The ever increasing demand for a clean and renewable energy source has stimulated research for alternatives for the use of fossil fuels, which contribute significantly to global warming. The SO2 oxidation reaction was studied for production of hydrogen as a clean and renewable energy carrier. This reaction occurs at a lower standard electrode potential (0.158 V vs. SHE) than normal water electrolysis (1.23 V vs. SHE). This is a theoretical indication that the SO2 oxidation reaction has possible potential when compared to normal water electrolysis, since hydrogen production may occur at lower potentials and therefore lower cost. Rh was compared with Pt for the SO2 oxidation reaction since little research has been done on this catalyst and many studies exist in which Pt was used as catalyst. The oxygen reduction reaction and ethanol oxidation reaction were also included in this study to create a foundation for the catalysts studied, since the SO2 oxidation reaction is complicated by different adsorbed species that can form according to various mechanisms. The electrochemical techniques employed in this study to characterize the catalysts included cyclic voltammetry from which onset potentials and limiting current densities were determined, as well as from which some qualitative analysis was done. Linear polarization experiments were used during rotating disk electrode studies from which Levich and Koutecky-Levich analyses were done and the number of electrons transferred calculated and compared between the two catalysts. From the Koutecky-Levich analysis the kinetic current density was also obtained for use in Tafel analysis for further comparison between catalysts. It was found that Rh showed good behaviour for the oxygen reduction reaction when compared to Pt with similar onset potentials and limiting current densities. From Levich analysis it was concluded that both catalysts achieved diffusion limitation at high overpotentials. However, from the calculated number of electrons transferred it was evident that a difference in mechanism existed between catalysts and that the mechanism for both changed in the potential range studied, which is confirmed by the Tafel slopes. For the ethanol oxidation reaction it was shown that Rh exhibited very low catalytic activity in comparison with Pt. However, it was concluded from cyclic voltammetry and rotating disk electrode studies that more adsorbed species were present on the surface of Rh than on Pt. These results confirmed the possibility of using Rh as a co-catalyst together with Pt since it was shown from rotating disk electrode studies that low adsorption of ethanol and its oxidation products caused species to be transported away from the surface of the electrode during rotation. For the SO2 oxidation reaction it was found that Rh exhibited very poor catalytic activity together with being very susceptible to poisoning by adsorbed species. Pt showed very good behaviour, which corresponded well with what had been observed in literature. Levich analysis revealed that Pt did not exhibit diffusion limitation and Koutecky-Levich analysis revealed that a 2 electron reaction occurred on Pt, which corresponds with the SO2 oxidation reaction during which 2 electrons are transferred. It was, therefore, shown that Rh could exhibit good behaviour and act as a suitable catalyst in certain circumstances. However, for the SO2 oxidation reaction, which was the main focus of this study it was shown that Rh is not a suitable catalyst, either alone or as co-catalyst. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

The ever increasing demand for a clean and renewable energy source has stimulated research for alternatives for the use of fossil fuels, which contribute significantly to global warming. The SO2 oxidation reaction was studied for production of hydrogen as a clean and renewable energy carrier. This reaction occurs at a lower standard electrode potential (0.158 V vs. SHE) than normal water electrolysis (1.23 V vs. SHE). This is a theoretical indication that the SO2 oxidation reaction has possible potential when compared to normal water electrolysis, since hydrogen production may occur at lower potentials and therefore lower cost. Rh was compared with Pt for the SO2 oxidation reaction since little research has been done on this catalyst and many studies exist in which Pt was used as catalyst. The oxygen reduction reaction and ethanol oxidation reaction were also included in this study to create a foundation for the catalysts studied, since the SO2 oxidation reaction is complicated by different adsorbed species that can form according to various mechanisms. The electrochemical techniques employed in this study to characterize the catalysts included cyclic voltammetry from which onset potentials and limiting current densities were determined, as well as from which some qualitative analysis was done. Linear polarization experiments were used during rotating disk electrode studies from which Levich and Koutecky-Levich analyses were done and the number of electrons transferred calculated and compared between the two catalysts. From the Koutecky-Levich analysis the kinetic current density was also obtained for use in Tafel analysis for further comparison between catalysts. It was found that Rh showed good behaviour for the oxygen reduction reaction when compared to Pt with similar onset potentials and limiting current densities. From Levich analysis it was concluded that both catalysts achieved diffusion limitation at high overpotentials. However, from the calculated number of electrons transferred it was evident that a difference in mechanism existed between catalysts and that the mechanism for both changed in the potential range studied, which is confirmed by the Tafel slopes. For the ethanol oxidation reaction it was shown that Rh exhibited very low catalytic activity in comparison with Pt. However, it was concluded from cyclic voltammetry and rotating disk electrode studies that more adsorbed species were present on the surface of Rh than on Pt. These results confirmed the possibility of using Rh as a co-catalyst together with Pt since it was shown from rotating disk electrode studies that low adsorption of ethanol and its oxidation products caused species to be transported away from the surface of the electrode during rotation. For the SO2 oxidation reaction it was found that Rh exhibited very poor catalytic activity together with being very susceptible to poisoning by adsorbed species. Pt showed very good behaviour, which corresponded well with what had been observed in literature. Levich analysis revealed that Pt did not exhibit diffusion limitation and Koutecky-Levich analysis revealed that a 2 electron reaction occurred on Pt, which corresponds with the SO2 oxidation reaction during which 2 electrons are transferred. It was, therefore, shown that Rh could exhibit good behaviour and act as a suitable catalyst in certain circumstances. However, for the SO2 oxidation reaction, which was the main focus of this study it was shown that Rh is not a suitable catalyst, either alone or as co-catalyst. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

In this study the focus was on the electrochemical techniques and aspects behind the establishment of the better catalyst (platinum or gold) for the sulphur dioxide oxidation reaction (SDOR). One of the primary issues regarding the SDOR is the catalyst material, thus the comparative investigation of the performance of platinum and gold in the SDOR, as found in this study. Ultimately, the SDOR could lead to an effective way of producing hydrogen gas, which is an excellent energy carrier. The electrochemical application of the oxygen reduction reaction (ORR) and ethanol oxidation reaction (EOR) is an integral part of the catalytic process of water electrolysis, and by using fuel cell technology, it becomes even more relevant to this study and can therefore be used as a control, guide and introduction to the techniques required for electrochemical investigation of catalyst effectiveness. Subsequently, the EOR as well as the ORR was used as introduction into the different electrochemical quantification and qualification techniques used in the electrochemical analyses of the SDOR. Considering the ORR, gold showed no viable activity in acidic medium, contrarily in alkaline medium, it showed good competition to platinum. Gold also lacked activity towards the EOR in acidic medium compared to platinum, with platinum the best catalyst in both acidic and alkaline media. Ultimately, platinum was established to be the material with better activity for the ORR with gold a good competitor in alkaline medium, and platinum the better catalyst for the EOR in both acidic and alkaline media. With the main focus of this study being the SDOR, gold proved to be the best catalyst in salt and gaseous forms of SO2 administration compared to platinum when the onset potential, maximum current density, Tafel slope and number of electrons transferred are taken into consideration. The onset potential was determined as 0.52 V vs. NHE for both platinum and gold using SO2 gas and 0.54 V and 0.5 V for gold and platinum respectively, using Na2SO3 salt. The maximum current density using gaseous SO2 for platinum at 0 RPM was 400 mA/cm2 with a Tafel slope of 891 mV/decade whereas gold had a maximum current density of 300 mA/cm2 and a Tafel slope of 378 mV/decade. Using Na2SO3 salt, the maximum current density of gold was 25 mA/cm2 with a Tafel slope of 59 mV/decade whereas platinum only achieved 18 mA/cm2 with a Tafel slope of 172 mV/decade. Concerning the number of electrons transferred, gold achieves a transfer of 2 while platinum only 1 for both SO2 gas and Na2SO3 salt. Taking all these summarised determinations into account, gold was established to be a very competitive catalyst material for the SDOR, compared to platinum. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2015

In this study the focus was on the electrochemical techniques and aspects behind the establishment of the better catalyst (platinum or gold) for the sulphur dioxide oxidation reaction (SDOR). One of the primary issues regarding the SDOR is the catalyst material, thus the comparative investigation of the performance of platinum and gold in the SDOR, as found in this study. Ultimately, the SDOR could lead to an effective way of producing hydrogen gas, which is an excellent energy carrier. The electrochemical application of the oxygen reduction reaction (ORR) and ethanol oxidation reaction (EOR) is an integral part of the catalytic process of water electrolysis, and by using fuel cell technology, it becomes even more relevant to this study and can therefore be used as a control, guide and introduction to the techniques required for electrochemical investigation of catalyst effectiveness. Subsequently, the EOR as well as the ORR was used as introduction into the different electrochemical quantification and qualification techniques used in the electrochemical analyses of the SDOR. Considering the ORR, gold showed no viable activity in acidic medium, contrarily in alkaline medium, it showed good competition to platinum. Gold also lacked activity towards the EOR in acidic medium compared to platinum, with platinum the best catalyst in both acidic and alkaline media. Ultimately, platinum was established to be the material with better activity for the ORR with gold a good competitor in alkaline medium, and platinum the better catalyst for the EOR in both acidic and alkaline media. With the main focus of this study being the SDOR, gold proved to be the best catalyst in salt and gaseous forms of SO2 administration compared to platinum when the onset potential, maximum current density, Tafel slope and number of electrons transferred are taken into consideration. The onset potential was determined as 0.52 V vs. NHE for both platinum and gold using SO2 gas and 0.54 V and 0.5 V for gold and platinum respectively, using Na2SO3 salt. The maximum current density using gaseous SO2 for platinum at 0 RPM was 400 mA/cm2 with a Tafel slope of 891 mV/decade whereas gold had a maximum current density of 300 mA/cm2 and a Tafel slope of 378 mV/decade. Using Na2SO3 salt, the maximum current density of gold was 25 mA/cm2 with a Tafel slope of 59 mV/decade whereas platinum only achieved 18 mA/cm2 with a Tafel slope of 172 mV/decade. Concerning the number of electrons transferred, gold achieves a transfer of 2 while platinum only 1 for both SO2 gas and Na2SO3 salt. Taking all these summarised determinations into account, gold was established to be a very competitive catalyst material for the SDOR, compared to platinum. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2015

The pressure on clean and sustainable energy supplies is increasing. In this regard energy conversion by electrochemical processes plays a major role, for both fuel cell reactions and electrolysis reactions. The sulphur dioxide oxidation reaction (SOR) is a common reaction found in the Hybrid Sulphur Cycle (HyS) and the HyS is a way to produce large-scale hydrogen (H2). The problem with the use of the HyS and fuel cells is the cost involved as large amounts of Pt are required for effective operation. The aim of the study was to determine whether there was an alternative catalyst which was more efficient and cost-effective than Pt. The oxygen reduction reaction (ORR), the ethanol oxidation reaction (EOR) and SOR were studied by means of different electrochemical techniques (cyclovoltammetry (CV), linear polarization (LP) and rotating disk electrode (RDE)) on polycrystalline platinum (Pt) and palladium (Pd). The SRR and EOR are common reactions occurring at the cathode and anode, respectively, in fuel cells and these reactions have been investigated extensively. The reason for studying the reactions was as a preparation for the SOR. This study compared polycrystalline Pt and Pd for the different reactions, with the main focus on the SOR as Pd is considerably cheaper than Pt, and for the SOR polycrystalline Pd has by no means been investigated intensively. Polycrystalline Pt and Pd were compared by different electrochemical techniques and analyses. The Koutecky-Levich and Levich analyses were used to (i) calculate the number of e- involved in the relevant reaction, (ii) to determine whether the reaction was mass transfer controlled at high overpotentials and (iii) whether the reaction mechanism changed with potential. Next the kinetic current density ( k) was calculated from Koutecky-Levich analyses, which was further used for Tafel slope analyses. If it was not possible to carry out the analyses, the activation energy (Ea) was used to determine the electrocatalytic activity of the catalyst. The electrocatalytic activity was also determined by comparing onset potentials (Es), peak potentials (Ep) and limited/maximum current density ( b/ p) of each catalyst. This study was only a preliminary study for the SOR and therefore, further studies are certainly required. It seemed Pd shows better electrocatalytic activity than Pt for the SRR in an alkaline electrolyte because of similar Es, but Pd produced a higher cathodic current density. Pt showed a lower Es than Pd for the SRR in an acid electrolyte, but Pd delivered a higher cathodic current density. This, therefore, means that the SRR in an acid electrolyte is kinetically more favourable on Pd than on Pt. For the EOR better electrocatalytic activity was obtained with Pd than with Pt in an alkaline electrolyte due to higher current densities at lower potentials and Pd showed lower Ea values than Pt in the potential range normally used for fuel cells. Pd was inactive for EOR in an acid electrolyte, while a reaction occurred on Pt. A possible reason for this observation may be due to the H2 absorbing strongly on Pd thus blocking the active positions on the electrode surfaces, preventing further reaction. Pd showed higher electrocatalytic activity for the SOR due to lower Es and higher current densities at low potentials. From the RDE studies it was established that the SRR in an alkaline electrolyte on polycrystalline Pt and Pd was mass transfer controlled at low potentials (high overpotentials), but the SRR in an acid electrolyte was only mass transfer controlled on Pt. The SOR was not mass transfer controlled on polycrystalline Pt and Pd at high potentials (high overpotentials). These assumptions were confirmed by Levich analysis. Using Koutecky-Levich analysis, it was determined that the reaction mechanism on polycrystalline Pt and Pd changed with potential for SRR in an alkaline electrolyte and the SOR. For the SRR in an acid electrolyte the reaction mechanism remained constant with changes in potential on polycrystalline Pd, but the reaction mechanism on polycrystalline Pt changed with potential. These assumptions were confirmed by the number of e-, calculated using Koutecky-Levich analyses. Levich and Koutecky-Levich analyses were not performed for EOR as an increase in rotation speed did not produce an increase in current density. Tafel slope analyses were conducted by making use of overpotentials and k, where possible. As in the case of ethanol, it was not possible to execute Koutecky-Levich analyses and, therefore, it was not possible to perform Tafel slope analyses using k. Tafel slope analyses for the EOR was therefore performed with normal current densities at 0 rotations per minute (rpm). The reaction mechanisms on Pt and Pd for the SRR in alkaline and acidic electrolytes differed due to different Tafel slopes. Pt and Pd displayed similar Tafel slopes for the EOR in alkaline electrolyte, thus suggesting that the reaction mechanisms on Pt and Pd were the same. For the SOR it seemed that the reaction mechanism on Pt and Pd were similar because of similar Tafel slopes. This was only a preliminary and comparative study for polycrystalline Pt and Pd, and the reaction mechanism was not further studied by means of spectroscopic techniques. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

The pressure on clean and sustainable energy supplies is increasing. In this regard energy conversion by electrochemical processes plays a major role, for both fuel cell reactions and electrolysis reactions. The sulphur dioxide oxidation reaction (SOR) is a common reaction found in the Hybrid Sulphur Cycle (HyS) and the HyS is a way to produce large-scale hydrogen (H2). The problem with the use of the HyS and fuel cells is the cost involved as large amounts of Pt are required for effective operation. The aim of the study was to determine whether there was an alternative catalyst which was more efficient and cost-effective than Pt. The oxygen reduction reaction (ORR), the ethanol oxidation reaction (EOR) and SOR were studied by means of different electrochemical techniques (cyclovoltammetry (CV), linear polarization (LP) and rotating disk electrode (RDE)) on polycrystalline platinum (Pt) and palladium (Pd). The SRR and EOR are common reactions occurring at the cathode and anode, respectively, in fuel cells and these reactions have been investigated extensively. The reason for studying the reactions was as a preparation for the SOR. This study compared polycrystalline Pt and Pd for the different reactions, with the main focus on the SOR as Pd is considerably cheaper than Pt, and for the SOR polycrystalline Pd has by no means been investigated intensively. Polycrystalline Pt and Pd were compared by different electrochemical techniques and analyses. The Koutecky-Levich and Levich analyses were used to (i) calculate the number of e- involved in the relevant reaction, (ii) to determine whether the reaction was mass transfer controlled at high overpotentials and (iii) whether the reaction mechanism changed with potential. Next the kinetic current density ( k) was calculated from Koutecky-Levich analyses, which was further used for Tafel slope analyses. If it was not possible to carry out the analyses, the activation energy (Ea) was used to determine the electrocatalytic activity of the catalyst. The electrocatalytic activity was also determined by comparing onset potentials (Es), peak potentials (Ep) and limited/maximum current density ( b/ p) of each catalyst. This study was only a preliminary study for the SOR and therefore, further studies are certainly required. It seemed Pd shows better electrocatalytic activity than Pt for the SRR in an alkaline electrolyte because of similar Es, but Pd produced a higher cathodic current density. Pt showed a lower Es than Pd for the SRR in an acid electrolyte, but Pd delivered a higher cathodic current density. This, therefore, means that the SRR in an acid electrolyte is kinetically more favourable on Pd than on Pt. For the EOR better electrocatalytic activity was obtained with Pd than with Pt in an alkaline electrolyte due to higher current densities at lower potentials and Pd showed lower Ea values than Pt in the potential range normally used for fuel cells. Pd was inactive for EOR in an acid electrolyte, while a reaction occurred on Pt. A possible reason for this observation may be due to the H2 absorbing strongly on Pd thus blocking the active positions on the electrode surfaces, preventing further reaction. Pd showed higher electrocatalytic activity for the SOR due to lower Es and higher current densities at low potentials. From the RDE studies it was established that the SRR in an alkaline electrolyte on polycrystalline Pt and Pd was mass transfer controlled at low potentials (high overpotentials), but the SRR in an acid electrolyte was only mass transfer controlled on Pt. The SOR was not mass transfer controlled on polycrystalline Pt and Pd at high potentials (high overpotentials). These assumptions were confirmed by Levich analysis. Using Koutecky-Levich analysis, it was determined that the reaction mechanism on polycrystalline Pt and Pd changed with potential for SRR in an alkaline electrolyte and the SOR. For the SRR in an acid electrolyte the reaction mechanism remained constant with changes in potential on polycrystalline Pd, but the reaction mechanism on polycrystalline Pt changed with potential. These assumptions were confirmed by the number of e-, calculated using Koutecky-Levich analyses. Levich and Koutecky-Levich analyses were not performed for EOR as an increase in rotation speed did not produce an increase in current density. Tafel slope analyses were conducted by making use of overpotentials and k, where possible. As in the case of ethanol, it was not possible to execute Koutecky-Levich analyses and, therefore, it was not possible to perform Tafel slope analyses using k. Tafel slope analyses for the EOR was therefore performed with normal current densities at 0 rotations per minute (rpm). The reaction mechanisms on Pt and Pd for the SRR in alkaline and acidic electrolytes differed due to different Tafel slopes. Pt and Pd displayed similar Tafel slopes for the EOR in alkaline electrolyte, thus suggesting that the reaction mechanisms on Pt and Pd were the same. For the SOR it seemed that the reaction mechanism on Pt and Pd were similar because of similar Tafel slopes. This was only a preliminary and comparative study for polycrystalline Pt and Pd, and the reaction mechanism was not further studied by means of spectroscopic techniques. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

Nous étudions expérimentalement diverses configurations d'entraînement et de drai- nage visqueux. Dans un premier temps, nous montrons que la rugosité modifie les lois de l'enduction par trempage : l'épaisseur est égale à la taille de la texture jusqu' à un nombre capillaire critique, à partir duquel elle augmente pour rejoindre la loi obtenue sur surface lisse lorsque'elle devient largement supérieure à la rugosité. Le drainage gravitaire est également modifié, et présente en particulier une marche d'épaisseur. Un modèle à deux couches permet de rendre quantitativement compte de toutes ces observations. Nous étudions ensuite le dépôt à l'aide d'une membrane flexible. Dans le cas où le racloir est juste tangent à la surface de dépôt, un modèle décrit les expériences à un facteur près. Cette déviation est en partie due à des effets de bords. Nous montrons ensuite que la loi de dépôt est très différente avec un racloir rigide, et peut être comprise en considérant l'écoulement dans un coin. Cette étude nous permet d'insister sur l'importance de la forme de la membrane dans détermination de la loi d'entraînement. Enfin, nous nous intéressons à l'entraînement vertical par un cylindre d'un filament visqueux, dont la taille résulte alors d'un équilibre entre viscosité et gravité. Le drainage de ces objets est très différent selon les dimensions du cylindre. Cette différence de com- portement en fonction de la géométrie se retrouve dans l'évolution d'un filament horizontal soumis à la gravité. Nous expliquons pourquoi un "gros" filament conserve une forme de chaînette tout au long de sa chute, tandis qu'un "petit" évolue sous l'effet de la capillarité vers une forme de "U".

The presented thesis investigates the transfer of drug molecules across interfaces that mimic biological membrane barriers. The permeability of drug molecules across biological membrane mimics has been investigated in a novel artificial membrane permeation assay configuration using an in situ time-dependent approach and reproducible rotation of the membrane. A method to determine the membrane permeability from the knowledge of measured permeability and the applied stirring rate is presented. The initial transient of the permeation response, previously not observed in situ, is investigated and its importance in data evaluation is discussed. The permeability coefficients of 31 drugs are optimised for the conditions found in vivo and a correlation with the fraction absorbed in humans is presented. The evidence for ionic and/or ion-pair flux across the artificial membrane obtained from measurement of permeability at different pH is supported by the investigation of the permeation assay with external membrane polarisation. The permeability coefficient of the solute's anionic form is determined. Liquid/liquid electrochemistry has been used to study the transfer of ionized species across the interface between water and 1,2-dichloroethane. An alternative method to study the transfer of partially ionised drug molecules employing a rotating liquid/liquid interface is presented. In addition, a bipolar electrochemical cell with a rotating-disc electrode is developed and its properties investigated in order to verify the hydrodynamics of the rotating artificial membrane configuration. Finally, in support of the electrochemical techniques used is this thesis, a detailed preparation and evaluation of the silver/silver sulphate reference electrode is presented.

No description available.

Ce travail de thèse, de nature théorique, présente quatre axes de recherche portant sur la dynamique d'interfaces molles. (1) Gouttes et films de liquide sur substrats poreux : Nous avons étudié la déformation d'une goutte soumise simultanément à une aspiration de liquide et à un ancrage de sa ligne de contact avec le substrat. Nous nous sommes aussi intéressés au problème de l'entraînement d'un film de liquide sur une surface poreuse tirée hors d'un bain : le film a une hauteur finie, que nous avons calculée, et présente une structure non-triviale à l'approche de la ligne de contact. (2) Réticulation et interdiffusion à l'interface entre deux polymères : La formation de joints entre deux pièces de polymère nécessite une bonne interdiffusion des chaînes, qui peut cependant être considérablement contrariée lorsqu'un agent réticulant est introduit (dans le but de renforcer le matériau final). Nous avons modélisé la compétition qui s'installe, en montrant qu'il existait un paramètre de contrôle simple permettant d'optimiser le système et en donnant des prédictions sur l'énergie d'adhésion attendue dans deux régimes-limites. (3) Ecoulements granulaires : Nous donnons le scénario analytique complet du déroulement d'une avalanche sur un tas de sable, en tenant compte de l'effet d'un profil de vitesse linéaire dans la couche roulante. Parmi les prédictions, nous avons trouvé que l'épaisseur maximale devait varier comme la racine carrée de la taille de l'empilement. (4) Dynamique de films de savon verticaux : Les propositions actuelles concernant le mécanisme du drainage de ces films font appel à des instabilités hydrodynamiques se développant au bord du film ("régénération marginale"). Nous avons cherché à en déterminer précisément l'état précurseur : de manière générique, le profil forme une zone de striction, dont nous avons calculé analytiquement les dimensions typiques ; celle-ci pourrait rassembler les caractéristiques nécessaires à l'émergence des instabilités.