| Abstract: | A series of synthetic and biogenicmagnesian calcites was dissolved in weak acetic acidsolutions to measure the enthalpies of dissolution at25°C. For the synthetic phases, heat releasedwas 33.5 kJ/mol for calcite, decreasing to 33 kJ/molfor a phase of 2 mol % MgCO3, and increasing to35 kJ/mol for a phase of 15 mol %. Values of excessenthalpies, ΔHxs, calculated using calciteand magnesite end-members, average about -1 kJ/mol forthe synthetic phases. Total entropies of solidsolution formation, ΔSSS, also werecalculated using available data on Gibbs free energiesof formation and these excess enthalpies. Values ofΔSSS range from -2 J/(mol-K) at 2 mol % to-5 J/(mol-K) at 15 mol % MgCO3. These negativevalues of ΔHxs and ΔSSSsuggest that some form of ordering (cation?) isobtained in the synthetic phases, and that vibrationalentropies of the solid solution are diminished incomparison to the end-members. In contrast, biogenic samples generally have positivevalues of ΔHxs, increasing from +1 kJ/molat 5 mol % to +3 kJ/mol at 20 mol % MgCO3. Mostvalues of ΔSSS are equal (within errors)to values expected from configurational enthalpyalone. Thus, in most biogenic materials cationordering probably is not obtained, and most phases aremore typical of equivalent-site solid solutions. |
