Simultaneous Thermodynamic and Kinetic Parameters Determination Using Differential Scanning Calorimetry

Abstract

Problem statement: The determination of reaction kinetics is of major importance, as for industrial reactors optimization as for environmental reasons or energy limitations. Although calorimetry is often used for the determination of thermodynamic parameters alone, the question that arises is: how can we apply the Differential Scanning Calorimetry for the determination of kinetic parameters. The objective of this study consists to proposing an original methodology for the simultaneous determination of thermodynamic and kinetic parameters, using a laboratory scale Differential Scanning Calorimeter (DSC). The method is applied to the dichromate-catalysed hydrogen peroxide decomposition. Approach: The methodology is based on operating of experiments carried out with a Differential Scanning Calorimeter. The interest of this approach proposed is that it requires very small quantities of reactants (about a few grams) to be implemented. The difficulty lies in the fact that, using such microcalorimeters, the reactants temperature cannot directly be measured and a particular calibration procedure has thus to be developed, to determine the media temperature in an indirect way. The proposed methodology for determination of kinetics parameters is based on resolution of the coupled heat and mass balances. Results: A complete kinetic law is proposed. The Arrhenius parameters are determined as frequency factor k₀ = 1.39×109 s⁻¹ and activation energy E = 54.9 kJ mol⁻¹. The measured enthalpy of reaction is ΔrH=−94 kJ mol⁻¹. Conclusion: The comparison of the results obtained by such an original methodology with those obtained using a conventional laboratory scale reactor calorimetry, for the kinetics determination of, shows that this new approach is very relevant.