Thermodynamics of water in cordierite and some petrologic consequences of cordierite as a hydrous phase

R. C. Newton*, B. J. Wood

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

    110 Citations (Scopus)

    Abstract

    The H2O content of cordierite is often regarded as incidental to its stability, probably because cordierite has substantial fields of stability at low pressures both in wet and dry experimental systems. In this paper we show that, in contrast, the molecular water content of cordierite has profound effects on many equilibria involving this phase. Mg-cordierite has been modelled as an ideal solid solution of the hydrous and anhydrous end-members Mg2Al4Si5O18·1.2H2O and Mg2Al4Si5O18 respectively. The H2O-solubility data of Mirwald and Schreyer (1977) fit this model within experimental uncertainty and yield 1 bar enthalpy and entropy changes for the reaction: {Mathematical expression} of -12,300 cal and -32.87 cal/K. This implies that the partial molal entropy of H2O in cordierite at 298 K/l bar is almost exactly the same as the molar entropy of liquid water (16.9 cal/K as opposed to 16.7 cal/K) and that the interaction energy of liquid water with cordierite is only of the order of a few hundred calories per mole. Application of the model to the hydrous experiments of Fawcett and Yoder (1966) and Chernosky (1974) yields a value for ΔGf,2980of anhydrous Mgcordierite of between -2,062.71 and -2,074.21 Kcal per mole. This in in good agreement with the calorimetric data of Charlu, Newton and Kleppa (1975) which yield ΔGf,2980of -2,067.03±1.18 Kcal. Water pressure has a considerable influence on the (Mg, Fe) isopleths of coexisting cordierite and garnet, and hence, their use as geobarometric curves. Pressures estimated from the Mg/Fe ratios in the high-Mg range can vary by two kilobars or more, depending on the assumed {Mathematical expression}, with highest estimates for {Mathematical expression}. The stability field of the talc-kyanite "white-schist" assemblage (Schreyer, 1973) is found to expand appreciably as {Mathematical expression} is lowered. Thus the minimum pressure required to form this assemblage can be considerably less than the 10 kb required under conditions of {Mathematical expression}=Ptotal, as anticipated by Schreyer (1977). The high partial molal entropy of H2O in cordierite results in small entropy changes coupled with large volume changes in dehydration reactions forming cordierite. This greatly influences the slopes and positions of univariant reactions involving cordierite. The stability of cordierite is promoted to higher pressures in H2O-bearing systems where none of the cordierite breakdown products is a hydrate. Cordierite-forming reactions from hydrates can have the H2O released on the relatively low-temperature sides of the reaction curves, an anomalous situation known only in zeolite stability curves. These considerations can have profound effects on model "petrogenetic grids" involving cordierite.

    Original languageEnglish
    Pages (from-to)391-405
    Number of pages15
    JournalContributions to Mineralogy and Petrology
    Volume68
    Issue number4
    DOIs
    Publication statusPublished - Dec 1979

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