Abstract
The dependence was found between relative diffusion current decrease and the deviation from Ilković-Stokes-Einstein (ISE) equation (1a). This dependence is given by eqn. (7) 1−idc=z(idcη0.5−1 where idr is the relative diffusion current, ηr is the relative viscosity, and z is the coefficient of proportionality. This dependence was established on the basis of results of measurements of diffusion current and viscosity. These measurements were carried out in concentrated polyethylene glycol (PEG) solutions containing Cd2+ or Tl+ ions as reactant. The coefficient z is dependent on the mean polymerization degree(̄). This dependence is given by eqn. (9) z(n−1)a=b where a and b are constants for a given reactant. These constants were determined for Cd2+ and Tl+ ions. Both eqns. (7) and (9) may be used to find the dependence between̄ idr and ηr in the form of eqn. (11) n=1−[b(idcη0.5−1)/1−idc]a−1 The new method, suitable for determination of the mean polymerization degree, is based on this equation and on the measurements of diffusion current and viscosity in concentrated PEG solutions. Results of̄ obtained with this method have relative low standard deviations in comparison with the method based on determination of intrinsic viscosity and also (for̄>10) with the method based on determination of the hydroxyl number.
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