Journal of Colloid and Interface Science, Vol.215, No.1, 131-139, 1999
Comparison of the Poisson-Boltzmann model and the Donnan equilibrium of a polyelectrolyte in salt solution
A sequence of charged parallel hat plates immersed in a salt solution is used to model the swelling behavior of a polyelectrolyte. The solution of the nonlinear Poisson-Boltzmann equation gives rise to an analytical expression of the plate distance as a function of swelling pressure (p), plate charge density (sigma), and salt concentration (n). The exact treatment of the system also yields the connection between polyelectrolyte concentration n(P), p, sigma, and n. A formula for the electric potential difference between polyelectrolyte and salt solutions is derived. On the other hand, the relation between n(P), p, and n is known from the Donnan equilibrium. It is shown that the Donnan potential, U-D(n(p), n), and swelling pressure, p(D)(n(P), n), are always larger than the equivalent quantities in the Poisson-Boltzmann theory (U-PB(sigma, n(P), n) and p(PB)(sigma, n(P), n), respectively). The transition from the Poisson-Boltzmann theory to the Donnan model is achieved by the limiting process theta --> 0 which reveals the intrinsic linkage between the two theories. P-D(n(P), n) = lim(sigma-->0) p(PB)(sigma, n(P), n) and U-D(n(P), n) = lim(sigma-->0) U-PB(sigma, n(P), n).