Os primeiros estudos sobre a utilização do azoteto de sódio, NaN3, como eletrólito de suporte em polarografia, revelaram a existência de onda catalítica quando o meio era acidulado, contendo HN3, na presença de íons de cobalto(II). O presente trabalho procurou esclarecer a natureza da onda catalítica com os íons de cobalto(II). Para isto foram estudados diversos fatores como ânions indiferentes, a presença de íons de hidrogênio, a influência do oxigênio, composição da solução em relação à concentração de azoteto, de cobalto(II) e papel da substância tensoativa. Os resultados experimentais levaram à conclusão de que se tratava de onda catalítica com evolução de hidrogênio, cujo mecanismo se assemelha muito ao observado no sistema CO(II)/CN-. Há evidências de participação de fenômenos de adsorção de complexos de cobalto(II) com azoteto, passando intermediariamente ao estado de oxidação (I) e reoxidação a hidreto complexo de cobalto(III). Este por ação catalítica de espécie neutra Co(N3)2 se decompõe liberando hidrogênio molecular e regenerando o complexo de cobalto(II). Verificou-se também corrente catalítica no sistema HN3N-3 na presença de níquel(II). / Previous studies about sodium azide as suporting electrolyte in polarography showed existence of a catalytic wave in acidic media, HN3, in the presence of cobalt(II). The aim of this work was to elucidate the nature of the catalytic wave obtained with cobalt(II) ions. For this purpose several factors were studied such as: indifferent anions, the presence of hydrogen protons, the influence of oxygen, composition of the solution concerning the azide ion concentration, cobalt(II) and the role of surface active substances (Triton X-100). From the experimental data it was concluded that there is a catalytic wave with hydrogen libertion whose mechanism is very similar to the one observed in the Co(II)/CN- system. There is evidences of adsorption phenomena of cobalt(II) azide complexes going through an oxidation state(I) and reoxidation to cobalt(III) hydride complex. This complex is then decomposed catalytically by the neutral species Co(N3)2 with molecular hydrogen liberation and regeneration of the cobalt(II) complex. Catalytic wave has been found to occur in HN3/N-3 buffer as caused by the presence of nickel(II).

Os primeiros estudos sobre a utilização do azoteto de sódio, NaN3, como eletrólito de suporte em polarografia, revelaram a existência de onda catalítica quando o meio era acidulado, contendo HN3, na presença de íons de cobalto(II). O presente trabalho procurou esclarecer a natureza da onda catalítica com os íons de cobalto(II). Para isto foram estudados diversos fatores como ânions indiferentes, a presença de íons de hidrogênio, a influência do oxigênio, composição da solução em relação à concentração de azoteto, de cobalto(II) e papel da substância tensoativa. Os resultados experimentais levaram à conclusão de que se tratava de onda catalítica com evolução de hidrogênio, cujo mecanismo se assemelha muito ao observado no sistema CO(II)/CN-. Há evidências de participação de fenômenos de adsorção de complexos de cobalto(II) com azoteto, passando intermediariamente ao estado de oxidação (I) e reoxidação a hidreto complexo de cobalto(III). Este por ação catalítica de espécie neutra Co(N3)2 se decompõe liberando hidrogênio molecular e regenerando o complexo de cobalto(II). Verificou-se também corrente catalítica no sistema HN3N-3 na presença de níquel(II). / Previous studies about sodium azide as suporting electrolyte in polarography showed existence of a catalytic wave in acidic media, HN3, in the presence of cobalt(II). The aim of this work was to elucidate the nature of the catalytic wave obtained with cobalt(II) ions. For this purpose several factors were studied such as: indifferent anions, the presence of hydrogen protons, the influence of oxygen, composition of the solution concerning the azide ion concentration, cobalt(II) and the role of surface active substances (Triton X-100). From the experimental data it was concluded that there is a catalytic wave with hydrogen libertion whose mechanism is very similar to the one observed in the Co(II)/CN- system. There is evidences of adsorption phenomena of cobalt(II) azide complexes going through an oxidation state(I) and reoxidation to cobalt(III) hydride complex. This complex is then decomposed catalytically by the neutral species Co(N3)2 with molecular hydrogen liberation and regeneration of the cobalt(II) complex. Catalytic wave has been found to occur in HN3/N-3 buffer as caused by the presence of nickel(II).

Ce travail porte sur l’étude expérimentale et numérique de l’écoulement des mousses humides dans un canal horizontal droit de section carrée avec ou sans singularités. Il est consacré tout particulièrement à déterminer les paramètres pertinents de l’écoulement dont la chute de pression longitudinale, les champs de vitesse de l’écoulement de mousse en proche parois, les épaisseurs de films liquides minces et épais en paroi et l’évolution de la contrainte pariétale pour une mousse humide dont la fraction gazeuse varie de 55 à 85% et la vitesse débitante de la mousse est 2, 4 puis 6 cm/s. Une fois ces paramètres déterminés en conduite horizontale droite, nous avons ensuite effectué des mesures sur différentes géométries représentant un élargissement brusque, une chicane verticale et écoulement de mousse autour d’un cylindre, dont le but est d’étudier la réorganisation de l’écoulement en vue de déterminer le comportement rhéologique des mousses en écoulement à l’aval et à l’amont des singularités. Finalement, une étude de simulation numérique (CFD) en utilisant les lois de comportement de type Bingham, pour fluides non newtoniens, a été effectuée afin de tester sa capacité de représenter des écoulements type mousse humide dans une conduite horizontale avec ou sans singularités. Nous avons vérifié tout d’abord l’évolution longitudinale de la pression statique qui est linéaire à l’amont comme à l’aval loin des zones influencées par les singularités. La chute de pression singulière reste à peu près constante pour une vitesse débitante donnée de la mousse. À partir de la technique de Vélocimétrie par Image de Particule (PIV), nous avons déterminé les composantes de vitesse au voisinage immédiat des singularités. Ces mesures nous ont permis de mettre en évidence l’existence de différents régimes d’écoulement, et de déterminer la réorganisation et le comportement rhéologique de l’écoulement de mousse autour des géométries étudiées. L’analyse des mesures d’épaisseur de films liquides, obtenues par la méthode conductimétrique, indique que la paroi reste mouillée par un film liquide suffisamment épais pour qu’on puisse appliquer la méthode électrochimique. Les signaux polarographiques obtenus avec la mousse présentent alors de fortes fluctuations. La comparaison de celles-ci avec les contraintes pariétales déduites à partir des mesures de la chute de pression montre bien une bonne concordance. L’étude numérique (CFD), effectuée pour une fraction volumique de gaz égale à 70% et qui s’écoule avec une vitesse débitante de 2 cm/s, montre que le modèle rhéologique de Bingham pourrait être bien adapté à ce genre de mousse humide évoluant en écoulement en bloc. / This work is an experimental and numerical study of aqueous foam flow inside a horizontal square duct, with and without flow disruption devices (fdd). It is especially devoted to determine the pertinent parameters of the flow: longitudinal pressure losses, velocity fields of foam flow near the walls, liquid film thickness (thick and thin), and the wall shear stress evolution, for an aqueous foam with a void fraction range between 55 and 85%, for a mean foam flow velocity of 2, 4 and 6 cm/s. Once they were determined, inside the horizontal channel, we carried out measurements over different geometries: half-sudden expansion, vertical fence and foam flow around a cylinder. The goal was to study the foam flow reorganization to well understand the rheological behavior of aqueous foam flow in the vicinities of different fdd. Finally, a numerical simulation (CFD), using the Bingham behavior model of non-Newtonian fluid, was undertaken to test its capacity to represent the aqueous foam flow inside the horizontal duct with flow disruption devices. First of all, we verified the static longitudinal pressure evolution, which varies linearly upstream and downstream far from the fdd. The singular pressure loss remains constant for a given mean foam velocity and a foam quality (void fraction). From the Particle Imaging Velocimetry (PIV) technique (2D), we determined the two velocity components in the immediate vicinities of the disruption devices. They allowed us to put into evidence the different foam flow regimes and to observe the foam flow reorganization and rheological behavior through the studied fdd. The slip-layer thickness analysis, obtained using the conductimetry method, shows that the wall presents a liquid film thick enough to apply an electrochemical technique (polarography). Thus, the polarographic signals, obtained for the foam flow, present important fluctuations. They were compared to the wall shear stress deducted from the measurement of pressure losses, showing a good similarity between them. The numerical study (CFD), carried out for aqueous foam flow with a void fraction of 70% and a mean foam flow velocity of 2 cm/s, shows that the Bingham rheological model can be adapted to this kind of aqueous foam flow which is flowing like a block.