Digital Commons Network^™

The Isolation And Purification Of A Fluorescent Compound From Pseudomonas, Thomas M. Davey

Masters Theses

Fluorescence in certain land snails has been found to arise from a bacteria carried by the snails. The bacteria, a genus of Pseudomonas, produce a pigment complex in iron-deficient media. The pigment complex consists of both fluorescent and non-fluorescent pigments. One of the fluorescent compounds was isolated and purified by paper chromatography using several different solvent systems.

Absorption and fluorescent spectra of the compound at a number of pH values were measured and the changes with pH of both the intensity and the color of the fluorescence were observed. The purified compound was ninhydrin negative but after acid hydrolysis …

Mechanistic Studies Of Cobalt Super Nucleophiles, Audrey Yeh Ku

Masters Theses

A study was initiated on the hypothesis, by Ugi and co-workers, that cyclopropyl, cyclobutyl, and cyclopentyl electrophiles might undergo nucleophilic substitution reactions with retention of configuration.

A simple, high yield synthesis of both cis and trans-2-phenylcyclopropyl chlorides from styrene and chloroform is described. Reaction of each of these alkylating agents with the very nucleophilic cobaloxime super-nucleophile ultimately gave peroxy compounds which appear to arise from insertion of oxygen into the carbon-cobalt bond.

Neither trans-2-phenylcyclopentyl tosylate nor trans-2-phenylcyclohexyl tosylate would alkylate low valent cobaloximes under standard conditions.

A partial synthesis of the 2-phenylcyclobutyl tosylate is described along with suggestions for future …

Synthesis And Chemistry Of Thione-Iron Carbonyl Complexes, Albert Shil-Kwan Chan

Graduate Dissertations and Theses

The first examples of sulfur-donor ligand ortho-metallated complexes were obtained in good to excellent yields by reaction of various thiobenzophenones and a thiobenzoate with diiron enneacarbonyl in benzene at room temperature. The known trinuclear complex S₂Fe₃(CO)₉ was a by-product of these reactions, and complexes of the type (Ar₂C)S₂Fe₂(CO)₆ were formed in several instances. The structures of these complexes were established on the basis of microanalytical and spectral data as well as by reductive cleavage experiments. Oxidative or photolytic cleavage of the ortho-metallated complexes provides a convenient …

Provocative Opinion: Chemistry Is Real And Relevant - Let's Teach It As Such, Enno Wolthuis

University Faculty Publications and Creative Works

No abstract provided.

Oxidation Of Thin Silver Films By Ozone And Atomic Oxygen, Lawrence R. Thorne

Undergraduate Honors Capstone Projects

Recently, thin silver film detectors have been used to determine atomic oxygen profiles in the 70-100 km region of the upper atmosphere. The detectors' sensitivity to atomic oxygen is the result of the formation of silver oxide(s) which cause their electrical resistance to increase. A common procedure to calibrate and to make these detectors more sensitive is to cycle them through a series of three or more oxidations and reductions. This paper indicates that this cycling makes silver films more sensitive to ozone, causing them to be usable only at heights greater than 38 km. Also reported herein are experimentally …

The Atomic Absorption Determination Of Ultra-Trace Tellurium In Rocks Utilizing High Sensitivity Sampling Systems, Richard D. Beaty

Doctoral Dissertations

"The sampling boat and the graphite furnace have been shown to possess the required sensitivity to detect tellurium at ultra-trace levels, in a variety of sample types, by atomic absorption. In the sampling boat approach, tellurium in sample solutions is chemically separated and concentrated by extraction into methyl isobutyl ketone before measurement. For samples exhibiting extraction interferences or excessively high background absorption, a preliminary separation of tellurium by coprecipitation with selenium is described. Using this technique, tellurium can be quantitatively detected down to 5 nanograms and linear response is observed to 100 nanograms. Relative standard deviations of better than 7% …

Anionic Polymerization Of A Series Of 5-Membered Cyclocarbosiloxanes, Balaraman Suryanarayanan

Doctoral Dissertations

"A study has been made on the anionic polymerization of a series of 5-membered cyclocarbosiloxanes with methyl and/or phenyl substituents. The polymerization was initiated by lithium n-butyldiphenylsilanolate in the presence of tetrahydrofuran. Six 5-membered cyclocarbosiloxanes (2,2,5,5-tetramethyl-1-oxa-2,5-disilacyclopentane; 2,2,5- trimethyl-5-phenyl-1-oxa-2,5-disilacyclopentane; 2,5-dimethyl-2,5-diphenyl- 1-oxa-2,5-disilacyclopentane; 2,2-dimethyl-5 ·,5-diphenyl-1-oxa- 2,5-disilacyclopentane; 2-methyl-2,5,5-triphenyl-1-oxa-2,5-disilacyclopentane; 2,2,5,5-tetraphenyl-1-oxa-2,5-disilacyclopentane) were synthesized. Since the chemical shifts of the protons of the cyclic monomers and the polymers formed were different, the rate of polymerization of the cyclic monomers was measured utilizing an NMR spectrometer. The effects of tetrahydrofuran concentration, initiator concentration and water concentration on the rate of polymer formation and on the molecular weight of …

Approaches To The Synthesis Of Azabullvalene, Thomas Rudolph Steinheimer

Doctoral Dissertations

"Three approaches to the synthesis of the heretofore unknown azabullvalene, the pi electron equivalent heterocyclic congener of bullvalene itself, are described. Two of the schemes are based upon the assumption that the most convenient method for the introduction of the nitrogen atom is via thermal rearrangement of the appropriate azide.

The first involved the generation of the homobarrelene carbon skeleton and sub sequent decomposition of its azide. This compound arises formally as the product of the Diels-Alder addition of acetylene to the bicyclic valence isomer of tropyl azide (cyclohepta-1, 3, 5- trienyl-7-azide). In order to achieve this goal, Diels-Alder additions …

A Study Of The Pulse-Height Response Of Silicon Surface-Barrier Detectors To High-Energy Heavy Ions, Gregory Dan Smith

Doctoral Dissertations

"The pulse-height defect (PHD) of high-energy heavy ions in silicon surface-barrier detectors can be divided into three components: (1) energy loss in the gold-surface layer, (2) a nuclear-stopping defect, and (3) a defect due to recombination of electron-hole pairs in the plasma created by the heavy ion. The plasma recombination portion of the PHD was the subject of this study using the variation of the PHD with (1) the angle of incidence of incoming heavy ions, and (2) changes in the detector bias. The Tandem Van de Graaff accelerator at Argonne National Laboratory was used to produce scattered beam ions …

Pmr Spectra Of The 4-Alkylnitrobenzenes, Donald W. Beistel, Hsin-Liang Chen

Chemistry Faculty Research & Creative Works

Evidence of first-order alkyl-ring proton coupling is reported for the 4-alkylnitrobenzenes. Typical coupling constants of 0.7 Hz and 0.3 Hz were found for α-alkyl coupling with the ortho and meta ring protons, respectively, when the alkyl function was methyl, ethyl, and isopropyl. No β-alkyl coupling with ring protons was observed for the ethyl, isopropyl, or t -butyl groups, suggesting that the magnitude of the coupling constant is vanishingly small.

The Synthesis And Spectroscopic Properties Of Vanadium(Iii) Squarate Trihydrate, S. M. Condren, Hector O. Mcdonald

Chemistry Faculty Research & Creative Works

Vanadium(III) squarate trihydrate has been prepared; and the infrared, X-ray diffraction, and electronic spectra of the complex indicate that the central metal atom is in a slightly distorted octahedral field. A thermogravimetric study has shown that the complex loses three water molecules upon heating. A hydroxy-bridged, dimeric structure has been proposed from these data. © 1973, American Chemical Society. All rights reserved.

Adsorption Of Water On Gold, Jean-Marc Louis Deschanel

Masters Theses

"Water adsorption isotherms on gold films were measured with a quartz crystal microbalance. Two gold films were studied: a "dirty" gold film contaminated by approximately one monolayer of carbon, and a "clean" gold film prepared by evaporating gold from a heated tungsten wire under high vacuum.

Water was found to chemisorb on both films according to a Freundlich type adsorption isotherm. Isosteric heats of adsorption were computed from the isotherm data. On the "clean" gold surface the isosteric heat showed a logarithmic decrease with increasing water coverage. The highest measured value for the heat of adsorption was 35 kcal mole …

Scavenging Of Atmospheric Particles By Water Drops, Ming-Shian Wu

Doctoral Dissertations

"In the first paper, the mechanisms of particle capture and coalescence of aerosols by a moving water drop in the atmosphere are studied using the boundary-layer flow approximation. The particle trajectory is computed by solving the equations of motion of the particle both outside and inside the boundary layer using the Adams-Moulton method. The grazing trajectory is found by a trial-and-error technique. The collision and collection efficiencies of scavenging due to particle inertia and to the velocity gradient of the flow field are then computed for water drops ranging from 0.1 to 1.0 mm in radius and for particle of …

A Computer-Oriented Course In Chemical Spectroscopy, D. (Donald) W. Beistel

Chemistry Faculty Research & Creative Works

No abstract provided.

Some Aspects Of Mercury Accumulation By The Purple Shore Crab Hemigrapsus Nudus Dana (Crustacea: Decapoda), Ralph Gene Swanson

University of the Pacific Theses and Dissertations

The present study has attempted to investigate some of the more basic questions concerning the toxicity and accumulation of mercury in the purple shore crab, Hemigrapsus nudus. This rocky intertidal denizen is found in abundance along the entire Pacific coast of the United States from Sitka, Alaska, to the Gulf of California where it dominates the mid-tide pool region. Local specimens were collected just north of the Pacific Marine Stations, Dillon Beach, Marin County, California. The animal is hearty and can be kept in a state of good health for long periods of time in the laboratory with minimum care …

The Effect Of Organic Solvents On The Sensitivity Of Rare Earths Atomic Absorption, Keith A. Geiken

Dissertations and Theses @ UNI

Atomic absorption of the rare earths erbium, europium, and dysprosium was studied in 10% organic solvent-water systems, water miscible solvent-water systems, and in 100% solvent solutions of the metal acetylacetonates. Sensitivity was found to depend on the solvent system used and instrument parameters. All solvent systems used enhanced absorption, with (1) higher number of carbon atoms, (2) tertiary and secondary alcohols, and (3) high boiling point solvents producing the largest increase in absorption. No significant viscosity relationships existed in the 10% solvent-water systems for either miscible or partially soluble solvents; however, viscosity might have been a factor in absorption in …

A Study Of The Ability Of Surface Active Materials To Increase The Evaporation Rates Of Small, Freely Falling Water Drops, David Alan Sierawski

Masters Theses

"The evaporation rate at 30°C of water droplets partially covered by surface active materials (SAM) were determined. While two of the SAM were studied at a single dew point depression (ΔT_DP), seven others were examined over a range of ΔT_DP values. It was found, by comparison with pure water drops under identical conditions, that SAM increases the evaporation rate as compared to the rate of an uncontaminated drop. The lack of effect of the hydrophobic chain length and the possible effect of the hydrophilic group on this phenomenon are discussed. The explanation proposed is that at 30°C …

Photochemical Rearrangements Of 6/5 -Fused Cross-Conjugated Cyclohexadiensnes In Protic Solvents, Drury Caine, John T. Gupton, Ko Ming, William J. Powers Iii

Chemistry Faculty Publications

Irradiation of the ring A unsubstituted 6/5-fused cross-conjugated cyclohexadienone (1a) and its 2-methyl derivative (1b) in methanolic acetic acid yields, in addition to other products, novel tricyclononane derivatives which have been assigned the structures (3a) and (3b).

The Preparation And Characterization Of The Palladium(Ii) And Platinum(Ii) Chelates Of Three Cyclic Tertiary Amino Acids., Floyd Michael Hogue

University of the Pacific Theses and Dissertations

The purpose of this study was to prenare and characterize the palladium (II) and platinum (II) chelates of 1-pyrrolidineacetic acid, 1-piperidineacetic acid, and hexahydro-1-azepineacetic acid.

The ligands were prepared by reacting the cyclic secondary arnines (pyrrolidine, piperidine, and hexahydroazepine) with sodium chloroacetate. The resulting cyclic tertiary amino acids were saponified and, finally, converted to the hydrochloride salts by neutralization with hydrochloric acid.

The chelates were prepared by adding 1.0 millimole of K₂PdC1₄ or K₂PtC1₄ to a solution made by dissolving 2.0 Millimoles of amino acid hydrochloride in 25 ml. of water. The pH was …

Formation And Kinetics Of Dissociation Of Some Pentaaquotrihalomethyl Chromium(Iii) Ions., Sher Khan Malik

University of the Pacific Theses and Dissertations

The present.study was an investigation of the formation and kinetic stability of store complexes contain.ir)ing a chromium-carbon bond in an aqueous medium. An orange-brown pentaaquotrifluoromethylchromium(III) ion was obtained by the reduction of trifluororrethyl iodide with Cr(II) and is the most inert of any organochrotnium(III) complex known. The initial aquation rates of trifluoromethylchromium(III) ion were described by the differential rate law -dln [(H₂O)₅CrCF₃²⁺]/dt = k_{o + k1(H⁺)}

The products of the initial reaction were hexaaquochromium (III), carbon monoxide and HF. The values of k_o and k₁ at …

Ua66/7/2 Newsletter, Wku Chemistry

WKU Administration Documents

Newsletter created by and about the WKU Chemistry department.

Acidities In Ethanol/Water Solvents: The Pka Of Hf, Raymond M. Merrill

Chemistry and Chemical Biology ETDs

The acidity of hydrofluoric acid in mixed ethanol/ water solvent systems was studied by determining the pKa of HF in a number of different ethanol concentrations. The effect of changing temperature on the acidity of HF in these media was also examined. The pKa's were determined using a lanthanum fluoride membrane Fluoride Specific Ion Electrode and a glass pH electrode versus the same reference electrode. The method eliminates the need to determine liquid junction potentials. By determining the pKa for HF in each ethanol/water mixture, at a number of different temperatures, thermodynamic parameters, such as free energy, enthalpy, entropy, and …

The Effect Of Stereoelectronic Control And Long Range Interaction On The Stability Of Bicyclic Enolate Anions, Edwin M. Van Dam

Dissertations

No abstract provided.

Distribution Of Mass And Charge In The Spontaneous Fission Of ²⁴⁴Cm, K. F. Flynn, B. Srinivasan, Oliver Manuel, Lawrence Elgin Glendenin

Chemistry Faculty Research & Creative Works

The distribution of mass and charge in the spontaneous fission of ²⁴⁴Cm has been investigated by radiochemical and mass spectrometric determination of the fission yields for 40 mass chains and 2 shielded nuclides (independent yields). The mass distribution is highly asymmetric with a relative probability of asymmetric-to-symmetric fission (peak-to-valley ratio) of greater than 5700. The average masses of the light and heavy groups are 103.1 and 138.7, respectively. The characteristics of the mass distribution, as well as the division of nuclear charge indicated by the independent yields of the two shielded nuclides, are consistent with the systematics established from …

On Improved Wkb (Uniform Asymptotic) Quantum Conditions, Dunham Corrections, The Langer Modification, And Rkr Potentials, Russell T. Pack

Faculty Publications

An improvement to the WKB quantum condition for the rotation-vibration levels of diatomic molecules, known empirically to give RKR potentials of increased accuracy and to account for the Dunham correction Y00, is derived using uniform asymptotic methods. The role of the Langer transformation in this problem is also discussed.

Observation Of Excitons In A Molecular Liquid: Specular Reflection Spectrum Of Α -Methylnaphthalene, Craig J. Eckhardt, Leo F. Nichols

Craig J. Eckhardt Publications

The normal-incidence specular-reflection spectrum of liquid α-methylnaphthalene was obtained for the wavelength region from 215 to 400 nm. Comparison of the Kramers-Kronig transform of the reflection spectrum with the absorption spectrum of α-methylnaphthalene is cyclohexane shows the bands of the neat-liquid spectrum shift to lower energy and display significant broadening. These effects support the existence of excitons in molecular liquids.

Dipole Moments In Thomas-Fermi-Dirac And Thomas-Fermi Theories., Jerry Goodisman

Chemistry - All Scholarship

It is shown that the electronic contribution to the dipole moment, calculated from a solution to the Thomas—Fermi—Dirac or Thomas—Fermi equations, should be equal and opposite to the nuclear contribution. Thus, the Thomas—Fermi—Dirac and Thomas—Fermi theories predict vanishing dipole moments for all molecular systems.

Kinetics Of The Cope Rearrangement Of 3,4-Diphenylhexa-1,5-Diene, Harlan Albert Jerome Berg

Dissertations and Theses

Kinetics investigations of the thermal Cope rearrangement of meso- and dl-3,4-diphenylhexa-1,5-dienes were undertaken in order to gain information about the transition states for these reactions by determining the appropriate enthalpies and entropies of activation. Of particular interest were the activation parameters for the meso compounds' rearrangement as it represents the only known example in which both four- and six-centered transition states are of comparable energy.

Kinetics of the dl isomers' rearrangement in the temperature range 90-110° were determined using 5 X 10^-5 M solutions of the olefin in heptane contained within sealed Pyrex ampules. Extents of reaction …

The Reactions Of Sodium Naphthalenide With Carbonyl Compounds And Esters, Manhar Vora

Masters Theses & Specialist Projects

The purpose of this investigation was to study the reactions of sodium naphthalenide with various carbonyl and acyl compounds. J. W. Stinnett, Jr. investigated aspects of the reactions of carbonyl compounds and that study was expanded. The major emphasis, however, was to extend the investigation to the reactions of esters. With regard to the reactions of esters, it was thought that sodium naphthalenide might provide a synthetic advantage, as compared to the sodium metal solutions, in the reduction of the acyl compounds to their corresponding acyloins.

Principles Of Control Theory As Applied To A Thermostat, Joseph Peter Stidham

Master's Theses

The recent development of solid state electronics has opened new possibilities in instrumentation design. One development has been the availability of compact, low cost, high gain, D. C. amplifiers which can be used in the design and construction of sensitive laboratory instruments (11). Using these amplifiers a thermostat capable of precise control can be constructed and its performance compared with the performance expected by an analysis of the closed loop control equations.