Experimental Studies of the Mechanism and Kinetics of Hydration Reactions

The mechanism and the kinetics of hydration reactions are important for the application of a salt hydrate as a thermochemical heat storage material. MgSO4·H2O and Na2SO4 were chosen in this study because they are both promising candidates for such an application. Considering that the hydration of these salts yields MgSO4·7H2O and Na2SO4·10H2O as the reaction products, the maximum overall heat effect can be calculated from the heat of condensation of water vapor (44 kJ mol–1) and the heats of hydration of 75 kJ·mol-1 (for MgSO4·H2O) and 81 kJ mol-1 (for Na2SO4). Based on the densities of the two hydrated phases, this results in the very high theoretical energy densities of 2.3 GJ·m-3 and 2.4 GJ·m-3, respectively, for MgSO4·7H2O and Na2SO4·10H2O. Not only the energy density is important for the dimensioning of a storage system, but also the kinetics of hydration reactions play a major role for the application as storage material. In the present study, hydration reactions under varying climatic conditions were investigated by using water vapor sorption measurements and in-situ Raman microscopy. Using the phase diagrams, it can be clearly shown that the mechanism and the kinetics depend on the climatic conditions. Below the deliquescence humidity of the lower hydrated phase the hydration proceeds as solid state reaction, whilst above the deliquescence humidity a through solution mechanism takes place