Degradation thermique et etude vibrationnelle de MII(NH4)4(P3O9)2x4H2O(MII=Cu2+, Ni2+, Co2+)

Abstract

We have studied the thermal behaviour under atmospheric pressure of isotypic tetrahydrate cyclotriphosphates MII(NH4)4(P3O9)2x4H2O (M II=Cu, Ni and Co), between 25 and 1400°C, by X-ray diffraction, thermal analyses (TG and DTA) and infrared spectrometry. This study shows that the series of the compounds MII(NH4)4(P3O9)2x4H2O (M II=Cu, Ni and Co) after elimination of water, in two different stages, and ammonia leads, at 400°C to cyclotetraphosphate M2 IIP4O12 crystallized and to a thermal residue with a formula H4P4O12 which undergoes under a thermal degradation by evolving water and pentoxide phosphorus. The kinetic characteristics of the dehydration and elimination of ammonia have been determinated. The vibrational spectra of Cu(NH4)4(P3O9)2x4H2O were examined and interpreted, in the domain of the valency frequencies, on the basis of the crystalline structure of its isotypic compound Co(NH4)4(P3O9)2x4H2O whose cycle has the site symmetry C1, of our results of the calculation of the IR frequencies and the successive isotopic substitutions of the equivalent atoms (3P, 3Oi and 6Oe belonging to the P3Oi3Oe6 ring) of the P3O9 3− cycle with high symmetry D3h.