Comparison of immittance spectroscopy analyses of ultra-pure and “pure” water in the lower frequency regime

Two different analyses of impedance data obtained from ultra-pure water allowed to equilibrate with the atmosphere have recently appeared. They both thus show much smaller low-frequency resistances than does ultra-pure water. Different fitting models were used in these analyses and led to appreciably different parameter estimates from their data fits. Their two “pure” water experimental data sets are here analyzed with a Poisson-Nernst-Planck model that incorporates the possibility of dissociation of a neutral species to positive and negative charges of arbitrary mobilities, anomalous diffusion in the interface region, and reaction of mobile ions at the electrodes. Complex-nonlinear-least-squares fitting of these data sets with either charges of a single sign mobile or with those of both signs mobile showed that the one-mobile choice was far superior to the two-mobile one. These results were compared both with newly calculated theoretical ultra-pure water immittance ones and with the results obtained in the earlier two papers, where different Poisson-Nernst-Planck-related fitting models were employed. Both involved the restrictive assumptions of full dissociation and two-mobile behavior with equal mobilities of the positive and negative charges. The dominant mobile charge species present in the equilibrated “pure” water data sets (protons for the ultra-pure water), involved mobile impurity ions, possibly oxygen ones. The Poisson-Nernst-Planck model used here is simpler than the other models, and it led to better fits of the data sets and to more physically significant parameter estimates than did the earlier fits.