Journal of Computational Chemistry · 2014 · 44 citations · 21 references
Natural SciencesChemical EngineeringChemistryChemical KineticsReaction EngineeringThermal AnalysisChemical Kinetics ModelingChemical Reaction KineticsKinetic ModelingActivation EnergyCold CrystallizationKinetic Parameter EstimationKinetics Parameter EstimationNonisothermal CrystallizationNonisothermal Kinetic AnalysisNonlinearityPolyethylene Terephthalate
The parameters obtained from a kinetic analysis of thermoanalytical data often exhibit a conversion-dependent behavior. A novel incremental isoconversional method able to deal with this phenomenon is proposed. The kinetic model is directly fitted to the experimental data using nonlinear orthogonal least squares procedure. The data are processed without transformations, so their error distribution is preserved. As the objective function is based on a maximum likelihood approach, reliable uncertainties of the parameters can be estimated. In contrast to other methods, the activation energy and the pre-exponential factor are treated as equally important kinetic parameters and are estimated simultaneously. Validity of the method is verified on simulated data, including a dataset with local nonlinearity in the temperature variation. A practical application on the nonisothermal cold crystallization of polyethylene terephthalate is presented.
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