Behavior of the Silver, Silver Chloride Electrode in Concentrated Aqueous Sodium Chloride

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Abstract
The reported solute and solvent activities of concentrated aqueous sodium chloride are not thermodynamically consistent within the apparent experimental errors. This result is attributed to a deviation of the silver, silver chloride electrode owing to the formation of a solid solution of silver chloride and sodium chloride. Electrochemical cell measurements and x‐ray diffraction results are reported in support of these conclusions. The mole fractions and activities of silver chloride in the solid solutions are calculated from solubility equilibria and are correlated with literature values of the activity coefficients of sodium chloride.

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