Specific interactions of chromium (VI) oxoanions with anion-exchange membranes and their influence on the behavior of membranes in potassium dichromate solutions
Abstract
The thickness, ion exchange capacity, water content, gel phase volume fractions, specific electrical conductivity, and diffusion permeability of three anion-exchange membranes were determined in NaCl (pH 5.7) and K₂Cr₂O₇ (pH 4.0) solutions. The membranes studied included PFAEM and AEM Type 1 (pore-filled, manufactured by filling an inert substrate with an ion-exchange material) and MA-41P (hot-pressed from ground ion-exchange resin and low-pressure polyethylene powder). The behavior of the studied membranes in NaCl solutions matches independent experimental data for similar membranes and agrees well with the established microheterogeneous model. Near the isoelectric conductivity point, their specific conductivity increases in the series PFAEM ≪ MA-41P < AEM Type 1 with increasing exchange capacity, while in concentrated solutions it becomes governed by the volume fraction of electrically neutral solution in their pores. The integral diffusion permeability coefficients decrease with both increasing ion exchange capacity and external solution dilution due to enhanced Donnan exclusion of co-ions. Notably, commercial membranes show high diffusion permeability primarily caused by large extended macropores at the ion-exchange material/reinforcing fiber interfaces.
In K₂Cr₂O₇ solutions, the electrical conductivity of all membranes decreased by 1-2 orders of magnitude compared to NaCl, attributed to specific interactions between Cr(VI) oxoanions and the membranes’ fixed groups. The integral diffusion permeability coefficients decreased with increasing K₂Cr₂O₇ concentration, likely due to enrichment with polychromate anions. The MA-41P membrane exhibited rapid degradation (within 2-5 hours) due to chromate-induced oxidation of its aromatic polymer matrix and chemisorption by fixed groups. In contrast, PFAEM and AEM Type 1 porous membranes, based on a copolymer of vinylidene fluoride and hexafluoropropylene (PFAEM) or polyacrylamide (AEM Type 1), showed greater stability in chromate solutions. The (CH₃)N⁺(C₈H₁₇)₃ fixed groups of the PFAEM membrane remained stable in K₂Cr₂O₇, unlike the –N⁺(CH₃)₃ groups of the AEM Type 1 and MA-41P membranes.
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