published_or_final_version / Civil Engineering / Master / Master of Philosophy

Thesis (M.S.)--Villanova University, 2008. / Chemistry Dept. Includes bibliographical references.

Thesis (M.S.)--Baylor University, 2008. / Includes bibliographical references (p. 70-75).

Thesis (MIng) --Stellenbosch University, 1999. / ENGLISH ABSTRACT: A method was developed at the Atomic Energy Corporation of South Africa (AEC) for the plasma based production of tetrafluoroethylene (TFE). The process involves the feeding of carbon particles into a direct-current CF4 plasma. The resultant plasma gas is quenched rapidly to obtain TFE and other fluorocarbons. The mixing of the particles with the plasma gas is very important in order to achieve a high C:F-ratio in the gas phase, which promotes the desired reactions. The gas enthalpy in the reactor is a governing factor in the TFE yields that are obtained. In this study research was done on particle mixing and the enthalpy distribution in the laboratory scale reactor. An enthalpy probe was used as the main diagnostic tool. Results indicated that particle mixing is quite uniform throughout the reactor. A basic one-dimensional mechanistic model of the reactor was also expanded to assist in· the scale-up of the process. In its present form the model is adequate for predicting trends in the reactor. The model could still be expanded further to include reaction kinetics and internal heat transfer in the particles. Considering the restrictions of the model, satisfactory agreement was obtained between the model and experimental results. / AFRIKAANSE OPSOMMING: 'n Proses vir die plasmagebaseerde produksie van tetrafluoroetileen (TFE) is deur die Atoomenergiekorporasie van Suid-Afrika (AEK) ontwikkel. Koolstofpartikels word in 'n gelykstroomCF4- plasma gevoer en die resulterende plasmagas word vinnig geblus ten einde TFE en ander fluoor-koolstofverbindings as produkte te verkry. Goeie vermenging van die koolstofpartikels met die plasmagas is van uiterste belang ten einde 'n hoe C:F-verhouding, wat die gewenste reaksies bevorder, in die gasfase te verkry. Die entalpie van die plasmagas in die reaktor is 'n bepalende faktor in die opbrengs TFE wat verkry word. Vir die doel van hierdie werkstuk is navorsing op laboratoriumskaal gedoen oor partikelvermenging en die entalpie-verspreiding in die reaktor. Die hoof diagnostiese apparaat wat vir die doel aangewend is, is die entalpiesonde. Resultate toon dat partikelvermenging naastenby uniform deur die reaktor voorkom. Verder is 'n basiese een-dimensionele meganistiese model van die reaktor uitgebrei ten einde van nut te wees in die opskaling van die proses. In sy huidige vorm is die model voldoende om algemene neigings in die reaktor te voorspel. Die model kan nog verder uitgebrei word om reaksie-kinetika en interne hitte-oordrag in die partikels in te sluit. Die beperkings van die model in ag genome, is ooreenstemming tussen die model en eksperimentele resultate egter bevredigend.

Supercritical carbon-dioxide has long been considered an inexpensive, safe and environmentally benign alternative to organic solvents for use in industrial processing. However, at readily accessible conditions of temperature and pressure, it is by itself too poor a solvent for a large number of industrially important solutes and its use as solvent necessitates concomitant use of surfactants. Especially desirable are surfactants that stabilize dispersions of water droplets in carbon-dioxide. So far only molecules containing substantially fluorinated moieties e.g. fluoroalkanes and perfluorinated polyethers, as the CO₂-philes have proved effective in stabilizing dispersions in supercritical carbon-dioxide. These fluorocarbons are expensive, non-biodegradable and can degrade to form toxic and persistent environmental pollutants. Hence there is great interest in developing non-fluorous alternatives. Given the development of powerful computers, excellent molecular models and standardized molecular simulation packages we are in a position to augment the experiment-driven search for effective surfactants using the nanoscopic insights gleaned from analysis of the results of molecular simulations. We have developed protocols by which to use standard and freely available molecular simulation infrastructure to evaluate the effectiveness of surfactants that stabilize solid metal nanoparticles in supercritical fluids. From the results, which we validated against experimental observations, we were able to determine that the alkane-based surfactants, that are so effective in organic fluids, are ineffective or only partially effective in CO₂ because the weak C-H dipoles cannot make up for the energetic penalty incurred at the surfactant-fluid interface by CO₂ molecules due to loss of quadrupolar interactions with other CO₂ molecules. Though the effectiveness of purely alkane-based surfactants in carbon-dioxide can be improved by branching, they cannot approach the effectiveness of the fluoroalkanes. This is because the stronger C-F dipole can supply the required quadrupolar interactions and a unique geometry renders repulsive the fluorocarbons' electrostatic interactions with each other. We have also determined the source of the fluoroalkanes' hydrophobicity to be their size which offsets the effect of favourable electrostatic interactions with water. Hence we can provide guidelines for CO₂-philic yet hydrophobic surfactants. / text

Implantation of tissue engineered pancreatic constructs can provide for a physiologic regulation of blood glucose levels. A major concern in designing such constructs is ensuring sufficient oxygenation of the cells, as oxygen is usually the limiting nutrient affecting cell viability and function. Furthermore, in vivo factors influencing construct oxygenation often lead to implant failure, and are detected primarily on end physiologic effects. The ability of perfluorocarbons (PFCs) to dissolve large amounts of oxygen and their high fluorine content makes these compounds a potentially valuable oxygen delivery tool and good 19F Nuclear Magnetic Resonance (NMR) markers for dissolved oxygen concentration (DO). Experimental studies and simulations showed that although the addition of 10 vol% PFC increased construct oxygenation, this improvement was minimal and had limited benefits on the growth and function of encapsulated bTC-tet cells under normoxic and hypoxic conditions. A dual PFC method that utilizes 19F NMR spectroscopy was developed to noninvasively monitor DO within a tissue construct and in its surroundings. In vitro studies using an NMR-compatible bioreactor demonstrated the feasibility of this method to monitor the DO within alginate beads containing metabolically active bTC-tet cells, relative to the DO in the culture medium, under perfusion and static conditions. In vivo, the method was capable of acquiring real-time DO measurements in murine models. Measured DO can be correlated with the physiological state of the implant examined post-explantation and was compatible with the therapeutic function of the implant.

No description available.

Currently, techniques used to determine whether or not there is a concealed fire in an inaccessible area of a coal mine are not definitive. Inaccessible areas of coal mines include: 1. A mined-out area, such as a long-wall gob. 2. A mine area, or entire mine, that has been sealed to extinguish a fire. 3. The interior of pillars in a mine. 4. Abandoned mines. Mined-out areas — gobs — are particularly problematic. The standard practice is to obtain measurements for certain gas concentrations from an inaccessible area, and to apply certain rules to the obtained concentrations in order to try to decipher whether or not there is a fire in the area. Unfortunately, none of the gas measurements, and the associated rules that are applied, are free of potential problems. Therefore, there is always some degree of uncertainty in any decision that is based on the current methods. A more definitive method of determining whether or not a concealed fire exists would be valuable; perhaps avoiding unnecessary exposure of miners to risks, and unnecessary exposure of mining companies to economic loss. This study details the inadequacies of the current methods for determining the presence of a fire in an inaccessible area of a coal mine, and proposes two novel methods for overcoming the current inadequacies. The first method that was studied involves looking for the presence of the radioisotope carbon-fourteen in the carbon monoxide in the return airways of coal mines. For the vast majority of coal mines, if there is no fire anywhere in the coal mine, carbon monoxide should not have any carbon-fourteen in it. If there is a fire, the carbon monoxide should have carbon-fourteen in it. This method is based on the Boudouard Reaction, which documents a reaction between carbon, carbon monoxide, and carbon dioxide that only occurs at temperatures that only occur with a fire. Because of the very small amounts of carbon-fourteen in carbon dioxide in the atmosphere, and the small amount of carbon monoxide usually present in a coal mine atmosphere, there does not appear to be any way, currently, to implement this method. Instrumentation that may allow implementation of this method, in the future, is discussed. The second method, that was studied, involves introducing a select, gaseous, organic compound into an inaccessible area; and then using a gas chromatograph to test for the presence of definitive fire decomposition products of the initial organic compound in the atmosphere that is exiting the inaccessible area. Laboratory tests, conducted as part of this study, established the concept of this novel method of using select, organic compounds for definitively determining whether or not a concealed fire exists in an inaccessible part of a coal mine. Based on an initial screening of 5 different compounds, two compounds have been selected for use as 'fire indicator gases' with the acronym of 'FIGs.' These two compounds are: 1. C6-Perfluoroketone (CF3CF2C(=O)CF(CF3)2 ) 2. 1,1 Difluoroethane (CH3CHF2) This study provides suggestions as to how to look for other potential FIGs, and how to improve the testing of potential FIGs. Examples of all four of the types of inaccessible areas listed above are discussed, particularly from the viewpoint of how FIGs could be utilized in each case, and how FIGs could provide better information in each case. In addition, as a by-product of the experiments conducted for this work, this study identifies at least six gases that might be used simultaneously as tracer gases for complex ventilation studies in a mine, or elsewhere. / Ph. D.

This thesis is concerned with a range of chemical problems which are amenable to theoretical investigation via the application of current methods of computational quantum chemistry. These problems include the calculation of accurate thermochemical data, the prediction of reaction kinetics, the study of molecular potential energy surfaces, and the investigation of molecular structures and binding. The heats of formation (from both atomisation energies and isodesmic schemes) of a set of approximately 120 C1 and C2 fluorocarbons and oxidised fluorocarbons (along with C3F6 and CF3CHFCF2) were calculated with the Gaussian-3 (G3) method (along with several approximations thereto). These molecules are of importance in the flame chemistry of 2-H-heptafluoropropane, which has been proposed as a potential fire retardant with which to replace chloro- and bromofluorocarbons (CFC�s and BFC�s). The calculation of the data reported here was carried out in parallel with the modelling studies of Hynes et al.1-3 of shock tube experiments on CF3CHFCF3 and on C3F6 with either hydrogen or oxygen atoms. G3 calculations were also employed in conjunction with the experimental work of Owens et al.4 to describe the pyrolysis of CFClBr2 (giving CFCl) at a radiation wavelength of 265 nm. The theoretical prediction of the dissociation energy of the two C-Br bonds was found to be consistent with the energy at which carbene production was first observed, thus supporting the hypothesis that the pyrolysis releases two bromine radicals (rather than a Br2 molecule). On the basis of this interpretation of the experiments, the heat of formation of CFClBr2 is predicted to be 184 � 5 kJ mol-1, in good agreement with the G3 value of 188 � 5 kJ mol-1. Accurate thermochemical data was computed for 18 small phosphorus containing molecules (P2, P4, PH, PH2, PH3, P2H2, P2H4, PO, PO2, PO3, P2O, P2O2, HPO, HPOH, H2POH, H3PO, HOPO and HOPO2), most of which are important in the reaction model introduced by Twarowski5 for the combustion of H2 and O2 in the presence of phosphine. Twarowski reported that the H + OH recombination reaction is catalysed by the combustion products of PH3 and proposed two catalytic cycles, involving PO2, HOPO and HOPO2, to explain this observation. Using our thermochemical data we computed the rate coefficients of the most important reactions in these cycles (using transition state and RRKM theories) and confirmed that at 2000K both cycles have comparable rates and are significantly faster than the uncatalysed H + OH recombination. The heats of formation used in this work on phosphorus compounds were calculated using the G2, G3, G3X and G3X2 methods along with the far more extensive CCSD(T)/CBS type scheme. The latter is based on the evaluation of coupled cluster energies using the correlation consistent triple-, quadruple- and pentuple-zeta basis sets and extrapolation to the complete basis set (CBS) limit along with core-valence correlation corrections (with counterpoise corrections for phosphorus atoms), scalar relativistic corrections and spin-orbit coupling effects. The CCSD(T)/CBS results are consistent with the available experimental data and therefore constitute a convenient set of benchmark values with which to compare the more approximate Gaussian-n results. The G2 and G3 methods were found to be of comparable accuracy, however both schemes consistently underestimated the benchmark atomisation energies. The performance of G3X is significantly better, having a mean absolute deviation (MAD) from the CBS results of 1.8 kcal mol-1, although the predicted atomisation energies are still consistently too low. G3X2 (including counterpoise corrections to the core-valence correlation energy for phosphorus) was found to give a slight improvement over G3X, resulting in a MAD of 1.5 kcal mol-1. Several molecules were also identified for which the approximations underlying the Gaussian-n methodologies appear to be unreliable; these include molecules with multiple or strained P-P bonds. The potential energy surface of the NNH + O system was investigated using density functional theory (B3LYP/6-31G(2df,p)) with the aim of determining the importance of this route in the production of NO in combustion reactions. In addition to the standard reaction channels, namely decomposition into NO + NH, N2 + OH and H + N2O via the ONNH intermediate, several new reaction pathways were also investigated. These include the direct abstraction of H by O and three product channels via the intermediate ONHN, giving N2 + OH, H + N2O and HNO + N. For each of the species corresponding to stationary points on the B3LYP surface, valence correlated CCSD(T) calculations were performed with the aug-cc-pVxZ (x = Q, 5) basis sets and the results extrapolated to the complete basis set limit. Core-valence correlation corrections, scalar relativistic corrections and spin orbit effects were also included in the resulting energetics and the subsequent calculation of thermochemical data. Heats of formation were also calculated using the G3X method. Variational transition state theory was used to determine the critical points for the barrierless reactions and the resulting B3LYP energetics were scaled to be compatible with the G3X and CCSD(T)/CBS values. As the results of modelling studies are critically dependent on the heat of formation of NNH, more extensive CCSD(T)/CBS calculations were performed for this molecule, predicting the heat of formation to be 60.6 � 0.5 kcal mol-1. Rate coefficients for the overall reaction processes were obtained by the application of multi-well RRKM theory. The thermochemical and kinetic results thus obtained were subsequently used in conjunction with the GRIMech 3.0 reaction data set in modelling studies of combustion systems, including methane / air and CO / H2 / air mixtures in completely stirred reactors. This study revealed that, contrary to common belief, the NNH + O channel is a relatively minor route for the production of NO. The structure of the inhibitor Nd-(N'-Sulfodiaminophosphinyl)-L-ornithine, PSOrn, and the nature of its binding to the OTCase enzyme was investigated using density functional (B3LYP) theory. The B3LYP/6-31G(d) calculations on the model compound, PSO, revealed that, while this molecule could be expected to exist in an amino form in the gas phase, on complexation in the active site of the enzyme it would be expected to lose two protons to form a dinegative imino tautomer. This species is shown to bind strongly to two H3CNHC(NH2)2+ moieties (model compounds for arginine residues), indicating that the strong binding observed between inhibitor and enzyme is partially due to electrostatic interactions as well as extensive hydrogen bonding (both model Arg+ residues form hydrogen bonds to two different sites on PSO). Population analysis and hydrogen bonding studies have revealed that the intramolecular bonding in this species consists of either single or semipolar bonds (that is, S and P are not hypervalent) and that terminal oxygens (which, being involved in semipolar bonds, carry negative charges) can be expected to form up to 4 hydrogen bonds with residues in the active site. In the course of this work several new G3 type methods were proposed, including G3MP4(SDQ) and G3[MP2(Full)], which are less expensive approximations to G3, and G3X2, which is an extension of G3X designed to incorporate additional electron correlation. As noted earlier, G3X2 shows a small improvement on G3X; G3MP4(SDQ) and G3[MP2(Full)], in turn, show good agreement with G3 results, with MAD�s of ~ 0.4 and ~ 0.5 kcal mol-1 respectively. 1. R. G. Hynes, J. C. Mackie and A. R. Masri, J. Phys. Chem. A, 1999, 103, 5967. 2. R. G. Hynes, J. C. Mackie and A. R. Masri, J. Phys. Chem. A, 1999, 103, 54. 3. R. G. Hynes, J. C. Mackie and A. R. Masri, Proc. Combust. Inst., 2000, 28, 1557. 4. N. L. Owens, Honours Thesis, School of Chemistry, University of Sydney, 2001. 5. A. Twarowski, Combustion and Flame, 1995, 102, 41.

This thesis is concerned with a range of chemical problems which are amenable to theoretical investigation via the application of current methods of computational quantum chemistry. These problems include the calculation of accurate thermochemical data, the prediction of reaction kinetics, the study of molecular potential energy surfaces, and the investigation of molecular structures and binding. The heats of formation (from both atomisation energies and isodesmic schemes) of a set of approximately 120 C1 and C2 fluorocarbons and oxidised fluorocarbons (along with C3F6 and CF3CHFCF2) were calculated with the Gaussian-3 (G3) method (along with several approximations thereto). These molecules are of importance in the flame chemistry of 2-H-heptafluoropropane, which has been proposed as a potential fire retardant with which to replace chloro- and bromofluorocarbons (CFC�s and BFC�s). The calculation of the data reported here was carried out in parallel with the modelling studies of Hynes et al.1-3 of shock tube experiments on CF3CHFCF3 and on C3F6 with either hydrogen or oxygen atoms. G3 calculations were also employed in conjunction with the experimental work of Owens et al.4 to describe the pyrolysis of CFClBr2 (giving CFCl) at a radiation wavelength of 265 nm. The theoretical prediction of the dissociation energy of the two C-Br bonds was found to be consistent with the energy at which carbene production was first observed, thus supporting the hypothesis that the pyrolysis releases two bromine radicals (rather than a Br2 molecule). On the basis of this interpretation of the experiments, the heat of formation of CFClBr2 is predicted to be 184 � 5 kJ mol-1, in good agreement with the G3 value of 188 � 5 kJ mol-1. Accurate thermochemical data was computed for 18 small phosphorus containing molecules (P2, P4, PH, PH2, PH3, P2H2, P2H4, PO, PO2, PO3, P2O, P2O2, HPO, HPOH, H2POH, H3PO, HOPO and HOPO2), most of which are important in the reaction model introduced by Twarowski5 for the combustion of H2 and O2 in the presence of phosphine. Twarowski reported that the H + OH recombination reaction is catalysed by the combustion products of PH3 and proposed two catalytic cycles, involving PO2, HOPO and HOPO2, to explain this observation. Using our thermochemical data we computed the rate coefficients of the most important reactions in these cycles (using transition state and RRKM theories) and confirmed that at 2000K both cycles have comparable rates and are significantly faster than the uncatalysed H + OH recombination. The heats of formation used in this work on phosphorus compounds were calculated using the G2, G3, G3X and G3X2 methods along with the far more extensive CCSD(T)/CBS type scheme. The latter is based on the evaluation of coupled cluster energies using the correlation consistent triple-, quadruple- and pentuple-zeta basis sets and extrapolation to the complete basis set (CBS) limit along with core-valence correlation corrections (with counterpoise corrections for phosphorus atoms), scalar relativistic corrections and spin-orbit coupling effects. The CCSD(T)/CBS results are consistent with the available experimental data and therefore constitute a convenient set of benchmark values with which to compare the more approximate Gaussian-n results. The G2 and G3 methods were found to be of comparable accuracy, however both schemes consistently underestimated the benchmark atomisation energies. The performance of G3X is significantly better, having a mean absolute deviation (MAD) from the CBS results of 1.8 kcal mol-1, although the predicted atomisation energies are still consistently too low. G3X2 (including counterpoise corrections to the core-valence correlation energy for phosphorus) was found to give a slight improvement over G3X, resulting in a MAD of 1.5 kcal mol-1. Several molecules were also identified for which the approximations underlying the Gaussian-n methodologies appear to be unreliable; these include molecules with multiple or strained P-P bonds. The potential energy surface of the NNH + O system was investigated using density functional theory (B3LYP/6-31G(2df,p)) with the aim of determining the importance of this route in the production of NO in combustion reactions. In addition to the standard reaction channels, namely decomposition into NO + NH, N2 + OH and H + N2O via the ONNH intermediate, several new reaction pathways were also investigated. These include the direct abstraction of H by O and three product channels via the intermediate ONHN, giving N2 + OH, H + N2O and HNO + N. For each of the species corresponding to stationary points on the B3LYP surface, valence correlated CCSD(T) calculations were performed with the aug-cc-pVxZ (x = Q, 5) basis sets and the results extrapolated to the complete basis set limit. Core-valence correlation corrections, scalar relativistic corrections and spin orbit effects were also included in the resulting energetics and the subsequent calculation of thermochemical data. Heats of formation were also calculated using the G3X method. Variational transition state theory was used to determine the critical points for the barrierless reactions and the resulting B3LYP energetics were scaled to be compatible with the G3X and CCSD(T)/CBS values. As the results of modelling studies are critically dependent on the heat of formation of NNH, more extensive CCSD(T)/CBS calculations were performed for this molecule, predicting the heat of formation to be 60.6 � 0.5 kcal mol-1. Rate coefficients for the overall reaction processes were obtained by the application of multi-well RRKM theory. The thermochemical and kinetic results thus obtained were subsequently used in conjunction with the GRIMech 3.0 reaction data set in modelling studies of combustion systems, including methane / air and CO / H2 / air mixtures in completely stirred reactors. This study revealed that, contrary to common belief, the NNH + O channel is a relatively minor route for the production of NO. The structure of the inhibitor Nd-(N'-Sulfodiaminophosphinyl)-L-ornithine, PSOrn, and the nature of its binding to the OTCase enzyme was investigated using density functional (B3LYP) theory. The B3LYP/6-31G(d) calculations on the model compound, PSO, revealed that, while this molecule could be expected to exist in an amino form in the gas phase, on complexation in the active site of the enzyme it would be expected to lose two protons to form a dinegative imino tautomer. This species is shown to bind strongly to two H3CNHC(NH2)2+ moieties (model compounds for arginine residues), indicating that the strong binding observed between inhibitor and enzyme is partially due to electrostatic interactions as well as extensive hydrogen bonding (both model Arg+ residues form hydrogen bonds to two different sites on PSO). Population analysis and hydrogen bonding studies have revealed that the intramolecular bonding in this species consists of either single or semipolar bonds (that is, S and P are not hypervalent) and that terminal oxygens (which, being involved in semipolar bonds, carry negative charges) can be expected to form up to 4 hydrogen bonds with residues in the active site. In the course of this work several new G3 type methods were proposed, including G3MP4(SDQ) and G3[MP2(Full)], which are less expensive approximations to G3, and G3X2, which is an extension of G3X designed to incorporate additional electron correlation. As noted earlier, G3X2 shows a small improvement on G3X; G3MP4(SDQ) and G3[MP2(Full)], in turn, show good agreement with G3 results, with MAD�s of ~ 0.4 and ~ 0.5 kcal mol-1 respectively. 1. R. G. Hynes, J. C. Mackie and A. R. Masri, J. Phys. Chem. A, 1999, 103, 5967. 2. R. G. Hynes, J. C. Mackie and A. R. Masri, J. Phys. Chem. A, 1999, 103, 54. 3. R. G. Hynes, J. C. Mackie and A. R. Masri, Proc. Combust. Inst., 2000, 28, 1557. 4. N. L. Owens, Honours Thesis, School of Chemistry, University of Sydney, 2001. 5. A. Twarowski, Combustion and Flame, 1995, 102, 41.