Electrode Polarization and Conductivity

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SUMMARY

The discussion centers on the phenomenon of electrode polarization and its impact on conductivity measurements in solutions. It highlights the use of a four-electrode measurement system and the application of alternating current at approximately 1000 Hz to mitigate polarization effects. Participants express a need for deeper theoretical and experimental insights into the dynamics of polarization layers, referencing Kolrausch's theory on ion mobility and the concept of double layers as described by Helmholtz and Stern.

PREREQUISITES
  • Understanding of electrochemistry principles, specifically electrode polarization.
  • Familiarity with four-electrode measurement techniques.
  • Knowledge of ion mobility theories, particularly Kolrausch's theory.
  • Basic concepts of double layer formation in electrochemical systems.
NEXT STEPS
  • Research the mathematical modeling of double layer dynamics in electrochemistry.
  • Explore experimental methods for measuring electrode polarization effects.
  • Study the implications of alternating current frequency on conductivity measurements.
  • Investigate advanced electrochemical textbooks or journals focusing on electrode behavior and ion mobility.
USEFUL FOR

This discussion is beneficial for electrochemists, researchers in materials science, and professionals involved in conductivity measurement and analysis in various solutions.

fsonnichsen
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The common mantra is that when measuring conductivity in solutions the electrodes will build up a polarization layer and disturb the measurement, thus a 4 electrode measurement is used and an alternating current impressed up on the outer electrodes, usually around 1000 hz.

I have been trying to learn more about the dynamics of these layers but my search of the journals and my somewhat limited chemistry library reveal nothing on this issue other than a brief mention. I would expect the theory of Kolrausch et. al. for ion mobility would play into this but I cannot find either theoretical information on the evolution of the layer with time, nor any experimental data.

Does anyone here know of a journal or textbook resource that deliberates on this, especially mathematically?

Thanks
Fritz
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The tomes of electrochemistry never seem to state this explicitly, but it makes sense that these develop as double layers--Helmholtz, Stern etc.
thanks
Fritz
 

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