Original paper

Thermodynamic properties of carbonates at high pressures from vibrational modelling

Matas, Jan; Gillet, Philippe; Ricard, Yanick; Martinez, Isabelle

European Journal of Mineralogy Volume 12 Number 4 (2000), p. 703 - 720

76 references

published: Jul 17, 2000
manuscript accepted: Mar 13, 2000
manuscript received: Jun 24, 1999

DOI: 10.1127/ejm/12/4/0703

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ArtNo. ESP147051204002, Price: 29.00 €

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Abstract Simplified vibrational densities of states for five different carbonates are constructed using measured IR and Raman spectra. From the spectroscopic models we calculate thermodynamic and thermoelastic properties of magnesite, calcite, aragonite, dolomite, and siderite. The effects of temperature and pressure on the vibrational frequencies are explicitly introduced into the computations. These spectroscopic models provide high level agreement with the measured values of entropy and heat capacity (within ± 2 %), with the exception of aragonite (within ± 5 % above 600 K) due to its breakdown to calcite. For the molar volumes the agreement is within ±0.5%. The Gibbs free energies of each mineral are then computed in order to obtain pressure and temperature equilibrium conditions for different chemical reactions involving carbonates. Comparing the predicted phase diagrams with those experimentally determined provides an additional constraint on the validity of spectroscopic models and in the values of formation enthalpies


carbonatesvibrational modellingdensity of statesanharmonicitythermodynamic properties