Annite stability revised. 1. Hydrogen-sensor data for the reaction annite = sanidine + magnetite + H₂

Abstract

In P - T - logfO₂ space, the stability of annite (ideally KFe ²⁺₃ (OH)₂AlSi₃O₁₀) at high fO₂ (low fH₂) is limited by the reaction: annite = sanidine + magnetite + H₂. Using the hydrogen-sensor technique, the equilibrium fH₂ of this reaction was measured between 500 and 800° C at 2.8 kbar in 50° C intervals. Microbrobe analyses of the reacted annite+sanidine+magnetite mixtures show that tetrahedral positions of annite have a lower Si/Al ratio than the ideal value of 3/1. Silicon decreases from ∼2.9 per formula unit at low temperatures to ∼2.76 at high temperatures. As determined by Mössbauer spectroscopy in three experimental runs, the Fe³⁺ content of annite in the equilibrium assemblage is 11%±3. A least squares fit to the hydrogensensor data gives ΔH ⁰_R = 50.269 ± 3.987 kJ and ΔS ⁰_R = 83.01 ± 4.35 J/K for equilibrium (1). The hydrogene-sensor data are consistent with temperature half brackets determined in the classical way along the nickel-nickel oxide (NNO) and quartz-fayalite-magnetite (QFM) buffers with a mixture of annite+sanidine+magnetite for control. Compared to published oxygen buffer reversals, agreement is only found at high temperature and possible reasons for that discrepancy are discussed. The resulting slope of equilibrium (1) in logfO₂ − T dimensions is considerably steeper than previously determined and between 400 and 800°C only intersects with the QFM buffer curve. Based on the hydrogen-sensor data and on the thermodynamic dataset of Berman (1988, and TWEEQ data base) for sanidine, magnetite and H₂, the deduced standard-state properties of annite are: H ⁰_f =-5127.376±5.279 kJ and S ⁰=422.84±5.29 J/(mol K). From the recently published unit cell refinements of annites and their Fe³⁺ contents, determined by Mössbauer spectroscopy (Redhammer et al. 1993), the molar volume of pure annite was constrained as 15.568±0.030 J/bar. A revised stability field for annite is presented, calculated between 400 and 800°C.