Revised values for the Gibbs free energy of formation of [Al(OH)4 aq-], diaspore, boehmite and bayerite at 298.15 K and 1 bar, the thermodynamic properties of kaolinite to 800 K and 1 bar, and the heats of solution of several gibbsite samples

Geochimica et Cosmochimica Acta
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Abstract

Solution calorimetric measurements compared with solubility determinations from the literature for the same samples of gibbsite have provided a direct thermochemical cycle through which the Gibbs free energy of formation of [Al(OH)4 aq] can be determined. The Gibbs free energy of formation of [Al(OH)4 aq] at 298.15 K is −1305 ± 1 kJ/mol. These heat-of-solution results show no significant difference in the thermodynamic properties of gibbsite particles in the range from 50 to 0.05 μm.

The Gibbs free energies of formation at 298.15 K and 1 bar pressure of diaspore, boehmite and bayerite are −9210 ± 5.0, −918.4 ± 2.1 and −1153 ± 2 kJ/mol based upon the Gibbs free energy of [A1(OH)4 aq] calculated in this paper and the acceptance of −1582.2 ± 1.3 and −1154.9 ± 1.2 kJ/mol for the Gibbs free energy of formation of corundum and gibbsite, respectively.

Values for the Gibbs free energy formation of [Al(OH)2 aq+] and [AlO2 aq] were also calculated as −914.2 ± 2.1 and −830.9 ± 2.1 kJ/mol, respectively. The use of [AlC2 aq] as a chemical species is discouraged.

A revised Gibbs free energy of formation for [H4SiO4aq0] was recalculated from calorimetric data yielding a value of −1307.5 ± 1.7 kJ/mol which is in good agreement with the results obtained from several solubility studies.

Smoothed values for the thermodynamic functions CP0, (HT0- H2980)T, (GT0- H2980)T, ST0 - S00, ƒΔHƒ,2980 kaolinite are listed at integral temperatures between 298.15 and 800 K. The heat capacity of kaolinite at temperatures between 250 and 800 K may be calculated from the following equation: CP0 = 1430.26 − 0.78850 T + 3.0340 × 10−4T2 −1.85158 × 10−4T212+ 8.3341 × 106T−2.

The thermodynamic properties of most of the geologically important Al-bearing phases have been referenced to the same reference state for Al, namely gibbsite.

Publication type Article
Publication Subtype Journal Article
Title Revised values for the Gibbs free energy of formation of [Al(OH)4 aq-], diaspore, boehmite and bayerite at 298.15 K and 1 bar, the thermodynamic properties of kaolinite to 800 K and 1 bar, and the heats of solution of several gibbsite samples
Series title Geochimica et Cosmochimica Acta
DOI 10.1016/0016-7037(78)90024-8
Volume 42
Issue 10
Year Published 1978
Language English
Publisher Elsevier
Description 11 p.
First page 1533
Last page 1543
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