The rate constant for the reactions of oxygen atoms with nitric oxide and silane were determined using a discharge flow apparatus. A microwave discharge through O2N2 and Ar was used to produce oxygen atoms. The rate constant for the reaction O + NO + Ar was determined to be (7.0+0.4) x 10^32 cm^6 s^-1 and is in good agreement with previous measurements. Modeling of the O +SiH₄ reaction was performed to determine the correction to the rate constant due to secondary reactions. The rate constant for the reaction O + SiH₄ was determined to be (3.3 +/- 0.3) x 10⁻¹³ cm³ s⁻¹ and is in good agreement with previous measurements. Previous literature, thermochemistry, and spin conservation were used to determine a probable mechanism for the O + SiH₄ reaction.

Aqueous solubilities of twelve chlorinated benzenes were determined by two methods. In one method, the solutions in water were prepared by a vigorous stirring method followed by n-hexane extraction and GC-ECD analysis. In the second method, HPLC was used to prepare the saturated solutions. Experimental results were compared with the predictive values, the relative standard deviations are around 10%. Most of the chlorinated benzenes exhibit water induced transformations. The transformation products were either isomeric or with higher and lower numbers of chlorine substituents. The transformation phenomena can be explained by polarity, symmetry, reactivity of the chlorine atoms, and hydrophobic interactions. The mechanism of the transformation is governed by the radical mechanism.

Small weight percentages of certain high-molecular weight polymers added to liquids in turbulent flow through conduits can result in dramatic friction reduction. Although many current and potential uses of the drag reduction phenomenon exist, there is a fundamental problem: drag reduction efficacy decreases rapidly with flow time due to the mechanical degradation in flow of the added polymer. In this thesis study, dilute aqueous solutions of polyacrylamide were tested under turbulent flow conditions in an attempt to determine where mechanical degradation in flow occurs.

Conversion of 1-Methylpentacyclo[5.4.0.0²⋅⁶.0³⋅¹⁰.0⁵⋅⁹]undecane- 8,11-dione into the corresponding mono(ethylene ketal) followed by Wolff-Kishner reduction resulted in a mixture of two isomers (i.e., 1- and 7-methyl-8-[2',-(1',3',dioxolano)]pentacyclo[5.4.0.0²⋅⁶.0³⋅¹⁰.0⁵⋅⁹] undecane. Hydrolysis of each isomer in turn resulted in 1- and 7- methyl pentacyclo[5.4.0.0²⋅⁶.0³⋅¹⁰.0⁵⋅⁹ ]undecan-8-ones (i.e.,"methylated PCU-8-ones"), respectively. "Titanium-promoted reductive dimerization of each of the methylated pentacycloundecane (PCU)-8-ones afforded mixtures of "methylated PCU alkene dimers". Individual isomers have been isolated from these mixtures via column chromatography by using silver nitrate impregnated silica gel as adsorbent followed by fractional recrystallizations of individual chromatography fractions. Structures of three isomerically pure methylated PCU alkene dimers (C₂₄H₂₈) have been established unequivocally by application of single crystal X-ray crystallographic methods.

The synthesis of o-(N,N-dimethylamino)methylphenyl tris (trimethylsilyl) silane (II), a photochemical precursor of o- (N,N-dimethylamino) methylphenyl (trimethylsilyl) sila ammonium ylide (intramolecular silylene complex) and otolyl(trimethylsilyl)silylene is reported. Photolysis of II at room temperature in a cyclohexane solution of triethyl silane produced the silylene ylide and the presumably uncomplexed isomer, a silylene, which is trapped to afford the 2-(o-(N,N-dimethylamino)methylphenyl) -1,1,1-triethyl 3,3,3-trimethyltrisilane, 33% yield. A second decomposition pathway, a photodeamination, produced o-tris(trimethyl silyl) silyltoluene. UV spectra of the silaammonium ylide formed in the photochemical reaction of II was observed at 77k in hard or soft matrices.

The thermocyclic fatigue behavior of the low-melting solder 43Sn/43Pb/14Bi has been investigated and compared to that of standard 60Sn/4OPb solder via metallographic analysis (using scanning electron microscopy) and evaluation of the degree of fatigue development (using a fatigue scale as a function of thermocycles). Specimens were subjected to shearing strains imposed by several hundred fatigue thermocycles. Both solder types fatigue by the same microstructural failure mechanism as described by other workers. The mechanism is characterized by a preferential coarsening of the solder joint microstructure at the region of maximum stress concentration where cracks originate.

Exchange reactions of anions, especially ferrocyanide and carbonate, with layered double hydroxides (LDHs) were investigated in relation to the origin of life on the early Earth. The effect on ferrocyanide exchange of concentration, pH, reaction time and cations are discussed. It was found that there were two different kinds of ferrocyanide species: one was that intercalated into the layered structure, occupying a site of D symmetry within the LDHs, while in the other, the ferrocyanide group retains full O symmetry. In addition, very low concentration, ferrocyanide associated with LDH will change its FTIR absorption shape. Carbonate was much more strongly intercalated than ferrocyanide into the LDHs, probably because of the strong hydrogen bonding.

This study examines the waste of cotton gins as a potential alternative energy source, on account of its heat content, availability, and low emission rates. To confirm that this potential energy source meets minimum industrial fuel standards, this research has carried out an investigation of some important physical characteristics and toxic element analysis of cotton gin waste. Using cotton gin waste as fuel is an attractive solution to the problems of disposing of a surplus agricultural waste as well as supplementing fuel must meet both environmental emission standards and industrial fuel standards, the physical and chemical characteristics of cotton gin waste and its toxic element concentrations are important for its objective evaluation as a fuel. Constituent components, moisture contents, and ash contents of four separate parts of cotton gin waste were determined and evaluated closely following the American Society for Testing and Materials (ASTM) test methods. The three most toxic heavy metals, Arsenic (As), Chromium (Cr), and Lead (Pb), chosen for quantitative analysis were determined by using an inductively coupled plasma atomic emission spectrometry and a microwave oven sample digestion method.

This work concerns some synthetic processes and basic properties of layered double hydroxides (LDHs). A series of LDHs, a family of newly developed materials found to have many potential uses in industry, were investigated in relating to the origin of life on early Earth. In this work, I successfully intercalated some inorganic as well as organic species. Ammonium, accompanied with ferrocyanide ion, can enter the layered space. It was found there were two kin go f intercalated ferrocyanide species: one is that exchanged with anions and became a part of layered double hydroxide, while the other is suggested to be related to ammonium ferrocyanide neutral species. Formaldehyde, ethanolamine and formate can also be involved into LDHs. To improve the crystallinity, homogeneous precipitation method, which used Urea and Hexamine, was employed. The results reveal the success in the case by Urea but not in that by Hexamine. Annealing could also be used for this purpose. However, it needs to be preocessed in its mother liquor; no improvement on the crystallinity if the material has been washed before annealing.

Flash photolysis techniques were applied to studies of solvent displacement by Lewis bases (L) from solvated metal carbonyl complexes of Cr, Mo, and W. On the basis of extensive studies of the reaction rate laws, activation parameters , and linear-free-energy-relationships, it was concluded that the mechanisms of solvent displacement reactions depend on the electronic and steric properties of the solvents and L, as well as the identities of the metal atoms. The strengths of solvent-metal bonding interactions, varying from ca. 7 to 16 kcal/mol, and the bonding "modes" of solvents to metals are sensitive to the structures of the solvent molecules and the identities of the metal centers. The results indicate dissociative desolvation pathways for many arene solvents in (solvent)Cr(CO)_5 (solvent = benzene, fluorobenzene, toluene, etc.) complexes, and are consistent with competitive interchange and dissociative pathways for (n-heptane)M(CO)_5. Different types of (arene)-Cr(CO)_5 interactions were suggested for chlorobenzene (CB) vs. fluorobenzene and other non-halogenated arenes, i.e. via σ-halogen-Cr bond formation in the CB solvate vs. π-arene-Cr bond formation through "isolated" double bonds in solvates of the other arenes. The data also indicate the increasing importance of interchange pathways for solvent displacement from the solvates of Mo and W vs. that of …

The United States leads the world in per capita production of Municipal Solid Waste (MSW), generating approximately 200 million tons per year. By 2000 A.D. the US EPA predicts a 20% rise in these numbers. Currently the major strategies of MSW disposal are (i) landfill and (ii) incineration. The amount of landfill space in the US is on a rapid decline. There are -10,000 landfill sites in the country, of which only 65-70% are still in use. The Office of Technology Assessment (OTA) predicts an 80% landfill closure rate in the next 20 years. The development of a viable energy resource from MSW, in the form of densified Refuse Derived Fuel (dRDF), provides solutions to the problems of MSW generation and fossil fuel depletions. Every 2 tons of MSW yields approximately 1 ton of dRDF. Each ton of dRDF has an energy equivalent of more than two barrels of oil. At current production rates the US is "throwing away" over 200,000,000 barrels of oil a year. In order to be considered a truly viable product dRDF must be extensively studied; in terms of it's cost of production, it's combustion properties, and it's potential for environmental pollution. In 1987 a research …

The purpose of this dissertation is to investigate the thermodynamic properties of nonelectrolyte solutes dissolved in ternary solvent mixtures, and to develop mathematical expressions for predicting and describing that behavior in the solvent mixtures. Thirty-four ternary solvent systems were studied containing either alcohol (1-propanol, 2-propanol, 1-butanol, and 2-butanol), alkane (cyclohexane, heptane, and 2,2,4-trimethylpentane) or alkoxyalcohol (2-ethoxyethanol and 2-butoxyethanol) cosolvents. Approximately 2500 experimental measurements were performed. Expressions were derived from the Combined Nearly Ideal Multiple Solvent (NIMS)/Redlich-Kister, the Combined Nearly Ideal Multiple Solvent (NIMS)/Bertrand, Acree and Burchfield (BAB) and the Modified Wilson models for predicting solute solubility in ternary solvent (or even higher multicomponent) mixtures based upon the model constants calculated from solubility data in sub-binary solvents. Average percent deviation between predicted and observed values were less than 2%, documenting that these models provide a fairly accurate description of the thermodynamic properties of nonelectrolyte solutions. Moreover, the models can be used for solubility prediction in solvent mixtures in order to find the optimum solvent composition for solubilization or desolubilization of a solute. From a computational standpoint, the Combined Nearly Ideal Multiple Solvent/Redlich-Kister equation is preferred because the needed model constants can be calculated with a simple linear regressional analysis. Model constants …

The kinetics of ligand substitution for CO in Co4(CO)10(mu4-PPh2) , 1, have been investigated for the ligands P(OMe)3, P(OEt)3, PPh2H, P(0-i-Pr)3, P(n-Bu)3, PPh3, P(i-Pr)3, and PCy3 over a wide temperature range.

The characteristics of seventy-six calix[4]arene crystal structures derived from the Cambridge Crystallographic Database are presented. This survey is a discussion of the inter and intramolecular effects on the solid state cavity shape and molecular recognition ability of the compounds. In addition to this survey, four new calix[4]arene crystal structures are presented. The conformational characteristics of these four calixarenes are determined by a complicated array of inter and intramolecular interactions in the crystal packing.

A group of azabiphenyl complexes and supramolecules, and their reduced and oxidized forms when possible, were characterized by cyclic voltammetry and electronic absorption spectroscopy. The oxidized and reduced species, if sufficiently stable, were further generated electrochemically inside a specially designed quartz cell with optically transparent electrode, so that the spectra of the electrochemically generated species could be taken in situ. Assignments were proposed for both parent and product electronic spectra. Species investigated included a range of Ru(II) and Pt(II) complexes, as well as catenanes and their comparents. Using the localized electronic model, the electrochemical reduction can be in most cases assigned as azabiphenyl-based, and the oxidation as transition metal-based. This is consistent with the fact that the azabiphenyl compounds have a low lying π* orbital. The electronic absorption spectra of the compounds under study are mainly composed of π —> π* bands with, in some cases, charge transfer bands also.

The syntheses of the unsymmetrical 14-membered bismacrolides have been reviewed. A total synthesis of clonostachydiol, the latest to join this family, has been attempted using trimethylsilyl acetylene as the builiding block and palladium catalyzed reactions for the formation of key bonds. The alkyne groups were introduced by Stille coupling of trimethylstannylethynyltrimethylsilane with an acid chloride for one fragment and by addition of lithiotrimethylsilyl acetylene to an aldehyde for the other. Lactic acid derivatives were chosen as starting materials for both fragments, thus introducing two of the chiral centers. The remaining stereocenters were introduced using stereoselective reductions of ketones.

This research investigated the chemistries and mechanisms involved in lead-cement systems through the study of a larger number of lead compounds.

Experimental mole fraction solubilities of benzil, thianthrene, trans-stilbene, thioxanthen-9-one, diphenyl sulfone and dibenzothiophene sulfone are determined in pure noncomplexing and complexing solvents. Predicted solubility values are calculated for benzil, thianthrene, trans-stilbene and thioxanthen-9-one using expressions derived from Mobile Order theory. Large deviations between experimental and predicted solubilities in alcohol solvents exist, therefore optimized solute - solvent association constants are determined. Previously measured thianthrene solubilities in five binary alkane + cyclohexane solvent mixtures are compared with values predicted from Mobile Order theory using the measured solubility in each of the pure solvents as input parameters. The experimental mole fraction solubility of benzil in eight binary alcohol + 1-octanol solvent mixtures are also measured and compared with predicted values.

Dissertation research involves development of Mobile Order Theory thermodynamic models to mathematically describe and predict the solubility, spectral properties, protonation equilibrium constants and two-phase partitioning behavior of solutes dissolved in binary solvent mixtures of analytical importance. Information gained provide a better understanding of solute-solvent and solvent-solvent interactions at the molecular level, which will facilitate the development of better chemical separation methods based upon both gas-liquid and high-performance liquid chromatography, and better analysis methods based upon complexiometric and spectroscopic methods. Dissertation research emphasizes chemical equilibria in systems containing alcohol cosolvents with the understanding that knowledge gained will be transferable to more environmentally friendly aqueous-organic solvent mixtures.

A novel crown ether precursor was developed in which a rigid 4-oxahexacyclo (5.4.1.26.3,10.05,9.08,11) dodecyl cage moiety ("cage functionality") was incorporated.

Sulfur adsorbed on metallic and oxide surfaces, whether originating from gaseous environments or segregating as an impurity to metallic interfaces, is linked to the deterioration of alloy performance. This research dealt with investigations on the interactions between sulfur and iron or iron alloy metallic and oxide surfaces under ultrahigh vacuum conditions. Sulfur was either intentionally dosed from a H2S source on an atomically clean metal surface, or segregated out as an impurity from the bulk to the metal surface by annealing at elevated temperatures.

Chain conformations and the presence of chain overlaps and entanglements in dilute polymer solutions have been analyzed. The fundamental problem of existence of chain overlaps in dilute solutions is related to the drag reduction phenomenon (DR). Even though DR occurs in solutions with the concentration of only few parts per million (ppm), some theories suggest that entanglements may play an important role in DR mechanism. Brownian dynamics technique have been used to perform simulations of dilute polymer solutions at rest and under shear flow. A measure of interchain contacts and two different measures of entanglements have been devised to evaluate the structure of polymer chains in solution. Simulation results have shown that overlaps and entanglements do exist in static dilute solutions as well as in solutions under shear flow. The effect of solution concentration, shear rate and molecular mass have been examined. In agreement with the solvation theory of DR mechanism, simulation results have demonstrated the importance of polymer + polymer interactions in dilute solutions.

Precipitates of a series of alkaline earth metal (barium and strontium) carbonates, chromates, phosphates, and sulfates were formed at high supersaturation by diffusion through silica hydrogel, agarose hydrogel, and the freshly developed agarosesilica mixed gels. The reaction vessels could be a small test tube, a recently designed standard micro slide cassette and a enlarged supercassette. Homogeneous nucleation is thought to have taken place, and particle development led to the formation of an unusual category of materials, known as Induced Morphology Crystal Aggregates [IMCA], at high pH under far-from-equilibrium conditions. Standard procedures were developed in order to produce homogeneous gels. Particle development led to characteristic style of pattern formation, which I have called monster, spiral, and flake. Among these IMCA, barium carbonate, chromate, and sulfate were moderately easy to grow. Barium phosphate was very difficult to grow as IMCA due to formation of poorly crystalline spherulites. IMCA of strontium carbonate, chromate and sulfate could be developed at high basic pH in the presence of silicate. Strontium carbonate sheet morphology displays a unique property, double internal layer structure, which was identified by backscattering electron imaging (BEI). Selected electron diffraction (SAD) revealed a new crystal phase which was called "Dentonite". Precipitate particles were …

Hartree-Fock, Moller-Plesset, and density functional theory calculations have been carried out using 6-31+G(d), 6-31+G(d,p) and 6-31++G(d,p) basis sets to study the properties of low-barrier or short-strong hydrogen bonds (SSHB) and their potential role in enzyme-catalyzed reactions that involve proton abstraction from a weak carbon-acid by a weak base. Formic acid/formate anion, enol/enolate and other complexes have been chosen to simulate a SSHB system. These complexes have been calculated to form very short, very short hydrogen bonds with a very low barrier for proton transfer from the donor to the acceptor. Two important environmental factors including small amount of solvent molecules that could possibly exist at the active site of an enzyme and the polarity around the active site were simulated to study their energetic and geometrical influences to a SSHB. It was found that microsolvation that improves the matching of pK as of the hydrogen bond donor and acceptor involved in the SSHB will always increase the interaction of the hydrogen bond; microsolvation that disrupts the matching of pKas, on the other hand, will lead to a weaker SSHB. Polarity surrounding the SSHB, simulated by SCRF-SCIPCM model, can significantly reduce the strength and stability of a SSHB. The residual strength …