Evaporation maps for ternary non-ideal liquid mixtures

This thesis deals with the evaporation of non-ideal liquid mixtures using a multicomponent mass transfer approach. It develops the concept of evaporation maps as a convenient way of representing the dynamic composition changes of ternary mixtures during an evaporation process. Evaporation maps represent the residual composition of evaporating ternary non-ideal mixtures over the full range of composition, and are analogous to the commonly-used residue curve maps of simple distillation processes. The evaporation process initially considered in this work involves gas-phase limited evaporation from a liquid or wetted-solid surface, over which a gas flows at known conditions. Evaporation may occur into a pure inert gas, or into one pre-loaded with a known fraction of one of the ternary components. To explore multicomponent masstransfer effects, a model is developed that uses an exact solution to the Maxwell-Stefan equations for mass transfer in the gas film, with a lumped approach applied to the liquid phase. Solutions to the evaporation model take the form of trajectories in temperaturecomposition space, which are then projected onto a ternary diagram to form the map. Novel algorithms are developed for computation of pseudo-azeotropes in the evaporating mixture, and for calculation of the multicomponent wet-bulb temperature at a given liquid composition. A numerical continuation method is used to track the bifurcations which occur in the evaporation maps, where the composition of one component of the pre-loaded gas is the bifurcation parameter. The bifurcation diagrams can in principle be used to determine the required gas composition to produce a specific terminal composition in the liquid. A simple homotopy method is developed to track the locations of the various possible pseudo-azeotropes in the mixture. The stability of pseudo-azeotropes in the gas-phase limited case is examined using a linearized analysis of the governing equations. Algorithms for the calculation of separation boundaries in the evaporation maps are developed using an optimization-based method, as well as a method employing eigenvectors derived from the linearized analysis. The flexure of the wet-bulb temperature surface is explored, and it is shown how evaporation trajectories cross ridges and valleys, so that ridges and valleys of the surface do not coincide with separation boundaries. Finally, the assumption of gas-phase limited mass transfer is relaxed, by employing a model that includes diffusion in the liquid phase. A finite-volume method is used to solve the system of partial differential equations that results. The evaporation trajectories for the distributed model reduce to those of the lumped (gas-phase limited) model as the diffusivity in the liquid increases; under the same gas-phase conditions the permissible terminal compositions of the distributed and lumped models are the same.

Optically injected multi-mode semiconductor lasers

As a device, the laser is an elegant conglomerate of elementary physical theories and state-of-the-art techniques ranging from quantum mechanics, thermal and statistical physics, material growth and non-linear mathematics. The laser has been a commercial success in medicine and telecommunication while driving the development of highly optimised devices specifically designed for a plethora of uses. Due to their low-cost and large-scale predictability many aspects of modern life would not function without the lasers. However, the laser is also a window into a system that is strongly emulated by non-linear mathematical systems and are an exceptional apparatus in the development of non-linear dynamics and is often used in the teaching of non-trivial mathematics. While single-mode semiconductor lasers have been well studied, a unified comparison of single and two-mode lasers is still needed to extend the knowledge of semiconductor lasers, as well as testing the limits of current model. Secondly, this work aims to utilise the optically injected semiconductor laser as a tool so study non-linear phenomena in other fields of study, namely ’Rogue waves’ that have been previously witnessed in oceanography and are suspected as having non-linear origins. The first half of this thesis includes a reliable and fast technique to categorise the dynamical state of optically injected two mode and single mode lasers. Analysis of the experimentally obtained time-traces revealed regions of various dynamics and allowed the automatic identification of their respective stability. The impact of this method is also extended to the detection regions containing bi-stabilities. The second half of the thesis presents an investigation into the origins of Rogue Waves in single mode lasers. After confirming their existence in single mode lasers, their distribution in time and sudden appearance in the time-series is studied to justify their name. An examination is also performed into the existence of paths that make Rogue Waves possible and the impact of noise on their distribution is also studied.

Asymmetric oxidation of sulfides

This review discusses synthesis of enantiopure sulfoxides through the asymmetric oxidation of prochiral sulfides. The use of metal complexes to promote asymmetric sulfoxidation is described in detail, with a particular emphasis on the synthesis of biologically active sulfoxides. The use of non-metal-based systems, such as oxaziridines, chiral hydroperoxides and peracids, as well as enzyme-catalyzed sulfoxidations is also examined.