Samples along the dolomite-ankerite join were synthesized using a piston-cylinder apparatus and the double-capsule method. Some of the ankerite samples may be disordered. Thermal analysis and X-ray diffraction showed that all samples can be completely decomposed to uniquely defined products under calorimetric conditions (770 °C, O2). and a well-constrained thermodynamic cycle was developed to determine the enthalpy of formation. The energetics of ordered and disordered ankerite solid solutions were estimated using data from calorimetry, lattice-energy calculations, and phase equilibria. The enthalpies of formation of ordered dolomite and disordered end-member ankerite from binary carbonates, determined by calorimetry, are -9.29 ± 1.97 and 6.98 ± 2.08 kJ/mol, respectively. The enthalpy of formation of ordered ankerite appears to become more endothermic with increasing Fe content, whereas the enthalpy of formation of disordered ankerite becomes more exothermic with increasing Fe content. The enthalpy of disordering in dolomite (approximately 25 kJ/mol) is much larger than that in pure ankerite, CaFe(CO3)2 (approximately 10 kJ/mol), which may explain the nonexistence of ordered CaFe(CO3)2.
ASJC Scopus subject areas
- Geochemistry and Petrology