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Phase Equilibria in the Pyroxene Quadrilateral
Authors:SAXENA  S K; SYKES  JULIA; ERIKSSON  G
Institution:1Department of Earth and Environmental Sciences, CUNY, Graduate Center and Department of Geology, Brooklyn College Brooklyn, New York 11210
2Department of Inorganic Chemistry, University of Umea S-95187 Sweden
Abstract:Experimental phase equilibrium data on compositions of coexistingpyroxenes in the quadrilateral enstatite-diopside-ferrosilite-hedenbergitehave been used to model pyroxene solid solutions and to formulatepyroxene geothermometers. Each pyroxene is treated as a solidsolution of four quad-components using the Kohler formulation Formula where {Delta}Gij* is the excess free energy of mixing in a binary solutioncalculated with binary mole fractions (e.g. Xio = Xi/(Xi+Xj))and Xi is the mole fraction in a multicomponent solution. Thefit to the experimental data is achieved by minimizing the totalGibbs free energy of the assemblage. The following set of thermochemicaldata and simple mixture parameters (Wij) are found to be bestsuited. Standard (T = 298?15 K) enthalpy and entropy of formationfrom elements for fictive orthohedenbergite are –1416?8kJ and 84?88 J K–1 mol –1 respectively. The heatcapacity is given by 114?67+17?09E-3T–31?40E5T–2.The Wij data are: Opx: W12 = W21 = 25 W13 = (13?1–0-015T),W31 = (3?37–0?005T), W23 = 20, W32 = 16, W24 = 5, W42= 7, W34 = 15, W43 = 15; Cpx: W12 = (25?484+0?0812P), W21 =(31?216–0?0061P),W31 = W13 = 0W14 = (93?3–0?045T), W41 = (–20?0+0?028T),W23 = 24, W32 = 15, W24 = 12, W42 = 12, W34 = (16?941+0?00592P),W43 = (20?697–0?00235P). Coexisting pyroxene compositionshave been computed in the temperature range of 700 to 1400?C. Two geothermometers have been constructed, one based on atomicfraction of iron (Fe/(Fe + Mg)) in orthopyroxene and the Fe-Mgdistribution coefficient and the other, based on wollastonitecontent of clinopyroxene. The two scales yield different temperatureswhen applied to the same rock. In igneous pyroxenes, the Catransfer ceased at 150 to 200?C above the closure temperatureof the Fe-Mg ion-exchange. In metamorphic rocks an oppositeeffect seems to have prevailed.
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