Thermokinetic study of the zero, first and second order reactions in a pseudo-adiabatic calorimeter: numerical approach and experimental dat

Abstract

The signal produced by a pseudo-adiabaticcalorimeter is simulated by numericalsolution of the differential equations thatmodel the chemical kinetics [1], the thermalproperties of the calorimetric cell[2], and the response of the thermistorused as a thermometric sensor [3]. These equations show that the calorimetricsignal is related with concentrationin a complex way. Therefore, a comparisonbetween the signals of the threebasic kinetics reactions (zero, first andsecond order) was made, as a first stepto obtain a standard procedure to followchemical kinetics using a calorimeter. Inorder to help understanding this relationship,the initial rate method was applied to the simulated data to assess the relationshipbetween the order and the kineticconstants calculated with those usedfor the simulations. As it was expected,the initial rate method for the calorimetricdata, do not give a slope directly relatedwith the order of the reaction, as itwould be produced, for example, in datafrom a spectrophotometer. However, alinear relationship was found betweenwhat we call the “calorimetric order”and the kinetic order. Finally, the developedprocedure was applied to the studyof the H2O2 decomposition catalyzedwith Fe3+ in homogeneous phase andwith activated carbon in heterogeneousphase, finding the order and the kineticsconstants of the global processes, whichwere in close agreement with those inthe literature.