Matrix isolation technique for the study of some factors affecting the partitioning of trace elements

Some of the factors that affect the preferred positions of cations in ionic-solid solutions were investigated utilizing vibrational spectroscopy. Solid solutions of the sulfate and chromate ions codoped with La³⁺ and Ca²⁺ in a KBr host lattice were examined as a function of the polyvalent-cation concentration. The cation—anion pairing process was found to be random for Ca²⁺ whereas the formation of La³⁺SO₄^2? ion-pairs with a C_2v bonding geometry is highly preferential to any type of La³⁺CrO₄^2? ion-pair formation. The relative populations of ion-pair site configurations are discussed in terms of an energy—entropy competition which can be applied to the partition of trace elements during magmatic processes.