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Frumkin’s adsorption model – a successful approach for understanding surfactant adsorption layers

  • Nayereh Sadat Mousavi ORCID logo , Aliyar Javadi ORCID logo , Volodymyr I. Kovalchuk ORCID logo , Eugene V. Aksenenko ORCID logo , Giuseppe Loglio ORCID logo , Dieter Vollhardt , Emanuel Schneck ORCID logo and Reinhard Miller ORCID logo EMAIL logo
Published/Copyright: August 13, 2025
Zeitschrift für Physikalische Chemie
From the journal Zeitschrift für Physikalische Chemie Volume 239 Issue 10

Abstract

There are various thermodynamic models to quantitatively describe the adsorption of surfactant molecules at the surface of their aqueous solutions. The Frumkin adsorption model is one of the most successful ones as it provides essential parameters, such as the surface activity of the studied surfactant, the minimal required molecular area at the interface, and the intermolecular interaction in the adsorption layer. Since it was published 100 years ago, the model has served as the starting point for various refinements, such as for molecular reorientations or two-dimensional aggregations at fluid interfaces or as generalized model for the adsorption of surfactant mixtures. Also, the recently developed approach for understanding the cooperativity in the formation of surfactant adsorption layers at water/oil interfaces is based on Frumkin’s model. Due to its clear physical idea, it was successfully applied to quantitatively describe various types of surfactant systems. The values of the three model parameters allow for a categorization of surfactants with respect to their efficient application in numerous technological fields.

Keywords: surfactant adsorption; interfacial tension; thermodynamic model; equation of state; Frumkin adsorption model; interfacial interaction
Corresponding author: Reinhard Miller, Institute for Condensed Matter Physics, TU Darmstadt, 64289, Darmstadt, Germany, E-mail:

Appendix: Brief Curriculum Vitae of Alexander Naumowitsch Frumkin (1895–1976)

Alexander Frumkin, a pioneer in electrochemistry, was born 1895 in Kishinev, Russian Empire (now Chişinău, Moldova) and passed away in 1976 in Tula (Soviet Union, now Russia). He showed an early talent for science. He pursued his studies at the University of St. Petersburg, where his passion for physical chemistry led to groundbreaking contributions in electrochemistry. In 1932, Frumkin was elected to the Russian Academy of Sciences. He founded the journal Elektrokhimiya (Russian Journal of Electrochemistry), providing a platform for electrochemical research both within the Soviet Union and internationally. His pioneering work shaped modern electrochemistry and surface science, particularly in adsorption at interfaces, electrode kinetics, and electrochemical double layers. Frumkin played a central role in developing the modern theory of the electrochemical double layer, emphasizing the impact of specific adsorption on electrode potential and kinetics – insights that influenced later models such as those of Stern and Grahame. 52 His studies on hydrogen overpotential and charge transfer reactions remain foundational in fuel cell technology and corrosion science. 53 He demonstrated that adsorption affects electrode reaction rates, a phenomenon now known as the Frumkin correction in electrochemical kinetics, which has significant implications for catalysis, electro-sorption, and battery performance. 54 His research also led to the identification of what is now called the Frumkin effect, highlighting how electrode reaction rates depend not only on the potential but also on the adsorption and interactions of reaction intermediates. This understanding has been crucial in electrocatalysis and the optimization of electrochemical processes. Frumkin’s investigations into the electrochemical double layer included extensive studies on the potential of zero charge (PZC). His work clarified the ion distribution at the electrode-electrolyte interface and the factors influencing PZC, crucial for electrode kinetics and colloidal stability. 55 , 56 His contributions to electrochemistry have been widely recognized, including through the establishment of the Frumkin Medal by the International Society of Electrochemistry. This prestigious award, given biennially, honors outstanding lifetime achievements in fundamental electrochemistry. His legacy continues to shape contemporary research in electrochemistry, surface science, and related fields, underscoring the lasting significance of his work. Further details on Frumkin’s CV are given for example in. 57 , 58

  1. Research ethics: Not applicable.

  2. Informed consent: Not applicable.

  3. Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  4. Use of Large Language Models, AI and Machine Learning Tools: None declared.

  5. Conflict of interest: The authors state no conflict of interest.

  6. Research funding: None declared.

  7. Data availability: Not applicable.

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Received: 2025-02-21
Accepted: 2025-07-25
Published Online: 2025-08-13
Published in Print: 2025-10-27

© 2025 Walter de Gruyter GmbH, Berlin/Boston

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https://doi.org/10.1515/zpch-2025-0017
Keywords for this article
surfactant adsorption; interfacial tension; thermodynamic model; equation of state; Frumkin adsorption model; interfacial interaction

Articles in the same Issue

  1. Frontmatter
  2. Review Articles
  3. Surfactants in action: chemistry, behavior, and industrial applications
  4. Smart nanomaterials for clean water and a comprehensive exploration of the potentials of metal oxide nanoparticles in environmental remediation
  5. Nanomaterials at the forefront: classification, fabrication technique, and cross-sector applications
  6. Original Papers
  7. Unlocking the potential of FeNbGe Half Heusler: stability, electronic, magnetic and thermodynamic properties
  8. Investigating the antibacterial potency of Schiff base derivatives as potential agents for urinary tract infection: DFT, solvation, molecular docking and pharmacokinetic studies
  9. Continuous rapid cooling of polarized electrons initiates Mpemba superfreezing
  10. Synthesis and characterization of CNTs doped polymeric composites: comparative studies on exploring impact of CNT concentration on morphological, structural, thermokinetic and mechanical attributes
  11. Frumkin’s adsorption model – a successful approach for understanding surfactant adsorption layers
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