This thesis explores the structures and dynamics of optically confined matter, ranging from single particle traps to complex optically bound colloidal arrays, investigating and quantifying the behaviour of each system. It begins with an introduction to optical manipulation techniques and a discussion of the development of the single beam gradient force trap, more commonly referred to as optical tweezers. Following this, the building of a single beam optical trap will be presented alongside a discussion of some of the key components in such a setup, before it is calibrated, allowing a demonstration of some of the techniques which are utilised later in the thesis. The optical trapping of aerosol droplets is an area of key importance in atmospheric chemistry, as optical tweezers provide a valuable and versatile tool for droplet manipulation and characterisation. Trapping single aerosol droplets is facilitated by using annular rather than conventional Gaussian beams, as will be demonstrated, with significant advantages in increasing the size range of trappable droplets, and improving their axial localisation. These improvements will be demonstrated experimentally with an in-depth comparison of Gaussian and annular beam trapping. These enhancements are also verified theoretically using a model developed by Burnham and McGloin, showing excellent agreement with experimental results. Ionic liquids, defined as organic salts with melting points below room temperature, are another area of great contemporary interest. They are highly tunable and so have been referred to as "designer solvents", and also have important applications as "green" solvents in organic chemistry. Trapping particles within these novel liquids allows a micro-rheological investigation of their properties to be conducted. This is demonstrated by determining the temperature dependent viscosity changes of these media, showing excellent agreement with previous macro-rheological studies. In addition, hydrodynamic effects such as Faxen's correction to viscous drag in proximity to a surface, and hydrodynamic coupling between pairs of colloids trapped in ionic liquids are demonstrated. Following these single and dual particle studies, this thesis continues with an investigation of the structures and dynamics of optically bound matter formed of larger numbers of particles. The behaviour of these optically bound structures is particularly sensitive to the number of particles involved, and so a counter-propagating evanescent field trap in conjunction with an inverted optical tweezers setup is utilised in order to controllably assemble these structures and study the factors affecting their behaviour. Initially one-dimensional chains of optically bound 3.5 um diameter silica particles are studied, allowing an implementation of Generalized Lorentz-Mie Theory (GLMT) to be developed through collaboration with Dr. Jonathan Taylor of The University of Glasgow. Experimental and theoretical insights allow further understanding of the processes involved in the formation of these structures. Having studied the behaviour of 3.5 um diameter silica particles in a counter-propagating evanescent wave trap, the effects of changing particle size and refractive index are presented by using smaller silica and melamine particles. These results are explained in terms of the increased importance of interference fringes in determining the arrangement of the optically bound structures of smaller particles, and due to the increased interaction of the melamine particles with the evanescent field as a result of the larger refractive index contrast between them and the trapping medium. The thesis then concludes with a study of the dynamics of the previously presented optically bound chains. Initially the diffusion of single particles in the evanescent field is compared to their freely-diffusing behaviour, quantifying the confining effect of the field. The addition of particles to the field then allows the diffusive behaviour to be studied as a function of particle number, and understood in terms of on-axis confinement by adjacent particles. The tilting of these optically bound chains relative to the inter-beam axis is also explored as a function of particle number, as is the rigidity of these chains. Finally a more complex, dynamic effect is presented, dubbed "Newton's Cradle", in which particles are ejected from the ends of the chains before returning and repeating this process. This behaviour is understood by utilising the previously developed GLMT simulations.

Previous studies from laboratory experiments and a similar process at a plant in Switzerland, led to the pilot plant project at Renova AB, which will be described in this master thesis. In cooperation with Götaverken Miljö AB it was investigated if fly ash, produced at the Renova Waste-to-Energy plant in Gothenburg, could be treated with own scrubber liquids in order to recover zinc. If successful, Renova might build this tested pilot process in to a big scale. The pilot plant has a scale of 16 times smaller than a future big scale process. The goal of the project is to leach zinc from fly ash and gain a fly ash residue, which is classified as non-hazardous waste. The filtrate from the leaching campaign is treated so that the containing zinc is recovered. The zinc cake end product shall has a quality so that it can be sold to other industries or upgraded to high purity zinc metal. The evaluation of the experiments showed that the pilot plant process was successful. It was possible to leach out zinc by a maximum quote of 74%. The total recovery of zinc could be achieved by a maximum of 72%. The final zinc cake product was achieved through a precipitation and filtration campaign. This thesis evaluates, which process set-ups for zinc recovery through leaching and precipitation & filtration are the best and can be recommended for a big scale process. In addition, it briefly analyses the zinc product quality. Future studies will be necessary within: cost analysis of the process, zinc product quality and an analysis of the ash residue.

The use of ionic liquids (ILs) as both reagents and solvents is widely recognised. ILs offer a number of advantages compared to regular molecular solvents. These advantages include: chemical and thermal stability, no measurable vapour pressure, no or lower toxicity, non-flammability, catalytic ability, high polarity and they can be recycled. There are a number of research groups investigating the various applications of this reaction medium and most studies have focused on solvents derived from the imidazolium cation. The use of the imidazolium-based ILs in the Diels-Alder reaction has been studied in detail and higher yields compared to conventional methods have been reported. The IL affects the rate and interesting selectivities have been observed. However, not much attention has been paid to the scope and limitations of phosphonium ILs (PILs). Therefore the focus of this thesis is the synthesis and application of novel chiral PILs as environmentally benign, task-specific solvents for the Diels-Alder reaction. In addition, this research seeks alternative ways to eliminate the use of toxic heavy metal catalysts and to exploit methodologies which reduce the energy consumption of the Diels-Alder reaction. A series of CILs were synthesised from the chiral pool and they were characterised by thermogravimetric analysis, differential scanning calorimetry and spectroscopy. They were then investigated as solvents and catalysts in the Diels-Alder reactions of a series of dienes (cyclopentadiene, isoprene, 2,3-dimethylbuta-1,3-diene, furan, pyrrole, N-methyl pyrrole) and dienophiles (methyl acrylate, methyl vinyl ketone, acrylonitrile, dimethyl maleate, acrolein, dimethylacetylene dicarboxylate, maleic anhydride and maleimide). Investigation of the effect of PILs in the presence of three heterogeneous catalysts Al2O3, SiO2 and K-10 montmorillonite were studied. Ultrasound and microwave-assisted Diels-Alder reactions in the PILs, in the absence and presence of the catalysts, were also studied. The reactions of these prototypical substrates illustrated that the solvents are indeed task-specific.

Energy and water are two precious natural resources with which demand will continue to grow with increased population growth. Coal provides a cheap and abundant source of energy but with important environmental effects on air and water. An analysis of the current coal production in Texas, one of the leading providers of energy in the United States, will be discussed along with the possibility of creating a coal-to-liquids market in Texas from existing and future coal mining operations. An in-depth discussion into the water requirements for traditional coal production and coal-to-liquids will assist in analyzing its possible production and sustainability. / text

The thermal velocity fluctuations of microscopic particles mediate the transition from microscopic statistical mechanics to macroscopic long-time diffusion. Prior to this work, detection methods lacked the sensitivity necessary to resolve motion at the length and time scales at which thermal velocity fluctuations occur. This dissertation details two experiments which resulted in velocity measurement of the thermal motion of dielectric microspheres suspended by an optical trap in gases and liquids. First, optical tweezers were used to trap glass microspheres in air over a wide range of pressures and a detection system was developed to track the trapped microspheres' trajectories with MHz bandwidth and <100 fm/rt(Hz) position sensitivity. Low-noise trajectory measurements allowed for observation of fluctuations in the instantaneous velocity of a trapped particle with a signal to noise ratio (SNR) of 26 dB, and provided direct verification of the equipartition theorem and of the Maxwell-Boltzmann velocity distribution for a single Brownian particle. Next, the detection technology was further optimized and used to track optically trapped silica and barium titanate glass microspheres in water and acetone with >50 MHz bandwidth and <3 fm/rt(Hz) sensitivity. Brownian motion in a liquid is influenced by hydrodynamic, time-retarded coupling between the particle and the fluid flow its motion generates. Our measurements allowed for instantaneous velocity measurement with an SNR of up to 16 dB and confirmed the Maxwell Boltzmann distribution for Brownian motion in a liquid. The measurements also revealed several unusual features predicted for Brownian motion in the regime of hydrodynamic coupling, including faster-than-exponential decay of the velocity autocorrelation function, correlation of the thermal force and non-zero cross-correlation between the particle's velocity and the thermal force preceding it. / text

In Situ Thermal Treatment (ISTT) is a candidate remediation technology for dense non-aqueous phase liquids (DNAPLs). However, the relationships between gas production, gas flow, and contaminant mass removal during ISTT are not fully understood. A laboratory study was conducted to assess the degree of mass removal, as well as the gas generation rate and the composition of the gas phase as a function of different heating times and initial DNAPL saturations. The temperature of the contaminated soil was measured continuously using a thermocouple to identify periods of heating, co-boiling and boiling. Samples were collected from the aqueous and DNAPL phase of the condensate, as well as from the source soil, at different heating times, and analyzed by gas chromatography/mass spectrometry. In addition to laboratory experiments, a mathematical model was developed to predict the co-boiling temperature and transient composition of the gas phase during heating of a uniform source. Predictions for single-component sources matched the experiments well, with a co-boiling plateau at 88°C ± 1°C for experiments with tetrachloroethene (PCE) and water. A comparison of predicted and observed boiling behaviour showed a discrepancy at the end of the co-boiling period, with earlier temperature increases occurring in the experiments. The results of this study suggest that temperature observations related to the co-boiling period during ISTT applications may not provide a clear indication of complete NAPL mass removal, and that multi-compartment modeling associated with various NAPL saturation zones is required to consider mass-transfer limitations within the heated zone. Predictions for multi-component DNAPL, containing 1,2-Dichloroethane (1,2-DCA), PCE and Chlorobenzene, showed no co-boiling plateau. CB is the least volatile component and dominates in the vapour phase at the end of the co-boiling process, and it can be used as an indicator of the end of the co-boiling stage. Two field NAPL mixtures were simulated using the screening-level analytical model to demonstrate its potential application on ISTT. The two mixtures with similar composition but different mass fractions result in distinct co-boiling temperature and mass transfer behaviour. The non-volatile component in the NAPL mixture results in larger amounts of water consumption and longer ISTT operation time. / Thesis (Master, Civil Engineering) -- Queen's University, 2013-09-30 09:26:00.857

Fractured rock formations represent a valuable source of groundwater and can be highly susceptible to contamination by dense, non-aqueous phase liquids (DNAPLs). The goal of this research is to evaluate the effectiveness of three accepted remediation technologies for addressing DNAPL contamination in fractured rock environments. The technologies under investigation in this study are chemical oxidation, bioremediation, and surfactant flushing. Numerical simulations were employed to examine the performance of each of these technologies at the field scale. The numerical model DNAPL3D-RX, a finite difference multiphase flow-dissolution-aqueous transport code that incorporates RT3D for multiple species reactions, was modified to simulate fractured rock environments. A gridding routine was developed to allow the model to accurately capture DNAPL migration in fractures and aqueous phase diffusion gradients in the matrix while retaining overall model efficiency. Reaction kinetics code subroutines were developed for each technology so as to ensure the key processes were accounted for in the simulations. The three remedial approaches were systematically evaluated via simulations in two-dimensional domains characterized by heterogeneous orthogonal fracture networks parameterized to be representative of sandstone, granite, and shale. Each simulation included a DNAPL release at the water table, redistribution to pools and residual, followed by 20 years of ‘ageing’ under ambient gradient conditions. Suites of simulations for each technology examined a variety of operational issues including the influence of DNAPL type and remedial fluid injection protocol. Performance metrics included changes in mass flux exiting, mass destruction in the matrix versus the fractures, and percentage of injected remedial fluid interacting with the target contaminant. The effectiveness of the three remediation technologies covered a wide range; the mass of contaminants destroyed were found to range from 15% to 99.5% of the initial mass present. Effectiveness of each technology was found to depend on a variety of critical factors particular to each approach. For example, in-situ chemical oxidation was found to be limited by the organic material present in the matrix of the rocks, while the efficiency of enhanced bioremediation was found to be related to factors such as the location of indigenous bacteria present in the domain and rate of bioremediation. In the chemical oxidation study, the efficiency of oxidant consumption was observed to be poor across the suite of scenarios, with greater than 90% of the injected permanganate consumed by natural oxidant demand. This study further revealed that the same factors that contributed to forward diffusion of contaminants prior to treatment are critical to this remediation method as they can determine the extent of contaminant destruction during the injection period. Bioremediation in fractured rock was demonstrated to produce relatively good results under robust first-order decay rates and active microorganisms throughout the fractures and matrix. It was demonstrated that under ideal conditions, of the total initial mass present, up to 3/4 could be reduced to ethene, indicating bioremediation may be a promising treatment approach due to the effective penetration of electron donor into the matrix during the treatment period and the ongoing treatment that occurs after injection ceases. However, when indigenous bacteria was assumed to exist only within the fractured walls of sandstone, it was found that under the same conditions, the rate of dechlorination was 200 times less than the Base Case. Since the majority of the mass resided in the matrix, lack of bioremediation in the matrix significantly reduced the effectiveness of treatment. Surfactant treatment with Tween-80 was proven to be a relatively effective technique in enhanced solubilisation of DNAPL from the fractures within the domain. However, by comparing the aqueous and sorbed mass at the start and end of the Treatment stage, it is revealed that surfactant treatment is not efficient in removing these masses that reside within the matrix. Furthermore, DNAPLs identified in dead end vertical fractures were found to remain in the domain by the end of the simulations across all scenarios studied; indicating that the injected surfactant experiences difficulty in accessing DNAPLs entrapped in dead end fractures. Altogether, the results underscore the challenge of restoring fractured rock aquifers due to the field scale limitations on sufficient contact between remedial fluids and in situ contaminants in all but the most ideal circumstances.

The work presented in this thesis involves the use of room temperature ionic liquids (RTILs) as solvents in electrochemical experiments for the detection of hydrogen sulfide. The fundamentals of electrochemistry are presented, followed by an overview of RTILs in terms of their properties, applications and their behaviour as electrochemical solvents compared to conventional solvents. This is followed by an outline of electrochemical detection of various gases in aqueous, organic and ionic solvents. The results of 8 original studies are then presented as follows: <ul><li>The study of the electrochemical window of twelve different room temperature ionic liquids using cyclic voltammetry vs. an internal redox couple for two defined current densities, and observation of water uptake of different ionic liquids under different conditions using a Karl Fischer titrator.</li><li>The reduction of hydrogen sulfide in various room temperature ionic liquids at a platinum electrode, measured using cyclic voltammetry. Also, solubilities and diffusion coefficients of hydrogen sulfide determined by potential step chronoamperometry.</li><li>The oxidation of hydrogen sulfide in various room temperature ionic liquids at a platinum electrode measured using cyclic voltammetry and the simulation of the electrochemical signal using experimentally defined parameters.</li><li>The disproportionation of N,N-dimethyl-p-phenylenediamine (DMPD) in room temperature ionic liquids using cyclic voltammetry, and computational simulation of the voltammetry of DMPD using experimentally defined parameters to elucidate kinetic and thermodynamic data. DMPD was examined as a mediating species for hydrogen sulfide detection.</li><li>The oxidation of catechol and dopamine in ionic liquids using cyclic voltammetry and observing adsorption effects when varying solvent anion. Catechol was examined as a mediating species for hydrogen sulfide detection.</li><li>The electrochemical oxidation of NADH in ionic liquids using cyclic voltammetry and observing the ”switching on or off” of the electrochemical signal when varying the solvent anion. NADH was examined as a mediating species for hydrogen sulfide detection.</li><li>The mediated detection of hydrogen sulfide utilizing various mediating species in several ionic liquids using cyclic voltammetry, and the elucidation of the mediating mechanism of hydrogen sulfide in 3,5-tert-butyl-o-benzoquinone.</li><li>The observation of the diffusion of ferrocene in an ionic liquid at ring-recessed disc microelectrode arrays in generator-collector mode using potential step chronoamperometry.</li><ul> The results presented show that room temperature ionic liquids perform well as solvents in gas sensors, and could be viable alternatives to traditional organic solvents. Ionic liquids have also been observed to be tuneable in their reactions with analytes depending on the constituent cations and, in particular, anions. This tuneability is advantageous as specific combinations of cations and anions can be chosen to suit particular experiments.

Raman vibrational bands are sensitive to fluctuations in the molecular environment. Variations in the bandwidth and peak position can then be utilized to monitor molecular forces and interactions present in condense phases. Nuclear Magnetic Resonance (NMR) provides a convenient probe for the study of molecular reorientation in liquids since nuclear spin relaxation times are dependent on the details of molecular motion. Presented here is the solvent study of the Raman bandwidths and frequency displacements of the mode of the compounds CH3MCI3 (M = C, Si, Ge, Sn) in a number of solvents of widely varying molecular structure. Also, a detailed isotope dilution study of the modes in CH2CI2/CD2CI2 mixtures is presented. In this set of experiments, I observed broadening of the v1 mode of CH2C12 upon dilution,which is the first experimental observation of such behavior. The temperature-dependent carbon-13 relaxation times and nuclear Overhauser enhancements in neat dichloromethane were measured. In this study we found that the molecular reorientation of this molecule was highly anisotropic, but could be well characterized assuming quasi-symmetric top behavior. In addition, in order to gain a more complete understanding of the reorientational dynamics in dichloromethane, we analyzed the 13-C NMR relaxation of CH2CI2 both in "inert" solvents of differing viscosities and in interactive solvents of varying Lewis basicities. Various theoretical models were also applied in order to characterize dichloromethane1s reorientational dynamics.

The frequency shifts and Q changes of a resonant microwave cavity were utilized as a basis for determining microwave properties of solids and liquids. The method employed consisted of varying the depth of penetration of a cylindrical sample of the material into a cavity operating in the TM0 1 0 Mode. The liquid samples were contained in a thin-walled quartz tube. The perturbation of the cavity was achieved by advancing the sample into the cavity along the symmetry axis by employing a micrometer drive appropriately calibrated for depth of penetration of the sample. A differentiation method was used to obtain the half-power points of the cavity resonance profile at each depth of penetration. The perturbation techniques for resonant cavities were used to reduce the experimental data obtained to physical parameters for the samples. The probing frequency employed was near 9 gHz.