Anhydrous halides, preparation

The reactions with water are summarised in Table 6.3. Since the metals are powerful reducing agents (p. 98) they cannot be prepared in aqueous solution electrolysis of the fused anhydrous halides is usually employed using a graphite anode. 

Metallic Sr can be prepared by methods similar to those used for Ca manufacture (sec 7.2.3.3.1). Thus thermal reduction of SrO using A1 and electrolysis of anhyd SrCU both yield pure Sr. Reduction of SrO by CH4 is also successful on a pilot scale. Metallic Ba is produced by thermal reduction of BaO by Al alternative reducing agents arc Na, Mg, Si and FeSi. Electrolysis of fused anhydrous halides (c.g., BaCK) is not applicable since the reaction yields a subhalide rather than the pure metal. 

Rowley, A. T. et al., Inorg. Chem. Acta, 1993, 211(1), 77 Preparation of metal oxides by fusing metal halides with lithium oxide in a sealed tube leads to explosions if halide hydrates are employed, particularly lanthanide trihalide hydrates. The preparation succeeds with anhydrous halides. This will be purely a question of vapour pressure above an exothermic reaction the question is whether the vapour is water, or metal halide, and the reaction oxide formation, or hydration of lithium oxide. Like other alkali metal oxides, hydration is extremely energetic. 

This is similar to the behavior of aluminum halides discussed earlier in this chapter, and it illustrates the fact that dehydration of a hydrated solid cannot be used as a way to prepare anhydrous halide compounds in some instances. 

No, the editor didn t know what this name meant either.) It means salts of the triva-lent anions of Group V, restricted in [1] to arsenides, antimonides and bismuthides and prepared by reaction of sodium pnictides with anhydrous halides of transition and lanthanide metals. This violently exothermic reaction may initiate as low as 25°C. Avoidance of hydrated halides is cautioned since these are likely to react uncontrollably on mixing. Another paper includes a similar reaction of phosphides, initiated by grinding [2], Nitrides are reported made from the thermally initiated reaction of sodium azide with metal halides, a very large sealed ampoule is counselled to contain the nitrogen [3],... 

Praesodymium metal can be obtained from its anhydrous halides by reduction with calcium. The metal also may be prepared by electrolysis of fused praesodymium chloride at elevated temperatures (about 1,000°C). Alternatively, an eutectic mixture of praesodymium chloride, potassium chloride, and sodium chloride may be electrolyzed. In such electrolysis graphite is the anode and tungsten the cathode. 

The anhydrous halides are also prepared by the methods in Section 35.3.7. 

These have been known for many years.1052-1054 Chromium(III) is approximately octahedral ( ie(f = 3.69-4.1 BM) the compounds have a layer structure. In the chloride, r(Cr—Cl) is 5.76 A between layers and 3.46 A within layers. The iodide is isomorphous with the chloride and the bromide has a similar but distinct structure. All may be prepared by the direct halogenation of the metal. Other methods are available, e.g. CrCl3 may be prepared by heating Cr203-xH20 in CCU vapour at 650 °C.1055 The anhydrous halides are insoluble in water, however reducing agents such as zinc catalyze dissolution. The trichloride reacts with liquid ammonia to form ammine complexes. 

The preparation of the anhydrous halides of vanadium is possible only in the dry way, since attempts to remove the water from the hydrated halide result in the formation of a basic salt, as in the cases of the halides of iron, chromium, aluminium, bismuth, etc. The general methods of preparation employed are ... 

The hydrated trihalides of the rare earths are easily obtained by reacting the oxides with appropriate HX acid solution. Anhydrous halides are, however, difficult to prepare. Attempts to dehydrate the hydrated halides usually result in oxyhalides. In the case of the chlorides and bromides... 

Various methods [282] have been used to prepare anhydrous chlorides of the rare earths. Taylor and Carter [283] describe a general method for the preparation of high purity anhydrous halides in good yield. This method involves heating in vacuo, a molecularly dispersed mixture of hydrated rare earth halide with proper ammonium halide until the water and ammonium halide are expelled. All the trihalides except the iodides of Sm and Eu can be obtained using this proceedure. In the case of Sm and Eu the divalent iodides, Sml2 and Eul2 are obtained. 

Unlike the other zinc halides, zinc fluoride, Znp2, is only slightly soluble in cold water. The anhydrous halides are prepared by direct union of the elements, In solution, zinc chloride, bromide, and iodide exhibit anomalous conductance properties attributed to undissodated molecules and complex ions. On heating these solutions, halogen acids, HX, are evolved, leaving... 

The usual synthetic routes to the halo type cluster compounds begin with preparation of the anhydrous halides. The preparation of Mo6C1i2, a yellow, nonvola-... 

Covalent hahdes can be prepared by various synthetic routes. The simplest are direct reactions of elemental halogens (equation 9), or hydrogen halides with elements (equation 10) or oxides (equation 11). In other processes, the oxides are reacted with a halogen halide in the presence of carbon to combine with the oxygen (equation 12) or other reactive carbon-halides (equation 13). Exchange of halogens can also take place (equations 14 16). Anhydrous halides can also be obtained by dehydration of metal halide hydrates, using reactants such as thionyl halide, which react with the hydrated water (equation 17). 

DMSO) complexes (18) are relatively unstable toward oxidative decomposition. The known complexes are listed in Table X, together with infrared data, and are compared with the complexes formed by other actinide halides in Table XI. The protactinium(IV) complexes have been prepared by reacting the anhydrous halide with the appropriate ligand in nonaqueous, oxygen-free solvents such as methylene dichloride, chloroform, or methyl cyanide. 

The absorption of ammonia by many solid halides has been known for a long time. The products vary widely in composition and stability. For example, CaCl2. 8 NH3 and CUCI2. 6 NH3, prepared from the anhydrous halides and ammonia gas, readily lose ammonia, but many other amminohalides may be prepared from ammoniacal salt solutions and some possess considerable stability. The simplest compounds of this type have the general formula MX . mNH3 (with sometimes water of crystallization), where m is the normal coordination number of M. They contain complex ions M(NH3), and X" ions. Typical ions of this sort are Ag(NH3)2,... 

Metallurgy. — The metals of most of the cerium group elements have been prepared, three general methods having been used t (1) fusion of the anhydrous halides with sodium, potassium, calcium, or aluminium (2) electrolysis of the fused chlorides or of a solution of the oxide in the molten fluoride (3) heating the oxides with magnesium, calcium, or silicon. Reduction with aluminium has also been tried, but it is not satisfactory except possibly for cerium itself. Electrolysis has been the most successful, the other methods usually giving at best an alloy. 

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