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[EN] Electrodialysis is mostly used for drinking water production but it has gained applicability in different new fields in recent decades. Membrane characteristics and ion transport properties strongly influence the efficiency of electrodialysis and must be evaluated to avoid an intense energy consumption and ensure long membrane times of usage. To this aim, conducting studies on ion transport across membranes is essential. Several dynamic characterization methods can be employed, among which, chronopotentiometry has shown special relevance because it allows a direct access to the contribution of the potential in different states of the membrane/solution system. The present paper provides a critical review on the use of chronopotentiometry to determine the main membrane transport properties and to evaluate mass transfer phenomena. Properties, such as limiting current density, electrical resistances, plateau length, transport number of counter-ions in the membrane, transition times, and apparent fraction of membrane conductive area have been intensively discussed in the literature and are presented in this review. Some of the phenomena evaluated using this technique are concentration polarization, gravitational convection, electroconvection, water dissociation, and fouling/scaling, all of them also shown herein. Mathematical and experimental studies were considered. New trends in chronopotentiometric studies should include ion-exchange membranes that have been recently developed (presenting anti-fouling, anti-microbial, and monovalent-selective properties) and a deeper discussion on the behaviour of complex solutions that have been often treated by electrodialysis, such as municipal wastewaters. New mathematical models, especially 3D ones, are also expected to be developed in the coming years.

[EN] The use of cyanide-free complexing agents in brass electroplating has been tested in recent years and EDTA has shown to be a promising alternative. Herein, a rotating disc electrode was used to construct voltammetric curves and to evaluate the influence of the rotation speed on the quality of brass electrodepositionwith EDTA on steel. The reference and counter electrodes were made of Ag/AgCl and platinum, respectively. The influence of the galvanostatic/potentiostatic mode, charge density and bath concentration were also studied. By the voltammetric curves and the Koutecky-Levich equation, the diffusion coefficient of copper-EDTA was determined (2.9 x 10(-6) cm(2)/s) and it was verified that the electrodeposition of this metal is controlled bymass transport. For Zn-EDTA deposition, a mixed control (charge and mass transport) was suggested. The agitation generally darkened the deposits due to the hydrogen evolution and lower Cu/Zn proportions. However, for agitated solutions at -1.3 V, very good deposits were obtained with brightness and typical color of brass. Therefore, the operation at -1.3 V with agitation may be more interesting than at higher potentials. Charge densities between 0.5 and 1.0C/cm(2) must be used. Finally, the effluent generatedwas treated, by electrodialysis, and the recovery of the metals and EDTA on the bath was studied. In general, uniform and bright deposits were obtained.

[EN] After long-term electrodialysis, cleaning the membranes is crucial to extend their lifetime. In this work, we evaluate the effects of a three-stage chemical cleaning on electrochemical and structural properties of anion- and cation-exchange membranes. Membranes used in the electrodialytic treatment of a synthetic effluent from the cyanide-free brass electrodeposition were cleaned using 0.1, 0.5 and 1.0 mol.L-1 NaOH solutions. The electrochemical behavior of the membranes was evaluated after each cleaning step by chronopotentiometry. Additionally, changes in the membrane structure and composition were analyzed by FTIR-ATR and SEM/EDS. While the membranes undergo a decline in some electrochemical features after the electrodialysis process, the cleaning with 0.1 mol.L-1 NaOH showed to be the most effective in recovering the properties characteristic of the virgin membranes: the limiting current density increased by 84% after the cleaning, whereas the ohmic and overlimiting resistances decreased by 47% and 55%, respectively. In contrast, the 0.5 and 1.0 mol.L-1 NaOH solutions degraded the membranes and reduced their fraction of conducive area, especially for the anion-exchange one. This favored fouling/scaling occurrence, as noticed by a prominent increase in the potential drop of the anion-exchange membrane. FTIR-ATR and SEM/EDS analyses confirmed fouling/scaling, as well as degradation of the ion-exchange membranes.

[EN] The use of EDTA as a complexing agent in electrodialysis has gained increasing attention in several industrial applications. Variations in pH at the membrane surface are known to alter the chemical equilibrium of EDTA species during electrodialysis. In this work, we investigate the simultaneous transport of EDTA species and hydroxyl ions through an anion-exchange membrane under alkaline conditions, and the influence of their relative concentrations on relevant membrane transport properties. Chronopotentiometric and current-voltage curves were obtained using solutions at different pH and electrolyte concentrations. Intense oscillations in membrane potential drop and a reduction in membrane resistance over time were verified for the solution at pH 11, where EDTA(4-) and OH- ions presented similar molar concentrations. While the intense oscillations can be associated with the onset of electroconvection, the reduction in membrane potential drop can be explained based on the alteration of the chemical equilibrium in the system. At an advanced stage of concentration polarization, the increased exclusion of protons in the membrane phase induces an equilibrium shift and the dissociation of HEDTA(3-) into EDTA(4-) and H+ ions. The formed EDTA(4-) ions migrate to the enriched solution, while protons are released back to the diluting diffusion boundary layer, increasing the conductivity in this region. The equilibrium shift in the membrane/electrolyte system and intense electroconvection at the membrane surface were also noted with the solution at pH 12. When the concentrations of OH- and EDTA species are similar, the equilibrium shift and the occurrence of overlimiting phenomena become more prominent.

[EN] Growing environmental concerns have led to the development of cleaner processes, such as the substitution of cyanide in electroplating industries and changes in the treatment of wastewaters. Hence, we evaluated the treatment of cyanide-free wastewater from the brass electroplating industry with EDTA as a complexing agent by electrodialysis, aimed at recovering water and concentrated solutions for reuse. The electrodialysis tests were performed in underlimiting and overlimiting conditions. The results suggested that intense water dissociation occurred at the cathodic side of the commercial anion-exchange membrane (HDX) during the overlimiting test. Consequently, the pH reduction at this membrane may have led to the reaction of protons with complexes of EDTA-metals and insoluble species. This allowed the migration of free Cu2+ and Zn2+ to the cation-exchange membrane as a result of the intense electric field and electroconvection. These overlimiting phenomena accounted for the improvement of the percent extraction and percent concentration, since in the electrodialysis stack employed herein, the concentrate compartments of cationic and anionic species were connected to the same reservoir. Chronopotentiometric studies showed that electroconvective vortices minimized fouling/scaling at both membranes. The electrodialysis in the overlimiting condition seemed to be more advantageous due to water dissociation and electroconvection.

[EN] Growing concerns about environment and human health have led to the development of cleaner industrial processes. In recent years, the replacement of cyanide by EDTA in the brass electroplating baths has been assessed. However, the treatment of the wastewater generated has not been studied yet. Traditionally, wastewaters from electroplating processes are treated by chemical precipitation, which requires the addition of chemicals and produces sludges that are disposed in hazardous waste landfills. Hence, other techniques must be investigated and electrodialysis is a promising alternative since it allows the recovery of metals and water. Although electrodialysis is generally operated at current densities lower than the limiting current density of the membrane system (underlimiting), researchers have verified that operations at current densities above the limiting one (overlimiting) improve the ions transfer. To ensure its feasibility, studies on transport properties of ionic species are crucial and, among the dynamic characterization methods, chronopotentiometry stands out, since the dynamic voltage response in time can be analyzed. Therefore, this thesis aims to propose an alternative to the treatment of a synthetic solution that simulates the major wastewater from the cyanide-free brass electroplating industry. Firstly, chronopotentiometric tests were performed to compare transport properties of Cu2+ ions, in acid medium, across two ion exchange membranes, the PC-SK and the HDX100. The use of HDX membrane in electrodialysis showed to be more appropriate, due to its lower tendency of fouling/scaling occurrence. Then, transport properties of copper and zinc complexes, present in the synthetic wastewater from the brass electroplating, across the anion exchange membrane HDX200 were assessed. The effects of the solution pH, Cu2+/Zn2+ proportion and EDTA concentration on the transport properties were studied. For the solution with Cu2+/Zn2+ proportion of 0.4, an insol, [ES] Las crecientes preocupaciones por el medio ambiente y la salud humana han llevado al desarrollo de nuevos procesos industriales. En los últimos años, se ha evaluado la sustitución del cianuro por EDTA en los baños de electrodeposición de latón. Sin embargo, el tratamiento de las aguas residuales generadas no se ha estudiado aún. Tradicionalmente, los efluentes de los procesos de electrodeposición se tratan por precipitación química, que requiere la adición de reactivos y produce lodos que se almacenan en los vertederos de residuos peligrosos. Por lo tanto, es necesario investigar otras técnicas y la electrodiálisis es una alternativa prometedora, ya que permite la recuperación de metales y del agua. Aunque la electrodiálisis generalmente se opera a corrientes inferiores a la corriente límite del sistema de membrana (underlimiting), algunos investigadores han verificado que las operaciones a corrientes superiores a la límite (overlimiting) intensifican la transferencia de iones. Para garantizar su viabilidad, los estudios sobre las propiedades de transporte de los iones son cruciales y, entre los métodos de caracterización, la cronopotenciometría destaca por permitir el análisis del voltaje en función del tiempo. Por lo tanto, esta tesis tiene por objetivo proponer una alternativa al tratamiento de una disolución sintética que simula las aguas residuales de la industria de electrodeposición de latón libre de cianuro. Primero, se realizaron pruebas cronopotenciométricas para comparar las propiedades de transporte de iones Cu2+, en medio ácido, a través de dos membranas de intercambio iónico, la PC-SK y la HDX100. El uso de la HDX en electrodiálisis demostró ser más apropiado debido a su menor tendencia a formar incrustaciones. Luego, se evaluaron las propiedades de transporte de los complejos de cobre y zinc, presentes en las aguas residuales de la electrodeposición de latón, a través de la membrana de intercambio aniónico HDX200. Se estudiaron los efectos del pH, [CA] Les creixents preocupacions pel medi ambient i la salut humana han conduït al desenvolupament de nous processos industrials. En els últims anys, s'ha avaluat la substitució del cianur per EDTA als banys d'electrodeposició de llautó. No obstant això, el tractament de les aigües residuals generades no s'ha estudiat encara. Tradicionalment, els efluents dels processos d'electrodeposició es tracten per precipitació química, que requereix l'addició de reactius i produeix fangs que s'emmagatzemen en els abocadors de residus perillosos. Per tant, és necessari investigar altres tècniques i l'electrodiàlisi és una alternativa prometedora, ja que permet la recuperació de metalls i de l'aigua. Tot i que l'electrodiàlisi generalment s'opera a corrents inferiors al corrent límit del sistema de membrana (underlimiting), alguns investigadors han verificat que les operacions a corrents superiors al límit (overlimiting) intensifiquen la transferència de ions. Per garantir la seua viabilitat, els estudis sobre les propietats de transport dels ions són crucials i, entre els mètodes de caracterització, la cronopotenciometria destaca per permetre l'anàlisi del voltatge en funció del temps. Per tant, aquesta tesi té per objectiu proposar una alternativa al tractament d'una dissolució sintètica que simula les aigües residuals de la indústria d'electrodeposició de llautó lliure de cianur. Primer, es van realitzar proves cronopotenciomètriques per comparar les propietats de transport de ions Cu2+, en medi àcid, a través de dues membranes d'intercanvi iònic, la PC-SK i l`HDX100. L'ús de l'HDX en electrodiàlisi va demostrar ser més apropiat a causa de la seua menor tendència a formar incrustacions. Després, es van avaluar les propietats de transport dels complexos de coure i zinc, presents a les aigües residuals de l'electrodeposició de llautó, a través de la membrana d'intercanvi aniònic HDX200. Es van estudiar els efectes del pH, la relació molar Cu2+/Zn2+ i la concentració d'EDTA sobr, [PT] Preocupações crescentes com o meio ambiente e com a saúde humana têm levado ao desenvolvimento de novos processos industriais. Nos últimos anos, a substituição do cianeto pelo EDTA nos banhos de eletrodeposição de latão tem sido avaliada. No entanto, o tratamento dos resíduos líquidos gerados ainda não foi estudado. Tradicionalmente, resíduos líquidos provenientes de indústrias galvânicas são tratados por precipitação química, que requer a adição de reagentes e produz lamas que são descartadas em aterros de resíduos perigosos. Portanto, outras técnicas devem ser investigadas e a eletrodiálise é uma alternativa promissora, pois permite recuperar os metais e a água. Embora a eletrodiálise seja geralmente operada sob densidades de corrente inferiores à densidade de corrente limite do sistema da membrana (underlimiting), alguns pesquisadores têm verificado que operações sob densidades de corrente superiores à limite (overlimiting) intensificam a transferência dos íons. Para garantir sua viabilidade, estudos sobre propriedades de transporte das espécies iônicas são cruciais, e dentre os métodos de caracterização dinâmica, a cronopotenciometria se destaca por permitir a análise da diferença de potencial entre as membranas em função do tempo. Portanto, esta tese tem como objetivo propor uma alternativa ao tratamento de uma solução sintética que simula o principal resíduo líquido proveniente da indústria de eletrodeposição de latão, isenta de cianeto, com EDTA. Primeiramente, testes cronopotenciométricos foram realizados a fim de comparar as propriedades de transporte dos íons Cu2+ , em meio ácido, através de duas membranas trocadoras de cátions, a PC-SK e a HDX100. O uso da HDX mostrou-se mais adequado, devido à menor tendência de ocorrência de incrustações na sua superfície. Em seguida, foram avaliadas as propriedades de transporte dos complexos de cobre e zinco, presentes no resíduo líquido da eletrodeposição de latão, através da membrana trocadora de ânions HDX200.