Potentialities of mass spectrometry on activation energy and secondary reactions determination of calcium oxalate thermal decomposition

Abstract

This work investigates the potentialities of the thermal analysis (TA) coupled with the mass spectrometry (MS) technique by studying the thermal decomposition of calcium oxalate monohydrate (CaC2O4·H2O). The aim of this work is twofold: to demonstrate, at first, the efficacy of coupling the thermal gravimetric (TG)‐MS experimental approach to check the presence of intermediate reactions beyond the conventional three‐step decomposition: dehydration, decarbonylation, and decarbonation; second, to test the reliability of different modeling approaches in determining the activation energy (E) including, as innovative alternative, the use of the MS signals. The TA is carried out at selected constant heating rates by recording both the thermal gravimetric analysis, differential thermal analysis) profiles, and, simultaneously from the MS data, the signals of the total ion current and the ion currents selected to monitor the release of the H2O, CO, and CO2 species. These experimental results are effective in determining the E through different modeling approaches based on the maximum reaction rate method and isoconversional procedures including both TG and MS signals. Coupling the TA‐MS technique has allowed us to check the concurrent presence of the dismutation reaction of carbon monoxide, occurring during the decarbonylation event, and to determine the corresponding E value (E = 169.7 kJ/mol). These results present a surprising correlation between the global enthalpy of the two reactions involved in this second step and their activation energy values. On the whole, the results satisfy the conventional constraints usually adopted to test the reliability of the E results and are consistent with the majority of the datasets published in the literature on this subject.

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“…The average value of Ea for P-CO and P-CC were 259 kJ mol -1 and 237 kJ mol -1 for SLN, 233 kJ mol -1 and 171 kJ mol -1 for TQL, and 167 kJ mol -1 and 175 kJ mol -1 for WCK, respectively. These results are in agreement with those reported by Campostrini et al [62], who obtained Ea values for decarbonylation and decarboxylation reactions, using different kinetic methods, which were at the range of 150-300 kJ mol -1 and 215-290 kJ mol -1 , respectively. Additionally, they showed values of 165-187 kJ mol -1 and 170-180 kJ mol -1 when calculated based on volatile detection by mass spectrometry.…”