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Related Concept Videos

Theory of Strong Electrolytes01:23

Theory of Strong Electrolytes

The interionic forces of the strong electrolytes depend on the solvent's dielectric constant, which is the ability of a solvent to store electrical energy, based on its polarizability. and the solution's concentration. In high-dielectric solvents and in dilute solutions, weak electrostatic forces keep ions apart. However, in low-dielectric solvents or concentrated solutions, stronger interionic forces may cause ions to pair up as ionic doublets despite being fully ionized. The theory of strong...
The Debye–Hückel Theory of Electrolyte Solutions01:27

The Debye–Hückel Theory of Electrolyte Solutions

The Debye–Hückel theory, established by Peter Debye and Erich Hückel in 1923, is a fundamental concept in physical chemistry. It provides an understanding of the behavior of strong electrolytes in solution, particularly explaining their deviations from ideal behavior.The theory is based on Coulombic interactions (the attraction or repulsion between charged particles) between ions in solution. In an ionic solution, oppositely charged ions tend to attract each other. This means that cations...
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Water and other polar molecules are attracted to ions. The electrostatic attraction between an ion and a molecule with a dipole is called an ion-dipole attraction. These attractions play an important role in the dissolution of ionic compounds in water.
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Electrochemical Systems01:24

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Electrochemical systems provide a fascinating insight into the dynamic interplay of charged species within various phases. One notable example is the interaction between a membrane permeable to K⁺ ions but not to Cl⁻ ions, separating an aqueous KCl solution from pure water. As K⁺ ions diffuse through the membrane, they generate net charges on each phase, leading to a potential difference between them.Similarly, when a piece of Zn is immersed in an aqueous ZnSO₄ solution, the Zn metal, composed...
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Pure water is a weak electrolyte; only a small amount ionizes into hydrogen and hydroxide ions. At any given temperature, the concentration of undissociated water is almost constant, so the ionic product of water is the product of the hydrogen and hydroxide ion concentrations, denoted as Kw. The square root of Kw gives the individual ion concentrations.
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Protein Film Infrared Electrochemistry Demonstrated for Study of H2 Oxidation by a [NiFe] Hydrogenase
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Linking Local Water Electrostatic Potentials to Measured Hydrogen Evolution Onset in Aqueous Electrolytes.

Abdullah Ozkanlar1, Jacob I Morton2, Emily T Nienhuis2

  • 1Department of Chemistry, The University of Utah, Salt Lake City, Utah 84112, United States.

The Journal of Physical Chemistry Letters
|July 2, 2026
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Summary

Electrochemical stability in aqueous electrolytes is limited by the hydrogen evolution reaction (HER). This study reveals that the local electrostatic potential at water oxygen atoms controls HER onset potential, offering a molecular understanding of electrolyte stability.

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Published on: August 17, 2016

Area of Science:

  • Electrochemistry
  • Physical Chemistry
  • Materials Science

Background:

  • Electrochemical stability of aqueous electrolytes is limited by the hydrogen evolution reaction (HER).
  • The molecular origin of HER onset potential's dependence on salt concentration is unresolved.
  • Previous studies suggested a link between redox potential and local electrostatic potential.

Purpose of the Study:

  • To investigate the molecular origin of the concentration dependence of the hydrogen evolution reaction (HER) onset potential in aqueous electrolytes.
  • To establish a link between local electrostatic potentials and bulk electrochemical observables.
  • To develop a predictive model for concentration-dependent HER onset potentials.

Main Methods:

  • Voltammetric measurements of HER onset potential in aqueous NaNO2.
  • Molecular dynamics simulations to determine local electrostatic potential at water oxygen atoms (V_OW).
  • Analysis of the correlation between V_OW and HER onset potential (U_HER).

Main Results:

  • Water reduction is controlled by the local electrostatic potential at water oxygen atoms (V_OW).
  • A quadratic concentration dependence was observed for both V_OW and U_HER, indicating a linear correlation.
  • The study successfully predicted concentration-dependent U_HER, linking electrostatic potentials to a bulk electrochemical observable.
  • Electrochemical stability was found to be complementary and anticorrelated with pKw.

Conclusions:

  • The local electrostatic potential at water oxygen atoms is the key factor governing HER onset potential in aqueous electrolytes.
  • The developed model provides a molecular handle on the electrochemical stability window of aqueous electrolytes.
  • This approach requires only classical sampling and is extensible to other salts, offering a simpler alternative to DFT or ab initio MD.