Synthesis, characterization and thermochemistry of a Pb-jarosite
Forray, F.L. and Smith, Adrian M.L. and Drouet, C. and Navrotsky, A. and Wright, K. and Hudson-Edwards, Karen A. and Dubbin, W.E. (2010) Synthesis, characterization and thermochemistry of a Pb-jarosite. Geochimica et Cosmochimica Acta 74 (1), pp. 215-224. ISSN 0016-7037.
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 (View the MathML source = −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: View the MathML source = −3118.1 ± 4.6 kJ/mol, View the MathML source = −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.
|School:||Birkbeck Schools and Departments > School of Science > Earth and Planetary Sciences|
|Date Deposited:||09 Feb 2011 09:06|
|Last Modified:||17 Apr 2013 12:18|
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