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The response of a suspension under a variety of static or alternatingexternal fields strongly depends on the equilibrium electric double layer thatsurrounds the colloidal particles in the suspension. The theoretical models forsalt-free suspensions can be improved by incorporating non-uniform size effectsand orientational ordering of water dipoles neglected in previous mean-fieldapproaches, which are based on the Poisson-Boltzmann approach. Our modelincluding non-uniform size effects and orientational ordering of water dipolesseems to have quite a promising effect because the model can predict thephenomena like a heavy decrease in relative permittivity of the suspension andcounterion stratification near highly charged colloidal particle. In this workwe numerically obtain the electric potential, the counterions concentration andthe relative permittivity around a charged particle in a concentrated salt-freesuspension corrected by non-uniform size effects and orientational ordering ofwater dipoles. The results show the worth of such corrections for medium tohigh particle charges at every particle volume fraction. We conclude thatnon-uniform size effects and orientational ordering of water dipoles arenecessary for the development of new theoretical models to studynon-equilibrium properties in concentrated colloidal suspensions.

physical chemistry chemical physics/pccp. physical chemistry chemical physics

Electric double layer of colloidal particles in salt-free concentrated  suspensions including non-uniform size effects and orientational ordering of  water dipoles