F J M Schipper et al 1997 J. Phys.: Condens. Matter 9 11179 doi:10.1088/0953-8984/9/50/019
F J M Schipper, J G Hollander and J C Leyte
Show affiliationsThe self-diffusion coefficient of
, tetra-methylammonium
, tetra-ethylammonium
, tetra-propylammonium
and tetra-butylammonium
in solutions of the weak polymethacrylic acid (PMA) were measured with PFG NMR. No additional salt was present in any of the experiments. The polyion concentration and degree of neutralization were varied. The maximum relative counterion self-diffusion coefficient against polyion concentration, that was reported earlier, was observed for both alkali and tetra-alkylammonium
counterions. We propose that the maximum is due to the combination of the obstruction by the polyion and the changing counterion distribution at increasing polyion concentration. An explanation of this proposal is offered in terms of the Poisson - Boltzmann - Smoluchowski (PBS) model for polyelectrolytes. Qualitative agreement of this model with experiment was found for the dependence of the counterion self-diffusion coefficient on the degree of neutralization of the polyion, on counterion radius and on polyion concentration, over a concentration range from 0.01 to 1
. Adaption of the theoretical obstruction, to fit the self-diffusion data of the solvent, also greatly improves the model predictions on the counterion self-diffusion.
Issue 50 (15 December 1997)
Received 4 June 1997, in final form 26 August 1997
F J M Schipper et al 1997 J. Phys.: Condens. Matter 9 11179
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