The extraction of anionic complexes of divalent manganese,cobalt, nickel and copper from aqueous thiocyanate solutions by tricaprylmethylammonium chloride

The extraction of divalent manganese, cobalt, nickel and copper-thiocyanato anionic species from aqueous solutions by tricaprylmethylammonium chloride (R₃R′NCl) in benzene has been investigated under different conditions. Both the aqueous and organic phases have been examined by spectrophotometry. Infrared spectro-photometry and measurements of water content, apparent molecular weight and magnetic moment have been applied to the organic extracts, and electron spin resonance experiments to the organic manganese(II)- and copper(II)-complexes. The mechanism of the extractions and the structures of the extracted complexes are discussed on the basis of the results obtained. As a result, it is found that although the extraction efficiency follows the order Co > Cu > Mn > Ni, the extraction of divalent transition metals is expressed as [M(NCS)₄]²-(aq) + 2R₃R′NNCS(org)→(R₃R′N)₂-[M(NCS)₄](org) + 2NCS-(aq) in which M = Mn, Co, Ni and Cu. The extracted species of divalent manganese, cobalt and nickel give a tetrahedral T_d symmetry, and the copper(II) species is in a distorted tetrahedron (point group D_2d symmetry). In addition the species of nickel (II) extracted at low aqueous concentration exists as a complex (R₃R′N)₂[Ni(NCS)₄(H₂O)₂] in an octahedral arrangement.