Laser-interferometric study of the mechanism of phenylalanine transfer through heterogeneous Ralex CMH membranes with different content of cation exchange resin in the overlimiting current modes
Abstract
The paper presents the capabilities of the laser interferometry method for studying the features of transfer and mechanisms of transport of the neutral amino acid phenylalanine at different stages of concentration polarization of the electromembrane system. The objects of the study were mixed solutions of phenylalanine (0.05 M) and sodium chloride (0.01 M). Electrodialysis was carried out in a galvanostatic mode using experimental membranes Ralex CMH (Mega a.s., Czech Republic) with a fraction of sulfonated cation exchange resin in the range from 45 to 70 wt. %. An original setup was used that allows visualization of concentration profiles and the occurrence of hydrodynamic phenomena in the solution at the boundary with ion-exchange membranes with simultaneous recording of the current-voltage characteristics (CVC) of the membranes and analysis of the concentrations of components in the solutions flowing out of the electrodialyzer compartments. It is shown that for all experimental cation-exchange membranes at the degree of polarization of the system i/ilim<2.0, the amino acid fluxes had a traditional form for the ampholyte with an extremum at i/ilim=1.0, reflecting the presence of a barrier effect. It was shown experimentally and by calculation that the effects of catalytic water splitting and electroconvection determine the features of transport through the cation-exchange membrane. The role of catalytic water splitting due to the reaction between water molecules and amino acid, consisting in alkalization of the solution of the demineralization compartment and acidification of the solution of the adjacent concentration compartment in the entire range of currents, was revealed. The limitation of the transmembrane transfer of the amino acid at currents of 1.0<i/ilim<2.0 occurs due to a sharp decrease in the concentration of cations and bipolar ions of the amino acid due to the catalytic water splitting and an increase in the pH value at the interface with the cation-exchange membrane and in the volume of the demineralization compartment.
The use of membranes with a variable content of ion-exchange resin made it possible to reveal an insignificant share of the contribution of the coupled amino acid transfer in the hydration shell of counterions in the range of underlimiting currents and with the products of catalytic water splitting in the high-intensity current modes. A negative correlation was found between the sulfocation-exchange resin content in the membrane and the amino acid mass transfer in the underlimiting current modes of electrodialysis. The method of dynamic laser interferometry was used for the first time to obtain direct evidence that the main reason for the increase in amino acid transfer through the sulfonated cation exchange membrane in the overlimiting current modes is the occurrence of electroconvective mixing of the solution at the interface. At currents i/ilim>2.0, the establishment of an unstable electroconvection mode was revealed, manifested in a non-stationary oscillatory nature of interference bands, potential oscillations and an increase in the thickness of the region of electroconvective vortices in the solution with an increase in the current density. In this region of currents, differentiation of amino acid fluxes through membranes with different resin contents completely disappears. The presence of volumetric turbulent mixing of the solution at the interface of the CMH membrane with an ion-exchange resin content of 70 wt. % was confirmed by the flicker-noise spectroscopy method based on the analysis of the power spectrum of interference band fluctuations. It was shown that electroconvection negatively affects the process of catalytic water splitting and destroys the barrier effect of the near-membrane layers of the solution with a high pH value.
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