Infrared and Raman spectra of magnesium ammonium phosphate hexahydrate (struvite) and its isomorphous analogues. Part VI: FT-IR spectra of isomorphously isolated species. [formula omitted] ions isolated in MKPO 4·6H 2O (M = Mg; Ni) and [formula omitted] ions isolated in MgNH 4AsO 4·6H 2O

Abstract

Examination of mixed crystals, especially those with isomorphously isolated ions, has proved very useful in spectra-structure correlation studies. Room (RT) and low temperature (LNT) FT-IR spectra of ammonium doped in MgKPO 4·6H 2O and NiKPO 4·6H 2O and phosphate doped in MgNH 4AsO 4·6H 2O in different degrees were recorded. All three compounds are isostructural with struvite, MgNH 4PO 4·6H 2O, space group Pmn2 1, forming substitutional mixed crystals with C s symmetry of the anions. Analysis of the region of ν 4(NH 4), ν 3(PO 4) and ν 4(PO 4) modes of LNT FT-IR difference spectra of analogues with a small content of NH 4 + and PO 4 3 - revealed the expected decrease of T d symmetry of free NH 4 + and PO 4 3 - ions to C s site symmetry. Due to the C s site symmetry of the anions, the degeneration of the ν 4(NH 4), ν 3PO 4) and ν 4PO 4) modes is raised and, hence, three components are observed in the difference FT-IR spectra. This conclusion can not be derived only from studies of no-doped polycrystalline samples of struvite type compounds.