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.

Potential Arctic tundra vegetation shifts in response to changing temperature, precipitation and permafrost thaw

Over the past decades, vegetation and climate have changed significantly in the Arctic. Deciduous shrub cover is often assumed to expand in tundra landscapes, but more frequent abrupt permafrost thaw resulting in formation of thaw ponds could lead to vegetation shifts towards graminoid-dominated wetland. Which factors drive vegetation changes in the tundra ecosystem are still not sufficiently clear. In this study, the dynamic tundra vegetation model, NUCOM-tundra (NUtrient and COMpetition), was used to evaluate the consequences of climate change scenarios of warming and increasing precipitation for future tundra vegetation change. The model includes three plant functional types (moss, graminoids and shrubs), carbon and nitrogen cycling, water and permafrost dynamics and a simple thaw pond module. Climate scenario simulations were performed for 16 combinations of temperature and precipitation increases in five vegetation types representing a gradient from dry shrub-dominated to moist mixed and wet graminoid-dominated sites. Vegetation composition dynamics in currently mixed vegetation sites were dependent on both temperature and precipitation changes, with warming favouring shrub dominance and increased precipitation favouring graminoid abundance. Climate change simulations based on greenhouse gas emission scenarios in which temperature and precipitation increases were combined showed increases in biomass of both graminoids and shrubs, with graminoids increasing in abundance. The simulations suggest that shrub growth can be limited by very wet soil conditions and low nutrient supply, whereas graminoids have the advantage of being able to grow in a wide range of soil moisture conditions and have access to nutrients in deeper soil layers. Abrupt permafrost thaw initiating thaw pond formation led to complete domination of graminoids. However, due to increased drainage, shrubs could profit from such changes in adjacent areas. Both climate and thaw pond formation simulations suggest that a wetter tundra can be responsible for local shrub decline instead of shrub expansion.