Item talk:Q240380

From geokb

{

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   "name": "Thermodynamic properties in the Fe(II)-Fe(III)-As(V)-HClO4\u2013H2O and Fe(II)-Fe(III)-As(V)-HCl\u2013H2O systems from 5 to 90 \u00b0C",
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   "abstract": "Fe-As mineral solubility and associated aqueous species have been intensively studied because of the environmental need to immobilize arsenic. The thermodynamic data for aqueous iron-arsenic species are inadequately characterized, however. The\u00a0Gibbs free energy, enthalpy, entropy, and heat capacity and\u00a0activity coefficients\u00a0were refined in the Fe(II)-Fe(III)-As(V)-HClO4-H2O and Fe(II)-Fe(III)-As(V)-HCl-H2O systems using\u00a0redox potential\u00a0measurements from 5 to 90\u00a0\u00b0C. The association constants for FeHAsO4+\u00a0and FeH2AsO42\u00a0+\u00a0at 25 \u00b0C were 1010.28\u00a0and 104.02\u00a0and the corresponding association reaction enthalpies and heat capacities were 25.74 and 8.73\u00a0kJ\u00a0mol\u2212\u00a01\u00a0and 843.1 and \u2212\u00a0529.6\u00a0J K\u00a0\u22121mol\u2212\u00a01, respectively. Activity coefficients for H+, ClO4\u2212, Fe2\u00a0+, Fe3\u00a0+, HAsO42\u00a0\u2212, and H2AsO4\u2212\u00a0at 25\u00a0\u00b0C in the form of the H\u00fcckel equation were derived for ionic strengths up to 1\u00a0mol\u2212\u00a01\u00a0kg\u2212\u00a01. Newly derived activity coefficients and thermodynamic data were incorporated into PHREEQCI to calculate the Eh of laboratory solutions. The differences between calculated and measured Eh were all within 10 mV and relative differences were all lower than 1.5%.",
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