Chemistry Commons^™

Spectroscopic Studies Of The Hydrogen-Chlorine Flame, Gonzalo Pizarro

Masters Theses

No abstract provided.

Synthesis And Analysis Of Dimers Of Alpha-Methylstyrene, Bhadreshkumar J. Mehta

Masters Theses

Introduction

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

Roberts and Jessup carried out the first quantitative work to determine ∆Hp if AMS.¹ Their data displayed a ∆Hp dependence on the degree of polymerization, DP. Several other reports were also published with new values for ∆Hp and new explanations for the apparent DP dependence.^{2, 3, 4, 5.}

Samples of dimers of AMS have been prepared by various workers.^{6, 7, 8} The reactions were mostly carried out by using sulfuric …

Reactions Of Tungsten Carbonyl Complexes Containing Diphenylvinylphosphine, George S. Leotsakos

Masters Theses

A new synthetic route for the production of the tungsten carbonyl complex (OC)₅WPPh₂CH₂CH₂PPh₂ has been discovered. It has been found that lithiumdiphenylphosphide reacts with diphenylvinylphosphinepentacarbonyltungsten(0) in tetrahydrofuran to produce upon hydrolysis a good yield of the pentacarbonyl product […]. No evidence for the formation of secondary products was noted nor was there evidence for preferential attack of the carbonyl group by LiPPh₂ to form a carbene complex.

Diphenylvinylphosphinepentacarbonyltungsten(0) (mp 62-64°C), was prepared for the first time by two different methods.

I. Displacement of aniline from anilinepentacarbonyltungsten(0) complex with diphenylvinylphosphine.

II. …

Mechanistic Studies Of Alkylation Of Cobalt(I) By Cyclobutyl Derivatives, Hao Ku

Masters Theses

A study was initiated on the hypothesis, by Ugi and co-workers, that cyclopropyl, cyclobutyl, and cyclopentyl electrophiles might under go nucleophilic substitution reactions with retention of configuration.

The synthesis of benzocyclobutenol and 2-phenylcyclobutyl tosylate is described. The reactions of these tosylates with cobalt(I) "supernucleophiles" gave low yields of products which have not been purified sufficiently for assignment of stereochemistry.

Reaction of cyclopentyl tosylate and phenylethyl tosylate with the "supernucleophiles" cobaloxime(I) and cobalt(salen)(I) is discussed for the advance of future work.

The Intramolecular Torsional Potential And Dielectric Properties Of 2,3-Butanedione, Gevert H. Meyer

Masters Theses

Dipole moment measurements have been carried out on 2,3-butanedione in solution, pure liquid, and the vapor phase. A dipole moment of 1.03 ± .01 Debye was observed for dilute solutions of 2,3-butanedione in carbon tetrachloride. Pure liquid samples exhibit an anomalous dipole of 1.56 ± .01 Debye. The following results were obtained for vapor phase measurements: 1.04, 1.07, 1.08, 1.11, and 1.17 ± .01 Debye at 310.15, 350.15, 370.15, 431.70 and 472.10 ± .02°K respectively.

The acetyl torsional potential was characterized from the observed temperature dependence of dipole moment. This torsional mode was described by a two-parameter potential function: V(Ø) …

Mechanistic Studies Of Alkylation Of Cobalt(I) By Cyclopropyl Derivatives, Lailing Magdalene Soong

Masters Theses

A second order nucleophilic substitution reaction with retention of configuration is predicted by Ugi and co-workers if electrophiles such as cyclopropyl, cyclobutyl, or cyclopentyl derivatives undergo substitution under conditions where the S_N2 process is faster than the competing S_N1 process.

A synthesis of both cis and trans-7-chlorobicyclo [4.1.0] heptane from olefin and dichlorocarbene is described. The compound, bicyclo [4.1.0] heptylpyridine [bis(salicylaldehyde)ethylenediiminato] cobalt(III), which contains an alkylcobalt σ-bond, is obtained from the reaction of pyridine [bis(salicylaldehyde)ethylenediiminato] cobalt(I) and 7-chlorobicyclo [4.1.0] heptane. The great light sensitivity of this compound has prevented its isolation in purity sufficient for nmr …

Studies Of Acetylcholinesterase In Synaptosomes, Syed Abbas Rizvi

Masters Theses

Acetylcholinesterase from rat brain was studied in crude homogenates, partially purified enzyme fractions, and in synaptosomes, to observe modification of the enzyme as a consequence of the modification of the membrane containing it.

Sodium dodecyl sulfate decreases the absorbance due to particles in the homogenate. This change in absorbance was proportional to both the concentration of sodium dodecyl sulfate and the concentration of the particles. Further, sodium dodecyl sulfate caused sulfhydryl groups to appear in the crude homogenate and in partially purified enzyme fractions. Synaptosomal preparations did not give such results. At concentrations of sodium dodecyl sulfate sufficient to cause …

Zwitterionic Carbonyl Halide Complexes Of Tungsten, Dragoslav Marcovich

Masters Theses

The first carbonyl halide zwitterionic complexes have been synthesized and are of the type cis- (OC)₄XWPPh₂(CH₂)nPPh₂R in which X is Cl, Br, or I, n is 1 or 2, and R is an alkyl group. The complexes were prepared by the reaction […]. The temperature of the reaction must be carefully controlled since the decomposition point of the product is only 10°C higher than that of the reactant.

The zwitterionic complexes are sensitive to light in solution but are insensitive to light in the solid state. Unlike carbonyl halide complexes of the …

The Effect Of Sheet Moisture On The Anisotropy Of Paper Subjected To Various Degrees Of Restraint During Drying, Ivan T. Mascarenhas

Masters Theses

No abstract provided.

Ortho-Substituent Effects On Reactivities Of Benzohydroxamic Acids, Irl E. Ward

Masters Theses

No abstract provided.

Mechanism Of Solvolysis Of 3-Methyl-2-Butyl Brosylates., Luu Le Nghi

Masters Theses

"The brosylates of 3-methyl-2-butanol and it's a-d₁-, ß-d₁-, B-d₃-, and S-d₄- analogs have been synthesized. The solvolytic rate data for these compounds were determined. The solvolytic products in 70% (vol.) ethanol-water have been identified by flame ionization gas chromatography using a Carbowax 20M column. The amount of each product was measured by integrating the peak areas from the chromatograms. By analyzing the isotope effect data, the rate determining step is shown to be the formation of the hydrogen bridged ion pair intermediate. By evaluating the GC-mass spectral analysis of the isopentenes, a …

A Kinetic Study Of The Cerium (Iv)-Oxalic Acid System In Acidic Sulfate Media., Robert Richard Kessler

Masters Theses

"The kinetics of the cerium (IV) oxidation of oxalic acid was studied by a stopped-flow spectrophotometric technique in acidic sulfate media. The media consisted of perchloric acid, sodium sulfate and sodium perchlorate which allowed for the determination and control of the various sulfate and hydroxo species of cerium (IV) at prescribed hydrogen ion concentrations. The rate of reaction decreases rapidly with increasing sulfate concentration which yields evidence against previous reports indicating Ce (SO₄)₂ and Ce (SO₄)^2-₃ as the reactive cerium (IV) species. The results indicate that Ce (SO₄)²⁺ is the …

A Study On Two Iodine Containing Peptides Isolated From Porcine Thyroglobulin, Frederick E. Bishop Jr.

Masters Theses

"Two iodopeptides were isolated from thyroglobulin that had been digested with trypsin by paper electrophoresis and paper chromatography. The amino acid analysis demonstrated that the amino acid compositions were similar. The N-terminal amino acid of both iodopeptides was shown to be leucine. The amino acid sequence of one of the iodopeptides was determined by the Edman degradation method and digestion with the enzyme Carboxypeptidase A. The sequence was shown to be: NH₂-Leu-Asn-Ala-Ser-Glu-MIT-Gly-Thr-Ser-Gly-COOH. Other workers have shown that synthetic tyrosyl peptides with the sequence Glu-Tyr are iodinated by the thyroid peroxidase enzyme with a greater specificity than other tyrosyl peptides. This …

Metal Salt Catalyzed Carbenoids The Catalysts In Trialkyl Phosphite Copper (I) Complex Catalyzed Decomposition Of Diazo Compounds, Nguyen Van Thinh

Masters Theses

"Partial rate data, asymmetric induction studies, interrupted experiments and additives studies indicate that copper(I) salt-phosphite complexes are destroyed during the course of reactions with dimethyl diazomalonate (1) and ethyl diazoacetate (2). All evidence is consistent with the copper(I) being oxidized to copper(II) and copper(0) being oxidized by impurities in the olefin which most probably are hydroperoxides.

Several new copper(I) salt-phosphite complexes were prepared and examined but none proved as effective for decomposing (1) as copper(II) bis acetylacetonate.

The utility of the copper (I) chloride-trimethyl phosphite complex for decomposing (1) is a function of the means of preparation. The three general …

Metal Promoted Reactions Of Enamino Ketones, Suhas Satchidanand Joshi

Masters Theses

The reaction of 4-amino-3-allyl-3-penten-2-one (7) with mercuric acetate in acetic acid was found to produce 4-amino-1-pentene (12) in 70% yield. The scope of this unusual cleavage reaction was investigated by systematic variation of substituents on the enamino ketone framework, the metal salt and the solvent. The presence of the allyl group was necessary for the reaction to produce compound 12.

Under a variety of conditions there was no evidence for cyclization of 7 to give heterocyclic compounds. Neither was there evidence for cyclization in reactions of 4-amino-3-penten-2-one with vinyl acetate in the presence of mercury (II) or thallium (III) salts …

The Synthesis And Reactions Of Some Α, Β-Unsaturated Diazoketones, Virendra K. Sood

Masters Theses

No abstract provided.

Kinetics Of The Metal Exchange Reaction Between N, N'-Bis (2-Picolyl) Ethylenediaminenickel (Ii) And Copper (Ii), Craig Lee Barsuhn

Masters Theses

No abstract provided.

Rate Of Initiation Of Pyrolysis Of Pentachloroethane Using The Toluene Carrier Gas Technique, Teodomiro Cuzcano

Masters Theses

No abstract provided.

The Effect Of The Degree Of Cationic Charge On The Binding Strength Of A Cationic Starch-Kaolin Clay Coating, Hugh K. Myers

Masters Theses

No abstract provided.

The Kinetics Of The Metal Exchange Reaction Between Biseminodiacetatonickelate (Ii) And Copper (Ii), Stephen H. Erickson

Masters Theses

No abstract provided.

Simultaneous Knudsen- And Torsion-Effusion Measurements Of The Vapor Pressures Of Tetraphenyl Silane And Hexaphenyl Disilane, Luz Marina Calle

Masters Theses

No abstract provided.

A Study Of The Ability Of Surface Active Materials To Increase The Evaporation Rates Of Small, Freely Falling Water Drops, David Alan Sierawski

Masters Theses

"The evaporation rate at 30°C of water droplets partially covered by surface active materials (SAM) were determined. While two of the SAM were studied at a single dew point depression (ΔT_DP), seven others were examined over a range of ΔT_DP values. It was found, by comparison with pure water drops under identical conditions, that SAM increases the evaporation rate as compared to the rate of an uncontaminated drop. The lack of effect of the hydrophobic chain length and the possible effect of the hydrophilic group on this phenomenon are discussed. The explanation proposed is that at 30°C …

The Consideration Of Some Aspects Of Two Methods Used To Study Ion Association, Richard Karl Gard

Masters Theses

An investigation was made into the possibility of determining thermodynamic ion association equilibrium constants for salts important in the study of seawater using spectrophotometry and ion selective electrodes. Calcium sulfate was used as the test salt. The success of the spectrophotometric method was found to depend upon the choice of a suitable indicator and refinement of the proper instrumental techniques. The indicators investigated were 1-(2'-hydroxy-1'-benzeneazo)-2-hydroxynaphthalene, 1-(2'-hydroxy-5'-chloro-1'-benzeneazo)-2-hydroxynaphthalene, and ammonium purpurate (murexide). Ammonium purpurate was found to be the most suitable indicator. Spectra of these three indicators and their calcium complexes at pH 10 are included in the paper. The ion selective …

Adsorption Of Water On Gold, Jean-Marc Louis Deschanel

Masters Theses

"Water adsorption isotherms on gold films were measured with a quartz crystal microbalance. Two gold films were studied: a "dirty" gold film contaminated by approximately one monolayer of carbon, and a "clean" gold film prepared by evaporating gold from a heated tungsten wire under high vacuum.

Water was found to chemisorb on both films according to a Freundlich type adsorption isotherm. Isosteric heats of adsorption were computed from the isotherm data. On the "clean" gold surface the isosteric heat showed a logarithmic decrease with increasing water coverage. The highest measured value for the heat of adsorption was 35 kcal mole …

Desorption Of Phosphorus From Si (111) Surfaces, Cesar Michel Magnin

Masters Theses

"Auger electron spectroscopy and mass analysis are used as complementary methods in evaluating desorption kinetics. For phosphorus on silicon, the order of desorption and activation energies of desorption are determined from continuously monitored phosphorus Auger electron signals during heating. These measurements indicate that diatomic phosphorus dissociates when adsorbed onto clean silicon. Mass spectrometer flash desorption spectra show that at least four distinct surface bonds are associated with the desorption of phosphorus. The dominant desorbed species is diatomic phosphorus at high coverage (> 0. 1 monolayer) and atomic phosphorus at low coverage (< 0.07 monolayer)"--Abstract, page ii.

Computer Investigation Of The Variation Of Conductivity With Concentration, Larry Macpeers Shadwick

Masters Theses

Computer programs were developed tor the conductance equations of R. M. Fuoss and L. Onsager as well as for the conductance equations of T. J. Murphy and E. G. D. Cohen. These programs were used to calculate values from selected conductance measurements. The resulting values were compared with values produced by other computer programs using the equations of Fuoss and Onsager as well as the equations of E. Pitts. The comparisons demonstrated the equations of Murphy and Cohen to be the equal of or superior to the other equations for the majority of cases. The equations of Pitta were superior …

The Conductance Of Some Polyvalent Electrolytes, Jack Lee Worthington

Masters Theses

A new compound, 1,3,5-triphenylbenzene-4' ,4",4"'-trisulfonic acid, was synthesized by treating triphenylbenzene in 1,2-dichloroethane with chlorosulfonic acid. The reaction appears to be quantitative. Conductance measurements were then made on the sodium, potassium, and lanthanum salts of this new acid and of 1,3,5-benzenetrisulfonic acid.

The choice of these acids was based on two factors: 1) the desire to prepare a 3-3 symmetrical unassociated electrolyte which would allow the determination of a more reliable equivalent ionic conductance value for La³⁺ and 2) an interest in using the Murphy-Cohen equation to determine solute parameters such as association constants if association is present.

Conductance …

The Isolation And Purification Of A Fluorescent Compound From Pseudomonas, Thomas M. Davey

Masters Theses

Fluorescence in certain land snails has been found to arise from a bacteria carried by the snails. The bacteria, a genus of Pseudomonas, produce a pigment complex in iron-deficient media. The pigment complex consists of both fluorescent and non-fluorescent pigments. One of the fluorescent compounds was isolated and purified by paper chromatography using several different solvent systems.

Absorption and fluorescent spectra of the compound at a number of pH values were measured and the changes with pH of both the intensity and the color of the fluorescence were observed. The purified compound was ninhydrin negative but after acid hydrolysis …

Mechanistic Studies Of Cobalt Super Nucleophiles, Audrey Yeh Ku

Masters Theses

A study was initiated on the hypothesis, by Ugi and co-workers, that cyclopropyl, cyclobutyl, and cyclopentyl electrophiles might undergo nucleophilic substitution reactions with retention of configuration.

A simple, high yield synthesis of both cis and trans-2-phenylcyclopropyl chlorides from styrene and chloroform is described. Reaction of each of these alkylating agents with the very nucleophilic cobaloxime super-nucleophile ultimately gave peroxy compounds which appear to arise from insertion of oxygen into the carbon-cobalt bond.

Neither trans-2-phenylcyclopentyl tosylate nor trans-2-phenylcyclohexyl tosylate would alkylate low valent cobaloximes under standard conditions.

A partial synthesis of the 2-phenylcyclobutyl tosylate is described along with suggestions for future …

The Formation And Study Of Certain Bicyclic Enolate Monoanions And Dianions, Ernest William Crowe

Masters Theses

No abstract provided.