Digital Commons Network^™

The Effects Of Ultrasonic Vibration, Tension And Torsion On The Charge Acceptance Of The Alkaline Silver Electrode ; Ii. Potentiostatic Studies Of The Oxide Growth Rate Law For The Alkaline Silver Electrode ; Iii. The Determination Of Ionic Transport In Silver Oxide Using Radiotracer Techniques With Ag[Superscript 110m], Reed Harold Chase

Theses and Dissertations

The effect of ultrasonic vibration on the anodic oxidation of silver foil in KOH was studied. An increase in charging capacity of approximately 20% was found to be the result of cavitation erosion. Silver wire was exposed to tension and torsion during oxidation but no change in charge acceptance was caused by these stresses. The oxide growth rate on silver foil electrodes was compared to rate equations that have been proposed for other metals. Uhlig's equations for the growth of semiconductor oxides was found to describe most of the data. The data did not fit other rate equations. Determination of …

Voltammetric And Electrochemical Kinetic Studies Of The Halides And Halogens At A Platinum Rotating Ring-Disk Electrode In Anhydrous Acetic Acid, Donald Harrison Cranney

Theses and Dissertations

The electrochemical behavior of the iodine-iodide couple was investigated in both basic and neutral acetic acid solutions at a platinum rotating ring-disk electrode. Voltammetric curves were obtained and discussed. Various kinetic parameters were determined and by comparing to theoretical kinetic parameters a probable reaction mechanism was deduced. The mechanism that best fit experimental results is the following I- + S = I(S) + e- I(S) + I- = I2 + S + e (slow). The electrochemical behavior of bromine, bromide, and chloride was also investigated in the same media. Voltammetric curves were recorded and discussed with emphasis on the hysteresis …

A Study Of Selected Photo Fries Rearrangements, Elwood Lloyd Loveridge

Theses and Dissertations

The Fries rearrangement of phenyl esters is reviewed and compared to the reaction when light is the source of energy. The products are different due to different mechanism of reaction. Light energy causes either free radical or concerted reactions. The S-phenylthiol esters and anilides were studied also. Although many of the rearrangements are the same, we did not see any alkyl migration nor decarboxylation type reactions with either the sulfur or nitrogen compounds. Three papers have been published from this work: Bradshaw, J. S., Knudsen, R. D. and Loveridge, E. L., J. Org. Chem., 35, 1219 (1970); Bradshaw, J. S., …

An Fe (Iii) - Initiated Oxidase Reaction With Ferroxidase-Ii, Glenn Alexander Hegamyer

Master's Theses

A reaction involving iron as an intermediary electron carrier for the coupling of electron transfer from an endogenous substrate to ferroxidase-I has been proposed.

The enzymic nature of the reacti on has been established and studies with iron chelating agents have demonstrated the involvement of Fe(III). The kinetic parameters of ferroxidase-11 with Fe (lll) were found to be quite similar to those previously established for Fe(Il). The participation by the copper associated with ferroxi dase-11 was ascertained by use of the copper chelating agent, diethyl -di thio-carbamate .

A variety of substances normally found in blood were surveyed as possible …

The Effect Of Stabilizing Groups On The Extent Of Long-Range Π Electron Participation And The Effect Of The Negative Charge On The Chemical Shift Of Neighboring Protons In Carbanions, Atilla Tuncay

Dissertations

No abstract provided.

A Potentiometric Method, A Convenient And Rapid Technique For Determination Of The Thermodynamics Of Ionization Reactions For Water, Weak Acids, And Some Slightly Soluble Salts In Aqueous Organic Mixed Solvents, Charanai Panichajakul

Theses and Dissertations

A potentiometric method which is devised to be rapid and convenient for determining ionization constants for water, weak acids (or bases), and certain solids in mixed solvents is described. The method has been applied to the determination of ionization for water, acetic acid, benzoic acid, and phenol and the solubility product constant for silver chloride in mixtures of water with methanol, ethanol, acetone, tetrahydrofuran, and p-dioxane containing from 0 to 70 mass percent organic co-solvent at several temperatures between 10 and 40°C. Results are used to study the thermodynamics of ionization in each mixture which is discussed relative to various …

The Intermolecular Potential And Vibrational Relaxation Of The Ar-Co System, Gregory Allen Parker

Theses and Dissertations

The angle, distance and vibration dependence of the Ar-CO intermolecular potential is calculated using the electron gas model to obtain the short range interaction which is smoothly joined onto the long range van der Waals tail which is obtained from accurate C_6, C_7, and C_8 coefficients. Our calculated second interaction virial coefficients are compared with experiment and with a simple adjustment of the Ar-CO potential an excellent agreement is obtained. Our spherically averaged potential is also in excellent agreement with a spherical potential inferred from high energy scattering data. Simplified expressions for the scattering amplitude and differential cross section are …

A Comparison Of Free Radical Detection Methods, Danny Kiang-Wah Pan

Theses and Dissertations

The methods used for free radical detection are chemical titration, spectrophotometry, Gouy magnetic measurements and NMR shift technique. The free radicals chosen for this study are Fremy' s salt (ON(SO_3 )K_2),2,2-diphenyl-1-picryl hydrazyl (DPPH) 3-carbamoyl-2,2,5,5-tetramethylpyrrolidin-1-yloxy (CTM-pyrrolidin), 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolin-1-yloxy (CTM-pyrrolin), 4-acetamido-2,2,6,6-tetramethylpiperidino-1- oxyl (ATMP) and galvinoxyl. The detectable range for each method is given. The NMR method is a fast and convenient method for the magnetic susceptibility determination of a sample in solution, with. accuracy up to ± 1%.

Solid-Liquid Phase Equilibria In Systems Of (I) Para-Xylene, (Ii) Mesitylene, And (Iii) N,N-Dimethylformamide ; Excess Volume Determination In Systems Containing Cyclohexane ; Calculations Of Activities For The N-Hexane + Cyclohexane System, John F. Moellmer

Theses and Dissertations

Solid-liquid phase equilibria studies were used to investigate possible compolllld formation in solutions of (i) para-xylene, (ii) mesitylene, and (iii) N,N-dimethyl-formamide (DMF) with mono- and di- halobenzenes that were selected to give a wide range of acceptor properties. Solid 1:1 intermolecular compounds were identified from solutions of p-C_6H_4F_2 with mesitylene, p-C_6H_4Br_2 with p-xylene, and p-C_6H_4Cl_2 with p-xylene. The results suggest that compound formation occurs because of favorable geometry rather than a charge transfer process. A vibrating tube densimeter was used to determine, with high precision, the densities and subsequently excess volumes of mixing of the n-hexane plus cyclohexane system. Temperature …

The Addition Of Sf5br To Unsaturated Systems, Qui-Chee Wendy Wang

Dissertations and Theses

Addition reactions of pentafluorosulfur bromide with unsaturated substrates were studied and four new compounds containing the pentafluorosulfur group have been prepared.

The mechanism for these reactions seems to involve a radical addition pathway. In reaction with CH₂=CFC1, CF₃C≡CH and CH₃C≡CH the SF₅ radical attacks the carbon atoms carrying the most hydrogens. The reaction with CF₂=CHCl is interesting, as by analogy with other fluoroolefins, the SF₅ primary attack should occur.at the CHCl group, however, SF₅CF₂CHC1Br was found as the only product for this reaction. The reaction of …

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 had 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 …

Effect Of Solvent Polarity On The Singlet-Triplet Energy Gap Of Methyl-2-Anthroate, William Gregg Hawkins

Honors Theses

Nonradiative processes cause the fluorescence quantum yield to be less than one. Elucidation of nonradiative decay mechanisms without knowing the location of triplet states is difficult. Determination of the fluorescence quantum yield (Øf) as a function of temperature can provide valuable information about relative location of triplet states and the nonradiative processes which result from having a triplet near the energy of the first excited singlet state. Methyl-2-anthroate is very sensitive to solvent polarity. The Øf values and S1 energies vary greatly, depending on the solvent environment. Temperature studies on Øf have indicated the intersystem crossing (ISC) to a nearby …

The Design, Development And Construction Of A Low Cost Multi-Purpose Computer/Interface System For On-Line Experimentation: Applications To Time Averaging Of Nmr Spectra And Other Chemical Instrumentation Problems, Steven A. Carr

Honors Theses

The project goal was the development of a low cost multipurpose microprocessor interfacing system that would be adaptable to a number of commonly encountered chemical instruments (such as NRM, GC, IR, and UV-VIS.) for the purpose of control, data acquisition processing. The Altair Microprocessor with 4K random access memory was constructed from kit form; it functions as the computer portion of the system. The digital to analog and analog to digital signal conversion elements as well as timing, control and other necessary logic functions are incorporated in the electronic interface portion of the system. The computer, interface, principles of time …

The Synthesis And Decomposition Of O-Substituted Phenylhydroxylamines, Helen Carol Kennicott

Honors Theses

0-(phenyl)hydroxylamine and its p-nitrated derivative were synthesized for use in a study of substitution reactions at an sp3 hybridized nitrogen atom. The 0-(phenyl)hydroxylamine was decomposed thermally in several nonnucleophilic solvents and in water, with base present. It is proposed that in organic solvents, the decomposition proceeds by a radical mechanism involving a solvent cage intermediate. Ammonia and aminophenols are the major products. In water, it appears that an SN1 reaction producing phenoxide may compete with the radical mechanism.

The Preparation And Kinetic Studies Of Two Sterically Hindered Gold (Iii) Complexes, James Forrest Stevens

Honors Theses

Previous studies indicate substitution of bromide ion for chloride ion in [Au(Et4dien~H)c.i] +occurs at a rate almost independent of the bromide ion concentration, while similar reactions with [Au(dien-H)Cl]+, [Au(Me2dien-H)c!]+ and [Au(Me4dien-H)c~+ show rates dependent on bromide ion concentration as usually encountered for square planar complexes. There is retardation of the reaction by steric and electronic effects with increased N-alkyl substitution of the triamine. It has also been postulated that substitution of [Au(Et2dien-H)cJ]+ proceeds via a ring-opening mechanism. The purpose of this research was to study further the effect of steric hindrance on rates of substitution of two additional gold(III) complexes. …

The Synthesis Of 2, 11-Dithiabenzo - [3.3] - Paracyclophane And An Octadeutero Derivative, Paul M. Begley

Honors Theses

The purpose of this work was the synthesis of 2, 11 -dithia-benzo- [3.3] -paracyclophane and its octadeutero derivative 2,11-dithia- 3,3, 5, 6, 8, 9, 10, 10-octa­deutero-benzo - [3.3] paracyclophane. A comparison of their nuclear magnetic resonance spectra as well as their mass spectra will unequivocably provide proof of their successful synthesis.

Ozone Complexes With Substituted Aromatic Compounds, David C. Eaton

Honors Theses

Ozone has been observed to complex with aromatic compounds at low temperatures. The ability of an aromatic system to complex with ozone appears to be due to the inductive effect of the substituent on the pi system. The experimental work was done in the solid phase at temperatures of -175° C to -186° C. Under these conditions all the substituted aromatics with electron withdrawing groups did not complex including benzene. The complexes are highly colored. To insure the reversibility of the pi complex, infrared spectra were taken of some of the aromatic species before and after complexing.

Preparations And Reactions Of Two Aldoketenes: T-Butyl And Benzyl, Donna E. Loeffler

Chemistry Honors Papers

This 25 page thesis examines preparations and reactions of aldoketenes.

An Inexpensive Differential Thermal Analyzer: Construction, Qualitative And Quantitative Applications, Kenneth T. Miller

Chemistry Honors Papers

This 33 page thesis examines the process of constructing an inexpensive, versatile differential thermal analysis instrument which can be easily modified and adapted to many applications.

The Chemistry Of Chromium (Vi) And Chromium (V) Oxide Fluorides, Patrick Jay Green

Dissertations and Theses

New preparative routes to chromyl fluoride were sought. It was found that chlorine monofluoride reacts with chromium trioxide and chromyl chloride to produce chromyl fluoride. Attempts were made to define a mechanism for the reaction of ClF and Cr0₃ in light of by-products observed and previous investigations. Carbonyl fluoride and chromium trioxide react to form chromyl fluoride and carbon dioxide. A mechanism was also proposed for this reaction. Chromium trioxide with MoF₆ or WF₆ reacts to produce chromyl fluoride and the respective oxide tetrafluoride.

The Synthesis Of Analogs Of Toxoflavin And Fervenulin As Potential Antimetabolites, Bernadette Kuo Billings

Theses and Dissertations

The synthesis of analogs of toxoflavin: 1,3,4,6-tetramethyl-1,5,6, 7-tetrahydropyrimido[4,5-c]-5,7-pyridazinedione; 1,6-dimethyl-3,4-diphenyl-1,5,6,7-tetrahydropyrimido[4,5-c]-5,7-pyridazinedione; 3,5,7-trimethyl-8-phenyl-2,3,4,8-tetrahydropyrido[2,3-d]-2,4-pyrimidinedione are discussed. The synthesis of analogs of fervenulin: 3,4,6-trimethyl-5,6,7,8-tetrahydropyrimido[4,5-c]-5,7-pyridazinedione; 6-methyl-3,4-diphenyl-5,6,7,8-tetrahydropyrimido[4,5-c]-5,7-pyridazinedione; 2-hydroxy-3,5,7-trimethyl-4(3H)pyrido[2,3-d]-2,4-pyrimidinone are discussed. Several intermediates have been prepared: 6 -methylamino-3-methyluracil by a new method; 6-n-propylamino-3-methyluracil: 6-n-butylamino-3-methyluracil and 3-ethyl-2-ethylthio-2-hydroxy-4(3H)pyrimidinone.

Hard And Soft Nucleophilic Substitution Patterns In Amino-Methylsulfonylazines, Calvin Wilson Mccausland

Theses and Dissertations

The selectivity observed with 2,4,7-triamino-6-methylsulfonyl-pteridine when reacted with "hard" aliphatic amines and "soft" aryl-thiols resulting in amine exchange at the 2-, 4-, and 7-positions and displacement of the 6-methylsulfonyl moiety, respectively, was further investigated in other ring systems. The substrates tested were disubstituted with amino- and methylsulfonyl- moieties, and included the benzene, pyridine, pyrazine, quinoxaline, quinazoline and pteridine ring systems. The methylsulfonyl moiety is preferentially displaced by both thiols and amines with quinoxaline and quinazoline substrates, and is more reactive towards displacement by thiol than amine nucleophiles. Amine exchange occurs with the quinoxaline substrate subsequent to displacement of the methylsulfonyl …

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

Master's Theses

No abstract provided.

The Synthesis Of Some Potential Antimalarials : The 3-(4- Choloropheny1) -5, 7- Dichloronaphthylaminoalcohols, Dwight Allen Shamblee

Master's Theses

A new scheme is presented for the preparation of 3~(4-chlorophenyl)-5,7-dichloro-l-methylnaphthalene, from which, four derivatives, 3~(4-chlorophenyl)-~-di(n-butyl)aminomethyl~5,7-dichloro-l-naphthalene-methanol hydrochloride, 3-(4-chlorophenyl)-5,7-dichloro-~-(2-piperidyl)-1-naphthalenemethanol acetate, l-[3-(4-chlorophenyl)-5,77dichloro-lnaphthyl]-3-di(n-butyl)aminopropanol hydrochloride, and 1-[3-(4-chlorophenyl)-5, 7-dichloro-l-naph,thyl]-2-(2-piperidyl) ethanol hydrochloride, were prepared. These four derivatives were submitted to Walter Reed Army Institute of Research for. the determination of their potential as antimalarial agents.

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% …

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 …

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 …

Titanium Assisted Alkylations Of Selected Alkynols, Leslie C. Smedley

Dissertations, Theses, and Masters Projects

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.

The Mechanism Of The Meyer-Schuster Rearrangement, Carol Virginia Roane

Dissertations, Theses, and Masters Projects

No abstract provided.