Thermal behavior and kinetics of the reaction between liquid sodium and calcium hydroxide

Thermally-induced reaction between liquid sodium (Na(l)) and calcium hydroxide (Ca(OH)2(s)) was investigated as one of the possible component reactions when Na(l) was reacted with concrete materials under a postulated severe accidental condition in a sodium-cooled fast reactor. The Na(l)–Ca(OH)2(s) reaction was traced using a differential scanning calorimetry (DSC), placed in an argon substituted glove box. An exothermic DSC peak appeared in the temperature range of 550–700 K was attributed to the Na(l)–Ca(OH)2(s) reaction to form a mixed phase comprised of calcium oxide (CaO(s)), sodium hydroxide (NaOH(s,l)) and sodium oxide (Na2O(s)). Based on morphological analyses of reacting system, a physico-geometrical reaction model was proposed: the reaction initiates at the initial contact area of Na(l) and Ca(OH)2(s) and proceeds by the movement of the reaction interface toward Ca(OH)2(s), where the product layer is composed of CaO(s), NaOH(s,l), and Na2O(s). Therefore, the Na(l) diffusion through the product layer is the necessary process to promote the reaction between Na(l) and Ca(OH)2(s), for which a significant influence of the melting of NaOH(s) that has on the overall kinetic behavior is expected. This melting occurs midway through the Na(l)–Ca(OH)2(s) reaction at 594 K. The overall Na(l)–Ca(OH)2(s) reaction was analyzed kinetically using the DSC curves recorded at different heating rates. A partially overlapping two-step reaction feature was evidenced, in which the primary and secondary reaction steps were characterized by the apparent activation energy values of 128 and 138 kJ mol−1, respectively. The multistep feature of the Na(l)–Ca(OH)2(s) reaction could result from the melting of NaOH(s) in the product layer.