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Thermodynamic properties in the Fe(II)-Fe(III)-As(V)-HClO4–H2O and Fe(II)-Fe(III)-As(V)-HCl–H2O systems from 5 to 90 °C

January 16, 2017

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 Gibbs free energy, enthalpy, entropy, and heat capacity and activity coefficients were refined in the Fe(II)-Fe(III)-As(V)-HClO4-H2O and Fe(II)-Fe(III)-As(V)-HCl-H2O systems using redox potential measurements from 5 to 90 °C. The association constants for FeHAsO4+ and FeH2AsO42 + at 25 °C were 1010.28 and 104.02 and the corresponding association reaction enthalpies and heat capacities were 25.74 and 8.73 kJ mol− 1 and 843.1 and − 529.6 J K 1mol− 1, respectively. Activity coefficients for H+, ClO4, Fe2 +, Fe3 +, HAsO42 −, and H2AsO4 at 25 °C in the form of the Hückel equation were derived for ionic strengths up to 1 mol− 1 kg− 1. 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%.

    Publication Year 2017
    Title Thermodynamic properties in the Fe(II)-Fe(III)-As(V)-HClO4–H2O and Fe(II)-Fe(III)-As(V)-HCl–H2O systems from 5 to 90 °C
    DOI 10.1016/j.chemgeo.2017.04.010
    Authors Xiangyu Zhu, D. Kirk Nordstrom, R. Blaine McCleskey, Rucheng Wang, Xiancai Lu
    Publication Type Article
    Publication Subtype Journal Article
    Series Title Chemical Geology
    Index ID 70250956
    Record Source USGS Publications Warehouse
    USGS Organization Volcano Science Center