Electron probe analyses of diagenetic illites in Eocene sandstones from Kettleman North Dome, California, along with analyses of coexisting interstitial waters were used to calculate apparent molal free energies of formation of the illites at the in situ conditions of 100°C and 150 bars. Various triangular and rectangular compositional plots, once contoured for free energy, crudely indicate that the free energy decreases as the potassium content increases, decreases as the Al-for-Si substitution increases, and appears to be a minimum along a narrow composition valley having ~3% Fe2O3 of octahedral cations. Qualitatively, the shape of the free energy surface suggests only small departures from ideality.

The illites and water samples used in the calculations were chosen as close to each other as possible and are in equilibrium. The waters contain mainly Cl−, SO42−, Na+, and Ca2+ and have a total salinity of ~10,000 ppm. The illites, which coexist in the sandstones with diagenetic quartz, albite, and K-feldspar, are phen-gitic and contain 5–9% K2O, 1–3% total FeO, 1% MgO, and minor Na2O, MnO, and TiO2. The Fe2O3/FeO ratio has been set arbitrarily to 7 by comparison with published analyses.

Log K (100°C) was first calculated for the equilibrium illite ⇄ ions from the ionic activities obtained through speciation calculations for each water sample. The apparent free energies of formation of illites at 100°C were then calculated. The effect of instrumental uncertainty on the values of ΔGf was assessed by accepting a 2.5 or 3.5% error in the probe analyses and by using a Monte Carlo method of error propagation. The free energies of formation obtained (on the basis of O10(OH2)) range from -1280 to -1320 kcal/mole at 100°C and 150 bars, and their Monte-Carlo uncertainties are less than ±2 kcal/mole. Combining the compositions of natural, coexisting aqueous solutions and mineral solid solutions through thermodynamic equations constitutes a fast method to determine, at least crudely, the free energy-composition surface for the solid solution. This is in contrast to experimental methods such as calorimetry or hydrothermal equilibrium, which are very time-consuming and difficult.

Activity expressions are presented for a six end-member, regular solution, site-mixing model for chlorites. The end members are ideal 14-Å chlorites for which experimental stability data are lacking. Estimates were made of the standard state 25°C and 1 bar molar 3rd law entropies, volumes, and the Maier-Kelley heat capacity coefficients. Experimental stability data from the literature for 14-Å chlorites were used with different sets of exchange energies, for cations on adjacent sites, to compute estimates of the standard state chemical potentials of the end members at 25°C and 1 bar. More experimental data are needed for an adequate definition of the exchange energies and the standard state chemical potentials. The model was applied to diagenesis in clastic reservoirs. Aqueous activity ratios of Mg2+:Fe2+ were computed as an equilibrium function of the corresponding molar ratios in authigenic chlorites. The aqueous activity ratio was independent of the chlorite Al content at a constant molar ratio of Mg2+:Fe2+ in the chlorite. The model predicts a wide range of molar Mg2+:Fe2+ ratios in authigenic chlorites in equilibrium with reservoir fluids. Trends in these molar ratios should be independent of the Al content in the chlorites. The model can be applied directly to 7-Å chlorites when experimental data become available to estimate the various thermodynamic parameters of the 7-Å end members.

High-Mg chlorites from Vermont and Quebec and high-Fe chlorites from Michigan and New Mexico were equilibrated at room temperature in the near-neutral pH range. Gibbsite, kaolinite, and hematite of known stability were added to the samples to control unmeasurable variables at calculable levels. Equilibrium solution compositions were obtained from undersaturation and from supersaturation. Other indicators of equilibrium were good agreement between successive analyses over a long period of time, between duplicate samples, between independent systems, and between independent measures of equilibrium. All four chlorites were stable relative to brucite and, with a few exceptions, relative to talc under the conditions of study. When in equilibrium with gibbsite, the pH − ½Mg2+ value of the chlorites ranged from 6.3 to 6.5, at a pH4SiO4 value of 4.0. These values are in good agreement with prior estimates of chlorite stability. The calculated standard free energy of formation of the chlorites is dependent upon solution Fe2+ calculated from the sample Eh and assumed equilibrium with hematite, with the assumption that the Fe2+-Fe3+ couple is at the same Eh as the sample.