Abstract
A model is proposed for the thermodynamic properties of multicomponent pyroxenes in the composition space defined by the end-member component CaMgSi2O6 and the exchange components Fe(Mg)-1, TiAl2(MgSi2)-1, Fe3+(Al)-1, Fe3+Al(MgSi)-1, and Mg(Ca)-1. It is formulated for the simplifying assumptions that: (1) a molecular mixing type approximation describes changes in the molar configurational entropy associated with the coupled exchange substitutions TiAl2⇔MgSi2, Fe3+Al⇔MgSi, and Al2⇔MgSi (and their ferroan equivalents), and (2) Fe2+ and Mg2+, and Al3+ and Fe3+ display long-range non-convergent ordering between M2 and octahedral M1 sites, and octahedral M1 and tetrahedral sites, respectively. The molar vibrational Gibbs energy is described by a Taylor expansion of second degree in seven linearly independent composition and ordering variables, which is extended to third degree to account for asymmetry in the mixing of Ca and Mg, and Ca and Fe on the M2 site, and is further modified for the assumption that the standard state properties of Ca end-member components of clinopyroxenes are linearly dependent on the coordination number of Ca2+ on the M2 site. The model is shown to be consistent with miscibility gap feaures of pyroxenes in the system CaMgSi2O6−CaTiAl2O6−CaAl2SiO6. In subsequent papers, the model is calibrated for the simplifying assumptions that: (1) all regular-solution-type parameters are constants independent of temperature, (2) Pbca and C2/c end-members have identical heat capacities and coefficients of thermal expansion and compressibility, and (3) the heat capacities and coefficients of thermal expansion and compressibility are zero for all reciprocal reactions relating Pbca and pigeonite or high-calcium pyroxene C2/c endmember components.
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Sack, R.O., Ghiorso, M.S. Thermodynamics of multicomponent pyroxenes: I. Formulation of a general model. Contr. Mineral. and Petrol. 116, 277–286 (1994). https://doi.org/10.1007/BF00306497
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DOI: https://doi.org/10.1007/BF00306497