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The Electrochemical Oxidation Of 1-Pentyne On Platinum And Gold, Michael Jensen Danielson

Doctoral Dissertations

"The anodic oxidation of 1-pentyne was studied at 70°C on Pt and Au electrodes in solutions of H₂SO₄, K₂SO₄, K₂CO₃, and KOH. Pt was studied in a pH range of 0.35 - 12.7 and Au in a range of 10.9 - 12.7. Reaction rates were measured as a function of potential, pH, temperature, and 1-pentyne partial pressure. The coulombic efficiencies for the oxidation to CO₂ were 77 percent in 1 N H₂SO₄ and 69 percent in 1 N KOH on Pt and 43 percent in 1 N KOH on Au. The kinetic parameters on Pt were [partial derivative]V/[partial derivative]log i …

The Ultraviolet Absorption Spectra Of Solutions Of 2, 4, 6-Trimethoxybenzoic Acid In Sulfuric Acid, Kathy Show-Shing Ho

Masters Theses

"Studies of the ultraviolet and proton magnetic resonance spectra of solutions of 2,4,6-tribromo-, trichloro-, trimethyl- and trinitro-benzoic acids dissolved in concentrated sulfuric acid by Dr. D. W. Beistel and his coworkers lead to the synthesis of the corresponding benzoate esters. In the present work the nature of ionic species formed in mixtures of sulfuric acid and 2,4,6-trimethoxybenzoic acid was examined, The spectral data suggest the presence of species similar to those assigned for the previous trisubstituted analogs, together with a species capable of fluorescence in the 2400 Å region. The reason of this unprecedented fluorescence has not been established"--Abstract, Page …

Metabolism Of 3-Iodotyrosine And 3,5-Diiodotyrosine By Thyroid Extracts, Shih-Ying Sun

Masters Theses

"A porcine thyroid enzyme was extracted from thyroid tissue by homogenization and differential centrifugation. The enzyme was capable of metabolizing both 3-iodotyrosine and 3,5-diiodotyrosine. All of the thyroid subcellular particles produced a fluorescent compound when incubated with these substrates. When the 1,000 x g sediment was supplemented with the 48,000 x g supernatant a second compound was formed. The compound was UV absorbing and has been identified as either 3-iodo-4-hydroxybenzaldehyde or 3,5-diiodo-4-hydroxybenzaldehyde depending upon which substrate was used. The 1,000 x g sediment was solubilized with 1% Conoco 1012-6 detergent. The activating factor in the 48,000 x g supernatant was …

Amino Acid Sequence Of An Iodotyrosyl-Containing Peptide Produced By Tryptic Digestion Of Thyroglobulin, Pai-Chun Chiang

Masters Theses

"Thyroglobulin was digested with trypsin. An iodotyrosyl-containing peptide was isolated from tryptic digests by a combination of electrophoresis and paper chromatography. The amino acid sequence of this peptide was determined by applying the Edman degradation and by using the proteolytic enzyme, carboxypeptidase A. The sequence of this peptide is: NH₂-Ala-Ile(Leu)-Ala-Ser-Phe-Gly-Asp-Tyr-Glu-Phe-COOH The importance of the position of the tyrosyl residue which is iodinated to form monoiodotyrosine (MIT) , diiodotyrosine (DIT) , and thyroxine (T₄) is considered in connection with the structure-activity relationship of the protein"--Abstract, page ii.

The Semibullvalene Question: A Semi-Empirical Molecular Orbital And Bond Energy Approach, Shiow Yeh Lee

Masters Theses

"Semi-empirical molecular orbital calculations of the Extended Ruckel and MIND0/1 type have been performed on semibullvalene and the supposed transition state for its degenerate [3,3] sigmatropic rearrangement. The results have been coupled with bond energy calculations to ascertain whether semibullvalene is homo-aromatic or is undergoing a rearrangement of exceedingly low activation energy. A preponderance of the resulting data suggests that semibullvalene is homo-aromatic"--Abstract, page ii.

Enhanced Evaporation Of Water Droplets Due To Surface Contamination, Robert Bernard Hughes

Masters Theses

"Experimental evidence for enhanced evaporation of small (3-9 µ radius) water droplets are presented. Both "pure" droplets and droplets contaminated with surface active materials fell into air of known relative humidity (96-99 per cent) at an ambient temperature of 29.9C and evaporated. The rates of evaporation were determined by photographing the evaporating drops, measuring the distance a drop fell during a fixed time interval, and applying Stokes law. The contaminated droplets exhibited a rate of evaporation 1.8µ² sec⁻¹ faster than "pure" drops. This can be compared with rates for pure drops of 1.9 and 5.7µ² sec⁻¹ at 0.1 and 0.3C …

A Modification Of The Spectrophotometric Determination Of Zinc With Methylene Blue And Thiocyanate In An Aqueous System, Roger William Craig

Dissertations and Theses @ UNI

The analysis of zinc in the 0-10 microgram range, determined by the loss in absorbance of a buffered methylene blue solution in the presence of thiocyanate in an aqueous system, is described. The technique was best performed with a 1.0 M NaSCN and 6.0 x 10^-5 M methylene blue solution buffered with citrate-phosphate to a pH of 3.2. Absorbance readings were taken from the Cary Model 14 recording spectrophotometer in the range of 500-700 mµ with 666 mµ being used as the most useful wavelength for the attempted zinc analysis. The analysis of zinc was found to be satisfactory …

Glory Scattering In Molecular Collisions: Formal Expressions For The Total Cross Section, Louis Biolsi

Chemistry Faculty Research & Creative Works

An Extended Distorted-Wave Treatment is Used to Obtain Formal Expressions for the Total Cross Section When Two Rigid Diatomic Molecules with Orbital and Nuclear-Spin Angular Momenta Collide. Explicit Expressions Are Obtained through Second Order, Including the Lowest-Order Inelastic Effects.

Some Physical And Mechanical Properties Of Cabal Glass-Aluminum Composites, Hussein Baher Mohamed Abdul Moneim

Archived Theses and Dissertations

No abstract provided.

Papain-Papaya Protein Interactions : Resistance Of Papaya Protein To Proteolytic Digestion By Papain, John Leonard Rudy

University of the Pacific Theses and Dissertations

The proteolytic actjvity of papain was investigated with respect to its action on both natural substrates (native papaya protein and bovine serum albumin) and artificial synthetic substrate (benzoyl~l-arginine ethyl ester). Following removal of 30 percent and 40 percent of the amino acid residues from the amine terminus, the activity of the degraded papain was determined with respect to the above substrates, and compared to the activity of the intact papain molecule.

Native papaya protein showed resistance to digestion by both intact papain and 30 percent 'degraded papain. This resistance to digestion persisted for time periods ranging from three to six …

The Determination Of Stability Constants For Some Metal Chelates Of O-Phenylene-Dinitrilo-Tetraacetic Acid, Charles E. Faraci

Dissertations and Theses @ UNI

The chelating agent, o-phenylene-dinitrilo-tetraacetic acid, has been synthesized, by a method previously reported, and characterized. The formation constants for the reactions between a group of divalent metal ions and the chelon, o-phenylene-dinitrilo-tetraacetic acid, have been determined potentiometrically with a mercury electrode. The stability constants for the metal ions Hg2+, Mg2+, Mn2+, Zn2+, Co2+, Cd2+, and Pb2+ were determined. Log K values of 18.6, 7.2, 11.8, 13.3, 13.4, 13.7, and 14.1, respectively, were found at an ionic strength of 0.1 and 25°C. These stability constants were compared to those of ethylene-dinitrilo-tetraacetic acid chelate. Some of the effects of ligand structure on …

The Possible Correlation Of Carcinogenic Activity With Electronic Structure Of Benz(A)Anthracene, Patricia Joan Blair

Masters Theses

"The electronic structure of benz(a)anthracene based on the sigma and pi electrons was predicted by the modified intermediate neglect of differential overlap (MINDO) molecular orbital method and compared with the pi electronic structure determined by the Pople method. The crystalline molecular structure was used for both methods. The Pople calculation was also done on the aromatic molecular structure and a combination structure which assumed the bond lengths of the crystal structure and the bond angles of the aromatic structure. Chemical properties predicted by the MINDO and POPLE electronic structures were compared; the MINDO results provided the best agreement with experimental …

Mass Spectrometric Study Of "Anomalous" Water, Bernard Jean Bouy

Masters Theses

"Considerable interest has developed recently in a material called "polywater" or "anomalous water". This material has properties quite different from those normally associated with liquid water. The purpose of this study is to give some mass spectrometric observations of "polywater". The "polywater" samples were produced within silica capillaries. These capillaries were heated by means of a helical coil to vaporize the "polywater". The vapor was directed into the source of a mass spectrometer. The results of this study show that a significant portion of the "anomalous water" samples is composed of a polymer of dimethylsiloxane. To date, the observations are …

The Radial Distribution Curve Of "Anomalous" Water By X-Ray Diffraction, Jerome Dechelette

Masters Theses

"Amorphous and liquid samples, believed to be "anomalous" water were studied by X-ray diffraction. A diffusion ring, characteristic of liquids and glass was observed at Θ =10.5º. For purposes of comparison an X-ray diffraction pattern was obtained for pure water under nearly identical conditions. By means of a microdensitometer, X-ray intensity curves were prepared from the diffraction patterns and corrected for absorption and polarization. From the Fourier transform of the intensities, we obtained the radial distribution curves. The radial distribution curve for water, obtained in previous work, shows an initial peak at 2.9Å. This peak is due to the nearest …

The Anodic Oxidation Of Oxalic Acid On Au, Jean Louis Lucien Desmartin

Masters Theses

"The anodic oxidation of oxalic acid on Au has been studied at 25ºC in aqueous media. The reaction rate was measured as a function of potential, oxalic acid concentration, pH, and temperature in H₂SO₄-K₂SO₄ solutions. A change in the Tafel slope in going from the lower to the higher Tafel region is explained by an alteration of the reaction mechanism due to electrical interactions between adsorbed species and the anode. Further details of an oxidation sequence involving resonant forms of oxalic acid are proposed"--Abstract, page 1.

A Study Of The Oxygen Exchange Between Chromate Ion And Water, James Hsiao-Hsin Chiang

Masters Theses

"The kinetics of the isotopic exchange reaction between O¹⁸-enriched chromate ion and solvent water have been measured as a function of pH and chromate ion concentration. The exchange kinetics can be explained in terms of the dimerization equilibria HCrO_4̄ + Cr₂O[subscript 7 with double dash above] [double arrows] Cr₂O[subscript 7 with double dash above] + OH⁻ and 2HCrO_4̄ [double arrows] Cr₂O[subscript 7 with double dash above] + H₂O except at high pH, where it is independent of pH. Rate constants at 30ºC for the reactions of the dimerization equilibria and the first order reaction at the high pH …

On The Physical Properties Associated With Omega Phase In Titanium-Chromium Alloys, Serag El Din El Sayed Habib

Archived Theses and Dissertations

No abstract provided.

Ua66/7/2 Newsletter, Wku Chemistry

WKU Administration Documents

Newsletter created by and about the WKU Chemistry department.

Dimethyl Sulfoxide Oxydation Of Hydroxy-Steroids And Studies On The Oxidation Of The 5’–Hydroxy Group Of Nucleosides, Carmen V. Zenarosa

Dissertations

Introduction

In our earlier work we demonstrated the usefulness of the acidcatalyzed reaction between N-(p -tolyl)diphenylketenimine (21) and dimethyl sulfoxide (DMSO) for the oxidation of secondary alcohols. This was exemplified by the oxidation of 2',3'-O-isopropylideneadenosine and other secondary alcohols.¹ We have now extended this procedure to the oxidation of hydroxy-steroids.

Alkynylamines or ynamines can be written in two resonance forms: R-C≡C-N R'₂ and R-C=C=NR'₂. Because of the close similarity between the latter structure and the structure of a ketenimine (R₂C=C=N-R') and the ability of sulfoxide-ketenimine to effect the oxidation of secondary alcohols, we …

Simultaneous Knudsen- And Torsion- Effusion Measurements Of The Vapor Pressures Of Tetraphenyltin And Hexaphenylditin, Dale Keiser

Masters Theses

No abstract provided.

Transpiration Measurements Of The Decomposition Pressures Of Barium Hexafluorosilicate, Kemal Cankaya

Masters Theses

No abstract provided.

Preparation And Lead Tetraacetate Oxidation Of Aldehydic Hydrazones, Alan J. Quarfoot

Masters Theses

No abstract provided.

The Effect Of The Rate Of Formation On The Structure And Properties Of Paper, William M. Reif

Masters Theses

Paper contains an uneven distribution of fiber fractions through its cross section. The objective of this study was to determine how the rate of formation affected the structure and properties of paper. The structure of paper was analyzed with reference to the cross-sectional distribution of fines and the fines to long fibers ratio in the paper.

The formation rate and distribution of fins were varied by applying a vacuum to the British sheetmold system. As the fines were a different color than the long fibers, their distribution was determined by analyzing the brightness values of layers split from the paper. …

The Isoelectronic Principle And The Accuracy Of Binding Energies In The Hückel Method, Jerry Goodisman

Chemistry - All Scholarship

In the Hükkel and other methods, binding energies are calculated by subtracting the sum of orbital electronic energies for the molecule from the sum of orbital electronic energies for the separated atoms, and not considering the internuclear repulsion. Since this last may be several orders of magnitude greater than the binding energy, reasonable results could not be obtained without an approximate cancellation with another neglected term. It is shown that such a cancellation is a consequence of the isoelectronic principle (invariance of binding energy to change in atomic number of constituent atom). Numerical examples are given.

Mössbauer Effect In The Ferroelectric Pbtio₃-Bifeo₃ Solid Solutions, C. M. Yagnik, James P. Canner, Robert Gerson, William Joseph James

Physics Faculty Research & Creative Works

The Mössbauer spectra of the system (PbTiO₃)_0.95(BiFeO₃)_0.05 have been studied from room temperature to 585°C. From the isomer-shift of 0.491±0.02 mmsec^-1 at room temperature, the ionicity is found to be 60% ± 20%. A discontinuity in the plot of isomer-shift versus temperature at T_c is observed. The quadrupole splitting at room temperature is 0.295 ± 0.02 mm/sec^-1. A dip in the Mössbauer fraction is observed at the Curie temperature.

Quasilattice Interpretation Of The Thermodynamic Properties Of Mixing Of Binary Alkali-Metal Systems, J. Bevan Ott, J. Rex Goates

Faculty Publications

Quasilattice theory was applied to heats of mixing in the six systems formed from the binary combinations of Na, K, Rb, and Cs. The alkali-metal systems are particularly well suited for a critical test of the quasi-crystalline assumption since the theoretical model for these systems is relatively simple and the thermodynamic data are fairly complex. Very good fits of the heat-of-mixing data were achieved by assuming that the larger atom in the binary system covered multiple sites on the quasilattice. The values of the empirically determined constants appear to fit the physical significance accorded to them by the quasilattice model. …

Thermodynamics Of Proton Ionization In Dilute Aqueous Solution At 25°, Ernest J. Baca Jr.

Chemistry and Chemical Biology ETDs

This dissertation consists of four studies and is divided into five parts. Part I contains a description of the calculations and equipment used for these four studies.

Part II is a study of tris(hydroxymethyl)nminomethane (THAM) for use as a standard in solution calorimetry. The heat of solution of THAM in 0.100 M HCL was determined at 25°.

Part III is a study of the thermodynamics of proton ionization

from some unsaturated, five membered, nitrogen ring compounds in dilute aqueous solution at 25°. Values of deltaK, pK and deltaS are reported for 1,2,3-triazole, benzotriazole, 4,5-dibromo-1,2,3-triazole, 1-phenyl- 5-methyl-1, 2, 3-triazole-4-carboxylic acid, …

Spectroscopic Studies Of Complexes Of Rhodium (Iii) And Iridium (Iii), Dean H. W. Carstens

Chemistry and Chemical Biology ETDs

A comprehensive experimental and theoretical study of complex compounds of two d6 transition metal ions, rhodium(III) and iridium(III), was made to characterize the electronic transitions responsible for the various bands seen in the absorption and emission spectra and to determine the dependence of the energies of the excited states of a complex ion on the nature of the ligands and the central metal ion. All the complex compounds contained organic ligands—pyridine, 2,2’-bipyridine, or l,l0-phenanthroline—in the principal coordination sphere. Most also had halide ions bonded directly to the central ion. An ancillary study was made of 2,2’,2’’-terpyridine complexes of two d10 …

11th Annual Rocky Mountain Spectroscopy Conference

Rocky Mountain Conference on Magnetic Resonance

Program and abstracts from the 11th 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 4-5, 1969.

The Attempted Synthesis Of Ethylenimine, Rabindranath Patnaik

Masters Theses & Specialist Projects

The object of this investigation was to study the homogeneously catalyzed reaction of acetylene and ammonia and particularly to attempt to synthesize ethylamine by the reaction of acetylene and ammonia.