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Kinetic approach to partially overlapped thermal decomposition processes
Authors:Nobuyoshi Koga  Yuri Goshi  Shuto Yamada  Luis A Pérez-Maqueda
Institution:1. Chemistry Laboratory, Department of Science Education, Graduate School of Education, Hiroshima University, 1-1-1 Kagamiyama, Higashi-Hiroshima, 739-8524, Japan
2. Faculty of Arts and Science, Kyushu University, 744 Motooka, Fukuoka, 819-0395, Japan
3. Instituto de Ciencia de Materiales de Sevilla, C.S.I.C-Universidad de Sevilla, C. Américo Vespucio No. 49, 41092, Sevilla, Spain
Abstract:Practical usefulness of the kinetic deconvolution for partially overlapped thermal decomposition processes of solids was examined by applying to the co-precipitated basic zinc carbonate and zinc carbonate. Comparing with the experimental deconvolutions by thermoanalytical techniques and mathematical deconvolutions using different statistical fitting functions, performance of the kinetic deconvolution based on an accumulative kinetic equation for the independent processes overlapped partially was evaluated in views of the peak deconvolution and kinetic evaluation. Two-independent kinetic processes of thermal decompositions of basic zinc carbonate and zinc carbonate were successfully deconvoluted by means of the thermoanalytical measurements in flowing CO2 and by applying sample controlled thermal analysis (SCTA). The deconvolutions by the mathematical curve fittings using different fitting functions and subsequent formal kinetic analysis provide acceptable values of the mass-loss fractions and apparent activation energies of the respective reaction processes, but the estimated kinetic model function changes depending on the fitting functions employed for the peak deconvolution. The mass-loss fractions and apparent kinetic parameters of the respective reaction processes can be optimized simultaneously by the kinetic deconvolution based on the kinetic equation through nonlinear least square analysis, where all the parameters indicated acceptable correspondences to those estimated through the experimental and mathematical deconvolutions. As long as the reaction processes overlapped are independent kinetically, the simple and rapid procedure of kinetic deconvolution is useful as a tool for characterizing the partially overlapped kinetic processes of the thermal decomposition of solids.
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