The syntheses, extensive spectroscopic characterization, photophysical and photochemical studies have been conducted for a variation of d10 metallophthaloycanines (MPcs). Comparisons have been made taking into consideration the nfluence of the central metal ion, solvent properties, substituent type and position. Coordination to heavy central metals i.e. Hg gives enhanced triplet state properties. Low symmetry metallophthalocyanine complexes were similarly haracterized and the influence of nteractions with nanoparticles on their photophysical and photochemical properties determined. The MPcs have been linked and adsorbed or mixed with nanoparticles i.e. hemically functionalized single-walled carbon nanotubes SWCNT) and mercaptocarboxylic acid capped CdTe quantum dots (QDs) and changes in the spectra accounted for with respect to the proposed conjugate structures. Distinct differences ccur for linked and adsorbed or mixed conjugates in the bsorption, infrared (IR) and Raman spectra and for thermal ravimetric decay profiles, suggesting successful formation f covalent bonds (linked) and point to structurally ifferent materials. SWCNT quench MPc fluorescence by a photoinduced electron transfer mediated process to give low fluorescence quantum yields. The QDs were used as energy transfer donors and facilitate energy transfer, through Förster resonance energy transfer (FRET) from the QDs to the MPcs. Improved FRET efficiencies were found for linked MPc-QD conjugates relative to the mixed species. Photophysicochemical properties of MPcs were, in general, improved as a result of interactions with nanoparticles.

New cobalt (13, 16 19 and 22), manganese (14, 17, 20 and 23) and iron (15, 18, 21 and 24)phthalocyanine complexes were synthesized and characterized. The UV-Vis spectral properties of the complexes were typical of the nature of central metal and position of substituent on the Pc ligand. Their electrochemical behaviors were signatures of the central metals, with varying influences of the nature and position of substituents. Nanocomposite of complex 18 and single walled carbon nanotubes (SWCNTs) (SWCNT-18)was fabricated. Formation of this nano-composite was confirmed by infrared (IR)spectroscopy, X-ray diffraction (XRD) spectroscopy and transmission electron microscopy (TEM). Self-assembled monolayers (SAMs) of SWCNT-18, complexes 13-15, and 20 were electropolymerized on glassy carbon electrodes (GCE). Complex 14 was also electrodeposited on GCE. Surface properties of the SAMs were consistent with the molecular feature of the substituent and the nature of central metal in the adsorbed species, while those of the MnPc modified GCEs were dependent on point of substitution and number of substituent. The SAM-modified gold electrodes were used for the electrocatalytic oxidation of the carbamate insecticide, carbofuran. Amplification of the current signal of the insecticide, at more energetically feasible oxidation potentials, on the SAM-modified gold electrodes, relative to bare gold electrode,justified electrocatalysis. There was enhanced sensitivity (attributed to the presence of SWCNT) of the SWCNT-18-SAM-modified gold electrode towards carbofuran, relative to the signals observed on the other SAMs. Current response of the insecticide,bendiocarb, was also intensified, at more favorable oxidation potentials, on the MnPc (14 and 17) modified GCEs, relative to the response on bare GCE, substantiating electrocatalysis. Also, catalysis of the oxidation of the herbicide, bentazon, was observed on polymeric film of complex 20. The current response of the herbicide on this film was better than that observed on bare GCE. Electrocatalysis of the analytes, on the respective modified electrodes, occurred via closely related mechanisms.

The synthesis of symmetrically and unsymmetrically substituted zinc phthalocyanines (ZnPc) derivatives is done according to reported procedures. The unsymmetrical ZnPc derivatives are synthesized by ring expansion of sub-phthalocyanine complexes. Ring substitution is effected with tert-butyl phenol, naphthol, and hydroxybenzoic acid. Comparison of the redox potentials for the complexes substituted with varying numbers of tert-butyl phenol: 1, 2, 3, 6 and 8 show that the complex with the highest number of substituents are more difficult to oxidize and easier to reduce. Water soluble sulphonated ZnPc (ZnPcSn) was prepared. The possibility of using axial ligation to increase the solubility and the photochemical activity of sulphotnated ZnPc in aqueous solutions was investigated. Pyridine, aminopyridyl and bipyridyl were used as axial ligands. When bipyridyl was used as the axial ligand, solubility of the ZnPcSn increased, shown by the increase in the Q-band of the monomer species in solution and the singlet oxygen quantum yields was relatively higher than that of the unligated ZnPcSn. The singlet oxygen quantum yields by the various complexes in DMF using diphenylisobenzofuran as a chemical quencher for organic solvent were determined. Singlet oxygen quantum yields for the unsymmetrically ring substituted complexes range from 0.22 to 0.68. Photobleaching quantum yields are in the order of 10-5, which means that the complexes are relatively photostable.

Cysteine plays an important role in many biological and pharmaceutical systems. Therefore, in view of its importance, it is essential to find means of detecting it at the lowest possible levels. In this regard, electrochemical techniques have been found to be capable of detecting analytes even at micro levels. However, electrochemical determination of cysteine occurs at a very high potentials. These overpotentials makes quantitative analysis or detection of cysteine difficult at most conventional carbon electrodes. On platinum electrode, the oxidation of cysteine has been reported to occur in the potential range 0.7 to 1.45 V (vs NHE). Therefore, the object of this investigative study has been to find an active complex that could replace platinum and other expensive metals as electrodes. Such a complex should also be capable of reducing the potential at which the oxidation of cysteine occurs on carbon electrodes. As a result, this manuscript gives a full report on the investigative study of electrocatalytic activity of molybdenum phthalocyanine complexes towards detection of cysteine. Molybdenum phthalocyanine, OMo(OH)Pc, and its tetrasulfonated derivative, [OMo(OH)TSPc]⁴⁻ were successfully used to reduce the potential needed to initiate the oxidation of cysteine on carbon paste electrodes (CPE). The oxidation of cysteine on CPE modified with [OMo(OH)Pc]⁴⁻ was found to occur at 0.29 V (vs Ag/AgCl), and in the presence of [OMo(OH)TSPc]⁴⁻ species in solution the oxidation occurred at 0.33 V (vs Ag/AgCl). Molybdenum, in the oxidation states of Mo(IV), Mo(V) and Mo(VI), is found in biological systems as an essential trace element, participating in a number of enzymatic reactions, where it is believed to be coordinated to sulphur-containing ligands in many molybdenum enzymes. This therefore explains why molybdenum phthalocyanines were employed in electroanalytical detection of sulphur containing amino acid, cysteine. Electrochemical methods have also been successfully used in detection of environmental pollutants such as phenolic compounds. Phenolic compounds are oxidised at readily accessible potentials. However, like cysteine, there are problems associated with the electrochemical detection of these important environmental pollutants. Their electrooxidation is known to form dimeric and/or polymeric oxidation products which adsorb onto the electrode surface, thus -videactivating it. Therefore, to address this problem, cobalt phthalocyanine (CoPc) and its tetrasulfonated derivative, [CoTSPc]⁴⁻ were employed in electrocatalytic detection of phenolic compounds. These complexes were found to increase the anodic peak currents for the oxidation of o-cresol, m-cresol, p-cresol, phenol, 2-chlorophenol and 4-chlorophenol. In addition, CoPc deposited onto the glassy carbon electrode improved the stability of the electrode, by reducing electrode poisoning caused by the electrooxidation products of the mentioned phenolic compounds. The potential at which the oxidation occurred and the current response of individual phenolic compounds depended on the degree of substitution and the type of substituent on the phenol molecule. In general, the current response was found to be lower for chlorinated phenols compared with the cresols and phenol. To establish the role of the central metal in the catalytic process, comparison of the electrocatalytic activity of some of the first row transition metal phthalocyanines, for the detection of mono-substituted phenolic compounds, showed the following trend: Co⁽¹¹⁾ > Mn⁽¹¹⁾ > Fe⁽¹¹⁾Pc > Ni⁽¹¹⁾Pc > Cu⁽¹¹⁾Pc > H₂Pc > Zn⁽¹¹⁾Pc > Bare GCE. A report is also given on electrocatalysis using [CoTSPc]⁴⁻ electrochemically deposited on the glassy carbon electrode. This was also found to enhance the anodic peak currents for the oxidation of all phenolic compounds. A report on the effects of scan rate, operating potential, analyte concentration and other variables is also given.

Syntheses, spectral, photophysical and photochemical studies of some neutral, anionic and cationic metallophthalocyanine derivatives are presented. The effects of central metal ions, solvents, aggregation, surfactant, nanoparticles and bovine serum albumin on the photophysical and photochemical behaviour are investigated. Mercaptocarboxylic acid stabilized CdTe quantum dots (QDs) were used as energy donors to anionic water-soluble MPcs through Förster resonance energy transfer (FRET). Energy transfer (ET) from the QDs to the MPcs occurred upon photoexcitation of the QDs. An enhancement in efficiency of ET with the nature of the cappings on the QDs was observed with few occurrences of a non-Förster type ET. QDs were found to improve the photophysicochemical behaviour of the MPcs, with the possibility of indirect production of singlet oxygen (Φ[subscript Δ]) via FRET mechanism. Interaction of the QDs with cationic water-souble MPcs produced ion-pair complexes resulting in aggregates due to strong electronic coupling. The stoichiometry of the reaction and association constants are evaluated by the continuous variation method. Improved photophysicochemical behaviour with no spectral alterations was observed in MPcs in the presence of magnetic fluid. Complexes showed high triplet quantum yields with corresponding long lifetimes and high photostability. Elucidation of the results of the interaction of bovine serum albumin (BSA) with MPcs or QDs is presented. Increased efficiency of Φ[subscript Δ] generation of MPcs in the presence of BSA coupled with large binding constants, suggesting strong interaction of the MPcs with BSA was observed. Enhanced emission intensity of QDs when linked to or in a mixture with BSA due to radiationless recombination at the surface vacancies was also observed. The study revealed positive deviation from Stern-Volmer relationship suggesting the occurrence of static and dynamic mechanisms of quenching together. Fluorescence quenching of the MPcs by benzoquinone, analysed by Stern-Volmer relationship is also presented; the results were employed in determining fluorescence lifetimes of the complexes. Photoelectrochemical characteristics of MPc-sensitized electrodeposited ZnO thin films were studied; ZnOCPc / ZnO films have been improved to an incident photon-to-currentconversion (IPCE) value of 31.1 % with an absorbed photon-to-current conversion (APCE) of 59.6 %. The best obtained so far with phthalocyanine-type sensitizers on nanocrystalline ZnO films. Fluorescent-magnetic nanocomposite with excellent photophysical properties which can be exploited for combined photodynamic and hyperthermia therapies is also presented.

Electrocatalytic reduction and oxidation of nitric oxide (NO) using cobalt phthalocyanine complexes have been studied and compared to vitamin B₁₂ and other metallophthalocyanine (MPc) complexes. Modifying a glassy carbon electrode with these complexes resulted in improved sensitivity of the electrode allowing detection of NO to 10⁻⁹ mol dm⁻³. The mechanisms of catalysis were studied. Electrocatalysis of NO involves coordination of NO to the MPc complex. Hence catalytic activity is affected by the nature of the metal center. However coordination of NO to the MPc complex has to be reversible to eliminate poisoning of the electrode. Though FePc gave the best sensitivity and lowered the reduction potential more than CoPc, the strong Fe-NO bond resulted in the poisoning of the electrode hence, rendering the electrode unstable. Rate constants for NO coordination to the MPc complexes were studied. These rates were smaller than the studied NO porphyrin coordination rates. Electrocatalytic reduction of NO using MPc complexes involves a transfer of an electron from the metal center to the NO ligand. Hence, substitution of electron-donating grohps on the cobalt pthalocyanine complex resulted in improved sensitivity and catalytic activity. A CoPc modified microelectrode (11μm) was used to monitor NO in human blood components and to detect NO in a rat brain. Detections of NO were also done in aqueous solutions in the presence of interfering species such as dopamine and serotonin. An interaction between NO and serotonin was observed.

A crescente necessidade de preservação e/ou manutenção da água disponível para o consumo humano gera uma incessante busca por alternativas e métodos eficientes para o tratamento dos efluentes industriais. O objetivo deste trabalho foi avaliar o processo de eletrocoagulação (EC) para tratamento de efluentes galvânicos cianídricos. Avaliou-se as seguintes variáveis de processo, utilizando-se análises estatísticas: tempo de eletrólise, quantidade de eletrólito suporte (NaCl), densidade de corrente aplicada, distância entre eletrodos e área superficial de eletrodos. Utilizouse uma solução sintética simulando o efluente galvânico cianídrico, um reator construído com acrílico transparente e eletrodos de alumínio ligados a uma fonte de corrente contínua para a geração do agente coagulante, com um inversor de pólos acoplado. Determinou-se a perda de massa dos eletrodos pelo método gravimétrico e a quantidade de alumínio remanescente no efluente por absorção atômica. Avaliou-se o comportamento eletroquímico dos eletrodos de alumínio no efluente galvânico cianídrico através de curvas de polarização potenciostáticas. A morfologia e os elementos químicos presentes nos eletrodos de alumínio após o tratamento, foram avaliados pelas análises de microscopia eletrônica de varredura e espectroscopia de energia dispersiva. O lodo galvânico gerado no processo foi caracterizado pelas técnicas de difração de Raios-X e espectroscopia de infravermelho. Obteve-se as seguintes condições ótimas de operação no experimento denominado ECO: tempo de eletrólise de 30 minutos, 5,0 g/L de NaCl adicionado, 8 mA/cm² de densidade de corrente, 1 cm entre eletrodos e 104 cm²/L de área superficial e as remoções de 99,55% de cianeto total, 22,49% de íons níquel, 52,66% de íons cobre e 100,00% de íons zinco. Os resultados dos parâmetros de turbidez, SST, DQO, pH e, remoção de zinco, atendem aos valores passíveis de descarte, não sendo obtidos para os parâmetros de cianeto total, íons cobre e níquel. Obteve-se 8,50 mg/L de alumínio no experimento ECO, passível de descarte e aumento de 20,00% de eficiência para a remoção de cianeto total, íons níquel e cobre com a utilização do inversor de pólos. A eficiência da EC e da cloração alcalina foram semelhantes para a remoção de cianeto total e íons zinco, obtendo-se remoções superiores à 70,00% e 40,00% para os íons níquel e cobre através da cloração alcalina. Nas análises de MEV observou-se corrosão por pitting nas faces externas dos eletrodos de alumínio e corrosão generalizada nas faces internas. As análises de EDS apontaram a presença de óxido de alumínio e cobre na superfície dos eletrodos. Os resultados eletroquímicos mostraram que, quanto maior a quantidade de NaCl adicionada ao efluente galvânico, maior a dissolução anódica dos eletrodos de alumínio, maior a densidade de corrente no circuito e menor o potencial necessário a ser aplicado. Quanto ao lodo galvânico, nas análises de DRX e FT-IR identificou-se agentes coagulantes na forma de hidróxidos de alumínio, e na análise de FT-IR comprovou-se a presença ds metais cobre, níquel e zinco, cianeto e cianato. Atribui-se os resultados de remoção obtidos àsinergia dos processos de EC e da oxidação eletrolítica dos complexos cianídricos metálicos em função da diferença de potencial aplicado. O processo de EC mostrou-se eficiente para a remoção de contaminantes de efluentes galvânicos cianídricos e se obteve parâmetros finais passíveis de descarte de acordo com as normativas vigentes. / Submitted by Ana Guimarães Pereira (agpereir@ucs.br) on 2014-11-24T12:37:56Z No. of bitstreams: 1 Dissertacao Tais Sabedot Pertile.pdf: 4298069 bytes, checksum: aea769b9a9953a1a4957813f5a0e08f9 (MD5) / Made available in DSpace on 2014-11-24T12:37:56Z (GMT). No. of bitstreams: 1 Dissertacao Tais Sabedot Pertile.pdf: 4298069 bytes, checksum: aea769b9a9953a1a4957813f5a0e08f9 (MD5) / The growing need for preservation and/or maintenance of water available for human consumption generates an endless search for alternative and efficient methods for the treatment of industrial effluents. The aim of the present work was to evaluate the process of electrocoagulation (EC) for the treatment of hydrocyanic galvanic effluent. The following process variables were evaluated, using statistical analysis: electrolysis time, amount of supporting electrolyte (NaCl), applied current density, distance between electrodes and electrode surface area. It was used a synthetic solution simulating the hydrocyanic galvanic effluent, an reactor built with transparent acrylic and aluminum electrodes connected to a continuous current source for generation of coagulating agent, coupled with an polarity inverter. The mass loss of the electrodes was determined by gravimetric method and the amount of aluminum remaining in the effluent by atomic absorption. The electrochemical behavior of aluminum electrodes in the hydrocyanic galvanic effluent was evaluated by potentiostatic polarization curves. The morphology and chemical elements present in the aluminum electrodes after treatment were evaluated by analysis of scanning electron microscopy and energy dispersive spectroscopy. The galvanic sludge generated in the process was characterized by the techniques of X-ray diffraction and infrared spectroscopy. The following optimal operating conditions were obtained in experiment named ECO: electrolysis time of 30 minutes, addition of 5.0 g/L NaCl, current density of 8 mA/cm², 1 cm between electrodes and surface area of 104 cm²/L and the removal results of 99.55% total cyanide, 22.49% nickel ions, 52.66% copper ions and 100,00% zinc ions. The results of turbidity, TSS, COD, pH and removal of zinc parameters, meet the amounts subject to disposal of treated effluent, not being obtained for total cyanide, copper and nickel ions parameters. It was obtained 8.50 mg/L of aluminum in the ECO experiment, amenable to disposal and increased by 20,00% the efficiency removal of nickel and copper ions and total cyanide using the polarity inverter. The efficiency of EC and alkaline chlorination removal were similar for total cyanide and zinc ions, obtaining removal greater than 70,00% and 40,00% for nickel and copper ions by the alkaline chlorination. SEM analysis showed pitting corrosion in the external faces of the aluminum electrodes and general corrosion in internal faces. EDS analysis indicated the presence of aluminum oxide and copper on the surface of the electrodes. The electrochemical results showed that the higher the amount of NaCl added to the galvanic effluent, the higher the anodic dissolution of aluminum electrodes, the higher the current density in the circuit and lower the necessary potential to be applied. Regarding the galvanic sludge, in the analyzes of XRD and FT-IR were identified coagulating agents in the form of hydroxides of aluminum, and the FT-IR analyzes proved the presence of the metals copper, nickel and zinc, cyanide and cyanate. The obtained removal results are attributed to the synergy of EC process and the electrolytic oxidation of the metal cyanide complexes as function of applied potential difference. The EC process was efficient for removing contaminants from hydrocyanic galvanic effluent and resulted in final parameters amenable of disposal according to current regulations.

Made available in DSpace on 2014-06-11T19:29:08Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-08-05Bitstream added on 2014-06-13T18:38:49Z : No. of bitstreams: 1 zezza_trc_me_araiq.pdf: 582173 bytes, checksum: 4a292895c03467921ab48f3ddcc6e37b (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / O biodiesel pode ser definido como sendo um mono-alquil éster de ácidos graxos derivado de fontes renováveis, como óleos vegetais e gorduras animais, obtido através de um processo de transesterificação. Essa reação, dificilmente consegue ser quantitativa e, por isso, o biodiesel encontra-se contaminado com outros componentes. O cálcio e o magnésio encontram-se presentes no biodiesel devido ao seu processo de fabricação. O valor máximo de Ca+Mg permitido em amostras de biodiesel estabelecidos pela ANP é de 5 mg kg-1. Assim, a presença de cálcio e magnésio no biodiesel deve ser controlada, pois pode degradar o combustível, causar danos ao motor e envenenar os catalisadores automotivos. Devido à isso, foi desenvolvido um método alternativo utilizando eletrodo de pasta de carbono com filme de mercúrio utilizando vermelho de bromopirogalol (BPR) em meio de tampão bórax e tiopentato de sódio (TPS) em meio de tampão fosfato. Estudos eletroquímicos foram feitos utilizando-se as técnicas de voltametria de onda quadrada e pulso diferencial para ambos íons e ambos agentes complexantes. A formação do complexo Mg(II)-BPR pode ser usada para determinação de magnésio com um limite de detecção de 9,0 x 10-6 mol L-1 utilizando voltametria de onda quadrada e 4,8 x 10-9 mol L-1 utilizando voltametria de pulso diferencial. Já a formação do complexo Ca(II)-BPR pode ser usada para determinação de cálcio com um limite de detecção de 3,5 x 10-6 mol L-1 através da voltametria de onda quadrada e 3,9 x 10-8 mol L-1 para voltametria de pulso diferencial. Utilizando-se tiopentato de sódio foi possível apenas a determinação indireta de magnésio através da formação do complexo Mg(II)-TPS, com um limite de detecção de 2,9 x 10-7 mol L-1 para VOQ e 3,9 x 10-7 mol L-1 para VPD. Através da curva de adição de padrão foi possível determinar cálcio e magnésio em amostras de biodiesel de soja / Biodiesel can be defined as a mono-alkyl ester of fatty acids derived from renewable sources such as vegetable oils and animal fats, obtained through a transesterification process. This reaction can hardly be complete and so the biodiesel is contaminated with other compounds. Calcium and magnesium are present in biodiesel due to its manufacturing process. The maximum allowed Ca + Mg in samples of biodiesel is established by the ANP 5mg kg-1. Thus, the presence of calcium and magnesium in the biodiesel should be controlled because it can degrade the fuel, causing engine damage and poison the automotive catalyst. Because of this, we developed an alternative method using a carbon paste electrode with mercury film using bromopyrogallol red (BPR) in buffer borax medium and thiopentone sodium (TPS) in a phosphate buffer. Electrochemical studies were performed using the techniques of square wave voltammetry and differential pulse for both ions and both complexing agents. The formation of the complex Mg(II)-BPR can be used for determination of magnesium with a limit of detection of 9.0 x 10-6 mol L-1 using square wave voltammetry and 4.8 x 10-9 mol L-1 using a differential pulse voltammetry. The formation of the complex Ca(II)-BPR can be used for the determination of calcium with a limit of detection of 3.5 x 10-6 mol L-1 through the square wave voltammetry and 3.9 x 10-8 mol L-1 for differential pulse voltammetry. Using thiopentone sodium was possible only indirect determination of magnesium through the formation of the complex Mg(II)-TPS, with a limit of detection of 2.9 x 10-7 mol L-1 to SWV and 3.9 x for 10-7 mol L-1 to DPV. Through the curve of standard addition was possible to determine calcium and magnesium in samples of biodiesel

A crescente necessidade de preservação e/ou manutenção da água disponível para o consumo humano gera uma incessante busca por alternativas e métodos eficientes para o tratamento dos efluentes industriais. O objetivo deste trabalho foi avaliar o processo de eletrocoagulação (EC) para tratamento de efluentes galvânicos cianídricos. Avaliou-se as seguintes variáveis de processo, utilizando-se análises estatísticas: tempo de eletrólise, quantidade de eletrólito suporte (NaCl), densidade de corrente aplicada, distância entre eletrodos e área superficial de eletrodos. Utilizouse uma solução sintética simulando o efluente galvânico cianídrico, um reator construído com acrílico transparente e eletrodos de alumínio ligados a uma fonte de corrente contínua para a geração do agente coagulante, com um inversor de pólos acoplado. Determinou-se a perda de massa dos eletrodos pelo método gravimétrico e a quantidade de alumínio remanescente no efluente por absorção atômica. Avaliou-se o comportamento eletroquímico dos eletrodos de alumínio no efluente galvânico cianídrico através de curvas de polarização potenciostáticas. A morfologia e os elementos químicos presentes nos eletrodos de alumínio após o tratamento, foram avaliados pelas análises de microscopia eletrônica de varredura e espectroscopia de energia dispersiva. O lodo galvânico gerado no processo foi caracterizado pelas técnicas de difração de Raios-X e espectroscopia de infravermelho. Obteve-se as seguintes condições ótimas de operação no experimento denominado ECO: tempo de eletrólise de 30 minutos, 5,0 g/L de NaCl adicionado, 8 mA/cm² de densidade de corrente, 1 cm entre eletrodos e 104 cm²/L de área superficial e as remoções de 99,55% de cianeto total, 22,49% de íons níquel, 52,66% de íons cobre e 100,00% de íons zinco. Os resultados dos parâmetros de turbidez, SST, DQO, pH e, remoção de zinco, atendem aos valores passíveis de descarte, não sendo obtidos para os parâmetros de cianeto total, íons cobre e níquel. Obteve-se 8,50 mg/L de alumínio no experimento ECO, passível de descarte e aumento de 20,00% de eficiência para a remoção de cianeto total, íons níquel e cobre com a utilização do inversor de pólos. A eficiência da EC e da cloração alcalina foram semelhantes para a remoção de cianeto total e íons zinco, obtendo-se remoções superiores à 70,00% e 40,00% para os íons níquel e cobre através da cloração alcalina. Nas análises de MEV observou-se corrosão por pitting nas faces externas dos eletrodos de alumínio e corrosão generalizada nas faces internas. As análises de EDS apontaram a presença de óxido de alumínio e cobre na superfície dos eletrodos. Os resultados eletroquímicos mostraram que, quanto maior a quantidade de NaCl adicionada ao efluente galvânico, maior a dissolução anódica dos eletrodos de alumínio, maior a densidade de corrente no circuito e menor o potencial necessário a ser aplicado. Quanto ao lodo galvânico, nas análises de DRX e FT-IR identificou-se agentes coagulantes na forma de hidróxidos de alumínio, e na análise de FT-IR comprovou-se a presença ds metais cobre, níquel e zinco, cianeto e cianato. Atribui-se os resultados de remoção obtidos àsinergia dos processos de EC e da oxidação eletrolítica dos complexos cianídricos metálicos em função da diferença de potencial aplicado. O processo de EC mostrou-se eficiente para a remoção de contaminantes de efluentes galvânicos cianídricos e se obteve parâmetros finais passíveis de descarte de acordo com as normativas vigentes. / The growing need for preservation and/or maintenance of water available for human consumption generates an endless search for alternative and efficient methods for the treatment of industrial effluents. The aim of the present work was to evaluate the process of electrocoagulation (EC) for the treatment of hydrocyanic galvanic effluent. The following process variables were evaluated, using statistical analysis: electrolysis time, amount of supporting electrolyte (NaCl), applied current density, distance between electrodes and electrode surface area. It was used a synthetic solution simulating the hydrocyanic galvanic effluent, an reactor built with transparent acrylic and aluminum electrodes connected to a continuous current source for generation of coagulating agent, coupled with an polarity inverter. The mass loss of the electrodes was determined by gravimetric method and the amount of aluminum remaining in the effluent by atomic absorption. The electrochemical behavior of aluminum electrodes in the hydrocyanic galvanic effluent was evaluated by potentiostatic polarization curves. The morphology and chemical elements present in the aluminum electrodes after treatment were evaluated by analysis of scanning electron microscopy and energy dispersive spectroscopy. The galvanic sludge generated in the process was characterized by the techniques of X-ray diffraction and infrared spectroscopy. The following optimal operating conditions were obtained in experiment named ECO: electrolysis time of 30 minutes, addition of 5.0 g/L NaCl, current density of 8 mA/cm², 1 cm between electrodes and surface area of 104 cm²/L and the removal results of 99.55% total cyanide, 22.49% nickel ions, 52.66% copper ions and 100,00% zinc ions. The results of turbidity, TSS, COD, pH and removal of zinc parameters, meet the amounts subject to disposal of treated effluent, not being obtained for total cyanide, copper and nickel ions parameters. It was obtained 8.50 mg/L of aluminum in the ECO experiment, amenable to disposal and increased by 20,00% the efficiency removal of nickel and copper ions and total cyanide using the polarity inverter. The efficiency of EC and alkaline chlorination removal were similar for total cyanide and zinc ions, obtaining removal greater than 70,00% and 40,00% for nickel and copper ions by the alkaline chlorination. SEM analysis showed pitting corrosion in the external faces of the aluminum electrodes and general corrosion in internal faces. EDS analysis indicated the presence of aluminum oxide and copper on the surface of the electrodes. The electrochemical results showed that the higher the amount of NaCl added to the galvanic effluent, the higher the anodic dissolution of aluminum electrodes, the higher the current density in the circuit and lower the necessary potential to be applied. Regarding the galvanic sludge, in the analyzes of XRD and FT-IR were identified coagulating agents in the form of hydroxides of aluminum, and the FT-IR analyzes proved the presence of the metals copper, nickel and zinc, cyanide and cyanate. The obtained removal results are attributed to the synergy of EC process and the electrolytic oxidation of the metal cyanide complexes as function of applied potential difference. The EC process was efficient for removing contaminants from hydrocyanic galvanic effluent and resulted in final parameters amenable of disposal according to current regulations.

The instrumentation for digitally driven electrochemical experiments has been developed. Software has been written for experimental control and high speed data aquisition. The digital control methods were successfully used in the study of the electrochemistry of the porous lead electrode (the lead-acid battery negative plate), over an extended temperature range. The effects of a number of commercially pertenent additives have been studied at reduced temperatures. These reaction enhancing materials (expanders) have been studied in detail on both planar and porous lead electrode in sulphuric acid in the range 1M to 5M. Deductions concerning the energetics of the reactions have been made from experimental results. The modes of action of certain expanders are discussed. It was concluded that on the plane lead surface solution phase expander materials modify the mechanism of the lead sulphate electrocrystallisation - the current limiting reaction. This was an effect on the solid state process although a solution Pb2+ process was identified (for the first time) in battery strength acid. Electrode incorporated organic expander materials act by modifying pore geometies and reaction penetration depths. The current transients due to electrocrystallization in porous lead are very complex and require very sophisticated modelling techniques to provide a useful fit.