RESUMO
The features of the electrochemical behavior of experimental heterogeneous ion-exchange membranes with different mass fractions of sulfonated cation-exchange resin (from 45 to 65 wt%) have been studied by voltammetry during electrodialysis. Electromembrane systems with 0.01 M NaCl solution and with a mixed 0.01 M NaCl + 0.05 M phenylalanine (Phe) solution have been investigated. A significant influence of the ion-exchanger content on the parameters of current-voltage curves (CVCs) was established for the first time. Electrodialysis of the sodium chloride solution revealed a decrease in the length of the limiting current plateau and in the resistances of the second and third sections of the CVCs with an increase in the resin content in the membrane. The fact of the specific shape of the CVCs of all studied cation-exchange membrane samples in mixed solutions of the mineral salt and the amino acid was established. A specific feature of current-voltage curves is the presence of two plateaus of the limiting current and two values of the limiting current, respectively. This phenomenon in electromembrane systems with neutral amino acids has not been found before. The value of the first limiting current is determined by cations of the mineral salt, which are the main current carriers in the system. The presence of the second plateau and the corresponding second limiting current is due to the appearance of additional carriers due to the ability of phenylalanine as an organic ampholyte to participate in protolytic reactions. In the cation-exchange electromembrane system with the phenylalanine containing solution, two mechanisms of H+/OH- ion generation through water splitting and acid dissociation are shown. The possibility of the generation of H+/OH- ions at the enriched solution/cation-exchange membrane interface during electrodialysis of amino acid containing solutions is shown for the first time. The results of this study can be used to improve the process of electromembrane demineralization of neutral amino acid solutions by both targeted selection or the creation of new membranes and the selection of effective current operating modes.
RESUMO
A comparative analysis of the effect of the manufacturing technology of heterogeneousion-exchange membranes Ralex CM Pes manufactured by MEGA a.s. (Czech Republic) on the structural properties of their surface and cross section by SEM was carried out. The CM Pes membrane is a composite of a sulfonated ion-exchanger with inert binder of polyethylene and reinforcing polyester fiber. In the manufacture of membranes Ralex the influence of two factors was investigated. First, the time of ion-exchange grain millingvaried at a constant resin/polyethylene ratio. Second, the ratio of the cation-exchanger and the inert binder of polyethylene varied. It has been found that the membrane surface becomes more electrically homogeneous with the growth of the ion-exchanger loading and a decrease in its particle size. With an increase in the milling time of resin grainsfrom 5 to 80 min a more than 1.5-fold decrease in their radius and in the distance between them was revealed.Besides, there is a 1.5-fold decrease in the fraction, as well as in the size of pores and structure defects. The fraction of the ion-exchange phase on the membrane surface decreases by 7%. With an increase in the resin loading from 45 to 70 wt %, the growth of the fraction of conducting regions on the surface is almost twofold, while their sizes remain practically unchanged. More significant changes in the surface structure of the studied membranes are established in comparison with the cross section.An increase in the resin content in the membranes from 45 to 70 wt % corresponds to a 43% increment of its fraction on the cross-section.The increase in the ion-exchanger content of Ralex membranes is accompanied by the growth of the fraction of macropores and structure defects on the membrane surface by 70% and a twofold decrease in the distance between conducting zones.
