Counterion condensation and effective charge of poly(styrenesulfonate)

The effective charge of poly(styrenesulfonate) has been investigated by diffusion and electrophoresis nuclear magnetic resonance (NMR). While the electrophoretic mobility is determined in the electrophoresis NMR experiment, the hydrodynamic friction is determined from diffusion NMR using Einstein's formula. On the timescale of the NMR experiment a steady state is reached, which results from the force balance between the electric field and the hydrodynamic friction from that the effective charge is calculated without any further model. For the monomer and short polymers the effective charge is equal to the nominal charge, the difference increases with an increasing degree of polymerisation. Increasing the ionic strength of the solution leads to enhanced counterion condensation. If the dielectric constant of the solution is lowered, condensation of counterions is enhanced as well. A lowered effective charge results in reduced repelling forces along the polymer chain and thus in a more compact conformation of the polymer as reflected in the hydrodynamic size. The effective charge of poly(styrenesulfonate) has been studied experimentally as a function of the degree of polymerisation, of the ionic strength and the dielectric constant of the solution.