Digital Commons Network^™

Vapor Phase Oxidation Of Chloropropenes Over Heterogeneous Catalyst Systems, Tim Ellis Owen

Retrospective Theses and Dissertations

Propylene Dichloride (PDC) is a byproduct of several Dow processes. The thermal cracking of PDC produces 1-cis-chloropropene, 1-trans-chloropropene, 2-chloropropene, and allyl chloride . By oxidizing the l- and 2-chloropropenes to 3- and 2- chloroacrylic acids, respectively, a potentially valuable product could be made. The chloropropenes, air, and steam were passed over various heterogeneous oxidation catalyst systems to attempt this oxidation. Contact time was varied between 0.0951 to 0.915 sec. Temperature was varied between 275C to .25C. The air content of the feed was varied between .1 to 75%. The chloropropene content of the feed was varied between 2.9% to 5.0% …

A Study Of Some Tetraarylborate-Pvc Membrane Electrodes, Boonrod Hirunmitnakon

Master's Theses

No abstract provided.

Interactive Pace Approach To Learning In Physics : Method And Materials, Mario Amézquita

University of the Pacific Theses and Dissertations

This study has the following general objectives: first, to present in detail the techniques that the author has developed and used in designed the course and the final materials produced for am introductory physics course in Mechanics; second, to state and examine the important blended ingredients used to get a new strategy for teaching-learning in which and individualized pace together with a group interaction is used; third, to analyze a combination of structural and operational course where concept, structure formation, and problem solving are emphasized.

Polymerization Of Amino Acids On Kaolinite, Z. Badri Adnani-Gleason

Dissertations and Theses

In the origin of life on the primitive earth a major step must have involved the condensation of amino acids to form the first polypeptides. Several suggestions as to how this might have occurred have been made by other workers. One of the more appealing proposals is that the polymerization was catalyzed by clay minerals. It has been reported, for example, that L-apartic acid polymerizes significantly faster than D-aspartic in the presence of kaolinite in aqueous suspension at 90˚. In this work an attempt was made to repeat this report and extend the pH range to include values presumably present …

A Study Of The Spectroscopic, Thermodynamic, And Dielectric Properties Of The T-Butylbenzene/Tetracyanoethylene Molecular Complex, Donald W. Mundell

Masters Theses

No abstract provided.

Ab Initio Investigations Of The Potential Curves Of The Ground State Of The Hydrogen Molecule And Of Several States Of The Lithium Molecule, Mark L. Olson

Graduate Dissertations and Theses

Abstract for this work is available in the additional materials.

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 …

The Internal Chemical Shift - A Key To Bonding In Aromatic Molecules. 2. Substituent Effects On The Carbon-13 Magnetic Resonance Spectra Of The 1,4-Disubstituted Benzenes, Donald W. Beistel, W. Dan Edwards

Chemistry Faculty Research & Creative Works

Carbon-13 magnetic resonance shifts were determined for six families of 1,4-disubstituted benzenes. Linear least-squares correlations between the internal shifts of the families suggest an additivity relationship for 13C substituent effects at all four nonidentical ring carbons and at the α position when one of the substituents has a central carbon. The correlation of 1H and 13C shifts for these compounds is also linear, implying that the additivity relationships derived in a previous 1H study can be generalized to 13C.

Planning A Kinetic And Mechanistic Study With Cerium (Iv), Samir B. Hanna, Robert R. Kessler, André Merbach, Steve Ruzicka

Chemistry Faculty Research & Creative Works

No abstract provided.

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 …

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, …

Anion Assisted Redox Rates Between Cobalt (Ii) - Cobalt (Iii) Polypyridyl Complexes In Acetophenone, Seyed Garmestani

Masters Theses & Specialist Projects

The effects of ionic strength and various anions on the rate of electron transfer between tris(2,2'-dipyridine) cobalt(III) and bis(2,2',2"-tripyridine) cobalt(II) complexes have been examined in acetophenone. The redox rate was found to increase with increasing ionic strength in both the presence and absence of added salts. The reaction was first order with respect to each reactant and second order overall in all cases. The influence of the C10₄, BF₄, and B(C₆H₅)₄ anions on the reaction rate was studied with their order of effectiveness being: C10₄- > BF₄ >> B(C_{6 …}

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 …

Calorimetric Determination Of The Interaction Of Cu, Fe, And V Oxides With So₂ And Measurement Of Sulfur (Iv) And Sulfur (Vi) In Particulate Samples From Utah Valley, Douglas F. Cannon

Theses and Dissertations

The adsorption of SO2 by metal oxides suspended in decane were studied by calorimetric titration. The adsorption per surface area decreases in order CuO > Cu2O > Fe2O3 > V2O5. An Andersen High Volume sampler was used to obtain particulate samples from five sites in Utah County. Particulate sulfur (IV) and sulfur (VI) was analyzed by thermometric titration with K2Cr2O7 and by a direct injection enthalpimetric determination using BaCl2. Results show that little oxidation of the S(IV) occurs after it is released from the Kennecott smelter stack.

The P-Nitrobenzyl System. Iv. Base-Induced Transformations In P-Nitrobenzyl Chloride, Bromide, Iodide, Tosylate, And Sulfonium Salts, Samir B. Hanna, Paul H. Ruehle

Chemistry Faculty Research & Creative Works

No abstract provided.

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 …

17th Annual Rocky Mountain Spectroscopy Conference

Rocky Mountain Conference on Magnetic Resonance

Final program and abstracts from the 17th 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 4-8, 1975.

Isolation And Characterization Of Two Sterols From The Green Alga, Selenastrum Capricornutum, Raymond Mark Owings

Dissertations and Theses

The green alga, Selenastrum capricornutum, was cultured in artificial nutrient medium utilizing five-gallon carboys, each of which contained 16 1. of culture. The algal cells were separated from the nutrient medium by continuous-flow centrifugation at 7500 RPM, and were then lyophilized. The lyophilized cells were extracted by refluxing with ether, acetone, and chloroform:methanol (2:1). Free sterols and sterol esters were separated from the crude extract using preparative thin-layer chromatography. Sterol esters were saponified and both the sterols and the fatty acids were recovered.

Individual sterols were separated from the free sterol fraction using argentation thin-layer chromatography. Gas chromatograms, mass …

A Spectrophotometric Equilibrium Study Of Nickel(Ii)-3, 4', 4", 4'"-Tetrasulfophthalocyanine, Stephen Lowery

Masters Theses & Specialist Projects

There have been several studies made on the effects of various central metal ions on the aggregation of tetrasulfonated Phthalocyanine dye complexes in aqueous solution, but there have been no studies made on the aggregation of the nickel(II)-4, 4', 4", 4'"-tetrasulfoohthalocyanine (Ni^II-TSPC) complex. Therefore, a study of the effects of nickel(II) on the aggregation of its aqueous tetrasulfonated Phthalocyanine dye complex was Proposed so that a comparison might be made with nrevious studies of central metal ion effects. It was found, however, that Ni^II-TSPC gives a much higher degree of aggregation in water than the metal …

Electronic Transitions Of Metal Complexes With Triphenylphosphine As A Ligand, Thomas Zimmer

Masters Theses & Specialist Projects

The spectra of transition metal complexes with triphenylphosphine have been measured near 260 nm and the results interpreted in terms of perturbation of the it electron system of the phenyl ring. All complexes studied show sou degree of delocalization of the d-orbital electrons of the metal into the phenyl ring. However, for first row transition metals, the primary affect was found to be polarization of the phenyl ring due to the presence of the metal ion. For second and third row transition metal ions, the primary effect was found to be metal-ligand back-bonding. However, the effect of polarization of the …

A Stereochemical Study Of Some 2,2'-Bridged Biphenyls, Alan J. Quarfoot

Dissertations

No abstract provided.

A Study Of The Electrolytic Oxidation Of Antioxidants At A Stationary Platinum Microelectrode, Mark Anthony Forte

Master's Theses

Phenolic antioxidants have a Wide variety of uses. They are em- ployed to prevent oxidative and thermal degradation of everything from plastics to foodstuffs. They may even have potential as carcinostatic agents. In general, they act as chain terminators in free radical type reactions.

Kinetics Of The Thermal Decomposition Of Pyridine, Tesfaye Biftu

Masters Theses

No abstract provided.

The Effect Of Nitroalkanes On The Electrolytic Oxidation Of Tertiary Butyl Amine And Tertiary Amyl Amine, Karl Lloyd Bergen

Theses and Dissertations

The electrolyses of tert.-butyl and tert.-amyl amines were run with a voltage of approximately 3v., as measured across the cell, with and without the presence of 1-2% nitro-tert.-alkane. A graphite anode was used; the supporting electrolyte was NaClO4; the solvent was the reacting amine(s) with 10-20% water to solubilize the NaClO4. The products were azo compounds, azoxy compounds, 1,3-disubstituted ureas and traces of nitroso compounds. In the case of tert.-butyl amine di-tert.-butyl carbodiimide was also shown to be a product. The presence of nitro compounds increased the yields of azoxy and nitroso compounds and decreased the yields of azo compounds. …

An Atomic Absorption Method For Determining Micromolar Quantities Of Primary Aliphatic Amines In The Presence Of Secondary And Tertiary Aliphatic Amines, Nathalie Harwood Perkins

Master's Theses

A method for the determination of primary aliphatic amines in the presence of secondary and tertiary amines is described. The primary amine is reacted wit ha complexing reagent containing cupric chloride, salicylaldehyde and triethanolamine. The copper complex formed is extracted into 10% hexanol in toluene. The amount of copper in the toluene layer is determined by atomic absorption spectroscopy. This is a measure of the primary amine in the sample. The method can be successfulyl applied to both monoamines and diamines as well as an amino alcohol. Data for the analysis is + 0.05% at the 2% level and below. …

Synthesis And Analysis Of Dimers Of Alpha-Methylstyrene, Bhadreshkumar J. Mehta

Masters Theses

Introduction

The heat of polymerization ∆Hp, of Alpha-methylstyrene (AMS) has been a source of study for many years. The structure of AMS is shown in Figure 1.

Roberts and Jessup carried out the first quantitative work to determine ∆Hp if AMS.¹ Their data displayed a ∆Hp dependence on the degree of polymerization, DP. Several other reports were also published with new values for ∆Hp and new explanations for the apparent DP dependence.^{2, 3, 4, 5.}

Samples of dimers of AMS have been prepared by various workers.^{6, 7, 8} The reactions were mostly carried out by using sulfuric …

Synthesis And Stereochemistry Of 2,6,10-Triazatricyclo [5.2.1.0⁴ ¹⁰] Decane Derivatives, Susan Elaine Foulger

Theses and Dissertations

The synthesis and stereochemical aspects of derivatives of the new ring system 2,6,10-triazatricyclo [5.2.1.04,10] decane are discussed. Sythesis of 2-nitro-2-methyl-1,3-disubstitutedaminopropanes, followed by reduction of these compounds to 2-amino-2-methyl-1,3-disubstituted aminopropanes afforded the necessary starting materials for a cyclization reaction similar to that resulting in already known 2,6-dioxa-10-azatricyclo [5.2.1.04,10] decanes. Reaction of the triamines with 2,5-hexanedione resulted in 2,6-disubstituted-1,4,7-trimethyl-2,6,10-triazatricyclo [5.2.1.04,10] decanes. The stereochemical aspects of this ring system are interesting from the standpoint of nitrogen inversion barriers on nitrogens 2 and 6. Existence of a high inversion barrier for these nitrogens in shown by isolation of different diastereomers of the tricycle. Methods …