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Updated: Nov 7, 2025

Dynamic Electrochemical Measurement of Chloride Ions
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On the time-dependent electrolyte Seebeck effect.

André Luiz Sehnem1, Mathijs Janssen2

  • 1Institute of Physics, University of São Paulo, CEP 05508-090 São Paulo, Brazil.

The Journal of Chemical Physics
|May 4, 2021
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Summary
This summary is machine-generated.

The electrolyte Seebeck effect generates an electric field from temperature gradients due to differing ion movement. This study derives a new model and finds experimental results are one order of magnitude larger than predicted.

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Area of Science:

  • Physical Chemistry
  • Electrochemistry
  • Materials Science

Background:

  • Single-ion Soret coefficients (αᵢ) quantify ion movement in thermal gradients.
  • Differences in cation and anion Soret coefficients can generate electric fields (electrolyte Seebeck effect).
  • Previous models often neglect the role of electrode boundary layers in thermoelectric field generation.

Purpose of the Study:

  • To derive a time-dependent Seebeck coefficient (S(t)) model for binary electrolytes under time-dependent thermal gradients, enforcing local electroneutrality.
  • To experimentally measure S(t) for various electrolytes near titanium electrodes.
  • To compare experimental findings with theoretical predictions and literature values for Soret coefficients.

Main Methods:

  • Theoretical derivation of S(t) for binary electrolytes, incorporating local charge neutrality at boundaries.
  • Experimental measurement of S(t) for five different acids, bases, and salts using titanium electrodes.
  • Fitting the derived S(t) expression to experimental data, treating αᵢ as adjustable parameters.

Main Results:

  • The derived model accounts for the time-dependent thermoelectric field generation in electrolytes.
  • Experimental steady-state Seebeck coefficients (S) were approximately 2 mV K⁻¹, an order of magnitude higher than literature predictions.
  • Fitted αᵢ values were consistently larger than those reported in existing literature.

Conclusions:

  • The electrolyte Seebeck effect is significantly influenced by boundary phenomena, not solely a bulk effect.
  • Existing literature values for single-ion Soret coefficients may underestimate their contribution to thermoelectric effects in electrolytes.
  • The developed model and experimental validation provide a more accurate understanding of thermoelectric phenomena in electrolyte solutions.