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Equilibrium potentials of membrane electrodes.

J H Wang, E Copeland

    Proceedings of the National Academy of Sciences of the United States of America
    |July 1, 1973
    PubMed
    Summary
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    A new thermodynamic theory for membrane electrodes, including the glass electrode for pH measurement, was developed. This theory explains electrode potentials based on ion adsorption and was validated by a novel coated electrode exhibiting linear pH response.

    Area of Science:

    • Electrochemistry
    • Physical Chemistry
    • Materials Science

    Background:

    • Traditional theories of membrane electrode potentials often focus solely on ion transport.
    • A more comprehensive understanding is needed to account for surface interactions.
    • The glass electrode is a key tool for pH measurement, but its theoretical underpinnings can be complex.

    Purpose of the Study:

    • To formulate a simple thermodynamic theory for equilibrium potentials of membrane electrodes.
    • To apply this theory to the glass electrode for accurate pH measurement.
    • To incorporate selective ion adsorption as a primary mechanism, with ion transport as a special case.

    Main Methods:

    • Developed a thermodynamic theory based on selective ion adsorption at the membrane surface.

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  • Created a novel electrode by coating platinum wire with stearic acid and methyl-tri-n-octyl-ammonium stearate.
  • Tested the electrode's performance in aqueous phosphate solutions across a range of pH values.

    • Main Results:

    • The developed theory successfully explains equilibrium potentials of membrane electrodes.
    • The novel coated electrode demonstrated a linear potential response as a function of pH from pH 2 to 12.
    • The observed slope of 59.0 mV per pH unit at 24°C matched the theoretical prediction.

    Conclusions:

    • The new thermodynamic theory provides a robust framework for understanding membrane electrode potentials.
    • Selective ion adsorption is a critical factor in electrode behavior, complementing existing transport theories.
    • The developed coated electrode shows promise for reliable and accurate pH measurements.