Physical Sciences and Mathematics Commons^™

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 …

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 …

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 …

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.

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.

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 …

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 …

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 …

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 …

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 …

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 …

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. …

Molecular Orbital Study Of Internal Rotation, Mark S. Gordon

Mark S. Gordon

The CND0/2 molecular orbital method is used to predict and explain the barriers to internal rotation in a number of molecules. The observed 3: 2: 1 ratio of the barriers in ethane, methylamine, and methyl alcohol is approximately reproduced as are most trends in the barriers of fluoro-substituted propenes; however, the calculated trends for fluoro-substituted ethanes are incorrect. The barriers in H202, F202, N2H4, N2F4, and NH20H and the effect of geometry optimization on these barriers are also discussed. The major source of the barriers in the first group of molecules is predicted to be due primarily to nonbonded interactions …

A Fluorometric Study Of Carbamic Acids And Carbamates As An Explanation Of Carbon Dioxide Transport In The Blood, Gerald John Tiberio

Honors Theses

The original project was conceived during the summer of 1967 while Bruce Cassidy was a research fellow of the Maine Heart Association. It is through his efforts I became aware of the problem.

This research project was undertaken in order to determine the applicability of fluorometry as a means of studying the carbamate reaction of simple amino acids to model the physiological substrate hemoglobin.

Nmr Investigation Of Alkylated Diethylene - Triamine Chloro Complexes Of Trivalent Gold, Alan Robert Case

Honors Theses

The rate expression for the su~stitution of a ligand in a square planar complex was first introduced in 1953 by Taube and Rich (1). The present study was undertaken in the hope of gathering some evidence for this postulated steric hinderance by use of Nuclear Magnetic Resonance Spectra (NMR). Study was limited to one family of complexes, the alkylated diethylenetriamine chloro complexes of gold (III).

Radiolysis Of Saturated Aqueous Iodine Solutions, Gregg Alan Foster

Honors Theses

It is a well-known fact that water, when subjected to ionizing radiation such as x-ray or gamma radiation, undergoes a decomposition. The generally accepted decomposition, although complex, may be represented by (1): It is also accepted that "when dilate solutions are irradiated, practically all the energy absorbed is deposited in water molecules and the observed chemical changes are brought about indirectly via the molecular and, particularly, the radical products. Direct action due to energy deposited in the solute is generally unimportant in dilute solutions (i.e at solute concentration below about 0.1M)” (3). Realizing that iodine is an excellent radical scavenger …

Energy Calculations For The 1Εg+, 1Δg, And 3Εg- Electronic States Of The Oxygen Molecule Using A Tangent Spheres Approach, Donald Francis Durocher

Honors Theses

J. W. Linnett has proposed in his book, The Electronic Structure of Molecules (l), an approach to molecular orbital theory which he calls the double-quartet approach. The double-quartet, or d-q approach in a molecule with a completed octet, states that electrons of each spin set assume, or try to assume a tetrahedral array around their 'mother atom'. In the case of molecular oxygen, there are three d-q figures representing the molecule in its ground and 1∑+g , 2∆g, states. This representation is shown in Figure 1. Henry A. Bent, at the University of Minnesota, has proposed that the electrons in …

The Radiolysis Of Aqueous Chloroform Solutions, Francis John Simone

Honors Theses

Saturated aqueous chloroform solutions have been irradiated with a 250 Curie gamma source. G-values for the production of hydrogen gas in neutral and acidic solutions have been determined.

Qualitative Thermodynamic Study Of Linkage Isomerism In Palladium (Ii) Complexes, Walter Michael Gantenbein

Honors Theses

The purpose of this research was to investigate linkage isomerism in dithiocyanatobistriphenylarsinepalladium (II), dithiocyanato-2,2'­bipyridinepalladium (II), and thiocyanatotetraethyldiethylenetriammine­palladium (II) thiocyanate. Studies of linkage isomerism in these compounds were made in the pure solid state using a Differential Scanning Calorimeter. The instrumental data was supplemented with visual observations of the isomerization.

Synthesis Of Silicon Compounds For Use In (P -> D) Pi-Bond Studies, Mark Thomas Messe

Honors Theses

A new compound, (CH3CH2)2 NCH2Si (CH3)3 (I), was prepared. Attempts at synthesis of Ø-N (CH3) – CH2Si (CH3)3 (II) failed while synthesis of CH30 – CH2Si (CH3)3 (III) gave approximately 85 percent product. Difficulty was incurred in the purification of III, probably because the reactants were not sufficiently dry. Compound I was only slightly miscible in CD2=S-CD3 in dimethylsulfoxide-D6. The soluble portion showed no exchange of the methylene hydrogens in I by deuterium from the solvent although some decomposition might have occured. The apparent complete absence of an exchange reaction suggests that even in the presence of the electronegative nitrogen, …

Towards Synthesis Of Bis -(N,N'-1,8-Naphthylene)- 1,8 - Diaminonaphthalene, William Chiu-Sheung Ng

Honors Theses

This project is concerned with attempted synthesis of a special highly symetrical compound. In the process of synthesis, It is conceivable than an intermediate product will be formed.

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 …

Electrogeneration Of Molybdate Ion, Michael John Milano

Honors Theses

The electrogeneration of molybdate ion (MoO4-2) for possible use in a coulometric determination of thorium or lead has been investigated. Constant current electrolyses were used to study the oxidation of molybdenum to molybdate. It was found that molybdate can be generated in 1N HCl with from 96 to 100% efficiency. The current efficiency for molybdate generation in less acidic media could not be determined accurately. Coulometric titrations of known amounts of thorium with electrogenerated molybdate have been carried out. The endpoints, which were determined amperometrically, were found to be inexact and reproducible to only ± 5%. Coulometric titrations of lead …

Synthesis Of Benzyl-Beta-D Alcohol For Use In Studies Of Photolytic Solvolysis Reactions, John Crest Anes

Honors Theses

This project proposes a means for determining whether certain photochemical solvolysis reactions proceed by an SN1 or SN2 type mechanism. The method uses optically active substrates to determine whether the displacement reaction occurs with racemization or retention of configuration. This paper deals with the synthesis of optically active benzyl-α-d alcohol from which various appropriate substrates required for the study can be prepared. Benzaldehyde---d is first prepared by the Stephens reduction of benzonitrile using stannous chloride and deuterium chloride. The optically active alcohol is then prepared by the reduction of thebenzaldehyde-d with optically active isobornyloxymagnesium bromide.

Toward A Synthesis Of Acenaphth (1,2-A) Acenaphth (1,2-A) Acenaphthene, John Isaac Gerson

Honors Theses

The purpose of this project was to synthesize acenaphth (1, 2-a) acenaphth (1, 2-a) acenaphthene. The project originally followed Letsinger's preparation of a synthetic precursor called acenaphth (1, 2-a) acenaphthylene, which was to be dibrominated, giving the cis-6b, 12b derivative. This derivative was to be reacted with naphthalene to yield the desired product; but this route was abandoned when a necessary forerunner of Letsinger's hydrocarbon called 1, 8-dibromonaphthalene was obtained in very low yield. An alternate procedure leading to Letsinger's hydrocarbon, involving the Friedel-Crafts addition of 1, 8-di (chloromethyl) - naphthalene to naphthalene, was devised, and a synthetic precursor of …

Potentiometric Edta Titrations Using A Bismuth Amalgam Electrode As Indicator, Wayne Michael Butler

Honors Theses

Previous work in the field of potentiometric titrations using bismuth-mercury electrodes with ethylenediaminetetraacetic acid as the titrant have been largely reproduced. The bismuth amalgam electrode has been further developed to provide ease of preparation and maintenance and through improved techniques of cleaning to eliminate electrode poisoning effects. Various titrations have been studied to determine the solution conditions necessary for maximum end point breaks, good electrode poise, and rapid and steady equilibrium of the electrode. These conditions have been adapted to make the electrode suitable for use with automatic titration equipment and for the analysis of multicomponent mixtures.

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 …

Breaching The Walls, Wendell W. Hess

Honorees for Teaching Excellence

No abstract provided.