Physical Sciences and Mathematics Commons^™

Applications Of New Methods Of Structure Determination, Richard Earl Wagner

Electronic Theses and Dissertations

The structures of: 1) 2-piperidino-5-chlorornethyl-5-rnethyl-2- oxo-1, 3,2-dioxaphosphorinan; 2) 2-phenoxy-5-chloromethyl-5-methyl-2- oxo-1, 3,2-dioxaphosphorinan; 3) 2-p-bromophenoxy-5-chloromethyl-5- chloromethyl-5-methyl-2-oxo-1, 3, 2-dioxaphosphorinan have been resolved by x-ray single crystal studies. A Picker 4 circle diffractometer employing molybdenum x-rays and a zirconium filter was used to obtain accurate data. The space group of the first two compounds is P2₁/c while that of the third is Pca2₁. The lattice constants of the compounds are: 1) a = 10.035(8)Å, b = 6.503(4), c = 20.19(1), β = 96.8(3)°; 2) a = 6.237(3)Å, b = 11.437(5), c = 19.419(9), β = 109.95(3); and 3) a = …

A Kinetic Examination Of 1,3-Di-T-Butyl-3-Methylbromoallene Solvolysis, Dwight Ellen Foster Ellis

Dissertations, Theses, and Masters Projects

No abstract provided.

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 …

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 …

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 …

Desorption Of Phosphorus From Si (111) Surfaces, Cesar Michel Magnin

Masters Theses

"Auger electron spectroscopy and mass analysis are used as complementary methods in evaluating desorption kinetics. For phosphorus on silicon, the order of desorption and activation energies of desorption are determined from continuously monitored phosphorus Auger electron signals during heating. These measurements indicate that diatomic phosphorus dissociates when adsorbed onto clean silicon. Mass spectrometer flash desorption spectra show that at least four distinct surface bonds are associated with the desorption of phosphorus. The dominant desorbed species is diatomic phosphorus at high coverage (> 0. 1 monolayer) and atomic phosphorus at low coverage (< 0.07 monolayer)"--Abstract, page ii.

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 …

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

University Faculty Publications and Creative Works

No abstract provided.

Synthesis Of Uranium Fluorosulfates And The Group Vi B Difluorophosphates, Larry Mccain Emme

Dissertations and Theses

Some reactions leading to several anhydrous Uranium fluorosulfates through the use of fluorosulfonic acid or peroxydisulfuryl di-fluoride have been studied. It was found that HS0F can oxidize uranium 3metal to the +4 state or the +2 state depending on the reaction conditions. The synthesis of the tan solid; U(S0₃F)₄ and the pale green solid thought to be U(S0₃F)₂ were prepared in this manner. It was found that S₂0₆F₂ can also oxidize uranium to yield the green solid U(S0₃F)₃. S₂0₆F₂ was …

Ua66/7/2 Newsletter, Wku Chemistry

WKU Archives Records

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.

Magnetic Nonequivalence In Higher Alkyl Groups, Philip Anthony Reitano

Masters Theses

The phenomenon of magnetic nonequivalence has been growing in recent years. Unequal populations of the various conformers in such molecules are normally accepted as the cause of nonequivalence, but nuclei which are stereochemically nonequivalent are not necessarily magnetically nonequivalent. This nonequivalence has been demonstrated for molecules of the type ABDC⁸CHR₁R₂, where R + H, F, and Me. Although in principle the effect is quite general this has not been previously observed in "freely rotating" systems for groups larger than methyl. The role of steric factors, the size of the substituents and the distances between …

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.

The Wittig Reaction With Carbohydrates And The Addition Of Benzenesulfonyl Azides To Indoles, George R. Wellman

Dissertations

No abstract provided.

The Dimetalation And Subsequent Functionalization Of 1,3-Dimethylnaphthalene By Means Of Amylsodium In The Presence Of Certain Tertiary Amines, Atilla Tuncay

Masters Theses

I. Introduction

It is well known that the hydrogen atoms of a methyl group directly attached to an aromatic system are sufficiently acidic to be abstracted by suitable bases to generate the corresponding α-anion.^1,2 These monoanions have frequently served as suitable intermediates for the formation of a large variety of a-condensation products in good to excellent yields² On the other hand, attempts to obtain α,α-dianions from various dimethylaromatic systems have met with limited success.² Due to the lack of sufficiently strong bases, dimetalation products were obtained only in poor yields even at high temperatures and prolonged reaction …

Kinetics Of The Formation Of Nickel(Ii) Complexes With N,N’-Dibenzylethylenediamine And N,N’-Bis(2-Picolyl)Ethylenediamine, Zahid Amjad

Masters Theses

No abstract provided.

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.

The Formation And Study Of Certain Bicyclic Enolate Monoanions And Dianions, Ernest William Crowe

Masters Theses

No abstract provided.

14th Annual Rocky Mountain Spectroscopy Conference

Rocky Mountain Conference on Magnetic Resonance

Program and abstracts from the 14th annual meeting of the Rocky Mountain Spectroscopy Conference, sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Denver, Colorado, July 31 - August 1, 1972.

Relation Of Aromatic Substitution Patterns To Nmr Shifts Produced Tris - (1,1,1,2,2,3,3 - Heptafluoro - 7,7, Dimethyl - 4,6 - Octanedione) Europium (Iii), Roy R. Reeves

Morehead State Theses and Dissertations

A thesis presented to the faculty of the School of Sciences and Mathematics at Morehead State University in partial fulfillment of the requirements for the Degree of Master of Science in Chemistry by Roy R. Reeves on July 27, 1972.

Relation Of Shift Magnitude Of Alkyl Substituents To Aromatic Substitution Patterns, Michael E. Evans

Morehead State Theses and Dissertations

A thesis presented to the faculty of the School of Science and Mathematics at Morehead State University in partial fulfillment of the requirements for the Degree of Master of Science by Michael E. Evans on July 27, 1972.

A Correlation Of The Idealized Heat Of Vaporization To Molecular Weight, Harold Earl Bennett

Master's Theses

Using the Clausius-Clapeyron equation as a base, many investigators have tried to develop variations to better describe both ideal and non-ideal systems. The literature is abundant with correlations of vapor pressure to temperature and associated correlations of latent heats of vaporization to molecular characteristics; often molecular weight or carbon number.

The Synthesis And Characterization Of The 2,2'-Bisacylazide Of 3,3'-Bipyridine, Magdy Adly Guirguis El-Fayoumy

Chemistry & Biochemistry Theses & Dissertations

The primary objective of this research has been the synthesis and characterization of a new heterocyclic diacylazide, the 2,2'-bisacylazide of 3,3'-bipyridine 19. This heterocyclic diacylazide has been successfully synthesized from the phenanthrolin-5,6-dione 14, and examined with regard to its.thermal and photolytic decomposition.

Thermal decomposition of this disacylazide seems to go by a double-barreled Curtius rearrangement leading to a series of pyridonaphthyridinone (20) compounds such as 22 and 29.

An initial study of the photolysis of this bisacylazide has been initiated to examine the possible formation of nitrene-type intermediates.