Gas-Solid Reactions: Photochemical Oxidation of Thioketones in the Crystalline State

Photochemical oxidation of 11 diaryl thioketones (1-11) was conducted in the solid state. Quite interestingly, of these only six were oxidized to the corresponding carbonyl compound whereas the rest were photostable. However, in solution all were readily oxidized. The difference in behavior between the thioketones in the solid state has been rationalized on the basis of molecular arrangement in the crystal. X-ray crystal structure analyses of four thioketones were carried out in this connection.

Intermolecular Interactions of Noble-Gas-Containing Species

The importance of intermolecular interactions to chemistry, physics, and biology is difficult to overestimate. Without intermolecular forces, condensed phase matter could not form. The simplest way to categorize different types of intermolecular interactions is to describe them using van der Waals and hydrogen bonded (H-bonded) interactions. In the H-bond, the intermolecular interaction appears between a positively charged hydrogen atom and electronegative fragments and it originates from strong electrostatic interactions. H-bonding is important when considering the properties of condensed phase water and in many biological systems including the structure of DNA and proteins. Vibrational spectroscopy is a useful tool for studying complexes and the solvation of molecules. Vibrational frequency shift has been used to characterize complex formation. In an H-bonded system A∙∙∙H-X (A and X are acceptor and donor species, respectively), the vibrational frequency of the H-X stretching vibration usually decreases from its value in free H-X (red-shift). This frequency shift has been used as evidence for H-bond formation and the magnitude of the shift has been used as an indicator of the H-bonding strength. In contrast to this normal behavior are the blue-shifting H-bonds, in which the H-X vibrational frequency increases upon complex formation. In the last decade, there has been active discussion regarding these blue-shifting H-bonds. Noble-gases have been considered inert due to their limited reactivity with other elements. In the early 1930 s, Pauling predicted the stable noble-gas compounds XeF6 and KrF6. It was not until three decades later Neil Bartlett synthesized the first noble-gas compound, XePtF6, in 1962. A renaissance of noble-gas chemistry began in 1995 with the discovery of noble-gas hydride molecules at the University of Helsinki. The first hydrides were HXeCl, HXeBr, HXeI, HKrCl, and HXeH. These molecules have the general formula of HNgY, where H is a hydrogen atom, Ng is a noble-gas atom (Ar, Kr, or Xe), and Y is an electronegative fragment. At present, this class of molecules comprises 23 members including both inorganic and organic compounds. The first and only argon-containing neutral chemical compound HArF was synthesized in 2000 and its properties have since been investigated in a number of studies. A helium-containing chemical compound, HHeF, was predicted computationally, but its lifetime has been predicted to be severely limited by hydrogen tunneling. Helium and neon are the only elements in the periodic table that do not form neutral, ground state molecules. A noble-gas matrix is a useful medium in which to study unstable and reactive species including ions. A solvated proton forms a centrosymmetric NgHNg+ (Ng = Ar, Kr, and Xe) structure in a noble-gas matrix and this is probably the simplest example of a solvated proton. Interestingly, the hypothetical NeHNe+ cation is isoelectronic with the water-solvated proton H5O2+ (Zundel-ion). In addition to the NgHNg+ cations, the isoelectronic YHY- (Y = halogen atom or pseudohalogen fragment) anions have been studied with the matrix-isolation technique. These species have been known to exist in alkali metal salts (YHY)-M+ (M = alkali metal e.g. K or Na) for more than 80 years. Hydrated HF forms the FHF- structure in aqueous solutions, and these ions participate in several important chemical processes. In this thesis, studies of the intermolecular interactions of HNgY molecules and centrosymmetric ions with various species are presented. The HNgY complexes show unusual spectral features, e.g. large blue-shifts of the H-Ng stretching vibration upon complexation. It is suggested that the blue-shift is a normal effect for these molecules, and that originates from the enhanced (HNg)+Y- ion-pair character upon complexation. It is also found that the HNgY molecules are energetically stabilized in the complexed form, and this effect is computationally demonstrated for the HHeF molecule. The NgHNg+ and YHY- ions also show blue-shifts in their asymmetric stretching vibration upon complexation with nitrogen. Additionally, the matrix site structure and hindered rotation (libration) of the HNgY molecules were studied. The librational motion is a much-discussed solid state phenomenon, and the HNgY molecules embedded in noble-gas matrices are good model systems to study this effect. The formation mechanisms of the HNgY molecules and the decay mechanism of NgHNg+ cations are discussed. A new electron tunneling model for the decay of NgHNg+ absorptions in noble-gas matrices is proposed. Studies of the NgHNg+∙∙∙N2 complexes support this electron tunneling mechanism.

Copper Diffusion Barrier Deposition on Integrated Circuit Devices by Atomic Layer Deposition Technique

Transfer from aluminum to copper metallization and decreasing feature size of integrated circuit devices generated a need for new diffusion barrier process. Copper metallization comprised entirely new process flow with new materials such as low-k insulators and etch stoppers, which made the diffusion barrier integration demanding. Atomic Layer Deposition technique was seen as one of the most promising techniques to deposit copper diffusion barrier for future devices. Atomic Layer Deposition technique was utilized to deposit titanium nitride, tungsten nitride, and tungsten nitride carbide diffusion barriers. Titanium nitride was deposited with a conventional process, and also with new in situ reduction process where titanium metal was used as a reducing agent. Tungsten nitride was deposited with a well-known process from tungsten hexafluoride and ammonia, but tungsten nitride carbide as a new material required a new process chemistry. In addition to material properties, the process integration for the copper metallization was studied making compatibility experiments on different surface materials. Based on these studies, titanium nitride and tungsten nitride processes were found to be incompatible with copper metal. However, tungsten nitride carbide film was compatible with copper and exhibited the most promising properties to be integrated for the copper metallization scheme. The process scale-up on 300 mm wafer comprised extensive film uniformity studies, which improved understanding of non-uniformity sources of the ALD growth and the process-specific requirements for the ALD reactor design. Based on these studies, it was discovered that the TiN process from titanium tetrachloride and ammonia required the reactor design of perpendicular flow for successful scale-up. The copper metallization scheme also includes process steps of the copper oxide reduction prior to the barrier deposition and the copper seed deposition prior to the copper metal deposition. Easy and simple copper oxide reduction process was developed, where the substrate was exposed gaseous reducing agent under vacuum and at elevated temperature. Because the reduction was observed efficient enough to reduce thick copper oxide film, the process was considered also as an alternative method to make the copper seed film via copper oxide reduction.

Comprehensive Two-Dimensional Gas Chromatography: Instrumental and Methodological Development

Comprehensive two-dimensional gas chromatography (GC×GC) offers enhanced separation efficiency, reliability in qualitative and quantitative analysis, capability to detect low quantities, and information on the whole sample and its components. These features are essential in the analysis of complex samples, in which the number of compounds may be large or the analytes of interest are present at trace level. This study involved the development of instrumentation, data analysis programs and methodologies for GC×GC and their application in studies on qualitative and quantitative aspects of GC×GC analysis. Environmental samples were used as model samples. Instrumental development comprised the construction of three versions of a semi-rotating cryogenic modulator in which modulation was based on two-step cryogenic trapping with continuously flowing carbon dioxide as coolant. Two-step trapping was achieved by rotating the nozzle spraying the carbon dioxide with a motor. The fastest rotation and highest modulation frequency were achieved with a permanent magnetic motor, and modulation was most accurate when the motor was controlled with a microcontroller containing a quartz crystal. Heated wire resistors were unnecessary for the desorption step when liquid carbon dioxide was used as coolant. With use of the modulators developed in this study, the narrowest peaks were 75 ms at base. Three data analysis programs were developed allowing basic, comparison and identification operations. Basic operations enabled the visualisation of two-dimensional plots and the determination of retention times, peak heights and volumes. The overlaying feature in the comparison program allowed easy comparison of 2D plots. An automated identification procedure based on mass spectra and retention parameters allowed the qualitative analysis of data obtained by GC×GC and time-of-flight mass spectrometry. In the methodological development, sample preparation (extraction and clean-up) and GC×GC methods were developed for the analysis of atmospheric aerosol and sediment samples. Dynamic sonication assisted extraction was well suited for atmospheric aerosols collected on a filter. A clean-up procedure utilising normal phase liquid chromatography with ultra violet detection worked well in the removal of aliphatic hydrocarbons from a sediment extract. GC×GC with flame ionisation detection or quadrupole mass spectrometry provided good reliability in the qualitative analysis of target analytes. However, GC×GC with time-of-flight mass spectrometry was needed in the analysis of unknowns. The automated identification procedure that was developed was efficient in the analysis of large data files, but manual search and analyst knowledge are invaluable as well. Quantitative analysis was examined in terms of calibration procedures and the effect of matrix compounds on GC×GC separation. In addition to calibration in GC×GC with summed peak areas or peak volumes, simplified area calibration based on normal GC signal can be used to quantify compounds in samples analysed by GC×GC so long as certain qualitative and quantitative prerequisites are met. In a study of the effect of matrix compounds on GC×GC separation, it was shown that quality of the separation of PAHs is not significantly disturbed by the amount of matrix and quantitativeness suffers only slightly in the presence of matrix and when the amount of target compounds is low. The benefits of GC×GC in the analysis of complex samples easily overcome some minor drawbacks of the technique. The developed instrumentation and methodologies performed well for environmental samples, but they could also be applied for other complex samples.

Baseline and greenhouse-gas emissions in extensive livestock enterprises, with a case study of feeding lipid to beef cattle

For accurate calculation of reductions in greenhouse-gas (GHG) emissions, methodologies under the Australian Government's Carbon Farming Initiative (CFI) depend on a valid assessment of the baseline and project emissions. Life-cycle assessments (LCAs) clearly show that enteric methane emitted from the rumen of cattle and sheep is the major source of GHG emissions from livestock enterprises. Where a historic baseline for a CFI methodology for livestock is required, the use of simulated data for cow-calf enterprises at six sites in southern Australia demonstrated that a 5-year rolling emission average will provide an acceptable trade off in terms of accuracy and stability, but this is a much shorter time period than typically used for LCA. For many CFI livestock methodologies, comparative or pair-wise baselines are potentially more appropriate than historic baselines. A case study of lipid supplementation of beef cows over winter is presented. The case study of a control herd of 250 cows used a comparative baseline derived from simple data on livestock numbers and class of livestock to quantify the emission abatement. Compared with the control herd, lipid supplementation to cows over winter increased livestock productivity, total livestock production and enterprise GHG emissions from 990 t CO2-e to 1022 t CO2-e. Energy embodied in the supplement and extra diesel used in transporting the supplement diminished the enteric-methane abatement benefit of lipid supplementation. Reducing the cow herd to 238 cows maintained the level of livestock production of the control herd and reduced enterprise emissions to 938 t CO2-e, but was not cost effective under the assumptions of this case study.

Prediction of Intrinsic kinetics in diffusion disguised immobilized enzyme systems

When immobilized enzyme kinetics are disguised by inter- and intraparticle diffusion effects, an approximate mathematical procedure is indicated whereby experimental data obtained in the limiting ranges of first- and zeroth-order Michaelis-Menten kinetics could be used for the prediction of the kinetic constants.

Line tension of a two dimensional gas-liquid interface

In two dimensional (2D) gas-liquid systems, the reported simulation values of line tension are known to disagree with the existing theoretical estimates. We find that while the simulation erred in truncating the range of the interaction potential, and as a result grossly underestimated the actual value, the earlier theoretical calculation was also limited by several approximations. When both the simulation and the theory are improved, we find that the estimate of line tension is in better agreement with each other. The small value of surface tension suggests increased influence of noncircular clusters in 2D gas-liquid nucleation, as indeed observed in a recent simulation.

LPG Gas-Sensing System With SnO2 Thin-Film Transducer and 0.7-mu m CMOS Signal Conditioning ASIC

The design and implementation of a complete gas sensor system for liquified petroleum gas (LPG) gas sensing are presented. The system consists of a SnO2 transducer, a lowcost heater, an application specific integrated circuit (ASIC) with front-end interface circuitry, and a microcontroller interface for data logging. The ASIC includes a relaxation-oscillator-based heater driver circuit that is capable of controlling the sensor operating temperature from 100degC to 425degC. The sensor readout circuit in the ASIC, which is based on the resistance to time conversion technique, has been designed to measure the gas sensor response over three orders of resistance change during its interaction with gases.

Experimental investigation of catalytic and non-catalytic surface reactions on SiO2 thin films with shock heated oxygen gas

The present study is to investigate the interaction of strong shock heated oxygen on the surface of SiO2 thin film. The thermally excited oxygen undergoes a three-body recombination reaction on the surface of silicon dioxide film. The different oxidation states of silicon species on the surface of the shock-exposed SiO2 film are discussed based on X-ray Photoelectron Spectroscopy (XPS) results. The surface morphology of the shock wave induced damage at the cross section of SiO2 film and structure modification of these materials are analyzed using scanning electron microscopy and ion microscopy. Whether the surface reaction of oxygen on SiO2 film is catalytic or non-catalytic is discussed in this paper.

Experimental investigation of interaction of strong shock heated oxygen gas on the surface of ZrO2 - a novel method to understand re-combination heating

Interaction of shock heated test gas in the free piston driven shock tube with bulk and thin film of cubic zirconium dioxide (ZrO2) prepared by combustion method is investigated. The test samples before and after exposure to the shock wave are analyzed by X-ray diffraction (XRD), X-Ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscope (SEM). The study shows transformation of metastable cubic ZrO2 to stable monoclinic ZrO2 phase after interacting with shock heated oxygen gas due to the heterogeneous catalytic recombination surface reaction.

Does manure management affect the latent greenhouse gas emitting potential of livestock manures?

With livestock manures being increasingly sought as alternatives to costly synthetic fertilisers, it is imperative that we understand and manage their associated greenhouse gas (GHG) emissions. Here we provide the first dedicated assessment into how the GHG emitting potential of various manures responds to the different stages of the manure management continuum (e.g., from feed pen surface vs stockpiled). The research is important from the perspective of manure application to agricultural soils. Manures studied included: manure from beef feedpen surfaces and stockpiles; poultry broiler litter (8-week batch); fresh and composted egg layer litter; and fresh and composted piggery litter. Gases assessed were methane (CH4) and nitrous oxide (N2O), the two principal agricultural GHGs. We employed proven protocols to determine the manures’ ultimate CH4 producing potential. We also devised a novel incubation experiment to elucidate their N2O emitting potential; a measure for which no established methods exist. We found lower CH4 potentials in manures from later stages in their management sequence compared with earlier stages, but only by a factor of 0.65×. Moreover, for the beef manures this decrease was not significant (P < 0.05). Nitrous oxide emission potential was significantly positively (P < 0.05) correlated with C/N ratios yet showed no obvious relationship with manure management stage. Indeed, N2O emissions from the composted egg manure were considerably (13×) and significantly (P < 0.05) higher than that of the fresh egg manure. Our study demonstrates that manures from all stages of the manure management continuum potentially entail significant GHG risk when applied to arable landscapes. Efforts to harness manure resources need to account for this.

Application of sorbers to mitigate greenhouse gas emissions from land-applied pig litter

Nitrous oxide is the foremost greenhouse gas (GHG)generated by land-applied manures and chemical fertilisers (Australian Government 2013). This research project was part of the National Agricultural Manure Management Program and investigated the potential for sorbers (i.e. specific naturally-occurring minerals) to decrease GHG emissions from spent piggery litter (as well as other manures)applied to soils. The sorbers investigated in this research were vermiculite and bentonite. Both are clays with high cation exchange capacities, of approximately 100–150 cmol/kg Faure 1998). The hypothesis tested in this study was that the sorbers bind ammonium in soil solution thereby suppressing ammonia (NH3)volatilisation and in doing so, slowing the kinetics of nitrate formation and associated nitrous oxide (N2O) emissions. A series of laboratory, glasshouse and field experiments were conducted to assess the sorbers’ effectiveness. The laboratory experiments comprised 64 vessels containing manure and sorber/manure ratios ranging from 1 : 10 to 1 : 1 incorporated into a sandy Sodosol via mixing. The glasshouse trial involved 240 pots comprising manure/sorber incubations placed 5 cm below the soil surface, two soil types (sandy Sodosol and Ferrosol) and two different nitrogen (N) application rates (50 kg N/ha and 150 kg N/ha) with a model plant (kikuyu grass). The field trial consisted of 96, 2 m · 2 m plots on a Ferrosol site with digit grass used as a model plant. Manure/ sorber mixtures were applied in trenches (5 cm below surface) to these plots at increasing sorber levels at anNloading rate of 200 kg/ha. Gas produced in all experiments was plumbed into a purpose-built automated gas analysis (N2O, NH3, CH4, CO2) system. In the laboratory experiments, the sorbers showed strong capacity to decreaseNH3 emissions (up to 80% decrease). Ammonia emissions were close to the detection limit in all treatments in the glasshouse and field trial. In all experiments, considerable N2O decreases (>40%) were achieved by the sorbers. As an example, mean N2O emission decreases from the field trial phase of the project are shown in Fig. 1a. The decrease inGHGemissions brought about by the clays did not negatively impact agronomic performance. Both vermiculite and bentonite resulted in a significant increase in dry matter yields in the field trial (Fig. 1b). Continuing work will optimise the sorber technology for improved environmental and agronomic performance across a range of soils (Vertosol, Dermosol in addition to Ferrosol and Sodosols) and environmental parameters (moisture, temperature, porosity, pH).