Theoretical investigations of phase separation in polyelectrolyte solutions have so far assumed that the effective charge of the polyelectrolyte chains is fixed. The ability of the polyelectrolyte chains to self-regulate their effective charge due to the self-consistent coupling between ionization equilibrium and polymer conformations, depending on the dielectric constant, temperature, and polymer concentration, affects the critical phenomena and phase transitions drastically. By considering salt-free polyelectrolyte solutions, we show that the daughter phases have different polymer charges from that of the mother phase. The critical point is also altered significantly by the charge self-regularization of the polymer chains. This work extends the progress made so far in the theory of phase separation of strong polyelectrolyte solutions to a higher level of understanding by considering chains which can self-regulate their charge.

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