Thermal decomposition of zinc oxalate dihydrate: Kinetics of dehydration and pyrolysis in various atmospheres

Abstract

AbstractThermogravimetric analysis has indicated that a convenient range for the study of Zn(COO)2.2H2O dehydration is 120–300 °C, while for pyrolysis it is 320–400 °C. Kinetics of isothermal dehydration and pyrolysis were studied as two consecutive steps in various atmospheres, namely in constant water vapour pressure of 4.8 and 8 mm Hg, in air saturated with water vapour at 25 °C and in vacuo. The kinetic data indicated that dehydration is a pseudo‐first order reaction, which is highly dependent on the surrounding atmosphere. The mechanism of dehydration is either activated diffusion (alternatively surface diffusion) for dehydration in vacuo or in low water vapour pressures, or activated desorption for dehydration in presence of high water vapour pressure. On the other hand pyrolysis is independent of the prevailing atmosphere, and the energy of activation is of the order of the enthalpy change of the reaction.Earlier studies have involved contact of the dehydrated oxalate with air, or have obscured the influence of the prevailing atmosphere, by dehydrating the sample material at the pyrolysis temperature. These conditions are considered in the present investigation.