests at about

Method/Apparatus/Procedure: −52 °C which were only observed between YCl3 ·15H2O Solutions of YCl were prepared from Y O and HCl solution taken in 3 2 3 and YCl3 ·9H2O; this fact may be rather connected with a proper amounts. The stock solutions were precisely adjusted to their equivalence concentrations by titration with HCl solution. The saturating polymorphic phase transition in one of these compounds but concentration of YCl3 was determined by using 9 or 10 d of isopiestic not with a eutectic formation which should occur between equilibration. Solutions of CaCl2 and KCl were used as the isopiestic ͑ ͒ YCl3 ·15H2O and H2O s . The compilers read out other ex- standards. Duplicate samples were used for the equilibration. The details related to the apparatus were the same as described in Ref. 52 ͑see the perimental points of the liquidus of a YCl3 –H2O phase dia- corresponding data sheet in this section͒. gram ﬁgure in the original paper and recalculated composi-

Source and Purity of Materials: tions from mass % to mole fractions.

Y2O3 used for preparation of the stock solution was puriﬁed by ion Experimental points on the liquidus in the YCl3 –H2O system exchange method. Mass-spectroscopic analysis indicated impurities: 0.0024% of other rare earth metals, 0.046% Ca, 0.002% Fe, and 0.0023 % t/ °C 100w x a of other elements. 1 1 HCl was of “analytical reagent grade.” −11 15 0.016 −13 17 0.018 Estimated Error: −20 21 0.024 Solubility: precision of Ϯ0.1%. −41 31 0.041 Temperature: precision of Ϯ0.005 K. −43 32 0.042 −3 41 0.060 3 42 0.063 Components: Original Measurements: ͑ ͒ 60 a 1 Yttrium chloride; YCl3; N.P. Sokolova, Zh. Neorg. mole fractions calculated by the compilers ͓10361-92-9͔ Khim. 28, 782 ͑1983͒. ͑ ͒ ͓ ͔ 2 Water; H2O; 7732-18-5 Auxiliary Information

Variables: Prepared by: Method/Apparatus/Procedure:

Composition: 0–62 mass % YCl3 T. Mioduski and C. Gumiński The binary system was studied by differential thermal analysis between

Temperature: 153–293 K −120 °C and room temperature. Proper amounts of water and YCl3 ·6H2O were placed in glass ampoules and sealed. The samples were homogenized in liquid state or were equilibrated in heterogeneous state Experimental Values for several days. The ampoules were placed in an apparatus for thermal analysis and cooled to −120 °C. Then they were heated at a rate of Nonvariant equilibria in the YCl –H O system 3 2 0.2–0.5 K/min to observe the phase transitions. Temperatures were recorded by means of a calibrated thermocouple ͓N.P. Sokolova, K.A. Equilibrium Khaldoyanidi, and I.I. Yakovlev, Zh. Neorg. Khim. 25, 2584 ͑1980͔͒. / a a t °C 100w1 m1 x1 type Reaction Source and Purity of Materials: −42 32 2.4 0.042 Eutectic melt=YCl ·15H O+H O͑s͒ 3 2 2 YCl ·6H O was prepared by dissolving Y O ͑99.9% pure͒ in HCl −52.5 37 3.0 0.051 Eutectic melt=YCl ·8H O+H O͑s͒ 3 2 2 3 3 2 2 solution ͑specially pure͒. The salt was recrystallized twice from HCl ͑metastable͒? solution and once from water. The salt composition was conﬁrmed by −23 37 3.0 0.051 Peritectic melt+YCl3 ·15H2O=YCl3 ·9H2O titration of Y ions with EDTA solution. 0 41 3.5 0.060 Peritectic melt+YCl3 ·9H2O=YCl3 ·8H2O 2.5 41.5 3.6 0.061 Peritectic melt+YCl3 ·8H2O=YCl3 ·6H2O Estimated Error: Solubility: nothing speciﬁed; reading-out procedure of Ϯ0.5 mass %. amolalities and mole fractions calculated by the compilers

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1781

Temperature: precision of Ϯ0.5 K ͓N.P. Sokolova, K.A. Khaldoyanidi, and Temperature: precision of Ϯ2K. I.I. Yakovlev, Zh. Neorg. Khim. 25, 2584 ͑1980͒.͔; reading-out procedure Pressure: precision of Ϯ͑0.3–0.8͒ kg cm−2. of Ϯ1 K due to poor correspondence between the data in the table and in a ﬁgure of the original paper.

Components: Original Measurements: 3.3. YCl3–Inorganic Salt–H2O Systems ͑ ͒ 61 1 Yttrium chloride; YCl3; M.A. Urusova and V.M. 3.3.1. YCl3 –MCl–H2O „M=H,K… Systems ͓10361-92-9͔ Valyashko, Zh. Neorg. Khim. 38, ͑ ͒ ͓ ͔ ͑ ͒ 2 Water; H2O; 7732-18-5 1074 1993 . Components: Original Measurements: Variables: Prepared by: ͑ ͒ 21 Composition: 49–77 mass % C. Gumiński 1 Yttrium chloride; W. Fischer, J. Wernet and ͓ ͔ YCl YCl3; 10361-92-9 M. Zumbusch-Pﬁsterer, 3 ͑ ͒ ͑ ͒ Temperature: 425–653 K 2 Hydrochloric acid; HCl; Z. Anorg. Chem. 258,157 1949 . ͓ ͔ Pressure: elevated but not always 7647-01-0 ͑ ͒ ͓ ͔ speciﬁed 3 Water; H2O; 7732-18-5 ͑ ͒ 4 Diethyl ether; C4H10O; ͓60-29-7͔ ͑ ͒ ͓ ͔ Experimental Values 5 Ethanol; C2H6O; 64-17-5

Variables: Prepared by: Solubility of YCl3 in H2O at several temperatures Solvents T. Mioduski and C. Gumiński / / −2 a One temperature: 273 K t °C p kg cm 100w1 x1 Experimental method

152 — 49 0.081 Visual observation of last crystal dissolution Experimental Values 179 — 58 0.113 Visual observation of last crystal Solubility of YCl in various solvents at 0 °C dissolution 3 185 — 65 0.146 Visual observation of last crystal gYO /100 cm3 dissolution 2 3 Solvent saturated solution c /mol dm−3a 250 ϳ13 69 0.170 Vapor-pressure measurement 1 355 — 75 0.217 Visual observation of last crystal 40 mass % HCl 0.024 0.0011 dissolution 40 mass % HCl+diethyl ether ͑1:1͒ 0.0015 0.000 06 380 — 77 0.236 Visual observation of last crystal 43 mass % HCl in 95 mass % ethanol 0.098 0.0043 dissolution acalculated by the compilers amole fraction calculated by the compiler The equilibrium solid phases were not speciﬁed. YCl3 ·6H2O was the equilibrium solid phase up to 185 °C. Auxiliary Information The authors claimed that anhydrous YCl3 was the solid solute at higher temperatures, but no experimental evidence of Method/Apparatus/Procedure: this statement was reported in the paper. The solvents were saturated with HCl gas in a glass apparatus. Filtrates of The authors observed hydrolysis of the salt especially at the saturated solutions were probably analyzed gravimetrically for Y higher temperatures, which was manifested by an increase in content after its precipitation as Y2O3. HCl content in the vapor phase over the solution. Source and Purity of Materials: Auxiliary Information The materials used were of reagent grade.

Method/Apparatus/Procedure: Estimated Error: The solubility was determined by means of visual observation of the Solubility: nothing specified. disappearance of the last solute crystal at a fixed temperature. The Temperature: nothing specified. solution and the salt were contained in a quartz ampoule. The authors corrected the solution composition for water evaporation above 300 °C. The solubility was also determined in a steel autoclave by measurement of Components: Original Measurements: ͑ ͒ 23 vapor pressure over undersaturated and supersaturated solutions. Pressure 1 Yttrium chloride; YCl3; W. Fischer, H. Bauer, I. Dillo, was measured with a mercury valve and a calibrated manometer. The ͓10361-92-9͔ T. Molaug, J. Nier, H. Rohrer, relation of pressure versus concentration showed a pressure plateau for the ͑2͒ Hydrochloric acid; HCl; and K. Trovaag, Z. Anorg. Chem. supersaturated solution and the break point on such a plot corresponded to ͓7647-01-0͔ 357, 177 ͑1968͒. ͑ ͒ ͓ ͔ the solubility. 3 Water; H2O; 7732-18-5

Source and Purity of Materials: Variables: Prepared by:

Purity of YCl3 ·6H2O was not speciﬁed. The salt was further dehydrated Concentration of HCl: T. Mioduski and C. Gumiński ϳ at 250 °C and YCl3 ﬁnally contained less than 2 mass % Y2O3. 0–45 mass % One temperature: 273 K Estimated Error: Solubility: precision of Ϯ1 mass %.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1782 MIODUSKI, GUMIŃSKI, AND ZENG

Experimental Values Source and Purity of Materials: ͑ ͒ YCl3 ·6H2O was obtained by dissolving Y2O3 99.8+% pure in HCl Solubility of YCl3 in HCl solutions at 0 °C solution and crystallization of the product.

␳/ −3 a a Estimated Error: gcm 100w2 m2 100w1 m1 Nothing speciﬁed. 1.48 0 0 43.0 3.86 1.42 5 2.3 35.7 3.08 1.36 10 4.5 28.5 2.37 Components: Original Measurements: ͑ ͒ 42 1.30 15 6.5 21.4 1.72 1 Yttrium chloride; YCl3; Z.N. Shevtsova, L.S. Nam, and 18 7.6 17.2 1.36 ͓10361-92-9͔ B.G. Korshunov, Zh. Neorg. 1.24 20 8.4 14.6 1.14 ͑2͒ Hydrochloric acid; HCl; Khim. 13,1682͑1968͒. 22 9.1 11.9 0.92 ͓7647-01-0͔ ͑ ͒ ͓ ͔ 24 9.9 9.4 0.72 3 Water; H2O; 7732-18-5 26 10.7 7.1 0.54 Variables: Prepared by: 28 11.5 5.1 0.39 Concentration of HCl: T. Mioduski and C. Gumiński 1.18 30 12.3 3.3 0.25 0–25.4 mass % 32 13.3 1.9 0.15 One temperature: 298 K 34 14.3 0.95 0.075 36 15.5 0.43 0.035 Experimental Values 38 16.9 0.22 0.018

40 16.5 0.115 0.0098 Solubility of YCl3 in HCl solutions at 25 °C 42 19.9 0.060 0.0053 ␳/ −3 a a 44 21.5 0.038 0.0034 gcm 100w2 m2 100w1 m1 45b 22.5 0.034 0.0031 0 0 44.14 4.047 acalculated by the compilers 2.57 1.23 39.89 3.550 b saturated with HCl gas at 0.1 MPa 4.10 1.93 37.54 3.294 5.02 2.37 36.84 3.245 The equilibrium solid phase was found to be YCl3 ·6H2O. 9.75 4.46 30.25 2.582 According to subsequent phase diagram studies, YCl3 ·8H2O 17.13 7.44 19.70 1.597 and YCl3 ·9H2O phases should be in equilibrium at 0 °C. 17.89 7.68 18.25 1.464 Densities of the solutions with more than 35 mass % HCl 19.23 8.22 16.64 1.329 had practically the same value as the densities of pure HCl 23.00 9.83 12.80 1.021 ͑ ͒ 1.5514 0.44 0.21 42.68 3.836 solutions without YCl3 . 1.5019 2.57 1.23 39.89 3.550 Based on the experimental data from the table above, the 1.4338 7.25 3.27 31.91 2.686 authors reported smoothed values of YCl3 solubility in HCl 1.3759 14.47 6.39 23.41 1.930 solutions at 0 °C. 1.2762 21.41 8.67 10.88 0.823 1.2266 23.41 9.58 9.60 0.734 Smoothed values of YCl3 solubility in HCl solutions at 0 °C acalculated by the compilers / −1 a m2 m1 g−equivalent kg m1 The equilibrium solid phase was found to be YCl3 ·6H2O. 0 11.60 3.87 Auxiliary Information 5 6.7 2.23 10 2.1 0.70 Method/Apparatus/Procedure: 14 0.28 0.093 The isothermal method was applied. The solutions were equilibrated for 18 0.03 0.01 6 d. The method of sample analysis was not reported. The composition of 22.5 0.009 0.003 the solid phase was determined by the method of Schreinemakers. Optical observation of the crystals was also carried out. The densities of the acalculated by the compilers solutions were determined in a pycnometer calibrated with doubly distilled Auxiliary Information water. Source and Purity of Materials: Method/Apparatus/Procedure: YCl ·6H O was prepared by dissolving Y O ͑unknown purity͒ in HCl The isothermal method was used. Equilibrium was approached from 3 2 2 3 ͑chemically pure͒. The resulting salt was recrystallized three times. undersaturation and supersaturation. The content of Y in the saturated Doubly distilled water was used. solution was determined gravimetrically as Y2O3 after precipitation of Y͑OH͒ with NH solution; the chlorides were earlier transformed into 3 3 Estimated Error: nitrates with the use of concentrated HNO . The total Cl content was 3 Solubility: nothing speciﬁed; precision of better than Ϯ2%͑as estimated determined by potentiometric titration with AgNO solution. Free HCl 3 by the compilers from scatter on a graphical presentation of all results in was found from the difference of the total Cl and Y contents. The the paper͒. equilibrium solid phase composition was determined graphically by the Ϯ method of Schreinemakers or by chemical analysis of the crystals after Temperature: stability of 0.1 K. Ϯ −3 washing them with acetone and prolonged drying in a vacuum desiccator. Density: precision of 0.0005 g cm .

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1783

Components: Original Measurements: Components: Original Measurements: ͑ ͒ 45 ͑ ͒ 39 1 Yttrium chloride; YCl3; A.N. Zelikman, N.V. 1 Yttrium chloride; YCl3; Z.N. Shevtsova and I. ͓10361-92-9͔ Baryshnikov and A.I. Khokhlov, ͓10361-92-9͔ Vei-Tszyuan, Zh. Neorg. Khim. ͑2͒ Hydrochloric acid; HCl; Zh. Neorg. Khim. 16, 2023 ͑2͒ Potassium chloride; KCl; 8,1749͑1963͒. ͓7647-01-0͔ ͑1971͒. ͓7447-40-7͔ ͑ ͒ ͓ ͔ ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 3 Water; H2O; 7732-18-5

Variables: Prepared by: Variables: Prepared by: Concentration of HCl: T. Mioduski and C. Gumiński Salt composition T. Mioduski and C. Gumiński 0–34.2 mass % Temperature: 298 and 323 K Temperature: 323–373 K Experimental Values

Experimental Values Composition of saturated solutions in the ternary YCl3 −KCl−H2O system at two temperatures Solubility of YCl3 in HCl solutions at several temperatures t/ °C 100w m a 100w m a Equilibrium solid phaseb / a a 1 1 2 2 t °C 100w2 m2 100w1 m1 Equilibrium solid phase 25 44.14 4.047 0 0 A 50 0 0 43.6 3.96 YCl ·6H O 3 2 43.31 3.974 0.87 0.209 A 3.4 1.6 39.1 3.48 42.34 3.885 1.85 0.445 A+B 6.2 2.9 35.1 3.06 42.36 3.890 1.87 0.450 A+B 11.2 5.0 27.6 2.31 42.34 3.888 1.89 0.455 A+B 16.4 7.1 20.6 1.63 39.18 3.480 3.16 0.735 B 23.8 10.0 11.2 0.88 33.48 2.831 5.95 1.318 B 31.6 13.5 4.4 0.35 27.93 2.262 8.82 1.870 B 34.2 14.8 2.5 0.20 19.81 1.474 11.36 2.214 B 75 0 0 44.3 4.07 YCl ·6H O 3 2 13.42 0.963 15.19 2.854 B 6.7 3.2 35.3 3.12 3.19 0.222 23.29 4.249 B 9.6 4.3 31.5 2.74 0 0 26.27 4.779 B 15.3 6.9 24.0 2.02 50 45.27 4.236 0 0 A 19.3 8.6 19.0 1.58 43.35 4.053 1.87 0.458 A 23.3 10.3 14.7 1.21 42.51 4.091 4.27 1.076 A+B 24.2 10.7 13.8 1.14 42.56 4.098 4.25 1.072 A+B 100 0 0 45.1 4.21 YCl ·6H O 3 2 42.58 4.102 4.26 1.075 A+B 2.3 1.1 42.2 3.89 40.34 3.702 3.86 0.928 B 3.8 1.9 40.2 3.68 34.35 2.985 6.71 1.527 B 5.9 2.9 37.6 3.41 29.76 2.474 8.63 1.879 B 20.96 1.641 13.62 2.792 B acalculated by the compilers 15.76 1.204 17.18 3.436 B Auxiliary Information 8.11 0.594 21.95 4.209 B 0 0 30.72 5.947 B Method/Apparatus/Procedure: The isothermal method was used. Equilibrium was approached from acalculated by the compilers b supersaturation and undersaturation. Equilibrium was reached after A=YCl3 ·6H2O; B=KCl 2–2.5 h, but the solutions were kept in a thermostat for 1 h more. The content of Y was determined by complexometric titration with EDTA The system was found to be of eutonic type. solution in acetate buffer using a xylenol orange indicator. The HCl concentration was determined by titration with a base solution. The solid Auxiliary Information phases were analyzed by Schreinemakers’ method of wet residues. Method/Apparatus/Procedure: Source and Purity of Materials: The isothermal method was used. Equilibrium at 298 and 323 K was ͑ ͒ reached within 5 and 4 d, respectively. It was conﬁrmed by the YCl3 ·6H2O was prepared by dissolving Y2O3 99.8+% pure in aqueous HCl solution ͑chemically pure͒. The resulting solution was evaporated coincidence of two chemical analysis results made at time intervals. The until the crystals were formed. The product was twice recrystallized and compositions of the solid phases were determined by chemical analysis, dried at room temperature. the method of Schreinemakers, and optical observation of the crystals.

Estimated Error: Source and Purity of Materials: Solubility: nothing speciﬁed. Y2O3 was the starting material which contained “no traces of impurities.” No other details are available. Temperature: stability of Ϯ0.1 K. Estimated Error: Solubility: precision of Ϯ1%͑as estimated from the eutonic points by the compilers͒. Temperature: nothing speciﬁed.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1784 MIODUSKI, GUMIŃSKI, AND ZENG

3.3.2. YCl3 –MCl2 –H2O „M=Mg,Cd… Systems Components: Original Measurements: ͑ ͒ 63 1 Yttrium chloride; YCl3; Zh.P. Qiao, L.H. Zhuo, and H. Components: Original Measurements: ͓10361-92-9͔ Wang, Wuji Huaxue Xuebao 20, ͑ ͒ 56 ͑ ͒ ͑ ͒ 1 Yttrium chloride; YCl3; A.V. Nikolaev, A.A. Sorokina, 2 Cadmium chloride; CdCl2; 929 2004 . ͓10361-92-9͔ P.A. Stabnikov, N.P. Sokolova, ͓10108-64-2͔ ͑ ͒ 2 Magnesium chloride; MgCl2; and G.S. Kotlyar-Shapirov, Izv. ͑3͒ Hydrochloric acid; HCl; ͓7786-30-3͔ Sibir. Otd. Akad. Nauk SSSR, ͓7647-01-0͔ ͑ ͒ ͓ ͔ ͑ ͒ ͑ ͒ ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 Ser. Khim. Nauk 6 ,44 1977 . 4 Water; H2O; 7732-18-5

Variables: Prepared by: Variables: Prepared by: Salt composition T. Mioduski and C. Gumiński Composition of mixtures C. Gumiński and D. Zeng One temperature: 298 K One temperature: 298 K

Experimental Values Experimental Values

Composition of saturated solutions in the ternary YCl3 −MgCl2 −H2O sys- Composition of saturated solutions in the ternary YCl3 –CdCl2 –H2O system at 25 °C tem at 25 °C

a a b a a b 100w2 m2 100w1 m1 Equilibrium solid phase 100w1 m1 100w2 m2 Equilibrium solid phase

35.7 5.83 0 0 A 0 0 57.23 7.300 A 35.0 5.77 1.3 0.10 A 3.03 0.359 53.75 6.784 A 33.6 5.56 2.9 0.23 A 4.16 0.494 52.74 6.675 A 33.3 5.53 3.5 0.28 A 5.58 0.671 51.85 6.644 A+B 30.6 5.17 7.3 0.60 A 6.06 0.722 50.98 6.474 B 28.1 4.81 10.5 0.88 A+B 8.40 1.004 48.74 6.204 B 28.1 4.81 10.6 0.89 A+B 13.78 1.728 45.39 6.065 B 25.1 4.34 14.1 1.19 B 15.69 2.078 45.64 6.439 B+C 24.3 4.23 15.3 1.30 B 15.95 2.082 44.82 6.233 B+C 21.9 3.80 17.6 1.49 B 17.72 2.259 42.11 5.719 C 14.4 2.55 26.4 2.28 B 17.24 2.186 42.38 5.725 C 11.3 2.04 30.5 2.68 B 20.29 2.532 38.67 5.140 C 9.3 1.69 32.9 2.92 B 21.84 2.758 37.60 5.057 C 8.1 1.47 34.2 3.04 B 23.05 2.928 36.64 4.959 C 7.1 1.30 35.4 3.15 B 16.51 2.097 43.23 5.858 D 3.9 0.72 39.3 3.54 B 17.58 2.250 42.41 5.782 D 1.3 0.24 42.5 3.87 B 20.98 2.643 38.37 5.149 D 1.1 0.21 42.8 3.91 B 21.67 2.696 37.16 4.924 D 0 0 43.8 3.99 B 22.15 2.780 37.04 4.951 D 23.50 2.927 35.39 4.696 D a molalities calculated by the compilers 24.28 3.051 34.96 4.679 D b A=MgCl2 ·6H2O; B=YCl3 ·6H2O 24.82 3.134 34.62 4.656 D+E 26.24 3.134 30.88 3.929 E Auxiliary Information 27.70 3.287 29.14 3.683 E Method/Apparatus/Procedure: 30.21 3.755 28.59 3.785 E The isothermal method was used.110 Solutions and crystals were mixed in 31.77 3.986 27.41 3.663 E closed glass vessels for 1 week in a thermostat. The crystals were 32.06 4.073 27.63 3.739 E+F continuously crushed. The metal ion content in the liquid phase was 32.85 4.083 25.95 3.436 F analyzed by titration with EDTA: Y at pH=5.5 in the presence of xylenol 33.92 3.991 22.56 2.828 F orange and the sum of Y+Mg at pH=10 in the presence of chromogen 35.71 3.763 15.69 1.761 F black. The compositions of the solid phases were determined by 38.89 3.844 9.30 0.979 F Schreinemakers’ method. 43.26 3.906 0 0 F

Source and Purity of Materials: a ͑ molalities calculated by the compilers Hydrate of YCl3 was obtained by dissolving Y2O3 in HCl solution of b special purity͒. The salt was recrystallized twice from HCl solution and A=CdCl2 ·2.5H2O; B=CdCl2 ·H2O; C=YbCl3 ·8CdCl2 ·15H2O; then from water, as in Ref. 110. D=YbCl3 ·4CdCl2 ·13H2O; E=2YCl3 ·5CdCl2 ·26H2O; F=YCl3 ·6H2O

Hydrate of MgCl2 was twice recrystallized from water, as in Ref. 110. The compounds C, D, and E were found to be congruently Estimated Error: soluble. The compound C was found to be metastable. Solubility: nothing speciﬁed. Temperature: stability of Ϯ0.1 K.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1785

Composition of saturated solutions in the quaternary 3.3.3. YCl3 –MCl3 –H2O „M=La, Ce, Pr, Nd, Eu, Gd, Ho… Systems YCl3 –CdCl2 –HCl–H2O system at 25 °C

a Components: Original Measurements: 100w 100w 100w Equilibrium solid phase 1 2 3 ͑ ͒ 40 1 Yttrium chloride; YCl3; A.V. Nikolaev, A.A. Sorokina, 0 48.37 9.78 B ͓10361-92-9͔ and V.G. Tsubanov, Dokl. Akad. ͑ ͒ ͑ ͒ 2.50 47.62 9.17 B 2 Cerium chloride; CeCl3; Nauk SSSR 172,1333 1967 . ͓ ͔ 3.49 47.22 8.32 B 7790-86-5 ͑3͒ Water; H O; ͓7732-18-5͔ 4.80 46.50 8.61 B+D 2 4.55 46.04 8.74 B+D Variables: Prepared by: 5.89 43.88 9.28 D Salt composition T. Mioduski and C. Gumiński 7.31 42.37 8.58 D One temperature: 298 K 8.08 41.44 8.78 D 10.48 38.87 8.00 D 12.88 37.50 7.56 D Experimental Values 13.50 36.62 7.67 D 12.41 34.65 9.88 E Composition of saturated solutions in the ternary YCl3 –CeCl3 –H2Osys- tem at 25 °C 15.28 32.28 8.99 E 19.67 29.38 7.60 E 100w m a 100w m a Equilibrium solid phaseb 21.77 28.08 7.12 E+F 1 1 2 2 19.13 23.61 10.46 F 0 0 48.5c 3.82 B 23.28 15.82 9.57 F 4.3 0.43 44.2 3.48 B 24.49 9.99 10.24 F 8.8 0.87 39.5 3.10 B 31.07 0 8.74 F 13.0 1.26 34.3 2.64 B 23.5 2.26 23.2 1.77 B a B=CdCl2 ·H2O; D=YbCl3 ·4CdCl2 ·13H2O; E=2YCl3 ·5CdCl2 ·26H2O; 24.1 2.28 21.7 1.62 B F=YCl3 ·6H2O 30.2 2.87 16.0 1.21 A+B 32.0 3.02 13.8 1.03 A+B The compounds D and E were found to be congruently 35.1 3.28 10.1 0.75 A+B soluble. 36.9 3.42 7.8 0.57 A+B 37.1 3.43 7.3 0.53 A+B Auxiliary Information 40.3 3.74 4.5 0.33 A+B 40.7 3.75 3.7 0.27 A+B Method/Apparatus/Procedure: 43.8c 3.99 0 0 A Mixtures of the components in polyethylene tubes were placed in a stirring device at constant temperature. The acidity of the mixtures with acalculated by the compilers HCl was checked after 8 d of equilibration and adjusted to the desired bA=YCl ·nH O ͑n is probably 6͒; B=CeCl ·7H O; A+B=solid solution acidity level with HCl. Then the mixtures were further equilibrated for 3 2 3 2 7–15 d, and the separated solid and liquid phases were analyzed. The based on YCl3 ·nH2O c content of Y was determined by titration with EDTA solution in read out from a ﬁgure by the compilers urotropine buffer using a dimethylorange indicator after Cd was masked by an organic reagent. The content of HCl was determined by titration Auxiliary Information with NaOH solution. The content of Cl was determined by titration with Method/Apparatus/Procedure: AgNO3 solution with the Fayans indicator. The content of Cd was found from the corresponding differences. The composition of the compounds C, The isothermal method was used. The solutions were equilibrated in glass ϳ D, and E was determined by the method of Schreinemakers as well as by containers for 1 month. The crystals were crushed continuously with a chemical analysis. The compounds D and E were characterized by special glass hammer during the equilibration. The method of analysis of differential scanning calorimetry ͑DSC͒, thermogravimetry, and x-ray the saturated solutions was not speciﬁed. The composition of the crystals diffraction. was analyzed by Schreinemakers’ method of residues.

Source and Purity of Materials: Source and Purity of Materials: ͑ ͒ Nothing specified. YCl3 ·6H2O was prepared by dissolution of Y2O3 99.99% pure in HCl solution. Estimated Error: CdCl ·2.5H O, EDTA, AgNO , and HCl were of analytical purity. 2 2 3 Solubility: nothing specified; reading-out procedure of Ϯ0.5 mass % ͑by Water was doubly distilled. the compilers͒. Estimated Error: Temperature: nothing specified. Solubility: nothing specified; precision of Ϯ͑0.5–3͒% in the determination of the eutonic points, as estimated by the compilers. Temperature: nothing specified. Components: Original Measurements: ͑ ͒ 41 1 Yttrium chloride; YCl3; A.V. Nikolaev, A.A. Sorokina, ͓10361-92-9͔ A.Ya. Vilenskaya, and V.G. ͑ ͒ 2 Cerium chloride; CeCl3; Tsubanov, Izv. Sibir. Otd. Akad. ͓7790-86-5͔ Nauk SSSR, Ser. Khim. Nauk ͑ ͒ ͓ ͔ ͑ ͒ ͑ ͒ 3 Water; H2O; 7732-18-5 6 ,5 1967 .

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1786 MIODUSKI, GUMIŃSKI, AND ZENG

Variables: Prepared by: Source and Purity of Materials: Salt composition T. Mioduski and C. Gumiński Both chlorides were prepared by dissolving the oxides ͑99.9+% pure͒ in One temperature: 298 K HCl solution ͑of “special” purity͒. The salts obtained were recrystallized subsequently from HCl solution and water. The salts were air dried at temperatures below 35 °C. The dry salts were analyzed for cation Experimental Values contents by titration with EDTA solution and for chloride content by the Volhard method. The water content was found from the corresponding

Composition of saturated solutions in the ternary YCl3 –CeCl3 –H2Osys- differences or was determined by Karl-Fischer titration. tem at 25 °C Estimated Error: a a Solubility: precision of probably better than Ϯ2% ͑by the compilers͒. 100w1 m1 100w2 m2 Temperature: precision of probably Ϯ0.2 K ͑by the compilers͒. 0b 0 48.6b 3.84 2.2b 0.22 46.4b 3.66 b b 5.4 0.53 42.5 3.31 Components: Original Measurements: b b 8.8 0.87 39.5 3.10 ͑ ͒ 44 1 Yttrium chloride; YCl3; A.V. Nikolaev and A.A. 9.4 0.91 37.8 2.90 ͓10361-92-9͔ Sorokina, Izv. Sibir. Otd. Akad. 12.4b 1.20 34.5b 2.64 ͑ ͒ 2 Europium chloride; EuCl3; Nauk SSSR, Ser. Khim. Nauk b b 18.2 1.71 27.4 2.04 ͓10025-76-0͔ ͑4͒,61͑1971͒. ͑ ͒ ͓ ͔ 24.1 2.27 21.6 1.61 3 Water; H2O; 7732-18-5 27.6 2.59 17.9 1.33 Variables: Prepared by: 29.4 2.79 16.7 1.26 29.6b 2.82 16.6b 1.25 Salt composition T. Mioduski and C. Gumiński One temperature: 298 K 29.8b 2.83 16.2b 1.21 30.2 2.87 16.6 1.25 30.3 2.88 15.9 1.20 Experimental Values 30.5 2.95 16.5 1.26 b b 30.6 2.96 16.4 1.26 Composition of saturated solutions in the ternary YCl3 –EuCl3 –H2Osys- 31.0 2.97 15.5 1.18 tem at 25 °C 32.0b 3.02 13.8b 1.03 a a 33.0 2.99 10.5 0.75 100w1 m1 100w2 m2 36.6b 3.43 8.7b 0.65 0 0 48.2 3.60 36.9 3.42 7.8 0.57 5.4b 0.52 41.9b 3.08 37.2 3.34 5.7 0.41 7.3b 0.70 39.2b 2.84 40.3b 3.75 4.6b 0.34 9.8b 0.92 35.9b 2.56 42.0b 3.88 2.5b 0.18 11.0b 1.05 35.2b 2.53 43.5 b 3.94 0b 0 14.8b 1.40 31.1b 2.23 acalculated by the compilers 19.1 1.79 26.1 1.84 b b balso reported by Nikolaev et al. ͓Osnovy Vzaimodeistviya Solei Redkoze- 23.0 2.16 22.5 1.60 b b melnykh Elementov v Vode ͑Nauka, Novosibirsk, 1977͒,p.33͔. 25.3 2.28 17.8 1.21 29.2b 2.64 14.2b 0.97 The equilibrium solid phases were not reported; however, 31.1 2.85 13.0 0.90 32.8b 3.01 11.3b 0.78 based on the solubility diagrams, the compilers conclude that 34.0 3.09 9.7 0.67 ͑ ͒ b b a solid solution of Y,Ce Cl3 ·6H2O is the solute at YCl3 35.2 3.21 8.6 0.59 contents higher than 30 mass %. The components in the bi- 35.8 3.27 8.2 0.57 b b nary systems were found to be YCl ·6H O and 36.2 3.29 7.4 0.51 3 2 37.2b 3.35 5.9b 0.40 CeCl3 ·7H2O. 38.7 3.43 3.5 0.23 39.6b 3.55 3.2b 0.22 Auxiliary Information 40.6 3.68 2.9 0.20 b b Method/Apparatus/Procedure: 40.9 3.71 2.6 0.18 b b The isothermal method was applied. The solids were continuously 43.3 3.91 0 0 pulverized by mechanical pestle strokes during equilibration. The solid a and liquid phases were analyzed: the sum of Y and Ce was determined by calculated by the compilers complexometric titration and Ce by a redox method. The compositions of balso reported in Ref. 54 the solid phases were determined graphically and algebraically by Schreinemakers’ method with concordant results. The equilibrium solid phases were not speciﬁed. At the ͑ ͒ higher YCl3 contents, formation of Y,Eu Cl3 ·6H2O solid solution is probable.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1787

Auxiliary Information Auxiliary Information

Method/Apparatus/Procedure: Method/Apparatus/Procedure: Nothing specified. Experimental details were probably the same as in Ref. The isothermal method was used. Initial samples contained either constant 41. molar amount of both salts with various amounts of water or different contents of salts with constant amount of water. The samples were Source and Purity of Materials: equilibrated for 5–6 d in a thermostat with continuous crushing of the Nothing was specified. salts and mixing. Approach to equilibrium was monitored by a periodic measurement of the refractive index of the solutions. Samples of the Estimated Error: saturated solutions and solid phases were analyzed chemically, but no Solubility: nothing specified; precision of better than Ϯ2% ͑as estimated details were reported. The solids were additionally analyzed by x-ray by the compilers from scatter on graphical presentation of all results͒. diffraction. Temperature: nothing specified. Source and Purity of Materials:

Hydrates of YCl3 and CeCl3 were prepared by dissolving proper oxides in HCl solution followed by crystallization from HCl solution and then from Components: Original Measurements: water. The salts obtained were analyzed for contents of the metal and ͑1͒ Yttrium chloride; YCl ; 50 A.V. Nikolaev, L.G. 3 chloride ions. ͓10361-92-9͔ Kosobudskaya, and A.A. ͑ ͒ 2 Cerium chloride; CeCl3; Sorokina, Izv. Sibir. Otd. Akad Estimated Error: ͓ ͔ 7790-86-5 Nauk SSSR, Ser. Khim. Nauk Solubility: precision of Ϯ͑1–3͒%, as speciﬁed in by Nikolaev et al. ͑ ͒ ͓ ͔ ͑ ͒ ͑ ͒ 3 Water; H2O; 7732-18-5 5 ,53 1975 . ͓Osnovy Vzaimodeistviya Solei Redkozemelnykh Elementov v Vode ͑Nauka, Novosibirsk, 1977͒,p.60͔. Variables: Prepared by: Temperature: nothing speciﬁed. Salt composition T. Mioduski and C. Gumiński One temperature: 298 K

Components: Original Measurements: ͑ ͒ 54 Experimental Values 1 Yttrium chloride; YCl3; A.V. Nikolaev, A.A. Sorokina, ͓10361-92-9͔ V.N. Lubkova, and N.G. Yudina, ͑ ͒ Composition of saturated solutions in the ternary YCl3 –CeCl3 –H2Osys- 2 Lanthanum chloride; LaCl3; Osnovy Vzaimodeistviya Solei tem at 25 °C ͓10099-58-8͔ Redkozemelnykh Elementov v ͑3͒ Praseodymium chloride; Vode ͑Nauka, Novosibirsk, 1977͒, a a b ͓ ͔ 100w2 m2 100w1 m1 Equilibrium solid phase PrCl3; 10361-79-2 p. 53. ͑ ͒ 4 Neodymium chloride; NdCl3; 48.8 3.87 0 0 A ͓10024-93-8͔ c ͑ ͒ 41.4 3.26 7.0 0.69 AЈ 5 Gadolinium chloride; GdCl3; 38.8 3.04 9.4 0.93 AЈc ͓10138-52-0͔ c ͑ ͒ ͓ ͔ 33.7 2.61 14.0 1.37 AЈ 6 Water; H2O; 7732-18-5 26.5 2.01 20.0 1.91 AЈc Variables: Prepared by: 21.2 1.62 25.7 2.48 AЈc Composition of salt pairs T. Mioduski and C. Gumiński 20.6 1.59 26.9 2.62 AЈc One temperature: 298 K 16.5 1.26 30.3 2.92 AЈc Јc 16.2 1.23 30.2 2.89 A Experimental Values Јc 16.6 1.28 30.7 2.98 B Composition of saturated solutions in the ternary YCl –LaCl –H O sys- c 3 3 2 16.4 1.25 30.5 2.94 BЈ tem at 25 °C 13.6 1.03 32.8 3.13 BЈc 11.9 0.90 34.2 3.25 BЈc a a 100w2 m2 100w1 m1 7.5 0.56 37.9 3.55 BЈc 0 0 43.6 3.96 B 0 0 43.5 3.94 2.7 0.21 44.4 4.30 amolalities calculated by the compilers 5.7 0.43 40.4 3.84 b A=CeCl3 ·7H2O; AЈ=solid solution of YCl3 ·7H2O in CeCl3 ·7H2O; 8.7 0.67 38.4 3.72

B=YCl3 ·6H2O; BЈ=solid solution of CeCl3 ·6H2OinYCl3 ·6H2O 11.8 0.90 34.6 3.31 cas read out from a ﬁgure by the compilers 15.4 1.19 32.0 3.12 15.6 1.22 32.2 3.16 The same results were also reported by Nikolaev et al. 15.7 1.22 31.9 3.12 ͓Osnovy Vzaimodeistviya Solei Redkozemelnykh Elementov v 15.3 1.20 32.6 3.20 17.7 1.37 29.7 2.89 ͑ ͒ ͔ Vode Nauka, Novosibirsk, 1977 ,p.60. 27.7 2.16 20.1 1.97 34.0 2.69 14.5 1.44 40.0 3.15 8.3 0.82 43.2 3.44 5.6 0.56 46.5 3.75 3.0 0.30 48.8 3.89 0 0

amolalities calculated by the compilers

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1788 MIODUSKI, GUMIŃSKI, AND ZENG

Composition of saturated solutions in the ternary YCl3 –PrCl3 –H2O sys- Composition of saturated solutions in the ternary YCl3 –GdCl3 –H2O system at 25 °C tem at 25 °C

a a a a 100w3 m3 100w1 m1 100w5 m5 100w1 m1

49.0 3.89 0 0 0 0 43.5 3.94 42.9 3.35 5.3 0.52 amolalities calculated by the compilers 36.9 2.87 11.1 1.09 33.9 2.63 14.0 1.38 The equilibrium solid phases were not reported. It was 30.6 2.36 17.0 1.66 observed in a diagram that the solid phases showed a ten- 24.9 1.91 22.3 2.16 22.2 1.70 25.1 2.44 dency to immiscibility when the ionic radii of the cations 22.7 1.75 24.7 2.40 were different. 22.3 1.71 25.0 2.43 Auxiliary Information 21.7 1.67 25.7 2.50 19.4 1.48 27.6 2.67 Method/Apparatus/Procedure: 17.4 1.32 29.2 2.80 The isothermal method was used. Water and crystals were mixed in closed 12.2 0.91 33.5 3.16 vessels in a thermostat. The crystals were continuously crushed. The metal 8.9 0.66 36.3 3.39 ion contents in the liquid and solid phases were analyzed with atomic 4.6 0.34 39.9 3.68 absorption spectroscopy. The concentration of chloride was determined by 0 0 43.5 3.94 the Volhard method. amolalities calculated by the compilers Source and Purity of Materials: Hydrates of rare earth metal chlorides were prepared by dissolving the Composition of saturated solutions in the ternary YCl3 –NdCl3 –H2O sys- corresponding oxides ͑99.9+% pure͒ in HCl solution ͑specially pure͒.The tem at 25 °C salts were recrystallized twice from HCl solution and then from water. They were dried in air at temperatures below 35 °C. The compositions of a a 100w4 m4 100w1 m1 the salts were conﬁrmed by chemical analyses: metals by titration with EDTA solution and chloride by the Volhard method. 49.7 3.94 0 0 45.3 3.65 4.5 0.46 Estimated Error: 39.5 3.15 9.8 0.99 Solubility: precision of better than Ϯ3%. 34.9 2.75 13.8 1.38 Temperature: nothing speciﬁed. 26.9 2.08 20.7 2.02 20.9 1.61 26.5 2.58 21.4 1.65 26.0 2.53 Components: Original Measurements: ͑ ͒ 58 18.0 1.35 27.9 2.64 1 Yttrium chloride; YCl3; A.A. Sorokina and N.G. 19.9 1.53 27.4 2.66 ͓10361-92-9͔ Yudina, Izv. Sibir. Otd. Akad. ͑ ͒ 17.6 1.34 29.1 2.80 2 Holmium chloride; HoCl3; Nauk SSSR, Ser. Khim. Nauk, ͓10138-62-2͔ ͑5͒,51͑1981͒. 16.6 1.25 29.6 2.82 ͑3͒ Water; H O; ͓7732-18-5͔ 11.9 0.89 34.0 3.22 2 10.6 0.79 34.9 3.28 Variables: Prepared by: 9.0 0.67 36.8 3.48 Salt composition T. Mioduski and C. Gumiński 2.9 0.21 41.7 3.85 One temperature: 298 K 0 0 43.5 3.94 amolalities calculated by the compilers Experimental Values

Composition of saturated solutions in the ternary YCl3 –GdCl3 –H2O sys- Composition of saturated solutions in the ternary YCl3 –HoCl3 –H2O system at 25 °C tem at 25 °C

a a a a ␳/ −3 100w5 m5 100w1 m1 100w2 m2 100w1 m1 gcm

48.7 3.60 0 0 51.4 3.90 0 0 1.773 45.9 3.40 2.9 0.29 44.3 3.28 5.9 0.61 1.737 42.8 3.15 5.7 0.57 39.6 2.90 10.0 1.02 1.715 36.9 2.68 10.8 1.06 34.5 2.49 14.4 1.44 1.692 23.9 1.68 22.1 2.10 32.1 2.32 16.8 1.68 1.680 19.6 1.36 25.8 2.42 26.9 1.91 21.3 2.11 1.657 18.1 1.26 27.2 2.55 24.7 1.74 23.0 2.25 1.646 12.4 0.85 32.5 3.02 20.4 1.42 26.6 2.57 1.633 11.7 0.81 33.5 3.13 20.1 1.40 26.9 2.60 1.634 11.4 0.79 33.6 3.13 15.5 1.07 31.2 3.00 1.612 8.4 0.58 36.3 3.36 12.0 0.82 34.0 3.22 1.597 5.4 0.37 39.1 3.61 7.1 0.48 38.4 3.61 1.575

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1789

Composition of saturated solutions in the ternary YCl3 –HoCl3 –H2O sys- Composition of saturated solutions in the ternary YCl3 –GdCl3 –H2O system at 25 °C tem at −10 °C

a a ␳/ −3 a a b 100w2 m2 100w1 m1 gcm 100w1 m1 100w2 m2 Equilibrium solid phase

0 0 44.2 4.06 1.550 18.7 1.75 26.6 1.84 C 11.8 1.14 35.0 2.50 C amolalities calculated by the compilers 5.68 0.561 42.5 3.11 C 2.50 0.246 45.4 3.31 C A series of solid solutions of YCl ·6H O and 3 2 0 0 48.4 3.56 D HoCl3 ·6H2O was found to be in equilibrium with the satu- amolalities calculated by the compiler rated liquid solutions. b A=YCl3 ·9H2O; B=solid solution based on YCl3 ·9H2O; C=solid solution based on GdCl ·6H O; D=GdCl ·6H O Auxiliary Information 3 2 3 2 Auxiliary Information Method/Apparatus/Procedure:

The isothermal method was used. Solid hydrates of YCl3 and HoCl3 in Method/Apparatus/Procedure: corresponding proportions were dissolved in water. The water from the The solutions and crystals were isothermally equilibrated for a long time ϳ solution was evaporated at 30 °C and the resulting solid was the solute in a cryostat with continuous agitation until equilibrium in the system was given to further equilibration with the liquid. The contents of Y and Ho in reached. The liquid and solid phases were separated by ﬁltration under the separated liquid and solid phases were determined with atomic vacuum at the selected temperature. The crystal hydrates were visually absorption spectroscopy. The chloride content was determined by the evaluated due to the difference in the crystal shapes of hexahydrates and Volhard method. Densities of the saturated solutions were measured with a nonahydrates. Samples of the saturated solutions and the crystals were pycnometer. The authors also performed isopiestic measurements of the diluted, or dissolved, and analyzed. The metals were determined by x-ray solutions. ﬂuorescence spectrometry with an internal standard.

Source and Purity of Materials: Source and Purity of Materials: Hydrates of YCl3 and HoCl3 were prepared by dissolving proper oxides in According to Ref. 55,YCl·6H O and GdCl ·6H O were prepared by ͑ ͒ 3 2 3 2 HCl solution specially pure . The salts were recrystallized twice from dissolution of the corresponding oxides ͑99.9+% pure͒ in HCl solution of HCl solution and then from water. special purity. The salts were recrystallized twice from HCl solution and then from water. They were dried in air at temperatures below 30 °C. The Estimated Error: composition of the salts was conﬁrmed by chemical analysis: metals by Solubility: precision of Y and Ho analysis of Ϯ3% and of Cl analysis of titration with EDTA solution and Cl by the method of Volhard. The water Ϯ1%. content was found by difference. Temperature: nothing speciﬁed; stability probably of Ϯ0.1 K, as in other reports from this laboratory. Estimated Error: Density: precision of Ϯ0.002 g cm−3. Solubility: precision of the metal determination of better than Ϯ3%. Temperature: precision of Ϯ0.1 K.

Components: Original Measurements: ͑ ͒ 57 3.3.4. YCl3 –YF3 –H2O System 1 Yttrium chloride; YCl3; N.P. Sokolova, I.I. Yakovlev, ͓10361-92-9͔ and L.N. Komissarova, Izv. Sibir. ͑ ͒ 2 Gadolinium chloride; GdCl3; Otd. Akad Nauk SSSR, Ser. Components: Original Measurements: ͓10138-52-0͔ Khim. Nauk, ͑6͒,45͑1980͒. ͑1͒ Yttrium chloride; YCl ; 53N. Levina, G. Dadabaeva, D.D. ͑3͒ Water; H O; ͓7732-18-5͔ 3 2 ͓10361-92-9͔ Ikrami, and A.S. Paramzin, Dep. ͑ ͒ Variables: Prepared by: 2 Yttrium ﬂuoride; YF3; VINITI Report No. N-478-77, ͓13709-49-4͔ 1977. Composition of salts C. Gumiński ͑3͒ Water; H O; ͓7732-18-5͔ One temperature: 263 K 2 Variables: Prepared by: Experimental Values Composition of mixtures C. Gumiński One temperature: 298 K

Composition of saturated solutions in the ternary YCl3 –GdCl3 –H2O system at −10 °C Experimental Values

100w m a 100w m a Equilibrium solid phaseb 1 1 2 2 Composition of saturated solutions in the ternary YCl3 –YF3 –H2O system at 25 °C 41.9 3.69 0 0 A 37.0 3.24 4.44 0.288 B a a 100w1 m1 100w2 m2 36.4 3.34 7.81 0.531 B 34.9 3.21 9.46 0.645 B 39.40 3.456 2.21 0.259 35.7 3.27 8.44 0.573 B+C 35.31 2.891 2.14 0.234 35.4 3.27 9.10 0.622 B+C 32.90 2.610 2.54 0.270 34.7 3.15 8.84 0.594 C 29.48 2.153 0.41 0.040 28.0 2.56 16.0 1.084 C 26.28 1.834 0.33 0.031 24.6 2.29 20.4 1.41 C 22.41 1.480 0.067 0.0059

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1790 MIODUSKI, GUMIŃSKI, AND ZENG

Composition of saturated solutions in the ternary YCl3 –YF3 –H2O system Experimental Values at 25 °C

Composition of saturated solutions in the ternary YCl3 –CH4N2O–H2O a a 100w1 m1 100w2 m2 system at 30 °C

20.29 1.304 0.016 0.0014 a a b 100w2 m2 100w1 m1 Equilibrium solid phase 18.80 1.186 0.033 0.0027 11.89 0.691 0.032 0.0025 57.3 22.4 0 0 A 56.7 29.2 10.95 1.734 A amolalities calculated by the compiler 59.5 44.0 18.0 4.10 A ͑ ͒ 62.3 62.5 21.1 6.51 A At still lower contents of YCl3 w1 in the ternary system, the amounts of YF ͑w ͒ in the liquid phase were not detect- 62.3 62.5 21.1 6.51 A+B 3 2 62.0 60.7 21.0 6.33 B able by the analytical method used; such incomplete data 59.1 52.9 22.3 6.14 B were omitted. 56.2 43.1 22.1 5.22 B The authors observed the formation of the ternary com- 52.9 38.8 24.4 5.50 B pound YCl3 ·4YF3 ·9H2O which was found to be gradually 51.6 40.0 26.9 6.41 B dehydrated upon heating; the first effect was recorded at 51.6 32.8 22.2 4.34 B+C 195 °C. The first step of YCl3 ·6H2O dehydration was re- 50.4 35.9 26.2 5.73 C corded at 180 °C. 46.4 29.6 27.5 5.40 C 39.9 22.1 31.0 5.29 C Auxiliary Information 35.0 19.1 34.5 5.79 C 32.5 18.0 37.5 6.40 C Method/Apparatus/Procedure: 32.5 17.8 37.16 6.27 C+D Isothermal method with chemical analysis of the saturated solutions was 32.9 18.4 37.4 6.45 D used. Mixtures of the components, taken in various ratios, were 29.4 15.2 38.5 6.14 D equilibrated for 50–60 d in a thermostat. The content of Cl in the liquid phase after the equilibration was determined by the method of Volhard. 23.7 11.3 41.4 6.08 D The content of Y was determined by titration with EDTA solution. The 19.4 8.71 43.5 6.09 D content of F was found by difference. The composition of the equilibrium 15.6 6.76 46.0 6.13 D solid phase was found by the graphical method of Schreinemakers. The 15.0 6.32 45.5 5.90 D+E crystals were analyzed after dissolution in water. The content of F in the 15.7 6.75 45.6 6.03 E solid was analyzed by titration with AlCl3 solution using a methyl red 9.8 3.48 43.3 4.73 E indicator after decomposition of the crystals with concentrated H2SO4 and 5.0 1.59 42.5 4.15 E collection of HF evolved. The complex solid phase formed was 0 0 42.8c 3.85 E characterized by infrared spectroscopy, x-ray diffraction, thermal analysis, and thermogravimetry. amolalities calculated by the compilers b Source and Purity of Materials: A=CH4N2O; B=YCl3 ·6CH4N2O; C=YCl3 ·4CH4N2O; D=2YCl ·3CH N O·4H O ͑as taken from the original text and figure be- YCl3 ·6H2O was precipitated from its saturated solution during cooling. 3 4 2 2 The crystals were dried on a water bath, in air, and finally in a dry box at cause formulas in the original table in the paper contained misprints͒;

40 °C. E=YCl3 ·6H2O cread out from a figure by the compilers ͑ ͒ YF3 was precipitated from Y NO3 3 solution with addition of HF solution ͑distilled in an apparatus made of Pt͒. The mixtures were filtered, washed with water ͑at 40 °C͒ and dried in a Pt container under ultraviolet The compound C was found to be congruently soluble and radiation to constant mass. The product contained 0.8–1.0 mol H2Oin compounds B and D were found to be incongruently soluble. the formula. Auxiliary Information Estimated Error: Nothing specified. Method/Apparatus/Procedure: Isothermal method was used. Experimental details were not reported, but presumably they were similar to other papers published by these authors.48,49 3.4. YCl3–Organic Compound–H2O Systems Source and Purity of Materials: Nothing specified. Components: Original Measurements: ͑ ͒ 47 1 Yttrium chloride; YCl3; G.A. Ashimkulova, K. Estimated Error: ͓ ͔ 10361-92-9 Sulaimankulov, Sh.T. Turdaliev Solubility: nothing specified; reading-out procedure at Ϯ0.3 mass %. ͑ ͒ ͓ ͔ 2 Urea; CH4N2O; 57-13-6 and K. Nogoev, Zh. Neorg. ͑ ͒ ͓ ͔ ͑ ͒ Temperature: nothing specified. 3 Water; H2O; 7732-18-5 Khim. 18, 2011 1973 .

Variables: Prepared by: Urea and salt composition T. Mioduski and C. Gumiński One temperature: 303 K

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1791

Source and Purity of Materials: Components: Original Measurements: Nothing specified. ͑ ͒ 48 1 Yttrium chloride; YCl3; G.A. Ashimkulova, ͓10361-92-9͔ Geterogennye Ravnovesiya v Estimated Error: ͑ ͒ ͓ ͔ 2 Thiourea; CH4N2S; 62-56-6 Sistemakh Neorganicheskikh i Solubility: nothing specified; precision of better than Ϯ1% ͑as estimated ͑ ͒ ͑ 3 Selenourea; CH4N2Se; Organicheskikh Soedinenii Ilim, by the compilers͒. ͓30-10-4͔ Frunze, 1974͒,p.21. Temperature: nothing specified. ͑ ͒ ͓ ͔ 4 Water; H2O; 7732-18-5

Variables: Prepared by: Solute and salt composition T. Mioduski and C. Gumiński Components: Components ͑ ͒ 49 One temperature: 303 K 1 Yttrium chloride; YCl3; G.A. Ashimkulova, K. Nogoev, ͓10361-92-9͔ and K. Sulaimankulov, Zh. ͑ ͒ ͑ ͒ 2 Acetamide; C2H5NO; Neorg. Khim. 19,2588 1974 . Experimental Values ͓60-35-5͔ ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 Composition of saturated solutions in the ternary YCl3 –CH4N2S–H2O system at 30 °C Variables: Prepared by: Acetamide and salt composition T. Mioduski and C. Gumiński a a b One temperature: 303 K 100w2 m2 100w1 m1 Equilibrium solid phase

18.2 2.92 0 0 A 12.9 2.59 11.6 0.91 A Experimental Values 8.04 1.54 23.5 1.76 A 7.07 1.53 32.2 2.72 A Composition of saturated solutions in the ternary YCl3 –C2H5NO–H2O 7.65 1.76 35.1 3.14 A system at 30 °C 6.4 1.50 37.35 3.40 A 100w m a 100w m a Equilibrium solid phaseb 6.1 1.48 39.9 3.78 A+B 2 2 1 1 5.0 1.21 40.5 3.81 B 78.0 60.0 0 0 A 1.7 0.40 41.9 3.80 B 70.6 57.9 8.75 2.17 A 0 0 43.5 3.94 B 67.3 65.5 15.3 4.50 A 69.5 123.8 21.0 11.3 A amolalities calculated by the compilers 69.5 123.8 21.0 11.3 A+B bA=CH N S; B=YCl ·6H O 4 2 3 2 68.5 113.7 21.3 10.7 B

Composition of saturated solutions in the ternary YCl3 –CH4N2Se–H2O 63.5 58.1 18.0 4.98 B system at 30 °C 54.2 36.3 17.5 3.17 B 47.4 24.2 19.5 3.02 B a a b 100w3 m3 100w1 m1 Equilibrium solid phase 34.9 14.9 25.5 3.30 B 27.5 11.0 30.0 3.52 B 14.5 1.38 0 0 C 20.0 7.87 37.0 4.41 B 11.85 1.24 10.4 0.68 C 16.0 6.61 43.0 5.37 B 9.9 1.19 22.7 1.73 C 15.9 6.81 44.6 5.78 B+C 11.1 1.52 29.4 2.53 C 14.9 6.06 43.5 5.36 C 8.35 1.16 33.0 2.88 C 9.2 3.22 42.4 4.49 C 8.3 1.35 41.6 4.25 C 4.0 1.27 42.5 4.07 C 7.4 1.21 43.0 4.44 C+B 0 0 43.6 3.96 C 7.4 1.22 43.1 4.46 C+B 7.26 1.19 43.1 4.45 B amolalities calculated by the compilers 4.58 0.70 42.2 4.06 B b A=C2H5NO; B=YCl3 ·4C2H5NO·5H2O; C=YCl3 ·6H2O 0 0 43.6 3.96 B Auxiliary Information a molalities calculated by the compilers b B=YCl3 ·6H2O; C=CH4N2Se Method/Apparatus/Procedure: Experimental details were not reported but certainly they were similar to Both systems were found to be congruently soluble. Ref. 48 ͑see above͒.

Auxiliary Information Source and Purity of Materials: Nothing specified. Method/Apparatus/Procedure: The isothermal method was used. The solutes were powdered to shorten Estimated Error: the equilibration time. Equilibrium was attained within 6–8 h. Aliquots of Nothing specified. the saturated solution were filtered through a Schott G3 filter. Thiourea and selenourea were determined by analysis of N content using the Kjeldahl method. The content of Y was determined by complexometric titration with EDTA solution using xylenol orange as indicator. The equilibrium solid phases were analyzed the same way.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1792 MIODUSKI, GUMIŃSKI, AND ZENG

Auxiliary Information Components: Original Measurements: ͑ ͒ 62 1 Yttrium chloride; YCl3; F. Ren, Sh.L. Gao, G.H. Chu, Method/Apparatus/Procedure: ͓10361-92-9͔ and Q.Zh. Shi, Yingyong Huaxue The components in proper amounts, placed in calibrated containers, were ͑2͒ ␤-phenylalanine; ͑Chin. J. Appl. Chem.͒ 17, 203 equilibrated for 30 d, then equilibrium in the system was reached, which 3-amino-3-phenylpropionic acid; ͑2000͒. was checked by refractometric measurements. The liquid phases were ͓ ͔ C9H11NO2; 614-19-7 analyzed in a thermostated refractometer. The content of Y was ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 determined in the solid phases by titration with EDTA solution. Phenylalanine was determined by the acetal method after Y was Variables: Prepared by: precipitated by K2C2O4 solution. Water was determined by evaporation at Composition of mixtures C. Gumiński and D. Zeng temperatures lower than 72 °C until constant weight of a sample was One temperature: 298 K achieved. The compounds B and C were characterized by infrared spectroscopy and thermal analysis.

Experimental Values Source and Purity of Materials: YCl3 ·6H2O was prepared according to method described in Ref. 71.Y2O3 Composition of saturated solutions in the ternary YCl3 –C9H11NO2 –H2O was dissolved in HCl solution. The solution was placed in a closed system at 25 °C KOH-dried container for 3–6 d. This allowed crystallization of

YCl3 ·6H2O from the solution. a a a b 100w1 m1 100w2 m2 Equilibrium solid phase Phenylalanine was of “spectroscopic purity.” Other chemicals used were analytically pure. 42.80 3.842 0 0 A 43.66 — −0.1 ͑?͒c —A Estimated Error: 42.68 3.959 2.11 0.231 A Solubility: nothing speciﬁed; precision of Ϯ0.1% in determination of the 42.34 3.929 2.47 0.271 A+B eutonic composition, as estimated by the compilers. 42.30 3.925 2.51 0.275 A+B Temperature: stability of Ϯ0.05 K. 42.32 3.926 2.47 0.271 A+B 42.28 3.928 2.59 0.284 B 42.05 3.922 3.04 0.335 B 3.5. Quaternary Systems 41.78 3.910 3.50 0.387 B 41.44 3.888 3.98 0.441 B Components: Original Measurements: 41.15 3.888 4.65 0.519 B+C ͑1͒ Yttrium chloride; YCl ; 46A.V. Nikolaev, A.A. Sorokina, 40.36 3.779 4.95 0.548 C 3 ͓10361-92-9͔ and N.G. Yudina, Izv. Sibir. Otd. 39.16 3.553 4.39 0.471 C ͑ ͒ 2 Cerium chloride; CeCl3; Akad. Nauk SSSR, Ser. Khim. 33.33 2.843 6.63 0.669 C ͓7790-86-5͔ Nauk, ͑5͒,28͑1972͒. 30.28 2.531 8.45 0.835 C ͑ ͒ 3 Europium chloride; EuCl3; 27.32 2.234 10.05 0.971 C ͓10025-76-0͔ ͑ ͒ ͓ ͔ 24.85 2.044 12.88 1.252 C+D 4 Water; H2O; 7732-18-5 24.66 2.027 13.04 1.267 D 23.82 1.905 12.15 1.149 D Variables: Prepared by: 21.55 1.616 10.16 0.901 D Salt composition T. Mioduski and C. Gumiński One temperature: 298 K 21.06 1.562 9.88 0.866 D 18.67 1.310 8.35 0.693 D 17.11 1.164 7.64 0.614 D Experimental Values 10.33 0.736 4.70 0.335 D 5.80 0.328 3.63 0.243 D Composition of saturated solutions in the quaternary 2.29 0.123 2.29 0.145 D YCl3 –CeCl3 –EuCl3 –H2O system at 25 °C

0 0 1.95 0.120 D a 100x1 100x2 100x3 n4 amolalities and mass % of C H NO calculated by the compilers 9 11 2 0 87.6 12.4 13.61 b A=YCl3 ·6H2O; B=YCl3 ·C9H11NO2 ·3H2O; C=YCl3 ·2C9H11NO2 ·6H2O; 12.6 74.7 12.7 13.73 D=C9H11NO2 15.2 71.7 13.1 13.55 c contents of the components are higher than 100 mass % 26.8 60.5 12.7 13.59 38.4 49.3 12.3 13.62 The compounds B and C were reported to be incongru- 53.3 39.3 7.4 13.07 ently soluble. 62.7 34.0 3.3 12.61 86.3 13.7 0 13.73 80.5 13.7 5.8 13.87 76.0 13.6 10.4 13.95 72.9 14.5 12.6 14.07 70.7 12.5 16.8 14.06 69.9 12.7 17.4 13.64 0 75.4 24.6 13.53 14.1 61.9 24.0 13.47

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1793

Composition of saturated solutions in the quaternary Composition of saturated solutions in the quaternary

YCl3 –CeCl3 –EuCl3 –H2O system at 25 °C YCl3 –CeCl3 –EuCl3 –H2O system at 25 °C

a a 100x1 100x2 100x3 n4 100x1 100x2 100x3 n4

21.2 54.9 23.9 13.56 18.4 43.2 38.4 13.97 37.3 46.0 16.7 13.48 25.6 41.2 33.2 13.81 45.4 42.8 11.8 13.20 35.2 39.6 25.2 13.94 56.3 38.6 5.1 13.32 42.4 37.2 20.4 13.69 57.6 36.8 5.6 13.00 47.4 35.1 17.5 13.53 42.1 0 57.9 14.94 59.6 29.6 10.8 13.45 37.6 11.7 50.7 14.73 a ͑ ͒ 37.5 13.7 48.8 14.66 moles of water per mole of salts YCl3 +CeCl3 +EuCl3 34.9 20.8 44.3 14.29 32.1 31.3 36.6 13.99 The equilibrium solid phases were not reported. The phase 32.9 35.2 31.9 14.14 diagrams in the paper indicated that a series of solid solu- 32.9 37.7 29.4 13.90 tions dominated. 28.2 43.6 28.2 13.75 27.5 51.8 20.7 13.54 The same results were also reported by Nikolaev et al. 27.6 51.5 20.9 13.47 ͓Osnovy Vzaimodeistviya Solei Redkozemelnykh Elementov v 0 65.5 34.5 13.70 Vode ͑Nauka, Novosibirsk, 1977͒,p.81͔. 14.0 57.7 28.3 13.71 19.2 54.6 26.2 13.33 Auxiliary Information 25.0 51.4 23.6 13.38 Method/Apparatus/Procedure: 34.4 46.2 19.4 13.44 The isothermal method with continuous pulverization of the solid was 40.8 44.0 15.2 13.23 used. Equilibrium was probably reached after 10–12 d. The solids and 46.4 41.0 12.6 13.29 liquids were analyzed for the sum of the metals by complexometric 52.2 36.6 8.2 12.28 titration with EDTA solution. The content of Ce was determined by 13.2 0 86.8 15.11 oxidation to Ce͑IV͒ and then titration with Mohr salt solution. Eu was ͑ ͒ / 13.2 11.7 75.1 14.85 reduced to Eu II and then titrated with K2Cr2O7 solution. The Eu Ce 7.8 34.4 57.8 14.36 ratio was also determined by atomic absorption spectrometry; then 10.2 45.3 44.5 14.08 contents of water and Y were found by the corresponding differences. The 0 14.2 85.8 15.19 composition of the solid phases was determined by Schreinemakers’ 9.8 11.9 78.3 14.89 method of wet residues. 18.2 12.0 69.8 14.78 Source and Purity of Materials: 23.4 11.7 64.9 14.75 Hydrates of the chlorides were prepared by dissolving the proper oxides 36.1 11.1 52.8 14.65 ͑99.9+% pure͒ in HCl solution ͑of special purity͒, followed by 47.4 10.3 42.3 14.90 crystallization from HCl solution and then from water. The solids were air 55.5 9.8 34.7 14.47 dried at temperatures below 35 °C. The salts were analyzed for cation 66.8 11.4 21.8 14.17 content by titration with EDTA solution and for Cl content by the Volhard 29.1 70.9 0 14.11 method. The water content was found from the differences and in some 28.3 61.5 10.2 13.61 cases was checked by the Karl-Fischer method. 26.9 57.7 15.4 13.63 Estimated Error: 26.5 52.8 20.7 13.42 Solubility: precision of Ϯ3%. 28.4 51.9 19.7 13.40 Temperature: nothing speciﬁed. 27.3 52.8 19.9 13.40 28.5 51.5 20.0 13.30 27.9 51.8 20.3 13.42 27.9 51.9 20.2 13.37 Components: Original Measurements: ͑ ͒ 64 28.3 51.4 20.3 13.35 1 Yttrium chloride; YCl3; H. Wang, J.X. Duan, X.Q. Ran, ͓10361-92-9͔ and Sh.Y. Gao, Chin. J. Chem. 53.7 46.3 0 13.34 ͑2͒ Cesium chloride; CsCl; 22, 1128 ͑2004͒. 54.4 37.4 8.2 13.51 ͓7647-17-8͔ 53.9 38.1 8.0 14.49 ͑3͒ Hydrochloric acid; HCl; 53.9 37.6 8.5 13.53 ͓7647-01-0͔ ͑ ͒ ͓ ͔ 51.7 39.1 9.2 13.77 4 Water; H2O; 7732-18-5 53.4 37.8 8.8 13.61 53.0 38.0 9.0 13.62 Variables: Prepared by: 53.9 37.9 8.2 14.09 Composition of mixtures C. Gumiński 54.0 37.7 8.3 13.58 One temperature: 298 K, although 298.15 K was originally 54.0 37.9 8.1 13.70 stated 0 48.7 51.3 14.00 14.3 44.4 41.3 14.12

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1794 MIODUSKI, GUMIŃSKI, AND ZENG

Experimental values 4. Solubility of Lanthanum Chloride

Composition of saturated solutions in the quaternary 4.1. Critical Evaluation of the Solubility of LaCl3 in a YCl3 –CsCl–HCl–H2O system at 298.15 K Aqueous Solutions

b 100w1 100w2 100w3 Equilibrium solid phase Components: Evaluators: 3.22 42.12 12.97 A ͑ ͒ 1 Lanthanum chloride; LaCl3; T. Mioduski, Institute of Nuclear 7.80 46.43 8.96 A+B ͓10099-58-8͔ Chemistry and Technology, ͑ ͒ ͓ ͔ 5.65 45.71 10.44 A+B 2 Water; H2O; 7732-18-5 Warsaw, Poland; 4.91 43.22 11.31 B C. Gumiński, Department of 11.12 40.60 9.40 B Chemistry, University of Warsaw, 15.78 38.96 8.11 B+C Poland; and D. Zeng, College of Chemistry 15.68 40.35 7.85 C and Chemical Engineering, 16.74 30.40 9.15 C Hunan University, People’s 22.44 23.85 8.09 C Republic of China 23.66 27.57 6.46 C December 2007 24.86 18.04 7.28 C 25.77 17.87 7.36 C+D 24.43 18.89 8.16 C+D Solubility phenomena in LaCl3 –H2O and aqueous multi- 22.35 19.07 9.31 C+D component LaCl3 systems have been studied 10,16,18,23,40–45,51–55,79–152 21.97 19.70 9.83 D intensively, and therefore this evalu- 24.77 11.73 9.42 D ation is the most voluminous of all aqueous rare earth metal 24.74 12.29 9.68 D chloride systems. Abundant information is available espe- 24.13 10.03 10.70 D cially on the solubilities of LaCl3 in aqueous ternary systems 25.79 3.99 11.01 D at selected temperatures with a wide variety of third compo- 26.25 0 11.70 D nents. a 51,52,54 because temperature stability in other papers of this group was stated as Three papers were compiled with the YCl3 –H2O Ϯ 1 K, it seems reasonable to assume the experimental temperature as system ͑Sec. 3͒. For various reasons, several reports were not 298 K compiled here in the form of data sheets. Only the abstracts b 109,117 A=CsCl; B=Cs4YCl7 ·10H2O; C=Cs3Y2Cl9 ·14H2O; D=YCl3 ·6H2O of two reports were available to the compilers. For the paper by Kanno and Akama,128 related to glass-formation Auxiliary Information studies of LaCl3 solutions, the solubility of LaCl3 in water, Method/Apparatus/Procedure: about 3.9 mol kg−1 at room temperature, was read out from a Samples containing the solid and liquid components were prepared by figure. Fukushi et al.135,136 studied activity coefficients of mixing in proper mass ratios in sealed plastic containers. The containers solutions and the solubility of LaCl in water; the solubility were kept in a thermostat filled with water and agitated by an electrical 3 stirrer. After 5–6 d, the content of HCl was controlled and adjusted to data in numerical form were not published and those read out about 10 mass %. The samples were placed again in the thermostat and from the figures are 3.81 mol kg−1 at 293 K ͑Ref. 135͒ and stirred again ͓H. Wang, J.X. Duan, X.Q. Ran, and Sh. Y. Gao, J. Chem. 3.88 mol kg−1 at 298 K.136 The paper of Petelina et al.43 was Thermodyn. 34, 1495 ͑2002͔͒. Equilibrium was attained after an additional not compiled due to erroneous results of the solubility and 8 d. The saturated solutions and the equilibrium solid phases of the samples were removed and analyzed. Contents of H, Cl, and Y were the equilibrium solid phase; see the table of collected solu- analyzed by titration with standard solutions of NaOH, a silver salt, and bility data below. Studies by Ren and co-workers were de- EDTA, respectively. The composition of solid phases was also found by voted to the formation of complexes between La ion and the graphical method of Schreinemakers. The compounds ͑B and C͒ were crown ethers B15C5 ͑Ref. 134͒ and 18C6 ͑Ref. 138͒ in eth- characterized by thermogravimetry, x-ray diffraction, and DSC. anol solution; the water content in these investigations was Source and Purity of Materials: marginal since water was introduced only with the starting ͑ ͒ YCl3 ·6H2O was prepared from Y2O3 99.9% pure and 37 mass % HCl salt LaCl3 ·3H2O; therefore no data sheets for these ͑analytically pure͒. The product was recrystallized and found to be 99.9% reports134,138 are prepared. pure. Historically, the first study on solubility of LaCl3 was CsCl was analytically pure, as that in the study by Wang et al. ͓J. Chem. 79 Thermodyn. 34, 1495 ͑2002͔͒. dated surprisingly late—in 1920. Solubilities of LaCl3 in −3 1–5 mol dm NH4Cl solutions, with and without addition Estimated Error: of NH , when the starting substance was La O , at 288, 303, a 3 2 3 Nothing specified; see footnote regarding the temperature. and 323 K, were presented in barely readable figures. The solubility values reported were many times lower than those observed at similar conditions in the subsequent studies and formulas of the equilibrium solid phases, which contained O, suggested rather the formation of oxychloride of La in these conditions. Therefore, Ref. 79 is not compiled. The solubilities of LaCl3 in aqueous systems were mainly

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1795 determined by analytical methods ͑gravimetry, titration, refractometry, chromatography, and spectrophotometry͒ at isothermal conditions. Spedding et al.52 used the isopiestic technique. Harkot16 analyzed the saturated solutions after polythermal crystallization. Friend and Hale80 recorded the temperature of the last crystal dissolution. Thermal analysis, used by Sokolova10 and Voigt,137 allowed the construction of the LaCl3 –H2O equilibrium phase diagram on the water-rich side. ͓ ͔ ͓ LaCl3 ·10H2O 117973-45-2 , LaCl3 ·9H2O 117973- ͔ ͓ ͔ ͓ 40-7 , LaCl3 ·7H2O 10025-84-0 , and LaCl3 ·6H2O 17272- 45-6͔ equilibrium solid phases were found10 to exist up to 239, 250, 367, and 394 K, respectively. According to Ref. ͓ ͔ 137, the existence of LaCl3 ·6H2O 17272-45-6 is question- able and this phase should rather be treated as metastable. The temperature of melting or the peritectic decomposition of LaCl3 ·7H2O was reported as 368 K in Refs. 82, 127, and 129, 364 K in Ref. 35, 362 K in Ref. 155, 365 K in Ref. 153, 364.6Ϯ1.4 K in Ref. 137, and 367Ϯ1 K in Refs. 10 and 75. The result of Ref. 137 was the mean value of many of the FIG. 3. Water-rich part of the LaCl –H O equilibrium phase diagram. author’s measurements and therefore it seems to be the most 3 2 precise and is selected in this evaluation; the author of the report showed that LaCl3 ·7H2O melts congruently in con- LaCl3 –H2O binary system are the most valuable for this trast to the finding of Ref. 10. The much too low value of critical evaluation. The remaining solubilities compiled and 330–332 K, given as the transition of solid into liquid reviewed here are relevant mostly to ternary systems contain- LaCl3 ·7H2O in Ref. 154, seems to correspond to nonequi- ing LaCl3 as one of the components. In many such studies, librium conditions in the experiments. Several overestimated the solubility of LaCl3 in water was measured once by a results of the melting point of LaCl3 ·7H2O were also pub- given research group, prior to a series of papers, and this lished: 374.2 K in Ref. 156, 373 K in Ref. 74, and 383 K in value was repeated in all subsequent studies by that group. Ref. 77. The melting temperature of LaCl3 ·6H2O was re- Thus the data reported for the ternary systems are generally ported to be 393 K in Refs. 10 and 53, but the authors did regarded as somewhat less reliable. not describe exact analyses of this compound. All solubility results for the LaCl3 –H2O system are col- According to many dehydration studies, water is released lected in Table 4. from LaCl3 ·7H2O gradually with the formation of Thus, the solubility of LaCl3 in water was observed to ͓ ͔ 68,71,82,137,145,157–160,162–165 LaCl3 ·3H2O 35564-84-2 , increase gradually up to 250 K, then it increased only ͓ ͔ 68,71,82,137,145,157–160,162–165 LaCl3 ·H2O 51305-40-9 , and fi- slightly up to about 320 K and strongly up to the melting ͑ nally anhydrous LaCl3 Refs. 27, 82, 145, 156–158, and point of LaCl3 ·7H2O. Further increase in the solubility, ͒ 161–165 at increasing temperatures, decreasing pressure, or when LaCl3 ·3H2O was the equilibrium phase, was relatively action of a dehydrating agent; the formation of significant, but the solubility of LaCl3 ·H2O was practically 10,53,157 ͓ ͔ 158 LaCl3 ·6H2O, LaCl3 ·5H2O 87720-86-3 , independent of temperature and the results in this range may ͓ ͔ 53 ͓ ͔ LaCl3 ·4H2O 10555-78-9 , and LaCl3 ·2H2O 87720-87-4 be attributed to the formation of the oxychloride. ͑Refs. 158 and 165͒ intermediate forms was sometimes re- The data from the studies by Petelina et al.,43,87 Harkot,16 ported but generally not accepted. Many Nikolaev et al.,112 Alieva and Sulaimankulov,92 Zholalieva et authors27,71,74,82,156,161 observed the formation of LaOCl as al.,108,113 Zelikman et al.,45 Shi et al.,130 Chen et al.,151 Li et the final product of dehydration or as a by-product of anhy- al.,139 and Wang et al.152 are excluded from further evalua- drous LaCl3 formation. tion. Probably, no equilibrium was achieved in their experi- ͑ The crystal structure of LaCl3 ·7H2O was investigated in mental conditions as in the experimental conditions of Ref. ͒ Refs. 145, 153, and 166–170 and of LaCl3 ·3H2O in Ref. 11. 16 , or the errors were connected with the analytical proce- The authors of Ref. 53 investigated LaCl3 ·6H2O crystals by dures used. No doubt, the most precise and accurate solubil- x-ray diffraction but no conclusions were drawn. Triclinic ity data of LaCl3 in water were obtained by Powell and 82 ͑ LaCl3 ·6H2O, reported in Ref. 3, should be treated in fact as Burkholder between 273 and 363 K but no error limits ͒ LaCl3 ·7H2O. were reported , whose results were confirmed by the less All these experimental achievements were taken into ac- precise determinations of Brunisholz and Nozari,86 Zhurav- count for the construction of the refined water-rich part of the lev et al.,94,98–103,105,107 Sheveleva et al.,96 Tang et al.118–122 ͑Ϯ Ϯ ͒ 42,81,83 LaCl3 –H2O phase diagram. Such a partial diagram is pre- 0.2% and 0.2 K , Shevtsova et al., Nikolaev et sented in Fig. 3. al.44,54,55,104,110 ͓Ϯ͑2–3͒% and Ϯ0.5 K͔, Sergeeva and The solubility data reported exclusively for the Karapetyants,106 Kost et al.,114,116,125–127,129 Zwietasch et

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1796 MIODUSKI, GUMIŃSKI, AND ZENG

TABLE 4. Experimental solubilities reported for the LaCl3 –H2O system as a function of temperature

/ / −1 T K m1 mol kg x1 Equilibrium solid phase References ͑ ͒ 209 2.89 0.049 5 H2O s +LaCl3 ·10H2O 10 229 3.21 0.054 6 LaCl3 ·10H2O 10

239 3.36 0.057 1 LaCl3 ·10H2O+LaCl3 ·9H2O 10 250 3.62 0.061 2 LaCl3 ·9H2O+LaCl3 ·7H2O 10 258 3.66 0.061 9 ͑nothing reported͒ 112 263 3.67 0.062 0 ͑nothing reported͒ 112

264 3.63 0.061 4 LaCl3 ·7H2O 10 268 3.59 0.060 7 ͑nothing reported͒ 112

273 3.66 0.061 9 LaCl3 ·7H2O 10

3.656 0.061 8 LaCl3 ·7H2O 82 3.62 0.061 2 LaCl3 ·7H2O 25 3.64 0.061 5 LaCl3 ·7H2O 55 3.768 0.063 6 LaCl3 ·7H2O 120 273.2 3.782 0.063 8 LaCl3 ·7H2O 80 283 3.78 0.063 8 LaCl3 ·7H2O 10

3.710 0.062 6 LaCl3 ·7H2O 82 3.64 0.061 5 LaCl3 ·7H2O 85 3.79 0.063 9 LaCl3 ·7H2O 55 283.2 3.833 0.064 6 LaCl3 ·7H2O 80 284.6 3.891 0.065 5 LaCl3 ·7H2O 80 288 3.96 0.066 6 LaCl3 ·7H2O 92 3.779 0.063 8 LaCl3 ·7H2O 132 288.6 3.891 0.065 5 LaCl3 ·7H2O 80 293 3.851 0.064 9 LaCl3 ·7H2O 82 3.76 0.063 4 LaCl3 ·7H2O 84, 85, and 89 3.86 0.065 0 LaCl3 ·7H2O 86 3.79 0.063 9 LaCl3 ·7H2O 90 3.84 0.064 7 LaCl3 ·7H2O 94, 98, 99,and101 3.84 0.064 7 LaCl3 ·7H2O 96 3.92 0.066 0 LaCl3 ·7H2O 100 3.849 0.064 8 LaCl3 ·7H2O 119 3.76 0.063 4 LaCl3 ·7H2O 102 3.79 0.063 9 LaCl3 ·7H2O 94 298 3.917 0.065 9 LaCl3 ·7H2O 81, 83, and 42 3.897 0.065 6 LaCl3 ·7H2O 82 3.93 0.066 1 LaCl3 ·7H2O 40 and 41 3.51 0.059 5 LaCl3 ·8H2O 43 3.95 0.066 4 LaCl3 ·6H2O 87 3.89 0.065 5 LaCl3 ·7H2O 44, 104, and 55 3.89 0.065 5 LaCl3 ·7H2O 106 3.90 0.065 6 LaCl3 ·7H2O 110

3.881 0.065 3 LaCl3 ·7H2O 114, 116, 126, 127, and 129 3.90 0.065 6 A hydrate was reported 123

3.96 0.066 6 LaCl3 ·7H2O 10 3.898 0.065 6 LaCl3 ·7H2O 132 3.925 0.066 03 LaCl3 ·7H2O 130 3.891 0.065 50 LaCl3 ·7H2O 131, 143, and 147 3.791 0.063 92 LaCl3 ·7H2O 151 298.15 3.8959 0.065 58 LaCl3 ·7H2O 18 and 51 3.8944 0.065 55 LaCl3 ·7H2O 18 and 52

3.896 0.065 6 LaCl3 ·7H2O 111 298.2 3.960 0.066 6 LaCl3 ·7H2O 80 299.4 3.980 0.066 9 LaCl3 ·7H2O 80 303 3.965 0.066 7 LaCl3 ·7H2O 83

3.92 0.065 9 LaCl3 ·7H2O 85 4.16 0.069 7 LaCl3 ·7H2O 92

3.774 0.063 6 LaCl3 ·6H2O 108 and 113 4.04 0.067 8 LaCl3 ·7H2O 55

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1797

TABLE 4. Experimental solubilities reported for the LaCl3 –H2O system as a function of temperature—Continued

/ / −1 T K m1 mol kg x1 Equilibrium solid phase References

3.968 0.066 7 LaCl3 ·7H2O 118 and 120–122

3.86 0.065 0 LaCl3 ·7H2O 16 3.997 0.067 16 LaCl3 ·7H2O 133, 140, and 144 4.14 0.069 40 LaCl3 ·7H2O 139

3.994 0.067 09 LaCl3 ·7H2O 141 4.000 0.067 21 LaCl3 ·7H2O 144 4.017 0.067 48 LaCl3 ·7H2O 145 3.997 0.067 16 LaCl3 ·7H2O 146

3.812 0.064 25 LaCl3 ·7H2O 152 306.2 4.027 0.067 65 LaCl3 ·7H2O 80 308 4.034 0.067 75 LaCl3 ·7H2O 132 4.034 0.067 75 LaCl3 ·7H2O 151 309.6 4.056 0.068 1 LaCl3 ·7H2O 80

312 3.87 0.065 1 LaCl3 ·7H2O 16

313 4.14 0.069 4 LaCl3 ·7H2O 82 4.11 0.068 9 LaCl3 ·7H2O 85 4.16 0.069 7 LaCl3 ·7H2O 94, 95, 98–103, 105, and 107 4.166 0.069 8 LaCl3 ·7H2O 119 3.83 0.064 6 LaCl3 ·7H2O 16 314 3.87 0.065 1 LaCl3 ·7H2O 16 318 4.290 0.071 74 LaCl3 ·7H2O 151 319 4.271 0.071 4 LaCl3 ·7H2O 80 322 4.33 0.072 4 LaCl3 ·7H2O 10 323 4.33 0.072 4 LaCl3 ·7H2O 84, 85, 89, 91, and 96 4.08 0.068 5 LaCl3 ·7H2O 45 4.35 0.072 7 LaCl3 ·7H2O 55 4.368 0.072 9 LaCl3 ·7H2O 118 4.352 0.072 7 Initially LaCl3 ·3H2O was used 118 4.361 0.072 8 LaCl3 ·7H2O 122 4.350 0.072 7 LaCl3 ·7H2O 125, 127, and 129 4.36 0.072 8 LaCl3 ·7H2O 90 4.385 0.073 2 LaCl3 ·7H2O 82 323.4 4.417 0.073 7 LaCl3 ·7H2O 80 327 3.89 0.065 5 LaCl3 ·7H2O 16 328.6 4.625 0.076 9 LaCl3 ·7H2O 80 329 3.84 0.064 7 LaCl3 ·7H2O 16 332 4.719 0.078 4 LaCl3 ·7H2O 80 4.64 0.077 1 LaCl3 ·7H2O 82 334 3.89 0.065 5 LaCl3 ·7H2O 16 336 3.86 0.065 0 LaCl3 ·7H2O 16 3.87 0.065 1 LaCl3 ·7H2O 16 336.8 4.844 0.080 3 LaCl3 ·7H2O 80

337.8 4.975 0.082 3 LaCl3 ·7H2O 80 4.951 0.081 9 LaCl3 ·7H2O 80 338 3.84 0.064 7 LaCl3 ·7H2O 16 4.852 0.080 46 LaCl3 ·7H2O 137 4.840 0.080 21 LaCl3 ·7H2O 137 343 5.03 0.083 1 LaCl3 ·7H2O 82 5.024 0.082 99 LaCl3 ·7H2O 137 5.024 0.082 99 LaCl3 ·7H2O 137 344 3.89 0.065 5 LaCl3 ·7H2O 16 3.76 0.063 4 LaCl3 ·7H2O 16

344.7 5.339 0.087 7 LaCl3 ·7H2O 80 345 3.83 0.064 6 LaCl3 ·7H2O 16 347 3.95 0.066 4 LaCl3 ·7H2O 16

348 5.229 0.086 09 LaCl3 ·7H2O 137 5.1956 0.085 59 LaCl3 ·7H2O 137

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1798 MIODUSKI, GUMIŃSKI, AND ZENG

TABLE 4. Experimental solubilities reported for the LaCl3 –H2O system as a function of temperature—Continued

/ / −1 T K m1 mol kg x1 Equilibrium solid phase References

4.981 0.082 3 LaCl3 ·7H2O 127 and 129

5.11 0.084 3 LaCl3 ·7H2O 45 349.2 5.536 0.090 7 LaCl3 ·7H2O 80 353 5.55 0.091 0 LaCl3 ·7H2O 82

5.673 0.092 72 LaCl3 ·7H2O 137 8.659 0.134 9 LaCl3 ·7H2O+LaCl3 ·3H2O 137 353.6 5.836 0.095 1 LaCl3 ·7H2O 80 354 3.97 0.066 7 LaCl3 ·7H2O 16

4.09 0.068 6 LaCl3 ·7H2O 16 355 3.92 0.066 0 LaCl3 ·7H2O 16 3.93 0.066 1 LaCl3 ·7H2O 16 358 6.117 0.099 26 LaCl3 ·7H2O 137 6.100 0.099 02 LaCl3 ·7H2O 137

8.659 0.134 9 LaCl3 ·3H2O 137

8.804 0.136 9 LaCl3 ·3H2O 137 360.7 6.472 0.104 4 LaCl3 ·7H2O 137 6.417 0.103 6 LaCl3 ·7H2O 137 363 6.6 0.106 LaCl3 ·7H2O 82 6.872 0.110 2 LaCl3 ·7H2O 137 6.861 0.110 0 LaCl3 ·7H2O 137 8.693 0.135 4 LaCl3 ·3H2O 137 8.609 0.134 3 LaCl3 ·3H2O 137 8.609 0.134 3 LaCl3 ·3H2O 137 ͑ ͒ 364.7 7.931 0.125 0 LaCl3 ·7H2O congruent melting 137 365.3 6.948 0.111 2 LaCl3 ·7H2O 80 ͑ ͒ 367 4.60 0.076 5 LaCl3 ·7H2O+LaCl3 ·6H2O ? 10 7.6 0.120 LaCl3 ·7H2O 82 368 8.937 0.138 7 LaCl3 ·3H2O 137 8.931 0.138 6 LaCl3 ·3H2O 137 373 9.120 0.141 1 LaCl3 ·3H2O 137 9.153 0.141 6 LaCl3 ·3H2O 137 378 9.287 0.143 3 LaCl3 ·3H2O 137 9.276 0.143 2 LaCl3 ·3H2O 137 383 9.370 0.144 4 LaCl3 ·3H2O 137 9.337 0.144 0 LaCl3 ·3H2O 137 393 9.936 0.151 8 LaCl3 ·3H2O 137 9.903 0.151 4 LaCl3 ·3H2O 137 ͑ Ͻ ͒ 394 5.87 0.095 6 LaCl3 ·6H2O+LaCl3 ·nH2O n 6 10 403 10.46 0.158 5 LaCl3 ·3H2O 137 10.40 0.157 8 LaCl3 ·3H2O 137 413 10.91 0.164 3 LaCl3 ·3H2O 137 10.97 0.165 1 LaCl3 ·3H2O 137

423 11.69 0.174 0 LaCl3 ·3H2O 137 11.57 0.172 5 LaCl3 ·3H2O 137 433 12.33 0.181 7 LaCl3 ·3H2O 137 11.92 0.176 8 LaCl3 ·3H2O 137 438 12.83 0.187 7 LaCl3 ·3H2O 137 13.16 0.191 6 LaCl3 ·3H2O 137 443 13.96 0.200 9 LaCl3 ·3H2O 137 445.7 13.81 0.199 2 LaCl3 ·3H2O 137 13.87 0.198 9 LaCl3 ·3H2O 137 448 15.73 0.220 8 LaCl3 ·3H2O 137

453 15.73 0.220 8 LaCl3 ·H2O 137 15.75 0.221 1 LaCl3 ·H2O 137 458 15.62 0.219 6 LaCl3 ·H2O 137

463 16.11 0.224 9 LaCl3 ·H2O 137 15.64 0.219 8 LaCl3 ·H2O 137

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1799

TABLE 4. Experimental solubilities reported for the LaCl3 –H2O system as a function of temperature—Continued

/ / −1 T K m1 mol kg x1 Equilibrium solid phase References

16.10 0.224 8 LaCl3 ·H2O 137

16.19 0.225 8 LaCl3 ·H2O 137 ͑ ͒ 16.82 0.232 5 LaCl3 ·H2O with hydroxide 137 ͑ ͒ 16.77 0.232 1 LaCl3 ·H2O with hydroxide 137

15.96 0.223 4 LaCl3 ·H2O 137 468 15.84 0.222 0 LaCl3 ·H2O 137 15.64 0.219 8 LaCl3 ·H2O 137 15.86 0.222 3 LaCl3 ·H2O 137

473 15.84 0.222 0 LaCl3 ·H2O 137 16.18 0.225 7 LaCl3 ·H2O 137 16.16 0.225 5 LaCl3 ·H2O 137 15.80 0.221 6 LaCl3 ·H2O 137 15.92 0.222 9 LaCl3 ·H2O 137

478 16.16 0.225 6 LaCl3 ·H2O 137

16.25 0.226 5 LaCl3 ·H2O 137 483 15.91 0.222 8 LaCl3 ·H2O 137 16.81 0.232 4 LaCl3 ·H2O 137 493 15.81 0.221 7 LaCl3 ·H2O 137 15.83 0.221 9 LaCl3 ·H2O 137

al.,123 Berecz and Török,132 Friend and Hale80 at Ͼ323 K ͑Ϯ ͕ 4͑ ͒3͑ ͒4+3 −3͓ ͑ ͒ ͔−͑4+3͖͒ ln x1 1−x1 4+3 3 1+ 4−1 x1 = Ϯ ͒ 90 10 “several” percent and 0.2 K , Volkov et al., Sokolova at −1 137 − 99.661 + 3727.6T − 15.764 ln T − 0.011 04T. 273–322 K ͑Ϯ0.5% and Ϯ1K͒, Voigt ͑Ϯ0.2% and Ϯ0.5 K͒, Chen et al.,131 Xu et al.,133 Liang et al.,140 Cui et ͑7͒ al.,141 Liu et al.,143,145 Ren et al.,147 and the especially pre- 18,51,52,111 The constants in both equations were obtained by a fitting cise values obtained by Spedding et al. at 298.15 K procedure with the least-squares method using the selected ͑Ϯ Ϯ ͒ 0.1% and 0.02 K . solubility results from Table 4. The solubility values obtained The liquidus points obtained by Sokolova10 at tempera- for LaCl3 ·H2O as the equilibrium solid phase were not ap- tures lower than 273 K may be treated as the tentative solu- proximated with a solubility equation. bilities of the corresponding phases; however, the results at The recommended, tentative, and doubtful solubilities of 367 and 394 K should be placed at significantly more salt- LaCl3 in water, which were selected by the compilers and rich values. It seems that the phase relations established by obtained from the solubility equations, are collected in Table 137 Voigt are much more convincing and reliable in this tem- 5. perature range. Harkot16,17 investigated the polythermal crystallization Due to insufficient data, no solubility equations may be process of LaCl3 ·7H2O in water in the temperature range of formulated below 250 K when the equilibrium solid phase is 291.2–362.9 K and detected the formation of either LaCl3 ·10H2O or LaCl3 ·9H2O. For LaCl3 ·7H2O, as polycondensation-type structures of the solute in the satu- the equilibrium solid phase between 250 and 365 K, one rated solution that deviated slightly from the salt stoichiom- may describe the solubility behavior based on the general etry. Due to the large scatter of the solubility data obtained in form ͓see Eq. ͑3͒ in Sec. 1͔ by fitting the equation to the Refs. 16 and 17, one should be cautious about the quantita- most precise experimental data 10,18,51,52,82,111,132,137,151 and tive conclusions drawn by this author. get the following parameters: Powell and Burkholder82 measured metastable solubilities of LaCl3 ·6H2O in the temperature range of 313–345.7 K; these values have a tentative character. The solubilities of ͕ 4͑ ͒7͑ ͒4+7 −7͓ ͑ ͒ ͔−͑4+7͖͒ LaCl3 ·6H2O were always higher than those of LaCl3 ·7H2O. ln x1 1−x1 4+7 7 1+ 4−1 x1 The solubilities of LaCl3 in HCl solutions were measured = 188.251 − 3771.3T−1 − 35.139 ln T + 0.080 53T. in several studies23,42,45,80,132,142,148,149,151 as a function of ͑6͒ HCl concentration and temperature. As pointed out by a summary,132 the solubilities decreased smoothly with in- For LaCl3 ·3H2O between 353 and 448 K, the following creasing HCl concentration at all temperatures between 273 solubility equation was fitted to the experimental data of Ref. and 363 K; however, at the highest HCl concentrations, a 137: small increase in the solubility was observed. Scatter of the

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1800 MIODUSKI, GUMIŃSKI, AND ZENG

͑ ͒ ͑ ͒ ͑ ͒ TABLE 5. Recommended R , tentative T , and doubtful D solubilities of LaCl3 in H2O at selected temperatures; the data between 250 and 448 K were conﬁrmed by the ﬁtting equations

/ / −1 T K m1 mol kg x1 Equilibrium solid phase References ͑ ͒ ͑ ͒ 209 2.9 0.049 T H2O s +LaCl3 ·10H2O 10 ͑ ͒ 239 3.4 0.057 T LaCl3 ·10H2O+LaCl3 ·9H2O 10 ͑ ͒ 250 3.6 0.061 T LaCl3 ·9H2O+LaCl3 ·7H2O 10 ͑ ͒ 273 3.66 0.061 9 R LaCl3 ·7H2O 10 and 82 ͑ ͒ 293 3.85 0.064 9 R LaCl3 ·7H2O 82 and 119 ͑ ͒ 298.15 3.896 0.065 58 R LaCl3 ·7H2O 18, 51, 52, 111, and 132 ͑ ͒ 308 4.03 0.067 7 R LaCl3 ·7H2O 132 and 151 ͑ ͒ 323 4.34 0.072 6 T LaCl3 ·7H2O 55, 84, 90, 118, and 125 ͑ ͒ 343 5.03 0.0831 T LaCl3 ·7H2O 82 and 137 ͑ ͒ 365 7.93 0.125 T LaCl3 ·7H2O congruent melting point 137 ͑ ͒ 353 8.7 0.135 T LaCl3 ·7H2O+LaCl3 ·3H2O eutectic point 137 ͑ ͒ 400 10.2 0.156 T LaCl3 ·3H2O 137 ͑ ͒ 448 16 0.22 D LaCl3 ·3H2O+LaCl3 ·H2O 137 ͑ ͒ 473 16 0.22 D LaCl3 ·H2O 137 ͑ ͒ 493 16 0.22 D LaCl3 ·H2O 137

experimental solubility results from all sources increased Ternary LaCl3 –LnCl3 –H2O systems have been inten- from only a few percent in water to about 15% at the highest sively studied by the group of Nikolaev et al., with Ln being HCl contents,12 indicating that the data related to the ternary Y, 54 Ce,40,41 Eu,44 and Yb ͑Ref. 104͒ at 298 K, as well as by systems are less precise. The equilibrium solid phase identi- Brunisholz and Nozari86 for Nd and Sm at 293 K. The qua- ͑ ͒ fied at these experimental conditions was independently ternary systems LaCl3 –NdCl3 –SmCl3 –H2O Ref. 86 and ͑ ͒ found to be LaCl3 ·7H2O. LaCl3 –CeCl3 –EuCl3 –H2O Refs. 54 and 93 were also in- The solubilities of LaCl3 in solutions of acetic acid at vestigated at 293 and 298 K, respectively. It was found that 303 K were unexpectedly found to be independent of the no double salts were formed in these systems. If the second acetic acid concentration ͑up to 49 mass %͒ when the solu- Ln chloride also formed a heptahydrate, solid solutions or 139 ͑ ͒ bilities were expressed in molal concentrations. This may mixed crystals La,Ln Cl3 ·7H2O were the equilibrium solid ͑ ͒ suggest that the same solvate hydrate of LaCl3 may exist in phases. However, if Ln chloride formed a hexahydrate, a ͑ ͒ the whole range of acetic acid concentrations. discontinuity between two forms, La,Ln Cl3 ·7H2O and ͑ ͒ The ternary LaCl3 –MCl–H2O systems, with M being Ln,La Cl3 ·6H2O, was observed at certain salt composi- 84,129 81,85,115,126,127 83,89,125,126 83,114,125 96,116 Li, Na, K, NH4, Rb, tions. or Cs,91,126,142 were investigated. The first four systems were Mixed crystals were also found in the ternary 123 found to be of a simple eutonic type. One congruently LaCl3 –LaBr3 –H2O system. A double salt of formula soluble salt was formed in the LaCl3 –RbCl–H2O system LaCl3 ·LaF3 ·9H2O was identified in the LaCl3 –LaF3 –H2O 53 and two salts in the case of the LaCl3 –CsCl–H2O system. system. No double chloride formation was seen in the quaternary Ternary systems containing LaCl3,H2O, and the following 97 139 systems LaCl3 –LiCl–KCl–H2O, LaCl3 –NaCl–NH4Cl– organic compounds have been investigated: acetic acid, 115 115 92 94 H2O, and LaCl3 –KCl–NH4Cl–H2O; however, two urea, methylamine hydrochloride, trimethylamine double chlorides were isolated in the hydrochloride,94 hydrazine dihydrochloride,95 ethanediamine 91 95 98 LaCl3 –NaCl–CsCl–H2O system. The corresponding de- dihydrochloride, hydroxyloamine hydrochloride, dim- tails may be found in the respective data compilations. ethylamine hydrochloride,98 hexamethylenediamine 99 100 The ternary LaCl3 –MCl2 –H2O systems, with M being dihydrochloride, piperazine dihydrochloride, Mg,110 Ca,81,90 Sr,90 and Ba,90 were reported to be of a simple 1,2-ethanediamine-N,N,NЈ,NЈ-teramethyl dihydro- eutonic type. The formation of two incongruently soluble chloride,100 1,2-benzenediamine dihydrochloride,100 1,3- 100 double chlorides was observed in the LaCl3 –CdCl2 –H2O benzenediamine dihydrochloride, triethylamine 152 102 102 system. In the case of the quaternary LaCl3 –CdCl2 –HCl hydrochloride, triethanolamine hydrochloride, diethy- ͑ ͒ ͑ ͒ 103 103 9.7 mass % –H2O Ref. 148 as well as the lamine hydrochloride, diethanolamine hydrochloride, ͑ ͒ ͑ ͒ 102 105 LaCl3 –ZnCl2 –HCl 7 mass % –H2O Ref. 149 systems, butylamine hydrochloride, aniline hydrochloride, pip- two congruently soluble double chlorides and three double eridine hydrochloride,105 hexamethyleneimine chlorides were reported to be formed, respectively. The for- hydrochloride,105 acetone,106 pyridine hydrochloride,107 mation of three double chlorides was observed in the quater- quinoline hydrochloride,107 acetamide,108,120 choline ͑ ͒ 109 113,121 113,118 nary LaCl3 –CsCl–HCl 13.23% –H2O and LaCl3 –CsCl– chloride, acetylurea, thiourea, ͑ ͒ 142 122 acetic acid 42% –H2O systems. 1-acetyl-2-thiourea, hexamethylenetetramine

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Khim. 31, 1610 ͑1986͒. mun. 8,511͑1979͒. 128H. Kanno and Y. Akama, J. Phys. Chem. 91, 1263 ͑1987͒. 154N. P. Sokolova and E. A. Ukraintseva, Izv. Sibir. Otd. 129D. A. Storozhenko, Yu. V. Shirai, and N. F. Eskova, Zh. Akad. Nauk SSSR, Ser. Khim. Nauk ͑1͒,24͑1984͒.

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155 J. G. Tang, C. K. S. Lee, and L. A. Belﬁore, J. Polym. Sci, Melting temperatures of LaCl3 –H2O mixtures as read from a ﬁgure and Part B: Polym. Phys. 41, 2200 ͑2003͒. recalculated to mol % by the compiler 156H. B. Chen, P. Zh. Yang, Ch. Y. Zhou, Ch. Y. Jiang, and J. 100w 100x t/ °C Equilibrium solid phase G. Pan, Cryst. Growth Des. 6, 809 ͑2006͒. 1 1 157 a a A. N. Zelikman, N. V. Baryshnikov, and A. N. Khokhlov, 47.0 6.12 −23 LaCl3 ·9H2O+LaCl3 ·7H2O a a Izv. Vyssh. Ucheb. Zaved., Tsvetn. Metall. ͑6͒,89͑1971͒. 45.2 5.71 −34 LaCl3 ·10H2O+LaCl3 ·9H2O 158 Zh. Gong, P. H. Chen, Zh. Zh. Guo, J. H. Ma, and Y. Sh. 44.0 5.46 −44 LaCl3 ·10H2O a a ͑ ͒ Chen, Huaxue Xuebao 41, 391 ͑1983͒. 41.5 4.95 −64 H2O s +LaCl3 ·10H2O ͑ ͒ 159N. P. Sokolova and E. A. Ukraintseva, Izv. Sibir. Otd. 37.8 4.27 −49 H2O s 35.5 3.89 −41 as above Akad. Nauk SSSR, Ser. Khim. Nauk ͑1͒,24͑1984͒. 160 ͑ ͒ 32.3 3.39 −32 as above V. V. Hong and D. V. Minh, Tap Chi Hoa Hoc J. Chem. 24.3 2.30 −15 as above ͑ ͒ ͑ ͒ 36 4 ,44 1998 . 15.3 1.31 −6 as above 161 G. C. Zhu, F. P. Li, and M. G. Xiao, Trans. Nonferrous 9.3 0.75 −2 as above Met. Soc. China 13, 1454 ͑2003͒. 0a 00a as above 162Zh. Gong, P. H. Chen, Zh. Zh. Guo, J. H. Ma, and Y. Sh. a Chen, Zhongguo Xitu Xuebao 3͑2͒,13͑1985͒. numerical result 163 Zh. Gong, P. H. Chen, Zh. Zh. Guo, J. H. Ma, and Y. Sh. Auxiliary Information Chen, Huaxue Xuebao 41, 463 ͑1983͒. 164Zh. Gong, P. H. Chen, Zh. Zh. Guo, J. H. Ma, and Y. Sh. Method/Apparatus/Procedure: Chen, Gaodeng Xuexiao Huaxue Xuebao 4, 493 ͑1983͒. Mixtures of the components were investigated by means of differential 165 thermal analysis. The samples were prepared in sealed glass ampoules. S. J. Ashcroft and C. T. Mortimer, J. Less-Common. Met. They were heated and cooled between −120 and ϳ130 °C with a rate of 14, 403 ͑1968͒. 0.2–0.5 K/min. The heating curves were recorded with the use of a 166V. I. Ivernova, V. P. Tarasova, and M. M. Umanskii, Izv. thermocouple. Stoichiometry of the hydrates was determined from the Akad. Nauk. SSSR, Ser. Fiz. 15, 164 ͑1951͒. extent of the thermal effects by the method of Tammann for 10–18 167 samples of compositions changed by 0.3–0.5 mass %. Samples of J. H. Burns and J. R. Peterson, Inorg. Chem. 10, 147 ͑ ͑ ͒ stoichiometric hydrates annealed 1–2 d within their temperature 1971 . existence ranges͒ were additionally investigated many times by thermal 168 C. Brouty and P. Herpin, Compt. Rend. C 272, 2049 analysis. ͑1971͒. 169V. V. Bakakin, R. F. Klevtsova, and L. P. Soloveva, Zh. Source and Purity of Materials: ͑ ͒ As in the study by Sokolova et al. ͓Zh. Neorg. Khim. 25,2584͑1980͔͒, Strukt. Khim. 15, 820 1974 . ͑ ͒ 170 LaCl3 ·7H2O was prepared by dissolving La2O3 99.9% pure in excess of C. J. Kepert, B. W. Skelton, and A. H. White, Aust. J. HCl solution. The product was twice recrystallized from HCl ͑“very Chem. 47, 385 ͑1994͒. pure”͒ and from water.

Estimated Error: Solubility: precision of better than Ϯ0.3 mass %; reading-out procedure at 4.2. Data for the LaCl3 –H2O System Ϯ0.5 mass %. Composition of the hydrates: precision of within 2%–3%. Temperature: precision of Ϯ1 K; reading-out procedure at Ϯ1K. Components: Original Measurements: ͑ ͒ 10 1 Lanthanum chloride; LaCl3; N.P. Sokolova, Radiokhimiya ͓10099-58-8͔ 30,435͑1988͒. ͑ ͒ ͓ ͔ 2 Water; H2O; 7732-18-5 Components: Original Measurements: ͑ ͒ 16 1 Lanthanum chloride; LaCl3; J. Harkot, Pol. J. Chem. 63, Variables: Prepared by: ͓10099-58-8͔ 337 ͑1989͒. ͑ ͒ ͓ ͔ Composition: 0–66.5 mass % C. Gumiński 2 Water; H2O; 7732-18-5 LaCl3 Variables: Prepared by: Temperature: 303–354 K C. Gumiński Experimental Values

Melting temperatures of LaCl3 –H2O mixtures as read from a ﬁgure and Experimental Values recalculated to mol % by the compiler

Solubility data of LaCl3 in H2O were presented in a ﬁgure; they were read / 100w1 100x1 t °C Equilibrium solid phase out from the ﬁgure and recalculated to molalities by the compiler a ͑ Ͻ ͒ 59.0 9.56 121 LaCl3 ·6H2O+LaCl3 ·nH2O n 6 T/ w m a a K 100 1 1 Rate of crystallization 53.0 7.65 94 LaCl3 ·7H2O+LaCl3 ·6H2O a a 51.5 7.24 49 LaCl3 ·7H2O 303 48.63 3.86 Fast 49.0 6.66 25 as above 314 48.7 3.87 Fast 48.1 6.38 10 as above 327 48.8 3.89 Fast 47.3 6.19 0 as above 334 48.7 3.87 Fast 47.1 6.14 −9 as above 338 48.5 3.84 Fast

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1804 MIODUSKI, GUMIŃSKI, AND ZENG

Solubility data of LaCl3 in H2O were presented in a ﬁgure; they were read Experimental Values out from the ﬁgure and recalculated to molalities by the compiler

Solubilities and densities of saturated solutions of LaCl3 in water at vari- / T K100w1 m1 Rate of crystallization ous temperatures

344 48.8 3.89 Fast / a a ␳/ −3 t °C 100w1 m1 c1 gcm 347 49.2 3.95 Fast 354 49.3 3.97 Fast 0 47.2 3.64 — — 312 48.7 3.87 Slow 10 48.2 3.79 3.29 1.677 313 48.4 3.83 Slow 25 48.8 3.89 3.38 1.696 329 48.5 3.84 Slow 30 49.8 4.04 3.46 1.7035 336 48.6 3.86 Slow 50 51.6 4.35 3.68 1.749 336 48.7 3.87 Slow amolalities and molarities were calculated by the compilers 344 48.0 3.76 Slow 345 48.4 3.83 Slow The equilibrium solid phase reported was LaCl3 ·7H2O, 355 49.0 3.92 Slow −3 355 49.1 3.93 Slow whose density was found to be 2.195 g cm and molar vol- 3 −1 354 50.0 4.09 Slow ume was 169.2 cm mol at an unspeciﬁed temperature. anumerical result Auxiliary Information

A similar figure with the results was also published by Method/Apparatus/Procedure: Harkot ͓Zesz. Nauk. Politechn. Slask. 119, 325 ͑1988͔͒. The isothermal method was used. The salt and water were continuously ͑ ͒ LaCl ·7H O was reported to be the equilibrium solid phase. agitated in a thermostat for 3–10 d at low temperatures for 6–8 d . The 3 2 La content in a sample of the saturated solution was determined by The influence of rate and degree of polythermal crystalliza- titration with EDTA. The reported solubilities are mean values of five to tion on the solubility and composition of the crystals was ten independent determinations. The densities of the saturated solutions investigated. The scattered solubility data for slow and fast were measured with a pycnometer. The density of the hydrated chloride crystallizations were approximated by curves of untypical was also measured pycnometrically using dry toluene. shapes ͑expressed by smoothing equations͒. The existence of Source and Purity of Materials: ͑ ͒ several crystalline structures of the heptahydrate formed in LaCl3 ·7H2O was prepared by dissolving La2O3 99.9+% pure in HCl the system was postulated in this way. solution ͑of special purity͒ followed by double crystallization of the salt from HCl solution and then from water. The crystals obtained were dried Auxiliary Information at temperatures below 30 °C. The salt composition was tested for La and Cl contents. Method/Apparatus/Procedure: The solubility was determined by polythermal crystallization at different Estimated Error: rates and degrees of crystallization. The supersaturated solutions were Solubility: nothing specified. prepared by dissolution of the heptahydrate in water while heating, or an Temperature: stabilities of Ϯ0.1 and Ϯ1Kat0°C. undersaturated solution of the solute was evaporated. Then the Density: precision of Ϯ0.003 g cm−3. oversaturated solutions were exposed to polythermal crystallization for 130–230 min. The solutions were carefully filtered. La in the filtrate was determined by precipitation of the oxalate and its subsequent roasting at Components: Original Measurements: 1200 K to form the oxide. La in the crystals was determined by the same ͑1͒ Lanthanum chloride; LaCl ; 80J.N. Friend and R.W. Hale, J. method. 3 ͓10099-58-8͔ Chem. Soc. 1940, 670. ͑ ͒ Source and Purity of Materials: 2 Hydrochloric acid; HCl; ͓7647-01-0͔ LaCl3 ·7H2O was prepared in the author’s laboratory. ͑3͒ Water; H O; ͓7732-18-5͔ Redistilled water was used. 2 Variables: Prepared by: Estimated Error: Concentration of HCl: T. Mioduski and C. Gumiński Solubility: nothing specified; reading-out procedure at Ϯ0.05 mass %. 0–2.6 mol dm−3 Temperature: nothing specified; reading-out procedure at Ϯ1K. Temperature: 273–365.2 K

Components: Original Measurements: Experimental Values ͑ ͒ 55 1 Lanthanum chloride; LaCl3; A.V. Nikolaev, A.A. Sorokina, ͓10099-58-8͔ N.P. Sokolova, G.S. Solubility of LaCl3 in aqueous HCl solutions at 25 and 50 °C ͑ ͒ ͓ ͔ 2 Water; H2O; 7732-18-5 Kotlyar-Shapirov, N.P. Anoshina, / / −3 / / −1a L.I. Bagryantseva, and A.P. t °C c2 mol dm 100w1 mass % m1 mol kg Olovyanishnikova, Izv. Sibir. Otd. Akad. Nauk SSSR, Ser. 25 0 49.27 3.960 Khim. Nauk ͑4͒,84͑1977͒. 0.174 48.79 0.817 45.87 Variables: Prepared by: 1.471 43.55 Temperature: 273–323 K T. Mioduski and C. Gumiński 1.644 42.78

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1805

Solubility of LaCl3 in aqueous HCl solutions at 25 and 50 °C Source and Purity of Materials: ͑ ͒ LaCl3 ·7H2O was prepared by dissolving La2O3 pure in diluted HCl and / / −3 / / −1a t °C c2 mol dm 100w1 mass % m1 mol kg concentrating the solution on a water bath. The crystals were drained on a sintered glass funnel. The crystallization product analysis resulted in the 2.611 39.47 Cl/La ratios of 2.965 and 3.047. 50 0 52.00 4.417 0.171 51.46 Estimated Error: 0.400 50.88 Solubility: precision of several percent. 0.597 50.28 Temperature: stability of Ϯ0.2 K, as in the study by Friend ͑J. Chem. ͒ 1.568 47.66 Soc. 1930, 1633 . 1.831 46.95 amolalities calculated by the compilers Components: Original Measurements: 82 Lanthanum chloride; LaCl3; J.E. Powell and H.R. The equilibrium solid phase was not reported; presumably ͓10099-58-8͔ Burkholder, J. Inorg. Nucl. ͓ ͔ ͑ ͒ Water; H2O; 7732-18-5 Chem. 14,65 1960 . LaCl3 ·7H2O was used in the experiments. Variables: Prepared by: Solubility of LaCl3 in H2O at various temperatures Solute: LaCl3 ·7H2Oor T. Mioduski and C. Gumiński LaCl ·6H O t/ °C 100w /mass % m /mol kg−1a 3 2 1 1 Temperature: 273–368 K 0 48.12 3.782 10.0 48.46 3.833 Experimental Values 11.4 48.83 3.891 15.4 48.99 3.916 Solubility of LaCl3 ·7H2OinH2O at various temperatures 25.0 49.27 3.960 26.2 49.40 3.980 / a t °C g LaCl3 ·7H2O in 100 g H2O m1 33.0 49.69 4.027 36.4 49.87 4.056 0 251.6 3.655 45.8 51.16 4.271 10 258.9 3.710 50.2 52.00 4.417 20 275.5 3.851 55.4 53.15 4.625 25 284.5 3.897 59 53.65 4.719 30 294.9 3.965 63.6 54.30 4.844 40 321.7 4.141 64.6 54.84 4.951 50 364.3 4.385 54.96 4.975 60 415 4.64 71.5b 56.70 5.339 70 512 5.03 76.0 57.59 5.536 80 686 5.55 80.4 58.87 5.836 90 1500 6.6 92.1b 63.02 6.948 94 6300 7.6

a amolalities calculated by the compilers molalities calculated by the compilers bdetermined by a synthetic method LaCl3 ·7H2O was found to melt at 95 °C. Analysis of the equilibrium solid phase indicated the for- Solubility of LaCl3 ·6H2OinH2O at various temperatures mula LaCl3 ·7H2O. t/ °C g LaCl ·6H O in 100 g H O m a Auxiliary Information 3 2 2 1 40 526 5.70 Method/Apparatus/Procedure: 45 576 5.91 Analytical method ͑J.N. Friend, J. Chem. Soc. 1930, 1633͒ was used in 50 621 6.06 the majority of determinations and synthetic method ͑J.N. Friend, R.W. 55 750 6.46 Hale, and S.A.E. Ryder, J. Chem. Soc. 1937, 970͒ for two determinations indicated. In the analytical method, equilibrium was reached during 24 h 60 850 6.68 65 1200 7.3 contact of aqueous solution with LaCl3 ·7H2O at the desired temperature. Prior to withdrawal of a portion of the solution for analysis, the mixture 70 2100 8.0 was vigorously agitated for 6–8 h. La was precipitated from diluted 71.2 2300 8.1 solutions as the oxalate, converted later to oxide, and weighed as La2O3. 72.5 2700 8.3 The content of Cl was determined gravimetrically as AgCl. HCl was determined by acidimetric titration with alkali in the presence of methyl a molalities calculated by the compilers orange as an indicator. In the synthetic method, mixtures of the solute and water were heated in sealed tubes in an oil bath with repeated shaking The equilibrium was found to be metastable with until the solid phase disappeared, and the mean temperature after repeated trials was evaluated. LaCl3 ·6H2O as the saturating phase. The same results were also reported in Ref. 38.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1806 MIODUSKI, GUMIŃSKI, AND ZENG

Auxiliary Information Composition of saturated solutions in the ternary LaCl3 –NaCl–H2Osys- tem at 20 and 50 °C Method/Apparatus/Procedure: / a a b The equilibrium between the solute and the solution was reached from the t °C 100w1 m1 100w2 m2 Equilibrium solid phase supersaturation side. Samples were heated until complete dissolution and then cooled to the desired temperature. A small crystal was added to each 46.5 3.65 1.5 0.49 B supersaturated solution and the phases were equilibrated for 24–28 h. 48.0 3.76 0 0 B Weighed aliquots of the saturated solutions were evaporated and La was 50 0 0 26.8 6.26 A converted to its oxide by heating with concentrated HNO3 until the 12.3 0.84 18.0 5.16 A evolution of brown fumes. The crucibles were ﬁnally heated to 800 °C, 26.5 1.68 9.0 2.39 A cooled in a desiccator, and weighed as La O . The solutes were analyzed 2 3 27.4 1.74 8.5 2.27 A the same way. 35.5 2.44 5.3 1.53 A Source and Purity of Materials: 49.1 3.43 2.6 0.76 A+B

La2O3, obtained by ion exchange method, was 99.9+% pure. The oxide 50.3 4.23 1.2 0.42 B was dissolved in a slight excess of HCl. The material ͑heptahydrate͒ was 51.5 4.33 0 0 B recrystallized to eliminate HCl excess. The moist heptahydrate was then a recrystallized six times. molalities calculated by the compilers b The hexahydrate was prepared from heptahydrate by melting above A=NaCl; B=LaCl3 ·7H2O 95 °C, cooling the liquid to 60 °C, shaking, redissolving the hexahydrate at 70 °C, and recooling at 60 °C. The hexahydrate crystals were isolated The system was found to be of eutonic type. from the syrupy solution by blotting between pieces of ﬁlter paper. The salt composition was tested. Auxiliary Information

Estimated Error: Method/Apparatus/Procedure: Nothing specified. The solubility was determined by the method of isothermal sections involving measurement of the refractive index of the saturated solutions. Homogeneous and heterogeneous mixtures of the solute and solution of known composition were equilibrated until their refractive indices Components: Original Measurements: remained constant. The results were plotted on a graph of the refractive ͑1͒ Lanthanum chloride; LaCl ; 85E.N. Khutorskoi and A.D. 3 index versus composition and the break points on such plots corresponded ͓10099-58-8͔ Sheveleva, Ucheb. Zap. Perm. to the saturation levels. Concentrations of the bisaturated solutions were ͑2͒ Sodium chloride; NaCl; Univ. 178,57͑1968͒. confirmed by chemical analysis. The composition of the solid phases was ͓7647-14-5͔ ͑ ͒ ͓ ͔ determined in the same way. 3 Water; H2O; 7732-18-5 Source and Purity of Materials: Variables: Prepared by: Pure grade LaCl ·7H O was twice recrystallized before use. Its La Salt composition T. Mioduski and C. Gumiński 3 2 content was confirmed by the oxalate gravimetric method and water Temperature: 293.2 and 323.2 K content was apparently found by difference. The melting point of ͑ ͒ LaCl3 ·7H2O unspecified was reported to be in accordance with literature data. Experimental Values Analytically pure NaCl as used as received. Solubilities of LaCl in water at various temperatures 3 Estimated Error: / a Solubility: nothing specified. t °C 100w1 m1 Temperature: precision of Ϯ0.2 K, as in other papers from this laboratory. 10.0 47.2 3.64 20.0 48.0 3.76 30.0 49.0 3.92 Components: Original Measurements: ͑ ͒ 111 40.0 50.2 4.11 1 Lanthanum chloride; LaCl3; F.H. Spedding, C.W. DeKock, 50.0 51.5 4.33 ͓10099-58-8͔ and other rare earth G.W. Pepple, and A. metal chlorides Habenschuss, J. Chem. Eng. Data amolalities calculated by the compilers ͑ ͒ ͓ ͔ ͑ ͒ 2 Water; H2O; 7732-18-5 22,58 1977 . The equilibrium solid phase was reported to be Variables: Prepared by: LaCl3 ·7H2O within the whole temperature range studied. Salts M. Salomon and C. Gumiński One temperature: 298.15 K Composition of saturated solutions in the ternary LaCl3 –NaCl–H2O system at 20 and 50 °C Experimental Values / a a b t °C 100w1 m1 100w2 m2 Equilibrium solid phase Solubilities of rare earth metal chlorides at 25.00 °C 20 0 0 24.6 6.14 A 12.4 0.72 17.5 4.27 A Salt m1 Equilibrium solid phase 25.0 1.55 9.3 2.42 A

27.6 1.75 8.0 2.13 A LaCl3 3.896 LaCl3 ·7H2O ͓ ͔ 35.0 2.38 5.0 1.43 A PrCl3 10361-79-2 3.891 PrCl3 ·7H2O ͓ ͔ 46.1 3.61 1.9 0.63 A+B NdCl3 10024-93-8 3.929 NdCl3 ·6H2O

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1807

Solubilities of rare earth metal chlorides at 25.00 °C Variables: Prepared by: Temperature: 258–268 K T. Mioduski and C. Gumiński

Salt m1 Equilibrium solid phase ͓ ͔ SmCl3 10361-82-7 3.641 SmCl3 ·6H2O Experimental Values ͓ ͔ EuCl3 10025-76-0 3.587 EuCl3 ·6H2O ͓ ͔ Solubility of LaCl3 in H2O at various temperatures GdCl3 10138-52-0 3.590 GdCl3 ·6H2O TbCl ͓10042-88-3͔ 3.571 TbCl ·6H O 3 3 2 / a ͓ ͔ t °C 100w1 m1 DyCl3 10025-74-8 3.631 DyCl3 ·6H2O ͓ ͔ HoCl3 10138-62-2 3.694 HoCl3 ·6H2O −5 46.8 3.59 ͓ ͔ ErCl3 10138-41-7 3.782 ErCl3 ·6H2O −10 47.4 3.67 ͓ ͔ TmCl3 13537-18-3 3.881 TmCl3 ·6H2O −15 47.3 3.66 YbCl ͓10361-91-8͔ 4.003 YbCl ·6H O 3 3 2 a ͓ ͔ molalities calculated by the compilers LuCl3 10099-66-8 4.128 LuCl3 ·6H2O The saturating solid phase ͑or phases͒ was not specified. Auxiliary Information From the irregular solubility variation with temperature, the Method/Apparatus/Procedure: compilers suppose that the equilibrium solid͑s͒ could be of a Preparation of saturated solutions was not specified but the saturation was higher degree of hydration than the heptahydrate ͑the equi- likely performed at isothermal conditions. The solutions were analyzed for librium solid phase at higher temperatures͒. cation content by titration with EDTA solution or/and gravimetrically as the oxide or the sulfate. The content of Cl was determined by Auxiliary Information potentiometric titration with AgNO3 solution. The ratio of rare earth metal chloride to number of water molecules was determined by titrations with Method/Apparatus/Procedure: EDTA solutions. Heats of dilution of the saturated solutions were The solutions and the solid solutes were equilibrated for 10–12 d in glass measured in an adiabatically jacketed differential calorimeter. vessels placed in a cryostat. The solute crystals during equilibration were continuously crushed by special pestles. Samples of the saturated solutions Source and Purity of Materials: were withdrawn with a syringe and analyzed for La content by titration The initial oxides were purified by ion exchange. Solutions of the with EDTA solution. The determinations were repeated several times. chlorides were prepared from the oxides and very pure HCl solution. The hydrated crystals were grown from the saturated solutions at 25.00 °C and Source and Purity of Materials: ͑ were dried over anhydrous BaCl2 or CaCl2. pH of the stock solutions As in Ref. 55, LaCl3 ·7H2O was prepared by dissolving La2O3 99.9+% were adjusted to guarantee a 1:3 ratio of cation to anion. pure͒ in HCl solution ͑of special purity͒ followed by double crystallization Conductivity water with its electrolytic conductance of 10–6 Scm−1 was of the salt from HCl solution and then from water. The crystals obtained used. were dried at temperatures below 30 °C. The salt composition was checked by analysis of La and Cl contents. Estimated Error: Solubility: accuracy of Ϯ0.1% or better. Estimated Error: Composition of the equilibrium solid phases: precision of Ϯ0.1%. Solubility: maximal deviation from the mean value of Ϯ2%. Temperature: precision of Ϯ0.02 K. Temperature: precision of Ϯ0.5 K.

Components: Original Measurements: Components: Original Measurements: ͑ ͒ 112 ͑ ͒ 137 1 Lanthanum chloride; LaCl3; A.V. Nikolaev, A.A. Sorokina, 1 Lanthanum chloride; LaCl3; H. Voigt, Report No. Vo ͓10099-58-8͔ N.P. Sokolova, G.S. ͓10099-58-8͔ 511/1-2 ͑Bergakademie, Freiberg, ͑ ͒ ͓ ͔ ͑ ͒ ͓ ͔ ͒ 2 Water; H2O; 7732-18-5 Kotlyar-Shapirov, and L.I. 2 Water; H2O; 7732-18-5 Germany, 1994 . Bagryantseva, Izv. Sibir. Otd. Akad. Nauk SSSR, Ser. Khim. Variables: Prepared by: Nauk ͑1͒,46͑1978͒. Temperature: 338–493 K C. Gumiński

Experimental Values

͑ ͒ Solubility of LaCl3 in water at various temperatures and elevated unspeciﬁed pressures

Soly/ Wet residue / / a b c t °C mol LaCl3 1000 mol H2O x1 stoichiometry Equilibrium solid phase

65 87.4 0.080 46 7.095; 7.077 A 87.2 0.080 21 7.083; 7.080 A 70 90.5 0.082 99 6.785; 6.785 A 90.5 0.082 99 7.021; 7.026 A 75 94.2 0.086 09 6.946; 6.945 A 93.6 0.085 59 6.808; 6.704 A 80 102.2 0.092 72 — A 156.0 0.134 9 5.889; 5.875 A+B

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1808 MIODUSKI, GUMIŃSKI, AND ZENG

͑ ͒ Solubility of LaCl3 in water at various temperatures and elevated unspeciﬁed pressures

Soly/ Wet residue / / a b c t °C mol LaCl3 1000 mol H2O x1 stoichiometry Equilibrium solid phase

85 110.2 0.099 26 6.971; 6.966 A 109.9 0.099 02 7.030; 7.002 A 156.0 0.134 9 3.389; 3.592 B 158.6 0.136 9 3.341; 3.344 B 87.5 116.6 0.104 4 6.971; 6.966 A 115.6 0.103 6 6.931; 6.923 A 90 123.8 0.110 2 7.025 A 123.6 0.110 0 6.998 A 156.6 0.135 4 3.733; 3.726 B 155.1 0.134 3 3.684 B 155.1 0.134 3 3.728; 3.740 B 95 161.0 0.138 7 3.224 B 160.9 0.138 6 3.219 B 100 164.3 0.141 1 3.279; 3.296 B 164.9 0.141 6 3.613; 3.585 B 105 167.3 0.143 3 3.192 B 167.1 0.143 2 3.221 B 110 168.8 0.144 4 3.067; 3.065 B 168.2 0.144 0 3.085; 3.079 B 120 179.0 0.151 8 3.108; 3.104 B 178.4 0.151 4 3.038; 3.037 B 130 188.4 0.158 5 3.109 B 187.4 0.157 8 3.115 B 140 196.6 0.164 3 3.132 B 197.7 0.165 1 3.213 B 150 210.6 0.174 0 3.227 B 208.4 0.172 5 3.138 B 160 222.1 0.181 7 3.203; 3.201 B 214.8 0.176 8 3.815; 3.805 B 165 231.1 0.187 7 3.030 B 237.0 0.191 6 3.083 B 170 251.4 0.200 9 3.075 B 172.5 248.8 0.199 2 3.129 B 248.3 0.198 9 3.141 B 175 283.4 0.220 8 2.992; 2.988 B 180 283.3 0.220 8 1.187 C 283.8 0.221 1 0.991 C 185 281.45 0.219 6 1.354; 1.348 C 190 290.2 0.224 9 1.322; 1.317 C 281.7 0.219 8 1.334; 1.337 C 290.1 0.224 8 — C 291.6 0.225 8 1.112; 1.113 C 303.0 0.232 5 1.052 C with hydroxide 302.2 0.232 1 1.101 C with hydroxide 287.6 0.223 4 1.252; 1.253 C 195 285.4 0.222 0 1.349 C 281.8 0.219 8 — C 285.8 0.222 3 — C 200 285.4 0.222 0 — C 291.5 0.225 7 — C 291.1 0.225 5 1.422 C 284.7 0.221 6 1.364 C 286.8 0.222 9 1.381 C 205 291.2 0.225 6 — C 292.8 0.226 5 — C 210 286.6 0.222 8 1.704; 1.689 C 302.8 0.232 4 1.625; 1.623 C

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1809

͑ ͒ Solubility of LaCl3 in water at various temperatures and elevated unspeciﬁed pressures

Soly/ Wet residue / / a b c t °C mol LaCl3 1000 mol H2O x1 stoichiometry Equilibrium solid phase

220 284.9 0.221 7 1.557 C 285.2 0.221 9 1.567 C amolalities calculated by the compiler bevery second value was from Karl-Fischer titration c A=LaCl3 ·7H2O; B=LaCl3 ·3H2O; C=LaCl3 ·H2O

The compounds A, B, and C were found to melt at 91.4 Experimental Values ͑congruently͒, 179.0 ͑peritectically͒, and 317.5 °C, respec- Solubility of LaCl3 in aqueous solution of HCl at 0 °C tively. a a 100w2 m2 100w1 m1 Auxiliary Information 0 0 47.0 3.62 Method/Apparatus/Procedure: 5 2.4 38.2 2.74 The solubility experiments were performed in thermostated twin 10 4.5 29.5 1.99 autoclaves made of Pd–Ti alloy which was resistant to elevated pressure 15 6.4 20.9 1.33 and temperature. The salt ͑hydrate͒ and water were placed in Teﬂon 18 7.5 15.8 0.97 containers. The free volume over the condensed phase was kept at a minimum. The solution and solute were equilibrated in isothermal 20 8.2 12.9 0.78 conditions for 60–100 h. Sampling and phase separation were carried out 22 8.9 10.3 0.62 with the use of a centrifuge and a quartz ﬁlter. The samples were analyzed 24 9.7 7.9 0.47 for chloride ion content by potentiometric argentometry. The hexa-, tri-, 26 10.5 5.8 0.35 and monohydrates were characterized by DSC and thermogravimetry in a 28 11.3 4.2 0.25 commercial apparatus. The water content in the equilibrium solids was 30 12.2 2.8 0.17 also determined by Karl-Fischer titration. 32 13.3 1.8 0.11 34 14.5 1.2 0.076 Source and Purity of Materials: 36 15.7 1.0 0.065 LaCl3 ·7H2O was analytically pure from Merck. The salt hydrates were obtained by isopiestic equilibration in an apparatus constructed by the 38 17.1 1.1 0.074 author. 40 18.9 1.8 0.13 42 21.1 3.4 0.25 Estimated Error: 42.5b 22.0 4.6 0.36 Ϯ Solubility: precision of Cl analysis of 0.2%; precision of H2O analysis of Ϯ0.5%. a molalities calculated by the compilers Temperature: precision of Ϯ0.05 K in the thermostat; precision of Ϯ0.5 K b solution saturated with gaseous HCl at 0.1 MPa in the centrifuge; precision of Ϯ1.2 K in DSC.

The equilibrium solid phase was found to be LaCl3 ·7H2O.

Smoothed values of LaCl3 solubility in HCl solutions at 0 °C

/ −1 / −1 / −1a m2 mol kg m1 g-equivalent kg m1 mol kg

4.3. LaCl3–Inorganic Salt–H2O Systems 0 10.85 3.62 5 5.6 1.9 4.3.1. LaCl3 –MCl–H2O „M=H,NH4 ,Li,Na,K,Rb,Cs… Systems 10 1.2 0.4 14 0.24 0.08 Components: Original Measurements: 18 0.26 0.09 ͑1͒ Lanthanum chloride; LaCl ; 23W. Fischer, H. Bauer, I. Dillo, 3 22.5b ͑1.25͒͑0.42͒ ͓10099-58-8͔ T. Molaug, J. Nier, H. Rohrer, ͑2͒ Hydrochloric acid; HCl; and K Trovaag, Z. Anorg. Chem. a ͓ ͔ ͑ ͒ molalities calculated by the compilers 7647-01-0 357, 177 1968 . b ͑ ͒ ͓ ͔ solution saturated with gaseous HCl at 0.1 MPa 3 Water; H2O; 7732-18-5

Variables: Prepared by: Concentration of HCl: T. Mioduski and C. Gumiński 0–42.5 mass % One temperature: 273 K

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1810 MIODUSKI, GUMIŃSKI, AND ZENG

Auxiliary Information Estimated Error: Solubility: nothing speciﬁed; precision of better than Ϯ0.5 mass % Method/Apparatus/Procedure: ͑estimated by the compilers from scatter of all results on a graphical The isothermal method was used. Equilibrium was approached from presentation in the paper͒. undersaturation and supersaturation. The content of La was determined Temperature: stability of Ϯ0.1 K. ͑ ͒ gravimetrically as La2O3 after precipitation of La OH 3 with NH3 solution; chlorides were earlier transformed into nitrates with concentrated

HNO3. The total Cl content was determined by potentiometric titration Components: Original Measurements: with AgNO3 solution. Free HCl was determined by titration with NaOH ͑ ͒ 45 using methyl yellow as an indicator. The equilibrium solid phase 1 Lanthanum chloride; LaCl3; A.N. Zelikman, N.V. composition was determined graphically by the method of Schreinemakers ͓10099-58-8͔ Baryshnikov, and A.I. Khokhlov, as well as by chemical analysis of the crystals after washing them in ͑2͒ Hydrochloric acid; HCl; Zh. Neorg. Khim. 16, 2023 acetone and prolonged drying in a vacuum desiccator. ͓7647-01-0͔ ͑1971͒. ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 Source and Purity of Materials: ͑ ͒ Variables: Prepared by: LaCl3 ·7H2O was prepared by dissolving La2O3 99.8+% pure in HCl solution and crystallization of the product. Concentration of HCl: T. Mioduski and C. Gumiński HCl solutions were prepared by saturating water with gaseous HCl. 0–30 mass % Temperature: 323–363 K Estimated Error: Nothing speciﬁed. Experimental Values

Solubility of LaCl in aqueous solutions of HCl at various temperatures Components: Original Measurements: 3 ͑1͒ Lanthanum chloride; LaCl ; 42Z.N. Shevtsova, L.S. Nam, and 3 t/ °C 100w m a 100w m a ͓10099-58-8͔ B.G. Korshunov, Zh. Neorg. 2 2 1 1 ͑ ͒ ͑ ͒ 2 Hydrochloric acid; HCl; Khim. 13, 1682 1968 . 50 0 0 50.0 4.08 ͓7647-01-0͔ 3.3 1.75 45.0 3.55 ͑3͒ Water; H O; ͓7732-18-5͔ 2 7.5 3.79 38.2 2.87 Variables: Prepared by: 11.7 4.80 31.4 1.91 Concentration of HCl: T. Mioduski and C. Gumiński 14.8 6.90 26.4 1.83 0–28.7 mass % 22.4 9.97 16.0 1.06 One temperature: 298 K 25.5 11.28 12.5 0.82 27.1 12.15 11.7 0.78 30.0 14.19 12.0 0.84 Experimental Values 75 0 0 55.6 5.11 1.5 0.91 53.4 4.83 Solubility of LaCl3 in aqueous solutions of HCl at 25 °C 3.3 1.96 50.6 4.48 a a 100w2 m2 100w1 m1 5.9 3.41 46.7 4.02 8.0 4.54 43.7 3.69 0 0 49.00 3.917 9.4 5.33 42.2 3.55 2.55 1.29 43.25 3.115 11.4 6.57 41.0 3.51 5.08 2.46 38.31 2.546 90 1.0 0.76 63.1 7.17 9.54 4.26 29.10 1.934 1.9 1.45 62.2 7.06 13.32 5.82 23.85 1.548 2.9 2.24 61.6 7.07 20.05 8.37 14.23 0.883 3.7 2.91 61.4 7.17 23.53 9.64 9.50 0.578 28.68 11.71 4.13 0.251 a molalities calculated by the compilers amolalities calculated by the compilers The equilibrium solid phase in all cases was found to be

The equilibrium solid phase was found to be LaCl3 ·7H2O LaCl3 ·7H2O. at all HCl concentrations. Auxiliary Information Auxiliary Information Method/Apparatus/Procedure: Method/Apparatus/Procedure: The isothermal method was used. Equilibrium was approached from The isothermal method was used. The solutions were equilibrated with the supersaturation and undersaturation. Equilibrium was reached after solute for 6 d. The method of solution analysis was not reported. The 2–2.5 h but the solutions were conditioned in a thermostat 1 h more. La composition of the solid phases was determined graphically by the method was determined by titration with EDTA in acetic buffer using xylenol of Schreinemakers. The solid phases were also identiﬁed optically. orange as an indicator. The HCl concentration was determined by titration with base. The solid phases were analyzed by Schreinemakers’ method. Source and Purity of Materials: ͑ ͒ LaCl3 ·7H2O was prepared by dissolving La2O3 unspeciﬁed purity in HCl solution ͑chemically pure͒. The resulting salt was triple recrystallized. Probably bidistilled water was used.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1811

Source and Purity of Materials: LaCl ·7H O was prepared by dissolving La O ͑99.8+% pure͒ in aqueous Components: Original Measurements: 3 2 2 3 ͑ ͒ 151 HCl ͑chemically pure͒. The resulting solution was evaporated until the 1 Lanthanum chloride; LaCl3; Y.G. Chen, Zh. Fang, Q.R. crystals of the solute were formed. The product was twice recrystallized ͓10099-58-8͔ Zhang, K.Y. Yuan, and Sh.F. and dried at room temperature. ͑2͒ Hydrochloric acid; HCl; Wang, Xiyou Jinshu ͑Chin. J. ͓7647-01-0͔ Rare Met.͒ 27,601͑2003͒. ͑ ͒ ͓ ͔ Estimated Error: 3 Water; H2O; 7732-18-5 Solubility: nothing speciﬁed. Variables: Prepared by: Temperature: stability of Ϯ0.1 K. Concentration of HCl: C. Gumiński and D. Zeng 0–29.73 mass % Temperature: 298–318 K Components: Original Measurements: ͑ ͒ 132 1 Lanthanum chloride; LaCl3; E. Berecz and T.I. Török, Z. ͓10099-58-8͔ Anorg. Chem. 583,177͑1990͒. Experimental Values ͑2͒ Hydrochloric acid; HCl; ͓ ͔ 7647-01-0 Composition of saturated solutions in the ternary LaCl3 –HCl–H2Osys- ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 tem at several temperatures

Variables: Prepared by: / a a t °C 100w2 m2 100w1 m1 Equilibrium solid phase Concentration of HCl: C. Gumiński −1 0–13.22 mol kg 25 0 0 48.18 3.791 LaCl3 ·7H2O 1.68 0.822 42.29 3.077 LaCl3 ·6.98H2O 2.41 1.163 40.73 2.921 LaCl3 ·7.00H2O Experimental Values 3.00 1.432 39.52 2.803 LaCl3 ·7.02H2O 5.33 2.445 34.88 2.379 LaCl3 ·6.99H2O Solubility of LaCl3 in HCl solutions at several temperatures 7.58 3.371 30.75 2.033 LaCl3 ·6.97H2O / 7.89 3.471 29.76 1.946 LaCl3 ·7.00H2O t °C m1 m2 12.50 5.210 21.70 1.345 LaCl3 ·7.02H2O 15 3.779 0 17.31 6.970 14.57 0.872 LaCl3 ·7.01H2O 2.852 2.538 26.10 10.29 4.34 0.254 LaCl3 ·7.00H2O 2.794 2.730 35 0 0 49.73 4.034 LaCl3 ·7H2O 2.559 3.380 1.46 0.741 44.51 3.361 LaCl3 ·7.02H2O 1.431 6.665 2.53 1.256 42.24 3.118 LaCl3 ·7.01H2O 0.169 13.22 5.97 2.778 35.09 2.427 LaCl3 ·6.99H2O 25 3.898 0 7.35 3.357 32.60 2.214 LaCl3 ·7.00H2O 3.576 0.845 10.37 4.538 26.95 1.753 LaCl3 ·6.98H2O 3.515 1.024 15.94 6.671 18.52 1.153 LaCl3 ·7.01H2O 2.661 3.460 24.05 9.710 8.02 0.481 LaCl3 ·7.00H2O 1.520 6.823 29.73 12.47 4.86 0.303 LaCl3 ·6.97H2O 0.959 8.748 45 0 0 51.27 4.290 LaCl3 ·7H2O 35 4.034 0 1.55 0.851 48.50 3.959 LaCl3 ·6.99H2O 3.149 2.538 2.27 1.243 47.63 3.876 LaCl3 ·7.01H2O 2.182 5.299 4.00 2.099 43.72 3.410 LaCl3 ·7.02H2O 6.51 3.210 37.87 2.776 LaCl3 ·7.01H2O 9.33 4.517 34.02 2.449 LaCl3 ·6.98H2O The authors deduced that the equilibrium solid phase is 11.54 5.453 30.42 2.137 LaCl3 ·7.00H2O LaCl·7H2O at all experimental conditions. 21.23 9.181 15.35 0.987 LaCl3 ·7.01H2O

Auxiliary Information a molalities calculated by the compilers

Method/Apparatus/Procedure: The authors reported the following solubility equations: The components were equilibrated by continuous mixing in a container ͑ ͒ ͑ ͒2 for 6–24 h in a thermostat. The saturated solutions were analyzed for La 100w1 =46.90−2.39 100w2 +0.03 100w2 , R=0.9983 at and for total Cl content. In parallel, four to six samples of each solution 25 °C, were analyzed. ͑ ͒ ͑ ͒2 100w1 =48.75−2.45 100w2 +0.03 100w2 R=0.9987 at Source and Purity of Materials: 35 °C, ͑ ͒ LaCl3 ·7H2O pure for analysis was recrystallized. ͑ ͒ ͑ ͒2 100w1 =51.46−1.98 100w2 +0.013 100w2 , R=0.9998 HCl ͑pure for analysis͒ was double distilled. at 45 °C. Estimated Error: The solubility values at w2 =0 do not correspond to the Solubility: nothing speciﬁed. solubilities determined in pure water at these temperatures. Temperature: stability of Ϯ0.02 K.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1812 MIODUSKI, GUMIŃSKI, AND ZENG

Auxiliary Information Composition of saturated solutions in the ternary LaCl3 –KCl–H2Osys- tem at 25 °C Method/Apparatus/Procedure: a a b The components with an excess of LaCl3 ·7H2O were placed in glass 100w1 m1 100w3 m3 Equilibrium solid phase containers and shaken in a water bath at constant temperature for 48 h. A sample of liquid saturated phase was withdrawn, diluted, and divided into 49.00 3.917 0 0 A two equal parts. One part was titrated with NaOH solution using a methyl 48.31 3.940 1.70 0.456 A orange indicator, thus giving the content of HCl. The second part was 48.01 3.925 2.12 0.571 A adjusted to pH 4.0–6.0 and titrated with AgNO3 solution using a K2Cr2O7 47.79 4.008 3.59 0.990 A+C indicator, thus giving the content of total Cl. The content of La was then 45.72 3.721 4.18 1.124 C found by difference. The equilibrium solid phase was analyzed similarly. 38.83 2.833 5.28 1.272 C The composition of the solids found by the method of Schreinemakers 28.51 1.784 6.35 1.311 C was in agreement with the analysis. The authors discussed the inﬂuence of pH during the titrations on the results obtained. 16.31 0.914 10.93 2.650 C 10.08 0.568 17.50 3.241 C Source and Purity of Materials: 4.83 0.271 22.48 4.148 C

LaCl3 ·7H2O used was of unspeciﬁed purity. The stoichiometric ratio of 0 0 26.52 4.841 C La:Cl was found to be 1:3.01. a molalities calculated by the compilers HCl was analytically pure. Its purity was checked by titrations with b standard solution of NaOH with a methyl orange indicator. A=LaCl3 ·7H2O; C=KCl

Estimated Error: The solubility isotherm was found to be of eutonic type. Solubility: nothing specified. Temperature: stability of Ϯ0.002 K. Auxiliary Information Method/Apparatus/Procedure: The isothermal method with analytical detection was used. Equilibrium Components: Original Measurements: between the saturated solution and the solutes was reported to be reached ͑ ͒ 83 1 Lanthanum chloride; LaCl3; Z.N. Shevtsova, L.I. Zhizhina, within 3–4 d. The composition of the saturated solutions and the solid ͓10099-58-8͔ and L.E. Eltsberg, Izv. Vyssh. phases was determined by an unspecified chemical analysis. The solid ͑ ͒ 2 Ammonium chloride; NH4Cl; Ucheb. Zaved., Khim. Khim. phases were also determined graphically by the dry residue method of ͓12125-02-9͔ Tekhnol. 4,176͑1961͒. Schreinemakers. ͑3͒ Potassium chloride; KCl; ͓7447-40-7͔ Source and Purity of Materials: ͑ ͒ ͓ ͔ 4 Water; H2O; 7732-18-5 Nothing specified.

Variables: Prepared by: Estimated Error: Salt composition T. Mioduski and C. Gumiński Nothing speciﬁed. One temperature: 298 K

Components: Original Measurements: Experimental Values ͑ ͒ 114 1 Lanthanum chloride; LaCl3; L.L. Kost, Yu.V. Shirai, and ͓10099-58-8͔ V.G. Shevchuk, Zh. Neorg. Composition of saturated solutions in the ternary LaCl3 –NH4Cl–H2O ͑ ͒ ͑ ͓͒ 2 Ammonium chloride; NH4Cl; Khim. 25,579 1980 Russ. J. system at 25 °C ͓12125-02-9͔ Inorg. Chem. 25, 320 ͑1980͔͒. ͑3͒ Water; H O; ͓7732-18-5͔ a a b 2 100w1 m1 100w2 m2 Equilibrium solid phase Variables: Prepared by: 49.00 3.917 0 0 A Salt composition M. Salomon and C. Gumiński 48.05 3.869 1.31 0.484 A One temperature: 298 K 47.92 3.943 2.53 0.955 A 47.32 3.915 3.40 1.290 A ϩ B 45.20 3.667 4.55 1.693 B Experimental Values 40.05 2.978 5.12 1.751 B Composition of saturated solutions in the ternary LaCl –NH Cl–H O 28.32 1.872 10.01 3.035 B 3 4 2 system at 25 °C 15.41 0.910 16.05 4.378 B 9.10 0.536 21.63 5.838 B a a b 100w1 m1 100w2 m2 Equilibrium solid phase 5.12 0.295 24.00 6.330 B 0 0 26.52 6.747 B 48.77 3.881 0 0 A 47.75 3.888 2.18 0.814 A a molalities calculated by the compilers 47.07 3.999 4.94 1.923 A+B b A=LaCl3 ·7H2O; B=NH4Cl 44.03 3.558 5.52 2.051 B 34.49 2.449 8.10 2.642 B The solubility isotherm was found to be of eutonic type. 24.15 1.562 12.81 3.799 B 17.91 1.107 16.13 4.572 B 10.92 0.652 20.84 5.709 B 4.32 0.250 25.23 6.695 B

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1813

Composition of saturated solutions in the ternary LaCl3 –NH4Cl–H2O Composition of saturated solutions in the ternary LaCl3 –KCl–H2Osys- system at 25 °C tem at 50 °C

a a b a a b 100w1 m1 100w2 m2 Equilibrium solid phase 100w1 m1 100w2 m2 Equilibrium solid phase

1.87 0.107 27.10 7.133 B 51.62 4.350 0 0 A 0 0 28.21 7.346 B 50.65 4.528 3.74 1.100 A 49.47 3.945 9.40 2.466 A+C a molalities calculated by the compilers 37.35 2.871 9.61 2.430 C b A=LaCl3 ·7H2O; B=NH4Cl 25.46 1.675 12.56 2.718 C 22.13 1.436 15.03 3.208 C The system was found to be of a simple eutonic type. 15.61 0.977 19.27 3.969 C 8.24 0.498 24.27 4.823 C Auxiliary Information 5.02 0.299 26.48 5.185 C Method/Apparatus/Procedure: 0 0 30.00 5.748 C The isothermal method was used. Equilibrium between the saturated amolalities calculated by the compilers solution and the crystals was attained after continual stirring for 3–5 d. b A=LaCl3 ·7H2O; C=KCl The compositions of the saturated solutions and residues were found by chemical analysis. La was determined by titration with EDTA solution The system was reported to be of eutonic type. using xylenol orange indicator at pH 5.5. Ammonium, alkaline displaced from the chloride, was determined by titration with an acid. Auxiliary Information

Source and Purity of Materials: Method/Apparatus/Procedure: ͑ ͒ “Chemically pure” grade LaCl3 hydrate and NH4Cl were used. Equilibrium was attained during continuous agitation of the components Source and purity of water was not speciﬁed. for 15–24 h. Thermostats with dry air and water heaters were employed. Both saturated solutions and equilibrium solids were analyzed.114 La was Estimated Error: determined by titration with EDTA solution. Cl was determined by the Nothing speciﬁed. Volhard method. Alkaline-displaced ammonium was titrated with an acid solution. Potassium determination was not described.

Components: Original Measurements: Source and Purity of Materials: ͑ ͒ 125 Chemically pure LaCl3 ·7H2O, NH4Cl, and KCl were used. 1 Lanthanum chloride; LaCl3; D.A. Storozhenko, Yu.V. ͓10099-58-8͔ Shirai, and N.M. Lazorenko, Zh. Estimated Error: ͑2͒ Ammonium chloride; NH Cl; Neorg. Khim. 31, 537 ͑1986͒. 4 Solubility: nothing speciﬁed ͓12125-02-9͔ Ϯ ͑3͒ Potassium chloride; KCl; Temperature: precision of 0.1 K. ͓7447-40-7͔ ͑ ͒ ͓ ͔ 4 Water; H2O; 7732-18-5 Components: Original Measurements: Variables: Prepared by: ͑ ͒ 84 1 Lanthanum chloride; LaCl3; E.N. Khutorskoi and A.D. Composition of salts T. Mioduski and C. Gumiński ͓10099-58-8͔ Sheveleva, Ucheb. Zap. Perm. One temperature: 323 K ͑2͒ Lithium chloride; LiCl; Univ. 178,49͑1968͒. ͓7447-41-8͔ ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 Experimental Values Variables: Prepared by:

Composition of saturated solutions in the ternary LaCl3 –NH4Cl–H2O Salt composition T. Mioduski and C. Gumiński system at 50 °C Temperature: 293 and 323 K

a a b 100w1 m1 100w2 m2 Equilibrium solid phase Experimental Values 51.62 4.350 0 0 A 49.80 4.321 3.21 1.281 A Composition of saturated solutions in the ternary LaCl3 –LiCl–H2Osys- 48.42 4.372 6.43 2.663 A+B tem at 20 and 50 °C 38.61 3.150 11.42 4.273 B t/ °C 100w m a 100w m a Equilibrium solid phaseb 30.25 2.303 16.19 5.651 B 1 1 2 2 23.63 1.707 19.93 6.602 B 20 0 0 45.5 19.7 A 11.88 0.783 26.27 7.940 B 3.9 0.30 43.0 19.1 A 6.52 0.413 29.14 8.467 B 8.7 0.69 40.0 18.4 A 0 0 33.51 9.422 B 9.5 0.76 39.7 18.4 A+B 11.5 0.84 32.5 13.7 B amolalities calculated by the compilers 19.0 1.30 21.5 8.52 B bA=LaCl ·7H O; B=NH Cl 3 2 4 22.5 1.55 18.5 7.40 B 25.0 1.73 16.2 6.50 B The system was reported to be of eutonic type. 40.0 2.97 5.1 2.20 B

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1814 MIODUSKI, GUMIŃSKI, AND ZENG

Composition of saturated solutions in the ternary LaCl3 –LiCl–H2O sys- Composition of saturated solutions in the ternary LaCl3 –LiCl–H2Osys- tem at 20 and 50 °C tem at several temperatures

/ a a b / a a b t °C 100w1 m1 100w2 m2 Equilibrium solid phase t °C 100w1 m1 100w2 m2 Equilibrium solid phase

48.0 3.76 0 0 B 12.99 0.854 25.01 9.516 B 50 0 0 48.3 22.0 A 28.20 1.996 14.19 5.811 B 3.7 0.30 46.0 21.6 A 39.99 3.024 6.09 2.664 B 7.8 0.65 43.5 21.1 A 48.77 3.881 0 0 B 12.5 1.10 41.0 20.8 A+B 50 0 0 47.79 21.59 A 13.9 1.19 38.5 19.1 B 7.34 0.573 42.90 20.34 A 17.5 1.43 32.5 15.3 B 9.56 0.798 41.60 20.09 A 25.0 1.98 23.5 10.8 B 17.42 1.556 36.94 19.09 A 33.0 2.59 15.0 6.80 B 19.89 1.841 35.05 18.77 A 45.6 3.69 4.0 1.87 B 29.07 2.928 30.45 17.75 A+B 51.5 4.33 0 0 B 24.30 1.997 26.15 12.45 B 23.44 1.784 22.99 10.12 B amolalities calculated by the compiler 31.89 2.419 14.36 6.302 B bA=LiCl·H O; B=LaCl ·7H O 2 3 2 41.92 3.349 7.04 3.254 B The system was found to be of eutonic type. 45.98 3.784 4.21 1.989 B 51.62 4.350 0 0 B Auxiliary Information 75 0 0 52.53 26.11 A 4.42 0.380 48.11 23.91 A Method/Apparatus/Procedure: 10.81 0.936 42.10 21.09 A The solubility was determined by method of isothermal sections involving 18.20 1.672 37.43 19.90 A measurement of the refractive index of saturated solutions. The 24.02 2.323 33.83 18.93 A undersaturated and supersaturated systems were equilibrated 7–8 h at 29.46 3.086 31.62 19.17 A 50 °C and 9–10 h at 20 °C, after which the refractive indices of solutions 32.99 3.638 30.04 22.30 A were constant. The compositions of solid phases were determined from 36.02 4.176 28.81 19.32 A break points on relations of the refractive index versus composition. 37.56 3.880 22.97 18.73 B Source and Purity of Materials: 41.35 3.795 14.23 7.56 B Both salts were twice recrystallized before use. The water content in the 43.00 3.784 10.67 5.43 B salt hydrates was checked by a gravimetric method. 48.21 4.243 5.47 2.79 B 51.59 4.604 2.72 1.40 B Estimated Error: 54.99 4.981 0 0 B Nothing speciﬁed. 100 0 0 55.84 29.83 C 5.83 0.553 51.22 28.13 C 12.71 1.259 46.13 26.44 C Components: Original Measurements: 20.11 2.133 41.45 25.44 C ͑1͒ Lanthanum chloride; LaCl ; 129D.A. Storozhenko, Yu.V. 3 26.37 2.946 37.14 24.01 C ͓10099-58-8͔ Shirai, and N.F. Eskova, Zh. 30.99 3.561 34.53 22.96 C ͑2͒ Lithium chloride; LiCl; Neorg. Khim. 33, 2438 ͑1988͒. ͓7447-41-8͔ a ͑ ͒ ͓ ͔ molalities calculated by the compilers 3 Water; H2O; 7732-18-5 b A=LiCl·H2O; B=LaCl3 ·7H2O; C=LiCl Variables: Prepared by: Composition of mixtures T. Mioduski and C. Gumiński The system was reported to be of a simple eutonic type. One temperature: 298–373 K No solubility of LaCl3 in water was determined at 100 °C due to melting of the solute LaCl3 ·7H2Oat95°C. Experimental Values Auxiliary Information

Composition of saturated solutions in the ternary LaCl3 –LiCl–H2O system at several temperatures Method/Apparatus/Procedure: The experimental method was based on analysis of the saturated solutions / a a b and the equilibrium solid phase after isothermal equilibration.125 The t °C 100w1 m1 100w2 m2 Equilibrium solid phase content of La was determined by titration with EDTA solution. The 25 0 0 45.79 19.93 A content of Cl was determined by the method of Volhard. The content of Li 4.21 0.320 42.17 18.55 A was found by difference. 8.14 0.637 39.79 18.03 A+B Source and Purity of Materials: 13.47 1.114 37.24 17.82 B Chemically pure LaCl ·7H O and LiCl·H O were recrystallized before 12.23 0.975 36.62 16.89 B 3 2 2 use. 10.11 0.743 34.42 14.64 B 9.24 0.637 31.58 12.59 B 10.45 0.689 27.73 10.58 B

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1815

Estimated Error: Composition of saturated solutions in the ternary LaCl3 –CaCl2 –H2Osys- Solubility: nothing speciﬁed. tem at 25 °C Temperature: precision of Ϯ0.1K,asinRef.125. a a b 100w1 m1 100w3 m3 Equilibrium solid phase

14.04 1.035 30.67 4.998 A Components: Original Measurements: 11.21 0.834 33.98 5.586 A ͑1͒ Lanthanum chloride; LaCl ; 81Z.N. Shevtsova, V.S. Zelova, 3 10.69 0.803 35.02 5.812 A ͓10099-58-8͔ and L.I. Ushakova, Nauch. Dokl. ͑2͒ Sodium chloride; NaCl; Vyssh. Shkoly, Khim. Khim. 9.23 0.695 36.63 6.096 A ͓7647-14-5͔ Tekhnol. 3,417͑1958͒. 7.58 0.591 40.10 6.905 A+C ͑ ͒ 7.56 0.589 40.15 6.918 A+C 3 Calcium chloride; CaCl2; ͓10043-52-4͔ 7.56 0.589 40.12 6.910 A+C ͑ ͒ ͓ ͔ 4 Water; H2O; 7732-18-5 6.98 0.540 40.31 6.890 C 2.53 0.191 43.32 7.208 C Variables: Prepared by: 0 0 45.24 7.443 C Salt composition T. Mioduski and C. Gumiński One temperature: 298 K amolalities calculated by the compilers b A=LaCl3 ·7H2O; C=CaCl2 ·6H2O Experimental Values The system was reported to be of eutonic type.

Composition of saturated solutions in the ternary LaCl3 –NaCl–H2O system at 25 °C Auxiliary Information Method/Apparatus/Procedure: 100w m a 100w m a Equilibrium solid phaseb 1 1 2 2 The isothermal method with analytical detection was used. Equilibrium 49.00 3.917 0 0 A between the saturated solution and the solutes was reported to be reached 48.72 3.889 0.20 0.067 A within 3 d. The composition of the solid phases was determined by unspecified chemical analysis, refractometry, and graphical method of dry 47.98 3.832 0.97 0.325 A+B residues of Schreinemakers. 47.92 3.824 0.99 0.332 A+B 48.00 3.836 0.98 0.329 A+B Source and Purity of Materials: 47.96 3.827 0.95 0.318 A+B All chemicals were analyzed before use and their purity was found to be 47.93 3.826 0.99 0.332 A+B satisfactory. 47.56 3.784 1.20 0.401 B 46.54 3.634 1.25 0.410 B Estimated Error: 43.84 3.277 1.62 0.508 B Solubility: nothing specified; precision seems to be similar to the differences in the eutonic point estimation; no better than Ϯ1% ͑by the 42.36 3.103 1.98 0.609 B compilers͒. 40.02 2.833 2.39 0.710 B Temperature: nothing specified. 35.30 2.386 4.38 1.243 B 21.82 1.335 11.55 2.966 B 15.45 0.919 16.00 3.994 B 11.04 0.640 18.60 4.524 B Components: Original Measurements: ͑ ͒ 126 9.72 0.560 19.47 4.705 B 1 Lanthanum chloride; LaCl3; Yu.V. Shirai, Zh. Neorg. Khim. ͓10099-58-8͔ 31, 1049 ͑1986͒. 8.23 0.470 20.36 4.879 B ͑2͒ Sodium chloride; NaCl; 4.29 0.241 23.21 5.478 B ͓7647-14-5͔ 2.64 0.147 24.73 5.826 B ͑3͒ Potassium chloride; KCl; 0 0 26.40 6.138 B ͓7447-40-7͔ ͑ ͒ amolalities calculated by the compilers 4 Cesium chloride; CsCl; ͓ ͔ bA=LaCl ·7H O; B=NaCl 7647-17-8 3 2 ͑ ͒ ͓ ͔ 5 Water; H2O; 7732-18-5

The system was reported to be of a simple eutonic type. Variables: Prepared by: Composition of salts T. Mioduski and C. Gumiński Composition of saturated solutions in the ternary LaCl3 –CaCl2 –H2O system at 25 °C One temperature: 298 K

100w m a 100w m a Equilibrium solid phaseb 1 1 3 3 Experimental Values 49.00 3.917 0 0 A Composition of saturated solutions in the ternary LaCl –NaCl–H Osys- 48.84 3.908 0.21 0.037 A 3 2 tem at 25 °C 47.88 3.801 0.76 0.134 A 45.92 3.645 2.72 0.477 A a a b 100w1 m1 100w2 m2 Equilibrium solid phase 42.62 3.306 4.82 0.826 A 32.43 2.456 13.74 2.300 A 48.77 3.881 0 0 A 25.15 1.876 20.18 3.326 A 47.97 3.832 0.99 0.333 A+B 16.16 1.196 28.77 4.707 A 35.63 2.398 3.78 1.074 B

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1816 MIODUSKI, GUMIŃSKI, AND ZENG

Composition of saturated solutions in the ternary LaCl3 –NaCl–H2O sys- Auxiliary Information tem at 25 °C Method/Apparatus/Procedure: a a b 100w1 m1 100w2 m2 Equilibrium solid phase The systems were investigated by the isothermal method. Equilibrium was reached during continuous agitation for 2–7 d. The saturated solutions 20.83 1.250 11.22 2.825 B and the equilibrium solid phases were analyzed. La was determined by 15.93 0.936 14.66 3.614 B titration with EDTA solution. Cl was determined by the Volhard method. 7.42 0.419 20.39 4.833 B Na, K, and Cs were found from corresponding differences. 3.78 0.211 23.03 5.384 B Source and Purity of Materials: 0 0 26.48 6.163 B LaCl3 ·7H2O, NaCl, KCl, and CsCl were of chemical purity. a molalities calculated by the compilers Estimated Error: b A=LaCl3 ·7H2O; B=NaCl Solubility: nothing speciﬁed; composition of the equilibrium solid phases D and E differed from their formulas by less than 1%. The system was reported to be of eutonic type. Temperature: precision of Ϯ0.1 K.

Composition of saturated solutions in the ternary LaCl3 –KCl–H2O system at 25 °C Components: Original Measurements: a a b ͑1͒ Lanthanum chloride; LaCl ; 127D.A. Storozhenko, Yu.V. 100w1 m1 100w3 m3 Equilibrium solid phase 3 ͓10099-58-8͔ Shirai, and N.M. Lazorenko, Zh. 48.77 3.881 0 0 A ͑2͒ Sodium chloride; NaCl; Neorg. Khim. 31,1610͑1986͒. 47.52 3.860 2.29 0.612 A ͓7647-14-5͔ ͑ ͒ ͓ ͔ 47.14 3.852 2.97 0.798 A+C 3 Water; H2O; 7732-18-5 39.61 2.878 4.28 1.023 C Variables: Prepared by: 30.45 1.966 6.39 1.357 C Composition of salts T. Mioduski and C. Gumiński 23.71 1.460 10.06 2.037 C Temperature: 298–373 K 16.38 0.965 14.39 2.788 C 8.32 0.476 20.48 3.858 C 0 0 26.57 4.853 C Experimental Values a molalities calculated by the compilers Composition of saturated solutions in the ternary LaCl3 –NaCl–H2Osys- b A=LaCl3 ·7H2O; C=KCl tem at 25, 50, 75, and 100 °C

/ a a b The system was reported to be of eutonic type. t °C 100w1 m1 100w2 m2 Equilibrium solid phase 25 0 0 26.48 6.163 A Composition of saturated solutions in the ternary LaCl3 –CsCl–H2O system at 25 °C 7.42 0.419 20.39 4.833 A 15.93 0.936 14.66 3.614 A a a b 100w1 m1 100w4 m4 Equilibrium solid phase 20.83 1.214 11.22 2.825 A 35.63 2.398 3.78 1.067 A 48.77 3.881 0 0 A 47.97 3.832 0.99 0.332 A+B 47.08 3.933 4.12 0.501 A 48.77 3.881 0 0 B 45.55 3.954 7.48 0.946 A 50 0 0 26.90 6.297 A 44.83 4.014 9.63 1.216 A+D 3.87 0.219 23.92 5.668 A 43.21 3.899 11.61 1.526 D 10.63 0.617 19.12 4.657 A 42.41 3.924 13.52 1.822 D 18.02 1.083 14.11 3.557 A 41.72 3.932 15.02 2.062 D 23.41 1.453 10.90 2.839 A 41.21 4.022 17.02 2.420 D+E 27.11 1.732 9.08 2.431 A 39.42 3.777 18.03 2.517 E 35.54 2.488 6.21 1.824 A 36.12 3.430 20.94 2.897 E 44.75 3.523 3.46 1.143 A 32.97 3.198 24.99 3.531 E 49.86 4.239 2.18 0.778 A+B 27.46 2.842 33.14 4.996 E 51.62 4.350 0 0 B 23.36 2.553 39.34 6.265 E 75 0 0 27.46 6.478 A 17.47 2.097 48.56 8.491 E+F 3.78 0.213 24.01 5.690 A 11.86 1.356 52.49 8.745 F 13.39 0.784 17.02 4.185 A 9.84 1.131 54.68 9.154 F 19.58 1.189 13.30 3.391 A 0 0 66.12 11.592 F 25.89 1.648 10.07 2.691 A 32.96 2.245 7.19 2.056 A amolalities calculated by the compilers 42.93 3.266 3.47 1.114 A bA=LaCl ·7H O; D=LaCl ·7H O; E=LaCl ·3CsCl·5H O; F=CsCl 3 2 3 2 3 2 54.14 4.967 1.42 0.547 A+B ͑ ͒ 54.99 4.981 0 0 B Two complex compounds D and E and two eutonic 100 0 0 28.23 6.731 A points in between were found in the system. 11.21 0.891 20.47 5.127 A

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1817

Composition of saturated solutions in the ternary LaCl3 –NaCl–H2O sys- Composition of saturated solutions in the LaCl3 –KCl–H2O ternary system at 25, 50, 75, and 100 °C tem at 20 and 50 °C

/ a a b / a a b t °C 100w1 m1 100w2 m2 Equilibrium solid phase t °C 100w1 m1 100w2 m2 Equilibrium solid phase

20.74 1.300 14.19 3.732 A 11.8 0.72 21.0 4.19 A 28.65 1.877 9.12 2.508 A 26.4 1.75 12.0 2.61 A 38.99 2.831 4.86 1.481 A 40.0 3.08 7.0 1.77 A 47.69 3.923 2.74 0.946 A 49.0 4.39 5.5 1.62 A+B 56.33 5.525 2.10 0.864 A+B 50.5 4.35 2.2 0.62 B 51.0 4.36 1.3 0.37 B a molalities calculated by the compilers b 51.5 4.33 0 0 B A=NaCl; B=LaCl3 ·7H2O amolalities calculated by the compilers The system is reported to be of eutonic type. LaCl ·7H O b 3 2 A=KCl; B=LaCl3 ·7H2O melts above 95 °C, therefore it was impossible to determine the solubility of LaCl3 in H2O using LaCl3 ·7H2O as the The system was found to be of simple eutonic type. solute. Auxiliary Information Auxiliary Information Method/Apparatus/Procedure: Method/Apparatus/Procedure: Presumably the isothermal method of sections was used as described by ͓ ͑ ͔͒ Equilibrium was reached during continuous agitation of the components Zhuravlev and Sheveleva Zh. Neorg. Khim. 5, 2630 1960 . Refractive for several days. A dry air or a liquid thermostat was used to ensure indices of solutions were measured along directed sections of the phase isothermal conditions of the experiments. The saturated solutions and the diagram, and the results were used to plot relations between the refractive equilibrium solid phases were analyzed. La was determined by titration index and composition at all sections studied. Equilibrium between the with EDTA solution. Cl was determined by the Volhard method. Na was solid and liquid phases was confirmed by constancy of the refractive found by difference. The composition of the solid phases was found by indices of a solution in time. the graphical method of Schreinemakers and was confirmed by chemical Source and Purity of Materials: analysis as well as by optical observation of the crystals. Pure grade LaCl3 ·7H2O was twice recrystallized before use. Source and Purity of Materials: Chemically pure KCl was presumably used as received. LaCl ·7H O and NaCl used were chemically pure. 3 2 Estimated Error: Estimated Error: Nothing specified. Solubility: nothing specified. Temperature: precision of Ϯ0.1 K. Components: Original Measurements: ͑ ͒ 97 1 Lanthanum chloride; LaCl3; A.D. Sheveleva, K.I. Mochalov, Components: Original Measurements: ͓10099-58-8͔ E.N. Khutorskoi, and N.A. ͑ ͒ ͑1͒ Lanthanum chloride; LaCl ; 89E.N. Khutorskoi and A.D. 2 Rubidium chloride; RbCl; Torgashina, Ucheb. Zap. Perm. 3 ͓ ͔ ͑ ͒ ͓10099-58-8͔ Sheveleva, Ucheb. Zap. Perm. 7791-11-9 Univ. 289,3 1973 . ͑ ͒ ͓ ͔ ͑2͒ Potassium chloride; KCl; Univ. 207,11͑1970͒. 3 Water; H2O; 7732-18-5 ͓7447-40-7͔ Variables: Prepared by: ͑3͒ Water; H O; ͓7732-18-5͔ 2 Composition of salts T. Mioduski and C. Gumiński Variables: Prepared by: Temperature: 293 and 323 K Composition of salts T. Mioduski and C. Gumiński Temperature: 293 and 323 K Experimental Values

Experimental Values Composition of saturated solutions in the ternary LaCl3 –RbCl–H2Osys- tem at 20 and 50 °C

Composition of saturated solutions in the LaCl3 –KCl–H2O ternary sys- / a a b tem at 20 and 50 °C t °C 100w1 m1 100w2 m2 Equilibrium solid phase

/ a a b 20 0 0 47.6 7.51 A t °C 100w1 m1 100w2 m2 Equilibrium solid phase 12.8 1.02 36.0 5.81 A 20 0 0 25.5 4.59 A 21.2 1.75 29.5 4.95 A 12.4 0.72 17.0 3.23 A 30.0 2.66 24.0 4.31 A 27.3 1.75 9.0 1.89 A 30.5 2.65 22.5 3.96 A 40.0 2.94 4.5 1.09 A 37.0 3.59 21.0 4.13 A+B 47.0 3.86 3.2 0.86 A+B 37.5 2.86 19.0 2.94 B 47.2 3.79 2.0 0.53 B 38.5 3.51 16.8 3.11 B 47.5 3.80 1.5 0.39 B 40.0 3.58 14.5 2.64 B 48.0 3.76 0 0 B 41.0 3.59 12.5 2.22 B 50 0 0 30.0 5.75 A 44.5 3.82 8.0 1.39 B+C

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1818 MIODUSKI, GUMIŃSKI, AND ZENG

Composition of saturated solutions in the ternary LaCl3 –RbCl–H2O sys- Experimental Values tem at 20 and 50 °C

Composition of saturated solutions in the ternary LaCl3 –RbCl–H2Osys- / a a b t °C 100w1 m1 100w2 m2 Equilibrium solid phase tem at 25 °C

45.0 3.78 6.5 1.11 C a a b 100w1 m1 100w2 m2 Equilibrium solid phase 47.0 3.83 3.0 0.51 C 48.5 3.84 0 0 C 48.77 3.881 0 0 A 50 0 0 52.5 9.14 A 48.21 3.899 1.38 0.226 A 11.8 1.03 41.5 7.35 A 47.83 3.981 3.18 0.537 A 19.2 1.75 46.0c 6.65 A 47.28 3.948 3.89 0.659 A 28.0 2.72 30.0 5.91 A 47.09 3.988 4.77 0.819 A+B 30.0 2.95 28.5 5.68 A 46.01 3.938 6.36 1.104 B 35.0 3.61 25.5 5.34 A+B 44.15 3.800 8.48 1.480 B 38.5 3.71 19.2 3.75 B 42.11 3.615 11.26 1.997 B 40.0 3.79 17.0 3.27 B 39.13 3.615 16.74 3.137 B 41.0 3.82 15.2 2.87 B 37.62 3.513 18.78 3.562 B 42.5 3.85 12.5 2.30 B 36.45 3.489 20.95 4.067 B+C 47.0 4.08 6.0 1.06 B+C 34.93 3.226 20.93 3.921 C 47.5 4.15 5.8 1.03 C 27.81 2.315 23.22 4.321 C 50.5 3.79 2.5 0.44 C 17.40 1.383 31.29 5.043 C 51.5 4.33 0 0 C 11.03 0.872 37.37 5.989 C 4.11 0.321 43.74 6.936 C a molalities calculated by the compilers 0 0 48.74 7.863 C b A=RbCl; B=LaCl3 ·RbCl·5H2O; C=LaCl3 ·7H2O a cthe originally printed value seems to be a misprint because a value of molalities calculated by the compilers b 36 mass % RbCl may be read out from a ﬁgure in this paper A=LaCl3 ·7H2O; B=LaCl3 ·RbCl·5H2O; C=RbCl

The double salt B was found to be congruently soluble. The system contained the congruently soluble compound B. Auxiliary Information Auxiliary Information Method/Apparatus/Procedure: The method of isothermal sections of the phase diagram identified by Method/Apparatus/Procedure: measurements of refractive indices of the solutions was used. The analytical method with continuous agitation of the components in a Homogeneous and heterogeneous mixtures of selected compositions of the thermostat was used. Equilibrium in the system was reached within salts and water were prepared and equilibrated until their refractive several days. The compositions of the saturated solutions and solid phases indices did not change ͑8–9 and 10–11 h at 50 and 20 °C, respectively͒. were determined by chemical analysis. La was determined by titration The compositions of the saturated solutions and the corresponding solid with EDTA solution using xylenol orange as an indicator. Cl was phases were determined as inflection points on plots of the refractive determined by the Volhard method. Rb was found by difference, and in index versus composition. The composition of the double salt was several cases it was determined gravimetrically as rubidium confirmed by chemical analysis. tetraphenylborate. Refractive indices of the solutions were measured. The equilibrium solid phases were investigated by optical observations, Source and Purity of Materials: thermogravimetry, and thermal analysis. LaCl3 ·7H2O of “pure” grade was twice recrystallized before use. RbCl of chemically pure grade was presumably used as received. Source and Purity of Materials: Chemically pure salts were used. Estimated Error: LaCl3 ·RbCl·5H2O was prepared by isothermal evaporation of water. Its Nothing specified. composition was confirmed by chemical analysis and differed from the compound formula by 0.1%.

Components: Original Measurements: Estimated Error: ͑ ͒ 116 Nothing speciﬁed. 1 Lanthanum chloride; LaCl3; Yu.V. Shirai and V.G. ͓10099-58-8͔ Shevchuk, Zh. Neorg. Khim. 26, ͑2͒ Rubidium chloride; RbCl; 1940 ͑1981͒. ͓7791-11-9͔ ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5

Variables: Prepared by: Salt composition T. Mioduski and C. Gumiński One temperature: 298 K

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1819

Composition of saturated solutions in the quaternary Components: Original Measurements: LaCl3 –CsCl–NaCl–H2O system at 50 °C ͑ ͒ 91 1 Lanthanum chloride; LaCl3; A.D. Sheveleva, N.A. ͓10099-58-8͔ Torgashina, and E.N. Khutorskoi, a a a b 100w1 m1 100w2 m2 100w3 m3 Equilibrium solid phase ͑2͒ Cesium chloride; CsCl; Ucheb. Zap. Perm. Univ. 229,21 ͓7647-17-8͔ ͑1970͒. 17.9 2.32 49.7 9.37 0.9 0.49 E+B ͑3͒ Sodium chloride; NaCl; 19.5 2.79 52.0 10.84 0 0 E+B ͓7647-14-5͔ 17.5 1.44 27.0 3.23 5.8 2.00 F+B ͑ ͒ ͓ ͔ 4 Water; H2O; 7732-18-5 22.2 1.84 22.2 2.67 6.3 2.19 F+B Variables: Prepared by: 24.4 2.01 19.5 2.34 6.6 2.28 F+C+B 25.5 2.10 20.2 2.42 4.8 1.66 C+B Composition of salts T. Mioduski and C. Gumiński One temperature: 323 K 32.8 3.43 26.5 4.04 1.7 0.75 C+B 33.5 3.59 27.1 4.24 1.4 0.63 C+B 37.0 4.57 30.0 5.40 0 0 C+B Experimental Values 28.0 2.20 14.7 1.68 5.3 1.74 F+C 31.9 2.42 10.6 1.17 3.8 1.21 F+C Composition of saturated solutions in the ternary LaCl –CsCl–H O sys- 3 2 36.6 2.83 6.6 0.74 4.1 1.33 F+C+D tem at 50 °C 41.4 3.48 8.0 0.98 2.1 0.74 C+D a a b 46.5 4.36 9.5 1.30 0.5 0.20 C+D 100w1 m1 100w2 m2 Equilibrium solid phase 48.0 4.66 10.0 1.41 0 0 C+D 0 0 68.5 12.92 A 39.2 2.99 4.3 0.48 3.0 0.96 F+D 3.6 0.46 64.5 12.01 A 49.1 4.14 0 0 2.6 0.92 F+D 7.9 1.02 60.5 11.37 A a molalities calculated by the compilers 11.0 1.42 57.5 10.84 A b B=LaCl3 ·3CsCl·5H2O; C=LaCl3 ·CsCl·7H2O; D=LaCl3 ·7H2O; 13.2 1.75 56.0 10.80 A E=solid solution of NaCl in CsCl; F=NaCl 16.0 2.17 54.0 10.69 A 19.5 2.79 52.0 10.84 A+B Auxiliary Information 21.0 2.72 47.5 8.96 B Method/Apparatus/Procedure: 22.0 2.64 44.0 7.69 B The authors used the method described in the previous data sheet of the 23.8 2.72 40.5 6.74 B LaCl3 –NaCl–H2O system in Sec. 4.2, performed by the same group 26.0 2.90 37.5 6.10 B ͑Khutorskoi and Sheveleva, Ref. 85͒. 27.0 2.98 36.0 5.78 B 28.0 3.09 35.0 5.62 B Source and Purity of Materials: 30.5 3.36 32.5 5.22 B Nothing speciﬁed; presumably similar to that described in other papers 32.0 3.60 31.8 5.26 B from this laboratory. 37.0 4.57 30.0 5.40 B+C Estimated Error: 37.5 4.50 28.5 4.98 C Nothing speciﬁed. 38.0 4.19 25.0 4.01 C 40.0 4.08 20.0 2.97 C 42.5 4.23 16.5 2.39 C 4.3.2. LaCl3 –MCl2 –H2O „M=Mg,Ca,Sr,Ba,Cd… Systems 45.0 4.32 12.5 1.75 C 48.0 4.66 10.0 1.41 C+D 48.5 4.55 8.0 1.09 D Components: Original Measurements: ͑ ͒ 110 49.0 4.33 4.9 0.63 D 1 Lanthanum chloride; LaCl3; A.A. Sorokina, N.P. Sokolova, ͓10099-58-8͔ G.S. Kotlyar-Shapirov, and P.A. 50.0 4.29 2.5 0.32 D ͑2͒ Magnesium chloride; MgCl ; Stabnikov, Izv. Sibir. Otd. Akad. 51.5 4.33 0 0 D 2 ͓7786-30-3͔ Nauk SSSR, Ser. Khim. Nauk no a ͑ ͒ ͓ ͔ ͑ ͒ ͑ ͒ molalities calculated by the compilers 3 Water; H2O; 7732-18-5 4 ,91 1977 . b A=CsCl; B=LaCl ·3CsCl·5H O; C=LaCl ·CsCl·7H O; 3 2 3 2 Variables: Prepared by: D=LaCl3 ·7H2O Composition of salts T. Mioduski and C. Gumiński Composition of saturated solutions in the quaternary One temperature: 298 K

LaCl3 –CsCl–NaCl–H2O system at 50 °C

a a a b Experimental Values 100w1 m1 100w2 m2 100w3 m3 Equilibrium solid phase Composition of saturated solutions in the ternary LaCl –MgCl –H Osys- 0 0 53.2 8.27 8.6 3.85 E+F 3 2 2 tem at 25 °C 6.8 0.68 45.6 6.64 6.8 2.85 E+F 10.7 1.09 42.8 6.36 6.5 2.78 E+F a a b 100w1 m1 100w2 m2 Equilibrium solid phase 11.4 1.17 42.4 6.34 6.5 2.80 E+F+B 13.7 1.55 45.7 7.54 4.6 2.19 E+B 0 0 35.9 5.88 A 12.3 1.11 36.7 4.84 6.0 2.28 F+B 1.3 0.08 35.1 5.80 A 15.4 1.85 47.6 8.32 3.0 1.51 E+B 1.9 0.12 34.7 5.75 A 16.0 1.95 48.0 8.51 2.5 1.28 E+B 2.6 0.17 34.3 5.71 A

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1820 MIODUSKI, GUMIŃSKI, AND ZENG

Composition of saturated solutions in the ternary LaCl3 –MgCl2 –H2O sys- Variables: Prepared by: tem at 25 °C Composition of salts T. Mioduski and C. Gumiński Temperature: 293 and 323 K a a b 100w1 m1 100w2 m2 Equilibrium solid phase

6.5 0.43 32.1 5.49 A Experimental Values 9.4c 0.64 30.3c 5.28 A+B 9.3 0.63 30.5 5.32 A+B Composition of saturated solutions in the ternary LaCl3 –CaCl2 –H2Osys- tem at 20 and 50 °C 10.8 0.73 29.0 5.06 B 20.1 1.40 21.2 3.79 B t/ °C 100w m a 100w m a Equilibrium solid phaseb 23.8 1.68 18.3 3.32 B 1 1 2 2 29.0 2.08 14.2 2.63 B 20 48.2 3.79 0 0 A 35.9 2.68 9.4 1.80 B 43.5 3.34 3.4 0.58 A 38.9 2.94 7.2 1.40 B 37.3 2.80 8.3 1.37 A 43.2 3.35 4.3 0.86 B 27.0 1.96 16.8 2.69 A 45.2 3.54 2.8 0.57 B 14.2 1.05 30.6 4.99 A 47.6 3.80 1.3 0.27 B 11.6 0.89 35.2 5.96 A 47.8 3.81 1.1 0.23 B 11.0 0.85 36.0 6.12 A+B 48.9 3.90 0 0 B 7.6 0.57 37.8 6.24 B 4.0 0.29 40.0 6.44 B a molalities calculated by the compilers 1.8 0.13 41.0 6.46 B b A=MgCl2 ·6H2O; B=LaCl3 ·7H2O 0 0 42.7 6.71 B c the result is reported twice 50 51.7 4.36 0 0 A 48.8 4.09 2.6 0.48 A The system was reported to be of a simple eutonic type 45.4 3.81 6.0 1.11 A and no solid solution or double chloride was formed. Based 38.9 3.22 11.9 2.18 A on isopiestic measurements of the system, the authors calcu- 28.8 2.41 22.5 4.16 A 17.8 1.59 36.5 7.20 A lated solubilities which showed satisfactory agreement with 14.0 1.42 45.8 10.26 A+B the experimental results; no numerical data were published. 11.4 1.12 47.0 10.18 B 6.5 0.62 50.7 10.67 B Auxiliary Information 2.8 0.26 53.8 11.17 B Method/Apparatus/Procedure: 0 0 57.0 11.94 B Equilibrium between the saturated solutions and the solid phases was amolalities calculated by the compilers b attained after more than 7 d. The content of La in the solutions and solids A=LaCl3 ·7H2O; B=CaCl2 ·6H2O was determined by titration with EDTA solution at pH=5.5 using a xylenol orange indicator. The corresponding sum of the La and Mg Composition of saturated solutions in the ternary LaCl3 –SrCl2 –H2O sys- contents was determined by titration with EDTA solution at pH=10 using tem at 20 and 50 °C a chromogen black indicator. The composition of the solid phases was / a a b found by Schreinemakers’ method. t °C 100w1 m1 100w3 m3 Equilibrium solid phase

Source and Purity of Materials: 20 48.2 3.79 0 0 A

LaCl3 ·7H2O was prepared by dissolving 99.9% pure La2O3 in specially 47.5 3.79 1.4 0.17 A pure HCl solution. 46.5 3.79 3.5 0.44 A+C The salt was recrystallized from HCl solution and then from water. 46.0 3.72 3.6 0.45 C MgCl2 ·6H2O was twice recrystallized from water. 41.4 3.14 4.8 0.56 C 32.0 2.22 9.3 1.00 C Estimated Error: 20.8 1.34 16.1 1.61 C Solubility: precision of Ϯ1% ͑by the compilers, taking into account the 12.0 0.76 23.5 2.30 C reliability of the eutonic point composition͒. 8.2 0.51 26.2 2.52 C Temperature: stability of Ϯ0.1 K 0 0 34.5 3.32 C 50 51.7 4.36 0 0 A 50.8 4.31 1.2 0.16 A Components: Original Measurements: 49.2 4.27 3.8 0.51 A ͑1͒ Lanthanum chloride; LaCl ; 90A.A. Volkov, M.P. Borodina, 3 48.0 4.26 6.0 0.82 A ͓10099-58-8͔ and A.I. Shapiro, Ucheb. Zap. ͑ ͒ ͑ ͒ 46.8 4.32 9.0 1.28 A+C 2 Calcium chloride; CaCl2; Perm. Univ. 229,3 1970 . ͓10043-52-4͔ 38.6 3.21 12.4 1.60 C ͑ ͒ 33.7 2.68 15.0 1.84 C 3 Strontium chloride; SrCl2; ͓10476-85-4͔ 24.7 1.85 21.0 2.44 C ͑ ͒ 4 Barium chloride; BaCl2; 16.0 1.16 27.9 3.14 C ͓10361-37-2͔ 9.0 0.65 34.2 3.80 C ͑ ͒ ͓ ͔ 5 Water; H2O; 7732-18-5 0 0 42.4 4.64 C

amolalities calculated by the compilers

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1821

b A=LaCl3 ·7H2O; C=SrCl2 ·6H2O Experimental Values

Composition of saturated solutions in the ternary LaCl –BaCl –H O sys- 3 2 2 Composition of saturated solutions in the ternary LaCl3 –CdCl2 –H2Osys- tem at 20 and 50 °C tem at 30 °C

t/ °C 100w m a 100w m a Equilibrium solid phaseb a a b 1 1 4 4 100w2 m2 100w1 m1 Equilibrium solid phase

20 48.2 3.79 0 0 A 54.65 6.575 0 0 A 47.9 3.76 0.1 0.009 A+D 52.24 6.414 3.33 0.306 A 41.6 2.92 0.4 0.033 D 48.64 6.108 7.92 0.743 A 30.4 1.84 2.4 0.171 D 47.22 5.911 9.20 0.861 A 20.5 1.15 6.9 0.46 D 46.88 6.034 10.74 1.033 A 12.5 0.68 12.3 0.78 D 45.41 6.321 15.40 1.602 A 4.9 0.27 20.4 1.31 D 45.71 6.350 15.02 1.559 A+B 0 0 26.3 1.71 D 44.40 6.386 17.67 1.899 B 50 51.7 4.36 0 0 A 44.39 6.416 17.87 1.931 B 51.6 4.36 0.2 0.02 A 43.64 6.350 18.87 2.052 B 51.3 4.31 0.2 0.02 A+D 43.58 6.429 19.44 2.143 B 39.6 2.76 1.8 0.15 D 42.54 6.564 19.61 2.112 B+C 28.0 1.72 5.8 0.42 D 42.32 6.056 19.56 2.092 C 22.0 1.31 9.3 0.65 D 41.82 6.039 20.40 2.201 C 17.0 0.99 12.7 0.87 D 41.04 5.913 21.12 2.275 C 10.2 0.59 19.5 1.33 D 33.81 4.858 28.22 3.027 C 3.6 0.21 25.5 1.73 D 33.63 4.680 27.17 2.826 C 0 0 30.0 2.06 D 32.88 4.598 28.11 2.938 C a 30.79 4.420 31.21 3.349 D molalities calculated by the compilers b 29.47 4.157 31.86 3.359 D A=LaCl3 ·7H2O; D=BaCl2 ·2H2O 23.99 3.525 38.88 4.269 D The solubility isotherms for all systems at both tempera- 24.65 3.629 38.30 4.215 D+E tures were found to be of a simple eutonic type. 23.95 3.540 39.14 4.324 D+E 23.65 3.546 39.66 4.407 D+E Auxiliary Information 20.06 2.816 41.08 4.310 E 15.78 2.028 41.77 4.012 E Method/Apparatus/Procedure: 7.89 0.923 45.52 3.984 E The method of isothermal sections with refractometric analysis of 0 0 48.32 3.812 E solutions was used as by Zhuravlev and Sheveleva ͓Zh. Neorg. Khim. 5, 2630 ͑1960͔͒. Mixtures of known amounts of the components along amolalities calculated by the compiler directed sections of the phase diagrams were equilibrated for 7–9 h until b A=CdCl2 ·2.5H2O; B=CdCl2 ·H2O; C=LaCl3 ·8CdCl2 ·16H2O; the refractive indices of the solutions measured in a thermostated D=LaCl ·4CdCl ·12H O; E=LaCl ·7H O refractometer were constant. The compositions of the saturated solutions 3 2 2 3 2 and the corresponding solid phases were found as break points on refractive index versus composition plots. The compounds C and D were found to be incongruently soluble. Source and Purity of Materials:

LaCl3 ·7H2O of analytical grade purity was recrystallized before use. Auxiliary Information Chemically pure CaCl2 ·6H2O was recrystallized at 40–100 °C. Method/Apparatus/Procedure: SrCl2 ·6H2O of analytical grade purity was recrystallized before use. The starting components were mixed in different weight ratios and placed BaCl2 ·2H2O of analytical grade purity was recrystallized before use. in sealed plastic containers. All containers were dipped in a large water Estimated Error: tank, thermostated at the selected temperature, and continuously stirred. Nothing speciﬁed. The solid-liquid equilibrium was established after 6–10 d. The saturated solutions and wet residues were separated and analyzed. According to Wang et al. ͓J. Chem. Eng. Data 51, 1541 ͑2006͔͒, the sum of contents ͑La+Cd͒ was determined by titration with EDTA solution. The content of Components: Original Measurements: Cd was determined by titration with EDTA solution after La was ͑ ͒ 152 1 Lanthanum chloride; LaCl3; H. Wang, X.F. Wang, F.X. sequestrated with F ion. The content of La was found by difference. The ͓ ͔ 10099-58-8 Dong, X.Q. Ran, L. Li, and Sh.Y. composition of the solid phases was found by the method of ͑ ͒ 2 Cadmium chloride; CdCl2; Gao, J. Chem. Eng. Data 52, 731 Schreinemakers and conﬁrmed by chemical analysis. The compounds C ͓ ͔ ͑ ͒ 10108-64-2 2007 . and D were characterized by powder x-ray diffraction and ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 thermogravimetry. Variables: Prepared by: Composition of salts C. Gumiński One temperature: 303 K

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1822 MIODUSKI, GUMIŃSKI, AND ZENG

Source and Purity of Materials: Source and Purity of Materials: ͓ LaCl3 ·7H2O was prepared, according to Wang et al. J. Chem. Eng. Data Nothing specified. ͑ ͔͒ ͑ ͒ 51, 1541 2006 , by dissolution of La2O3 analytically pure in HCl solution ͑analytically pure͒. The product was likely recrystallized. The Estimated Error: composition of the salt was confirmed by analyzing the Cl content by Solubility: nothing specified; reading-out procedure at Ϯ0.3 mass %. titration with AgNO3 solution. The analysis indicated purity of Temperature: nothing specified. ϳ LaCl3 ·7H2Oof 99.9%. All other chemicals were analytically pure ͑commercially available͒. Components: Original Measurements: Estimated Error: ͑1͒ Lanthanum chloride; LaCl ; 41A.V. Nikolaev, A.A. Sorokina, Solubility: precision of the analysis of better than Ϯ0.2%. 3 ͓ ͔ Ϯ 10099-58-8 A. Ya. Vilenskaya, and V.G. Temperature: precision of 1K. ͑ ͒ 2 Cerium chloride; CeCl3; Tsubanov, Izv. Sibir. Otd. Akad. ͓7790-86-5͔ Nauk SSSR, Ser. Khim. Nauk ͑ ͒ ͓ ͔ ͑ ͒ ͑ ͒ 3 Water; H2O; 7732-18-5 6 ,5 1967 . 4.3.3. LaCl3 –MCl3 –H2O „M=Ce,Eu,Yb,Sm,Nd… Systems Variables: Prepared by: Salt composition T. Mioduski and C. Gumiński Components: Original Measurements: ͑ ͒ 40 One temperature: 298 K 1 Lanthanum chloride; LaCl3; A.V. Nikolaev, A.A. Sorokina, ͓10099-58-8͔ and V.G. Tsubanov, Dokl. Akad. ͑2͒ Cerium chloride; CeCl ; Nauk SSSR 172, 1333 ͑1967͒. 3 Experimental Values ͓7790-86-5͔ ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 Composition of saturated solutions of the ternary LaCl3 –CeCl3 –H2Osys- Variables: Prepared by: tem at 25 °C

Salt composition T. Mioduski and C. Gumiński a a One temperature: 298 K 100w1 m1 100w2 m2 49.1 3.93 0 0 Experimental Values 48.3 3.87 0.8 0.06 40.7 3.22 7.7 0.61 Composition of saturated solutions of the ternary LaCl3 –CeCl3 –H2O sys- 40.7 3.17 6.9 0.53 tem at 25 °C 32.2 2.55 16.4 1.29 30.8 2.44 17.8 1.40 a a 100w1 m1 100w2 m2 30.1 2.39 18.6 1.47 45.4 3.61 3.3 0.26 26.4 2.09 22.2 1.75 42.8 3.44 6.45 0.52 24.7 1.94 23.5 1.84 40.8 3.14 6.25 0.48 22.5 1.79 26.2 2.07 38.8 3.07 9.75 0.77 19.2 1.51 28.9 2.26 30.35 2.40 18.0 1.41 19.2 1.49 28.4 2.20 22.9 1.77 24.4 1.88 19.0 1.49 29.1 2.27 20.45 1.62 28.1 2.22 15.0 1.12 30.6 2.28 16.2 1.28 32.3 2.55 14.1 1.11 34.2 2.68 11.5 0.89 35.9 2.77 9.0 0.72 39.8 3.15 9.3 0.75 40.1 3.22 1.2 0.09 46.8 3.65 9.0 0.72 39.8 3.15 0 0 48.6 3.84 2.2 0.18 47.1 3.77 amolalities calculated by the compilers amolalities calculated by the compilers The equilibrium solid phase was found to be a continuous Solubilities of 49.1 mass % LaCl and 48.6 mass % CeCl 3 3 series of solid solutions ͑La,Ce͒Cl ·7H O. in water were read out from a ﬁgure in the paper ͑by the 3 2 compilers͒ and were recalculated to be 3.93 and Auxiliary Information 3.84 mol kg−1, respectively. The equilibrium solid phase was found to be a continuous series of solid solutions Method/Apparatus/Procedure: ͑ ͒ The solutes and the solutions were equilibrated in isothermal conditions La,Ce Cl3 ·7H2O. with continuous pulverization of the solid phase. The separated phases were analyzed. The total La+Ce content was determined by a Auxiliary Information complexometric titration and Ce by an oxidimetric method. The Method/Apparatus/Procedure: composition of the solid phase was determined graphically and algebraically ͑giving very similar results͒ by the dry residue method of Equilibration of the solute and the solution at isothermal conditions was Schreinemakers. carried out for 1 month. The solid phase was continuously pulverized. The separated phases were analyzed. The total La+Ce content was determined Source and Purity of Materials: by a complexometric titration and Ce by an oxidimetric method. The Pure LaCl ·7H O and CeCl ·7H O were used. The water content in the composition of solid phases was estimated by the dry residue method of 3 2 3 2 salts was conﬁrmed by the Karl-Fischer method. Schreinemakers.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1823

Estimated Error: Source and Purity of Materials: Solubility: nothing specified; precision of Ϯ several percent, as estimated Heptahydrate of La and hexahydrate of Eu chlorides were prepared by by the compilers. dissolving the corresponding oxides ͑99.9+% pure͒ in HCl solution 54 Temperature: nothing specified. ͑specially pure͒. The salts were twice recrystallized from HCl solution and then from water. They were dried in air at temperatures below 35 °C. The compositions of the salts were confirmed by chemical analyses: metals by titration with EDTA and chloride by the Volhard method. Components: Original Measurements: ͑ ͒ 44 1 Lanthanum chloride; LaCl3; A.V. Nikolaev and A.A. Estimated Error: ͓ ͔ 54 10099-58-8 Sorokina, Izv. Sibir. Otd. Akad. Solubility: precision of Ϯ͑1.0–1.5͒%. ͑ ͒ 2 Europium chloride; EuCl3; Nauk SSSR, Ser. Khim. Nauk Temperature: nothing specified. ͓10025-76-0͔ ͑4͒,61͑1971͒. ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5

Variables: Prepared by: Components: Original Measurements: ͑ ͒ 104 Composition of salts T. Mioduski and C. Gumiński 1 Lanthanum chloride; LaCl3; A.V. Nikolaev, A.A. Sorokina, One temperature: 298 K ͓10099-58-8͔ and N.L. Kozyreva, Izv. Sibir. ͑ ͒ 2 Ytterbium chloride; YbCl3; Otd. Akad. Nauk SSSR, Ser. ͓10361-91-8͔ Khim. Nauk ͑6͒,86͑1974͒. ͑ ͒ ͓ ͔ Experimental Values 3 Water; H2O; 7732-18-5

Variables: Prepared by: Composition of saturated solutions in the ternary LaCl3 –EuCl3 –H2O system at 25 °C Composition of salts T. Mioduski and C. Gumiński One temperature: 298 K a a 100w2 m2 100w1 m1

0 0 48.8 3.89 Experimental Values 5.5 0.41 42.5 3.33 Composition of saturated solutions in the ternary LaCl –YbCl –H Osys- 7.9 0.59 40.3 3.17 3 3 2 tem at 25 °C 10.6 0.81 38.4 3.07 16.4 1.26 33.1 2.67 a a b 100w2 m2 100w1 m1 Equilibrium solid phase 20.2 1.57 29.9 2.44 20.6 1.59 29.3 2.38 48.1 3.68 5.1 0.44 A 19.7 1.50 29.6 2.38 46.5 3.64 7.8 0.70 A 19.8 1.53 30.2 2.46 42.2 3.28 11.8 1.06 A 41.1 3.09 7.4 0.59 41.8 3.27 12.5 1.12 A 39.3 2.98 9.6 0.77 41.6 3.24 12.5 1.11 A 36.4 2.73 12.0 0.95 41.4 3.21 12.4 1.09 A 33.5 2.48 14.2 1.11 41.6 3.22 12.2 1.08 A 30.9 2.36 18.5 1.49 5.4 0.38 43.3 3.44 B 27.0 2.06 22.2 1.78 8.7 0.61 40.4 3.24 B 24.0 1.85 25.7 2.08 13.8 0.99 36.1 2.94 B 20.2 1.55 29.5 2.39 26.0 1.97 26.8 2.31 B 48.2 3.60 0 0 35.4 2.74 18.4 1.62 B 53.3c 4.09 0 0 A a molalities calculated by the compilers 0 0 48.8c 3.89 B

The equilibrium solid phases were not reported; however, amolalities calculated by the compilers b A=YbCl3 ·6H2O; B=LaCl3 ·7H2O according to diagrams reported in the paper, LaCl3 ·7H2O cas reported in Ref. 54 exists in the La-rich mixtures, EuCl ·6H O exists in the Eu- 3 2 The solid phases were not explicitly reported by the au- rich mixtures, and solid solutions, based on these com- thors but could be deduced from a solubility diagram in the pounds, were formed in between. paper. The same results were also reported in Ref. 54. The same results were also reported in Ref. 54. Auxiliary Information Auxiliary Information Method/Apparatus/Procedure: Method/Apparatus/Procedure: No information was provided. Presumably the experimental details were Nothing speciﬁed. Experimental details were certainly the same as in Ref. the same as in Ref. 54. The components were mixed in closed vessels in a 54. The isothermal method was used. The solutions and solutes were thermostat. The crystals were continuously crushed during equilibration by mixed in closed vessels in a thermostat. The crystals were continuously special glass pestles. Samples of the saturated solutions and the crushed by special pestles. The sum of the metal ion contents in the liquid corresponding solid phases were analyzed. The total concentration of both and solid phases was analyzed by means of titration with EDTA. Eu͑III͒ metals was determined by titration with EDTA solution. Separate ͑ ͒ was reduced to Eu II with Zn amalgam and then titrated with K2Cr2O7 concentrations of the metals were found from atomic absorption solution. The concentration of chloride was determined by the method of spectrometry. The solid phases were identiﬁed by the residue method of Volhard. Schreinemakers.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1824 MIODUSKI, GUMIŃSKI, AND ZENG

Source and Purity of Materials: Composition of saturated solutions in the ternary LaCl3 –SmCl3 –H2Osys- Nothing speciﬁed, presumably as in Ref. 54. Heptahydrate of La and tem at 20 °C hexahydrate of Yb chlorides were prepared by dissolving the corresponding oxides ͑99.9+% pure͒ in HCl solution ͑of special purity͒. Equilibrium

The salts were twice recrystallized from HCl solution and then from Mol % Sm mol H2O per solid ͑ ͒ ͑ ͒ / −1a / −1a b water. They were dried in air at temperatures below 35 °C. The in Sm+La mol of Sm+La m2 mol kg m1 mol kg phase compositions of the salts were conﬁrmed by chemical analysis: metals by titration with EDTA and chloride by the Volhard method. 71.1 14.65 2.694 1.095 C 85.0 14.98 3.150 0.556 C Estimated Error: 100 15.26 3.638 0 D Solubility: precision of Ϯ͑1.0–1.5͒%.54 a Temperature: nothing speciﬁed. calculated by the compilers b ͑ ͒ ͑ ͒ A=LaCl3 ·7H2O; B= La,Sm Cl3 ·7H2O; C= La,Sm Cl3 ·6H2O; D=SmCl3 ·6H2O Components: Original Measurements: ͑ ͒ 86 The system showed a solid miscibility gap. 1 Lanthanum chloride; LaCl3; G. Brunisholz and M. Nozari, ͓10099-58-8͔ Helv. Chim. Acta 52, 2303 Composition of saturated solutions in the ternary LaCl –NdCl –H Osys- ͑2͒ Samarium chloride; SmCl ; ͑1969͒. 3 3 2 3 tem at 20 °C ͓10361-82-7͔ ͑ ͒ 3 Neodymium chloride; NdCl3; ͓10024-93-8͔ Equilibrium ͑4͒ Water; H O; ͓7732-18-5͔ Mol % Nd mol H2Oper solid 2 ͑ ͒ ͑ ͒ / −1a / −1a b in Nd+La mol of Nd+La m3 mol kg m1 mol kg phase Variables: Prepared by: 0 14.38 0 3.860 A Salt composition T. Mioduski and C. Gumiński One temperature: 293 K 14.7 14.37 0.568 3.291 E 26.3 14.35 1.021 2.852 E 42.5 14.33 1.652 2.234 E Experimental Values 51.0 14.28 1.983 1.903 E 67.3 14.25 2.623 1.271 E Composition of saturated solutions in the ternary LaCl –SmCl –H O sys- 3 3 2 76.7 14.18 3.001 0.912 E tem at 20 °C 81.8 14.14 3.211 0.714 E Equilibrium 86.5 14.07 3.414 0.533 E 90.0c 14.00 3.571 0.396 E+F Mol % Sm mol H2O per solid ͑ ͒ ͑ ͒ / −1a / −1a b in Sm+La mol of Sm+La m2 mol kg m1 mol kg phase 83.1 13.82 3.342 0.679 F ͑metastable͒ 0 14.38 0 3.860 A 86.5 13.96 3.442 0.537 F 3.6 14.30 0.140 3.742 B ͑metastable͒ 11.8 14.15 0.463 3.460 B 90.6 14.01 3.591 0.372 F 21.7 14.12 0.853 3.078 B 100 14.05 3.951 0 G 40.8 14.05 1.612 2.339 B a 45.6 14.00 1.808 2.157 B+C calculated by the compilers bA=LaCl ·7H O; E=͑La,Nd͒Cl ·7H O; F=͑La,Nd͒Cl ·6H O; 39.8 13.81 1.600 2.420 C 3 2 3 2 3 2 ͑metastable͒ G=NdCl3 ·6H2O cfrom extrapolation 46.4 14.02 1.837 2.122 C 59.4 14.35 2.298 1.570 C The system showed a solid miscibility gap.

Composition of saturated solutions in the quaternary LaCl3 –NdCl3 –SmCl3 –H2O system at 20 °C

mol H2O per / / / Mol % Sm in Mol % Nd in mol of m2 m3 m1 ͑La+Nd+Sm͒ ͑La+Nd+Sm͒ ͑La+Nd+Sm͒ mol kg−1a mol kg−1a mol kg−1a Equilibrium solid phaseb

7.9 79.5 14.09 0.311 3.132 0.496 H 11.6 71.7 14.06 0.458 2.831 0.659 H 14.4 66.4 13.82 0.578 2.667 0.771 H 19.1 55.4 13.86 0.765 2.219 1.021 H 23.6 45.3 13.92 0.941 1.806 1.240 H 29.3 32.6 13.90 1.170 1.302 1.122 H 34.7 20.5 13.96 1.380 0.815 1.781 H 39.3 10.3 13.96 1.380 0.410 2.004 H 42.3 4.7 13.95 1.683 0.187 2.109 H 25.4 5.5 13.99 1.008 0.218 2.742 I 34.5 10.4 13.82 1.386 0.418 2.213 I 20.8 17.0 14.09 0.819 0.670 2.450 I

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1825

Composition of saturated solutions in the quaternary LaCl3 –NdCl3 –SmCl3 –H2O system at 20 °C

mol H2O per / / / Mol % Sm in Mol % Nd in mol of m2 m3 m1 ͑La+Nd+Sm͒ ͑La+Nd+Sm͒ ͑La+Nd+Sm͒ mol kg−1a mol kg−1a mol kg−1a Equilibrium solid phaseb

19.5 25.9 13.96 0.775 1.030 2.171 I 14.6 32.5 13.99 0.579 1.290 2.100 I 9.8 47.1 14.10 0.386 1.854 1.697 I 12.6 60.9 14.04 0.498 2.408 1.048 I 6.1 75.6 14.10 0.240 2.976 0.720 I 47.8 4.3 13.90 1.909 0.172 1.913 J 41.2 20.8 14.11 1.621 0.818 1.495 J 43.0 37.6 14.40 1.658 1.449 0.748 J 33.5 33.2 14.12 1.317 1.305 1.309 J 27.2 50.8 14.16 1.066 1.991 0.862 J 31.0 56.6 14.15 1.216 2.220 0.486 J 15.7 70.9 14.12 0.617 0.787 0.527 J 12.7 82.1 14.17 0.497 3.216 0.204 J 5.4 90.7 13.99 0.214 3.599 0.155 J 25.3 29.5 13.60 1.033 1.204 1.845 K 19.9 34.4 13.44 0.822 1.421 1.845 K 22.8 39.4 13.73 0.922 1.593 1.488 K 14.0 48.5 13.51 0.575 1.893 1.541 K acalculated by the compilers b ͑ ͒ ͑ ͒ ͑ ͒ ͑ ͒ ͑ ͒ H= La,Nd,Sm Cl3 ·7H2O+ La,Nd,Sm Cl3 ·6H2O; I= La,Nd,Sm Cl3 ·7H2O; J= La,Nd,Sm Cl3 ·6H2O; K= La,Nd,Sm Cl3 ·6H2O metastable solid solution

Auxiliary Information 4.3.4. LaCl3 –LaA3 –H2O „A=F,Br,NO3… Systems Method/Apparatus/Procedure: The isothermal method with chemical analysis was used ͓G. Brunisholz, Components: Original Measurements: ͑ ͒ 53 J.P. Quinche, and A.M. Kalo, Helv. Chim. Acta 47,14͑1964͔͒. The salts 1 Lanthanum chloride; LaCl3; N. Levina, G. Dadabaeva, D.D. and water were placed in glass-stoppered vials which contained special ͓10099-58-8͔ Ikrami, and A.S. Paramzin, Dep. ͑ ͒ glass pestles. The vials were placed in a larger tube and sealed with 2 Lanthanum ﬂuoride; LaF3; VINITI Report No. N478-77, rubber stoppers. The tubes were placed in a thermostat and rotated. The ͓13709-38-1͔ 1977. ͑ ͒ ͓ ͔ salts were continuously pulverized by the pestles. The mixtures were 3 Water; H2O; 7732-18-5 equilibrated for 2–3 weeks and the separated phases analyzed. The sum of La+Sm was determined in urotropine buffer by titration with EDTA Variables: Prepared by: using xylenol orange as an indicator. The ratio of La/Sm was determined Composition of mixtures C. Gumiński by chromatography. The same procedure was applied to the La+Nd pair. One temperature: 298 K The solutions from the quaternary system were analyzed: the sum of Ln by titration and Ln content ratios by chromatography. The composition of Experimental Values the dry solid phases was determined by the algebraic method of Schreinemakers. The solid phases were also identiﬁed by x-ray diffraction. Composition of saturated solutions in the ternary LaCl3 –LaF3 –H2O sys- Source and Purity of Materials: tem at 25 °C

Nothing speciﬁed; however, they seem to be impeccable because the a a experiments were performed in a very experienced laboratory in this ﬁeld. 100w1 m1 100w2 m2

Estimated Error: 46.02 3.545 1.05 0.101 Solubility: precision of Ϯ0.2% ͑by the compilers͒. 44.41 3.313 0.94 0.088 Temperature: nothing speciﬁed. 42.39 3.043 0.81 0.073 41.63 2.927 0.37 0.033 39.10 2.626 0.20 0.017 37.40 2.445 0.22 0.018 35.20 2.225 0.305 0.024 30.92 1.826 0.022 0.0016

amolalities calculated by the compiler ͑ ͒ At still lower contents of LaCl3 w1 in the ternary system, ͑ ͒ no LaF3 w2 in the liquid phase was detected by the analytical method used; such incomplete data were omitted. The authors observed the formation of the ternary compound LaCl3 ·4LaF3 ·9H2O, which was found to be gradually

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1826 MIODUSKI, GUMIŃSKI, AND ZENG

dehydrated upon heating; the first effect was recorded at Composition of saturated solutions in the ternary LaCl3 –LaBr3 –H2O sys- ͑ ͒ tem at 25 °C 120 °C. The first step of LaCl3 ·6H2O dehydration melting was observed at 120 °C and the second at 160 °C. a a 100w1 m1 100w2 m2 LaCl3 ·6H2O was specified as the equilibrium solid phase in pure aqueous solution, but the structure ͑investigated by 8.9 0.85 48.6 3.02 x-ray diffraction͒ was not specified. 3.6 0.36 55.0 3.51 1.8 0.18 57.2 3.69 Auxiliary Information Ͻ0.2 Ͻ0.02 61.4 4.22 0 0 63.1 4.52 Method/Apparatus/Procedure: The isothermal method with chemical analysis of the saturated solutions amolalities calculated by the compilers was used. Mixtures of the components in various ratios were equilibrated for 50–60 d in a thermostat. The content of Cl in the liquid phase after Mixed crystals of LaCl3 and LaBr3 heptahydrates were equilibration was determined by the method of Volhard. The content of La was determined by titration with EDTA solution. The content of F was found to be the equilibrium solid phases. found by difference. The composition of the equilibrium solid phase was Auxiliary Information found by the graphical method of Schreinemakers. The crystals were also chemically analyzed after dissolution in water. The content of F in the Method/Apparatus/Procedure: solid was determined by titration with AlCl solution using a methyl red 3 No information about conditions of the equilibration was given. The indicator after decomposition of the crystals with concentrated H SO and 2 4 content of La in the saturated solution and in the solid phase was found collection of HF evolved. The complex solid phase formed was by titration with EDTA solution in the presence of a xylenol orange characterized by infrared spectroscopy, x-ray diffraction, thermal analysis, indicator. The contents of Cl and Br were determined by derivative and thermogravimetry. ͑ ͒ potentiometric titration with AgNO3 solution acidified by HNO3 using a Source and Purity of Materials: Ag-sensitive electrode, a calomel reference electrode, and an electrolytic bridge filled with 1 mol dm−3 KNO . The composition of the equilibrium LaCl ·6H O ͑formula reported in the paper͒ was precipitated from its 3 3 2 solid phases was determined by the method of Schreinemakers. saturated solution during cooling. The crystals were dried on a water bath, in air, and finally in a dry box at 40 °C. Source and Purity of Materials: ͑ ͒ LaF3 was precipitated from La NO3 3 solution with addition of HF Nothing specified. solution ͑distilled in an apparatus made of Pt͒. The mixtures were filtered, washed with water at 40 °C, and dried in a Pt container under ultraviolet Estimated Error: radiation to constant mass. The product contained 0.8–1.0 mol H2O. Solubility: precision of Cl determination of Ϯ͑1.3–25͒% in decreasing concentration range; precision of Br determination of Ϯ͑1.0–7͒%in Estimated Error: decreasing concentration range. Nothing specified. Temperature: nothing specified.

Components: Original Measurements: Components: Original Measurements: ͑1͒ Lanthanum chloride; LaCl ; 123K.J. Zwietasch, E.M. Kirmse, 3 ͑1͒ Lanthanum chloride; LaCl ; 87V.S. Petelina, R.V. Mertslin, ͓10099-58-8͔ and I. Krech, Z. Chem. 24, 144 3 ͓10099-58-8͔ N.I. Nikurashina, and L.K. ͑2͒ Lanthanum bromide; LaBr ; ͑1984͒. 3 ͑2͒ Lanthanum nitrate; La͑NO ͒ ; Sedova, Issledovaniya v Oblasti ͓13536-79-3͔ 3 3 ͓10099-59-9͔ Khimii Redkozemelnykh ͑3͒ Water; H O; ͓7732-18-5͔ 2 ͑ ͒ ͓ ͔ ͑ 3 Water; H2O; 7732-18-5 Elementov Saratovskii Variables: Prepared by: Universitet, Saratov, 1969͒,p.85. Composition of salts C. Gumiński Variables: Prepared by: One temperature: 298 K Composition of salts T. Mioduski, S. Siekierski, and One temperature: 298 K C. Gumiński Experimental Values

Composition of saturated solutions in the ternary LaCl3 –LaBr3 –H2O sys- Experimental Values tem at 25 °C Compositions of saturated solutions in the a a LaCl –La͑NO ͒ –H O ternary system at 25 °C were re- 100w1 m1 100w2 m2 3 3 3 2 ported in a ﬁgure with barely readable points. 48.9 3.90 0 0 ͑ ͒ 43.1 3.60 8.1 0.44 Solubilities of LaCl3 and La NO3 3 in water at 25 °C were 38.9 3.32 13.3 0.73 reported to be 49.2 and 59.8 mass %, respectively. The cor- 33.6 2.91 19.4 1.09 responding values recalculated to molalities ͑by the compil- 28.9 2.59 25.6 1.49 ers͒ are 3.95 and 4.58 mol kg−1, respectively. 23.0 2.09 32.2 1.89 ͑ ͒ 21.2 1.95 34.6 2.07 La NO3 3 ·6H2O and LaCl3 ·6H2O were reported to be the 18.8 1.74 37.0 2.21 equilibrium solid phases, but the composition of the latter 16.7 1.55 39.4 2.37 phase was not experimentally determined due to the small 13.6 1.31 43.9 2.79 amount of the liquid phase and high concentration of LaCl3.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1827

Auxiliary Information Composition of saturated solutions in the ternary LaCl3 –CH5N·HCl–H2O system at 20 and 40 °C Method/Apparatus/Procedure: / a a b The isothermal method of sections with refractometric analysis of t °C 100w1 m1 100w2 m2 Equilibrium solid phase solutions was used as reported by Mertslin ͓Zh. Obshch. Khim. 7, 1828 ͑1936͔͒. Homogeneous and heterogeneous mixtures of the salts and water 47.0 5.38 17.4 7.24 B were agitated until the refractive index of the solutions was constant ͑after 47.4 4.67 11.2 4.01 B about 20 d͒. The compositions of the saturated solutions and the 48.2 4.22 5.2 1.65 B corresponding solid phases were found from deﬂection points on 50.5 4.16 0 0 B refractive index versus composition plots. amolalities calculated by the compilers Source and Purity of Materials: b A=CH5N·HCl; B=LaCl3 ·7H2O The salts were prepared by dissolving La2O3 in HCl or HNO3 solutions. The resulting salts were recrystallized and the products were analyzed for La content by the oxalate method. The system was reported to be of a simple eutonic type.

Estimated Error: Composition of saturated solutions in the ternary Solubility: nothing speciﬁed. LaCl3 –C3H9N·HCl–H2O system at 20 and 40 °C Temperature: stability of Ϯ͑0.1–0.2͒ K. / a a b t °C 100w1 m1 100w3 m3 Equilibrium solid phase

20 0 0 72.5 27.6 C 3.1 0.46 69.3 26.3 C 4.4. LaCl3–Organic Compound–H2O Systems 6.9 1.02 65.5 24.8 C 4.4.1. LaCl –Amine hydrochloride–H O Systems 3 2 11.5 1.74 61.5 23.8 C 17.3 2.62 56.8 22.1 C Components: Original Measurements: 22.0 3.72 53.9 23.4 C ͑ ͒ 94 1 Lanthanum chloride; LaCl3; E.F. Zhuravlev, R.V. Yurkevich, 25.4 4.39 51.0 22.6 C+D ͓10099-58-8͔ and N.G. Kalegina, Zh. Neorg. 28.6 4.26 44.0 16.8 D ͑ ͒ ͑ ͒ 2 Methylamine hydrochloride; Khim. 17, 2536 1972 . 42.7 9.51 39.0 22.3 D ͓ ͔ CH5N·HCl; 593-51-1 35.7 4.97 35.0 12.5 D ͑3͒ Trimethylamine 39.0 5.39 31.5 11.2 D hydrochloride; C H N·HCl; 3 9 39.9 5.39 29.9 10.4 D+B ͓593-87-7͔ ͑ ͒ ͓ ͔ 39.9 4.99 27.5 8.8 B 4 Water; H2O; 7732-18-5 39.9 4.23 21.6 5.9 B Variables: Prepared by: 42.1 3.82 13.0 3.0 B Composition of mixtures T. Mioduski and C. Gumiński 45.0 3.75 6.1 1.3 B Temperature: 293 and 313 K 48.5 3.84 0 0 B 40 0 0 75.0 31.4 C Experimental Values 2.8 0.46 72.2 30.2 C 6.3 1.02 68.4 28.3 C

Composition of saturated solutions in the ternary LaCl3 –CH5N·HCl–H2O 10.8 1.75 64.0 26.6 C system at 20 and 40 °C 16.1 2.71 59.7 25.8 C 19.0 3.21 56.9 24.7 C+D / a a b t °C 100w1 m1 100w2 m2 Equilibrium solid phase 21.1 3.39 53.5 22.0 D 28.0 3.45 38.9 12.3 D 20 0 0 60.2 22.4 A 33.2 3.89 32.0 9.6 D 4.4 0.45 55.6 20.6 A 34.4 4.99 37.5 14.0 D 9.8 1.02 51.0 19.3 A 39.1 5.40 31.4 11.1 D+B 16.6 1.74 44.6 17.0 A 41.1 4.97 25.2 7.8 B 26.2 2.90 37.0 14.9 A 42.0 6.46 31.5 12.4 B 32.4 3.47 32.5 13.7 A 44.8 4.33 13.0 3.2 B 42.8 5.78 27.0 13.2 A+B 47.5 4.16 6.0 1.35 B 43.4 4.89 20.4 8.34 B 50.5 4.16 0 0 B 44.5 4.27 13.0 4.53 B 46.2 3.93 5.9 1.82 B amolalities calculated by the compilers 48.2 3.79 0 0 B b B=LaCl3 ·7H2O; C=C3H9N·HCl; D=LaCl3 ·5C3H9N·5HCl 40 0 0 64.0 26.3 A 4.0 0.46 60.2 24.9 A Solubility of LaCl ·5C H N·5HCl was determined by 8.9 1.02 55.5 23.1 A 3 3 9 ͓ ͑ ͔͒ 14.9 1.74 50.2 21.3 A Zhuravlev et al. Zh. Neorg. Khim. 24, 802 1979 to be 23.0 2.72 42.5 18.2 A 71.2 mass % at 40 °C. 30.5 3.77 36.5 16.4 A 37.1 4.98 32.5 15.8 A 47.3 7.42 26.7 15.2 A+B

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1828 MIODUSKI, GUMIŃSKI, AND ZENG

Auxiliary Information Composition of saturated solutions in the ternary

LaCl3 –NH2OH·HCl–H2O system at 20 and 40 °C Method/Apparatus/Procedure: / a a b The method of isothermal sections with refractometric measurements was t °C 100w1 m1 100w2 m2 Equilibrium solid phase used. Heterogeneous and homogeneous mixtures of known composition were equilibrated until their refractive indices did not change. The 49.2 4.15 2.5 0.74 B compositions of the saturated solutions and the equilibrium solid phases 50.5 4.16 0 0 B were found from break points on plots of the refractive index versus composition. The indices were measured in a thermostated refractometer. amolalities calculated by the compilers The solid phases were also examined by chemical analysis and x-ray b A=NH2OH·HCl; B=LaCl3 ·7H2O diffraction.

Source and Purity of Materials: The system was found to be of a simple eutonic type. The heptahydrate of LaCl was obtained by recrystallization of the 3 Composition of saturated solutions in the ternary anhydrous salt of pure grade. The product was characterized by water ͑ ͒ LaCl3 –C2H7N·HCl–H2O system at 20 and 40 °C content of 33.92 mass % H2O found analytically and density of 2.18 g cm−3 ͑found with a pycnometer͒. t/ w m a w m a b ͑ ͒ °C 100 1 1 100 3 3 Equilibrium solid phase CH5N·HCl and C3H9N·HCl of pure grade were recrystallized prior to use. 20 0 0 79.5 47.6 C Doubly distilled water was used. 3.0 0.59 76.1 44.6 C 5.5 1.04 73.0 41.6 C Estimated Error: 9.5 1.77 68.6 38.4 C Solubility: nothing speciﬁed; agreement of the analysis of the compound D with its formula: ͑0.5–0.6͒%. 15.2 2.91 63.5 36.6 C Temperature: nothing speciﬁed. 21.2 4.16 58.0 34.2 C+D 23.7 4.22 53.4 33.9 D 29.0 4.40 44.1 20.1 D 32.1 4.69 40.0 17.6 D+E Components: Original Measurements: 35.0 4.76 35.0 14.3 E ͑1͒ Lanthanum chloride; LaCl ; 98E.F. Zhuravlev, R.V. Yurkevich, 3 40.0 4.80 26.0 9.38 E ͓10099-58-8͔ and N.G. Kalegina, Zh. Neorg. ͑2͒ Hydroxyloamine Khim. 18, 1109 ͑1973͒. 41.0 4.83 24.4 8.65 E+B 41.2 4.64 22.6 7.66 B hydrochloride; NH2OH·HCl; ͓5470-11-1͔ 43.6 4.14 13.5 3.86 B ͑3͒ Dimethylamine 45.8 3.91 6.4 1.64 B hydrochloride; C2H7N·HCl; 48.5 3.84 0 0 B ͓506-59-2͔ 40 0 0 81.0 52.3 C ͑ ͒ ͓ ͔ 4 Water; H2O; 7732-18-5 2.9 0.65 78.9 53.2 C 5.0 1.10 76.5 50.7 C Variables: Prepared by: 8.7 1.89 72.5 47.3 C Composition of mixtures T. Mioduski and C. Gumiński Temperature: 293 and 313 K 13.2 3.11 69.5 49.3 C 18.1 4.37 65.0 47.2 C+D 23.9 4.40 54.0 30.0 D Experimental Values 30.0 4.85 44.8 21.8 D 33.8 5.38 40.6 19.4 D+E Composition of saturated solutions in the ternary 35.2 4.82 35.0 14.4 E LaCl3 –NH2OH·HCl–H2O system at 20 and 40 °C 40.0 4.80 26.0 9.58 E 43.8 4.95 20.1 6.82 E / a a b t °C 100w1 m1 100w2 m2 Equilibrium solid phase 46.0 4.94 16.0 5.16 E+B 20 0 0 47.5 13.0 A 46.9 4.61 11.6 3.43 B 9.2 0.68 36.0 9.46 A 49.0 4.34 5.0 1.33 B 23.5 2.16 22.2 7.22 A 50.5 4.16 0 0 B 34.5 2.72 13.7 3.81 A amolalities calculated by the compilers 44.0 3.70 7.5 2.23 A bB=LaCl ·7H O; C=C H N·HCl; D=LaCl ·5C H N·5HCl·4H O; 45.2 3.90 7.6 2.32 A+B 3 2 2 7 3 2 7 2 E=LaCl ·C H N·HCl 45.7 3.90 6.5 1.96 B 3 2 7 47.0 3.83 3.0 0.87 B 48.5 3.84 0 0 B The compound D was found to be congruently soluble and 40 0 0 55.3 17.8 A the compound E was found to be incongruently soluble. 8.0 0.69 44.5 13.5 A Solubility of LaCl3 ·5C2H7N·5HCl·4H2O was determined 20.7 1.77 31.5 9.50 A by Zhuravlev et al. ͓Zh. Neorg. Khim. 24, 802 ͑1979͔͒ to be 31.3 2.70 21.5 6.56 A 41.0 3.71 14.0 4.48 A 76.0 mass % at 40 °C. 45.2 4.28 11.7 3.91 A+B 47.7 4.17 5.7 1.76 B

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1829

Auxiliary Information Composition of saturated solutions in the ternary

LaCl3 –C6H16N2 ·2HCl–H2O system at 20 and 40 °C Method/Apparatus/Procedure: / a a b The method of isothermal sections with refractometric analysis of the t °C 100w1 m1 100w2 m2 Equilibrium solid phase equilibrium phases was used. Establishment of equilibrium was accomplished by systematic measurements of refractive indices of the 34.8 3.44 24.0 3.08 A phases until a constant value of the index was observed. The refractive 36.6 3.60 22.0 2.81 A+C indices were measured in a thermostated refractometer. The compound D 41.2 3.90 15.7 1.93 C was isolated by recrystallization and analyzed for La and Cl contents; it 42.3 3.99 14.5 1.77 C was also studied by x-ray diffraction. There were difficulties in complete 44.1 4.11 12.2 1.48 C isolation of compound E from the equilibrium liquid, and analysis results 47.5 4.35 8.0 0.95 B+C of the solid differed from the formula found from the isothermal section 48.5 4.28 5.3 0.61 B of the phase diagram. 50.5 4.16 0 0 B Source and Purity of Materials: amolalities calculated by the compilers Heptahydrate of LaCl3 was twice recrystallized and its analysis pointed to b −3 ͑ A=C6H16N2 ·2HCl; B=LaCl3 ·7H2O; C=LaCl3 ·C6H16N2 ·2HCl H2O content of 33.9 mass % and density of 2.18 g cm found in a pycnometer filled with absolute benzene͒. At 20 °C, the solubility isotherm was found to be of a NH2OH·HCl was of analytical purity and was probably used without further purification. simple eutonic type and at 40 °C the middle branch repre-

C2H7N·HCl was prepared by neutralization of the amine with HCl. The sented the double salt which was found to be congruently resulting salt was dried in a desiccator over anhydrous CaCl2. The melting soluble. point of this salt was in agreement with the literature data of 171 °C. Doubly distilled water was used. Auxiliary Information

Estimated Error: Method/Apparatus/Procedure: Nothing specified. The solubilities were studied by the method of isothermal sections. Agreement of analysis of the compound D with its formula ͑0.1–0.6͒%. Analyses of the solutions were made by measurements of refractive indices along directed sections of the phase diagram. The indices were plotted versus composition, and break points on such plots corresponded Components: Original Measurements: to the compositions of the saturated solutions. The compound C was 99 isolated and analyzed for La and Cl contents. It was also studied by x-ray ͑1͒ Lanthanum chloride; LaCl ; E.F. Zhuravlev, R.V. Yurkevich, 3 diffraction. ͓10099-58-8͔ A.G. Samatov, and L.F. ͑ ͒ 2 Hexamethylenediamine Shlentova, Zh. Neorg. Khim. 18, Source and Purity of Materials: dihydrochloride; 2247 ͑1973͒. Heptahydrate of LaCl was obtained by recrystallization of anhydrous 1,6-hexanediamine 3 LaCl of unspecified purity. dihydrochloride; C H N ·2HCl; 3 6 16 2 C H N ·2HCl was recrystallized and dried for a long time in a ͓6055-52-3͔ 6 16 2 ͑ ͒ ͓ ͔ desiccator over anhydrous CaCl2. 3 Water; H2O; 7732-18-5 Bidistilled water was probably used as in other studies performed in this Variables: Prepared by: laboratory. Composition of mixtures T. Mioduski and C. Gumiński Estimated Error: Temperature: 293 and 313 K Solubility: nothing specified; agreement of analysis of the compound C with its formula: ͑0.3–0.5͒%. Experimental Values Temperature: nothing specified.

Composition of saturated solutions in the ternary LaCl3 –C6H16N2 ·2HCl–H2O system at 20 and 40 °C Components: Original Measurements: ͑1͒ Lanthanum chloride; LaCl ; 100E.F. Zhuravlev, R.V. / a a b 3 t °C 100w1 m1 100w2 m2 Equilibrium solid phase ͓10099-58-8͔ Yurkevich, and N.A. Rasskazova, ͑2͒ Piperazine dihydrochloride; Zh. Neorg. Khim. 19, 534 20 0 0 61.7 8.82 A ͓ ͔ ͑ ͒ C4H10N2 ·2HCl; 142-64-3 1974 . 8.9 0.80 45.5 5.28 A ͑3͒ 1,2-ethanediamine-N,N,NЈ, 20.9 1.79 31.5 3.50 A NЈ-tetramethyl dihydrochloride; ͓ ͔ 31.5 2.72 21.3 2.39 A C6H16N2 ·2HCl; 7677-21-6 38.0 3.41 16.5 1.92 A ͑4͒ 1,2-benzenediamine

40.4 3.74 15.5 1.86 A+B dihydrochloride; C6H8N2 ·2HCl; 41.4 3.87 15.0 1.82 B ͓615-28-1͔ ͑ ͒ 43.0 3.87 11.7 1.37 B 5 1,3-benzenediamine dihydrochloride; C H N ·2HCl; 45.7 3.87 6.2 0.68 B 6 8 2 ͓541-69-5͔ 48.5 3.84 0 0 B ͑6͒ Water; H O; ͓7732-18-5͔ 40 0 0 67.0 10.7 A 2 7.5 0.76 52.2 6.85 A Variables: Prepared by: 18.5 1.77 39.0 4.85 A Composition of mixtures T. Mioduski and C. Gumiński 28.8 2.73 28.2 3.47 A Temperature: 293 and 313 K

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1830 MIODUSKI, GUMIŃSKI, AND ZENG

Experimental Values Composition of saturated solutions in the ternary LaCl3–1,2-benzenediamine dihydrochloride–H2O system at 20 and 40 °C Composition of saturated solutions in the ternary / a a b LaCl3 –C4H10N2 ·2HCl–H2O system at 20 and 40 °C t °C 100w1 m1 100w4 m4 Equilibrium solid phase

/ a a b 20 0 0 28.0 2.15 D t °C 100w1 m1 100w2 m2 Equilibrium solid phase 12.5 0.70 15.0 1.14 D 20 0 0 41.4 4.44 A 29.2 1.80 4.5 0.38 D 10.0 0.68 30.2 3.18 A 49.0 3.92 0 0 B 23.4 1.70 19.5 2.19 A 40 0 0 32.5 2.66 D 33.6 2.56 12.9 1.52 A 12.0 0.70 18.5 1.47 D 43.5 3.99 12.0 1.70 A 28.0 1.83 9.5 0.84 D 45.0 4.19 11.2 1.61 A+B 50.5 4.16 0 0 B 46.5 4.44 10.8 1.59 B a 48.0 3.99 3.0 0.38 B molalities calculated by the compilers b 49.0 3.92 0 0 B D=1,2-benzenediamine dihydrochloride; B=LaCl3 ·7H2O 40 0 0 46.3 5.42 A 8.7 0.64 36.0 4.09 A The solubility isotherms were found to be of eutonic type.

21.0 1.58 24.9 2.89 A LaCl3 showed a strong salting-out effect with respect to this 31.5 2.53 17.8 2.21 A diamine dihydrochloride. 39.5 3.55 15.1 2.09 A 45.2 4.75 16.0 2.59 A+B Composition of saturated solutions in the ternary

46.7 4.47 10.7 1.58 B LaCl3–1,3-benzenediamine dihydrochloride–H2O system at 20 and 40 °C 48.0 4.23 5.7 0.77 B / a a b 49.7 4.52 5.5 0.77 B t °C 100w1 m1 100w5 m5 Equilibrium solid phase 50.5 4.16 0 0 B 20 0 0 29.5 2.31 E amolalities calculated by the compilers 8.5 0.49 20.3 1.57 E b A=C4H10N2 ·2HCl·H2O; B=LaCl3 ·7H2O 17.8 1.02 11.0 0.85 E 29.0 1.76 4.0 0.33 E The solubility isotherms were found to be of eutonic type 49.0 3.92 0 0 B at both temperatures. 40 0 0 31.5 2.54 E 6.5 0.38 23.0 1.80 E Composition of saturated solutions in the ternary 17.5 1.02 12.5 0.99 E LaCl –C H N ·2HCl–H O system at 20 and 40 °C 3 6 16 2 2 28.0 1.70 4.8 0.39 E / a a b 50.5 4.16 0 0 B t °C 100w1 m1 100w3 m3 Equilibrium solid phase amolalities calculated by the compilers 20 0 0 50.0 5.29 C bE=1,3-benzenediamine dihydrochloride; B=LaCl ·7H O 8.5 0.71 43.0 4.69 C 3 2 21.5 1.89 32.0 3.64 C 32.8 2.96 22.0 2.57 C The solubility isotherms were found to be of eutonic type 37.5 3.44 18.0 2.14 C at both temperatures. LaCl3 showed a strong salting-out ef- 43.2 4.19 14.8 1.86 C+B fect with respect to this diamine dihydrochloride. 43.5 4.22 14.5 1.83 B 45.0 3.90 8.0 0.90 B Auxiliary Information 48.5 4.06 2.8 0.30 B Method/Apparatus/Procedure: 49.0 3.92 0 0 B The method of isothermal sections of the phase diagram with 40 0 0 53.5 6.08 C refractometric analysis of the solutions was used. The mixtures were 7.5 0.67 47.0 5.46 C equilibrated until their refractive indices remained constant. The time 19.5 1.78 35.8 4.23 C required to reach equilibrium was 5–6 h for homogeneous solutions and 1 30.0 2.82 26.7 3.26 C and 2 d at 40 and 20 °C, respectively, for heterogeneous mixtures. The 36.0 3.54 22.5 2.87 C compositions of the saturated solutions and the corresponding solid phases 41.0 4.23 19.5 2.61 C were found as break points on plots of the refractive index versus 43.5 4.51 17.2 2.31 C+B composition. The refractive indices were measured in a thermostated 45.5 4.42 12.5 1.57 B refractometer. 47.5 4.24 6.8 0.79 B Source and Purity of Materials: 49.5 4.16 2.0 0.22 B LaCl3 ·7H2O was obtained by recrystallization of anhydrous LaCl3 of pure 50.5 4.16 0 0 B grade. An analysis of Cl content in the heptahydrate conﬁrmed its amolalities calculated by the compilers formula. b Piperazine dihydrochloride was obtained from hexahydrate of piperazine C=C6H16N2 ·2HCl; B=LaCl3 ·7H2O ͑pure grade͒ and concentrated HCl ͑chemically pure grade͒. The resulting The solubility isotherms were found to be of eutonic type solution was evaporated and the salt was recrystallized. The chemical formula of the salt monohydrate was conﬁrmed by an analysis. at both temperatures.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1831

1,2-ethanediamine-N,N,NЈ,NЈ-tetramethyl ͑analytical purity͒ was Source and Purity of Materials: neutralized with concentrated HCl ͑chemical purity͒ solution. The product No information was given. Both salts seem to be recrystallized as was was recrystallized, dried, and analyzed, confirming its formula. reported in other papers from the same laboratory. 1,2-benzenediamine and 1,3-benzenediamine dihydrochlorides ͑chemically pure grade͒ were used as received. Estimated Error: Nothing specified. Estimated Error: Nothing specified. Components: Original Measurements: ͑ ͒ 102 1 Lanthanum chloride; LaCl3; E.F. Zhuravlev, R.V. Components: Original Measurements: ͓10099-58-8͔ Yurkevich, and N.G. Kalegina, ͑ ͒ 101 ͑ ͒ 1 Lanthanum chloride; LaCl3; E.F. Zhuravlev, R.V. 2 Triethylamine hydrochloride; Izv. Vyssh. Ucheb. Zaved., Khim. ͓ ͔ ͑ ͒ ͓10099-58-8͔ Yurkevich, and N.A. Rasskazova, C6H15N·HCl; 554-68-7 Khim. Tekhnol. 17,498 1974 . ͑2͒ Butylamine hydrochloride; Zh. Neorg. Khim. 19, 1977 ͑3͒ Triethanolamine ͓ ͔ ͑ ͒ C4H11N·HCl; 3858-78-4 1974 . hydrochloride; ͑ ͒ ͓ ͔ ͑ ͒ 3 Water; H2O; 7732-18-5 tris 2-hydroxyethyl amine hydrochloride; C6H12NO3 ·HCl; Variables: Prepared by: ͓637-39-8͔ ͑ ͒ ͓ ͔ Composition of mixtures T. Mioduski and C. Gumiński 4 Water; H2O; 7732-18-5 Temperature: 293 and 313 K Variables: Prepared by: Composition of mixtures T. Mioduski and C. Gumiński Experimental Values Temperature: 293 and 313 K

Composition of saturated solutions in the ternary

LaCl3 –C4H11N·HCl–H2O system at 20 and 40 °C Experimental Values

/ a a b Composition of saturated solutions in the ternary t °C 100w1 m1 100w2 m2 Equilibrium solid phase LaCl3 –C6H15N·HCl–H2O system at 20 and 40 °C 20 0 0 80.0 36.5 A / a a b 3.5 0.68 75.5 32.8 A t °C 100w1 m1 100w2 m2 Equilibrium solid phase 10.0 1.77 67.0 26.6 A 20 0 0 56.0 9.25 A 19.5 3.38 57.0 22.1 A 8.5 0.80 48.2 8.09 A 25.0 4.43 52.0 20.6 A+B 18.3 1.77 39.5 6.80 A 26.0 4.16 48.5 17.4 B 26.8 2.63 31.7 5.55 A 32.5 3.63 31.0 7.75 B 31.7 3.29 29.0 5.36 A+B 39.5 3.66 16.5 3.42 B 32.2 3.26 27.5 4.96 B 44.0 3.65 6.8 1.26 B 34.5 3.37 23.8 4.15 B 48.5 3.84 0 0 B 41.0 3.65 13.2 2.09 B 40 0 0 82.0 41.6 A 44.5 3.70 6.5 0.96 B 3.0 0.66 78.5 38.7 A 48.0 3.76 0 0 B 8.2 1.69 72.0 33.2 A 40 0 0 59.0 10.45 A 16.0 2.97 62.0 25.7 A 8.0 0.80 51.2 9.12 A 24.2 4.57 54.2 22.9 A+B 17.4 1.77 42.5 7.70 A 28.0 4.15 44.5 14.8 B 25.5 2.68 35.7 6.68 A 35.0 3.81 27.5 6.69 B 30.0 3.28 32.7 6.37 A 42.2 3.93 14.0 2.92 B 32.5 3.65 31.2 6.24 A+B 45.7 3.87 6.2 1.18 B 38.0 3.83 21.5 3.86 B 50.5 4.16 0 0 B 43.5 3.97 11.8 1.92 B amolalities calculated by the compilers 47.0 4.06 5.8 0.89 B b 50.5 4.16 0 0 B A=C4H11N·HCl; B=LaCl3 ·7H2O amolalities calculated by the compilers The system was reported to be of eutonic type. b A=C6H15N·HCl; B=LaCl3 ·7H2O

Auxiliary Information The system was reported to be of simple eutonic type. Method/Apparatus/Procedure: Composition of saturated solutions in the ternary The method of isothermal sections of the phase diagram with LaCl –C H NO ·HCl–H O system at 20 and 40 °C refractometric analysis was used, as in other papers from the same group, 3 6 12 3 2 see the preceding pages. Mixtures of the selected composition were t/ °C 100w m a 100w m a Equilibrium solid phaseb equilibrated until constancy of their refractive indices was observed. The 1 1 3 3 compositions of the saturated solutions and equilibrium solid phases were 20 0 0 29.7 2.28 C found from break points on plots of the refractive index versus sample 13.7 0.83 18.8 1.50 C composition. 26.6 1.73 10.8 0.93 C

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1832 MIODUSKI, GUMIŃSKI, AND ZENG

Composition of saturated solutions in the ternary Composition of saturated solutions in the ternary

LaCl3 –C6H12NO3 ·HCl–H2O system at 20 and 40 °C LaCl3 –C4H11N·HCl–H2O system at 20 and 40 °C

/ a a b / a a b t °C 100w1 m1 100w3 m3 Equilibrium solid phase t °C 100w1 m1 100w2 m2 Equilibrium solid phase

43.0 3.30 3.8 0.38 C 14.2 1.69 51.5 13.7 A 46.5 3.74 2.8 0.30 C+B 28.7 3.36 36.5 9.52 A 48.5 3.84 0 0 B 29.0 3.38 36.0 9.38 A+B 40 0 0 41.0 3.74 C 31.3 3.75 34.7 9.31 B 12.0 0.81 27.7 2.47 C 39.5 2.66 16.5 3.42 B 24.5 1.75 18.3 1.72 C 46.2 3.98 6.5 1.25 B 40.8 3.28 8.5 0.90 C 48.5 3.84 0 0 B 47.5 4.14 5.7 0.66 C+B 40 0 0 72.0 23.5 A 49.0 4.12 2.5 0.28 B 6.0 0.82 64.0 19.5 A 50.5 4.16 0 0 B 13.0 1.71 56.0 16.5 A 26.5 3.32 41.0 11.5 A amolalities calculated by the compilers b 31.0 3.91 36.7 10.4 A+B C=C6H12NO3 ·HCl; B=LaCl3 ·7H2O 32.0 3.73 33.0 8.60 B The system was reported to be of eutonic type. 33.0 3.64 30.0 7.40 B 42.0 3.95 14.7 3.10 B Auxiliary Information 47.2 4.09 5.7 1.10 B 50.5 4.16 0 0 B Method/Apparatus/Procedure: The method of isothermal sections of the phase diagram with amolalities calculated by the compilers refractometric analysis was used. Heterogeneous and homogeneous b A=C4H11N·HCl; B=LaCl3 ·7H2O mixtures of known composition were equilibrated until their refractive indices did not change. The compositions of the saturated solutions and The system was reported to be of eutonic type. the corresponding solid phases were found from break points on plots of the refractive index versus composition. The measurements were Composition of saturated solutions in the ternary performed in a thermostated refractometer. LaCl3 –C4H11NO2 ·HCl–H2O system at 20 and 40 °C Source and Purity of Materials: / a a b ͑ ͒ t °C 100w1 m1 100w3 m3 Equilibrium solid phase LnCl3 pure grade was twice recrystallized. It contained 33.92 mass % H2O which corresponds to LaCl3 ·7H2O. 20 0 0 30.8 3.14 C ͑ ͒ Triethylamine and triethanolamine hydrochlorides both chemically pure 13.7 0.83 18.8 1.97 C were twice recrystallized and dried in a desiccator over anhydrous CaCl . 2 27.5 1.78 9.5 1.06 C Estimated Error: 41.7 3.31 7.0 0.96 C Nothing speciﬁed. 46.2 3.98 6.5 0.97 C+B 46.3 3.97 6.2 0.92 B 48.0 3.99 3.0 0.43 B Components: Original Measurements: 48.5 3.84 0 0 B ͑ ͒ 103 40 0 0 39.8 4.67 C 1 Lanthanum chloride; LaCl3; E.F. Zhuravlev, R.V. ͓10099-58-8͔ Yurkevich, and N.A. Rasskazova, 12.5 0.85 27.5 3.24 C ͑2͒ Diethylamine hydrochloride; Izv. Vyssh. Ucheb. Zaved., Khim. 24.5 1.72 17.5 2.13 C ͓ ͔ ͑ ͒ C4H11N·HCl; 554-68-7 Khim. Tekhnol. 17, 1123 1974 . 39.7 3.42 13.0 1.94 C ͑3͒ Diethanolamine 46.2 4.40 11.0 1.82 C+B hydrochloride; 48.5 4.32 5.7 0.88 B ͑ ͒ bis 2-hydroxyethyl amine 49.7 4.26 2.7 0.40 B hydrochloride; C H NO ·HCl; 4 11 2 50.5 4.16 0 0 B ͓40321-53-7͔ ͑ ͒ ͓ ͔ 4 Water; H2O; 7732-18-5 amolalities calculated by the compilers b Variables: Prepared by: C=C4H11NO2 ·HCl; B=LaCl3 ·7H2O Composition of mixtures T. Mioduski and C. Gumiński Temperature: 293 and 313 K The system was reported to be of eutonic type.

Auxiliary Information Experimental Values Method/Apparatus/Procedure: Composition of saturated solutions in the ternary The method of isothermal sections of the phase diagram with

LaCl3 –C4H11N·HCl–H2O system at 20 and 40 °C refractometric analysis of samples was used. Heterogeneous and homogeneous mixtures were equilibrated for 2–5 d until the refractive / a a b t °C 100w1 m1 100w2 m2 Equilibrium solid phase index of a selected solution was constant. The refractive indices were measured in a thermostated refractometer. The saturating concentrations 20 0 0 68.5 19.8 A were found from break points on plots of the refractive index versus 6.6 0.82 60.5 16.8 A composition.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1833

Source and Purity of Materials: Composition of saturated solutions in the ternary

LaCl3 ·7H2O was obtained by double recrystallization of anhydrous LaCl3 LaCl3 –C5H11N·HCl–H2O system at 20 and 40 °C of pure grade. The product of recrystallization contained 33.92 mass % / a a b H2O and conﬁrmed the composition of this salt. t °C 100w1 m1 100w3 m3 Equilibrium solid phase Diethylamine hydrochloride of “reagent” grade purity was dried in a 28.7 2.80 29.5 5.80 C desiccator over anhydrous CaCl2. Diethanolamine hydrochloride was prepared by neutralizing the amine 35.0 3.44 23.5 4.66 C with a stoichiometric amount of HCl solution ͑chemically pure͒, followed 39.4 3.88 19.2 3.81 C+B by evaporation and recrystallization. The product was dried in a desiccator 41.5 3.95 15.7 3.02 B over anhydrous CaCl2. 44.5 4.05 10.7 1.96 B 47.0 3.98 4.9 0.84 B Estimated Error: 40 0 0 72.0 21.14 C Nothing speciﬁed. 6.0 0.79 63.0 16.71 C 16.0 1.80 47.8 10.86 C 27.0 2.94 35.5 7.78 C Components: Original Measurements: 33.4 3.60 28.8 6.27 C ͑ ͒ 105 1 Lanthanum chloride; LaCl3; R.V. Yurkevich and E.F. 40.5 4.45 22.4 4.96 C+B ͓10099-58-8͔ Zhuravlev, Izv. Vyssh. Ucheb. 42.0 4.40 19.1 4.04 B ͑2͒ Aniline hydrochloride; Zaved., Khim. Khim. Tekhnol. ͓ ͔ ͑ ͒ 44.5 4.37 14.0 2.77 B C6H7N·HCl; 142-04-1 18,140 1975 . ͑3͒ Piperidine hydrochloride; 47.0 4.43 9.7 1.84 B ͓ ͔ 49.7 4.42 4.4 0.79 B C5H11N·HCl; 6091-44-7 ͑4͒ Hexamethyleneimine amolalities calculated by the compilers hydrochloride; bB=LaCl ·7H O; C=C H N·HCl hexahydro-1H-azepine 3 2 5 11 hydrochloride; C6H13N·HCl; The system was reported to be of eutonic type. ͓2088-78-0͔ ͑5͒ Water; H O; ͓7732-18-5͔ 2 Composition of saturated solutions in the ternary Variables: Prepared by: LaCl3 –C6H13N·HCl–H2O system at 20 and 40 °C Composition of mixtures C. Gumiński / a a b Temperature: 293 and 313 K t °C 100w1 m1 100w4 m4 Equilibrium solid phase 20 0 0 58.2 10.26 D Experimental Values 8.3 0.77 48.0 8.10 D 20.4 1.90 35.8 6.03 D Composition of saturated solutions in the ternary 31.2 2.78 23.0 3.70 D LaCl3 –C6H7N·HCl–H2O system at 20 and 40 °C 38.5 3.39 15.2 2.42 D+B 42.7 3.80 11.5 1.80 B / a a b t °C 100w1 m1 100w2 m2 Equilibrium solid phase 43.5 3.86 10.5 1.68 B 45.5 3.84 6.2 0.95 B 20 0 0 47.8 7.07 A 40 0 0 63.7 12.94 D 10.7 0.72 28.8 3.68 A 7.5 0.80 54.5 10.57 D 28.0 1.76 7.0 0.83 A 18.5 1.92 42.2 7.92 D 39.5 2.71 1.0 0.13 A 29.0 2.82 29.0 5.09 D 48.5 3.84 0 0 B 36.0 3.40 20.8 3.55 D+B 40 0 0 55.5 9.63 A 42.5 4.03 14.5 2.49 B 8.8 0.70 40.3 6.11 A 45.2 4.07 9.5 1.55 B 26.6 1.79 12.8 1.63 A 47.3 4.09 5.5 0.86 B 38.8 2.72 3.0 0.40 A 50.5 4.16 0 0 B amolalities calculated by the compilers bB=LaCl ·7H O; D=C H N·HCl amolalities calculated by the compilers 3 2 6 13 bA=C H N·HCl; B=LaCl ·7H O 6 7 3 2 The system was reported to be of eutonic type. The system was reported to be of eutonic type; however, Auxiliary Information the eutonic point very near to pure LaCl3 was not determined. Method/Apparatus/Procedure: The solubilities were studied by the method of isothermal sections of Composition of saturated solutions in the ternary composition. No more experimental details were reported, but they seem LaCl3 –C5H11N·HCl–H2O system at 20 and 40 °C to be the same as described in other papers from this laboratory.

/ a a b Source and Purity of Materials: t °C 100w1 m1 100w3 m3 Equilibrium solid phase Nothing speciﬁed. 20 0 0 67.0 16.70 C 6.5 0.73 57.2 12.96 C Estimated Error: 18.2 1.82 41.0 8.26 C Nothing speciﬁed.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1834 MIODUSKI, GUMIŃSKI, AND ZENG

Auxiliary Information Components: Original Measurements: ͑ ͒ 119 1 Lanthanum chloride; LaCl3; Z.X. Tang and Y.Sh. Chen, Method/Apparatus/Procedure: ͓10099-58-8͔ Zhongguo Xitu Xuebao 1,43 Equilibrium between the solutes and the solution was ascertained by ͑2͒ Hexamethylenetetramine ͑1983͒. constancy of the refractive index of the solutions measured in a monohydrochloride; urotropine thermostated refractometer. Both saturated solutions and solid phases were monohydrochloride; analyzed. La was determined by titration with EDTA solution. The content 1,3,5,7-tetraazatricyclo͓3.3.1.13,7͔ of N in urotropine hydrochloride was determined by the Kjeldahl method. decane monohydrochloride; The composition of the solid phases was found graphically by the method ͓ ͔ C6H12N4 ·HCl; 24360-05-2 of Schreinemakers. The composition of the eutonic point was conﬁrmed ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 by the inﬂection point of the dependence of the refractive index versus composition. Variables: Prepared by: Composition of mixtures T. Mioduski and C. Gumiński Source and Purity of Materials: ͑ ͒ Temperature: 293 and 313 K LaCl3 ·7H2O was prepared by dissolving La2O3 99.99% pure in HCl solution and crystallization. The composition of the hydrate was checked by chemical analysis; water content was found by difference.

Experimental Values C6H12N4 ·HCl was prepared by neutralization of C6H12N4 base with HCl ͑1:1͒ solution. The composition of the product was controlled by N Composition of saturated solutions in the ternary analysis by the Kjeldahl method; the difference between the analysis and LaCl3 –C6H12N4 ·HCl–H2O system at 20 and 40 °C the formula was 0.07 mass % N.

/ a a b t °C 100w1 m1 100w2 m2 Equilibrium solid phases Estimated Error: Solubility: Ϯ0.1 mass %. 20 0 0 45.94 4.866 A Temperature: stability of Ϯ0.05 K; precision of Ϯ0.2 K. 8.91 0.691 38.54 4.199 A Refractive index: Ϯ0.0002. 15.24 1.221 33.86 3.809 A 29.42 2.757 27.08 3.564 A 34.84 3.597 25.67 3.722 A 35.43 3.697 25.49 3.692 A 4.4.2. LaCl3–Hydrazine hydrochloride–H2O Systems 37.48 4.079 25.06 3.830 A 40.18 4.633 24.46 3.961 A Components: Original Measurements: 42.07 5.039 23.89 4.018 A+B ͑ ͒ 95 1 Lanthanum chloride; LaCl3; R.V. Yurkevich and E.F. 41.98 5.025 23.96 4.028 A+B ͓10099-58-8͔ Zhuravlev, Zh. Neorg. Khim. 17, 42.78 4.598 19.29 2.912 B ͑2͒ Hydrazine dihydrochloride; 3063 ͑1972͒. ͓ ͔ 43.24 4.456 17.20 2.489 B N2H4 ·2HCl; 5341-61-7 44.15 4.255 13.55 1.834 B ͑3͒ 1,2-ethanediamine 44.74 4.150 11.31 1.473 B dihydrochloride; C2H8N2 ·2HCl; ͓333-18-6͔ 45.09 4.048 9.49 1.196 B ͑4͒ Water; H O; ͓7732-18-5͔ 45.88 3.983 7.16 0.873 B 2 46.99 3.874 3.56 0.412 B Variables: Prepared by: 48.56 3.849 0 0 B Composition of mixtures T. Mioduski and C. Gumiński 40 0 0 49.06 6.861 A Temperature: 293 and 313 K 12.78 1.073 38.67 4.561 A 25.64 2.413 31.03 4.100 A Experimental Values 35.70 3.938 27.34 4.235 A 39.29 4.602 25.90 4.260 A Composition of saturated solutions in the ternary 42.40 5.245 24.64 4.280 A+B LaCl3 –N2H4 ·2HCl–H2O system at 20 and 40 °C 43.23 5.277 23.37 4.006 B / a a b 43.75 5.157 21.66 3.585 B t °C 100w1 m1 100w2 m2 Equilibrium solid phase 45.95 4.906 15.86 2.378 B 46.33 4.418 10.91 1.461 B 20 48.5 3.84 0 0 A 47.42 4.241 6.99 0.878 B 47.5 3.73 0.6 0.11 A+B 50.54 4.166 0 0 B 27.8 1.73 6.7 0.97 B 12.6 0.72 16.0 2.08 B amolalities calculated by the compilers 0 0 26.2 3.38 B b ͑ ͒ 40 50.5 4.16 0 0 A A=C6H12N4 ·HCl urotropine monohydrochloride ; B=LaCl3 ·7H2O 49.6 4.09 1.0 0.19 A The system was reported to be of eutonic type and no 49.0 4.01 1.2 0.23 A+B double chloride was formed. 47.2 3.75 1.5 0.28 B 27.1 1.73 9.0 1.34 B 12.2 0.72 18.2 2.49 B 0 0 27.8 3.67 B amolalities calculated by the compilers b A=LaCl3 ·3H2O; B=N2H4 ·2HCl

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The system was found to be of simple eutonic type. Experimental Values

Composition of saturated solutions in the ternary Composition of saturated solutions in the ternary LaCl3 –C3H6O–H2O LaCl3 –C2H8N2 ·2HCl–H2O system at 20 and 40 °C system at 25 °C

/ a a b a a t °C 100w1 m1 100w3 m3 Equilibrium solid phase Organic phase Aqueous phase

100w1 100w2 100w1 100w2 20 48.5 3.84 0 0 A 47.9 3.87 1.7 0.25 A+C — — 48.8b 0 38.2 2.71 4.3 0.56 C — — 47.1 4.1 27.0 1.73 9.5 1.12 C — — 45.9 6.0 16.5 1.01 17.0 1.92 C 0 96.0 45.3 11.6 7.4 0.45 25.5 2.86 C 0 94.0 39.2 13.3 0 0 34.0 3.87 C 0 92.1 34.2 15.3 40 50.5 4.16 0 0 A 0.1 88.2 26.3 19.6 50.0 4.19 1.4 0.22 A 0.7 82.4 19.4 28.1 49.0 4.34 5.0 0.82 A+C 1.8 75.3 14.3 36.1 36.4 2.69 8.5 1.16 C a ͑ ͒ water content in mass % is 100 1−w1 −w2 25.2 1.68 15.3 1.93 C b −1 ͑ the corresponding solubility of LaCl3 in water is 3.89 mol kg as calcu- 14.7 0.98 24.0 2.94 C lated by the compilers͒ or 6.5 mol % 6.5 0.44 33.0 4.10 C 0 0 40.3 5.07 C The equilibrium solid phase was found to be LaCl3 ·7H2O. amolalities calculated by the compilers b Auxiliary Information A=LaCl3 ·3H2O; C=C2H8N2 ·2HCl Method/Apparatus/Procedure: The system was found to be of simple eutonic type. Experimental method was described by Sergeeva and Karapetyants ͓Termodinamika i Stroeniye Rastvorov, Ivanovo, ͑2͒ 75 ͑1974͔͒ but the Auxiliary Information paper was not available to the compilers. The concentration of La was determined by titration with EDTA solution. Method/Apparatus/Procedure: The solubility was studied by the method of isothermal sections using Source and Purity of Materials: refractometric analysis of the equilibrium phases along directed sections LaCl3 ·7H2O was recrystallized before use. of the phase diagram. Equilibria were checked by repeated measurements of refractive index as a function of time. The results obtained were used Estimated Error: to plot the refractive index versus composition. Break points on such plots Nothing speciﬁed. corresponded to saturating levels of the phases investigated. The refractive indices were measured in a thermostated refractometer.

Source and Purity of Materials: 4.4.4. LaCl3–Acetic acid–H2O System

Heptahydrate of LaCl3 was obtained by double crystallization of ͑ ͒ anhydrous LaCl3 pure grade . Cl content in this salt was found from Components: Original Measurements: argentometric titration which conﬁrmed the salt formula. ͑1͒ Lanthanum chloride; LaCl ; 139Y.H. Li, X.Q. Ran, and P.H. ͑ ͒ ͑ ͒ 3 N2H4 ·2HCl pure for analysis and C2H8N2 ·2HCl pure were dried over ͓10099-58-8͔ Chen, YanHu YanJiu ͑J. Salt anhydrous CaCl in a desiccator. ͑ ͒ ͒ ͑ ͒ ͑ ͒ 2 2 Acetic acid; C2H4O2; Lake Sci. 3 2 ,40 1995 . Doubly distilled water was used. ͓64-19-7͔ ͑3͒ Water; H O; ͓7732-18-5͔ Estimated Error: 2 Nothing speciﬁed. Variables: Prepared by: Concentration of acetic acid: C. Gumiński and D. Zeng 2.83–55.35 mass % One temperature: 303 K

4.4.3. LaCl3–Ketone–H2O Systems Experimental Values

Components: Original Measurements: Solubility of LaCl in aqueous acetic acid solutions at 30 °C ͑ ͒ 106 3 1 Lanthanum chloride; LaCl3; Ts.B. Sergeeva and M.Kh. ͓ ͔ 10099-58-8 Karapetyants, Izv. Vyssh. Ucheb. 100w m a 100w m a ͑2͒ Acetone; 2-propanone; Zaved., Khim. Khim. Tekhnol. 1 1 2 2 ͓ ͔ ͑ ͒ b C3H6O; 67-64-1 19,846 1976 . 50.4 4.14 0 0 ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 49.00 4.147 2.83 0.978 45.93 4.054 7.88 2.84 Variables: Prepared by: 42.03 4.168 16.85 6.82 Composition of mixtures T. Mioduski and C. Gumiński One temperature: 298 K 38.53 4.164 23.74 10.48 33.09 4.198 34.77 18.02 29.19 4.096 41.75 23.92

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1836 MIODUSKI, GUMIŃSKI, AND ZENG

Solubility of LaCl3 in aqueous acetic acid solutions at 30 °C Composition of saturated solutions in the ternary LaCl3 –C2H5NO–H2O system at 30 °C a a 100w1 m1 100w2 m2 a a b 100w1 m1 100w2 m2 Equilibrium solid phase 23.26 4.264 54.50 40.81 24.49 4.953 55.35 45.72 33.14 4.22 34.87 18.45 B 25.84 4.191 49.02 32.47 35.57 4.21 30.00 14.75 B 42.63 5.20 23.97 12.15 B amolalities calculated by the compilers 38.54 4.29 24.81 11.46 B bthe value obtained by extrapolation from higher concentrations of acetic acid 45.10 5.73 22.78 12.01 B+C 44.51 5.50 22.49 11.54 C

The equilibrium solid phase was found to be LaCl3 ·7H2O 45.97 5.27 18.47 8.79 C at all acetic acid concentrations. 46.38 4.88 14.84 6.48 C 47.28 4.71 11.76 4.86 C Auxiliary Information 47.32 4.19 6.64 2.44 C 48.07 3.77 0 0 C Method/Apparatus/Procedure: Mixtures of the components were sealed in polyethylene tubes. The tubes amolalities calculated by the compilers were placed in a thermostat at the selected temperature and the mixtures b ͑ A=C2H5NO; B=LaCl3 ·5C2H5NO·5H2O; C=LaCl3 ·6H2O the corre- were equilibrated for 5 d. Then samples of the separated liquid phase sponding point on a ﬁgure in the original paper is placed at 33.2 mass % were analyzed. The content of La was determined by titration with EDTA H O, which corresponds to the generally accepted formula LaCl ·7H O͒ solution using a xylenol orange indicator and hexamethylenetetramine 2 3 2 ͑ ͒ buffer pH=5.5 . The content of acetic acid was determined by titration Auxiliary Information with NaOH solution using a bromothymol blue sodium salt indicator. The composition of the equilibrium solid phase was found by the method of Method/Apparatus/Procedure: Schreinemakers. No details were reported. The authors measured the solubilities in isothermal conditions. The equilibrium solid phases were determined by Source and Purity of Materials: the method of Schreinemakers. ͑ ͒ LaCl37·H2O was prepared by dissolution of La2O3 99.99% pure in HCl solution. The reaction product was recrystallized several times. Source and Purity of Materials:

NaOH and C2H4O2 were analytically pure. Nothing specified. Water was doubly distilled. Estimated Error: Estimated Error: Nothing specified. Solubility: precision of Ϯ0.1%, but it seems to be too optimistic according to the compilers. Temperature: nothing specified. Components: Original Measurements: ͑ ͒ 120 1 Lanthanum chloride; LaCl3; Z.X. Tang, Zh.Zh. Guo, P.H. ͓10099-58-8͔ Chen, J.H. Ma, and Y.Sh. Chen, ͑2͒ Acetamide; C H NO; Gaodeng Xuexiao Huaxue 4.4.5. LaCl3–Amide–H2O Systems 2 5 ͓60-35-5͔ Xuebao 4, 419 ͑1983͒. ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 Components: Original Measurements: ͑ ͒ 108 Variables: Prepared by: 1 Lanthanum chloride; LaCl3; Z. Zholalieva, K. ͓10099-58-8͔ Sulaimankulov, and K. Nogoev, Composition of mixtures T. Mioduski and C. Gumiński ͑ ͒ 2 Acetamide; C2H5NO; Zh. Neorg. Khim. 21, 2290 Temperature: 273 and 303 K ͓60-35-5͔ ͑1976͒. ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 Experimental Values Variables: Prepared by:

Composition of mixtures T. Mioduski and C. Gumiński Composition of saturated solutions in the ternary LaCl3 –C2H5NO–H2O One temperature: 303 K system at 0 and 30 °C

/ a a b t °C 100w1 m1 100w2 m2 Equilibrium solid phase Experimental Values 0 0 0 52.72 23.11 A Composition of saturated solutions in the ternary LaCl3 –C2H5NO–H2O 21.77 3.446 52.47 34.48 A+B system at 30 °C 45.59 4.135 9.46 3.563 B+C 48.03 3.768 0 0 C 100w m a 100w m a Equilibrium solid phaseb 1 1 2 2 30 0 0 74.53 49.54 A 1.63 4.89 97.01 120.7 A 31 42 66 372 A+D 16.80 6.19 72.09 109.8 A 33 17 59 125 B+D 22.34 13.68 71.00 180.5 A 47.19 5.020 14.48 6.395 B+C 27.10 13.30 64.59 131.6 B 49.32 3.968 0 0 C 27.26 7.20 57.30 62.83 B amolalities calculated by the compilers 28.02 4.30 45.38 28.88 B b ͑ ͒ A=C2H5NO; B=LaCl3 ·4C2H4NO·5H2O; C=LaCl3 ·7H2O; D=LaCl3 ?

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1837

Complete dehydration of LaCl3 seems to be improbable at The compound B was found to be incongruently soluble. these conditions. The complex compound B formed in the Auxiliary Information system was found to melt at 68.4 °C. Method/Apparatus/Procedure: Auxiliary Information The mixtures were prepared from the components. The concentration in the liquid phase was isothermally analyzed by refractometry. The Method/Apparatus/Procedure: refractive index was measured in a thermostated refractometer as a The equilibrium solutions were chemically analyzed with a refractometer. function of time until reaching a constant value, which reflected La was determined by titration with EDTA solution using xylenol orange approaching equilibrium in the system. Equilibrium was found to be as an indicator. N in acetamide was determined by the Kjeldahl method. reached after 50 h. The content of La in the liquid phase was determined The composition of solid phases was determined by the residue method of by titration with EDTA solution. The content of C H N O was determined Schreinemakers. The compound formed was investigated by means of 6 6 2 by ultraviolet spectrometry. There was no interference in the analysis of photomicrography, densimetry, and x-ray diffraction. La and C6H6N2O. The composition of the solid phases was determined by Source and Purity of Materials: the method of Schreinemakers. Chemical analysis of the compound B, after drying for 2 d over silica gel, confirmed the result obtained by the Nothing specified on LaCl . 3 method of Schreinemakers. Acetamide was 99.38% pure. Source and Purity of Materials: Estimated Error: LaCl ·7H O was prepared from anhydrous LaCl ͑analytically pure͒ Nothing specified. 3 2 3 dissolved in H2O. The product was placed for drying over 60% H2SO4. Analysis of the salt showed a formula of LaCl3.00 ·7.10H2O. ͑ ͒ C6H6N2O chemically pure was twice recrystallized from water and dried Components: Original Measurements: at 105 °C over silica gel for 4 h; weight loss was then 0.5%. The product ͑ ͒ 130 1 Lanthanum chloride; LaCl3; Q.H. Shi, J.Q. Chen, and L.L. contained no water and its melting point was 130−131 °C. ͓10099-58-8͔ Wang, Huaxue Shijie 29, 484 Other chemicals were analytically pure. ͑ ͒ ͑ ͒ 2 Nicotinamide; 1988 . Water was doubly distilled. 3-pyridinecarboxamide; ͓ ͔ C6H6N2O; 98-92-0 Estimated Error: ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 Solubility: nothing specified. Temperature: precision of Ϯ0.2 K; precision in the refractometer of Variables: Prepared by: Ϯ0.05 K. Composition of mixtures C. Gumiński and D. Zeng One temperature: 298 K

Components: Original Measurements: Experimental Values ͑ ͒ 141 1 Lanthanum chloride; LaCl3; B. Cui, Z.X. Tang, Zh.Zh. Guo ͓ ͔ Composition of saturated solutions in the ternary LaCl –C H N O–H O 10099-58-8 and K.X. Chen, Gaodeng 3 6 6 2 2 ͑ ͒ Ј ͑ Ј ͒ system at 25 °C 2 N,N -bis antipyrine-4 -yl - Xuexiao Huaxue Xuebao 18, hexanedicarboxamide; 1742 ͑1997͒. a a b N,NЈ-bis͑2,3-dihydro-1,5-dimethyl-3- 100w m 100w m Equilibrium solid phase 1 1 2 2 oxo-2-phenyl-1H-pyrazol-4yl-hexanediamide; ͓ ͔ 0 0 47.01 7.265 A C28H32N6O4; 177910-32-6 ͑ ͒ ͓ ͔ 4.81 0.432 49.79 8.980 A 3 Water; H2O; 7732-18-5 7.80 0.674 45.01 7.810 A Variables: Prepared by: 10.66 0.980 44.97 8.299 A Composition of mixtures C. Gumiński and D. Zeng 18.02 1.965 44.59 9.766 A One temperature: 303 K 21.78 2.850 47.06 12.37 A+B 23.12 2.655 41.38 9.545 B 24.11 2.620 38.37 8.374 B Experimental Values 23.90 2.425 35.92 7.320 B Composition of saturated solutions in the ternary 25.72 2.341 29.49 5.391 B LaCl3 –C28H32N6O4 –H2O system at 30 °C 27.30 2.527 28.66 5.329 B 26.75 2.310 26.03 4.514 B a a b 100w1 m1 100w2 m2 Equilibrium solid phase 26.54 2.246 25.29 4.299 B 27.78 2.252 21.92 3.569 B 0 0 0.38 0.0074 A 29.89 2.280 16.66 2.552 B 4.12 0.175 0.34 0.0069 A 35.08 2.472 7.07 1.001 B 9.77 0.443 0.35 0.0075 A 38.82 2.766 3.96 0.567 B 16.46 0.807 0.36 0.0084 A 46.66 3.677 1.60 0.253 B 23.04 1.226 0.35 0.0088 A 48.89 4.025 1.58 0.261 B+C 29.51 1.715 0.32 0.0088 A 48.79 3.958 0.95 0.155 C 36.22 2.330 0.40 0.012 A 49.00 3.934 0.22 0.035 C 41.66 2.948 0.73 0.024 A 49.05 3.925 0 0 C 46.36 3.581 0.86 0.031 A 49.12 4.001 0.82 0.032 A+B amolalities calculated by the compilers b 49.12 4.001 0.82 0.032 A+B A=C6H6N2O; B=LaCl3 ·2C6H6N2O·7H2O; C=LaCl3 ·7H2O

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1838 MIODUSKI, GUMIŃSKI, AND ZENG

Composition of saturated solutions in the ternary The compound B was found to be incongruently soluble. LaCl3 –C28H32N6O4 –H2O system at 30 °C Auxiliary Information a a b 100w1 m1 100w2 m2 Equilibrium solid phase Method/Apparatus/Procedure: 49.50 3.997 0 0 B The components were mixed in different ratios and equilibrated in a water bath. Refractive indices of the solutions were measured at regular time amolalities calculated by the compilers intervals; their stabilities indicated that the system reached equilibrium. bA=C H N O ; B=LaCl ·7H O 28 32 6 4 3 2 The content of La was then analyzed by titration with EDTA solution. The The system was found to be of eutonic type. content of C24H24N6O4 was determined by ultraviolet spectrometry. The composition of the wet solid phases was determined by the method of Auxiliary Information Schreinemakers.

Method/Apparatus/Procedure: Source and Purity of Materials: The mixtures were equilibrated at the selected temperature. Refractive ͑ ͒ LaCl3 ·7H2O was prepared from La2O3 99.95% pure and HCl solution indices of the solutions were measured at various concentrations. Break ͑analytically pure͒ taken in stoichiometric ratio. The product was doubly points on such plots corresponded to the saturating concentrations. The recrystallized. The crystals were kept in a desiccator containing 50% equilibrium solid phases were found by the method of Schreinemakers. H2SO4. Source and Purity of Materials: C24H24N6O4 was analytically pure; its melting point was found at ͑ ͒ 289–290 °C. LaCl3 ·7H2O was prepared from La2O3 99.99% pure , which was dissolved in a stoichiometric amount of HCl solution. Doubly distilled water was used. C28H32N6O4 was characterized by its melting point of 310.7−311.3 °C. Estimated Error: Estimated Error: Solubility: nothing speciﬁed. Ϯ ͑ ͒ Solubility: nothing speciﬁed. Temperature: precision of 0.05 K in the thermostat ; precision of Ϯ0.2 K ͑in the refractometer͒. Temperature: precision of Ϯ0.05 K.

4.4.6. LaCl3–Urea „thiourea…–H2O Systems Components: Original Measurements: ͑ ͒ 144 1 Lanthanum chloride; LaCl3; H.B. Liang, W.H. Han, G.L. ͓10099-58-8͔ Gao, D.J. Zhang and B. Qian, Components: Original Measurements: ͑ ͒ ͑ ͑ ͒ 92 2 N,NЈ-bis antipyrine-4- Shaanxi Shifan Daxue Xuebao, 1 Lanthanum chloride; LaCl3; Z.F. Alieva and K.S. yl͒oxamide; N,NЈ-bis͑2,3- Ziran Kexueban ͑J. Shaanxi ͓10099-58-8͔ Sulaimankulov, Izv. Akad. Nauk ͒ ͑ ͒ ͓ ͔ ͑ ͒ dichloro-1,5-dimethyl-3-oxo-2- Norm. Univ., Nat. Sci. Edit. 27, 2 Urea; CH4N2O; 57-13-6 Kaz. SSR, Ser. Khim. 20 6 ,16 ͑ ͒ ͑ ͒ ͓ ͔ ͑ ͒ phenyl-1H-pyrazol-4- 73 1999 . 3 Water; H2O; 7732-18-5 1970 . yl-ethanediamide; C24H24N6O4; ͓3857-48-5͔ Variables: Prepared by: ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 Composition of mixtures T. Mioduski and C. Gumiński Temperature: 288 and 303 K Variables: Prepared by: Composition of mixtures C. Gumiński and D. Zeng One temperature: 303 K Experimental Values Composition of saturated solutions in the ternary LaCl –CH N O–H O Experimental Values 3 4 2 2 system at 15 and 30 °C Composition of saturated solutions in the ternary t/ °C 100w m a 100w m a Equilibrium solid phaseb LaCl3 –C24H24N6O4 –H2O system at 30 °C 2 2 1 1 15 50.14 16.74 0 0 A 100w m a 100w m a Equilibrium solid phaseb 1 1 2 2 52.25 24.86 12.75 1.48 A 0 0 0.15 0.0033 A 53.00 27.15 14.50 1.82 A 8.13 0.362 0.18 0.0043 A 54.02 31.31 17.25 2.45 A 17.64 0.875 0.14 0.0037 A 55.75 44.73 23.50 4.62 A 24.38 1.318 0.20 0.0058 A 58.00 70.24 28.25 8.38 A 32.76 1.991 0.15 0.0049 A 60.75 119.0 30.75 14.75 B 36.89 2.392 0.24 0.0083 A 49.00 52.31 35.40 9.25 B 42.28 2.994 0.14 0.0053 A 47.25 50.77 37.25 9.80 B 47.00 3.622 0.09 0.0037 A+B 43.50 51.74 42.50 12.38 B 47.17 3.649 0.13 0.0054 B 40.50 49.96 46.00 12.89 B 47.98 3.772 0.15 0.0063 B 39.01 54.18 49.00 16.66 B 48.28 3.827 0.28 0.0118 B 37.50 55.51 51.25 18.57 B+C 48.58 3.873 0.28 0.0119 B 34.98 40.08 50.49 14.17 C 48.70 3.884 0.18 0.0076 B+C 27.49 19.98 49.60 8.83 C 49.50 3.997 0 0 C 23.00 14.19 50.00 7.55 C 13.50 5.99 49.00 5.33 C amolalities calculated by the compilers b 6.50 2.46 49.50 4.59 C A=C24H24N6O4; B=LaCl3 ·C24H24N6O4; C=LaCl3 ·7H2O

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1839

Composition of saturated solutions in the ternary LaCl3 –CH4N2O–H2O system at 15 and 30 °C Components: Original Measurements: ͑ ͒ 113 1 Lanthanum chloride; LaCl3; Z.M. Zholalieva and K. / a a b ͓10099-58-8͔ Sulaimankulov, Zh. Neorg. Khim. t °C 100w2 m2 100w1 m1 Equilibrium solid phase ͑2͒ Acetylurea; 23, 1367 ͑1978͒. 0 0 49.25 3.96 C N-͑aminocarbonyl͒-acetamide; ͓ ͔ 30 57.50 22.53 0 0 A C3H6N2O2; 591-07-1 ͑ ͒ ͓ ͔ 58.00 27.99 7.50 0.89 A 3 Thiourea; CH4N2S; 62-56-6 ͑ ͒ ͓ ͔ 60.25 48.35 19.00 3.73 A 4 Water; H2O; 7732-18-5 61.50 60.24 21.50 5.16 A Variables: Prepared by: 63.50 95.27 25.40 9.33 A Composition of mixtures T. Mioduski and C. Gumiński 67.50 277.5 28.45 28.64 A One temperature: 303 K 63.25 135.9 29.00 15.26 B 58.50 88.56 30.50 11.31 B 56.10 72.42 31.00 9.80 B Experimental Values 50.00 51.71 33.90 8.59 B Composition of saturated solutions in the LaCl –C H N O –H O system 45.50 44.83 37.60 9.07 B 3 3 6 2 2 2 at 30 °C 41.80 39.55 40.60 9.41 B

38.65 39.61 45.10 11.32 B a a b 100w2 m2 100w1 m1 Equilibrium solid phase 36.30 37.77 47.70 12.15 B 35.10 39.76 50.20 13.92 B+D 3.23 0.327 0 0 A 32.50 31.41 50.27 11.90 D 4.82 0.550 9.34 0.444 A 30.00 24.37 49.50 9.85 D 5.92 0.737 15.35 0.795 A 25.70 17.01 49.15 7.97 D 8.23 1.140 20.85 1.199 A 22.50 13.38 49.50 7.21 D 10.52 1.689 28.47 1.903 A 17.50 8.75 49.20 6.02 D 14.68 2.883 35.45 2.898 A 14.91 6.93 49.25 5.60 D 21.23 5.347 39.88 4.181 A+B 12.52 5.42 49.00 5.19 D 20.82 5.407 41.46 4.481 B 10.50 4.32 49.00 4.93 C 19.39 5.307 44.82 5.106 B 6.00 2.25 49.50 4.54 C 18.72 5.174 45.84 5.274 B 0 0 50.50 4.16 C 19.21 5.549 46.88 5.637 B 19.26 5.603 47.07 5.670 B+C amolalities calculated by the compilers b 15.37 3.754 44.52 4.525 C A=CH4N2O; B=LaCl3 ·6CH4N2O; C=LaCl3 ·7H2O; D=LaCl3 ·CH4N2O 4.34 0.852 45.78 3.742 C The same results were reported by Sulaimankulov ͓So- 0 0 48.07 3.774 C edineniya Karbamidov s Neorganicheskimi Solami ͑Ilim, Frunze, 1971͒,p.147͔ and partly by Alieva et al. ͓Izv. Akad. amolalities calculated by the compilers b ͑ Nauk Kirgiz. SSR ͑5͒,38͑1970͔͒. The complex compound B A=C3H6N2O2; B=LaCl3 ·2C3H6N2O2 ·4H2O; C=LaCl3 ·6H2O the generally accepted formula is LaCl ·7H O͒ was found to be soluble in water without decomposition; 3 2 however, the compound D was found to be incongruently The complex compound B formed in the system was soluble in water and it was impossible to evolve it from the found to be incongruently soluble in water. solution. Composition of saturated solutions in the LaCl3 –CH4N2S–H2O system at Auxiliary Information 30 °C

Method/Apparatus/Procedure: a a b 100w3 m3 100w1 m1 Equilibrium solid phase The isothermal method with chemical analysis of phases was used. Equilibrium between the solids and the solution was reached within 18.00 2.884 0 0 D 6–8 h. The content of N in urea was determined by the Kjeldahl method. 15.31 2.597 7.23 0.381 D The La content was found from titration with EDTA using xylenol orange 13.23 2.488 16.91 0.987 D as an indicator. The Cl content was determined gravimetrically as AgCl. 12.33 2.602 25.41 1.664 D The crystal form of the compound B was isolated by isothermal 9.92 2.325 34.03 2.475 D evaporation of water from the corresponding solution ͓Z.F. Alieva, O.V. 9.93 2.764 42.88 3.705 D Agashkin and K. Sulaimankulov, Izv. Akad. Nauk Kirgiz. ͑5͒,38͑1970͔͒. 8.84 2.495 44.61 3.907 D+C The compositions of the solid phases were determined graphically by Schreinemakers’ method of dry residues. 9.53 2.851 46.56 4.323 D+C 8.85 2.552 45.59 4.070 D+C Source and Purity of Materials: 8.24 2.298 44.58 3.852 C

LaCl3 ·7H2O of chemical purity was probably used as received. 0 0 48.07 3.774 C Pure grade urea was recrystallized repeatedly from water before use. amolalities calculated by the compilers b ͑ Estimated Error: D=CH4N2S; C=LaCl3 ·6H2O the generally accepted formula is ͒ Solubility: nothing speciﬁed. LaCl3 ·7H2O Temperature: precision of Ϯ0.2 K. The system was found to be of simple eutonic type.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1840 MIODUSKI, GUMIŃSKI, AND ZENG

Auxiliary Information Composition of saturated solutions in the ternary LaCl3 –CH4N2S–H2O system at 30 and 50 °C Method/Apparatus/Procedure: / a a b The mixtures were isothermally equilibrated for 8–10 h. The saturated t °C 100w1 m1 100w2 m2 Equilibrium solid phase liquids were separated from the crystals with the Schott G3 filter. The content of La was determined by titration with EDTA. The concentrations 50.66 4.436 2.78 0.784 B of acetylurea and thiourea were determined by the Kjeldahl method for 51.72 4.368 0 0 B the corresponding N contents. The compositions of the equilibrium solid 51.63c 4.352 0 0 B phases were found by the method of Schreinemakers. amolalities calculated by the compilers b Source and Purity of Materials: A=CH4N2S; B=LaCl3 ·7H2O c All reagents used were analytically pure. LaCl3 ·3H2O was used as the initial solute The system was found to be of eutonic type. Estimated Error: Solubility: nothing specified. The discrepancies in the estimation of the Auxiliary Information eutonic point composition reach 8% ͑by the compilers͒. Temperature: nothing specified. Method/Apparatus/Procedure: The components were equilibrated until constancy of refractive index of a solution; the index was measured in a thermostated refractometer. The Components: Original Measurements: saturated solutions and the equilibrium solid phases were analyzed. La was determined by titration with EDTA solution. N in thiourea was ͑1͒ Lanthanum chloride; LaCl ; 118Z.X. Tang, Zh.Zh. Guo, P.H. 3 determined by the Kjeldahl method. The compositions of the solid phases ͓10099-58-8͔ Chen, J.H. Ma, and Y.Sh. Chen, were determined graphically by the method of Schreinemakers. The ͑2͒ Thiourea; CH N S; ͓62-56-6͔ Gaodeng Xuexiao Huaxue 4 2 compositions of the eutonic points were confirmed by inflection points on ͑3͒ Water; H O; ͓7732-18-5͔ Xuebao 3, 447 ͑1982͒. 2 a graph of the refractive index versus composition. Variables: Prepared by: Source and Purity of Materials: Composition of mixtures T. Mioduski and C. Gumiński LaCl ·7H O was prepared by dissolving La O ͑99.99% pure͒ in HCl Temperature: 303 and 323 K 3 2 2 3 solution and recrystallization. The composition of the heptahydrate was checked by a standard chemical analysis and the formula found was LaCl ·7.2H O; the Volhard method was used for Cl determination. Experimental Values 3.01 2 LaCl3 ·3H2O was obtained by dehydration of LaCl3 ·7H2Oat60°Cfor 24 h in a vacuum desiccator. The composition of the trihydrate, confirmed Composition of saturated solutions in the ternary LaCl3 –CH4N2S–H2O system at 30 and 50 °C by an analysis, differed from its formula: La by 0.1%, Cl by 0.1%, and H2O by 4%. / a a b Thiourea was 96.32% pure. t °C 100w1 m1 100w2 m2 Equilibrium solid phase

30 0 0 16.83 2.658 A Estimated Error: Ϯ 14.43 0.935 12.65 2.641 A Solubility: precision of 0.1 mass %. Ϯ 28.49 1.858 9.00 1.891 A Temperature: precision of 0.2 K. Ϯ 34.50 2.431 7.63 1.732 A Refractive index: 0.01 %. 41.93 3.315 6.50 1.656 A 46.71 4.041 6.16 1.717 A+B 46.72 4.043 6.16 1.717 A+B Components: Original Measurements: ͑ ͒ 121 46.74 4.044 6.13 1.709 A+B 1 Lanthanum chloride; LaCl3; Z.X. Tang, Zh.Zh. Guo, P.H. ͓10099-58-8͔ Chen, J.H. Ma and Y.Sh. Chen, 46.96 4.056 5.84 1.625 B ͑2͒ Acetylurea; Gaodeng Xuexiao Huaxue 47.33 4.046 4.98 1.372 B N-͑aminocarbonyl͒-acetamide; Xuebao 4, 631 ͑1983͒. 47.86 4.040 3.84 1.044 B ͓ ͔ C3H6N2O2; 34505-15-2 48.27 4.000 2.50 0.667 B ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 48.79 3.991 1.37 0.361 B 49.32 3.968 0 0 B Variables: Prepared by: 50 0 0 32.46 6.314 A Composition of mixtures T. Mioduski and C. Gumiński 15.77 1.018 21.07 4.383 A One temperature: 303 K 23.52 1.594 16.32 3.564 A 38.66 3.130 10.98 2.864 A Experimental Values

45.44 4.094 9.31 2.703 A Composition of saturated solutions in the ternary LaCl3 –C3H6N2O2 –H2O 46.61 4.300 9.20 2.735 A system at 30 °C 47.51 4.464 9.10 2.755 A a a b 48.06 4.561 8.98 2.746 A+B 100w1 m1 100w2 m2 Equilibrium solid phase 48.08 4.563 8.96 2.740 A+B 0 0 1.86 0.186 A 48.01 4.553 9.00 2.750 A+B 41.63 3.972 15.64 3.585 A+B 48.52 4.533 7.84 2.360 B 47.68 4.434 8.48 1.895 B+C 49.64c 4.497 5.35 1.562 B 49.32 3.968 0 0 C 49.70 4.479 5.06 1.469 B a 50.30c 4.438 3.49 0.992 B molalities calculated by the compilers b A=C3H6N2O2; B=LaCl3 ·2C3H6N2O2 ·5H2O; C=LaCl3 ·7H2O

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1841

The compound B was found to be incongruently soluble. 4.4.7. LaCl3 –N-heterocycle–H2O Systems

Auxiliary Information Components: Original Measurements: ͑ ͒ 107 Method/Apparatus/Procedure: 1 Lanthanum chloride; LaCl3; R.V. Yurkevich, E.F. ͓ ͔ Chemical analysis and refractive index measurements of the solutions 10099-58-8 Zhuravlev, and N.A. Rasskazova, ͑ ͒ were used. La was determined by titration with EDTA solution using a 2 Pyridine hydrochloride; Zh. Neorg. Khim. 21, 2234 ͓ ͔ ͑ ͒ xylenol orange indicator. N in acetylurea was determined by the Kjeldahl C5H5N·HCl; 628-13-7 1976 . ͑ ͒ method. The composition of the equilibrium solid phases was found by 3 Quinoline hydrochloride; ͓ ͔ Schreinemakers’ method. The compound formed in the system was C9H7N·HCl; 530-64-3 ͑ ͒ ͓ ͔ investigated by means of photomicrography and densimetry. 4 Water; H2O; 7732-18-5

Source and Purity of Materials: Variables: Prepared by: Composition of mixtures T. Mioduski and C. Gumiński Nothing speciﬁed; presumably LaCl3 ·7H2O was prepared as in the previous paper by this group. The composition of the product was Temperature: 293 and 313 K controlled by chemical analysis.

Estimated Error: Experimental Values Nothing speciﬁed. Composition of saturated solutions in the ternary

LaCl3 –C5H5N·HCl–H2O system at 20 and 40 °C Components: Original Measurements: / a a b ͑ ͒ 122 t °C 100w1 m1 100w2 m2 Equilibrium solid phase 1 Lanthanum chloride; LaCl3; Z.X. Tang, Zh.Zh. Guo, P.H. ͓ ͔ 10099-58-8 Chen, J.H. Ma, and Y.Sh. Chen, 20 0 0 87.5 60.6 A ͑ ͒ 2 Acetylthiourea; Gaodeng Xuexiao Huaxue 1.5 0.51 86.5 62.4 A N-͑aminothioxomethyl͒-acetamide; Xuebao 4, 634 ͑1983͒. ͓ ͔ 3.5 1.19 84.5 60.9 A C3H6N2OS; 591-08-2 ͑ ͒ ͓ ͔ 7.5 2.35 79.5 52.9 A+B 3 Water; H2O; 7732-18-5 9.5 2.21 73.0 36.1 B Variables: Prepared by: 12.5 2.37 66.0 26.6 B Composition of mixtures T. Mioduski and C. Gumiński 14.0 2.54 63.5 24.4 B Temperature: 303 and 323 K 23.2 2.97 45.0 12.2 B 35.0 3.99 29.2 7.06 B+C 36.0 4.10 28.2 6.81 C Experimental Values 39.7 4.02 20.0 4.29 C 42.5 3.98 14.0 2.79 C Composition of saturated solutions in the ternary LaCl3 –C3H6N2OS–H2O system at 30 and 50 °C 47.0 4.03 5.5 1.00 C 48.5 3.84 0 0 C / a a b t °C 100w1 m1 100w2 m2 Equilibrium solid phase 40 0 0 90.0 77.9 A 1.0 0.39 88.5 72.9 A 30 49.32 3.968 0 0 A 2.5 0.97 87.0 71.7 A 49.21 3.950 0.44 0.075 A+B 7.0 2.72 82.5 68.0 A 0 0 2.20 0.192 B 8.2 3.25 81.5 66.5 A+B 50 51.68 4.361 0 0 A 10.7 3.16 75.5 47.3 B 51.58 4.400 0.62 0.111 A+B 14.7 3.31 67.2 32.1 B 0 0 4.71 0.422 B 19.5 3.31 56.5 20.4 B amolalities calculated by the compilers 27.0 3.44 41.0 11.1 B b 38.0 4.19 25.0 5.85 B A=LaCl3 ·7H2O; B=C3H6N2OS 43.5 4.69 18.7 4.28 B+C The system was reported to be of a simple eutonic type. 44.0 4.60 17.0 3.77 C 46.0 4.50 12.3 2.55 C Auxiliary Information 48.3 4.26 5.5 1.03 C 50.5 4.16 0 0 C Method/Apparatus/Procedure: Isothermal investigations of the system were performed. The solubilities amolalities calculated by the compilers were determined by chemical analysis. Equilibrium in the system was bA=C H N·HCl; B=LaCl ·2C H N·HCl·3H O ͑since the authors re- ascertained by constancy of the refractive index of the solutions measured. 5 5 3 5 5 2 The equilibrium solids were estimated by the method of Schreinemakers. ported about dichloride, the correct formula of the adduct should be written ͒ as LaCl3 ·2C5H5N·2HCl·3H2O ; C=LaCl3 ·7H2O Source and Purity of Materials: Nothing speciﬁed, but it seems that the materials used were of the same The compound B was found to be congruently soluble. Its degree of purity as in the previous papers from the same laboratory. solubility was determined to be 64.0 and 64.8 mass % at 20 Estimated Error: and 40 °C, respectively; the corresponding values expressed Nothing speciﬁed, but it seems to be the same as in the previous papers in molalities, as calculated by the compilers, are 3.08 and from the same laboratory. 3.19 mol kg−1.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1842 MIODUSKI, GUMIŃSKI, AND ZENG

Composition of saturated solutions in the ternary C5H5N·HCl was prepared by neutralization of C5H5N with HCl. The ͑ LaCl3 –C9H7N·HCl–H2O system at 20 and 40 °C melting point of the product after double crystallization was 82.5 °C the reported value of 145−147 °C in the Aldrich Catalogue of Chemicals, / a a b ͒ t °C 100w1 m1 100w3 m3 Equilibrium solid phase 2005 is not in agreement and its density measured in a pycnometer was 1.39 g cm−3. 20 0 0 83.0 29.5 D C9H7N·HCl was prepared by neutralization of C9H7N with HCl. The 1.5 0.39 83.0 32.3 D melting point of the product after double crystallization was 95 °C and its 2.5 0.70 83.0 34.6 D density measured in a pycnometer was 1.28 g cm−3. 3.0 0.87 83.0 35.8 D+E Estimated Error: 8.7 1.59 69.0 18.7 E Nothing speciﬁed. 10.5 1.78 65.5 16.5 E 18.3 2.38 50.4 9.72 E 27.0 2.94 35.5 5.72 E 34.0 3.30 24.0 3.45 E Components: Original Measurements: ͑ ͒ 124 38.3 3.54 17.6 2.41 E+C 1 Lanthanum chloride; LaCl3; Y.Zh. Zou, Z.X. Tang and ͓ ͔ 39.5 3.62 16.0 2.17 C 10099-58-8 Y.Sh. Chen, Huaxue Xuebao 42, ͑2͒ Antipyrine; 913 ͑1984͒. 41.7 3.59 11.0 1.40 C 2,3-dimethyl-1-phenyl-3-pyrazolin-5-one; 44.0 3.66 7.0 0.86 C ͓ ͔ C11H12N2O; 60-80-0 44.5 3.67 6.0 0.73 C ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 45.0 3.54 3.2 0.37 C 48.5 3.84 0 0 C Variables: Prepared by: 40 0 0 85.0 34.2 D Composition of mixtures T. Mioduski and C. Gumiński 1.5 0.44 84.6 36.8 D Temperature: 273 and 293 K 2.5 0.76 84.0 37.6 D 4.0 1.25 83.0 38.6 D+E 6.5 1.71 78.0 30.4 E Experimental Values 14.0 2.38 62.0 15.6 E Although the whole range of composition was investigated 24.5 3.17 44.0 8.43 E at 0 and 20 °C, the results were presented only in a barely 32.5 3.58 30.5 4.98 E readable ﬁgure. The compositions of two eutonic points were 35.5 3.62 24.5 3.70 E 38.3 3.84 21.0 3.12 E reported numerically at both temperatures. 41.0 3.89 16.0 2.25 E+C Compositions of saturated solutions at the eutonic points in the ternary 41.7 3.88 14.5 2.00 C LaCl –C H N O–H O system at 0 and 20 °C 44.0 3.90 10.0 1.31 C 3 11 12 2 2 45.7 3.88 6.3 0.79 C / a a b t °C 100w1 m1 100w2 m2 Equilibrium solid phases 48.3 4.04 3.0 0.37 C 50.5 4.16 0 0 C 0 34.5 4.69 35.5 6.28 A+B 21.36 4.24 58.09 15.02 B+C a molalities calculated by the compilers 20 31.04 5.35 45.31 10.18 A+B b D=C9H7N·HCl; E=LaCl3C9 ·H7N·HCl·7H2O; C=LaCl3 ·7H2O 19.32 4.42 62.87 18.75 B+C

The compound E was found to be congruently soluble. Its amolalities calculated by the compilers b ͑ solubility was determined to be 62.4 and 63.4 mass % at 20 A=LaCl3 ·7H2O; B=LaCl3 ·6C11H12N2O·7H2O; C=C11H12N2O antipy- and 40 °C; the corresponding values expressed in molalities, rine͒ as calculated by the compilers, are 4.04 and 4.22 mol kg−1, The compound B was found to be incongruently soluble. respectively. Auxiliary Information Auxiliary Information Method/Apparatus/Procedure: Method/Apparatus/Procedure: Equilibrium between the solutes and the solution was ascertained by The method of isothermal sections of the phase diagram with constancy of the refractive index of the solutions measured in a refractometric analysis was used.94 Mixtures of selected compositions thermostated refractometer. Both saturated solutions and solid phases were along a directed section of the phase diagram were shaken for a long time analyzed. La was determined by titration with EDTA solution using until the refractive indexes of the solutions remained constant. The xylenol orange as an indicator. N in antipyrine was determined by the compositions of the saturated solutions and the corresponding solid phases Kjeldahl method. The composition of solid phases was found by the were determined from inflection points on plots of the refractive index graphical method of Schreinemakers. The composition of the eutonic versus composition. The refractive indices were measured in a points was confirmed by break points on the isotherms of refractive index thermostated refractometer. Both adduct compounds were studied by x-ray versus composition. diffraction, thermogravimetry, and thermal analysis. Source and Purity of Materials: Source and Purity of Materials: LaCl ·7H O was prepared by dissolving La O ͑99.99% pure͒ in HCl LaCl ·7H O was obtained by repeated recrystallization of anhydrous 3 2 2 3 3 2 solution and subsequent crystallization of the product. LaCl ͑pure grade͒. Water content of 33.92 mass % in the product 3 Antipyrine was purified prior to use. confirmed the formula of heptahydrate.94

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1843

Estimated Error: Estimated Error: Solubility: precision of Ϯ0.1 mass %. Solubility: nothing speciﬁed. Temperature: precision of Ϯ0.2 K; stability of Ϯ0.05 K. Temperature: stability of Ϯ0.1 K; stability in the refractive index Refractive index: Ϯ0.0002. measurements of Ϯ0.2 K. Refractive index: precision of Ϯ0.0002.

Components: Original Measurements: ͑ ͒ 133 Components: Original Measurements: 1 Lanthanum chloride; LaCl3; X.L. Xu, Z.X. Tang, Zh.Zh. ͑ ͒ 140 ͓10099-58-8͔ Guo, and Y.Sh. Chen, Gaodeng 1 Lanthanum chloride; LaCl3; H.B. Liang, Sh.J. Li, G.L. ͑2͒ 4-chloroacetylantipyrine; Xuexiao Huaxue Xuebao 12,728 ͓10099-58-8͔ Gao, N.H. Cao and Z.X. Tang, 4-͑chloroacetyl͒-1,2-dihydro-1, ͑1991͒. ͑2͒ Phthalimidoantipyrine; Shanxi Shifan Daxue Xuebao, 5-dimethyl-2-phenyl-3H-pyrazol-3-one; 2-͑2,3-dihydro-1,5-dimethyl-3-oxo- Ziran Kexueban ͑J Shaanxi ͓ ͔ 2-phenyl͒-1H-pyrazol-4-yl-1H- Norm. Univ., Nat. Sci. Edit.͒ C13H13ClN2O2; 6630-73-5 ͑ ͒ ͓ ͔ isoindole-1,3͑2H͒-dione; 25͑3͒,61͑1997͒. 3 Water; H2O; 7732-18-5 ͓ ͔ C19H15N3O3; 101896-02-0 ͑ ͒ ͓ ͔ Variables: Prepared by: 3 Water; H2O; 7732-18-5 Composition of mixtures C. Gumiński and D. Zeng One temperature: 303 K Variables: Prepared by: Composition of mixtures C. Gumiński and D. Zeng One temperature: 303 K Experimental Values Experimental Values Composition of saturated solutions in the ternary

LaCl3 –C13ClH13N2O2 –H2O system at 30 °C Composition of saturated solutions in the ternary LaCl3 −C19H15N3O3 a a b −H2O system at 30 °C 100w1 m1 100w2 m2 Equilibrium solid phase a a b 0 0 0.11 0.0042 A 100w1 m1 100w2 m2 Equilibrium solid phase 13.50 0.637 0.10 0.0044 A 0 0 0.28 0.0084 A 27.48 1.547 0.10 0.0052 A 12.43 0.580 0.19 0.0065 A 33.14 2.025 0.14 0.0079 A 27.49 1.549 0.16 0.0066 A 40.90 2.833 0.24 0.015 A 35.90 2.289 0.15 0.0070 A 45.90 3.483 0.37 0.026 A 40.26 2.753 0.12 0.0060 A 48.39 3.844 0.28 0.021 A+B 43.52 3.149 0.13 0.0069 A 49.50 3.997 0 0 B 44.97 3.339 0.11 0.0060 A 47.90 3.759 0.14 0.0081 A amolalities calculated by the compilers 49.39 3.989 0.13 0.0077 A+B bA=C ClH N O ; B=LaCl ·7H O 13 13 2 2 3 2 49.50 3.997 0 0 B The system was found to be of eutonic type. amolalities calculated by the compilers b A=C19H15N3O3; B=LaCl3 ·7H2O Auxiliary Information The system was found to be of a simple eutonic type. The Method/Apparatus/Procedure: same solubility results were later published in Ref. 150. The components were equilibrated in isothermal conditions. Equilibrium in the system was checked by periodic measurement of the refractive Auxiliary Information index of the liquid phase. It was found that equilibrium was reached after 20 d. The content of La in the saturated solution was determined by Method/Apparatus/Procedure: titration with EDTA solution. The content of C13ClH13N2O2 was Mixtures of the components were equilibrated in a thermostated water determined as a sum from gravimetry and ultraviolet spectrometry: the bath for 40 d. Reaching equilibrium in the system was monitored by wet residue was dissolved in boiling water, then cooled for the measurements of the refractive index of the solutions at regular time crystallization, dried, and weighed: subsequently the rest of the compound intervals. The content of La was determined by titration with EDTA in the solution was determined by ultraviolet spectrometry. The solution. The content of C19H15N3O3 was determined by ultraviolet composition of the solid phases was determined by the method of spectrometry. The composition of wet solid phases was determined by the Schreinemakers. method of Schreinemakers and conﬁrmed by chemical analysis.

Source and Purity of Materials: Source and Purity of Materials: LaCl ·7H O was prepared from La O and the stoichiometric amount of ͑ ͒ 3 2 2 3 LaCl3 ·7H2O was prepared by dissolution of La2O3 99.95% pure in a HCl solution. The mixture was stirred, evaporated on a water bath, cooled, stoichiometric amount of HCl solution of analytical purity. and crystallized, adding a small crystal of the product. The solid and the C19H15N3O3 was synthesized in the laboratory of the authors. solution were separated. The crystals were recrystallized and stored in a Doubly distilled water was used. dry container.

C13ClH13N2O2 was prepared in this laboratory and twice recrystallized. Estimated Error: Distilled water was used. Solubility: nothing speciﬁed. Temperature: precision of Ϯ0.05 K ͑in the thermostat͒; precision of Ϯ0.2 K ͑in the refractometer͒.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1844 MIODUSKI, GUMIŃSKI, AND ZENG

Source and Purity of Materials: Components: Original Measurements: LaCl ·7H O was obtained from La O ͑99.9% pure͒ which was dissolved ͑ ͒ 145 3 2 2 3 1 Lanthanum chloride; LaCl3; Sh.P. Liu, G.Q. Huang, Ch.D. in a slight excess of HCl solution. The product was recrystallized twice. ͓ ͔ 10099-58-8 Zhang, and H.Y. Wang, C H FN O was a commercial product ͑99.7 % pure͒ with melting point ͑ ͒ 4 3 2 2 2 Fluorouracil; Neimenggu Daxue Xuebao, Ziran of 280 °C. ͑ ͒ ͑ 5-fluoro-2,4 1H,3H -pyrimidinedione; Kexueban Acta Sci. Nat. Univ. All other chemicals were chemically or analytically pure. ͓ ͔ ͒ ͑ ͒ ͑ ͒ C4H3FN2O2; 51-21-8 NeMongol 30 1 ,53 1999 . ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 Estimated Error: Nothing specified. Variables: Prepared by: Composition of mixtures C. Gumiński and D. Zeng One temperature: 303 K Components: Original Measurements: ͑ ͒ 146 1 Lanthanum chloride; LaCl3; H.B. Liang, W.L. Wang, D.D. Experimental Values ͓10099-58-8͔ Hu and W.P. Zhang, J. Rare ͑2͒ 4-͑4-chlorobenzoyl͒ Earths 17͑1͒,81͑1999͒; Composition of saturated solutions in the ternary aminoantipyrine; 4-chloro-N- Zhongguo Xitu Xuebao 17͑1͒,64 LaCl3 –C4H3FN2O2 –H2O system at 30 °C ͑2,3-dichloro-1,5-dimethyl-3- ͑1999͒. oxo-2-phenyl-1H-pyrazol-4-yl-benzamide; a a b ͓ ͔ 100w1 m1 100w2 m2 Equilibrium solid phase C18H16ClN3O2; 56866-88-7 ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 0 0 1.380 0.108 A 2.350 0.099 1.335 0.107 A Variables: Prepared by: 9.616 0.439 1.147 0.099 A Composition of mixtures C. Gumiński 12.11 0.569 1.061 0.094 A One temperature: 303 K 21.75 1.148 1.021 0.102 A 28.97 1.687 1.009 0.111 A Experimental Values 34.25 2.161 1.122 0.133 A 35.63 2.335 2.157 0.267 A+B Composition of saturated solutions in the ternary LaCl3 −C18H16N3O2Cl 36.56 2.421 1.856 0.232 B −H2O system at 30 °C 38.39 2.611 1.652 0.212 B a a b 39.41 2.714 1.383 0.180 B 100w1 m1 100w2 m2 Equilibrium solid phase 42.31 3.042 0.983 0.133 B 46.12 3.556 0.997 0.145 B 0 0 0.03 0.0009 A 47.93 3.895 1.901 0.291 B+C 8.23 0.376 0.08 0.003 A 48.51 3.910 0.906 0.138 C 17.26 0.852 0.10 0.0035 A 49.63 4.017 0 0 C 31.00 1.833 0.05 0.002 A 40.06 2.727 0.04 0.002 A a molalities calculated by the compilers 46.28 3.519 0.09 0.005 A b A=C4H3FN2O2; B=LaCl3 ·4C4H3FN2O2 ·7H2O; C=LaCl3 ·7H2O 48.94 3.915 0.09 0.005 A+B 49.50 4.000 0 0 B Thermal and thermogravimetric analyses of the compounds B and C revealed gradual dehydration of these com- amolalities calculated by the compiler b A=C18H16N3O2Cl; B=LaCl3 ·7H2O pounds to LaCl3 ·4C4H3FN2O2 ·3H2O and finally LaCl3 ·4C4H3FN2O2, and also to LaCl3 ·3H2O, LaCl3 ·H2O The system was found to be of simple eutonic type. and finally LaCl3, respectively. Temperatures of the corresponding steps were observed at 73.9 and 104.8 °C, and also Auxiliary Information at 85.9, 119.8, and 156.8 °C, respectively. The x-ray diffrac- Method/Apparatus/Procedure: togram for LaCl3 ·7H2O powder was different from the one Mixtures of the components were prepared in appropriate proportions. published in the Powder Diffraction File. They were equilibrated in a thermostat. Equilibrium in the system was ascertained by monitoring the refractive indices of the solutions in a Auxiliary Information thermostated refractometer. The saturated solution and the wet residue were separated when the refractive index of a selected solution was Method/Apparatus/Procedure: constant in time. The content of La in the liquid phase was found by

The components in proper amounts were continuously mixed for 8 d. The titration with EDTA solution. The content of C18H16N3O2Cl was mother solution and the solid phase were analyzed: La by titration with determined by means of ultraviolet spectrophotometry, as in the study by ͓ ͑ ͒ ͑ ͔͒ EDTA solution, Cl by potentiometric titration with AgNO3 solution, and Cheng et al. Chem. Reagents in Chinese 19, 239 1997 . The C4H3FN2O2 by infrared spectrometry. After combustion of the compounds compositions of the solid phases were found by the method of A or B, a F-ion selective electrode was used for the determination of the Schreinemakers. F content. The compounds A–C were characterized by thermal analysis, thermogravimetry, x-ray diffraction, Fourier-transform infrared, and NMR Source and Purity of Materials: ͑ ͒ spectroscopy. Thermal analysis was performed in an Ar atmosphere with LaCl3 ·7H2O was prepared from La2O3 99.9 % pure and HCl solution / ␣ ͑ ͒ scan rate of 10 K min between 10 and 410 °C using Al2O3 as a analytically pure . Crystals of the product were recrystallized. reference. The compound B was dried with NaOH before the tests and C18H16N3O2Cl was prepared by the authors, as described by Cheng et al. was subjected to elemental analysis. ͓Chem. Reagents ͑in Chinese͒ 19, 239 ͑1997͔͒.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1845

Doubly distilled water was used. More experimental data related to the three systems are Estimated Error: included in the paper in barely readable ﬁgures. Solubility: nothing speciﬁed. Auxiliary Information Temperature: precision of Ϯ0.05 K ͑in the thermostat͒, precision of Ϯ ͑ ͒ 0.2 K in the refractometer . Method/Apparatus/Procedure: Mixtures were prepared from the components and equilibrated at isothermal conditions. Equilibrium was monitored by periodic measurements of the refractive indices of the solutions. It was found that the refractive index was constant after 22 d for glycine, 90 d for glutamic acid and 15 d for serine. After several days, the saturated solutions were 4.4.8. LaCl3–Amino acids–H2O Systems analyzed. The content of La was determined by titration with EDTA solution. The contents of glycine and serine were determined by the Components: Original Measurements: formaldehyde method. Content of glutamic acid was determined by ͑ ͒ 131 1 Lanthanum chloride; LaCl3; J.X. Chen, X.Q. Ran, Zh.Zh. pH-metric titration. Before analysis of the amino acids, La ion was ͓10099-58-8͔ Guo, and Y.Sh. Chen, Gaodeng masked by addition of the proper amount of K2C2O4 solution. Compounds ͑2͒ Glycine; aminoacetic acid; Xuexiao Huaxue Xuebao 11, 555 B, C, F, and H were characterized by molar conductivity in solution, ͓ ͔ ͑ ͒ C2H5NO2; 56-40-6 1990 . infrared spectroscopy, x-ray diffraction, thermogravimetry, and thermal ͑3͒ Glutamic acid; analysis of the solids. 2-amino-pentanedioic acid; ͓ ͔ Source and Purity of Materials: C5H9NO4; 56-86-0 ͑4͒ Serine; LaCl3 ·7H2O was prepared, as described in Ref. 118, by dissolution of ͑ ͒ 2-amino-3-hydroxypropionic La2O3 99.99 % pure in HCl solution and recrystallization. ͓ ͔ acid; C3H7NO3; 302-84-1 Glycine used was of analytical purity. ͑ ͒ ͓ ͔ 5 Water; H2O; 7732-18-5 Glutamic acid and serine used were “biological reagents.”

Variables: Prepared by: Estimated Error: Composition of mixtures C. Gumiński and D. Zeng Solubility: nothing speciﬁed. One temperature: 298 K Temperature: precision of Ϯ0.05 K.

Experimental Values Components: Original Measurements: ͑ ͒ 143 Composition of saturated solutions in the ternary LaCl3 −C2H5NO2 −H2O 1 Lanthanum chloride; LaCl3; J.R. Liu, M. Ji, Zh.J. Li, and system at 25 °C ͓10099-58-8͔ Sh.L. Gao, Xibei Daxue Xuebao, ͑2͒ L-serine; Ziran Kexueban ͑J. Northwest a a b 100w1 m1 100w2 m2 Equilibrium solid phase 2-amino-3-hydroxypropionic Univ., Nat. Sci. Edit.͒ 28͑1͒,44 ͓ ͔ ͑ ͒ acid; C3H7NO3; 56-45-1 1998 . 48.83 3.891 0 0 A ͑ ͒ ͓ ͔ 3 Water; H2O; 7732-18-5 49.40 4.369 4.50 1.30 A+B 23.47 2.283 34.65 11.01 C+D Variables: Prepared by: 0 0 19.99 3.328 D Composition of mixtures C. Gumiński and D. Zeng One temperature: 298 K amolalities calculated by the compilers b A=LaCl3 ·7H2O; B=LaCl3 ·C2H5NO2 ·H2O; C=LaCl3 ·3C2H5NO2 ·3H2O; D=C H NO 2 5 2 Experimental Values Composition of saturated solutions in the ternary LaCl −C H NO −H O 3 5 9 4 2 Composition of saturated solutions in the ternary LaCl −C H NO −H O system at 25 °C 3 3 7 3 2 system at 25 °C

a a b 100w1 m1 100w3 m3 Equilibrium solid phase a a b 100w1 m1 100w2 m2 Equilibrium solid phase 0 0 0.87 0.060 E 0 0 4.69 0.468 A 33.38 2.474 11.60 1.433 E+F 32.01 4.047 35.74 10.55 A+B 48.41 4.068 3.07 0.430 F+A 40.84 5.240 27.38 8.198 B+C amolalities calculated by the compilers 49.21 4.076 1.57 0.304 C+D b A=LaCl3 ·7H2O; E=C5H9NO4; F=LaCl3 ·3C5H9NO4 ·8H2O 48.83 3.891 0 0 D

a Composition of saturated solutions in the ternary LaCl3 −C3H7NO3 −H2O molalities calculated by the compilers system at 25 °C b A=C3H7NO3; B=LaCl3 ·2C3H7NO3 ·5H2O; C=LaCl3 ·C3H7NO2 ·3H2O;

a a b D=LaCl3 ·7H2O 100w1 m1 100w4 m4 Equilibrium solid phase

0 0 4.69 0.468 G The compounds B and C were found to be congruently 36.79 4.959 32.96 10.37 G+H soluble. More experimental results were presented in the pa- 49.04 4.025 1.28 2.45 H+A per in graphical form only. amolalities calculated by the compilers b A=LaCl3 ·7H2O; G=C3H7NO3; H=LaCl3 ·C3H7NO3 ·3H2O

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1846 MIODUSKI, GUMIŃSKI, AND ZENG

Auxiliary Information Composition of saturated solutions in the ternary LaCl3 –C9H11NO2 –H2O system at 25 °C Method/Apparatus/Procedure: a a a b The isothermal method with chemical and refractometric analyses of the 100w1 m1 100w2 m2 100w3 Equilibrium solid phase solutions was used. The samples of the system were investigated in semimicroscale using hundreds of milligrams of the solids and about 36.86 2.481 2.56 0.256 60.58 C 1cm3 of water. The components were placed in polyvinyl tubes which 35.18 2.320 2.99 0.293 61.83 C were continuously rotated. Equilibrium in the system was reached within 31.65 2.036 4.96 0.474 63.39 C 45 d, which was checked by periodic measurement of the refractive index 30.41 1.946 5.89 0.560 63.70 C of the solutions. Samples of the solutions were analyzed 2–3 d later. 27.25 1.765 9.85 0.948 62.90 C+D According to ͓Xibei Daxue Xuebao, Ziran Kexueban ͑J. Northwest Univ., 26.64 1.700 9.46 0.896 63.90 D Nat. Sci. Edit.͒ 26, 141 ͑1996͔͒, the content of La was determined by 23.72 1.401 7.23 0.634 69.05 D titration with EDTA solution. The content of serine was determined with formaldehyde addition and titration with NaOH solution when La was ﬁrst 20.05 1.091 5.01 0.405 74.94 D 18.24 0.963 4.52 0.354 77.24 D removed by precipitation with K2C2O4. The content of Cl was found by the method of Fayans. The equilibrium solid phases were determined by 18.15 0.956 4.45 0.348 77.40 D the method of Schreinemakers. The compounds B and C were 14.21 0.704 3.46 0.254 82.33 D characterized by chemical analysis, molar conductivity of their solutions, 10.86 0.514 3.05 0.214 86.09 D ultraviolet spectroscopy, x-ray diffraction, and thermogravimetric analysis. 7.08 0.320 2.83 0.190 90.09 D 2.41 0.103 1.96 0.124 95.63 D Source and Purity of Materials: ͓ 0 0 1.95 0.120 98.05 D LaCl3 ·7H2O was prepared, according to Gao et al. Xibei Daxue Xuebao, Ziran Kexueban ͑J. Northwest Univ., Nat. Sci. Edit.͒ 26, 141 ͑1996͒.͔,by amolalities calculated by the compilers ͑ ͒ b dissolution of La2O3 in HCl solution both analytically pure . The solution A=LaCl3 ·7H2O; B=LaCl3 ·C9H11NO2 ·6H2O; of LaCl3 obtained was placed in a closed KOH-dried container for 3–6 d, C=LaCl3 ·2C9H11NO2 ·6H2O; D=C9H11NO2 which caused the precipitation of LaCl3 ·7H2O. The composition of the product was checked by chemical analysis. The compounds B and C were found to be incongruently ͓ C3H7NO3 was, according to Gao et al. Xibei Daxue Xuebao, Ziran soluble. Kexueban ͑J. Northwest Univ., Nat. Sci. Edit.͒ 26, 141 ͑1996͔͒, biologic reagent. It was twice recrystallized and its ﬁnal purity was 99.5+%. Auxiliary Information

Estimated Error: Method/Apparatus/Procedure: Nothing speciﬁed. The system was investigated on semimicroscale. Equilibrium between the components was reached after 30 d, which was checked by periodic measurements of the refractive indices of the solutions. The content of La Components: Original Measurements: in the saturated solution was determined by titration with EDTA solution. The content of C H NO was determined by acidimetric titration with ͑1͒ Lanthanum chloride; LaCl ; 147F. Ren, Sh.L. Gao, and Q.Zh. 9 11 2 3 addition of formaldehyde; interference of La was previously masked by ͓10099-58-8͔ Shi, Xiamen Daxue Xuebao, precipitation with K C O . The content of water in the solids was ͑2͒ DL-phenylalanine; Ziran Kexueban ͑J. Xiamen 2 2 4 determined gravimetrically after evaporation to dryness at 72 °C. The 2-amino-3-phenylpropionic acid; Univ., Nat. Sci.͒ 39, 485 ͑2000͒. ͓ ͔ compounds B and C were characterized by chemical analysis, infrared C9H11NO2; 150-30-1 ͑ ͒ ͓ ͔ spectroscopy, and thermogravimetry. 3 Water; H2O; 7732-18-5 Source and Purity of Materials: Variables: Prepared by: LaCl ·7H O was prepared, according to the method described in Ref. 71, Composition of mixtures C. Gumiński and D. Zeng 3 2 by dissolution of La O in HCl solution. One temperature: 298 K 2 3 DL-C9H11NO2 was chromatographically pure. All other chemicals were of analytical purity. Experimental Values Estimated Error: Solubility: precision of analysis of ഛ0.2%. Composition of saturated solutions in the ternary LaCl3 –C9H11NO2 –H2O system at 25 °C Temperature: stability of Ϯ0.05 K.

a a a b 100w1 m1 100w2 m2 100w3 Equilibrium solid phase

48.83 3.891 0 0 51.17 A 48.07 3.854 1.08 0.129 50.85 A 4.5. Quaternary Systems 48.07 3.854 1.08 0.129 50.85 A+B 48.08 3.856 1.08 0.129 50.84 A+B 48.06 3.853 1.08 0.129 50.86 B Components: Original Measurements: ͑ ͒ 93 48.00 3.844 1.09 0.130 50.91 B 1 Lanthanum chloride; LaCl3; A.V. Nikolaev, A.A. Sorokina, 47.69 3.803 1.18 0.140 51.13 B+C ͓10099-58-8͔ N.G. Yudina, and V.N. Lubkova, ͑ ͒ 45.88 3.537 1.23 0.141 52.89 C 2 Cerium chloride; CeCl3; Izv. Sibir. Otd. Akad. Nauk ͓ ͔ ͑ ͒ 45.24 3.454 1.39 0.158 53.41 C 7790-86-5 SSSR, Ser. Khim. Nauk 5 ,35 ͑3͒ Europium chloride; EuCl ; ͑1972͒. 43.47 3.218 1.45 0.159 55.08 C 3 ͓10025-76-0͔ 41.43 2.966 1.61 0.171 56.96 C ͑ ͒ ͓ ͔ 4 Water; H2O; 7732-18-5 40.48 2.853 1.67 0.175 57.85 C

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1847

Variables: Prepared by: Composition of saturated solutions in the quaternary

Composition of salts T. Mioduski and C. Gumiński LaCl3 –CeCl3 –EuCl3 –H2O system at 25 °C One temperature: 298 K a 100x2 100x3 100x1 n4

Experimental Values 38.7 35.6 25.7 13.38 40.7 36.3 23.0 13.43 Composition of saturated solutions in the quaternary a ͑ ͒ LaCl3 –CeCl3 –EuCl3 –H2O system at 25 °C moles of water per mole of salts LaCl3 +CeCl3 +EuCl3

a 100x2 100x3 100x1 n4 The equilibrium solid phases in the system were not re-

78.1 0 21.9 13.90 ported. Phase diagrams indicated that a series of solid solu- 67.9 9.8 22.3 14.00 tions based on either EuCl3 hexahydrate or LaCl3 and CeCl3 64.7 16.3 19.0 13.97 heptahydrates was formed in the system. The same results 63.7 20.4 15.9 13.45 were reported in Ref. 54. 52.4 31.1 16.5 13.76 49.8 35.4 14.8 13.57 Auxiliary Information 47.5 34.3 18.2 13.58 56.6 0 43.4 13.83 Method/Apparatus/Procedure: 48.5 10.3 41.2 14.30 Isothermal equilibration with analysis of the saturated solutions and solids 54 46.5 15.6 37.9 14.26 was used. The salts were continuously pulverized and equilibrium with 44.7 21.2 34.1 13.81 the liquid phase was probably reached after 10–12 d. Samples of the phases were analyzed. Ce͑III͒ was oxidized to valence ͑IV͒ and then 40.2 30.9 28.9 13.40 titrated by Fe͑II͒ solution. Eu͑III͒ was reduced to valence ͑II͒ and then 37.7 36.7 25.6 13.69 ͑ ͒ titrated with K2Cr2O7 solution. The sum of the metals La+Ce+Eu was 36.7 36.0 27.3 13.66 determined by titration with EDTA. Eu and Ce were also determined by 26.1 0 73.9 13.87 atomic absorption spectroscopy. The contents of H2O and La were found 22.4 10.3 67.3 13.46 by difference. The composition of the solid phases was determined by the 21.5 15.9 62.6 13.83 method of Schreinemakers. 17.5 32.5 50.0 13.46 15.8 38.0 46.2 13.37 Source and Purity of Materials: 17.6 0 82.4 14.03 Chlorides of the metals were prepared by dissolving the corresponding oxides ͑99.9+% pure͒ in HCl solution ͑of special purity͒. The resulting 16.7 9.8 73.5 13.85 crystals were recrystallized from HCl solution and water and dried in air 13.9 23.6 62.5 13.60 at temperatures below 35 °C. The metal contents were determined by 12.4 34.8 52.8 13.64 titration with EDTA. The Cl content was determined by the Volhard 10.8 39.4 49.8 13.46 method. The water content was obtained by difference and “in some 10.6 41.5 47.9 13.50 cases” conﬁrmed by Karl-Fischer titration. 11.0 42.6 46.4 13.43 0 65.5 34.5 14.30 Estimated Error: 10.4 53.7 35.9 14.95 Solubility: precision of Ϯ3%. 19.0 47.7 33.3 13.49 Temperature: nothing speciﬁed. 27.8 37.7 34.5 13.27 39.0 35.3 25.7 13.47 39.4 35.5 25.1 13.64 Components: Original Measurements: ͑ ͒ 97 46.2 33.5 20.3 13.25 1 Lanthanum chloride; LaCl3; A.D. Sheveleva, K.I. Mochalov, 0 90.4 9.6 15.04 ͓10099-58-8͔ and N.A. Torgashina, Ucheb. 11.0 80.5 8.5 14.29 ͑2͒ Lithium chloride; LiCl; Zap. Perm. Univ. 289,15͑1973͒. ͓ ͔ 23.5 71.2 5.3 14.46 7447-41-8 ͑3͒ Potassium chloride; KCl; 28.7 59.6 11.7 13.94 ͓7447-40-7͔ 44.0 46.4 9.6 13.81 ͑4͒ Water; H O; ͓7732-18-5͔ 54.5 36.4 9.1 13.90 2 0 24.7 75.3 13.92 Variables: Prepared by: 9.5 22.2 68.3 16.12 Composition of salts T. Mioduski and C. Gumiński 16.5 21.1 61.4 13.12 Temperature: 293 and 323 K 23.7 21.9 54.4 13.77 33.5 22.3 44.2 13.47 38.6 21.9 39.5 13.40 43.9 18.6 37.5 13.44 0 48.3 51.7 13.87 10.0 38.8 51.2 13.30 17.9 38.1 44.0 13.13 23.7 37.3 39.0 13.37 29.6 39.1 31.3 13.46

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1848 MIODUSKI, GUMIŃSKI, AND ZENG

Experimental Values Components: Original Measurements: ͑ ͒ 115 Composition of saturated solutions in the quaternary 1 Lanthanum chloride; LaCl3; V.G. Shevchuk and Yu.V. LaCl –LiCl–KCl–H O system at 20 and 50 °C ͓10099-58-8͔ Shirai, Zh. Neorg. Khim. 25,843 3 2 ͑ ͒ ͑ ͒ 2 Ammonium chloride; NH4Cl; 1980 ; Russ. J. Inorg. Chem., / a a a b ͓12125-02-9͔ 25, 469 ͑1980͒. t °C 100w1 m1 100w2 m2 100w3 m3 Equilibrium solid phase ͑3͒ Sodium chloride; NaCl; 20 46.7 3.81 0 0 3.3 0.89 A+B ͓7647-18-5͔ 37.3 2.90 6.6 2.97 3.7 0.95 A+B ͑4͒ Potassium chloride; KCl; ͓ ͔ 24.2 1.76 16.1 6.78 3.7 1.56 A+B 7447-40-7 ͑ ͒ O; ͓7732-18-5͔ 18.0 1.27 20.3 8.26 3.7 0.86 A+B 5 Water; H2 13.8 0.93 22.7 8.85 3.0 0.67 A+B Variables: Prepared by: 9.6 0.65 27.4 10.77 3.0 0.67 A+B Salt composition in quaternary M. Salomon and C. Gumiński 7.8 0.53 28.5 11.11 3.2 0.71 A+B systems 6.4 0.43 30.2 11.72 2.6 0.57 A+B+C One temperature: 298 K 7.3 0.50 30.9 12.25 2.3 0.52 A+C 8.3 0.60 33.5 13.99 1.7 0.40 A+C 10.6 0.86 38.9 18.17 0 0 A+C Experimental Values 4.6 0.31 31.9 12.44 3.0 0.67 B+C Composition of saturated solutions in the quaternary 1.2 0.09 39.0 16.28 3.3 0.78 B+C LaCl –NH Cl–NaCl–H O system at 25 °C 0 0 44.4 19.95 3.1 0.79 B+C 3 4 2 50 49.0 4.44 0 0 6.0 1.79 A+B 100w m a 100w m a 100w m a Equilibrium solid phaseb 37.7 3.04 6.6 3.08 5.2 1.38 A+B 1 1 2 2 3 3 24.9 1.86 15.5 6.71 5.1 1.26 A+B 0 0 16.05 4.49 17.11 4.38 A+B 15.7 1.16 24.3 10.42 5.0 1.22 A+B 3.25 0.198 15.29 4.28 14.69 3.77 A+B 14.4 1.02 23.6 9.68 4.5 1.05 A+B 7.12 0.442 14.22 4.05 12.99 3.39 A+B 9.8 0.69 27.8 11.31 4.4 1.02 A+B 11.43 0.720 12.93 3.73 10.89 2.88 A+B 8.1 0.57 29.5 12.00 4.4 1.02 A+B 17.96 1.17 10.84 3.24 8.57 2.34 A+B 7.7 0.55 30.5 12.51 4.3 1.00 A+B+C 26.22 1.78 8.41 2.61 5.24 1.49 A+B 7.9 0.56 30.4 12.45 4.1 0.96 A+C 33.82 2.45 7.18 2.39 2.74 0.83 A+B 8.8 0.64 32.2 13.44 2.5 0.59 A+C 46.30 3.96 5.26 2.06 0.69 0.25 A+B+C 9.3 0.69 33.8 14.50 1.9 0.46 A+C 46.39 3.79 2.73 1.02 0.94 0.32 B+C 41.3 3.66 12.7 6.51 0 0 A+C 47.51 3.87 1.46 0.55 0.96 0.33 B+C 4.8 0.33 32.5 13.11 4.2 0.96 B+C 47.97 3.83 0 0 0.99 0.33 B+C 3.4 0.23 32.6 12.93 4.5 1.01 B+C 47.07 4.00 4.94 1.92 0 0 A+C 0 0 46.5 22.85 5.5 1.54 B+C amolalities calculated by the compilers a b molalities calculated by the compilers A=NH4Cl; B=NaCl; C=LaCl3 ·7H2O b A=LaCl3 ·7H2O; B=KCl; C=LiCl·H2O The authors claimed to conﬁrm precisely the solubility Two eutonic points were detected in the system. values for the ternary LaCl3 –NH4Cl–H2O and Auxiliary Information LaCl3 –NaCl–H2O systems obtained previously in Refs. 83 and 81, respectively; however, only a qualitative agreement Method/Apparatus/Procedure: The method of isothermal sections with refractometric analysis of the between the results may be observed. The quaternary system solutions was used. Mixtures of the salts and water were equilibrated until was found to be of eutonic type. their refractive indices remained constant. The compositions of the saturated solutions and the corresponding solid phases were found from break points on experimental plots of the refractive index versus composition. The compositions were conﬁrmed by standard chemical analyses at the eutonic compositions. The solid phases were also examined by microscopy.

Source and Purity of Materials: Nothing speciﬁed. The salts were probably recrystallized as in the previous papers published by the same laboratory.

Estimated Error: Nothing speciﬁed.

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1849

Composition of saturated solutions in the quaternary Experimental Values LaCl3 –NH4Cl–KCl–H2O system at 25 °C Composition of saturated solutions in the quaternary a a a b a 100w1 m1 100w2 m2 100w4 m4 Equilibrium solid phase LaCl3 –CsCl–HCl–H2O system at 25 °C

0 0 22.25 6.23 10.94 2.20 A+D b 100w3 100w1 100w2 Equilibrium solid phase 3.46 0.213 20.27 5.73 10.12 2.05 A+D 10.93 0.693 16.03 4.66 8.77 1.83 A+D 13 2.0 45.5 A 18.69 1.25 13.23 4.06 7.21 1.59 A+D 4.5 37.5 A 25.55 1.75 9.93 3.11 4.81 1.08 A+D 6.5 33.5 A 31.48 2.26 7.73 2.55 4.08 0.97 A+D 9.0 29.5 A 36.27 2.73 6.43 2.22 3.08 0.76 A+D 15.0 21.0 A 39.78 3.11 5.79 2.08 2.29 0.59 A+D 17.5 16.5 A 46.18 4.02 5.19 2.07 1.82 0.52 A+C+D 20.0 14.5 A+B 47.07 4.00 4.94 1.92 0 0 A+C 23.0 9.5 B 46.81 4.00 2.81 1.10 2.62 0.74 C+D 25.0 4.5 B 47.11 3.93 0.77 0.29 3.20 0.88 C+D 23 2.0 32.5 A 47.14 3.85 0 0 2.97 0.80 C+D 6.5 20.0 A+B 6.5 16.5 B a molalities calculated by the compilers 9.0 12.5 B b A=NH4Cl; C=LaCl3 ·7H2O; D=KCl 10.5 10.0 B 12.5 7.0 B+C The authors claimed to confirm precisely the solubility 11.5 4.0 C values for the ternary LaCl3 –NH4Cl–H2O and a the values related to the ternary LaCl3 –CsCl–H2O system were read from LaCl3 –KCl–H2O systems obtained previously in Ref. 83; figures ͑at 13 and 23 mass % HCl͒ by the compiler b however, only a qualitative agreement between the results A=LaCl3 ·3CsCl·3H2O; B=LaCl3 ·CsCl·4H2O; C=LaCl3 ·7H2O may be observed. The quaternary system was found to be of eutonic type. The compound A was found to be congruently soluble at 13 mass % HCl and incongruently soluble at 23 mass % Auxiliary Information HCl. The compound B was found to be incongruently Method/Apparatus/Procedure: soluble at 13 mass % HCl and congruently soluble at The isothermal method was employed. The liquid and solid phases 23 mass % HCl. reached equilibrium after continuous stirring in a thermostat for 10–13 d. La was determined by titration with EDTA. Alkaline-displaced ammonium Composition of saturated solutions in the ternary LaCl3 –CsCl–H2Osys- was determined by titration with an acid. Cl was determined by the a tem at 42 mass % C2H4O2 at 30 °C Volhard method. Na and K contents were found from the difference between the total Cl concentration and the sum of La3+ and NH +. Solid b 4 100w1 100w2 Equilibrium solid phase phases were estimated optically from microphotographs. 1.5 67.0 A+D Source and Purity of Materials: 7.0 54.0 A Chemically pure salts were twice recrystallized before use. 19.0 37.0 A Estimated Error: 28.0 27.0 A Nothing specified. 37.0 17.5 A+E 45.5 7.0 E 47.0 4.0 C+E

Components: Original Measurements: a the values in mass % related to the ternary system were read from a ﬁgure ͑1͒ Lanthanum chloride; LaCl ; 142Y.H. Li, X.Q. Ran, and P.H. 3 by the compiler ͓10099-58-8͔ Chen, J. Rare Earths 15͑2͒,113 b A=LaCl ·3CsCl·3H O; C=LaCl ·7H O; D=CsCl; ͑2͒ Cesium chloride; CsCl; ͑1997͒; Zhongguo Xitu Xuebao 3 2 3 2 ͓7647-17-8͔ 15͑2͒, 102 ͑1997͒. E=LaCl3 ·2CsCl·2H2O ͑3͒ Hydrochloric acid; HCl; ͓7647-01-0͔ The compound A was found to be congruently soluble. ͑ ͒ 4 Acetic acid; C2H4O2; The compound E was found to be incongruently soluble. ͓7647-01-0͔ ͑ ͒ ͓ ͔ 5 Water; H2O; 7732-18-5

Variables: Prepared by: Composition of mixtures C. Gumiński One temperature: 298 or 303 K

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 1850 MIODUSKI, GUMIŃSKI, AND ZENG

Auxiliary Information Composition of saturated solutions in the quaternary LaCl3 −CdCl2 −HCl −H2O system at 25 °C Method/Apparatus/Procedure: a Equilibration of the components in closed plastic containers, immersed in 100w1 100w2 100w3 Equilibrium solid phase a thermostat, was carried out for 3–4 d. Then acidity of the solutions was controlled by eventual addition of the corresponding acid to keep the 17.72 33.16 8.45 C acidity level constant. The mixtures were further equilibrated for 6–7 d 19.21 31.01 9.83 C and finally analyzed, as in the study by Wang et al. ͓Acta Chim. Sinica 19.41 30.96 9.76 C+D ͑ ͔͒ 52,789 1994 . The content of La in the liquid phase was determined by 20.07 30.27 9.38 C+D titration with EDTA solution. Content of Cl was determined by titration 19.42 30.32 9.72 C+D with AgNO solution using a fluorescence indicator. The content of each 3 19.61 30.84 9.61 C+D acid was determined by titration with NaOH solution using a methyl red 22.80 14.46 10.92 D indicator. The compositions of solid phases were estimated by the method of Schreinemakers. The compounds A, B, and E were characterized by 21.09 16.25 11.94 D x-ray diffraction, optical microscope observations, thermal analysis, and 20.09 22.39 11.31 D thermogravimetry. 16.93 29.75 11.87 D 25.30 6.04 12.11 D Source and Purity of Materials: 27.79 0 12.13 D LaCl3 ·7H2O was prepared by dissolution of La2O3 in HCl solution. The a reaction product recrystallized and its composition was confirmed by A=CdCl2 ·H2O; B=LaCl3 ·8CdCl2 ·16H2O; C=LaCl3 ·CdCl2 ·12H2O; chemical analysis. D=LaCl3 ·7H2O CsCl, HCl, and C2H4O2 were analytically pure, as in the study by Wang et al. ͓Acta Chim. Sinica 52,789͑1994͔͒. The compounds B and C were found to be congruently Estimated Error: soluble. Solubility: nothing specified; reading-out procedure of Ϯ0.5 mass %. Auxiliary Information Temperature: nothing specified. Method/Apparatus/Procedure: Components: Original Measurements: Mixtures of the components were prepared to keep HCl content at the 148 level of 9–10 mass %. The mixtures were closed in polyethylene tubes ͑1͒ Lanthanum chloride; LaCl ; L. Li, H. Wang, Sh.P. Xia, M.Ch. 3 and equilibrated with stirring at the selected temperature for 7–8 d. ͓10099-58-8͔ Hu, and Sh.Y. Gao, Wuji Huaxue Xuebao Then HCl concentration was controlled and adjusted to about ͑2͒ Cadmium chloride; CdCl ; 19,201͑2003͒. 2 10 mass %. The mixtures were again equilibrated for 7–8 d. The ͓10108-64-2͔ equilibrium liquid and solid wet phases were taken to analysis. The ͑3͒ Hydrochloric acid; HCl; content of HCl was determined by titration with NaOH standard solution ͓7647-01-0͔ using a methyl red indicator. The content of the sum ͑La+Cd͒ was ͑4͒ Water; H O; ͓7732-18-5͔ 2 determined by titration with EDTA solution using a dimethyl orange Variables: Prepared by: indicator. The content of Cd was determined by titration with EDTA Composition of mixtures C. Gumiński and D. Zeng solution after sequestering La with addition of NaF. The content of La One temperature: 298 K was found by difference. The composition of solids was found by the method of Schreinemakers and was confirmed by chemical analysis. The compounds B and C were characterized by x-ray diffraction, Experimental Values thermogravimetry, and DSC. Source and Purity of Materials: Composition of saturated solutions in the quaternary LaCl −CdCl −HCl 3 2 ͓ ͑ −H O system at 25 °C LaCl3 ·7H2O, as described by Wang Huaxue Xuebao Acta Chim. 2 ͒ ͑ ͔͒ ͑ Sinica 52, 789 1994 , was prepared by dissolution of La2O3 99.9% pure͒ in HCl solution. The reaction product was recrystallized and its 100w 100w 100w Equilibrium solid phasea 1 2 3 composition was checked. 0 50.06 9.23 A All other chemicals were analytically pure. 2.09 48.31 7.12 A Doubly distilled water was used. 2.29 46.78 8.88 A Estimated Error: 2.55 44.88 9.26 B Nothing specified. 3.39 46.81 9.13 B 3.34 47.56 8.42 B 4.60 46.31 8.86 B Components: Original Measurements: ͑ ͒ 149 4.81 43.54 9.27 B 1 Lanthanum chloride; LaCl3; Zh.P. Qiao, L.H. Zhuo. ͓ ͔ 5.67 41.95 9.71 B 10099-58-8 Sh.Sh. Zhang and H. Wang, ͑ ͒ ͓ ͔ 6.87 44.00 8.86 B 2 Zinc chloride; ZnCl2; 7646-85-7 Wuji Xuaxue Xuebao 19,303 ͑3͒ Hydrochloric acid; HCl; ͓7647-01-0͔ ͑2003͒. 7.33 43.24 8.92 B ͑4͒ Water; H O; ͓7732-18-5͔ 8.90 41.97 8.72 C 2 7.90 40.85 9.34 C Variables: Prepared by: 7.50 41.03 9.19 C Composition of mixtures C. Gumiński and D. Zeng 10.42 39.30 9.54 C One temperature: 298 K 11.31 38.96 9.37 C 14.05 33.88 10.36 C

J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008 IUPAC-NIST SOLUBILITY DATA SERIES. 87 1851

Experimental Values 5. Cumulative References

1 Composition of saturated solutions in the quaternary LaCl3 −ZnCl2 −HCl H. Stephen and T. Stephen, Solubilities of Inorganic and Organic Com- ͑ ͒ −H2O system at 25 °C pounds Pergamon, Oxford, 1979 . 2 J. Burgess and J. Kijowski, Adv. Inorg. Chem. Radiochem. 24,57 ͑ ͒ 100w 100w 100w Equilibrium solid phasea 1981 . 1 2 3 3 Gmelins Handbook ͑Springer-Verlag, Berlin, 1982͒, Vol. 39, P. C4a. 4 33.02 0 8.08 A S. Siekierski, T. Mioduski, and M. Salomon, IUPAC Solubility Data Se- ries ͑ ͒ 31.70 5.03 7.26 A Pergamon, Oxford, 1983 , Vol. 13. 5 T. Mioduski, Chem. Anal. ͑Warsaw͒ 43, 457 ͑1998͒. 25.80 12.99 9.06 A 6 T. Mioduski, J. Radioanal. Nucl. Chem. 128, 351 ͑1988͒. 28.93 15.60 6.41 A 7 H. Miyamoto, Current Topics Sol. Chem. 1,81͑1994͒. 23.88 26.17 7.72 A 8 T. Mioduski ͑unpublished͒. 25.14 27.65 7.24 A 9 T. Mioduski and M. Salomon, IUPAC Solubility Data Series ͑Pergamon, 26.73 28.49 6.10 A+B Oxford, 1985͒, Vol. 22. 10 ͑ ͒ 23.45 30.32 7.45 B N. P. Sokolova, Radiokhimiya 30,435 1988 . 11 G. Reuter, H. Fink, and H. J. Seifert, Z. Anorg. Allg. Chem. 620,665 23.91 32.84 7.08 B ͑1994͒. 25.80 35.69 6.25 B 12 C. Gumiński, Arch. Metall. Mater. 51, 617 ͑2006͒. 24.75 34.75 6.31 B+C 13 F. Teixeira da Silva, Trans. Inst. Min. Metall., Sect. C 114,C70͑2005͒. 23.18 35.49 6.82 C 14 W. Rafalski and K. Jonak, Przem. Chem. 48, 735 ͑1969͒. 15 16.86 39.03 9.27 C J. W. Lorimer and R. Cohen-Adad, in The Experimental Determination of ͑ 11.50 45.37 9.61 C Solubilities, edited by G. T. Hefter and R. P. T. Tomkins Wiley, Chich- ester, 2003͒,p.19. 8.94 56.62 7.95 C 16 J. Harkot, Pol. J. Chem. 63, 337 ͑1989͒. 10.33 57.12 7.63 C 17 J. Harkot, Pol. J. Chem. 64,53͑1990͒. 12.16 56.74 7.15 C+D 18 F. H. Spedding, J. A. Rard, and V. Saeger, J. Chem. Eng. Data 19,373 13.34 55.73 7.34 D ͑1974͒. 19 12.47 57.00 7.33 D L. G. Sillen and A. Martell, The Chemical Society Special Publication 10.27 59.44 7.55 D No. 17, 1964; The Chemical Society Special Publication No. 25, 1971. 20 C. S. Oakes, J. A. Rard, and D. 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Chem. Commun. 25,1143 1960 . 29 F. Petru, J. Hradilova, and B. Hajek, Collect. Czech. Chem. Commun. by the authors. The solution samples were checked for HCl content and 33, 2720 ͑1968͒. HCl concentration was eventually regulated. The system was further 30 W. Crookes, Philos. Trans. R. Soc. London, Ser. A 209,15͑1908͒. equilibrated with mixing for 12–13 d. After a further 3 d, the mother 31 I. V. Arkhangelskii, L. N. Komissarova, V. M. Shatskii, and N. P. solution was sampled, weighed, transferred to a calibrated container, and Shepelev, Zh. Neorg. Khim. 17, 310 ͑1972͒. analyzed. The content of HCl was determined by titration with NaOH 32 G. A. Melson, D. J. Olszanski, and A. K. Rahimi, Spectrochim. Acta, Part solution using methyl red and bromomethyl green indicators. The A 33, 301 ͑1977͒. content of the sum ͑La+Zn͒ was determined by titration with EDTA 33 S. V. Aleksandrovskii, Zh. Prikl. Khim. ͑S.-Peterburg͒ 70,1761͑1997͒. solution. The content of Zn in another sample was determined after La 34 K. H. Schröder, Thesis, Univ. of Münster, Germany, 1955, as quoted in was sequestered with addition of NaF. Then the content of La was found Ref. 3. by difference. The content of Cl was determined by titration with 35 Aldrich 2007–2008 Handbook of Fine Chemicals ͑Sigma-Aldrich, St. AgNO3 solution by the method of Fayans. Solid phases were identified Louis, 2007͒, p. 2170. by the method of Schreinemakers. The compound B was characterized 36 M. C. Crew, H. E. Steinert, and B. S. Hopkins, J. Phys. Chem. 29,34 by x-ray diffraction. ͑1925͒. 37 M. D. Williams, H. C. Fogg, and C. James, J. Am. Chem. Soc. 47,297 Source and Purity of Materials: ͑1925͒. 38 LaCl ·7H O was prepared, according to Wang et al. ͓Huaxue Xuebao J. E. Powell, US Atomic Energy Commission Report No. IS-15, 1959. 3 2 39 ͑Acta Chim. Sinica͒ 52, 789 ͑1994͔͒, from La O ͑99.9% pure͒ which Z. N. Shevtsova and I. Vei-Tszyuan, Zh. Neorg. Khim. 8, 1749 ͑1963͒. 2 3 40 was dissolved in HCl ͑analytically pure͒ solution. The product was A. V. Nikolaev, A. A. Sorokina, and V. G. Tsubanov, Dokl. Akad. Nauk ͑ ͒ recrystallized and its composition was confirmed by analysis. SSSR 172, 1333 1967 . 41 A. V. Nikolaev, A. A. Sorokina, A. Ya. Vilenskaya, and V. G. Tsubanov, All other chemicals used were of analytical purity. Izv. Sibir. Otd. Akad. Nauk SSSR, Ser. Khim. Nauk ͑6͒,5͑1967͒. 42 Estimated Error: Z. N. Shevtsova, L. S. Nam, and B. G. Korshunov, Zh. Neorg. Khim. 13, 1682 ͑1968͒. Nothing specified. 43 V. S. Petelina, N. I. Nikurashina, and G. V. Illarionova, Issledovaniya v Oblasti Khimii Redkozemelnykh Elementov, Saratovskii Universitet, Sa- ratov 3,48͑1971͒. 44 A. V. Nikolaev and A. A. Sorokina, Izv. Sibir. Otd. Akad. Nauk SSSR,

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