Physical Sciences and Mathematics Commons^™

Separation Of Optical Isomers By Solvent Extraction, George Truett Mccloud

Masters Theses

The purpose of this research was to develop a solvent extraction method to resolve optical isomers. Earlier work²⁵ done in this laboratory has indicated that partial resolution had been obtained by using D(+)-diisopropyl tartrate and water as the immiscible solvent system. Further work done by the author indicates that this method can be used to partially resolve racemic modifications. Before this method is discussed in detail, a summary of the known methods of resolution should be presented.

Intramolecular Spin-Orbit Coupling In Naphthalene Analogs, Francis Elliott Shoup Iii

Chemistry and Chemical Biology ETDs

The objective of this study was to gain additional insight into the phenomenon of spin-orbit coupling in molecules by examining the intramolecular mechanisms responsible for the phosphorescence of certain types of molecules. Spectrocopic investigations of a series of aromatic hydrocarbons, aromatic heterocyclics, and some of their halogen derivatives are reported. Experimental measurements included absorption spectra, total emission spectra, polarized emission spectra, obtained by the method of photoselection, and radiative lifetimes.

Crystal Field Splitting In Rare Earth Chelates, Walter George Perkins

Chemistry and Chemical Biology ETDs

Investigations of ligand field effects in the spectra of trisdibenzoyl­methide, trisbenzoylacetonate, and trisacetylacctonatc chelates of trivalent ytterbium and thulium are reported. Chelate absorption and luminescence spectra corresponding to intra-4f electronic transitions exhibit line split­tings similar in magnitude to the crystal field splitting observed in the spectra of inorganic complexes of the rare earth ions.

Absorption spectra of carbon tetrachloride solutions of all the che­lates studied were measured in the visible and near infrared regions. Each ytterbium chelate exhibits an absorption band at 9800A, consisting of three well-resolved peaks. Thulium intra-4f absorption bands appear at 4700A, 6800A, 8000A, 12000A, and 17000A. …

Studies Of Tetrakis (Pyridine Base) Nickel (Ii) Perchlorate And Bisperchloratotetrakis (Pyridine Base) Nickel (Ii) Complexes, Lawrence Edward Moore

Doctoral Dissertations

The stereochemistry of nickel (II) compounds has been one of the most active and controversial fields of research in inorganic chemistry during the last 10 years. The multitude of colorful nickel compounds has intrigued chemists for a much longer time, but only in relatively recent years have such tools as visible and infrared absorptiometry, group theory and quantum mechanics, magnetic measurements, x-ray studies, and conductance measurements been brought to bear effectively to unravel the questions on stereochemistry in metal complexes.

Evaluation Of Methods Used In The Determination Of Stability Constants Of The Thallium (Iii)-Chloride System At Twenty-Five Degrees, Nelson Kent Dalley

Theses and Dissertations

The difficulties encountered in the determination of equilibrium constants in systems with small, not directly rneasureable free ligand concentrations are discussed. These difficulties are illustrated using the determination of the formation constants of the Tl(III)-Cl- system as a specific example. Four methods are used and evaluated in this study. They are (1) the corresponding solutions method, (2) the method of Fronaeus, (3) the solubility of AgCl in Tl(III) solution method and (4) the method of Hugus. A discussion and derivation of each of these methods is given. The first three methods given and free ligand concentration data from which formation …

Metabolism Of Thiamine And The Effect Of Some Antagonists, Russel M. Bender

Theses and Dissertations

To investigate the possibility that thiamine has more than one vital role in the mammalian system, it was decided to use the antagonists pyrithiamine and oxythiamine, and to utilize carbon-14 labeled compounds to more effectively study the vitamin and the above-named antagonists. To make it more effective, we felt that perhaps differences between the localization of oxythiamine and pyrithiamine could be detected in the brain. We also considered and tested the possibility that either or both of the antagonists would alter the localization of thiamine. Essentially, two procedures were used in this study. One was a counting method and the …

Potential Pharmaceutical Derivatives Of Β-Aminoethylpiperazine, Brian A. Dementi

Master's Theses

This thesis is concerned with the design and preparation of certain organic compounds which are expected to have medicinal properties. A discussion will be given which has essentially a two-fold purpose. The first is to discuss somewhat briefly the currently accepted method of rug design, and the second to show to what extent this method has been followed in the design of the compounds prepared.

A Study Of The Infrared Spectra Of A Group Of Hydroxyalkylamine Hydrochlorides, Lawrence Ingram Briel

Master's Theses

The infrared spectra ot twenty amine bydroohlorides were obtained with the Perkin-Elmer Model 21 recording spectrophotometer. The positions of the absorption bands were compared with literature values for pertinent structural group frequencies. A system of coding the spectral data was devised so that an IBM 1620 digital computer could make the comparisons for a large number of' group frequencies. Good agreement was observed between the positions of the absorption bands in the experimental spectra and those of pertinent group frequencies reported in the literature.

Of the ten symmetrical diamines which were studied, six contained the primary hydroxyl group. Two …

The Reaction To Ketoacylhydrazones With Lead Tetraacetate, Lavern M. Weisenberger

Masters Theses

Introduction

It has been shown that ketohydrazones react with lead tetraacetate to give azoacetates in good yields (11) according to the following equation:

R₂C=N-NH-R + Pb(OAc)₄ → R₂C(OAc)-N=N-R + Pb(OAe)₂ + HOAc

The reaction of the structurally related 4,4- disubstituted ketosemicarbazones with lead tetraacetate quite unexpectedly gave carbamates in good yields (10) presumably according to the following equation:

R₂C=N-NH-Co-NR₂ + Pb(OAc)4 → R₂C-O-CO-NR₂ + N₂ + Pb(OAc)₂ + HOAc

CO

ı

CH₃

Spectroscopic Studies Of Tris (2,2'-Bipyridine)- And Tris (I, 10-Phenanthroline) Iron (Ii), -Ruthenium (Ii), And -Osmium (Ii)., Sonia Lee Sabath

Chemistry and Chemical Biology ETDs

The tris(2,2'-bipyridine)- and tris(l,10-phenanthroline) complexes of iron(II), ruthenium(II), and osmium(II) were synthesized, purified, and characterized by analyses. The solution absorption spectra of the compounds were measured both in the ultraviolet and visible regions. The observed ultraviolet absorption bands of the ruthenium and osmium complexes were assigned entirely to transitions, the prominent bands being assigned to ligand (perturbed) transitions by comparison with the published assignments of the corresponding bands in analogous iron complexes. The visible absorption spectra for iron(II) and ruthenium(II) complexes were attributed entirely to singlet-singlet charge transfer transitions. The strong visible absorption bands of osmium(II) complexes were also assigned …

Edta Titrations With Mercury Amalgam Indicator Electrodes, Kenneth Deardorff Legg

Honors Theses

A study of the characteristics of certain mercury amalgam electrodes as used in these types of analysis has been made. The overall applicability and usefullness of a bismuth-mercury slurry electrode is studied. The effect of several solution conditions on the electrode characteristics has been observed.

The Synthesis And Evaluation Of Some 2-Arylindenes And 2-Aryl-3h-Benz[E]Indenes As Liquid Scintillation Solutes, James Leslie Schornick

Chemistry and Chemical Biology ETDs

A scintillator, in the chemical sense, is a system which can convert radioactive particle energy to visible and near ultraviolet photon energy. A phenomenon related to scintillation is fluorescence. The difference between scintillation and fluorescence is the source of excitation energy. In the case of scintillation, the exciting energy comes from radioactive particles, while in fluorescence, the exciting energy comes from ultraviolet light.

A Polarographic Analysis Of The Tetracyanoaurate (Iii) And The Dicyanoaurate (I) Complexes, David Jefferson Mcclemens

Honors Theses

A polarographic analysis of the two gold complexes, dicyanoaurate (I) and tetracyanoaurate (III), was undertaken. Both complexes were shown to have distinguishable current-voltage curves. Previous work on the dicyanoaurate (I) was confirmed, and new data was added for the low concentrations. The tetracyanoaurate (III) was investigated, and the half-wave potential was found to be -0.32 volts. Maxima problems with the complex were encountered and resolved.

Aspects Of The Reactions Of Aliphatic Methoxydiazoketones, Francesco Gioacchino Belli

Honors Theses

It was the purpose of this research to investigate the cyclization of the aliphatic methoxydiazoketohe, 1-diazo-4-methoxy-4-penyl-2-butanone (I), when treated with BF3 in ether.

The Catalytic Decomposition Of Sucrose, Richard Wells Bishop

Honors Theses

The object of this research was to gain enough information from the products of sugar decompositions to allow the proposal of a mechanism for these decompositions. The information on sucrose would be combined with that for glucose and fructose to make this proposal.

Separation And Radiochemical Study Of Molybdic And Tungstic Oxides, John Hotchkiss Boles

Honors Theses

In the work presented here, tungsten and molybdenum are precipitated and chemically separated as much as is possible. The products are collected and irradiated with thermal neutrons and the concentration of tungsten determined. In this way only that tungsten forming a complex or dissolving into the molybdenum crystal will be measured.

A Proposed Method Of Separation And Analysis Of The Au(Cn)2 And Au(Cn)4 Complexes, Richard Edward Beane

Honors Theses

Due to its relative scarcity, gold has always held a high value to civilizations compared to other metals which are more common and easier to obtain. Various methods of extraction of the metal have been used throughout history, the most successful of which are washing and dissolution. The most important method of recovery at the present time is dissolution by cyanidation. In order to study the electron exchange between the Au(CN)-2 and Au(CN)-4 complexes, it must be possible to obtain both separately, mix them together in solution, separate them once again, and distinguish between the two complexes to determine the …

Synthesis Of The Bicyclo-(5,5,0)-Dodecane System, Anthony Angelo Gallo

Honors Theses

The bicycle-(5, 5, 0)-dodecane system consists of two fused seven membered rings. (I) The numbers five, five and zero are arrived at by the fact that counting the number of carbon atoms from one bridgehead carbon to the other yields five, five and zero by the three possible routes. This system can exist in several states of unsaturation. One such state has been given the name heptalene. (II) The object of this project is to propose a new synthesis of the bicycle-(5, 5, 0)-dodecane system.

On The Recovery Of The Nitrates Of Uranyl Ion And Silver (I) Ion From Laboratory Residua, Bruce Bertolette Hardman

Honors Theses

Uranium became known in the same epoch of history that saw the discovery of the planet Uranus. It was so named. Uranium is a rather active element and never occurs free in nature. Its ores include uraninite is by far the most important. This ore is sometimes called pitchblende and has a simplest empirical formula of UO2. Due to the fact that it is always found partially oxidized its composition may range between that of UO2 and U3O8. This latter form contains both tetra and hexavalent uranium. An illustrative structure is given below. It is sometimes regarded as uranyl uranate, …

An Examination Of Basicity Functions, Lewis Morton Gedansky

Honors Theses

Acids and bases have long been subjects of interest to the chemist. These two classes of chemical compounds play an important role in the chemical world in regards to their reaction with each other and their use as catalytic agents. They are known to react with each other in either of two ways. The reaction which is most familiar is the standard neutralization reaction which results in the formation of a salt and water. It can be illustrated by the reaction of an acidic substrate, HA, reacting with the base, sodium hydroxide. Such a reaction conforms with the Bronsted-Lowry definition …

The Determination Of The Ratios U234/U238 And Th228/Th232 As Leached From Storm King Granite, James Robert Lawrence

Honors Theses

In nature there are three major decay series that involve naturally occurring uranium and thorium as parent nuclides. Two of the three series; U-238, TH-232 and U-235; are shown in figure I. Of the three series two, U-238 and the Th-232 series, are examined in the study. This is because the amount of U-235 in nature is very small relative to the amount of U-238 and Th-232. This study is concerned with the presence of U-238 and Th-232 and their uranium, thorium and radium daughter products in the silicic intrusive rock, Storm King Granite. Uranium and thorium have large iconic …

An Investigation Of The Ternary System: Magnesium Sulfate - Urea - Water, David Brian Holland

Honors Theses

Magnesium sulfate hydrate and urea are common constituents of many commercial fertilizers. It is the purpose of this investigation into the ternary system: magnesium sulfate – urea – water to try to resolve these discrepancies and also to further investigate the ternary system.

A Hydrogen Electrode Via Ferrous Ion And Ultraviolet Light, Richard Leslie Harlow

Honors Theses

The purpose of this research is to investigate the photoelectric properties of an acidified ferrous-sulfate solution. It is known that in the presence of ultraviolet light, the equilibrium is shifted to the right. The idea is proposed that the hydrogen gas produced by this reaction might be absorbed on a platinum grid, thereby creating a hydrogen electrode. A cell is thus proposed in which two platinum electrodes are immersed in the same solution of ferrous sulfate and sulfuric acid. The area surrounding one electrode is to be illuminated with ultraviolet light. Some of the hydrogen gas produced in that area …

Synthesis Of 1-Diazo-3-Methoxy-3-Phenyl-2-Propanone And Reaction With Boron Trifluoride Etherate, Harvey Harris Kagan

Honors Theses

It has been found that the normal reaction of diazoketones with an acid to form substituted methyl ketones is often subverted by cyclization to form closed chain cyclic ketones. Some work has been done with aromatic diazoketones but very little has been done with the aliphatic diazoketones. The object of this research was to bring about ring closure of a four membered ring from an aliphatic diazoketone. It was decided to put a phenyl group on the aliphatic chain in order to obtain crystalline derivatives. Specifically, the object of this work was to bring about the cyclization of 1-diazo-3-methoxy-3-phenyl-2-propane. The …

Synthesis Of Some Polymers From Benzyl Alcohol Or Its Derivatives, John Oliver Rosser

Honors Theses

The original project was concerned with the production of ortho-nitro-para-[w-(β-napthyl)]-ethyl-benzyl alcohol or its alkyl-ether. This was to be accomplished by following a five step synthesis, the first step of which was a Friedel Crafts acylation of methyl-benzyl ether according to reaction (1).

Heats Of Solution Of Saturated Mixed Electrolytes, Stephen Alan Rudolph

Honors Theses

Reliable data on heats of solution of concentrated mixed electrolytes is a rather scarce. This work purports to give formulas for the heat of solution at saturation of an electrolyte in a solution saturated with respect to still another electrolyte. These formulas are in terms of solubility data and non-calorimetric thermodynamic data and are as follows.

Phosphoric Acid - Catalyzed Hydrolysis Of Benzeneboronic Acid, Kenneth Sumner

Honors Theses

At a phosphoric acid concentration of over 80%, the kinetics are not first - order, but instead, the reaction appears to be autocatalytic. Is it the purpose of this research to determine if this phenomenon is real, and if so, to elucidate the cause of the autocatalysis.

Attempted Preparation Of 1-Diazo-6-Methoxy-2-Hexanone, Edmund Joseph Zalewski

Honors Theses

To show the appreciable yield of cyclic compounds upon treating the methoxydiazokotones with boron trifluoride etherate.

Synthesis Of 3-(P-Methyl-M-Nitro-Phenyl)-Butyric Acid, Beverly Thomas Adams

Honors Theses

The purpose of the research reported in this thesis was the synthesis of one of a class of compounds, ω-napthyl-alkyl-substituted nitro benzaldehydes, for use in later work involving photochemistry. The compound chosen was p-(ω-naphthyl-propyl-)-2-nitro-banzaldehyde.

Molybdenum-L-Histidine Complexes, Jiing-Yun Lee

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

L- Histidine is a very important amino acid and is widely distributed in living systems. In the growth and multiplication of animal cells, it was found that L-histidine is one of the amino acids that must be present. From the kinetic studies of certain enzymes such as chymotrypsin and ribonuclease, it has been proposed that the imidazolyl group of the histidine residue may serve as the basic electron donor, and that the histidine residue in some cases may be the active site of the enzyme. The interactions of L-histidine with heavy metal ions, including Ni (II) (1), Zn (II) (1, …