Thermal kinetic analysis of a complex process from a solid-state reaction by deconvolution procedure from a new calculation method and related thermodynamic functions of Mn0.90Co0.05Mg0.05HPO4•3H2O

Three individual peaks of thermal solid-state reaction processes of the synthesized Mn0.90Co0.05Mg0.05HPO4 center dot 3H(2)O were observed corresponding to dehydration I, dehydration II and polycondensation processes. An alternative method for the calculation of the extent of conversion was proposed from the peak area of the individual DTG peak after applying the best fitting deconvolution function (Frazer-Suzuki function). An iterative integral isoconversional equation was used to compute the values of the apparent activation energy E-alpha and they were found to be 65.87, 78.16 and 119.32 kJ/mol for three peaks, respectively. Each individual peak was guaranteed to be a single-step kinetic system with its unique kinetic parameters. The reaction mechanism functions were selected by the comparison between experimental and model plots. The results show that the first, second and final individual peaks were two-dimensional diffusion of spherical symmetry (D-2), three-dimensional diffusion of spherical symmetry (D-3) and contracting cylinder (cylindrical symmetry, R-2) mechanisms. Pre-exponential factor values of 3.91x10(6), 1.35x10(7) and 2.15x10(7) s(-1) were calculated from the E-alpha values and reaction mechanisms. The corresponded standard thermodynamic functions of the transition-state (activated) complexes were determined and found to agree well with the experimental data.