A study of the oxygen electrochemistry of ruthenium and iridium

This thesis is concerned with an investigation of the anodic behaviour of ruthenium and iridium in aqueous solution and particularly of oxygen evolution on these metals. The latter process is of major interest in the large-scale production of hydrogen gas by the electrolysis of water. The presence of low levels of ruthenium trichloride ca. 10-4 mol dm-3 in acid solution give a considerable increase in the rate of oxygen evolution from platinum and gold, but not graphite, anodes. The mechanism of this catalytic effect was investigated using potential step and a.c. impedance technique. Earlier suggestions that the effect is due to catalysis by metal ions in solution were proved to be incorrect and it was shown that ruthenium species were incorporated into the surface oxide film. Changes in the oxidation state of these ruthenium species is probably responsible for the lowering of the oxygen overvoltage. Both the theoretical and practical aspects of the reaction were complicated by the fact that at constant potential the rates of both the catalysed and the uncatalysed oxygen evolution processes exhibit an appreciable, continuous decrease with either time or degree of oxidation of the substrate. The anodic behaviour of iridium in the oxide layer region has been investigated using conventional electrochemical techniques such as cyclic voltammetry. Applying a triangular voltage sweep at 10 Hz, 0.01 to 1.50V increases the amount of electric charge which the surface can store in the oxide region. This activation effect and the mechanism of charge storage is discussed in terms of both an expanded lattice theory for oxide growth on noble metals and a more recent theory of irreversible oxide formation with subsequent stoichiometry changes. The lack of hysteresis between the anodic and cathodic peaks at ca. 0.9 V suggests that the process involved here is proton migration in a relatively thick surface layer, i.e. that the reaction involved is some type of oxide-hydroxide transition. Lack of chloride ion inhibition in the anodic region also supports the irreversible oxide formation theory; however, to account for the hydrogen region of the potential sweep a compromise theory involving partial reduction of the outer regions of iridium oxide film is proposed. The loss of charge storage capacity when the activated iridium surface is anodized for a short time above ca. 1.60 V is attributed to loss by corrosion of the outer active layer from the metal surface. The behaviour of iridium at higher anodic potentials in acid solution was investigated. Current-time curves at constant potential and Tafel plots suggested that a change in the mechanism of the oxygen evolution reaction occurs at ca. 1.8 V. Above this potential, corrosion of the metal occurred, giving rise to an absorbance in the visible spectrum of the electrolyte (λ max = 455 nm). It is suggested that the species involved was Ir(O2)2+. A similar investigation in the case of alkaline electrolyte gave no evidence for a change in mechanism at 1.8 V and corrosion of the iridium was not observed. Oxygen evolution overpotentials were much lower for iridium than for platinum in both acidic and alkaline solutions.

Thomas Wolfe and the genre question: Beyond the "charge of autobiography"

The North Carolinian author Thomas Wolfe (1900‐1938) has long suffered under the “charge of autobiography,” which lingers to this day in critical assessments of his work. Criticism of Wolfe is frequently concerned with questions of generic classification, but since the 1950s, re‐assessments of Wolfe’s work have suggested that Wolfe’s “autobiographical fiction” exhibits a complexity that merits further investigation. Strides in autobiographical and narrative theory have prompted reconsiderations of texts that defy the artificial boundaries of autobiography and fiction. Wolfe has been somewhat neglected in the canon of American fiction of his era, but deserves to be reconsidered in terms of how he engages with the challenges and contradictions of writing about or around the self. This thesis investigates why Wolfe’s work has been the source of considerable critical discomfort and confusion with regard to the relationship between Wolfe’s life and his writing. It explores this issue through an examination of elements of Wolfe’s work that problematise categorisation. Firstly, it investigates the concept of Wolfe as “storyteller.” It explores the motivations and philosophies that underpin Wolfe’s work and his concept of himself as a teller of tales, and examines aspects of Wolfe’s writing process that have their roots in medieval traditions of the memorisation and recitation of tales. The thesis then conducts a detailed examination of how Wolfe describes the process of transforming his memory into narrative through writing. The latter half of the thesis examines narrative techniques used by Wolfe, firstly analysing his extensive use of the iterative and pseudo‐iterative modes, and then his unusual deployment of narrators and focalization. This project sheds light on elements of Wolfe’s approach to writing and narrative strategies that he employs that have previously been overlooked, and that have created considerable critical confusion with regard to the supposedly “autobiographical” genesis of his work.

Migration: A Heideggerian analysis

The phenomenon of migration has been widely researched by the social sciences. Theories regarding the migrant have been developed in terms of the oppressive social context that is often encountered, proposing different alternatives to understand and overcome such oppression. Through the current project, an alternative view is presented that first, questions the accuracy of the social theories of migration and second, proposes an alternative understanding of this experience. Martin Heidegger’s phenomenology of Being offers a contextualized view of existence that nonetheless includes elements of our experience that are shared due to a common mode of being. I use Heidegger’s philosophy in order to broaden the understanding of the migrant’s experience analyzing those elements that he identifies as shared (for instance: human sociability, a desire for a home, the uncanny, etc.) and comparing them with common issues raised by migrants (identity, homesickness, belonging, etc.). In this way, I intend to present a more complete picture of the experience of migration that considers both empirical evidence of individual migrants and an existential analysis that incorporates the defining elements of our world and our existence as crucial means to understand any experience, including that of migration.