Effective hard-sphere model of diffusion in aqueous polymer solutions

An effective hard-sphere model of the diffusion and cross-diffusion of salt in unentangled polymer solutions is developed. Given the viscosity, sedimentation coefficient and osmotic pressure of the polymer, the model predicts the diffusion and cross-diffusion coefficients as functions of the polymer concentration and molecular weight. The results are compared with experimental data on NaCl diffusion in aqueous polyethylene glycol solutions, showing good agreement at polymer molecular weights up to 400\,g/L. At higher molecular weights the model becomes less accurate, likely because of the effects of entanglement. The tracer Fickian diffusivity can be written in the form of a Stokes-Einstein equation containing the solution viscosity. For NaCl diffusion in polyethylene glycol solutions, the Stokes-Einstein equation breaks down as the polymer size increases. Using Batchelor's viscous correction factor to determine an effective viscosity experienced by the salt ions within the polymer matrix leads to much closer agreement with experiment.