Lanthanide salt solubility

Originally, general methods of separation were based on small differences in the solubilities of their salts, for examples the nitrates, and a laborious series of fractional crystallisations had to be carried out to obtain the pure salts. In a few cases, individual lanthanides could be separated because they yielded oxidation states other than three. Thus the commonest lanthanide, cerium, exhibits oxidation states of h-3 and -t-4 hence oxidation of a mixture of lanthanide salts in alkaline solution with chlorine yields the soluble chlorates(I) of all the -1-3 lanthanides (which are not oxidised) but gives a precipitate of cerium(IV) hydroxide, Ce(OH)4, since this is too weak a base to form a chlorate(I). In some cases also, preferential reduction to the metal by sodium amalgam could be used to separate out individual lanthanides. 

No product was formed in this reaction in the absence of the soluble lanthanide salt or even in the presence of CeCL. Heteroaryl Grignard reagents react smoothly in the presence of LaCl3 2LiCl even with highly sterically hindered ketones like 211 (equation 137). 

The dehydration of lanthanide perchlorates to obtain the anhydrous salt has been studied [13-15]. Lighter lanthanide perchlorate lose the water of hydration readily at 200°C under vacuum while the heavier lanthanide salts produced insoluble basic salts. Anhydrous heavier lanthanide perchlorates have been obtained by extraction with anhydrous acetonitrile. Utmost precaution should be exercised in the purification of lanthanide perchlorate, since the mixture of lanthanide perchlorate and acetonitrile can lead to an explosion. An alternate approach involves the addition of triethylorthoformate to the mixture or refluxing the solvent through a Soxhlet extractor packed with molecular sieves [3], In view of the hazardous nature of perchlorates, alternate materials such as lanthanide trifluoromethane sulfonates have received some attention. Lanthanide triflates are thermally stable, soluble in organic solvents, unreactive to moisture and are weak coordinating agents. Triflic acid is stronger than perchloric acid [17]. Lanthanide perchlorates and triflate have the same reduction potentials in aprotic solvents and the dissociation of the triflates is less than the perchlorates in acetonitrile [17],... 

In the context of replacing conventional Lewis acids in organic synthesis it is also worth pointing out that an alternative approach is to use lanthanide salts [39] that are both water soluble and stable towards hydrolysis and exhibit a variety of interesting activities as Lewis acids (see later). 

Different forms of lanthanide differ in their toxicity. There are three forms of lanthanides soluble (chlorides, nitrates, acetates), insoluble (oxides, carbonates), and chelated compounds (DTPA). Most of the available information on lanthanide absorption and toxicity comes from the soluble lanthanide salts. In one study, rats given DTPA (chelating agent) 1 or 2 days after oral administration of cerium chloride were found to have significantly reduced whole body retention of soluble cerium (from 40% to 2%). 

The soluble lanthanide salts (e.g., chlorides, nitrates, and acetates) can be severely irritating to the skin, eye, and mucous membranes. The irritation appears to be a result of exposure to the anion (e.g., nitrate) and not the lanthanide cation. 

The solubility of simple rare earth (lanthanide) salts depends strongly on the anion. Thus all the rare earth chlorides, perchlorates, carbonates and nitrates have high solubility. In these solutions the rare earths readily form species of the form [Ln(H20)J ", meaning that in solution the rare earth ion is not coordinated, but does have a sphere of water molecules, the waters of hydratioa The majority of the lanthanides exist as [Ln(HjO)J in solution, with the exceptions of cerium which can exist as Ce"", and Sm, Eu and Yb which can exist as Ln ion in solution. These lanthanides along with Pr can have mixed oxidation states in solids. Practically, from the perspective of abundance, only La, Ce, Pr and perhaps Nd are likely candidates for inhibitors. Of these, only Ce has two oxidation states that can exist in aqueous solution, namely Ce and Ce . ... 

It is not clear when dithiocarbamates were first prepared, but certainly they have been known for at least 150 years, since as early as 1850 Debus reported the synthesis of dithiocarbamic acids (1). The first synthesis of a transition metal dithiocarbamate complex is also unclear, however, in a seminal paper in 1907, Delepine (2) reported on the synthesis of a range of aliphatic dithiocarbamates and also the salts of di-iTo-butyldithiocarbamate with transition metals including chromium, molybdenum, iron, manganese, cobalt, nickel, copper, zinc, platinum, cadmium, mercury, silver, and gold. He also noted that while dithiocarbamate salts of the alkali and alkali earth elements were water soluble, those of the transition metals and also the p-block metals and lanthanides were precipitated from water, to give salts soluble in ether and chloroform, and even in some cases, in benzene and carbon disulfide. 

Solid Compounds. The tripositive actinide ions resemble tripositive lanthanide ions in their precipitation reactions (13,14,17,20,22). Tetrapositive actinide ions are similar in this respect to Ce . Thus the duorides and oxalates are insoluble in acid solution, and the nitrates, sulfates, perchlorates, and sulfides are all soluble. The tetrapositive actinide ions form insoluble iodates and various substituted arsenates even in rather strongly acid solution. The MO2 actinide ions can be precipitated as the potassium salt from strong carbonate solutions. In solutions containing a high concentration of sodium and acetate ions, the actinide ions form the insoluble crystalline salt NaM02(02CCH2)3. The hydroxides of all four ionic types are insoluble ... 

The chlorides, bromides, nitrates, bromates, and perchlorate salts ate soluble in water and, when the aqueous solutions evaporate, precipitate as hydrated crystalline salts. The acetates, iodates, and iodides ate somewhat less soluble. The sulfates ate sparingly soluble and ate unique in that they have a negative solubitity trend with increasing temperature. The oxides, sulfides, fluorides, carbonates, oxalates, and phosphates ate insoluble in water. The oxalate, which is important in the recovery of lanthanides from solutions, can be calcined directly to the oxide. This procedure is used both in analytical and industrial apptications. 

The lanthanides form many compounds with organic ligands. Some of these compounds ate water-soluble, others oil-soluble. Water-soluble compounds have been used extensively for rare-earth separation by ion exchange (qv), for example, complexes form with citric acid, ethylenediaminetetraacetic acid (EDTA), and hydroxyethylethylenediaminetriacetic acid (HEEDTA) (see Chelating agents). The complex formation is pH-dependent. Oil-soluble compounds ate used extensively in the industrial separation of rate earths by tiquid—tiquid extraction. The preferred extractants ate catboxyhc acids, otganophosphoms acids and esters, and tetraaLkylammonium salts. 

Fra.ctiona.1 Precipituition. A preliminary enrichment of certain lanthanides can be carried out by selective precipitation of the hydroxides or double salts. The lighter lanthanides (La, Ce, Pr, Nd, Sm) do not easily form soluble double sulfates, whereas those of the heavier lanthanides (Ho, Er, Tm, Yb, Lu) and yttrium are soluble. Generally, the use of this method has been confined to cmde separation of the rare-earth mixture into three groups light, medium, and heavy. 

The classical methods used to separate the lanthanides from aqueous solutions depended on (i) differences in basicity, the less-basic hydroxides of the heavy lanthanides precipitating before those of the lighter ones on gradual addition of alkali (ii) differences in solubility of salts such as oxalates, double sulfates, and double nitrates and (iii) conversion, if possible, to an oxidation state other than -1-3, e g. Ce(IV), Eu(II). This latter process provided the cleanest method but was only occasionally applicable. Methods (i) and (ii) required much repetition to be effective, and fractional recrystallizations were sometimes repeated thousands of times. (In 1911 the American C. James performed 15 000 recrystallizations in order to obtain pure thulium bromate). 

Most lanthanide compounds are sparingly soluble. Among those that are analytically important are the hydroxides, oxides, fluorides, oxalates, phosphates, complex cyanides, 8-hydroxyquinolates, and cup-ferrates. The solubility of the lanthanide hydroxides, their solubility products, and the pH at which they precipitate, are given in Table 2. As the atomic number increases (and ionic radius decreases), the lanthanide hydroxides become progressively less soluble and precipitate from more acidic solutions. The most common water-soluble salts are the lanthanide chlorides, nitrates, acetates, and sulfates. The solubilities of some of the chlorides and sulfates are also given in Table 2. 

This expression has been written in terms of concentration if activity coefficients sue known or estimated, then a thermodynamically ideal solubility product may be obtained from the Emalogous product of ionic activities. As the concentration of ions in solutions of lanthanide fluorides is low, the concentration and activity solubility products will not differ markedly, although activity coefficients for these salts of 3 + cations are significantly less than unity even in such dilute solutions (4a). 

There have been many determinations of solubility products for lanthanide fluorides over the years. We shall try to show the range of values presented for a given element, as well as the chemically important variation of solubility with the nature of the metal. Values for aqueous solution will be reviewed first, then the effects of added acid or salts on solubility considered. 

Comparisons of solubilities of trichlorides, tribromides, and triiodides of the lanthanides in a variety of nonaqueous solvents can be found in a Russian review (310). Perhaps the widest range of solubilities of lanthanide(III) salts in nonaqueous media refers not to the trihalides but to the nitrates, whose solubilities in 31 solvents have been measured (312). Unfortunately, these measurements were carried out on the hexahydrates rather than anhydrous materials. 

Strictly, the solubilities of salt hydrates in nonaqueous solvents, and of lanthanide trichlorides in 97% ethanol, mentioned in Section V,B,2,a,... 

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