This thesis is concerned with dynamic electrochemistry experiments in which faradaic processes are driven by the application of potential to an electrode immersed in an electrolyte solution. In particular, experimental methods are considered which could be used to study electrochemical systems in a more informative way if the processes occurring at the electrode were better understood. The work develops the theoretical models which describe these experiments, and details the approximations made in each model and the conditions under which they are appropriate. Numerical simulations are reported which demonstrate how the models can be used to infer quantitative details of chemical behaviour from experimentally recorded data. The first system studied in detail is linear sweep voltammetry at a microband electrode array. The diffusional behaviour of an electroactive species is shown to depend on the configuration of the microband array and on the potential scan rate used. Details are given on how experimental conditions can be optimised for the study of electrochemical systems. The next area of work develops the theory of nanoparticle-modified electrodes. Experiments are considered in which an electron transfer reaction is catalysed only at the site of the nanoparticles, whilst the supporting planar electrode remains electrochemically inert. Numerical simulations show how the current measured at these modified electrodes depends on the size and shape of the particles, on the distribution of the particles on the electrode surface, and on the timescale of the experiment. The final theme of work is on electrochemical experiments in poorly conducting solutions. A theoretical model is developed which takes into account the effects of an electric field on the mass transport of electroactive species and on the charge transfer kinetics at the electrode. The model is then used to rationalise the unusual current behaviour that is observed in the anodic stripping of thallium from an amalgam.

À cause de leurs propriétés antibactériennes, les nanoparticules d’argent sont couramment utilisées dans un grand nombre de produits tels les tissus, les savons et les produits médicaux. Dans cette industrie en pleine croissance, ces nanoparticules sont produites en grandes quantités et s’accumuleront éventuellement dans l’environnement. Pour comprendre le destin, le transport et la biodisponibilité des nanomatériaux, il est essentiel de comprendre leurs propriétés physicochimiques. Entre autres, il est particulièrement important de quantifier la dissolution des nanoparticules à l’aide de mesures de spéciation chimique. En effet, l’objectif de cette recherche est de déterminer la spéciation chimique des nanoparticules d’argent dans différents sols. Pour y parvenir, différentes concentrations de nanoparticules d’argent ont été incorporées dans un sol et après un certain laps de temps, la forme ionique a été mesurée à l’aide d’une électrode sélective d’argent tandis que l’argent total est mesuré par absorption atomique ou par ICP-MS. L’analyse de la spéciation dans trois sols différents révèle que les caractéristiques des sols influencent grandement la spéciation chimique, plus particulièrement la quantité de matière organique ainsi que le pH du sol. Ainsi, la tendance des résultats semble indiquer que plus un sol est acide, il y aura plus d’ions argent libres tandis que la matière organique adsorbe fortement les ions argent les rendant ainsi moins disponibles en solution. L’observation de la spéciation chimique à long terme indique aussi que les nanoparticules tendent à éventuellement se dissocier et ainsi émettre un plus grand nombre d’ions dans l’environnement. Ces résultats ont des implications importantes dans la détermination des risques environnementaux des nanoparticules métalliques. / Because of their antibacterial properties, silver nanoparticles are widely used in common items such as textiles, soaps and medical products. This practice has shown a drastic expansion during the last years thus leading to potential contamination of the environment by nanoparticles. To understand fate, transport and bioavailabity of nanoparticles, it is important to understand their physicochemical properties. More specifically, it is essential to quantify the dissolution of nanoparticles with chemical speciation measurements. The aim of this study is to quantify the speciation of silver nanoparticles in different soils. Different concentrations of silver nanoparticles have been injected in soil and after a specific time, the ionic form was measured with a silver specific electrode while total silver was quantified by atomic absorption or ICP-MS. Chemical speciation measurements in three different soils indicate that a soil’s properties has a large influence on the fate of silver nanoparticles, especially it’s pH and organic matter content. Results show that if a soil is acidic, it will lead to the release of more free silver ions while organic matter tends to adsorb ions making them less available. Over a six month period, nanoparticles seem to fix rapidly to soil solids but also seem to dissociate or oxidise over the months, leading to a greater amount of potentially bioavailable ions. These results have important implications to the determination of environmental risks of metal nanoparticles.

In this study the possibilities of utilization of boron-doped diamond (BDD) electrodes for electrochemical reduction of organic compounds and their determination in aqueous media were investigated. For this purpose BDD electrodes have several advantages (relative wide potential window in cathodic region, low sensitivity towards oxygen evolution) but are not frequently used. For the study were selected biologically active organic compounds with typical reducible groups. Vanillin (natural essential oil, synthetic aroma; reducible aromatic aldehyde) is not reducible at BDD electrode. Azidothymidine (antiviral drug; reducible azido group) shows voltammetric signal in Britton -Robinson buffer at pH 6.0 - 8.0, but its analytical utilization is difficult due to the close positioning to the decomposition of the supporting electrolyte. The height and potential of the reduction signal of 5-nitroquinoline (environmental pollutant; reducible nitro group on the aromatic nucleus and at higher potentials reducible heterocycle) is significantly influenced by the boron concentration in BDD film. Reduction of quinoline skeleton is visible in the range of pH6.0 - 11.0 in BR buffer. For differential pulse and DC voltammetry (reduction of nitro group) in BR buffer pH 5.0 limits of detection 0.2 µmol.l-1 and 2.7...

Anilazine (4,6-dichloro-N-(2-chlorophenyl)-1,3,5-triazin-2-amine) is a fungicide from a group of triazine pesticides. These have been very widely used but for their toxicity for water environment they are being cancelled. Use of anilazine is not allowed anymore in the European Union. However, traces of its residues are able to find in environmental samples. The diploma thesis deals with determination of anilazine using silver solid amalgam electrode modified by mercury meniscus (m-AgSAE). Differential pulse voltammetry was used. For the determination, an acidic solution is necessary. In the work Britton-Roninson buffer pH = 2 was used. This is because of electrochemical reduction of anilazine (and other triazines) which is started by protonization of heterocycle ring. Anilazine exhibits one single well-defined peak, the potential of the peak was about Ep = -827 mV (vs. 3 mol l-1 argentochloride electrode). The limit of quantification achieved in surface water was 2 µmol.l-1. Other two possibilities of getting lower limit of quantification were examined - Adsorptive Stripping Voltammetry (AdSV) and preconcentration by Solid Phase Extraction (SPE). Using AdSV the limit of quantification LQ = 0,5 µmol.l-1. Conditions of adsorption were as following: Eacc = -100 mV, tacc = 60 s. For SPE, 200-mg columns...

Rechargeable lithium ion batteries have been widely used in portable consumer electronic devices, hybrid and full electric vehicles, and emergency power supply systems, because of their high energy density and long lifespan. The lithium ion battery market was approximately $11.8 billion in 2010 and is expected to grow to $53.7 billion in 2020. However, there is an intrinsic safety issue in these batteries because electrolyte contains a flammable organic solvent which may cause fire and/or even explosion. All solid-state lithium ion battery is recognized as next-generation technology for rechargeable power sources due to improved safety, high energy density, and long cycle life. Inorganic solid electrolyte replace liquid one to eliminate flammable components. The major challenge for all solid-state lithium ion batteries is to develop solid electrolytes with high ionic conductivity and good stability against both electrodes. Amorphous lithium lanthanum titanium oxide (LLTO) is very promising as solid electrolyte owing to its high ionic conductivity, good stability, and wide electrochemical stability window. In this work, amorphous LLTO thin films (or powders) were successfully prepared by sol-gel process. The thin films are smooth and crack-free. The microstructure evolution from dried gel film to fired film to annealed film was examined. The microstructure of the annealed film, either amorphous or crystalline, depends on the annealing temperature and time. Theoretical analysis was conducted to understand the microstructure evolution. Induction time determines the longest annealing time without transformation from amorphous to crystalline state. The induction time decreases with annealing temperature until the time approaches a minimum, and after that, the time increases with the temperature. Ion transport properties were investigated by Electrochemical Impedance Spectroscopy (EIS). The plateau at low frequencies results from lithium ion long-range diffusion which contributes to dc conductivity, while the observed frequency dispersion at high frequencies is attributed to short-range forward¨Cbackward hopping motion of lithium ions. The relaxation processes are non-Debye in nature. Amorphous LLTO is compatible with Li metal due to its disordered atomic configuration. Finally, a 3D structure of electrode with amorphous LLTO was successfully prepared. This electrode displays promising electrochemical performance.

Dans les batteries ion lithium, la présence d’électrolytes organiques volatiles et inflammables engendre des problèmes récurrents de sécurité. Une possible solution consiste à les remplacer par des sels fondus liquides à température ambiante, les liquides ioniques (LI), présentant une tension de vapeur négligeable et sont considérés comme flamme retardant. Leur utilisation avec des électrodes carbone (les plus usitées dans les batteries commerciales) nécessitent la présence d’un additif pour améliorer les performances des batteries.Le but de cette thèse était de déterminer le rôle de cet additif par des méthodes analytiques et de la modélisation. Tout d’abord, l’impact de cet additif sur la solvatation et la diffusion des sels de lithium a été étudié par RMN 2-D [NOE et HOESY {1H-7Li}, {1H-19F}, et la sphère de coordination du cation lithium a été simulée par dynamique moléculaire. Puis des études électrochimiques ont été développées notamment le cyclage galvanostatique à potentiel sélectionné et le cyclage voltamétrique afin de déterminer la capacité de la batterie et d’étudier les étapes d‘insertion du cation lithium au cours de la première étape de réduction. Cette étape a également été analysée par impédance électrochimique. En complément, une analyse par XPS (spectrométrie photoélectronique X) sur les électrodes post-mortem de piles arrêtées aux potentiels déterminés par impédance, a permis de caractériser les composés chimiques formés à la surface des électrodes au cours de la première réduction, mais également après plusieurs cycles de charge/décharge / In lithium ion batteries, the commercial organic electrolytes induce difficulties in the manufacturing and the use of the battery (volatile and flammable components). There are active research to eliminate these safety problems, one of the approach is the replacement of conventional battery electrolytes with room temperature ionic liquids (RTILs), which exhibit negligible vapor pressure, low flammability, high flash point. The use of ILs based electrolytes for carbon based electrodes requires presence of organic additive for improving the cyclic performance. The aim of this thesis was to determine the exact role of the organic additive through experimental and computer simulation methodologies. Its impact onto the solvation and transportation of lithium cation was investigated through {1H-7Li}, {1H-19F} NOE correlations (HOESY), and pulsed field gradient spin-echo (PGSE) NMR experiences and Molecular Dynamic simulation. The electrochemical studies were developed such as electrochemical window, galvanostatic cycling with potential limitation and cycling voltammetry showing the obtained capacity of the cell and [Li+] insertion stages during the first reduction step. Moreover, the electrochemical impedance spectroscopy (EIS) during the first reduction process, and XPS analysis of post mortem Gr electrodes stopped at chosen potential during the first reduction process, as well as, after the several charge/discharge cycles were used

Afin d’augmenter la durabilité des PEMFC, des aérogels de dioxyde d'étain ont été étudiés pour remplacer le carbone comme support de catalyseur cathodique. SnO2 est un semi-conducteur de type n dont la conductivité électronique peut être améliorée en le dopant par des cations hypervalents tels que Nb5+, Ta5+ ou Sb5+. Pour être un support de catalyseur efficace, le matériau doit aussi posséder une surface spécifique élevée avec une morphologie mésoporeuse pour permettre à la fois la dispersion et l'activité du catalyseur (Pt). À cette fin, notre objectif était de développer des aérogels de SnO2 dopé. Dans cette étude, les aérogels ont été synthétisés par voie sol-gel en milieu acide à partir d’alcoxydes métalliques comme précurseurs. Nos matériaux présentent une morphologie aérée très intéressante avec une surface spécifique relativement élevée (80-90 m2/g). De plus, tous les aérogels SnO2 dopés au Sb ont présenté une amélioration très significative de la conductivité électronique pour atteindre une valeur d’environ 0,12 S/cm. Les nanoparticules de platine ont ensuite été déposées sur la surface de l'aérogel SnO2 dopé Sb en utilisant trois méthodes différentes. La méthode basée sur la réduction chimique par l’intermédiaire d’un polyol fournit le meilleur résultat en terme d'activité catalytique massique, mesurée en électrode à disque tournant (Is = 32 mA/mgPt). Cette valeur est, par ailleurs, encore plus élevée que celle de l'électrocatalyseur TEC10E40E (Is = 27 mA/mgPt). Les AMEs intégrant notre aérogel SnO2 dopé au Sb ont enfin montré une très bonne durabilité à des potentiels élevés. / In order to tackle the problem of low durability, tin dioxide aerogels were studied to replace carbon black as a catalyst support in proton exchange membrane fuel cells (PEMFCs). SnO2 is a well-known n-type semi-conductor whose electronic conductivity can be improved by doping with hypervalent cations such as Nb5+, Ta5+ or Sb5+. In addition, as a catalyst support, this material has to develop a high specific surface area with adequate mesoporous morphology to allow both good dispersion and activity of the catalyst (Pt). To this end, our objective was to develop doped SnO2 aerogels. In this study, SnO2 based-aerogels were successfully synthesized following an acid-catalyzed sol–gel route starting with metal alkoxides as precursors. Our materials have shown a very interesting airy morphology with among other a reasonable specific surface area (80–90 m2/g). Moreover, all Sb-doped aerogels exhibited significant improvement in electronic conductivity and reach a value of around 0.12 S/cm. Platinum nanoparticles were then deposed on the Sb doped SnO2 aerogel surface using three different methods. The method based on chemical reduction using a polyol route provided the best result in term of mass catalytic activity measured by RDE (Is = 32 mA/mgPt). This value is even higher than that of the reference electrocatalyst TEC10E40E (Is = 27 mA/mgPt). Sb doped SnO2 aerogel based MEAs have exhibited a very good durability at high potentials.

Resumo: Os polímeros condutores a Base de Tiofeno-Schiff despontam como materiais alternativos para obtenção de eletrodos modificados com potencial aplicação em sensores químicos devido as excelentes propriedades condutoras e quelantes conferidas pelo poli-tiofeno e pelas Bases de Schiff, respectivamente. Neste trabalho, o complexo Tiofeno-Salen foi sintetizado e caracterizado por UV8Vis e FTIR, em seguida, monômeros complexos metálicos-tiofeno-Schiff foram sintetizados com a complexação de cátions metálicos de transição como Ni2+, Cu2+, VO2+, Fe3+, Ru3+ e Ce4+ e novamente caracterizados por UV8Vis e FTIR para comprovar a formação dos monômeros complexos metálicos-tiofeno-Schiff. Filmes poliméricos desses complexos metálicos foram obtidos pela técnica de eletropolimerização anódica e foram caracterizados eletroquimicamente por voltametria cíclica em solução aquosa. Verificou-se a influência de diversas variáveis experimentais tais como solvente, eletrólito de suporte, intervalo de varredura de potenciais, velocidade de varredura de potenciais, concentração do monômero e número de ciclos durante a etapa de eletropolimerização. Os substratos condutores utilizados na etapa de eletropolimerização foram o eletrodo de platina e o eletrodo de carbono vítreo, demonstrando a influência do substrato condutor na etapa de eletropolimerização e verificou-se que o eletrodo de platina apresentou maior eficiência de transferência eletrônica quando comparado ao eletrodo de carbono vítreo devido a natureza amorfa do carbono vítreo para esses filmes poliméricos estudados. Os eletrodos de platina modificados com esses filmes poliméricos foram também utilizados no estudo das suas propriedades eletroquímicas para a detecção de analitos de interesse analítico como L-dopa, ditionito, piridoxina, sulfito, nitrito, L-tiroxina e ácido gálico. / Abstract: Conducting polymers of the Thiophene-Schiff Bases emerge as alternative materials to obtain modified electrodes with potential applications in chemical sensors due to the excellent conductive chelating properties conferred by the poly-thiophene and the Schiff Bases, respectively. In this work, the complex Thiophene-Salen was synthesized and characterized by UV-Vis and FTIR, then monomers complex metals8thiophene8Schiff were synthesized with the complexation of cations of transition metals such as Ni2+, Cu2+, VO2+, Fe3+, Ru3+ and Ce4+ and again characterized by UV-Vis and FTIR to confirm the formation of monomer-metal complexes with thiophene-Schiff. Polymer films of these complexes were obtained by anodic electropolymerization technique and were characterized electrochemically by cyclic voltammetry in aqueous solution. There was the influence of different experimental variables such as solvent, supporting electrolyte, potential scan range, potential scan rate, monomer concentration and number of cycles during the electropolymerization. The conductive substrates used in the electropolymerization were platinum electrode and a glassy carbon electrode, demonstrating the influence of the conductive substrate in the electropolymerization and was found that the platinum electrode showed a higher electron transfer efficiency when compared to the carbon electrode vitreous due to amorphous nature of glassy carbon for these polymer films studied. The platinum modified electrodes with these polymer films were also used to study their electrochemical properties for the detection of analytes of analytical interest as L-dopa, dithionite, pyridoxine, sulphite, nitrite, L-thyroxine and gallic acid presented higher apllication as chemical sensors for these analytes. / Orientador: Marcos Fernando de Souza Teixeira / Coorientador: Luiz Humberto Marcolino Junior / Banca: Lúcio Angnes / Banca: Homero Marques Gomes / Mestre

Neste trabalho foi realizada a funcionalização de grafite sem prévio tratamento em condições de Fridel-Crafts. Considerando que a grafite não possui hidrogênio em sua estrutura, não se observa uma reação de substituição eletrofílica. Por outro lado, o trabalho mostra o papel da umidade presente no grafite na reação de funcionalização. Dessa forma, foi proposto um mecanismo para a reação com a participação da água adsorvida na grafite estabilizando o carbocátion formado. O grafite funcionalizado obtido na reação foi utilizado como material eletródico. Para a reação de funcionalização, quatro moléculas foram utilizadas: ácido ferrocenomonocarboxílico, cloreto de 4-nitrobenzoíla, cloreto de 3,5-dinitrobenzoíla e ácido 3,4-dinitrobenzóico. Para o estudo das condições ótimas da reação, utilizou-se diferentes potências de radiação no reator de micro-ondas, sendo que a extensão da funcionalização mostrou-se sensível à variação deste parâmetro. Para a caracterização dos materiais, utilizou-se voltametria cíclica e análise térmica (TG e DTA). Resultados de infravermelho e Ramam são apresentados no Apêndice A. Os resultados eletroquímicos mostraram que os materiais funcionalizados em maiores potências apresentaram maior corrente Faradaica, mas ao mesmo tempo, o material obtido foi mais resistivo. A diferença de potencial relacionada ao processo redox do ferroceno aumentou conforme a extensão da funcionalização, uma vez que um sobrepotencial é necessário devido ao fluxo iônico (para a manutenção da eletroneutralidade) relativo ao número de espécies envolvidas. Os resultados eletroquímicos também indicaram que a funcionalização do grafite com os nitro compostos foi baixa. A análise térmica evidenciou que a reação de funcionalização do grafite com o ferroceno resultou em materiais com 15% a 20% (m/m) de material ligado ao grafite. Os materiais funcionalizados a maiores potências apresentaram maior massa ligada ao grafite. A funcionalização com os nitro compostos resultou em materiais com menos de 3% (m/m) de composto ligado ao grafite. Os resultados das duas técnicas mostraram coerência na análise da extensão da funcionalização. O material funcionalizado com o ácido ferrocenomonocarboxilico foi o que apresentou os melhores resultados e propõe-se uma explicação para tal baseado no mecanismo de reação sugerido. Com o objetivo de melhor elucidar o mecanismo da reação, foram realizadas algumas reações na ausência de alguns reagentes. Por exemplo, quando tenta-se funcionalizar o material sem a presença de cloreto de alumínio ou sem a umidade natural do grafite, a reação não ocorre. / In this work natural graphite functionalization in Fridel-Crafts conditions is performed using a one-step microwave assisted reaction. Since there is no hydrogen in graphite structure, it is not possible to observe electrophilic substitution. On the other hand this work shows the role of the moisture present on graphite in the functionalization reaction under this condition. Therefore, a reaction mechanism with the participation of the water naturally adsorbed on graphite stabilizing the formed carbocation has been suggested. After the reaction, the functionalized graphite was used as electrode material. Four molecules were used to functionalize graphite: Ferrocene monocarboxylic acid, 4-nitrobenzoyl chloride, 3,5-dinitrobenzoyl chloride and 3,4-dinitrobenzoic acid. To study the optimal conditions of the reaction, the microwave radiation power was varied and the extent of the functionalization on graphite was sensitive to this parameter. Two techniques were used to characterize the materials, cyclic voltammetry and thermal analysis (TG and DTA). IR and Raman data are shown in appendix A. Electrochemical results have shown that the materials functionalized at higher microwave radiation power have higher Faradaic current, but are more resistive. The potential difference between the peaks of the redox process of ferrocene increased with the extent of functionalization. This occurs because an overpotencial is needed to compensate the ionic flux (in order to maintain the electroneutrality) related to the number of species involved. The electrochemical results also indicated that the extent of functionalization of graphite with the nitro compounds was low. The thermal analysis have shown that the functionalization of graphite with ferrocene lead to values between 15% to 20% (m/m) of compound in the material. The materials functionalized at higher microwave radiation power presented higher relative mass in the material. The reaction with the nitro compounds lead to less than 3% (m/m) of compound in the final material. The results of both techniques were coherent about the extent of functionalization. The material functionalized with ferrocene monocarboxylic acid showed the best results, and an explanation for that based on the reaction mechanism is suggested. In order to elucidate the reaction mechanism, some experiments were realized in absent of some reagents. When the reaction were carried out without aluminum chloride or with dried graphite, the reaction has not occurred.

O presente trabalho procura dar continuidade a uma das linhas de pesquisa desenvolvida pelo Grupo de Química Analítica do Instituto de Química da Universidade de são Paulo: o estudo da formação de complexos. O sistema Hg(II) / S2O2-3 foi analisado potenciometricamente, com a finalidade de identificar o número de complexos formados, assim como estimar as constantes de estabilidade envolvidas no fenônemo de complexação. Tal equilíbrio foi levado a termo a 25,0 ± 0,1°C, e força iônica 2,00M, sendo detectados quatro espécies complexas. O modelo matemático que melhor se ajustou aos dados experimentais fornecidos pelo sistema, conta com os seguintes valores para as constantes globais de formação: β1 1 = x 1024 M-1 (valor atribuído) β2 = (8,0 ± 2,8) x 1027 M-2 β3 = (1,71 ± 0,03) x 1030 M-3 β4 = (3,07 ± 0,77) x 1030 M-4. Na região de baixa concentração analítica de ligante, 5mM, o acesso experimental foi limitado pela precipitação de sulfeto mercúrico sendo impossível obter informaçôes sobre a primeira espécie. O comportamento do mercúrio no sistema Hg(II) / S2O2-3 foi estudado de uma forma mais abrangente, sendo estendido ao meio não complexante, onde o equilíbrio de dismutação do cátion mercuroso governa. Nas mesmas condições de temperatura e força iônica anteriores, foram obtidos alguns parâmetros desse equilibrio, a saber: - potenciais formais de eletrodo: Eo\'Hg(I) / Hg(O) = ( 0,456 ± 0,014 ) V Eo\'Hg(II) / Hg(O) = ( 0,559 ± 0,0016) V Eo\'Hg(III) / Hg(I) = ( 0, 6625 ± 0,0023 ) V - constante do equilibrio heterogêneo: Qp (potenciométrica) = (3 ± 1) x 103 Adicionalmente, foram realizados estudos eletrogravimétricos sobre o mecanismo de oxidação coulométrica do mercúrio metálico, em diversos eletrólitos suporte, merecendo destaque a estabilização do Hg(I) por cloreto, e do Hg (II) por tiossulfato, mostrando que a transferência eletrônica é um processo por etapas. Complementando o estudo do sistema, a potencialidade análitica do tiossulfato na determinação dos cátions do mercúrio foi confirmada em titulações potenciométricas. / The present work belongs to one of the topics developed by the Analytical Chemistry Group in the Chemistry Institute of the são Paulo University: the study of complex formation equilibrium. The Hg(II)/S2O2-3 system was potentiometrically analysed with the purpose of identifying the number of formed complexes as well as computing their stability constants. Such equilibria study was performed at a 25.0 ± 0.1ºC temperature and 2.00 M ionic strengh, mantained with NaClO4. Four stepwise complexes have been detected by a calculus procedure based on non-linear regression. The best formation constants set is: β1 1 = x 1024 M-1 (arbitrary value) β 2 = (8,0 ± 2,8) x 1027 M-2 β3 = (1,71 ± 0,03) x 1030 M-3 β4 = (3,07 ± 0,77) x 1030 M-3. At lower ligand concentration, nearly 5mM, the experimental access was limited by the mercuric sulphide precipitation, being impossible to achieve data on the first specie. The mercury performance in the Hg(II)/S2O2-3 system was more widely studied with concern to the non-complexing media, where the disrnutation of mercurous cation leads. With the same previous temperature and ionic stengh conditions, some equilibria parameters have been determined: - electrode potentials: Eo\'Hg(I) / Hg(O) = ( 0,456 ± 0,014 ) V Eo\'Hg(II) / Hg(O) = ( 0,559 ± 0,0016) V Eo\'Hg(III) / Hg(I) = ( 0, 6625 ± 0,0023) V - heterogeneous equilibria constant: Qp = (3 ± 1) x 103. Electrogravimetric studies about the coulometric oxidation mecanism of metallic mercury have also been executed. The oxidation was carried out at several suporting electrolites, regarding the Hg(II) stabilization by the tiossulphate anion, and the Hg(I) by chloride, showing that the electrochemical transfer occurs in a step by step process. In addition to system study, the analytical potentiality of the tiossulphate on the determination of mercury cationic species was confirmed by potentiometric titulations.