Bulk Gas-Phase Acidity

Authors

  • Dr. Daniel Himmel,

    1. Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum (FMF) and Freiburg Institute for Advanced Studies (FRIAS), Universität Freiburg, Albertstrasse 19, 79104 Freiburg (Germany)
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  • Dipl.-Chem. Sascha K. Goll,

    1. Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum (FMF) and Freiburg Institute for Advanced Studies (FRIAS), Universität Freiburg, Albertstrasse 19, 79104 Freiburg (Germany)
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  • Prof. Dr. Ivo Leito,

    1. Institute of Chemistry, University of Tartu, 14a Ravila Street, 50411 Tartu (Estonia)
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  • Prof. Dr. Ingo Krossing

    Corresponding author
    1. Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum (FMF) and Freiburg Institute for Advanced Studies (FRIAS), Universität Freiburg, Albertstrasse 19, 79104 Freiburg (Germany)
    • Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum (FMF) and Freiburg Institute for Advanced Studies (FRIAS), Universität Freiburg, Albertstrasse 19, 79104 Freiburg (Germany)
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Abstract

The capability of a gaseous Brønsted acid HB to deliver protons to a base is usually described by the gas-phase acidity (GA) value of the acid. However, GA values are standard Gibbs energy differences and refer to individual gas pressures of 1 bar for acid HB, base B, and proton H+. We show that the GA value is not suited to describe the bulk acidity of a gaseous acid. Here the pressure dependence of the activities of HB, H(HB)n+, and B(HB)m that result from gaseous autoprotolysis have to be considered. In this work, the pressure-dependent absolute chemical potential of the proton in the representative gaseous proton acids CH4, NH3, H2O, HF, and HCl was worked out and the general theory to describe bulk gas phase acidity—that can directly be compared with solution acidity—was developed.

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