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Redox Reaction Kinetics Between Cobalt(Ii)-4,4',4",4'"-Tetrasulfophthalocyanine & Iodine In Various Solvents, Byung-Soo Yu

Masters Theses & Specialist Projects

Analyses of the kinetic data obtained on the redox reaction between cobalt(II)-4,4',4",4"-tetrasulfophthalocyanine [Co(II)TSPC4^-] and iodine in the presence of air show three reactions in dimethylsulfoxide(DMS0), N,N-dimethylacetamide(DMA), and diethylene glycol(DEG) while there are two reactions in methanol(Me0H). Two of the three reactions in DMSO, DMA, and DEG are biphasic with one reaction in all of the solvents being too fast to be accurately measured on the Cary Model 14 spectrophotometer. When the reactant solutions are purged with argon for 40 minutes under identical conditions, the same biphasic reactions are observed in DMSO and DEG while only one of the …

Characterization Of Potassium Promoted & Unpromoted Fischer-Tropsch Catalysts, Steven Miller

Masters Theses & Specialist Projects

The technique of x-ray photoelectron spectroscopy (XPS) has been applied to characterize iron-manganese catalysts used in Fischer-Tropsch synthesis. The catalysts, which vary in composition from 10 FE/90 Mn, to 50 Fe/50 Mn are analyzed after being placed in a slurry reactor and having synthesis gas reacted over them. Changes, in catalyst composition are investigated further using in situ techniques. Additionally, 20 Fe/80 Mn catalysts containing potassium in the range of 0.1 wt.% to 1.3 wt.% are analyzed in the same manner. These studies have permitted the identification of some of the factors influencing activation and deactivation, product selectivity, and surface …

Reductive Dechlorination Of Toxic Chlorocarbons, K. Grant Taylor

KWRRI Research Reports

The sodium hydride based reducing agents were prepared the method of Caubere (Angew. Chem. Int. Ed. Engl., 1983, 22, 599-613). Reagents were prepared containing nickel, iron and zinc metals. All were effective in dechlorinating 1,3-dichlorobenzene, 4-methoxy-chlorobenzene, and arochlor 1254. Most work focused on nickel based reagents, the most active. The nickel-based reducing agent used in THF at 65°C reduced to 200 ppm 1,3-dichlorobenzene (to benzene) and arochlor 1254 (to biphenyl) to below 0.2 ppm in less than 15 minutes. A two stage reduction reduced arochlor 1254 to below a detectable level as determined by gas chromatography using f.i.d. detector. Using …

Reactions Of Supercritical Water With Quinoline And Related Compounds, Zhuangjie Li

Masters Theses

One function which coal processing can perform is the removal of heteroatoms to yield a less polluting product. The removal of nitrogen atoms from the model compounds quinoline and aniline, which are believed to be representative of the nitrogen functional groups found in coal, was studied using supercritical water (SW) as the fluid. Water at these conditions serves as a reactant, helping to promote the rupture of the heterocyclic ring and in the removal of nitrogen attached to an aromatic ring. Heterocyclic ring rupture leads to the formation of several methylated products, methyl and dimethyl anilines, phenols and quinolines. The …

The Design And Construction Of Microprocessor-Computer Controlled Rapid Scanning Fiberoptic Spectrophotometer, Kathleen Marie Tobin

Masters Theses

Conventional spectrophometers require the transfer of a sample to a cuvette for obtaining spectra. The measurement of absorbance in situ can be accomplished using a fiber optic probe which can be placed directly in the sample. The fiber optic probe also minimizes environmental factors such as thermal or vibrational which may affect the absorbing species. A rapid scanning speed allows for essentially simultaneous wavelength monitoring.

The effect of coupling a rapid scanning spectrophotometer with a fiber optic probe provides for an extremely versatile system. When used in comjunction with a microprocessor or computer, this approach offers advantages such as data …

Cobalt (Iii) Complexes With (R) - 1, 2-Diaminopropane And Its Derivatives, Christopher John Rudy

Masters Theses

(R)-1, 2-Diethylaminopropane (N,N' -Etlpn) was prepared by LialH₄ reduction of (R)-1-2-diacetamidopropane (m.p. 153.5°C). The [∝]_D of N, N'-Melpn and N,N'-Etlpn was related to that of 1pn and was concentration dependent. (R)-1, 2-Dibenzylaminopropane was prepared. Complexes of trans, trans- and trans, cis-dinitrobis ((R)- 1, 2-diethylaminopropane) cobalt (III) were perpared. The hexadecadal rule was used to help assign the nitro oxygens of the complexes to sectors adjacent to the axial amine hydrogens and within the boundaries of the λ- chelate rings. The CD spectra was solvent dependent. The instability of trans-[Co (III)N₄X₂]⁺ complexes was related …

Synthesis Of Pyridine Nucleosides By Cycloaddition Reactions And Synthesis And Condensation Reactions Of 4-Aryl-2-Oxytetronimides, Glenn L. Heise

Masters Theses

Experiment 1: The reaction of various glutaconaldehyde salts (Na⁺ or K⁺) with glycosyl isothiocyanates has resulted in the formation of a novel class of compounds. Relatively mild conditions were utilized for the synthesis which occurs in four steps, and in good yield, starting from glucpseptentaacetate. These reactions were found to be regiospecific. The unique physical and spectral properties of the model compound 1-(2,3,4,6-tetra-0-acetyl-β-D-glycopranosyl)-2-thiono-3-pyridine carboxaldehyde are also discussed.

Experiement 2: Early synthetic methodologies have recently been utilized in the synthesis of 4-aryl-2-oxytetronimides. These compounds have been found to participate in condensation reactions with various substituted o-phenylene diamines. A …

Calculated Electronic Profiles For Liquid-Metal Surfaces, Jerry Goodisman

Chemistry - All Scholarship

The electronic density profile for a liquid-metal surface can be calculated by solving the self-consistent Lang-Kohn equations for the electronic wave functions. One requires a surface density profile for the ion cores, which enters the electrostatic and pseudopotential parts of the electronic Hamiltonian. We use oscillatory profiles, suggested by those found by molecular-dynamics simulations on a pseudoatom model. Calculating surface potentials and work functions, we obtain excellent agreement with experiment (within 0.2 eV). It is shown that use of either step-function ion profiles or a simple variational method leads to serious errors (12 eV) for these quantities.

Glycation Of Amino Groups In Protein, Nancy G. Watkins, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

Ribonuclease A has been used as a model protein for studying the specificity of glycation of amino groups in protein under physiological conditions (phosphate buffer, pH 7.4, 37 “C). Incubation of RNase with glucose led to an enhanced rate of inactivation of the enzyme relative to the rate of modification of lysine residues, suggesting preferential modification of active site lysine residues. Sites of glycation of RNase were identified by amino acid analysis of tryptic peptides isolated by reverse-phase high pressure liquid chromatography and phenylboronate affinity chromatography. Schiff base adducts were trapped with Na- BH&N and the a-amino group of Lys-1 …

The Survival Of Mesophilic And Thermophilic Bacteria Subjected To Uv Irradiation, Sajida A. Shaikh

Masters Theses

Survival curves were determined for the mesophile, Bacillus licheniformis and the thermophile, Bacillus stearothermophilus after subjecting the cells to ultraviolet irradiation. Cells were grown at 37°C for the mesophile and at 55°C for the thermophile.

At low UV exposure times, the thermophile was more resistant to UV irradiation (had a better survival rate) than was the case for the mesophile. At higher exposure times, the situation was reversed, the mesophile having a greater survival rate than the thermophile.

The effect of changes in the temperature during irradiation was also determined. Thermophiles were greatly affected by changes in temperature while the …

27th Rocky Mountain Conference

Rocky Mountain Conference on Magnetic Resonance

Program and abstracts from the 27th annual meeting of the Rocky Mountain Conference, co-sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy and the Rocky Mountain Chromatography Discussion Group. Held in Denver, Colorado, July 14-18, 1985.

Analytical Pyrolysis Of Thai Lignites, Naowarat Poolasap

Masters Theses & Specialist Projects

Samples of four different Thai lignites were utilized to study the effects of ceiling temperature and heating rate on the overall yield and product distribution by the technique of analytical pyrolysis (pyrolysis-gas chromatography). Ceiling temperatures of 450°, 550°, 650°, 750°, 850°, and 950°C, a heating rate of 500°C/sec and pyrolysis intervals of 20 seconds were investigated. The results were reported in terms of percentage high-volatile product and low-volatile product fraction, weight-loss (% by weight), and total yield (counts per milligram). One sample which showed the highest sensitivity to changing ceiling temperature was selected to study the effect of heating rate …

Predicting The Self-Heating Potential Of Coal, Seyed Mohammad Fatemi-Badi

Masters Theses & Specialist Projects

Self-heating in coal has been studied for well over one hundred years, yet there is no accurate or reliable method for predicting the potential of certain coals to undergo self-heating. Fires caused by self-heating, and eventually spontaneous combustion, have occurred in the high wall of surface mines, in underground mines, in coal stockpiles, and on trains, barges and ships. Self-heating in coal is brought about through a complex interplay of conditions depending on the specific properties of the coal as well as many external factors involved in the mining and handling of coal.

In a study supported by the United …

Hydrogenation Of Nitro Compounds To Amines Using Polymer Bound Catalysts, Eduardo Baralt

Masters Theses & Specialist Projects

A polymer bound catalyst is a relatively new type of catalyst. The basis of polymer bound catalysis lies in the chemical attachment of a homogeneous catalyst to a solid support, in our case, polystyrene. Applications of polymer bound catalysts started in the late 1960’s, and have been used in several types of reactions. In some cases such a catalyst offers a series of advantages over the classical models of catalysis, homogeneous and heterogeneous.

The hydrogenation of various aromatic and aliphatic nitro compounds, such as nitro-benzene and 2-nitropropane, were performed successfully. The hydrogenation activity in most cases was high, and in …

The Thirsty Earth: Acid Rain - A Sour Drink, Margaret R. Souza

Bridgewater Review

No abstract provided.

Development Of An On-Line Computer System For Cyclic Voltammetry Studies, Tai-Lee Leo Huo

Chemistry & Biochemistry Theses & Dissertations

An Apple II Plus microcomputer was interfaced to a PAR 174A Polarographic Analyser, an HP 7O4OA X-Y recorder and a three-electrode system. This on-line computer system was applied to Cyclic Voltammetry (CV) studies. The interfacing involved both hardware and software development. Various hardware components were used to amplify and transmit the analog signal both going into the computer and coming from the computer. Software programs were written for staircase waveform generation, data acquisition, and plotting the voltammograms obtained.

A package was designed for CV experiments to be used by the students in the instrumental analysis laboratory. This package contains several …

Reaction Of Atomic Hydrogen With Chloroform In A Discharge Flow Reactor, Wan-Kuen Jo

Theses

The reactions of atomic hydrogen with chloroform were studied in a tubular flow reactor both in a 4 cm i.d. and 2.6 i.d. discharge flow reactor at pressure of 2.22 to 2.82 mmHg and room temperature using GC and GC/MS for analysis of the reaction. The hydrogen atom concentration at the reaction flame was measured by Chemiluminescence titration with nitrogen dioxide. The hydrogen concentrations are in the 2.48 x 10⁺¹⁴ to 4.83 x 10⁺¹⁴ atoms/cc range at six different hydrogen flow rates. Evidence was found for the formation of atomic carbon intermediate in the reaction, but methane was …

Co-Oxidative Depolymerization Of Coal, Renae Rosencrans

Masters Theses & Specialist Projects

In contrast to current coal conversion technology, cooxidative depolymerization of coal is a novel approach to coal liquefaction in that the reactions are carried out under relatively mild conditions. This free radical process utilizes air or oxygen and a suitable co-oxidant (solvent) which acts as a radical and hydrogen transfer agent throughout the coal matrix. Ideally, co-oxidation would lead to the formation of hydroperoxide groups at the reactive bridging sites in the coal matrix, which upon decomposition would lead to C-C bond scission.

The effects of several variables on co-oxidation and subsequent post-treatment were investigated. Up to 49% conversion to …

Reactivity Of Some Nitrogen-Containing Compounds At Supercritical Water Conditions, David M. Tiffany

Masters Theses

The use of water at cuperctirical conditions to remove nitrogen from several nitrogen-containing compounds was studied with the purpose of exploring the use of supercritical water as a method of removing nitrogen from the extraction products of coal. Quinoline and isoquinolone were the primary model compounds used with benzonitrile and carbazole also being examined briefly. Reaction conditions varied in temperature (350-500°C), pressure (3500-5200 psi), and water density (0.170-.0.426g/cc). The major products formed by isoquinoline were benzene, toluene, ethylbenzene, and o-xylene as well as nonvolatile tar and char. Quinoline produced aniline and toluidine in addition to those obtained from isoquinoline. Most …

The Synthesis And Evaluation Of A New Analog Of Phencyclidine (Pcp), William H. Johnson Jr.

Chemistry & Biochemistry Theses & Dissertations

Based on an interpretation of the literature of phencyclidine (PCP) together with an examination of the relevant models or prototype structures, this research has attempted to design and synthesize a rigid analog of the phencyclidine structure. The parent ring systems suggested for this study were the 1-arnino and 2-arninornethyltetralins, 10 and, 12.

Several organic compounds, based on this design, have been prepared by classical examples of reductive alkylation reactions of the corresponding 2-hydroxyciethylene-1-tetralones, 11, and by the condensation and subsequent reductive alkylation of the 1-arninotetralin, 9. These arninomethyltetralones, 28, 29 and 30, together with an example of a substituted 1-arninotetralin, …

Piezomodulated Raman Spectroscopy Of Molecular Crystals: An Experimental Method For Study Of The Anharmonic Properties Of Solids, T. Luty, Craig J. Eckhardt

Craig J. Eckhardt Publications

Consideration of phonon-phonon coupling induced by strain serves as impetus for developing a theoretical structure for piezomodulated Raman spectroscopy which can be used for experimental realization of the coupling. The direct relation of the coupling constant to generalized stress Gruneisen parameters is shown. These describe the crystal's anharmonic properties such as the thermal expansivity and the temperature dependence of the phonon energies. Numerical calculations are performed for anthracene crystal which exemplify the use of the stress Gruneisen parameters as sensitive measures of anisotropy of intermolecular interactions. Further development shows how the measurement can be used to determine these parameters and …

Dilithiation Reactions Of N-Substituted Benzylamines, Richard Patrick Franks

Theses & Honors Papers

N-Cyclohexyl -2-methylbenzylamine was metalated with two equivalents of n-butyllithium activated with one equivalent of tetramethylethylenediamine (T.M.E.D.A.) , and the solvent system, time, and temperature were varied to establish a maximum yield . It was experimentally found that a thirty minute ice-water bath metalation in diethyl ether, followed by a fifteen minute condensation with benzophenone in refluxing diethyl ether gave the best yield with the benzophenone electrophile. The product was characterized by N.M.R. and found · to be 2- ( cyclohexylamino)-2-(2-toluyl ) -1 ,1-diphenylethanol (the benzylic adduct) in a 29% yield.

When N-cyclohexyl -2-methylbenzylamine was metalated for three hours in an …

Solvent Influence On Atomic Spectra: The Effect Of Finite Size, Randall W. Hall, Peter G. Wolynes

Collected Faculty Scholarship

Time dependent Hartree theory is used to determine the solvent effect on atomic spectra for a given solvent configuration. Configuration averaging is performed as in the mean spherical approximation, resulting in an upper bound to the polarizability. Comparisons are made with previous, more approximate theories, including path integral treatments. It is found that deviations from previous theories can be significant in certain regimes.

Vibrational Predissociation In Linear Hydrogen-Bonded Complexes, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

Dr. Shannon Lieb's contribution to Volume 95 of the Proceedings of the Indiana Academy of Science.

Thermodynamics Of Ion Association In Aqueous Fluoride Solutions. Determination Of Stability Constants For (Naf), (Mgf)+ And (Caf)+ Ion Pairs, Waldo Zamorano-Santander

Masters Theses

Stoichiometric ion-association constants were determined at several ionic strengths for (NaF) over the temperature range 15-40°C and for (MgF)⁺ and (CaF)⁺ over the temperature range 25-45°C using fluoride ion selective electrode measurements.

Thermodynamic association constants, K°, were obtained through extrapolation of the stoichiometric values to infinite dilution. Values of K° for (NaF) are 1.70, 2.16 and 2.54 at 15, 25 and 40°C, respectively. The K° values for (MgF)⁺ are 73.4, 88.0 and 98.2, and for (CaF)⁺ are 13.7, 17.5 and 21.9 at 25, 35 and 45°C., respectively.

The stoichiometric association constants for (NaF) can be reproduced …

Bimetallic Complexes Of Tungsten And Mercury, Zakariah Abdullah

Masters Theses

A tungsten-mercury bimetallic complex [(CO)₄W(PPh₂CH₂CH₂PPh₂)₂HgCl₂]_n has been synthesized from the reaction of trans-(CO)₄W(η¹-PPh₂CH₂CH₂PPh₂)₂ and HgCl₂. The value of n has not been determined due to the insolubility of the complex. The anologous reaction with HgI₂ gave an insoluble, uncharacterizable complex, which best corresponds to (CO)₄W(PPh₂CH₂CH₂PPh₂)₂Hg₂I₄.

The geometry about tungsten in [(CO)_{4 …}

Bimetallic Tungsten Carbonyl Complexes, Jin-Guu Wang

Masters Theses

Two heterobimetallic complexes, [(CO)₄W(PPh₂CH₂CH₂-PPh₂)₂MCl₂]_n ( M = Pd or Pt ), were prepared from the reaction of trans-W(CO)₄(ŋ¹-PPh₂CH₂CH₂PPh₂) ₂ with M(COD)Cl₂ (COD = cyclooctadiene). A trans arrangement about tungsten was found for both the palladium and platinum complexes. The square planar palladium center was shown to have a trans geometry in solution while a cis arrangement for the platinum moiety was observed. Far infrared studies indicated a mixture of cis and trans …

Attenuation Of Infrared Radiation By Diesel Fuel Generated Particle And Droplet Aerosols, Soodabeh Karimi

Retrospective Theses and Dissertations

The object of this project was to explore the absorbance and scattering properties of carbon particle smoke in the infrared and visible regions of the spectrum. Laboratory scale apparatus were developed to produce smoke in the form of carbon particles, droplet aerosols and combinations of the two. These smokes were made from diesel fuel and fog oil.

I. The Use Of Polyethers As Phase Transfer Catalysts For The Fluoroalkoxylation Of Halogenated Aromatic And Heteroaromatic Systems Ii. The Grignard Addition And Sodium Cyanoborohydride Reduction Of Arylchloropropeniminium Salts, Martin A.M. Moebus

Retrospective Theses and Dissertations

This research addresses two distinct areas of synthetic organic chemistry: the use of phase transfer catalysts for the fluoroalkoxylation of activated haloaromatic and haloheteroaromatic systems, as well as the Grignard addition and sodium cyanoborohydride reduction of aryl chloropropeniminium salts. In Part I of this research, a number of macrocyclic- and linear polytethers were studied as phase transfer catalysts in the nucleophilic aromatic substitution of haloaromitc systems. The most effective catalyst was determined to be poly(ethylene glycol)-8000 and the reaction conditions were optimized for this catalyst. Subsequently isomer reactivity, effects of activating groups, effects of leaving groups, and nucleophiles were studied …

Synergistic Effects In Bimetallic Hydrogenation Catalysts, Kathleen L. Mcintyre

Retrospective Theses and Dissertations

Mono and bimetallic catalysts of varying composition were prepared in order to examine any synergistic effect that may occur by mixing metals on a support. The test reactions were hydrogenation of 1, 3-butadiene and piperylene, a mixture of similar boiling 5-carbon olefins. Catalysts containing ruthenium and rhodium displayed some synergistic effects when supported on silica gel and 13X molecular sieves. The use of 5A molecular sieves as a support was used to examine the feasibility of selective hydrogenation as a separation tool for the piperylene mixture.