A new theory of strong polyelectrolyte solutions based upon the Poisson‐Boltzmann equation is presented. Assuming that the ratio of the effective charge of the macro ion to its original charge is very small, the Poisson‐Boltzmann equation is solved without adopting the Debye‐Hückel approximation. As a result of the calculation, the effective charge of the actual coiled macro ion with the strongly dissociative groups was found small enough to justify this assumption for the solutions of varying concentration over wide range. Moreover, the free energy, and consequently the chemical potential of the components, of the polyelectrolyte solution with or without simple salt are calculated. The idea of “ion fixation” is theoretically introduced as convenient for representing the state of the polyelectrolyte solution. The theoretical results obtained above are quantitatively compared with experimental data with very good agreement.
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