Forray, Ferenc Lázár and Smith, A.M.L. and Drouet, Christophe and Navrotsky, Alexandra and Wright, K. and Hudson-Edwards, K.A. and Dubbin, W.E. Synthesis, characterization and thermochemistry of a Pb-jarosite. (2010) Geochimica et Cosmochimica Acta, vol. 74 (n° 1). pp. 215-224. ISSN 0016-7037
|(Document in English) |
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Official URL: http://dx.doi.org/10.1016/j.gca.2009.09.033
The enthalpy of formation from the elements of a well-characterized synthetic Pb-jarosite sample corresponding to the chemical formula (H3O)0.74Pb0.13Fe2.92(SO4)2(OH)5.76(H2O)0.24 was measured by high temperature oxide melt solution calorimetry. This value (DH f = 3695.9 ± 9.7 kJ/mol) is the first direct measurement of the heat of formation for a lead-containing jarosite. Comparison to the thermochemical properties of hydronium jarosite and plumbojarosite end-members strongly suggests the existence of a negative enthalpy of mixing possibly related to the nonrandom distribution of Pb2+ ions within the jarosite structure. Based on these considerations, the following thermodynamic data are proposed as the recommended values for the enthalpy of formation from the elements of the ideal stoichiometric plumbojarosite Pb0.5Fe3(SO4)2(OH)6: DG f = 3118.1 ± 4.6 kJ/mol, DH f = 3603.6 ± 4.6 kJ/mol and S = 376.6 ± 4.5 J/(mol K). These data should prove helpful for the calculation of phase diagrams of the Pb–Fe–SO4–H2O system and for estimating the solubility product of pure plumbojarosite. For illustration, the evolution of the estimated solubility product of ideal plumbojarosite as a function of temperature in the range 5–45 C was computed (Log(Ksp) ranging from 24.3 to 26.2). An Eh–pH diagram is also presented.
|Additional Information:||Thanks to Elsevier editor. The definitive version is available at http://www.sciencedirect.com The original PDF of the article can be found at Geochimica et Cosmochimica Acta website : http://www.sciencedirect.com/science/journal/00167037|
|Audience (journal):||International peer-reviewed journal|
|Institution:||Other partners > University of California - UC Davis (USA)|
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French research institutions > Centre National de la Recherche Scientifique - CNRS
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Université de Toulouse > Institut National Polytechnique de Toulouse - INPT
Other partners > University of London (UNITED KINGDOM)
Université de Toulouse > Université Paul Sabatier-Toulouse III - UPS
|Deposited By:||Nihad Lahdifi|
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