A mechanistic approach on the solid state thermal decomposition of bimetallic oxalate coordination compounds of Mn(II), Fe(II) and Cu(II) with cobalt

Abstract

The mixed metal carboxylates, manganese(II)bis(oxalato)cobaltate(II)hydrate (MOC), iron(II)bis(oxalato)cobaltate(II)pentahydrate (IOC), and copper(II)bis(oxalato)cobaltate(II)trihydrate (COC) have been synthesized and characterized by elemental analysis, IR spectral and X-ray powder diffraction studies. Thermal decomposition studies (TG, DTG and DTA) in air showed that the compound MOC decomposed mainly to MnCoO 3 at 315 °C through the formation of a complete anhydrous compound. The species CoFeO 3 is generated at 274 °C from the compound IOC through the formation of a very transient anhydrous compound at around 218 °C. In case of the compound, COC the end product was found to be CuCoO 2 at ∼1000 °C through the existence of a quite stable mixture of CuO and CoO at ∼318 °C. DSC studies in nitrogen indicated the formation of a mixture of MnO and CoO in case of MOC, cobalt ferrite in case of IOC and a brown mixture of Cu 2O and CoO from COC as end products. The kinetic parameters have been evaluated for both the dehydration and decomposition steps of all the three compounds using four non-mechanistic equations. Using seven mechanistic equations, the rate controlling processes of the dehydration and decomposition mechanism are also inferred. The kinetic parameters, Δ H and Δ S obtained from DSC are presented. IR and X-ray powder diffraction studies identified some of the decomposition products.