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Surface enthalpy of goethite

Published online by Cambridge University Press:  01 January 2024

Lena Mazeina  and
Alexandra Navrotsky
Lena Mazeina
Affiliation:
Thermochemistry Facility and NEAT ORU, University of California at Davis, Davis, CA 95616, USA
Alexandra Navrotsky*
Affiliation:
Thermochemistry Facility and NEAT ORU, University of California at Davis, Davis, CA 95616, USA
*
*E-mail address of corresponding author: [email protected]
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Abstract

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High-temperature oxide-melt solution calorimetry and acid-solution calorimetry were used to determine the heat of dissolution of synthetic goethite with particle sizes in the range 2–75 nm and measured surface areas of 30–273 m2/g (27–240 × 103 m2/mol). Sample characterization was performed using X-ray diffraction, Fourier transform infrared spectroscopy, the Brunauer, Emmett and Teller method and thermogravimetric analysis. Water content (structural plus excess water) was determined from weight loss after firing at 1100°C. Calorimetric data were corrected for excess water assuming this loosely adsorbed water has the same energetics as bulk liquid water. The enthalpy of formation was calculated from calorimetric data using enthalpies of formation of hematite and liquid water as reference phases for high-temperature oxide-melt calorimetry and using enthalpy of formation of lepidocrocite for acid-solution calorimetry. The enthalpy of formation of goethite can vary by 15–20 kJ/mol as a function of surface area. The plot of calorimetric data vs. surface area gives a surface enthalpy of 0.60±0.10 J/m2 and enthalpy of formation of goethite (with nominal composition FeOOH and surface area = 0) of −561.5±1.5 kJ/mol. This surface enthalpy of goethite, which is lower than values reported previously, clarifies previous inconsistencies between goethite-hematite equilibrium thermodynamics and observations in natural systems.

Keywords

Enthalpy of FormationGoethiteSurface Enthalpy
Type
Research Article
Information
Clays and Clay Minerals , Volume 53 , Issue 2 , April 2005 , pp. 113 - 122
Copyright
Copyright © Clay Minerals Society 2005

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