Chemistry Commons^™

Toward Hydrogen Bonds Of Predictable Geometry, Robert Shao-Chih Hsu

Theses and Dissertations

A literature review on the geometry of hydrogen bonding showed that the geometry is often de-emphasized or even ignored, probably because of the inherent flexibility of many systems studied. Examination of molecular models suggested the geometrically constrained bicyclo [2, 2, 1] heptane system wherein hydrogen bond distances and angles might be more easily predicted. Dihydroboration-oxidation of norbornadiene was shown to yield exo, exo-2,5-norbornadiol, thus clarifying uncertainties in the literature. 2, 5-Norbornadiol was oxidized to the corresponding dione, heretofore inadequately characterized. Several derivatives of the dione were prepared, and spectral data were accumulated for the dione, its precursor, and its derivatives. …

Acid-Base Titrations In Sulfolane., Francine O. Lawrence

Chemistry and Chemical Biology ETDs

A study of the solvent effects of sulfolane (tetrahydrothiophene 1,1-dioxide, tetramethylene sulfone) upon a series of acids and several bases has been conducted. A procedure is presented for purifying sulfolane which results in a solvent of very low water content (5 x 10^-4 M ) and very few impurities, as shown by its cooling curve. Potentiometric and conductometric measurements of additions of acids and bases to purified sulfolane and of various acid-base titrations were made. The series of carboxylic acids included benzoic, orthomethoxybenzoic, and three different monochlorobenzoic acids. The bases investigated included sodium methoxide, pyridine, and diphenylguanidine. Interpretation of the …

Preparation And Reactions Of 2-Benzo [B] Thienylsodium, Larry Kennard

Morehead State Theses and Dissertations

A thesis presented to the faculty of the School of Science and Mathematics at Morehead State University in partial fulfillment of the requirements for the Degree of Master of Science in Chemistry by Larry Kennard on April 21, 1972.

19f Nmr And Bx3 Complexes, Nancy Toole Tucker

Morehead State Theses and Dissertations

A thesis presented to the faculty of the School of Sciences and Mathematics at Morehead State University in partial fulfillment of the requirements for the Degree of Master of Science in Chemistry by Nancy Toole Tucker on April 21, 1972.

A Spectrophotometric Study Of The Reaction Between Benzoyl Peroxide And N, N-Dimethyl-P-Phenylenediamine, Bertha Cosby King

Master's Theses

A special need for methods to determine low concentrations of organic peroxides originated because of their hazardous and harmful effects, Even the small amounts of organic peroxide formed by autoxidation in ethers exposed to air make the ethers highly explosive and unsuitable for use as anesthesia or laboratory solvents. The formation of organic peroxides in fats and oils causes rancidity. They have been named as pollutants, and some of them are known to have detrimental physiological effects.

The purpose of this research was to improve this method of analysis and to determine better conditions for the measurement of color by …

The Relationship Between Degree Of Clay Dispersion And The Optical And Pore Properties Of Starch - Clay Coatings, Chinu S. Dalal

Masters Theses

No abstract provided.

Kinetics Of Free Radical-Initiated Polymerization Of Α-Methylstyrene In The Region Of The Ceiling Temperature, Fred E. Huang

Masters Theses

No abstract provided.

Development Of An Ultra High Shear Recording Viscometer, David C. Thornton

Masters Theses

No abstract provided.

Heats Of Combustion Of Alpha-Methylstyrene Oligomers, Dale Keith Humbert

Masters Theses

Introduction

The heat of polymerization (∆H_p) of α-methylstyrene (AMS) has been a source of study for many years. The structure of AMS is shown in Figure 1.

The first quantitative work was done by Roberts and Jessup.¹ Their values were more positive than those theoretically calculated by Flory² and compared with ∆H_p data of other systems. This was not totally unexpected and could be satisfactorily explained on the basis of steric hindrance and loss of resonance energy of conjugation. This steric hindrance arose from "head-to-tail" polymerization of the 1, 1-disubstituted ethylene structure.³ Their data …

Continuous Wave Co2 Laser Degradation And Mass Spectrometric Analysis Of Organic Polymers., Stanley G. Coloff

Chemistry and Chemical Biology ETDs

Previous laser-mass spectrometer and laser-gas-chromatographic instruments for study of organic polymer degradation have used high power pulsed lasers (ruby, Nd-glass) which limit sample characterization due to extensive fragmentation.

A new experimental technique has been developed for high temperature pyrolysis and rapid analysis of organic polymers. The experimental technique combines a low power continuous wave CO2 laser for sample pyrolysis and a time-of-flight mass spectrometer to analyze degradation products. The laser built for use in this study was a continuous flow CO2 gas-molecular laser excited by high voltage direct current with maximum power of 10 watts at a wavelength of 10600 …

Spectral Studies Of Hydrogen Bonding In Alcohols, Linda Moree Higgins Collins

Masters Theses

The phenomenon of hydrogen bonding in alcohols has been known since the early 1900's. Using three series of alcohols, benzyl alcohols, norbornanols and substituted naphthalene alcohols, it was hoped that some meaningful data could be presented to help clarify and expand some of the theories on alcohol association. The techniques to be utilized were ir and nmr spectroscopies.

The synthetic route for those compounds that were not available as alcohols involved reduction of the corresponding acids to alcohols by use of lithium aluminum hydride. The strengths of the various types of hydrogen bonds, intramolecular and intermolecular, were detected by nmr …

Catechol Effected Dissolution Of Silicate Minerals, James Maurice Kelley

Dissertations and Theses

The chemical properties of guanidinium tris(catecholato)siliconate, [(H₂N)₂C=NH₂]₂[Si(C₆H₄O₂)₃]·XH₂O (0 < X < 1), precipitated from an ammoniacal solution of silica and catechol by adding guanidinium hydrochloride, (H₂N)₂C=NH·HC1, were studied, and infrared, nmr, x-ray powder diffraction, and analytical data were gathered.

This same compound was, upon addition of' (H₂N)₂C=NH·HC1, isolated from 0.25, M aqueous catechol solutions buffered at pH 10 and containing the silicate minerals albite, andradite, muscovite, pyrophyllite, talc, and wollastonite, and also from unbuffered catechol solutions containing wollastonite and andradite.

It is concluded from this work that the formation of an anionic catechol-silicon complex, Si(C₆H₄O₂)₃²⁻, is largely responsible for the dissolution of the minerals mentioned above. From this conclusion, it is proposed that naturally occurring members of the class of organic compounds to which catechol belongs, the aromatic v̲i̲̲c̲-diols, may play …

Reactions Of Trichloro(Beta-Diketonato)Titanium(Iv) Complexes With Alcohols In The Presence Of Pyridine, William R. C. Munsey

Dissertations, Theses, and Masters Projects

No abstract provided.

The Thermal Rearrangement Of Triarylacetonitrile Oxides., Leslie Wayne Gibbs

University of the Pacific Theses and Dissertations

This research is a detailed study of the rearrangement of triarylacetonitrile oxides to the corresponding triarylmethylisocyanates. The kinetics of the rearrangement of triphenylacetonitrlle oxide was followed by infrared absorption spectroscopy using the peak due to the N-0 stretching (1307cm^-1). A study, both, using the differential method (i.e., a plot of the logs of the initial slopes vs. the log of the concentration) and a check of the integrated forms of the rate expressions to determine which gave a constant value for the rate constant showed that the reaction is first order.

From measurements of the rate constant, k, …

Dipeptide Complexes Of Palladium(Ii) And Platinum(Ii), Lewis Enos Nance

University of the Pacific Theses and Dissertations

Due to recent interest in the role of heavy metals in enzymes. oxygen-carrying molecules. and anticarcinogenic compounds, the study of metal-protein bonding has assumed a new importance. Studies have been made utilizing platinum compounds as anticarcinogenic agents in several different types of cancerous activity. No study of the mechanism by which Pd(II) and Pt(II) compounds exhibit anticarcinogenic properties has been made to date.

The purpose of this research was to investigate the nature of bonding of Pd(II) and Pt(II) with various dipeptides, which were chosen in this study as a basic unit of protein-like material. These compounds have the advantage …

Birch Reduction Of Benzamide, N-Substituted Benzamides And Biphenylene, Luther Dickson

University of the Pacific Theses and Dissertations

The Birch reduction of benzamide with sodium and absolute ethanol. 95% ethanol, or tert-butanol in liquid ammonia gave 1,4-dihydrobenzamide in varying amounts. The amide group was not reduced. The two most important variables encountered were the alcohol used and whether or not ammonium chloride was added after the reduction was completed. Without this addition of ammonium chloride, little or no 1,4-dihydrobenzamide was present after workup, while with its addition some 1,4-dihydrobenzamide formed whether the proton source was absolute ethanol, 95% ethanol, or tert-butanol. The highest yield was obtained with tert-butanol with ammonium chloride being added. Addition of ammonium chloride apparently …

Birch Reduction Of Benzenesulfonamide, N,N-Dimethylbenzenesulfonamide, N,N-Diisobutylbenzenesulfonamide, And 2-Mesitylenesulfonamide, Vishnubhai V. Patel

University of the Pacific Theses and Dissertations

It has been previously shown that benzenesulfonamide gives thiophenol and diphenyldisulfide upon Birch reduction. The sulfonamide group is easily reduced. Probably the electron deficient sulfur atom in sulfonamide can accommodate an electron easily.

The present study involved the Birch reduction of benzenesulfonamide, N,N-dimethylbenzenesulfonamide, N,N-diisobutylbenzenesulfonamide and 2-mesitylenesulfonamide.

The Identification Of Barbiturates By Attenuated Total Reflectance, Robert Lewis

University of the Pacific Theses and Dissertations

The use of Attenuated Total Reflectance as an analytical technique in infrared spectroscopy has become increasingly important in the past few years. ATR (Attenuated Total Reflectance) is a relatively new analytical method. Producing spectra of compounds by this method requires no solvent for dissolving the sample and no salts for making pellets. The only requirements for spectra production, similar in quality to those produced by conventional methods, are that there is enough sample to cover both sides of the reflector be similar. The index of the sample is fixed; therefore, the index of the reflector is controlled by selecting a …

Spectrophotometric And Microbiological Determination Of The Stability Of Sodium Ampicillin As Affected By Ph, Enrico Frank Raffanti

University of the Pacific Theses and Dissertations

The specific purpose of this investigation was to determine the effect of pH on the stability of ampicillin sodium for injection. Then, to correlate this information, a pH profile may be established to predict chemical stability with ampicillin sodium alone or when other drugs may be included in the admixture. With a pH profile the pharmacist could predict the length of time after which more than a 10 percent loss of activity would occur. Stability measurements were to be accomplished through a microbiological assay after adding ampicillin sodium to different buffer solutions. At the end of four hours, eight hours, …

On The Mechanism Of The Diels-Alder Reaction--Dimerization Of Trans-Phenylbutadiene, Michael Ward Mcnicholas

Dissertations and Theses

The Diels-Alder dimerization of trans-1-substituted butadienes is expected to yield a cyclohexene adduct with the substituents in the 3 and 4 positions cis to one another. This prediction is based on past observations of other Diels-Alder additions. The cis-isomer is the only one consistent with a two-stage mechanism proposed by Woodward and Katz.

In the case of trans-phenylbutadiene, the expected adduct is cis-3-phenyl 1-4-(trans-styry1) cyclohexene. Alder, Haydn and Vogt, however, reported that the corresponding trans-isomer is the dimerization product. There is reason to believe that the observation of the trans-isomer may have been the result of product isomerization during purification. …

Reaction Of Aqueous Catechol Solutions With Minerals, Boonthong Poocharoen

Dissertations and Theses

The effectiveness of catechol, an aromatic vic-diol, in dissolving silicate minerals was studied. A synthetic amorphous magnesium trisilicate, Mg₂Si₃O₈∙5H₂O, as well as the minerals olivine, sepiolite, diopside, augite, and enstatite were used to react with catechol in slightly acidic, basic, and neutral solutions. It was found, depending on the solvent used, that 33-52, 8-17, 14-30, 5-11, 3-6, and 0.5-1 % of the minerals dissolved, respectively.

The reaction with Mg₂Si₃0₈·5H₂0 resulted in the formation of crystals of magnesium tris (catecholato) siliconate nonahydrate Mg[Si(Cat)₃]∙9H₂0. Dehydration of the crystals at room temperature resulted in the loss of 6 moles of water to form …

The Utilization Of High Sensitivity Noble Gas Mass Spectrometry In The Detection Of Iodine-129 And Plutonium-244, Mervet S. Boulos

Doctoral Dissertations

"Mass spectrometric analysis of the xenon isotopes in natural gas wells demonstrates that radioactive isotopes of element number 53 (I) and element number 94 (Pu) were present at the time of the Earth's formation. Evidence for the now extinct nuclide¹²⁹I (t_1/2 = 17 x 10⁶ years) was found in CO₂ -rich gas while evidence for the now extinct ²⁴⁴Pu (t_1/2 = 82 x 10⁶ years) was discovered in other natural gas wells. The amounts of ¹²⁹I in thyroids was measured by combining neutron activation analysis with noble gas mass spectrometry. The current …

The Study Of The Isomerization Of Trans-3-Acetoxy-2-Bromocyclooctene, Virginia Hill Lewis

University of the Pacific Theses and Dissertations

The isomerization of trans-3-acetoxy-2-bromocyclooctene (trans-1) to cis-3-acetoxy-2-bromocyclooctene (cis-1) was studied, trans-3- Methoxy-2-bromocyclooctene (trans-2) was used as a model compound for comparison. The rate of isomerization of both compounds increased tremendously with iodine (free radical catalysis) and decresed tremendously in the presence of hydroquinone (free radical inhibitor). This showed that the isomerizations of trans-1 and trans-2 are free radical catalyzed. It was anticipated that acetoxyl participation in trans-1, by stabilizing the free radical intermediate, would cause the rate of rearrangement of trans-1 to be much greater than the rate of rearrangement of trans-2. However, trans-1 iscented only about four times faster …

Kinetics Of The Cope Rearrangement Of 3,4-Diphenylhexa-1,5-Diene, Harlan Albert Jerome Berg

Dissertations and Theses

Kinetics investigations of the thermal Cope rearrangement of meso-and d1-3,4-diphenylhexa-1,5-dienes were undertaken in order to gain information about the transition states for these reactions by determining the appropriate enthalpies and entropies of activation. Of particular interest were the activation parameters for the meso compounds' rearrangement as it represents the only known example in which both four-and six-centered transition states are of comparable energy.

Kinetics of the dl isomers' rearrangement in the temperature range 90-110⁰were determined using 5 X 10¯⁵M solutions of the olefin in heptane contained within sealed Pyrex ampules. Extents of reaction were determined from UV absorbance measurements at …

Substituent Effects On The Magnetic Resonance Spectra Of 1, 4-Disubstituted Benzenes, Holger Er-Chah Chen

Doctoral Dissertations

"The Nuclear Magnetic Resonance spectra of five complete series of para-substituted benzenes have been investigated: the benzoic acids, benzonitriles, benzoyl chlorides, methyl benzoates and nitrobenzenes. Precise values of aromatic proton chemical shifts and coupling constants were obtained from LAOCOON3 computer analyses of the spectra. Using the relative internal chemical shift technique of Beachell and Beistel, excellent linear correlations among all five series were found. All substituents gave proton shifts which lay on the least-squares line, so it is concluded that all substituents are well behaved. Using the correlation plots the chemical shifts of the aromatic ring protons can be predicted …

Selected First Row Transition Metal Coordination Compounds Of 2-(N-Aminomethyl)-3-Quinuclidinone Chelates, Richard Cecil Dickinson

Doctoral Dissertations

"As part of a project directed towards elucidating the characteristics of ligands which coordinate to give complexes having tetrahedral structures, a study of chelates containing the bulky quinuclidine group has been made. With 2-(N-morpholinylmethyl)-3-quinuclidinone (MQN), complexes having the general formula M(MQN)X₂ were prepared where the metal ion was Co(II), Ni(II), Fe(II), Cu(II), and Mn(II). The ligands 2-(N-piperidinylmethyl)-3-quinuclidinone (PQN) and 2-(N-dimethylaminomethyl)-3-quinuclidinone (DQN) were prepared along with the analogous cobalt(II) chloride complexes. The series of complexes Co(MQN)X₂ where X = Cl, Br, or I were prepared, and magnetic susceptibilities and spectral data obtained. They have room temperature magnetic moments in the range …

Condensation And Sublimation Of Carbon Dioxide And Water Molecules At Cryogenic Temperatures, Victor Cazcarra

Doctoral Dissertations

"Measurements of the condensation coefficient of CO₂ and H₂O have been made using a molecular beam and quartz crystal microbalances. The dependence of the condensation coefficient on variables such as population density on the substrate, temperature of the substrate, molecular beam intensity and temperature of the molecular beam, was investigated. The results are explained using heterogeneous nucleation theory for low density population, and a new approach for high density population is presented. The rate of sublimation of these two gases was measured directly. The results are reported in terms of vapor pressure in the range 10⁻⁹ to 10⁻⁴ Torr. The …

Studies Of Neutron Capture Produced Rare Gas Isotopes In Rocks And Minerals Containing Chlorine, Selenium And Tellurium, David E. Sinclair

Masters Theses

"Noble gas mass spectrometry was used to study rare nuclear processes in terrestrial rocks and minerals. An excess of ³⁶Ar was detected in a chlorine-rich rock. The excess ³⁶Ar has been produced in rocks near the earth's surface due to capture of cosmic-ray-produced neutrons on ³⁵Cl. Measurement of ³⁶Ar formed by the ³⁵Cl(n, γ)³⁶Cl(β^-)³⁶Ar process makes possible a new method for determining the surface residence time of chlorine-rich minerals

Excess ⁸²Kr and excess ⁸³Kr were detected in selenium-rich ores. The excess ⁸²Kr results from double beta …

A Study Of Some Complexometric Titrations In Nonaqueous Solvents, Ngo The Hung

Masters Theses

"Complexometric titrations of calcium, zinc and lead with polyaminocarboxylic acids: ethylenediaminetetraacetic acid (EDTA), 1,2-diaminocyclohexanetetraacetic acid (DCTA), ethyleneglycol-bis(2-aminoethylether)tetraacetic acid (EGTA) and tetraethylenepentamine (tetren) have been investigated and compared in the following organic solvents: methanol, dimethyl formamide, dimethyl sulfoxide and methyl ethyl ketone. Various end point detection methods have been used: direct visual titration with metallochromic indicators and instrumental detection by photometry, potentiometry (mercury electrode and lead ion selective electrode) and amperometry. Calcium, zinc and lead can be determined up to trace levels (ppm) under specific conditions. A concrete application of this thesis is the determination of zinc or calcium in a …

Adsorption Of Dichromate At The Air-Solution Interface, Josephine Juch Wang

Masters Theses

"The adsorption of dichromate ion with the surfactants, tetradecylpyridinium bromide and tetradecyltrimethylammonium bromide at the air-solution interface was studied by surface tension and turbidity measurements in order to better understand the process of ion flotation. Surface tension measurements were used to study the effect of dichromate ion concentration on precipitation in dilute surfactant solutions. At higher concentration, near and above the cmc, light scattering was used to detect precipitation. The concentration of dichromate required to cause precipitation decreases with increasing surfactant concentration until the erne is approached, after which increasing concentrations of dichromate are required with increasing concentration of surfactant. …