Digital Commons Network^™

Matrix Isolation Studies Of Reactions Of Atomic Oxygen, Kwo-Tai Richard Sun

University of the Pacific Theses and Dissertations

The research reported here deals with a study of the reaction of atomic oxygen in the first excited electronic state with hexafluoroacetone (HFA). Matrix Isolation (MI) Spectroscopy was used to elucidate the reaction.

A Process For The Production Of 2-Alkyl Or 2-Cycloalkyl-4-Methyl-6-Hydroxypyrimidines, Joseph T. Blackwell Iii, John T. Gupton, Teruko U. Miyazaki, James B. Nabors, Joseph R. Pociask

Chemistry Faculty Publications

Production of 2-alkyl- or cycloalkyl-4-methyl-6- hydroxypyrimidines by first neutralizing an alkyl imidate ester hydrochloride with a base in the presence of a water-immiscible solvent for the alkyl imidate ester to be freed thereby; condensing the alkyl imidate ester with diketene to form an oxazinone intermediate, which is then reacted in organic solution with gaseous ammonia and recovering the desired substituted 6-hydroxypyrimidine.

Spectroscopic Study Of Ni(Ii)-4, 4’, 4’’, 4’ ’’ – Tetrasulfophthalocyanine In Aqueous Solution, Issa Ishaq Jabra

Masters Theses & Specialist Projects

It was determined spectrally that a monomer-dimer equilibrium exists in aqueous solutions of Ni-TSPC^4- over a concentration range of 5 x 10^-8 – 10^-4 M. Equilibrium measurements were made under natural ionic strength conditions at 29°, 39° and 49°C. The values obtained for the equilibrium constants at 29°, 39° and 49°C were 2.4 x 10⁸, 6.6 x 10⁷ and 2.9 x 10⁷ M^-1, respectively. These results indicated that the equilibrium strongly favors dimer formation. This study also showed that nickel is second to copper in enhancing the dimerization of metallotetrasulfophthalocyanine complexes. …

Electron Transfer Reactions Of An Osmium (Ii) Polypyridyl Complex With Oxidizing Agents, Stephen Mcclanahan

Masters Theses & Specialist Projects

Redox rates between polypyridyl osmium (II) complex, OsCl(py)₃(bipy)⁺, with tris(1,10-phenanthroline) cobalt (III), Co(phen)₃³⁺, and Ce(IV) were examined in aqueous solution. Both reaction systems exhibited second order kinetics. The osmium (II) - cobalt (III) redox reaction was found to have a rate constant of 2.3 x 10⁵ M^-1 sec^-1 at 22°C and µ = 0.003M from which the isotopic electronic exchange rate constant for the OsCl(py)₃(bipy)^+/2+ system was estimated to be 1.5 x 10⁹ M^-1sec^-1.

Ionic strength effects on the Ce(IV) - Os(II) …

Photochemistry Of Heteroaromatic Analogs Of Β-Methyl-Β-Nitrostyrene, Dale Willis

Masters Theses & Specialist Projects

2-(2-nitropropenyl)thionhene, 2-(2-nitropropenyl) pyrrole, and 2-(2-nitropropenyl) furan were prepared and irradiated in undenatured 95% ethanol and 2% aqueous acetone. The pyrrole derivative was found to undergo a slow photodecomposition to tars. The thiophene derivative produced 60% of an α-oximino ketone and 30% of an oxazine cyclization product when irradiated In ethanol. When irradiated in acetone 47% of the oxime was produced in addition to 7% of the oxazlne. The furan derivative produced 12% of an α-oximino ketone and 51% of an oxazine cyclization product when irradiated in ethanol. When irradiated in acetone 15% of the oxime and 32% of the oxazine …

An Emulsion Dye Laser, Kenneth Lee Matheson, James M. Thorne

Faculty Publications

A laser dye which is insoluble in water has been dissolved in hexane and emulsified in a water matrix. When pumped with a nitrogen laser, this mixture was observed to lase. The emulsion is superior to a simple hexane solution because the excellent thermo-optical properties of the water matrix help prevent refractive-index gradients from degrading laser performance. This is a useful characteristic for flash-pumped dye lasers, laser-pumped dye lasers, and liquid filters. Another type of solvent system, a critical solution, is also discussed. For certain dyes, a critical solution has even better thermo-optical properties because of its ability to absorb …

Light Scattering Studies Of Orientational Fluctuations Of Cs2, Scott Whittenburg

Chemistry Faculty Publications

We have measured the depolarized Rayleigh relaxation time of CS2 as a function of temperature and concentration in an optically isotropic solvent CCl4. The concentration dependence of the relaxation times indicates the importance of orientational pair correlation in CS2. The orientational pair correlation factor is found to depend on concentration at high CS2 concentration, as well as viscosity and temperature, in contrast to what is observed in other small molecules. The single particle reorientation times were obtained by extrapolating from the depolarized Rayleigh relaxation times to infinite dilution. These were compared with the predictions of the hydrodynamic slip and stick …

[3H]‑Raffinose, A Novel Radioactive Label For Determining Organ Sites Of Catabolism Of Proteins In The Circulation, Jonathon Van Zile, Lee A. Henderson, John W. Baynes, Suzanne R. Thorpe

Faculty Publications

The primary tissue sites of catabolism of plasma proteins with long circulating half-lives are unknown. It has been difficult to identify these sites because plasma proteins are delivered to tissues at relatively slow rates but are rapidly degraded intracellularly within lysosomes. Therefore, a tracer attached to protein is lost from the site of uptake before an amount sufficient for quantitation can accumulate. We hypothesized that sucrose (Glupal-2 /3Fruf) would be a useful label to circumvent this difficulty because of the stability of sucrose in lysosomes; and thus, sucrose should remain in tissue long after the protein to which it was …

A Model For The Surface Of A Molten Salt, Jerry Goodisman, R. W. Pastor

Chemistry - All Scholarship

A model is proposed for the two-particle distribution functions for the surface region of a system composed of two oppositely charged species with identical hard sphere repulsions. The distribution functions are formed from those for the bulk fluid by incorporating a cutoff corresponding to the surface and a multiplying factor defined so as to guarantee electroneutrality while maintaining the proper symmetry. Various methods for doing this are discussed. Good agreement is obtained for surface tension and surface energy. Density oscillations are predicted.

20th Annual Rocky Mountain Conference On Analytical Chemistry

Rocky Mountain Conference on Magnetic Resonance

Abstracts and program from the 20th annual meeting of the Rocky Mountain Conference on Analytical Chemistry, co-sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy and the Rocky Mountain Chromatography Discussion Group. Held in Denver, Colorado, August 7-9, 1978.

Redox Study Of Cobalt(Ii)-Cobalt(Iii) Polypyridyl, Larry Long

Masters Theses & Specialist Projects

The rate of reduction of [Co(dipy)₃]³⁺ by [Co(tripy)₂]²⁺ has been examined in six nonaqueous solvents and water. The kinetic results in these solvents were compared with those obtained in nine other solvents where the same reaction was investigated. Activation parameters were obtained over a temperature range of 5° to 50°C with the ionic strength at 0.0027 or 0.0046 M. The slowest rate of electron transfer was found in acetonitrile while the fastest occurred in acetophenone, the solvent of lowest dielectric constant. A linear correlation between ln k and the reciprocal dielectric constant of the …

The Unexpected Preferential Formation Of 1-Alkyl-1-Phenyl-2–Propanones On Monoalkylation Of The 1-Phenyl-2-Propanone Dianion, Jack M. Hinkley

Masters Theses

No abstract provided.

The Response Of The Micro-Adsorption Detector To Inorganic Anions, Maria E. Munera

Masters Theses

No abstract provided.

Structural Effects On Micellar Catalyzed Reaction Of Hydroxamic Acids, Nop Utrapiromsuk

Masters Theses

Introduction

For many years scientists have tried to find a model which resembles a biological system, so that they can use this model for studying biological systems in human and in living organisms. Micelle systems provide the environment to mimic enzyme systems to some degree.¹

Soaps and detergents generate micelles. Soaps and detergents have been used as cleansing agents for a long time. Their cleansing properties are related to micelle formation. Actually, soap is simply a mixture of sodium salts of long chain fatty acids, R-COO^- Na⁺, and some detergents are general sodium salts of straight …

The Effects Of Electron-Donating And Electron-Withdrawing Groups On The Alkylation Sites Of Para-Substituted Phenylacetones, Abraham L. Faburada

Masters Theses

The dianions of phenylacetone and its para-substituted derivatives were generated using potassium hydride and n-butyl lithium in tetrahydrofuran. Methyl, ethyl, and n-butyl iodides were used to alkylate the dianions. The results of alkulation indicated that C₁ is preferentially attacked by the less active ethyl and n-butyl iodides. The results further show that terminal alkylation is enhanced by electron-donating groups at the para-position of the phenyl ring. The results are rationalized in terms of the difference in electron density at C₁ and at C₃ in the dianion, on the basis of resonance theory. The regio-selectivity of alkylation as …

The Analysis Of N-Methylscopolamine Bromide By High Speed Ion Pair Partition Chromatography, John L. Nappier

Masters Theses

No abstract provided.

The Design And Construction Of A Nitrogen Laser And Its Use To Pump A Tunable Dye Laser To Measure The Multiphoton Ionization Spectrum Of Molecular Iodine, James Kintigh

Masters Theses & Specialist Projects

A nitrogen laser was constructed for use in multiphoton ionization studies. The short pulse duration and highly intense pulse make the nitrogen laser ideal for pumping a dye laser.

By using the nitrogen laser to pump a tunable dye laser, the multiphoton ionization spectrum for molecular iodine vapor was obtained for the visible spectrum between 23,188 cm^-1 (430 nm) and 16, 304 cm^-1 (615 nm) using pulsed electronics and a parallel plate ionization chamber. The ionization occurs in this region upon the absorption of four or five photons. The ionization appears to take place via a three-step process. …

Thermodynamics Of The Lanthanide Trifluorides. I. The Heat Capacity Of Lanthanum Trifluoride, Laf₃ From 5 To 350°K And Enthalpies From 298 To 1477°K, William G. Lyon, Darrell W. Osborne, Howard E. Flotow, Fernande Grandjean, Ward N. Hubbard, Gerald K. Johnson

Chemistry Faculty Research & Creative Works

The heat capacity of a sample of LaF₃ was determined in the temperature range 5-350°K by aneroid adiabatic calorimetry and the enthalpy from 298.15 to 1477°K by drop calorimetry. The heat capacity at constant pressure C°_p(298.15°K), the entropy S°(298.15°K), the enthalpy [H°(298.15°K)-H°(0)] and the Planck function -[G°(298.15°K)-H°(0)]/298.15°K; were found to be (90.29±0.09) J °K^-1·mole^-1, (106.98±0.11) J °K^-1·mole^-1, (16717±17) J mole^-1, and (50.91±0.05) J °K ^-1·mole^-1. The thermal functions from the present research were extended up to the melting temperature (1766°K) by combination with previously …

The Electrogenerated Chemiluminescence Of Trans-Stilbene Derivatives, James R. Wilson

Chemistry and Chemical Biology ETDs

A group of 15 compounds, all structurally related to trans­stilbene have been studied in systems of electrogenerated chemiluminescence (ECL). The compounds are substituted 2-phenyl indenes, dihydronapthalenes, and dihydrophenanthrenes. Absorption and fluorescence spectra, fluorescence quantum yield, cyclic voltammetry, and ECL were obtained for each compound. The ECL experiments were set up as single and mixed systems which used tri­para-tolylamine as the source of cation radicals. Each mixed system was studied in two different solvents, which were acetonitrile and a 1:1 mixture of acetonitrile and benzene. Single systems were studied only in the acetonitrile-benzene solution. Emissions at wavelengths longer than the fluorescence …

The Kinetics Of Solvent Reorientation In Hydroxylated Solvents From The Exciting-Wavelength Dependence Of Chromophore Emission Spectra, John Milton, Robert M. Purkey, William C. Galley

WM Keck Science Faculty Papers

The disappearance of the exciting-wavelength dependence of the phosphorescence spectra of polar, aromatic chromophores in supercooled glycol–water mixtures is utilized to monitor the kinetics of solvent reorientation. Reorientation times in the nanosecond to second range are obtained for (3:2 v/v) glycerol–water and (1:1 v/v) ethylene glycol–water at 140–240 °K. The results suggest that the process is one involving a cluster of solvent molecules and in which the chromophore plays a relatively passive role. Steady-state data and direct measurements of phosphorescence shifts as a function of time indicate that the solvent reorientation process is nonexponential in nature. The decay function derived …

An Investigation Of Arsenic(V)-Catechol Complexes, Ronald P. Haak

Dissertations and Theses

There is not, at this time, a simple method for the simultaneous determination of As (III) and As (V) at trace levels. The development of such as method is needed, as the toxicities of these two species differ so greatly.

As (III) and As (V) are polarographically reducible in the presence of excess catechol, but the wave produced by As (V) is depended on time, pH and catechol concentration as well as As (V) concentration. In order to understand this behavior, determination of formation constants for any complex species present were needed to identify which species is electroactive. The literature …

Synthesis Of Crown Ethers & Stereochemistry Of 1, 4-Ditertiarybutyl-1, 4-Dihydronaphthalene, Abdolreza-H-Hossein Nejad

Masters Theses & Specialist Projects

A. Cyclization of ethylene oxide in the presence of transition metal salts was studied. Several reactions with different catalysts were tried and some of these reactions produced compounds which show only one sharp singlet in their NMR spectra. These products were also soluble in benzene. The solubility of potassium permanganate in this mixture suggests the presence of cyclic polyethers. In spite of the above observations, all attempts to liberate cyclic ethers from their metal complexes were unsuccessful.

B. In the second project, the stereochemistry of 1,4-ditertiarybuty1- 1,4-dihydronaphthalene was elucidated using ¹H and ¹³C NMR. For this purpose, other …

Magnetic Properties Of Linear Chain Systems: Metamagnetism Of Single Crystal Co(Pyridine)₂Ci₂, Simon N. Foner, Richard B. Frankel, William Michael Reiff, Herbert Wong, Gary J. Long

Chemistry Faculty Research & Creative Works

The metamagnetic behavior of the low temperature properties of single crystal Co(pyridine)₂Cl₂ is discussed. At 1.25 K oriented single crystals exhibit a two-step metamagnetic transition at applied fields ~0.8 and 1.6 kG along the b-axis, a single transition at ~0.7 kG for applied fields along the a* axis, and a single transition at ~4.2 kG for an applied field along the c axis. Just above the transition fields a moment of 2µ_B/Co atom is measured for B₀ parallel to the a* axis or b axis, and 0.4µ_B/Co atom is measured for the …

Chemiluminescence Studies Of Silicon Fluoride And Uranium Oxide, Russell A. Armstrong

Chemistry and Chemical Biology ETDs

Spectroscopic studies of the reactions of fluorine with silicon, silane and deuterated silane, and of oxygen with uranium are reported. Chemiluminescence and atomic absorption techniques have been employed to determine the kinetics, photon yields and branching ratios of the chemistry leading to the excited states of the radical SiF. The reaction of silicon vapor with fluorine occurs at nearly a gas kinetic rate (k₂=1.3 x 10^-10 cc molecule^-1 sec^-1). The overall system photon yield from the reaction of silane and fluorine to produce SiF(A➔X) and SiF(a➔X) emission were 5 x 10^-2% and …

Crown Ethers : Applications In Inorganic Synthesis, Robert L. Sundberg

Senior Scholar Papers

The ability of macroheterocyclic compounds to complex with ionic species has led to the synthesis and investigation of many multidentate macroheterocyclic species. The most stable complexes are formed between macrocyclic polyetheral ligands (crown ethers) with alkali or alkaline earth metal iona. There is an excellent correlation of the stability of these complexes with the size of the cation and the site of the cavity in the macrocyclic ligand. Additional factors, such as the basicity of the ligand and the solvating ability of the solvent, also play important roles in the stabilization of the complex. The stability of such complexes has …

Removal Of Nitrogen & Sulfur From Coal-Derived Liquids & Identification Of Nitrogen & Sulfur Compounds In Coal-Derived Liquids, Tay-Yean Lin

Masters Theses & Specialist Projects

Since all the nitrogen compounds that have been identified in coal-derived liquids in the past have been basic in character, the effect of an acid-wash on the nitrogen content of coal-derived liquids was examined. Because sulfuric acid is the cheapest of the commerical strong acids, it was the natural choice, and its use was examined in detail. The greater the concentration of the sulfuric acid used, the greater the amount of nitrogen removed. :he sulfur compounds in coal-derived liquids were not removed noticeably by extraction with sulfuric acid. Column chromatography is a possible technique for removal of nitrogen compounds. The …

The Investigation Of 3,4- Dipheny1-3- Cyclobutene-1, 2-Dione As A Precursor To A Bis-Ketene, John Dana Myers

Master's Theses

The purpose of this research is to investigate the use of 3, 4-diphenyl-3-cyclobutene-1, 2-dione as a synthetic precursor to bis-ketenes and ultimately examine the chemical behavior of this relatively unknown system. We intend to investigate some of the chemical behavior of bis-phenylketene produced by the well-documented photochemical ring opening of 3, 4-diphenyl-3-cyclobutene-1, 2-dione. Specifically the use of alkenes a chemical traps for the bis-ketene will be investigated. These reactions will be compared and contrasted to the behavior of the ketenes and vinyl ketenes.

The Photochemistry Of Alpha, Beta-Unsaturated Nitro Compounds, Liang-Wuen Chang

Masters Theses & Specialist Projects

1-(9-Anthry1)-2-nitropropene and 1-(3-pyridy1)-2-nitropropene were prepared and irradiated with ultraviolet light.

Irradiation of 1-(9-anthry1)-2-nitropropene, in which the ethylene group was twisted out of the plane of the aromatic ring and the resonance stabilization between the ethylene group and the aromatic ring was limited , gave only cis-trans isomerization.

Irradiation of 1-(3-pyridy1)-2-nitropropene gave an oxime. The effect of added HC1 on the reactivity of 1-(3-pyridy1)-2-nitropropene showed that the rate for the formation of oximinoketone was decreasing., while irradiation of 1-phenyl-2-nitropropene with HC1 showed that the rate for the formation of oximinoketone was increasing.

From these observation, steric factors and resonance factors are …

Coordination Chemistry Of Bidentate Difluorophosphines, Darrell Lynn Gallup

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The reactions of 1, 2–bis(difluorophosphino)cyclohexane, PF₂C₆H₁₀PF₂, with hexacarbonyls of Cr(O), Mo(O), and W(O) have been extensively investigated. The hexacarbonyls react, either under photolytic or thermolytic conditions, to produce carbon monoxide and oily mixtures of products of the general formulations, [M(CO)₄(PF₂C₆H₁₀PF₂C)]_x, where x varies apparently from 1 – 4. The higher values of x, corresponding to species involving bridging ligands, are more common to the photolysis rather than the thermolysis reactions. Photolysis reactions of Mo(Co)₆ with increasing amounts of the …

Studies Toward The Synthesis Of A- And B- Mercapto Alanine Derivatives, And Of A,B- And B, B- Dimercapto Alanine Derivatives, Aldean James Kolar

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

A convenient, economical, large scale synthesis of N-acetyldehydro-alanine (a-acetamidoacrylic acid) and its methyl ester was developed via a sequence of N-chlorination-dehydrochlorination. The method was extended to the synthesis of the corresponding N-benzoyl, N-phenylacetyl and N-benzyloxycarbonyl derivatives.

The conversion of a-methoxy-N-acetyl alanine derivatives to the corresponding a-mercapto alanine derivatives, using zinc chloride and an appropriate mercaptan, was investigated. Methyl a-methoxy-N-acetyl-D, L-alaninate was successfully converted to the a-acetylthio derivative, in 24% yield; however, a 90% yield could be obtained by treatment of the dehydroalanine derivative with hydrogen chloride gas in neat thiolacetic acid.

A facile conversion of the a-acetylthio derivative to the …