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Toward robust computational electrochemical predicting the environmental fate of organic pollutants

Authors

  • Liudmila Sviatenko,

    1. Department of Chemistry and Biochemistry, Interdisciplinary Center for Nanotoxicity, Jackson State University, Jackson, Mississippi 39217
    2. Kirovograd State Pedagogical University, Kirovograd, Ukraine
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    • These two authors contributed equally to this work

  • Olexandr Isayev,

    1. Department of Chemistry, Case Western Reserve University, Cleveland, Ohio 44106
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    • These two authors contributed equally to this work

  • Leonid Gorb,

    1. SpecPro, Inc., Huntsville, Alabama 35805
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  • Frances Hill,

    1. US Army ERDC, Vicksburg, Mississippi 39180
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  • Jerzy Leszczynski

    Corresponding author
    1. Department of Chemistry and Biochemistry, Interdisciplinary Center for Nanotoxicity, Jackson State University, Jackson, Mississippi 39217
    2. US Army ERDC, Vicksburg, Mississippi 39180
    • Department of Chemistry and Biochemistry, Interdisciplinary Center for Nanotoxicity, Jackson State University, Jackson, Mississippi 39217
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Abstract

A number of density functionals was utilized for the calculation of electron attachment free energy for nitrocompounds, quinones and azacyclic compounds. Different solvation models have been tested on the calculation of difference in free energies of solvation of oxidized and reduced forms of nitrocompounds in aqueous solution, quinones in acetonitrile, and azacyclic compounds in dimethylformamide. Gas-phase free energies evaluated at the mPWB1K/tzvp level and solvation energies obtained using SMD model to compute solvation energies of neutral oxidized forms and PCM(Pauling) to compute solvation energies of anion-radical reduced forms provide reasonable accuracy of the prediction of electron attachment free energy, difference in free solvation energies of oxidized and reduced forms, and as consequence yield reduction potentials in good agreement with experimental data (mean absolute deviation is 0.15 V). It was also found that SMD/M05-2X/tzvp method provides reduction potentials with deviation of 0.12 V from the experimental values but in cases of nitrocompounds and quinones this accuracy is achieved due to the cancelation of errors. To predict reduction ability of naturally occurred iron containing species with respect to organic pollutants we exploited experimental data within the framework of Pourbaix (Eh − pH) diagrams. We conclude that surface-bound Fe(II) as well as certain forms of aqueous Fe(II)aq are capable of reducing a variety of nitroaromatic compounds, quinones and novel high energy materials under basic conditions (pH > 8). At the same time, zero-valent iron is expected to be active under neutral and acidic conditions. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011

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