Double complex salts precipitation

The Complex Thiocyanates.—The alkali thiocyanates show a marked tendency to form double and complex salts with the thiocyanates of other metals. The double salts in general resemble in type the double halides. Such compounds as KAg(CNS)2 and K2Ag(CNS)3 may be considered as derivatives of di- and tri-thiocyanic acids, but in the salt (NH4)6Ag(CNS)6 the silver is not precipitated by the addition of chloride ion.8... 

Classical methods of separation [7] are (1) fractional crystallization, (2) precipitation and (3) thermal reactions. Fractional crystallization is an effective method for lanthanides at the lower end of the series, which differ in cation radius to a large extent. The separation of lanthanum as a double nitrate, La(N03)3-2NH4N03-4H20, from praseodymium and other trivalent lanthanide with prior removal of cerium as Ce4+ is quite a rapid process and is of commercial significance. Other examples are separation of yttrium earths as bromates, RE(Br03>9H20 and use of simple nitrates, sulfates and double sulfate and alkali metal rare earth ethylenediamine tetraacetate complex salts in fractional crystallization separation. 

In aqueous solutions, calcium chloride undergoes double decomposition reactions with a number of soluble salts of other metals to form precipitates of insoluble calcium salts. For example, mixing solutions of calcium chloride with sodium carbonate, sodium tungstate and sodium molybdate solutions precipitates the carbonates, tungstates, and molybdates of calcium, respectively. Similar precipitation reactions occur with carboxylic acids or their soluble salt solutions. CaCb forms calcium sulfide when H2S is passed through its solution. Reaction with sodium borohydride produces calcium borohydride, Ca(BH4)2. It forms several complexes with ammonia. The products may have compositions CaCl2 2NH3, CaCb dNHs, and CaCb SNHs. 

Coprecipitation of the metals is usually achieved from an aqueous solution of nitrates upon addition of anions such as carbonates, citrates, or oxalates (10)(24-27). First reports in this field have underlined the necessity to neutralize the pH of the solution in order to obtain complete precipitation of barium or strontium. Also, oxalate or citrate ligands may bind to two different cations. This should allow a better mixing at a microscopic level. However, care should be taken since some cations such as Y or La may precipitate as double salt complexes with alkaline ions that have been added to the solution as hydroxides in order to control the pH (24). 

Thiosulphates.—The salts of thiosulphuric acid, with the exception of those of the alkali metals, are sparingly soluble in water but are commonly much more soluble in an aqueous solution of an alkali thiosulphate, soluble double salts being formed in which the heavier metal is probably situated in a complex acidic radical hence, on the addition of a solution of alkali thiosulphate to a salt of a heavy metal, the precipitate of the thiosulphate of the metal is generally soluble in excess. 

Potassium Vanadicyanide, K3[V(CN)6], is prepared by the addition of excess of concentrated potassium cyanide solution to a concentrated solution of vanadous chloride, VC18 precipitation in the cold with alcohol gives rise to small rhombohedral plates. The solution is not very stable and rapidly becomes turbid, while addition of an acid produces the green colour which is characteristic of the V ion. The complex ion [V(CN)8]" appears, therefore, to be unstable, unlike the corresponding [Fe(CN)e] ", [Cr(CN)J ", and [Co(CN)e] " complex ions. The solution reacts with salts of heavy metals to yield variously coloured precipitates of double cyanides.7... 

---