Physical Sciences and Mathematics Commons^™

Stereoselectivity In Bis-1 (2-Pyridyl) Ethylaminecobalt (Iii), Richard Lindsay Wellman

Honors Theses

Recently Michelsen reported the synthesis of a new series of bis-chelated cobalt (III) compounds using 2-pyridylmethylamine (pm) as a bidentate ligand.4 Replacement of a methylene hydrogen of pm with a methyl group gives the optically active compound 1-(2-pyridyl) ethylamine (pa). Model studies show that when bound to a cobalt molecule, the ligand methyl group can assume either and axial or an equatorial position. On the basis of predictions by Corey and Bailar1 using the ligand 1, 2-diaminopropane, it was thought stereoselectively might be observed in the reaction of pa with cobalt. To determine if this was so Michelsen’s reactions were …

Base Strength And Concentration Effects On Orientation In Elimination Reactions, Frederick Norman Preuninger

Honors Theses

The orientation of base promoted eliminations depends on several factors including base strength and size. Neither of these factors account for all of the observed results. A new factor, ion pairing of the base, is suggested. Results of elimination reactions using sodium benzoate derivatives are found to be consistent with this explanation. Kinetic data for an ion pair mechanism were sought but not obtained.

Relative Rate Of Ozonolysis Between Symmetrical And Unsymmetrical Olefins, Wai Lum Yuen

Honors Theses

There are two theories about the mechanism of the ozone-olefin reaction. One is that ozone makes a one-step four-center attack on the olefin to form a primary ozonide. Another theory is that ozone makes an electrophilic attack of the olefin to form a pi complex. The pi complex then collapses into the primary ozonide. The relative rates of reaction of a series of symmetrical and unsymmetrical olefins were determined. Gas chromatograph was used to measure the relative concentration of the various olefins before and after ozonolysis. The relative rates of ozonolysis were then calculated from the data. It was observed …

Sulfonium Salts, Aliphatic And Aromatic Diazonium Salts, Formation And Isolation, Geoffrey D. Picard

Honors Theses

An improved method for the preparation of diazonium salts was developed. Aliphatic diazonium salts were isolated for the first time. A method for their preparation was also worked out. The use of sulfonium salts as a route to deuteration of organic compounds was looked into.

Synthesis Of New Antimicrobial Agents, Michael John Burke

Honors Theses

Two new compounds have been synthesized in sufficient quantities to be tested for antimicrobial activity.

Dielectric Constants And Pair Interactions In Polar Molecules, Kurt Walter Hillig

Honors Theses

A qualitative description of dielectric processes in Pair interactions of polar molecules is presented, discussing such factors as molecular shape and polarizability. The mathematical treatment of these interactions is given, derived from classical electric field theory and statistical mechanics. The dielectric virial equation and the meaning of the dielectric virial coefficients is discussed. Due to the small magnitude of the coefficients, one must make measurements on the gas of the molar volume to one part in 10 4 and of the dielectric constant to one part in 106 to derive values of the second dielectric virial coefficient to within 10%. …

A Facile One Step Synthesis Of Some New 2-Hydroxy-4,6-Bis Aryl S-Triazines And Related Compounds, Howard Steven Grossberg

Honors Theses

In the past few years the symmetrical triazines have developed extreme importance in biochemical research as well as importance in industrial applications. In our research we have developed a facile, one-step synthesis of a number of 2-hydroxy-4, 6-bis aryl symmetrical triazines based upon the addition of the anion of urea and an aromatic nitrile, with the aryl group including a number of halogenated benzenes, pyridine, or benzene itself. The structure of these compounds has been proved by microanalysis and by both infra-red and mass spectroscopy. The further versatility of the synthesis has also been explored, and by replacing the urea …

Spectral Studies Of 9, 1 And 2-Methyl Anthroate And 2-Anthroic Acid, Thomas Glenn Matthews

Honors Theses

The substitution of a carboxyl group on the 9, 1 and 2-positions of anthracene produces several interesting changes in the characteristic spectral properties of the parent molecule. The absorption and fluorescence spectra, and fluorescence quantum yields of these carboxyl substituted anthracene compounds proved to be very solvent and position dependent. These spectra, quantum yields and related fluorescence lifetime data were used to determine the geometry of the ground and excited states for all three molecules. In the 9-position, molecular models and spectral evidence show that the plane of the carboxyl group is perpendicular to the plane of the ring in …

Steric Effects On The Dimerization Of Alkyl Substituted Aldoketenes, Barbara Carol Pittner

Chemistry Honors Papers

This 34 page thesis uses nmr spectral absorption to examine product yields in reactions of isovaleryl chloride and t-butyl acetyl chloride.

The Reaction Of Dimethyl-And Di-N-Butylcopper Lithium With 3-Bromo-2-(2-Phenylacetamido) Acrylic Acid, Kim David Richards

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The reaction of dimethylcopper lithium and di-n-butylcopper lithium with 3-bromo-2-(2-phenylacetamido) acrylic acid, mp 174 - 175°, produced as major products 3-methyl-2-(2-phenylacetamido) acrylic acid and 3-n-butyl-2-(2-phenylacetamido) acrylic acid, respectively. The dimethylcopper lithium reaction was stereospecific for the E geometrical isomer, mp 198 - 199°, and produced 3-methyl-2-(2-phenylacetamido) acrylic acid and 2-(2-phenylacetamido) acrylic acid in a 3:1 molar ratio, respectively. The di-n-butylcopper lithium reaction produced as the main products 3-n-butyl-2-(2-phenylacetamido) acrylic acid and 2-(2- phenylacetamido) acrylic acid in a 7:1 molar ratio, respectively, with the 3-n-butylacrylic acid comprising 83% of the product. The reaction …

Studies In Transition Metal Chemistry, Steven David Brown

Dissertations and Theses

The electronic and vibrational spectra of liquid chromium pentafluoride have been investigated. They were found to be consistent with a d¹ system that is extensively fluorine-bridged at room temperature. The vibrational spectra were not consistent with C_4v or D_3h monomers.

Close Coupling Test Of Classical And Semiclassical Cross Sections For Rotationally Inelastic Ar-N2 Collisions, Russell T. Pack

Faculty Publications

Accurate quantum mechanical close coupling (CC) integral cross sections are reported for rotationally inelastic Ar-N2 collisions at room temperature using an empirical intermolecular potential. These cross sections are used to test the infinite order sudden (IOS) approximation and the results of several methods [classical trajectories (CT), full sudden (SA), generalized phase shift (GPS), and classical limit generalized phase shift (CGPS)] as reported in the preceding paper by Pattengill. The IOS approximation works very well for cross sections involving low rotational states. The CT method works well for all the cross sections examined, justifying the popular belief that the rotational motion …

Double Beta Decay Of ¹²⁸Te, Edward W. Hennecke, Oliver Manuel, Dwarka D. Sabu

Chemistry Faculty Research & Creative Works

The half-life of ¹²⁸Te relative to the half-life of ¹³⁰Te has been found to be t12128t12130=(1.59±0.05)×10³ by measurement of the ββ-decay products, ¹²⁸Xe and ¹³⁰Xe, in a geologically old (2.4×10⁹ yr) telluride ore. These results yield an upper limit on the lepton nonconservation parameter, η≤0.8×10^-4. RADIOACTIVITY ββ-decay ¹²⁸Te; measured T_1/2=1.5×1024 yr; deduced η≤0.8×10^-4. Detected excess ¹²⁸Xe in old Te ore.

Composition, Time, And Size Distributions Of Airborne Particulate Material In Utah Valley, Douglas R. Lawson

Theses and Dissertations

The Lundgren impactor is used to determine the variations in time and size distributions of particulate matter in Utah Valley. Charged particle X-ray fluorescence is employed in this study to determine elemental concentrations. Air samples are taken during two 24-hour periods in downtown Provo, 24 hours near U.S. Steel Corporation, Geneva Works, and 12 hours at Lindon Elementary School, and diurnal particulate variations are compared. The amounts of lead and bromine are four times greater on a weekday than on a Sunday in downtown Provo, suggesting the effect of the automobile on atmospheric particulate concentrations. Paraffin coated impaction surfaces are …

The Kinetics And Mechanism Of A Free Radical Decay In Aqueous Solution, Denzel Lee Fillmore

Theses and Dissertations

The decomposition of nitrosyl disulfonate ion was studied in strongly alkaline solution of 10-2 to 5 m sodium hydroxide. The decomposition was found to be first-order in both hydroxide and nitrosyl disulfonate ions. A multi-step mechanism involving sulfite ion, sulfite ion radical and nitrosyl monosulfonate ion radical as intermediates was proposed, with the initiating step being the SN2 replacement of a sulfite ion by a hydroxide ion. The rate constant for the initiating step ranged from 1.2 x 10-7 to 2.25 x 10-5 M-1s-1 for the solution concentration range of the study. The products of the decomposition were identified as …

Development Of Proton-Induced X-Ray Emission Techniques With Application To Multielement Analyses Of Human Autopsy Tissues And Obsidian Artifacts, Kirk Kay Nielson

Theses and Dissertations

A method of trace element analysis using proton-induced X-ray emission (PIXE) techniques with energy dispersive X-ray detection methods is described. Data were processed using the computer program ANALEX. PIXE analysis methods were applied to the analysis of liver, spleen, aorta, kidney medulla, kidney cortex, abdominal fat, pancreas and hair from autopsies of Pima Indians. Tissues were freeze dried and low temperature ashed before analysis. Concentrations were tabulated for K, Ca, Ti, Mn, Fe, Co, Ni, Cu, Zn, Pb, Se, Br, Rb, Sr, Cd and Cs and examined for significant differences related to diabetes. Concentrations of Ca and Sr in aorta, …

A Comparative Investigation Of Mammalian Serine Transhydroxymethylases, Sanha Panichajakul

Theses and Dissertations

Serine transhydroxymethylase was purified one thousand-fold from bovine brain and one hundred and twenty-fold from bovine liver. Both enzymes were yellow due to the presence of the coenzyme pyridoxal 5'-phosphate. Polyacrylamide gel electrophoresis of the liver enzyme showed one major band containing 95% of the protein, while in the case of the brain enzyme two major bands of nearly equal intensity were observable. The specific activity of the crude liver enzyme was about sixty times higher than that of brain. The liver enzyme was also more heat stable than the brain enzyme. The purified enzymes exhibited L-allothreonine and L-threonine aldolase …

Localized Orbital Studies Of Hydrogen Bonding. Ii. Dimers Containing H 2 0, Nh 3, Hf, H 2 Co, And Hcn, Mark S. Gordon, Dennis E. Tallman, Cathy Monroe, Michael Steinbach, Jill Armbrust

Mark S. Gordon

INDO localized molecular orbitals (LMO's) are utilized for investigating the nature of intermolecular hydrogen bonding in the fully geometry optimized dimers (HFh, (Hz0)2, (NH3)2, FH-OH2, HOH-FH, FH-NH3, H 2NH-FH, H20-HNH2, HOH-NH3, HCN-HF, and HzCO-HF. The results suggest that a reasonable measure of relative hydrogen bond strengths should be the intra bond, two-center, one-electron interference energy connecting the acceptor atom and donated proton. This approach views the net stabilization energy of a hydrogen bonded dimer as arising from a large energy decrease due to formation of the hydrogen bond, modified by smaller energy increases due to internal decreases in monomer bond …

Photochemical Behavior Of Some Nitrogen Heterocyclics, James Wesley Harris

Master's Theses

The compounds, 3,6-dimethoxypyridazine, l,2-dimethyl- 3,6(1H,2H)-pyridazinedione, and 6-methoxy-2-methyl-3(2H)­ pyridazinone, were prepared by using reported preparations. Their photochemistry was investigated and compared to the thermal chemistry and photochemistry of maleic hydrazide.

Piericiden A Sensitivity, Site 1 Phosphorylation, And Reduced Nicotinamide Adenine Dinucleotide Dehydrogenase During Iron-Limited Growth Of Candida Utilis, John G. Cobley, T. P. Singer, H. Beinert, S. Grossman

Chemistry Faculty Publications

It has been reported that cells of Candida utilis, grown in continuous culture under iron-limited conditions, develop site 1 phosphorylation, without the appearance of piericidin sensitivity and without changes in the iron-sulfur centers of NADH dehydrogenase, on aeration in the presence of cycloheximide, as well as on increasing the supply of iron during growth. These findings were reinvestigated in the present study. The parameters and properties followed during these transitions were sensitivity of NADH oxidation to piericidin, presence or absence of coupling site 1, EPR signals appearing on reduction with NADH or dithionite, the specific activities of NADH oxidase, NADH-ferricyanide …

Progress In Extractive Metallurgy, Volume 1. Review By G.N. Dobrokhotov, Fathi Habashi

Fathi Habashi

Review of the first volume of Progress in Extractive Metallurgy edited by Fathi Habashi and published by Gordon & Breach in New York in 1975. The review was written by Professor Dobrokhotov at the Leningrad Mining Institute.

Properties Of Intercalated 2h-Nbse2, 4hb-Tas2 And 1t-Tas2, S. F. Meyer, R. E. Howard, G. R. Stewart, Juana Vivó Acrivos, T. H. Geballe

Faculty Publications, Chemistry

The layered compounds 2H-NbSe, 24Hb-TaS, 2and 1T-TaS2 have been intercalated with organic molecules; and the resulting crystal structure, heat capacity, conductivity, and superconductivity have been studied. The coordination in the disulfide layers was found to be unchanged in the product phase. Resistance minima appear and the superconducting transition temperature is reduced in the NbSe2 complex. Conversely, superconductivity is induced in the 4Hb-TaS2 complex. Corresponding evidence of a large change of the density of states, negative for 2H-NbSe2 and positive for 4Hb-TaS2, was also observed upon intercalation. The transport properties of all the intercalation complexes show a pronounced dependence upon the …

The Lippmann Equation And The Ideally Polarizable Electrode, Jean- Pierre Badiali, Jerry Goodisman

Chemistry - All Scholarship

The Lippmann equation for the ideally polarizable interface is normally derived by thermodynamics, using the Gibbs dividing surface. Therefore, the quantities appearing in the Lippmann equation can have no reference to the actual charge distribution in the interfacial region. For example, the quantity referred to as surface charge is actually a sum of surface excesses, rather than the integral of a true charge density. In this article we derive, by statistical mechanical methods, the Lippmann equation for a model at the molecular level, thus giving a precise physical definition to all quantities which appear. First, we derive the conditions for …

Principles Of Radioisotope Methodology, Gary Rothwell

Honors Theses

This honors project was designed for familiarization with modern instrumentation and experimentation methods for radioisotope detection and energy calculations. The two main instruments I studied were the Geiger-Mueller Counter and a single channel pulse height analyzer. This report will include a brief history of radiation and a description of the more important types. Next is a description of the two instruments mentioned and some simple experiments I conducted using them.

A Piagetian Approach To General Chemistry, Donald W. Beistel

Chemistry Faculty Research & Creative Works

No abstract provided.

Process Control Of Activated Sludge Treatment, Phase Ii, Richard I. Kermode, Robert W. J. Brett, Joseph D. Pault Jr.

KWRRI Research Reports

Material balances on substrate and microorganisms were derived in conjunction with various mixing configurations thought to accurately describe the activated sludge process. These models include the completely mixed with bypass, plug flow, and plug flow with bypass. Two sets of kinetic mechanisms for substrate utilization and bacterial growth were employed.

A feed forward controller was designed from linear approximations of the material balances derived in the completely mixed with bypass mixing model. Utilizing frequency response methods, the controller was found essentially identical to a completely mixed modeled controller developed in a prior investigation.

Through computer simulation the controller's effectiveness was …

Interactions Of Rhenium(V) Chloride And Oxotrichlorobis(Triphenlyphosphine)Rhenium(V) With Selected Solvents, Paul Luther Holm

Electronic Theses and Dissertations

The purpose of this study was to examine the solution interactions of rhenium(V) chloride and oxotrichlorobis(triphenylphosphine)rhenium(V) in a continuation of studies of rhenium(V) chemistry. These goals were accomplished using vacuum line and Schlenk tube techniques. As a result of this work, rhenium(V) chloride was found to dissolve with reaction in 1, 4-dioxane, diethyl ether and acetone. There was only a very small amount of rhenium(V) chloride which dissolved in carbon tetrachloride, chloroform and cyclohexane. Part of what did dissolve was shown by electronic and infrared spectroscopy to be oxotetrachlororhenium(VI) which was present as an impurity in small amounts. Oxotetrachlororhenium(VI) reacts …

Mechanistic Studies Of Alkylation Of Cobalt(I) By Cyclopropyl Derivatives, Lailing Magdalene Soong

Masters Theses

A second order nucleophilic substitution reaction with retention of configuration is predicted by Ugi and co-workers if electrophiles such as cyclopropyl, cyclobutyl, or cyclopentyl derivatives undergo substitution under conditions where the S_N2 process is faster than the competing S_N1 process.

A synthesis of both cis and trans-7-chlorobicyclo [4.1.0] heptane from olefin and dichlorocarbene is described. The compound, bicyclo [4.1.0] heptylpyridine [bis(salicylaldehyde)ethylenediiminato] cobalt(III), which contains an alkylcobalt σ-bond, is obtained from the reaction of pyridine [bis(salicylaldehyde)ethylenediiminato] cobalt(I) and 7-chlorobicyclo [4.1.0] heptane. The great light sensitivity of this compound has prevented its isolation in purity sufficient for nmr …

Reactions Of Tungsten Carbonyl Complexes Containing Diphenylvinylphosphine, George S. Leotsakos

Masters Theses

A new synthetic route for the production of the tungsten carbonyl complex (OC)₅WPPh₂CH₂CH₂PPh₂ has been discovered. It has been found that lithiumdiphenylphosphide reacts with diphenylvinylphosphinepentacarbonyltungsten(0) in tetrahydrofuran to produce upon hydrolysis a good yield of the pentacarbonyl product […]. No evidence for the formation of secondary products was noted nor was there evidence for preferential attack of the carbonyl group by LiPPh₂ to form a carbene complex.

Diphenylvinylphosphinepentacarbonyltungsten(0) (mp 62-64°C), was prepared for the first time by two different methods.

I. Displacement of aniline from anilinepentacarbonyltungsten(0) complex with diphenylvinylphosphine.

II. …

Properties Of Hxtas2, D. W. Murphy, F. J. Disalvo, G. W. Hull, J. V. Waszczak, S. F. Meyers, G. R. Stewart, S. Early, Juana Vivó Acrivos, T. H. Geballe

Faculty Publications, Chemistry

The preparation of Hx TaS2 (0 < x < 0.87) is described. The compounds are only marginally stable at room temperature, slowly evolving H2S and H2 (and possibly Hp in air). Magnetic susceptibility data show that a low temperature transformation in 2H ... TaS2 (at so•K) is suppressed with the addition of hydrogen, and· at the same time the superconducting transition temperature T c rises from 0.8 to ~4.2•K at x = 0.11. Heat capacity measurements near this concentration show the superconductivity to be a bulk effect. Finally, by correlation of this data with susceptibility and T c measurements in other intercalation compounds, we suggest that the rise of T c (at low electron transfer) is due to suppression of the low temperature transformation and not due to an excitonic mechanism of superconductivity.