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@ARTICLE{Janotta:1041223,
      author       = {Janotta, Benjamin and Schalenbach, Maximilian and Tempel,
                      Hermann and Eichel, Rüdiger-A.},
      title        = {{F}itting ambiguities mask deficiencies of the
                      {D}ebye–{H}ückel theory: revealing inconsistencies of the
                      {P}oisson–{B}oltzmann framework and permittivity},
      journal      = {Physical chemistry, chemical physics},
      volume       = {27},
      number       = {15},
      issn         = {1463-9076},
      address      = {Cambridge},
      publisher    = {RSC Publ.},
      reportid     = {FZJ-2025-02171},
      pages        = {7703 - 7715},
      year         = {2025},
      abstract     = {The more than 100-year-old Debye–Hückel theory displays
                      the most widely used approach for modeling ionic activities
                      in electrolytes. The Debye–Hückel theory finds widespread
                      application, such as in equations of state and Onsager's
                      theory for conductivities. Here, a theoretical inconsistency
                      of the Debye–Hückel theory is discussed, which originates
                      from the employed Poisson–Boltzmann framework that
                      violates the statistical independence of states presumed for
                      the Boltzmann statistics. Furthermore, the static
                      permittivity of electrolytic solutions is discussed as not
                      directly measurable, while common methods for its extraction
                      from experimental data are assessed as erroneous. A
                      sensitivity analysis of modeled activity coefficients with
                      respect to the permittivity and ionic radii as input
                      parameters is conducted, showing that their influences
                      overshadow physicochemical differences of common variations
                      of Debye–Hückel models. Eventually, this study points out
                      that the justification of the traditional and still often
                      used Debye–Hückel models by experimental validation is
                      affected by fitting ambiguities that eventually impede its
                      predictive capabilities.},
      cin          = {IET-1},
      ddc          = {540},
      cid          = {I:(DE-Juel1)IET-1-20110218},
      pnm          = {1231 - Electrochemistry for Hydrogen (POF4-123) / PRELUDE -
                      Verbundvorhaben PRELUDE: Prozess- und Meerwasser-Elektrolyse
                      für eine umweltverträgliche Grüne Wasserstoffwirtschaft
                      in Deutschland (BMBF-03SF0650A) / HITEC - Helmholtz
                      Interdisciplinary Doctoral Training in Energy and Climate
                      Research (HITEC) (HITEC-20170406)},
      pid          = {G:(DE-HGF)POF4-1231 / G:(DE-Juel1)BMBF-03SF0650A /
                      G:(DE-Juel1)HITEC-20170406},
      typ          = {PUB:(DE-HGF)16},
      pubmed       = {40151984},
      UT           = {WOS:001454550800001},
      doi          = {10.1039/D5CP00646E},
      url          = {https://juser.fz-juelich.de/record/1041223},
}