The true Hückel equation for electrolyte solutions and its relation with the Born term

Gabriel M. Silva, Xiaodong Liang, Georgios M. Kontogeorgis*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

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Abstract

In this work we present Hückel’s original derivation and considerations, verifying the approximations that were done in his paper. More complex equations are obtained by not applying some of Hückel’s approximations, and these equations are compared to the original Hückel equation. We explore the use of both a linear and an experimental concentration dependency of the relative permittivity to represent experimental data. We show that Hückel’s equation, as known today in its semi-empirical form, is not the full model or even the approximate model the author had derived in his original work, being only an approximation of his full theoretical method. Both the original Hückel equation, and the equation used in literature, represent important developments when compared to the original Debye-Hückel equation. We also show that Hückel had already derived and used the Born term in his work, clarifying thus the connection between the Hückel equation and the Born term. Finally, we derive different equations from Hückel and estimate the error introduced by his method of considering the concentration-dependency of the dielectric constant only after deriving the charge work.
Original languageEnglish
Article number120554
JournalJournal of Molecular Liquids
Volume368
Issue numberPart A
Number of pages15
ISSN0167-7322
DOIs
Publication statusPublished - 2022

Keywords

  • Electrolytes
  • Hückel Equation
  • Activity Coefficient
  • Born Term
  • Debye-Hückel
  • Charging Process
  • Relative Permittivity

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