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Part I. Thermodynamic Acidities Of Substituted Phenylacetylenes. Part Ii. Mercury Accumulation In Trout Of Southern Missouri, Eric T. Lloyd

Masters Theses

"PART I: THERMODYNAMIC ACIDITIES OF SUBSTITUTED PHENYLACETYLENES The thermodynamic acidities (pKa) of phenylacetylene and several para substituted phenylacetylenes in methanol were determined at 25ºC. These acidity constants were determined using a quenching technique which involves converting the phenylacetylenic anion, present at equilibrium as sodium phenylacetylide, to the tritium labelled carbon acid. By liquid scintillation counting techniques, the concentration of the anion was determined and the pKa of the phenylacetylene compound calculated. The resulting pKa's are: p-nitrophenylacetylene, 17.98, p-bromophenylacetylene, 18.10, p-fluorophenylacetylene, 18.14, phenylacetylene, 18.50, and p-methylphenylacetylene, 18.60. The effect of a substituent in the para position on the relative acidities is …

Synthesis Of Tcne And Tcnq Derivatives And The Preparation Of Conducting Polymers, Michael L. Runge

Theses and Dissertations

Tetracyanoethylene and tetracyanoquinodimethane were reacted with various N,N-dimethyl-a, w-alkyldiamines to produce TCNE and TCNQ diamino and monoamino derivatives. NMR and ir spectra of the monoamino derivatives, 1-(N,N-dimethyl-a,w-alkyldiamino)-1,2,2-tricyanoethylenes and 7-(N,N-dimethyl-a,w-alkyldiamino)-7,8,8-tricyanoquinodimethans, indicated that these compounds exhibited strong nitrogen-hydrogen-nitrogen intramolecular hydrogen bonding. This phenomenon was corroborated by molecular weight and preliminary x-ray analyses.

The 1,1-bis(N,N-dimethyl-a,w-alkyldiamino)-2,2-dicyanoethylene and 7,7-bis(N,N-dimethyl-a,m-alkyldiamino)-8,8-dicyanoquinodimethan derivatives were polymerized with a,m-alkyldibromides containing two to six methylene groups to produce the corresponding ionene polymers. Viscosity measurements of the polymers indicated that the TCNE copolymers were generally of higher molecular weight than the corresponding TCNQ copolymers.

The two polymer series were treated with lithium …

Studies On Glyoxalase-I, Liang-Po Bebe Han

Chemistry and Chemical Biology ETDs

Glyoxalase-I has been purified 3000-fold from rat erythrocytes by a procedure employing chloroform-ethanol fractionation and chromatography on CM-Sephadex, Sephadex G100, and DEAE-Sephadex. Two major chromatographically distinct glyoxalase-I activity peaks (designated Form I and Form II) were resolved when a shallow linear salt gradient was used on a DEAE-Sephadex A50 column. Form I showed a specific activity of 861 I.U./mg protein and Form II showed a specific activity of 783 I.U./mg protein although neither was purified to homogeneity. Form I and Form II were distinguishable by disc polyacrylamide gel electrophoresis but indistinguishable kinetically. Rat erythrocyte glyoxalase-I was shown to be similar …

A Precipitation Model And Experimental Correlation With Various Properties Of Pentaerythritol Tetranitrate, Thomas Rivera

Chemistry and Chemical Biology ETDs

A continuous precipitation method for the preparation of crystalline pentaerythritol tetranitrate (PETN) has been developed. The process involves the precipitation of PETN from an acetone solution by the addition of water in a static mixer. The principal independent variable is the ratio, R, of the acetone-PETN solution flow rate to the flow rate of water.

A mathematical model based on dispersed plug-flow equations adequately represents the physical process. The relationships developed can be used to predict particle size distributions, two explosion properties of PETN, and estimate the effective kinetics involved in the precipitation process. The mass-weighted mean particle size, L, …

A Study Of Selected Variables For Prediction Of Success And Placement In General Chemistry At Western Michigan University, Stephen M. Yekeson

Dissertations

Chapter I

The Problem

Introduction

The traditional philosophy that a college-or a university is an exclusive institution in which only highly selected individuals receive a concentrated training in the traditional liberal arts no longer exists. In America, for instance, as early as 1870, Harvard, the colonial college with a narrow curriculum, was transformed rather rapidly into a modern university with many new subjects and the elective system (Garrett, 1949). Also, since 1642, when the first entrance requirements were instituted for American higher education, a continuing debate has developed over what constitutes a sound curriculum for education. There are those who …

Rearrangements Of Stilbene And Derivatives Following Electron Impact, Gary Alan Braden

Chemistry and Chemical Biology ETDs

The electron impact generated mass spectra of ¹³C- labeled trans-stilbene, bibenzyl, trans-stilbene oxide, 1,2-dibromo-1,2-dyphenylethane, and tolan were studied. Scrambling of the molecular ion prior to fragmentation was examined, and the scrambling pattern occurring was determined wherever possible. Synthesis of 1,α’-¹³C₂-trans-stilbene was accomplished by strating with 1-¹³C- and 2-¹³C-acetic acid. 1,α’-¹³C₂-bibenzyl, starting with 1,α’-¹³C₂-trans-stilbene oxide, 1,α’-¹³C₂-l,2-dibromo-l,2-diphen­ylechane, and 1,α’-¹³C₂-tolan were all synthesized from the dilabeled stilbene. The mass spectral values for the phenyl ion, (pseudo)tropylium ion, (pseudo)phenylethyl …

Reactions Of 2-Aminopyridine With Picryl Halides, Betty Wright Harris

Chemistry and Chemical Biology ETDs

The purpose of this investigation was to study the reaction of 2-aminopyridine with picryl halides with the goal of providing evidence in support of a mechanism accounting for the formation of the observed products. Nuclear magnetic resonance spectroscopy was employed to measure the relative amounts of the various picryl protons in the product mixture, which were assumed to be proportional to the mole percent of the corresponding compounds. 2-Aminopyridine reacted with picryl chloride by a nucleophilic bimolecular substitution reaction to give 2-(N-picrylamino)pyridine as the major product; however, the major product of the reaction of 2-amino­pyridine with picryl fluoride is 1-picryl-2-(N-picrylimino)-1,2-dihydro­pyridine. …

Laser Pyrolysis Gas Chromatography And Plasma Stoichiometric Analysis, Ray Lorain Hanson

Chemistry and Chemical Biology ETDs

Normal-pulse laser interaction with organic solids was studied. Extensive interaction between the carrier gas and the plasma occurred in the quenching process. When hydrogen was used as the carrier gas, significantly greater quantities of products were detected from the laser pyrolysis of graphite and coal compared to laser pyrolysis in helium. Acetylene was shown to be the principal hydrocarbon product from plasma quenching. Equilibrium product distributions calculated at high temperatures by the minimization of free energy revealed that hydrogen and acetylene were the primary gaseous plasma quenching products for hydrocarbons. Organic solids with oxygen present in the molecule yielded carbon …

Macrocyclic Polyether Sulfide Syntheses :|Bthe Preparation Of Thia-Crown-6, 7, And 8 Compounds, Robert Askew Reeder

Theses and Dissertations

Macrocyclic polyether sulfides have been prepared by reacting an oligoethylene glycol dichloride with a dithiol in refluxing basic ethanol. The following new compounds were prepared: 1,5-dithia-(19- crown-6), 3-hydroxy-1,5-dithia-(19-crown-6), 1,4-dithia-(21-crown-7), 3-hydroxy-1,5-dithia-(22-crown-7), and 1,4-dithia-(24-crown-8). One other previously reported macrocyclic polyether sulfide was also prepared. The thesis includes a review of macrocyclic sulfides and other related compounds, the thermodynamics of interaction of several macrocyclic polyether sulfides with Ag^+, Hg^2+, and Pb^2+ ions, and a discussion of the structure of these materials.

Composition And Structure Of A Stress Relieving Removable Epoxy Resin, Cecelia Victoria Krapcha Carter

Chemistry and Chemical Biology ETDs

The aqueous modification of polyol modified anhydride cured diglycidyl ether of bisphenol A exhibits properties of a brittle solid when subjected to an impulse stress, and properties of a viscous fluid when subjected to a steady state stress. This behavior is markedly different from the nonaqueous system. Early attempts to understand the nature of the change in properties and the physical mechanism involved have not been completely successful. These attempts have typically taken a physical chemistry approach and have not fully investigated the organic nature of the polymer. In order to fully understand a polymer system an important step should …

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 …

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 …

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 …

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.

Electrochemical Machining (Ecm) With Alternating Current, S. J. Shine

Tanzania Journal of Science

Electrochemistry has had several practical uses in industry for a long time; but one of the more recent applications is the machining of metals. Direct current ECM has been applied in industry for the last two decades. However, ECM with alternating current is still in the early stage of research and development. This paper shows that ECM with normal a.c supply is feasible and practicable if special tools are used. ECM with d.c. is first introduced to provide a better insight for the machining with a.c.

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 …

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 …

Nucleophilic Substitution At Phosphorus: Phosphate Thioesters, Ronnie L. Wilde

Electronic Theses and Dissertations

It was my objective to try to determine the mechanism of nucleophilic substitution at phosphorus in monothiophosphate triesters and to apply what I learn to the other phosphate systems. I also tried to obtain more data to show that the Lewis acid-base type complex through the phosphoryl oxygen is existent and does influence the reaction.

3,3-Diphenyl-2-Morpholinone Derivatives Of 2-Amino-2-Deoxy-D-Allose., Ram Babu

University of the Pacific Theses and Dissertations

A new cyclic protective group has been fused to the cis amino alcohol group of benzyl 2-amino-3,5-o-benzylidene-2-deoxyβ-D-Allopyranoside, by way of a unique rearrangements mechanism. To establish the 2-morpholinone structure, chemical studies, such as reduction and acetylation were conducted.

Comparative spectroscopic studies using ir, pmr, and C-13 nmr confirmed the assigned structures.

The 2-morpholinone ring was cleaved by mild alkaline hydrolysis and could be closed again with acetic anhydride in pyridine. An oxazolidinone derivation of benzyl 2-amino-4,6-o-benzylidene-2-deoxyβ-D-allopyranoside was prepared in a quantitative yield by a modification of a known method.

Protective group properties of the oxazolidinone were studied prior to the …

Cyclic 4,6-Oxygen-Acetal Derivatives Of D-Glucopyrano-(2,3: 4',5')-2'-Oxazolidinones., Daniel Vernie Robinson

University of the Pacific Theses and Dissertations

No abstract provided.

Studies Of Acetylcholinesterase In Synaptosomes, Syed Abbas Rizvi

Masters Theses

Acetylcholinesterase from rat brain was studied in crude homogenates, partially purified enzyme fractions, and in synaptosomes, to observe modification of the enzyme as a consequence of the modification of the membrane containing it.

Sodium dodecyl sulfate decreases the absorbance due to particles in the homogenate. This change in absorbance was proportional to both the concentration of sodium dodecyl sulfate and the concentration of the particles. Further, sodium dodecyl sulfate caused sulfhydryl groups to appear in the crude homogenate and in partially purified enzyme fractions. Synaptosomal preparations did not give such results. At concentrations of sodium dodecyl sulfate sufficient to cause …

Ua66/7/2 Newsletter, Wku Chemistry

WKU Administration Documents

Newsletter created by and about the WKU Chemistry department.

Syntheses And Characterizations Of Vanadyl (Iv) Complexes With Dihydroxydicarboxylate Ligands, Sharon K. Hahs

Chemistry and Chemical Biology ETDs

Binuclear complexes of the vanadyl(IV) tartrates have already been shown to exist both in the solid state and in solution. These complexes consist of two vanadyl(IV) ions bridged by two tartrato(4-) ligands, either of the same--DD (or LL)-- or opposite--DL--enantiomeric configuration. (The meso isomer of tartaric acid will not form binuclear complexes with vanadyl(IV).) The DL complex is more stable than the DD complex due to a greater degree of staggering between the vicinal hydrogen atoms on each tartrate chain. Investigations of vanadyl(IV) complexes with substituted tartaric acid ligands--specifically, (±)-dimethyltartaric acid and (±)-threomethyltartaric acid--have been undertaken to determine whether this …

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

Faculty Publications

In Eqs. (28) and (29) p should be changed to t.

Electrochemical Investigations Of The Mechanisms Of Reduction Of Benzaldehyde Compounds In Sulfolane, Neal Russell Armstrong

Chemistry and Chemical Biology ETDs

The mechanisms of the reduction of benzaldehyde and several sub­stituted benzaldehydes in the dipolar, aprotic solvent sulfolane, have been investigated. A combination of cyclic voltammetry, transmission spectroelectrochemistry and ring-disk voltammetry was used in this study. Cyclic voltammetric studies indicated that the one-electron benz­aldehyde reduction was followed by a dimerization of the radical anion intermediate to the pinacol. The reduction peak potentials of the benzaldehydes were cathodically shifted in sulfolane compared to values obtained in aqueos media. This indicates an increase in the benzaldehyde reduction energy in the aprotic solvent. The rate of the following chemical reaction was also slower than …

16th Annual Rocky Mountain Spectroscopy Conference

Rocky Mountain Conference on Magnetic Resonance

Final program and abstracts from the 16th annual meeting of the Rocky Mountain Spectroscopy Conference, sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Denver, Colorado, August 5-6, 1974.

The Attack Of Hard And Soft Nucleophiles On 6-Methylsulfonyl-, 6-Methylsulfinyl-, And 6-Methylthioaminopteridines, William David Johnston

Theses and Dissertations

In an attempt to prepare 6-anilino and 6-benzylaminopteridines, 2,4,7-triamino-6-methylsulfonyl and 2,4,7-triamino-6-methylsulfinylpteridines were prepared and reacted with a number of benzylamines and aniline. These hard nucleophiles gave amine exchange products with no displacement at the 6 position. Aliphatic amines gave exchange in the 2,4-and 7-positions. The exchange occurring in the 7-position must be occurring by an AE mechanism. This is the first such exchange reported in a ring other than a 1,3-azine. Aniline gave no exchange product except in an acid catalyzed reaction, and then gave exchange in only the 2 and 4-positions. Numerous reactions on related substrates, are reported. Soft …

Chronopotentiometric And Chronoamperometric Investigations Of Uranium (Vi) In Molten Condensed Phosphates, John J. Miglio

Chemistry and Chemical Biology ETDs

The diffusion coefficient, D, of U (VI) in molten sodium metaphosphate at 694°C was determined by two independent methods. D was also determined at R values of 1.0, 1.1, 1.2, 1.3, 1.4, and 1.5, where R is the molar M₂O to P₂O₅ ratio and M is univalent. The relative amounts of various phosphate species present in the molten state were determined by thin layer chromatography after rapidly cooling the melt and dissolving the resultant glass in water. With the above information it was hoped to determine if D is inde­pendent of the experimental method of …

Locating Nuclear Power Plants Underground, Frank M. Scott

UMR-MEC Conference on Energy / UMR-DNR Conference on Energy

This paper reviews some of the questions that have been asked by experts and others as to why nuclear power plants are not located or placed underground. While the safeguards and present designs make such installations unnecessary, there are some definite advantages that warrant the additional cost involved. First of all, such an arrangement does satisfy the psychological concern of a number of people and, in so doing, might gain the acceptance of the public so that such plants could be constructed in urban areas of load centers. The results of these studies are presented and some of the requirements …

Energy From Biochemical Sources, G. J. Fennewald, D. L. Million, Efton Park, J. L. Gaddy

UMR-MEC Conference on Energy / UMR-DNR Conference on Energy

As available energy reserves decline, renewable sources must be utilized. Organic matter, grown agriculturally, represents a renewable energy source, which is readily available. This paper reviews the methods by which organic matter can be converted to energy sources by biochemical processes. The economics of conversion of agricultural crops and byproducts to alcohols by fermentation and conversion of these agricultural materials to methane by anaerobic digestion are examined. Projections of the potential of this energy source are quite promising.