Kinetics of Thermal Dehydroxylation and Carbonation of Magnesium Hydroxide

Abstract

The kinetics of simultaneous dehydroxylation and carbonation of precipitated Mg(OH)2 were studied using isothermal and nonisothermal thermogravimetric analyses. Specimens were analyzed using X‐ray diffraction, transmission electron microscopy, and through measurements of the volume of carbon dioxide evolved in a subsequent reaction with hydrochloric acid. From 275° to 475°C, the kinetics of isothermal dehydroxylation in helium were best fit to a contracting‐sphere model, yielding an activation energy of 146 kJ/mol, which was greater than values reported in the literature for isothermal dehydroxylation under vacuum (53–126 kJ/mol). The carbonation kinetics were complicated by the fact that dehydroxylation occurred simultaneously. The overall kinetics also could be fit to a contracting‐sphere model, yielding a net activation energy of 304 kJ/mol. The most rapid carbonation kinetics occurred near 375°C. At this temperature, Mg(OH)2 underwent rapid dehydroxylation and subsequent phase transformation, whereas thermodynamics favored the formation of carbonate. During carbonation, MgCO3 precipitated on the surface of disrupted Mg(OH)2 crystals acting as a kinetic barrier to both the outward diffusion of H2O and the inward diffusion of CO2.