Sorption of ions by hydrous ferric oxide (HFO) often shows a fast initial sorption reaction followed by a much slower sorption process. The second step is diffusion-controlled and can continue for days or months before equilibrium is reached. In this paper, we demonstrate that the diffusion rate may be explained by electrostatic interactions. The internal and external surfaces of HFO are generally positively charged and therefore repel cations. This can result in extremely low cation concentrations in pores, and therefore a significant reduction in pore diffusion rate. The theory is demonstrated here for sorption of Sr(2+) in HFO aggregates. The ion concentrations in the pore space are calculated using a Donnan model and diffusion is calculated from the Donnan concentration and potential gradients. This diffusion model is compared with nonelectrostatic pore diffusion, which does not take electrostatic interactions into account. The Donnan model predicts very low concentrations of Sr(2+) in the pores and diffusion rates that are up to 8000 times lower than predicted with a nonelectrostatic model.
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http://dx.doi.org/10.1016/j.jcis.2004.08.067 | DOI Listing |
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