RI 3776 Energies and Equilibria in the Decomposition of Nitrates of Maganese, Magnesium, Calcium, Barium and Aluminum and Reactions of Nitrogen Peroxide

"INTRODUCTION The Bureau of Mines nitrogen peroxide process (2) 3/ for extracting manganese from low-grade ores is essentially a two-stage process involving the reversible reactionMnO2 + 2NO2 + 6H2O = Mn (NO3)2 . 6H2O (1).At lower temperatures this reaction proceeds to the rigth and affords a means of dissolving manganece and separating it from unreacted ore. At higher temperatures the reaction proceeds to the left and manganese dioxide is recovered and nitrogen peroxide regenerated for recycling. Evidently, therefore, the energy required for decomposition of manganous nitrate is a matter of practical importance. Similar information for certain other nitrates also is desirable beceuse the nitration step of the process produces appreciable amounts of nitrates of other metals, such as iron, aluminum, magnesium, calcium, and barium, some of which are not broken down in the evaporation and decomposition steps. Thus, a portion of the nitrogen peroxide is not directly available for recycling. Whether or not it is feasible to recover nitrogen peroxide locked in the more-stable nitrates depends partly on the energy required and the conditions necessary for their decomposition.To supply information bearing directly on these subjects, several researches were undertaken at the Pacific Experiment Station: (a) Heats of formation (24, 25, 26) of nitrates of manganese, magnesium, calcium, barium, and aluminum were measured at 298.2° K:; (b) low-temperature specific heats (23), in the range 51° to 298.2° K,, and entropies of nitrates of magnesium, calcium, barium, and aluminumm were determined; and (c) heat contents (21) above 298.2° K. of the nitrates of manganese, magnesium, calcium., and barium were measured. The results of these studies, when correlated by thermodymamic methods, permit evaluation, at any temperature of interest, of the energies required to decomposethe nitrates and furnish information concerning the equilibrium pressure temperature relationships."