The nature of the approximations involved in the derivation of the Poisson‐Boltzmann equation of the Debye‐Hu¨ckel theory is investigated in detail from the standpoint of classical statistical mechanics. The validity of the initial Debye approximation, under the restrictions originally imposed upon it, is confirmed. Deviations arising from fluctuation terms and van der Waals forces are roughly estimated. An alternative to the Bjerrum method for the treatment of ions of small size and high valence is outlined.
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