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A new modified Poisson-Boltzmann equation accounting for the finite size ofthe ions valid for realistic salt-free concentrated suspensions has beenderived, extending the formalism developed for pure salt-free suspensions [Roaet al., Phys. Chem. Chem. Phys., 2011, 13, 3960-3968] to real experimentalconditions. These realistic suspensions include water dissociation ions andthose generated by atmospheric carbon dioxide contamination, in addition to theadded counterions released by the particles to the solution. The electricpotential at the particle surface will be calculated for different ion sizesand compared with classical Poisson-Boltzmann predictions for point-like ions,as a function of particle charge and volume fraction. The realistic predictionsturn out to be essential to achieve a closer picture of real salt-freesuspensions, and even more important when ionic size effects are incorporatedto the electric double layer description. We think that both corrections haveto be taken into account when developing new realistic electrokinetic models,and surely will help in the comparison with experiments for low-salt orrealistic salt-free systems.

Ion size effects on the electric double layer of a spherical particle in a realistic salt-free concentrated suspension