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Estimation of the standard molal heat capacities, entropies and volumes of 2:1 clay minerals

Authors
Journal
Geochimica et Cosmochimica Acta
0016-7037
Publisher
Elsevier
Publication Date
Volume
58
Issue
21
Identifiers
DOI: 10.1016/0016-7037(94)90189-9
Disciplines
  • Design
  • Earth Science
  • Geography
  • Physics

Abstract

Abstract The dearth of accurate values of the thermodynamic properties of 2:1 clay minerals severely hampers interpretation of their phase relations, the design of critical laboratory experiments and geologically realistic computer calculations of mass transfer in weathering, diagenetic and hydrothermal systems. Algorithms and strategies are described below for estimating to within 2% the standard molal heat capacities, entropies, and volumes of illites, smectites and other 2:1 clay minerals. These techniques can also be used to estimate standard molal thermodynamic properties of fictive endmembers of clay mineral solid solutions. Because 2:1 clay minerals like smectite and vermiculite are always hydrated to some extent in nature, contribution of interlayer H 2O to their thermodynamic properties is considered explicitly in the estimation of the standard molal heat capacities, entropies, and volumes of these minerals. Owing to the lack of accurate calorimetric data from which reliable values of the standard molal heat capacity and entropy of interlayer H 2O can be retrieved, these properties were taken in a first approximation to be equal to those of zeolitic H 2O in analcite. The resulting thermodynamic contributions per mole of interlayer H 2O to the standard molal heat capacity, entropy, and volume of hydrous clay minerals at 1 bar and 25°C are 11.46 cal mol −1, 13.15 cal mol −1 K −1 and 17.22 cm 3 mol, respectively. Estimated standard molal heat capacities, entropies and volumes are given for a suite of smectites and illites commonly used in models of clay mineral and shale diagenesis.

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