Vapour-liquid equilibrium studies at atmospheric to moderate pressures

A study of vapour-liquid equilibria is presented together with current developments. The theory of vapour-liquid equilibria is discussed. Both experimental and prediction methods for obtaining vapour-liquid equilibria data are critically reviewed. The development of a new family of equilibrium stills to measure experimental VLE data from sub-atmosphere to 35 bar pressure is described. Existing experimental techniques are reviewed, to highlight the needs for these new apparati and their major attributes. Details are provided of how apparatus may be further improved and how computer control may be implemented. To provide a rigorous test of the apparatus the stills have been commissioned using acetic acid-water mixture at one atmosphere pressure. A Barker-type consistency test computer program, which allows for association in both phases has been applied to the data generated and clearly shows that the stills produce data of a very high quality. Two high quality data sets, for the mixture acetone-chloroform, have been generated at one atmosphere and 64.3oC. These data are used to investigate the ability of the new novel technique, based on molecular parameters, to predict VLE data for highly polar mixtures. Eight, vapour-liquid equilibrium data sets have been produced for the cyclohexane-ethanol mixture at one atmosphere, 2, 4, 6, 8 and 11 bar, 90.9oC and 132.8oC. These data sets have been tested for thermodynamic consistency using a Barker-type fitting package and shown to be of high quality. The data have been used to investigate the dependence of UNIQUAC parameters with temperature. The data have in addition been used to compare directly the performance of the predictive methods - Original UNIFAC, a modified version of UNIFAC, and the new novel technique, based on molecular parameters developed from generalised London's potential (GLP) theory.

Phase equilibrium studies at normal pressures

A total pressure apparatus has been developed to measure vapour-liquid equilibrium data on binary mixtures at atmospheric and sub-atmospheric pressures. The method gives isothermal data which can be obtained rapidly. Only measurements of total pressure are made as a direct function of composition of synthetic liquid phase composition, the vapour phase composition being deduced through the Gibbs-Duhem relationship. The need to analyse either of the phases is eliminated. As such the errors introduced by sampling and analysis are removed. The essential requirements are that the pure components be degassed completely since any deficiency in degassing would introduce errors into the measured pressures. A similarly essential requirement was that the central apparatus would have to be absolutely leak-tight as any leakage of air either in or out of the apparatus would introduce erroneous pressure readings. The apparatus was commissioned by measuring the saturated vapour pressures of both degassed water and ethanol as a function of temperature. The pressure-temperature data on degassed water measured were directly compared with data in the literature, with good agreement. Similarly the pressure-temperature data were measured for ethanol, methanol and cyclohexane and where possible a direct comparison made with the literature data. Good agreement between the pure component data of this work and those available in the literature demonstrates firstly that a satisfactory degassing procedure has been achieved and that secondly the measurements of pressure-temperature are consistent for any one component; since this is true for a number of components, the measurements of both temperature and pressure are both self-consistent and of sufficient accuracy, with an observed compatibility between the precision/accuracy of the separate means of measuring pressure and temperature. The liquid mixtures studied were of ethanol-water, methanol-water and ethanol-cyclohexane. The total pressure was measured as the composition inside the equilibrium cell was varied at a set temperature. This gave P-T-x data sets for each mixture at a range of temperatures. A standard fitting-package from the literature was used to reduce the raw data to yield y-values to complete the x-y-P-T data sets. A consistency test could not be applied to the P-T-x data set as no y-values were obtained during the experimental measurements. In general satisfactory agreement was found between the data of this work and those available in the literature. For some runs discrepancies were observed, and further work recommended to eliminate the problems identified.

Phase equilibrium studies at moderate pressures

The theory of vapour-liquid equilibria is reviewed, as is the present status or prediction methods in this field. After discussion of the experimental methods available, development of a recirculating equilibrium still based on a previously successful design (the modified Raal, Code and Best still of O'Donnell and Jenkins) is described. This novel still is designed to work at pressures up to 35 bar and for the measurement of both isothermal and isobaric vapour-liquid equilibrium data. The equilibrium still was first commissioned by measuring the saturated vapour pressures of pure ethanol and cyclohexane in the temperature range 77-124°C and 80-142°C respectively. The data obtained were compared with available literature experimental values and with values derived from an extended form of the Antoine equation for which parameters were given in the literature. Commissioning continued with the study of the phase behaviour of mixtures of the two pure components as such mixtures are strongly non-ideal, showing azeotopic behaviour. Existing data did not exist above one atmosphere pressure. Isothermal measurements were made at 83.29°C and 106.54°C, whilst isobaric measurements were made at pressures of 1 bar, 3 bar and 5 bar respectively. The experimental vapour-liquid equilibrium data obtained are assessed by a standard literature method incorporating a themodynamic consistency test that minimises the errors in all the measured variables. This assessment showed that reasonable x-P-T data-sets had been measured, from which y-values could be deduced, but that the experimental y-values indicated the need for improvements in the design of the still. The final discussion sets out the improvements required and outlines how they might be attained.

Conflicting pressures and seductive contradictions:women’s participation and progress in management

Organisations operating in the West Midlands region of the UK. Based on over fifty interviews, the key themes to emerge from this research centre upon some of the factors that draw women into management (which we term seductive elements) as well as some of the hindering practices that prevent women from progressing. Significantly, managerial careers are associated with gendered assumptions and practices (e.g. facilitating and developing people) which might contribute to construct management (as done by women) as focused on feminine aspects. However, in terms of the lived reality of doing management, such women experience contradictions and conflicting pressures.

Monte Carlo and molecular dynamics simulations of methane in potassium montmorillonite clay hydrates at elevated pressures and temperatures

The structure and dynamics of methane in hydrated potassium montmorillonite clay have been studied under conditions encountered in sedimentary basin and compared to those of hydrated sodium montmorillonite clay using computer simulation techniques. The simulated systems contain two molecular layers of water and followed gradients of 150 barkm-1 and 30 Kkm-1 up to a maximum burial depth of 6 km. Methane particle is coordinated to about 19 oxygen atoms, with 6 of these coming from the clay surface oxygen. Potassium ions tend to move away from the center towards the clay surface, in contrast to the behavior observed with the hydrated sodium form. The clay surface affinity for methane was found to be higher in the hydrated K-form. Methane diffusion in the two-layer hydrated K-montmorillonite increases from 0.39×10-9 m2s-1 at 280 K to 3.27×10-9 m2s-1 at 460 K compared to 0.36×10-9 m2s-1 at 280 K to 4.26×10-9 m2s-1 at 460 K in Na-montmorillonite hydrate. The distributions of the potassium ions were found to vary in the hydrates when compared to those of sodium form. Water molecules were also found to be very mobile in the potassium clay hydrates compared to sodium clay hydrates. © 2004 Elsevier Inc. All All rights reserved.

Molecular dynamics simulation of methane in sodium montmorillonite clay hydrates at elevated pressures and temperatures

Computer simulation has been used to study the structure and dynamics of methane in hydrated sodium montmorillonite clays under conditions encountered in sedimentary basins. Systems containing approximately one, two, three and four molecular layers of water have followed gradients of 150 bar km-1 and 30Kkm-1, to a maximum burial depth of 6 km (900 bar and 460 K). Methane is coordinated to approximately 19 oxygen atoms, of which typically 6 are provided by the clay surface. Only in the three- and four-layer hydrates is methane able to leave the clay surface. Diffusion depends strongly on the porosity (water content) and burial depth: self-diffusion coefficients are in the range 0.12 × 10-9m2s-1 for water and 0.04 × 10−9m2s−1 < D < 8.64 × 10−9m2s−1 for methane. Bearing in mind that porosity decreases with burial depth, it is estimated that maximum diffusion occurs at around 3 km. This is in good agreement with the known location of methane reservoirs in sedimentary basins.

Defects in ZnO nanoparticles laser-ablated in water-ethanol mixtures at different pressures

The effect of liquid medium and its pressure on the photoluminescence of ZnO nanoparticles prepared via laser ablation of Zn targets in various water-ethanol mixtures is studied. As the ethanol content increases, the photoluminescence of the product changes, while metallic zinc is observed to emerge in nanomaterials prepared in ethanol-rich environments. The applied pressure had a less profound effect, mainly affecting materials produced in water or water-ethanol, and much less those generated in pressurized ethanol. Tuning the reactivity of the liquid and pressurizing it during laser ablation is demonstrated to be promising for tailoring the emission properties of the product.

The study of silicates and refractory materials at high pressures and temperatures

To better understand high pressure behavior of solids, both silicates and oxides have been investigated to clarify the high pressure melting, phase transformations and thermal parameters as well as their size dependences, both theoretically and experimentally. ^ To judge the precision of data determined experimentally, the reliabilities of different high pressure techniques have been discussed. A thermodynamic model has been developed and demonstrated to be able to closely reproduce the melting of solids by comparison between results calculated and data obtained experimentally, including metals (Al, Ni and Pt), Silicates (Mg3Al 2Si3O12 and CaMgSi2O6), Halides (NaCl, CsCl and LiF) and Oxides (MgO, FeO and Al2O3). The melting data obtained have been discussed to address the dynamics of the Earth's interior. ^ Results obtained with Raman spectroscopy and x-ray diffraction show that solids including silicates (andradite and pyrope) and oxides (CeO2 and TiO2) undergo a series of pressure-induced phase transformations. The effects of particle size under high pressures have been investigated. The results obtained indicate that the reduction of particle size leads to the enhancement of the bulk modulus and a significant decrease of transition pressure in TiO2 (rutile) and CeO2. The pressure-induced amorphization in anatase also results from the size effects. ^ Combining the data obtained with global seismic tomography, the physics and chemistry of the Earth's mantle and the dynamics of the core-mantle interaction have been discussed. The high pressure phases of Al3+- and Fe3+-bearing minerals play important roles in the dynamics of the lower mantle. ^

Exploring thermal and mechanical properties of selected transition elements under extreme conditions: Experiments at high pressures and high temperatures

Transition metals (Ti, Zr, Hf, Mo, W, V, Nb, Ta, Pd, Pt, Cu, Ag, and Au) are essential building units of many materials and have important industrial applications. Therefore, it is important to understand their thermal and physical behavior when they are subjected to extreme conditions of pressure and temperature. This dissertation presents: • An improved experimental technique to use lasers for the measurement of thermal conductivity of materials under conditions of very high pressure (P, up to 50 GPa) and temperature (T up to 2500 K). • An experimental study of the phase relationship and physical properties of selected transition metals, which revealed new and unexpected physical effects of thermal conductivity in Zr, and Hf under high P-T. • New phase diagrams created for Hf, Ti and Zr from experimental data. • P-T dependence of the lattice parameters in α-hafnium. Contrary to prior reports, the α-ω phase transition in hafnium has a negative dT/dP slope. • New data on thermodynamic and physical properties of several transition metals and their respective high P-T phase diagrams. • First complete thermodynamic database for solid phases of 13 common transition metals was created. This database has: All the thermochemical data on these elements in their standard state (mostly available and compiled); All the equations of state (EoS) formulated from pressure-volume-temperature data (measured as a part of this study and from literature); Complete thermodynamic data for selected elements from standard to extreme conditions. The thermodynamic database provided by this study can be used with available thermodynamic software to calculate all thermophysical properties and phase diagrams at high P-T conditions. For readers who do not have access to this software, tabulated values of all thermodynamic and volume data for the 13 metals at high P-T are included in the APPENDIX. In the APPENDIX, a description of several other high-pressure studies of selected oxide systems is also included. Thermophysical properties (Cp, H, S, G) of the high P-T ω-phase of Ti, Zr and Hf were determined during the optimization of the EoS parameters and are presented in this study for the first time. These results should have important implications in understanding hexagonal-close-packed to simple-hexagonal phase transitions in transition metals and other materials.

Science behind management of Shark Bay and Florida Bay, two P-limited subtropical systems with different climatology and human pressures

This special issue on ‘Science for the management of subtropical embayments: examples from Shark Bay and Florida Bay’ is a valuable compilation of individual research outcomes from Florida Bay and Shark Bay from the past decade and addresses gaps in our scientific knowledge base in Shark Bay especially. Yet the compilation also demonstrates excellent research that is poorly integrated, and driven by interests and issues that do not necessarily lead to a more integrated stewardship of the marine natural values of either Shark Bay or Florida Bay. Here we describe the status of our current knowledge, introduce the valuable extension of the current knowledge through the papers in this issue and then suggest some future directions. For management, there is a need for a multidisciplinary international science program that focusses research on the ecological resilience of Shark Bay and Florida Bay, the effect of interactions between physical environmental drivers and biological control through behavioural and trophic interactions, and all under increased anthropogenic stressors. Shark Bay offers a ‘pristine template’ for this scale of study.

Food Services Styles in Chinese Hotels: Traditions and Tourism Pressures Merge

Tourist often want to experience their hosts' culture including cuisines. Their reactions can be negatively influenced by vastly different customs which confront them. What can be done, for example, when traditional food serving styles violate the tourist's sanitation standards? The authors discuss a Chinese case study-- and tell what hoteliers in China gace done to make good serving more desirable, with minimal compromise to culinary traditions.

Study of Ammonia Borane and its Derivatives: Influence of Nanoconfinements and Pressures

Recently, ammonia borane has increasingly attracted researchers’ attention because of its merging applications, such as organic synthesis, boron nitride compounds synthesis, and hydrogen storage. This dissertation presents the results from several studies related to ammonia borane. The pressure-induced tetragonal to orthorhombic phase transition in ammonia borane was studied in a diamond anvil cell using in situ Raman spectroscopy. We found a positive Clapeyron-slope for this phase transformation in the experiment, which implies that the phase transition from tetragonal to orthorhombic is exothermic. The result of this study indicates that the rehydrogenation of the high pressure orthorhombic phase is expected to be easier than that of the ambient pressure tetragonal phase due to its lower enthalpy. The high pressure behavior of ammonia borane after thermal decomposition was studied by in situ Raman spectroscopy at high pressures up to 10 GPa. The sample of ammonia borane was first decomposed at ~140 degree Celcius and ~0.7 GPa and then compessed step wise in an isolated sample chamber of a diamond anvil cell for Raman spectroscopy measurement. We did not observe the characteristic shift of Raman mode under high pressure due to dihydrogen bonding, indicating that the dihydrogen bonding disappears in the decomposed ammonia borane. Although no chemical rehydrogenation was detected in this study, the decomposed ammonia borane could store extra hydrogen by physical absorption. The effect of nanoconfinement on ammonia borane at high pressures and different temperatures was studied. Ammonia borane was mixed with a type of mesoporous silica, SBA-15, and restricted within a small space of nanometer scale. The nano-scale ammonia borane was decomposed at ~125 degree Celcius in a diamond anvil cell and rehydrogenated after applying high pressures up to ~13 GPa at room temperature. The successful rehydrogenation of decomposed nano-scale ammonia borane gives guidance to further investigations on hydrogen storage. In addition, the high pressure behavior of lithium amidoborane, one derivative of ammonia borane, was studied at different temperatures. Lithium amidoborane (LAB) was decomposed and recompressed in a diamond anvil cell. After applying high pressures on the decomposed lithium amidoborane, its recovery peaks were discovered by Raman spectroscopy. This result suggests that the decomposition of LAB is reversible at high pressures.

Global Change Pressures on Soils from Land Use and Management

This work contributed to The input of PS and PCW contributes to the Belmont Forum/FACCE-JPI funded DEVIL project (NE/M021327/1) and for PS also contributes to the EU FP7 SmartSoil project (Project number: 289694)

Global Change Pressures on Soils from Land Use and Management

This work contributed to The input of PS and PCW contributes to the Belmont Forum/FACCE-JPI funded DEVIL project (NE/M021327/1) and for PS also contributes to the EU FP7 SmartSoil project (Project number: 289694)

Small-scale Fisheries and the Global Economy: Understanding Common-pool Resource Governance in the Context of Market Pressures, Neoliberal Policies, and Transnational Institutions

The purpose of this dissertation is to contribute to a better understanding of how global seafood trade interacts with the governance of small-scale fisheries (SSFs). As global seafood trade expands, SSFs have the potential to experience significant economic, social, and political benefits from participation in export markets. At the same time, market connections that place increasing pressures on resources pose risks to both the ecological and social integrity of SSFs. This dissertation seeks to explore the factors that mediate between the potential benefits and risks of global seafood markets for SSFs, with the goal of developing hypotheses regarding these relationships.

The empirical investigation consists of a series of case studies from the Yucatan Peninsula, Mexico. This is a particularly rich context in which to study global market connections with SSFs because the SSFs in this region engage in a variety of market-oriented harvests, most notably for octopus, groupers and snappers, lobster, and sea cucumber. Variation in market forms and the institutional diversity of local-level governance arrangements allows the dissertation to explore a number of examples.

The analysis is guided primarily by common-pool resource (CPR) theory because of the insights it provides regarding the conditions that facilitate collective action and the factors that promote long-lasting resource governance arrangements. Theory from institutional economics and political ecology contribute to the elaboration of a multi-faceted conceptualization of markets for CPR theory, with the aim of facilitating the identification of mechanisms through which markets and CPR governance actually interact. This dissertation conceptualizes markets as sets of institutions that structure the exchange of property rights over fisheries resources, affect the material incentives to harvest resources, and transmit ideas and values about fisheries resources and governance.

The case studies explore four different mechanisms through which markets potentially influence resource governance: 1) Markets can contribute to costly resource governance activities by offsetting costs through profits, 2) markets can undermine resource governance by generating incentives for noncompliance and lead to overharvesting resources, 3) markets can increase the costs of resource governance, for example by augmenting monitoring and enforcement burdens, and 4) markets can alter values and norms underpinning resource governance by transmitting ideas between local resource users and a variety of market actors.

Data collected using participant observation, survey, informal and structured interviews contributed to the elaboration of the following hypotheses relevant to interactions between global seafood trade and SSFs governance. 1) Roll-back neoliberalization of fisheries policies has undermined cooperatives’ ability to achieve financial success through engagement with markets and thus their potential role as key actors in resource governance (chapter two). 2) Different relations of production influence whether local governance institutions will erode or strengthen when faced with market pressures. In particular, relations of production in which fishers own their own means of production and share the collective costs of governance are more likely to strengthen resource governance while relations of production in which a single entrepreneur controls capital and access to the fishery are more likely to contribute to the erosion of resource governance institutions in the face of market pressures (chapter three). 3) By serving as a new discursive framework within which to conceive of and talk about fisheries resources, markets can influence norms and values that shape and constitute governance arrangements.

In sum, the dissertation demonstrates that global seafood trade manifests in a diversity of local forms and effects. Whether SSFs moderate risks and take advantage of benefits depends on a variety of factors, and resource users themselves have the potential to influence the outcomes of seafood market connections through local forms of collective action.