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Homogenous Catalytic Hydrogenation Of Organic Compounds Using Rhodium-Triarylphosphine Complexes, Jack Lee Parsons

Dissertations

Introduction

The purpose of this research was to study the homogeneous catalytic hydrogenation of α,β-unsaturated organic compounds containing a wide variety of reducible functional groups. The catalysts to be used were rhodium complexes of triarylphosphines. It was also desired to develop these catalytic systems into practical synthetic methods for the reduction of unsaturated compounds.

Data Retrieval In Mass Spectrometry By An Optical Coincidence System, Cynthia Helmintoller O'Donohue

Master's Theses

The object of this work was to develop an information storage and retrieval system for use in mass spectroscopy. The information to be stored was the compound's name, the mass spectrum, and distinctive physical and chemical properties. It was desirable that the system be one that could be used in the mass spectral laboratory. At the time this project was initiated, no system for mass spectroscopy had been developed with the characteristics of simplicity, rapid retrieval, and practicality of use in the laboratory without elaborate and space consuming equipment. Thus, a system was needed to aid the laboratory personnel in …

The Wittig Reaction Of Stabalized Phosphonium Ylids With Derivatives Of D-Ribose, George Robert Wellman

Masters Theses

No abstract provided.

Estimations Of The Effective Electrolytic Surface Area Of Rough And Porous Silver Electrodes ; Ii. Potentiostatic Oxidation Of Silver In Alkaline Electrolyte, James Glenn Bearss

Theses and Dissertations

This dissertation is written in two sections. The first section deals with the development of methods for the estimation of the effective electrolytic surface area of rough and porous silver electrodes in alkaline electrolyte. Data are presented comparing the results of three different methods of surface area estimation. Model pore electrodes were also prepared and oxidized to study the reactions in a pore. Data for constant current oxidations of these electrodes is given. The second section deals with the potentiostatic oxidations of silver in alkaline electrolyte. Data are presented on the total charge acceptance versus applied potential for a potential …

A Kinetic Study Of The Oxidation Of The 2, 3, And 4 Pyridine Aldehydes By Cobalt (Iii) Perchlorate In Aqueous Solution., Ronald Barry Giuntoli

All Master's Theses

Cobalt(III) perchlorate has been shown to be a powerful oxidizing agent and kinetic investigations of the mechanism of oxidation of many organic compounds including organic acids have been performed.

The Effects Of Herbicides On Three Soil Inhabiting Blue Green Algal Species, Lee C. Darlington

All Master's Theses

The object of this study was to examine the effects of varying concentrations of 2, 4-D, Dalapon, and Tordon on the growth of several nitrogen-fixing blue-green algal species obtained from soil samples and grown under culture conditions in the laboratory.

A Thermodynamic Approach To The Study Of Phase Equilibria In The Sodium-Potassium Alloy System I. The Phase Diagram For Nak At Atmospheric Pressure ; Ii. High Pressure Phase Studies, Donald Ray Anderson

Theses and Dissertations

Ultra-pure reagents, platinum resistance thermometry and modern inert atmosphere glove box facilities have made possible a detailed examination of the NaK system at atmospheric pressure. A thermoanalytical study of solid-liquid phase equilibria in the NaK alloy system was conducted in the tetrahedral press to 55 kbars to investigate possible intermediate compound formation and shifting of the invariant points at various pressures. An expected shift in the eutectic composition to lower potassium content with an increase in the halt temperature on increasing pressure was confirmed. A merging of the meritectic and eutectic points at 343 ±2°K and 37 ±3 kbars occurred …

Thermodynamics Of Proton Dissociation And Metal Ion Complexation In Aqueous Solution. I, Cation Binding With Cyclic Polyethers: Significance In Ion Transport Processes. Ii, Proton Dissociation From Adenosine, Several Monosaccharides And Related Compounds. Iii, Proton Dissociation From Several Pyrimidines And Their Nucleosides At 10, 25 And 40°, Joseph Howard Ryttling

Theses and Dissertations

The log K, ΔH° and ΔS° values for the interaction of several metal ions with the two isomers of the cyclic polyether, 2,5,8,15,-18,21 hexaoxatricyclo[20.4.0.0^9,14]hexacosane are reported. The stability order found for alkali metal ion interaction with either isomer is identical to the order of ion permeability through reconstituted biological membranes for structurally related antibiotics. The size of the metal ion is critical in determining the extent of interaction. A calorimetric titration study of proton ionization from several monosaccharides and derivatives, pyrimidine bases and their nucleosides, adenosine and its derivatives, and cycloheptaamylose is described. The heats of reaction obtained in this …

The Catalytic Hydrogenation Of Benzodiazines.|Ni.|Pphthlazine.|Nii.|Pquinazoline, Danny Lee Elder

Theses and Dissertations

Quinazoline and phthalazine were hydrogenated at low pressure and temperature (60 psi, room temperature) and high pressure and temperature (2000 psi, 100°C, 150°C} in neutral and acidic solvents over 5% Pd/C, 5% Ru/C, 5% Rh/Al2O3 , 5% Rh/C, and 5% Pt/C. Chromatographic methods for determining the qualitative and quantitative composition of hydrogenation mixtures were developed. The compositions of quinazoline and phthalazine-hydrogenation mixtures were determined. Eight phthalazine-hydrogenation products were detected and isolated: (1) 1,2-dihydrophthalazine, (2) 1,2,3,4-tetrahydrophthalazine, (3) a,a'-diamino-o-xylene, (4) o-methylbenzylamine, (5) 1,3-dihydroisoindole, (6) o-xylene, (7 and 8) cis- and trans- 1,2-dimethylcyclohexane. These products were identified by isolating them from reaction mixtures …

Solid-Liquid Phase Equilibria Of The Sodium-Rubidium And Sodium-Potassium-Rubidium Alloy Systems, Chen-Chao Hsu

Theses and Dissertations

Thermal methods were used, to determine with high precision, the solid-liquid phase equilibria diagrams for the sodium-rubidium and sodium-potassium-rubidium systems. In the sodium-rubidium system, the results differ greatly from those of earlier works, especially near the eutectic composition where differences in freezing points as large as 25°K occur. A detailed search was made for possible intermetallic compounds (especially Na2Rb). Neither slow temperature cycling in the temperature range where compound formation could occur nor extended periods of annealing just above the eutectic temperature produced any evidence for compound formation in the sodium-rubidium system. A 2:1 (sodium to rubidium) sample was subjected …

Mechanism Of Water Transport Through Reverse Osmotic Membranes, Cheryl Kay Murphy

Theses and Dissertations

Cellulose acetate membranes show a higher permeability to water than to salt and are being used for desalination of salt water by reverse osmosis. Use of highly acetylated cellulose membranes give a higher salt rejection but also decrease flow rate of the water. The addition of very-short-chain substances or alkyl groups larger than one carbon atom to the cellulose membrane also decreases water flux. A proposed mechanism of transport through the membrane is that the water molecule is passed along the chain by hydrogen bonding with the acetyl groups, The NMR shows a change in the chemical shift of water …

Trace Metal Analysis Of Barren River And Nolin River Reservoirs By Atomic Absorption Spectroscopy, Mary Jo Kennedy

Masters Theses & Specialist Projects

This research was part of a project underway at Barren River and Nolin River Reservoirs in south-central Kentucky. The research was partially supported by a grant through the Sport Fishing Institute, Washington, D.C.

The study reported herein was concerned with the analysis of trace metal concentrations in the two reservoirs. It is believed that the fish population may in part depend upon the trace metals present in the water. It is anticipated that the data presented in this paper will eventually be correlated with the biology studies of the reservoirs being carried out by the Department of Biology of Western …

Chemistry Of The Oxidant, Ferrate, Its Interaction With Specific Organics Found In Waste Water, Donald H. Williams, J. T. Riley

KWRRI Research Reports

It became obvious during this investigation that while much work has been done with ferrate (VI) chemistry, discrepancies existed in the literature and very little attention had been given possible engineering uses. This work attempted to fulfill these two needs in an exploratory manner.

The preparative techniques were reviewed and mechanical improvements made in one which allowed improved yields. Essentially what was done was to enlarge and improve the filtering technique of the product and use cooler temperatures throughout the preparation. This greatly shortened the time required. Then it was learned that the addition of ethyl alcohol to the final …

A Thermogravimetric Study Of Polyvinylidene Chloride In Polymers, Charles Edward Singleton

Master's Theses

In the manufacturing of thin films such as cellophane, polymers employed as coatings greatly improve film functionality. Polymers such as polyvinylidene chloride, polyvinyl chloride, polyvinyl acetate and many others are used as coatings or components of coatings designed to improve the functionality of a film. Selection of polymers with properties that will meet the requirements of the finished film product is a continuing process of film manufacturers. Physical and chemical characterization of the polymer along with coating functionality are the factors involved in the selection. Chemical composition is the most important factor affecting polymer characteristics and must be known if …

Peracid Oxidation Of 3-Phenylindene, Christopher Peter Johnson

Master's Theses

Indene oxide (indan, 1,2-epoxy; indene 2,3-oxid is first recorded in the literature in 1919. This compound was formed in practically quantitative yield by the treatment of indene bromo­ hydrin in ether with powdered potassium hydroxide. At this time Van Loon also reported the preparation of indene oxide by mechanical shaking of an anhydrous, ethere!al solution of the bromohydrin with finely powdered potassium hydroxide. The desired product was obtained in a 92-97% yield by this method. Indene oxide has been prepared in a similar manner from trans-2-chloro-l-indanol by treatment "with soda," distillation of the acetone in vacuo after 15 hours, and …

The Oxidative Decarboxylation Of Polyaminocarboxylic Acids - I. A Study Of The Reaction Of Ethylenedinitrilotetraacetic Acid (Edta) With Cerium (Iv) In Acid Solution, Samir B. Hanna, S. Al-Hashimi, William H. Webb, William R. Carroll

Chemistry Faculty Research & Creative Works

The reaction between Ce(IV) and EDTA was followed titrimetrically and spectrophotometrically and was found to occur in stages. Four equivalents of Ce(IV) are reduced per mole of EDTA almost instantaneously at room temperature. With increasing temperature and reaction time an ultimate of about 14 equivalents of Ce (IV) is consumed per mole of EDTA. Carbon dioxide, formaldehyde, and other yet unidentified compounds are the products of oxidation of EDTA. The kinetics of the reaction in aqueous sulfuric acid was studied over the temperature range 11.7°-40°C by a spectrophotometric technique. The effects of the acidity of the medium and of added …

Cyclization Studies Involving The Synthesis Of 5-Substituted-1-Naphthol, Clark Keelock Chow

Dissertations and Theses

The γ-o-substituted-phenylparaconic acids were prepared by a method patterned after that of Fuson. These paraconic acids were prepared in good yield. A re-investigation of the Perkin and Fittig methods of preparing γ-phenylisocrotonic acid was carried out without success.

The synthesis of γ-o-halophenylisocrotonic acids by thermal, and catalyzed decarboxylation of γ-o-halophenylparaconic acid, have been carried out in good yield. An effective catalyst, optimum temperature and reaction period of decarboxylation of the γ-o-halophenylparaconic acids have been determined. Infrared absorptions have characterized the γ-o-halophenylisocrotonic acids formed to be in the stable trans form. …

Syntheses Via Modifications Of The Knorr-Paal Procedure :|Ba. Derivatives Of 2,6-Dioxa-10-Azatricyclo[5.2.1.0[Superscript 4,10]]Decane ; B. Highly Sterically Crowded 1,2,5-Trialkylpyrroles And Pyrrolidines, Weldron Severin Burnham

Theses and Dissertations

Earlier work in these laboratories on the heterotricyclic system 2,6-dioxa-10-azatricyclo[5.2.1.04,10]-decane, formed from 1,4-diketones and 2-amino-1,3-propanediols by a product-water-azeotroping procedure, was extended with the synthesis of analogous compounds, e.g., the 1,4,7-triethyl-, 1,7-dimethyl-4-isopropyl-1,7-diethyl-4-isopropyl-, 1,7-dimethyl-3- and 4-phenyl- compounds. The 1,7-dimethyl heterotricycle, the kinetically-controlled product, was accompanied by the thermodynamically-controlled product, 2-(2,5-dimethyl-1-pyrryl)-1,3-propanediol. The 1,7-diethyl heterotricycle was also accompanied by the isomeric pyrrole as were the 1,7-dimethyl-3- and 4-phenyl compounds. A scheme postulating a common intermediate is presented. The interesting analogous compounds, 1,7-dimethyl-2-oxa-6-thia-10-azatricyclo[5.2.1.04,10]decane, 1,4,7-trimethyl-2,6-dioxa-11-azatricyclo[5.3.1.04,11]undecane and 11-hydroxymethyl- and 11-methyl-9,13-dioxa-14- azatetracyclo[6.5.1.02,7 011,14]tetradeca-2,4,6-triene were also prepared. The syntheses in good yields of a considerable number of moderately to …

High Pressure, High Temperature Syntheses Of Selected Lanthanide-Tellurium Compounds, John Francis Cannon

Theses and Dissertations

High pressure, high temperature technics were employed to successfully synthesize HoTe1.7, ErTe1.7, TmTe1.7, LuTe1.7, YTe1.7, and LuTe3. The pressure-temperature regions in which synthesis of each compound is successful were determined. Pressures to 100 kbars concurrently with temperatures to 1200 °C were used in an attempt to prepare ScTe1.7 and ScTe3, but these efforts met with failure. X-ray studies of these new compounds confirmed that they are extensions of the LTe2-X (0≤x

Glycosidic Enzymes Of The Tropaeolum Majus, Donald Richard Snowden

All Master's Theses

The purpose of this study is to investigate the hydrolytic enzymes of Tropaeolum majus. This particular plant is the only example of the Tropaeolum genus found in the northern hemisphere. It is the well-known Indian cress or common garden nasturtium.

A Comparison Of The Effects Of Fluoride And Chloride Ions Upon The Activity Of Yeast Alcohol Dehydrogenase, Ellen J. Hannan

Dissertations and Theses

Very little is known about the effect of hydrofluoric acid and of the fluoride ion on enzyme systems. The purpose of this work was to determine the effect of hydrofluoric acid and of the fluoride ion on the enzyme, yeast alcohol dehydrogenase and to distinguish between the effect of the fluoride ion and of hydrofluoric acid. The rate of the enzyme reaction was followed spectrophotometrically at 340 mμ on the Cary 14 Model spectrophotometer according to the method of Racker. The data taken from the instrument recordings were plotted on two types of graphs, the Lineweaver-Burk plot and the Hanes …

Liquid Scintillators. The Decomposition Of 2, 5-Diphenyloxazole In Ultraviolet Light. A Thin Layer Chromatography Study, John W. Hustler

Chemistry and Chemical Biology ETDs

A study has been initiated in order to understand more completely the manner in which a model organic scintil­lator decomposes in ultraviolet light. The compound, 2,5-diphenyloxazole (PPO), was dissolved in toluene in quartz vials and irradiated with ultraviolet light for various intervals of time. Both. vacuum-dried and untreated samples of PPO \·1ere subjected to UV excitation in sodium-dried and water-saturated solutions of toluene. The effect of passing oxygen and nitrogen through the solutions was also studied with the confirmation that dissolved oxygen and water accelerated the decomposition leading to the formation above the meniscus of the vial of a white …

The Chemical Behaviour Of Iodine At Low Concentrations In Strongly Acidic Solutions, Howard Allen Boyd Jr.

Chemistry and Chemical Biology ETDs

Radioactive tracers have been used extensively to investigate the behavior of substances at concentration too low to be detected by ordinary chemical or instrumental methods (1). Some elements exist only as short lived isotopes, and their chemistry is known only

in terms of their behavior at low concentrations, Other elements that have stable or long lived isotopes may be studied at low con­centrations by the use of suitable tracers, usually carrier-free radioisotopes when they are available,

Breaching The Walls, Wendell W. Hess

Honorees for Teaching Excellence

No abstract provided.

Relative Electronegativities Of The Propyl Groups, Barry Arkin

Senior Scholar Papers

Vapor pressure determinations in a vacuum line were made first on varied compositions of acetone and pyridine and second on varied compositions of acetone and trimethylamine. These experiments were conducted in the hope of noting a negative deviation from Raoult's Law, which is indicative of adduct formation between the two substances. No such deviation was found in either case. Vapor pressure determinations were then made on varied compositions of 1) acetone and chloroform, 2) 4-heptanone and chloroform, 3) dicyclopropyl ketone and chloroform, and 4) diisopropyl ketone and chloroform. In each of these systems a negative deviation from Raoult's Law was …

Relative Donor Properties Of Various Propyl Ketones In Iodine Solution Using Spectroscopic Methods, Christine Franchi

Senior Scholar Papers

Ketones in iodine solution are capable of transferring a nonbonding electron from the carbonyl oxygen to a halogen molecule forming a charge transfer complex. The electron-repelling nature of alkyl groups on either side of the carbonyl contributes to electron density and makes the ketone a better donor. The equilibrium constant of complex formation is an experimental measure of relative donor basicity and a theoretical measure of inductive effects. This study has determined that (1) the difference in inductive nature between a n-propyl and a methyl group is apparently negligible and (2) equilibrium constants may not be correlated with inductive effects …

Chemical Effects Of Beta Decay Of Molybdenum-99-Labeled Molybdate, Jane A. Seck

Student Scholarship

This research investigates the chemical consequences of the beta decay of molybdenum-99 when in the form of the molybdate ion, specifically focusing on how these effects impact the efficiency of technetium-99m generators used in medical diagnostics. Technetium-99m is a vital radiopharmaceutical for tumor localization and brain scanning due to its short half-life and ideal gamma emission energy. However, clinical generators often fail to yield the theoretically calculated maximum amount of technetium, typically eluting only 60 to 80 percent of the activity. This study hypothesizes that the recoil energy produced during beta decay is sufficient to rupture metal-oxygen bonds, leading to …

The Thermodynamics Of Transition Metal Chelation In Dilute Aqueous Solution.|Ni.|Pthe Thermodynamics Of Interaction Of Serinate Ion With Divalent Co, Ni, Cu, Zn, And Cd Ions In Aqueous Solution.|Nii.|Pthe Calorimetric Standardization Of Dilute Ferrous Ion Solutions For Use In Determining 2,2'-Bipyridine, Joseph Willard Richards

Theses and Dissertations

Calorimetrically determined ΔH° values are given for the stepwise formation of chelate species between serinate ion and the divalent metal ions of Co, Ni, Cu, Zn, and Cd. These values of ΔH° are compared with those reported in the literature and were combined with values of ΔG° (log K) found in the literature to calculate values of ΔS°. These values of ΔG° and ΔS° are listed also. A new method of standardizing dilute ferrous ion solutions is reported. This procedure makes use of the thermometric titration technique to detect the equivalence point for the reaction of K_2Cr_2O_7 with ferrous ion. …

The Synthesis And Reactions Of Isatoic P-Linear Bis Anhydride, Willis G. Frick

Chemistry Honors Papers

This 41 page thesis examines methods of synthesizing isatoic anhydrides.

Knudsen- And Torsion- Effusion Measurements Of The Vapor Pressure Of Manganese(Ii) Fluoride, Walter Clayton Hitchingham

Masters Theses

No abstract provided.