Physical Sciences and Mathematics Commons^™

Kinetic Investigation Of The Hydrochlorination Of Olefins In Aprotic Solvents And Sulfonation Of Idobenzene And The Selectivity Relation, Thomas Glen Davies

Theses and Dissertations

Kinetic investigation of the hydrochlorination of cyclohexene and cis-2-butene in n-heptane with SnCl4 as catalyst shows that the reaction is second order with respect to both olefin and catalyst. The specific rate constants at 25° , 0° and -23.8°C and the activation parameters were determined. Investigation of the Ga2Cl6 catalyzed hydrochlorination of cyclohexene and cis-2-butene in dichloromethane indicates that alkylation and polymerization compete with the hydrochlorination reaction in the presence of the solvent. The relative reaction rates and the isomer distribution for the sulfonation of iodobenzene by S35O3 have been determined in refluxing SO2 at -10°C. The reaction resulted in …

Sulfonation Of Chlorobenzene And The Selectivity Relation ; Bromine Addition To Cyclohexene In Dichloromethane ; Thorpe's Synthesis Of The Caged Acid, 4-Methyltricyclo[1.1.0.0[Superscript 2-4]] Butane-1,2,3-Tricarboxylic Acid, John A. Gurney

Theses and Dissertations

Aromatic sulfonation and some substitution reactions of chlorobenzene show deviations in the selectivity relation. A determination of chlorobenzene sulfonation provided the following rate ratio relative to benzene and partial rate factors: 1.0, [---] of 0.064 , mf 1.7 and pf 4. 2. Our work, Olah's nitration, Ferguson's bromination and Stock's chlorination define a new relation that can be express by adding an entropy term (A) to the selectivity relation. We determined the rate of bromine-cyclohexene addition in dichloro-methane at 0° to provide a basis for a systematic variation of solvents at low temperature. An unusual zero-order reaction was encountered. The …

The Correlation Of Spectra And Steric Effects In Alkyl And Aryl Hydrazones, Dennis J. Weber

Masters Theses

Introduction

The correlation of spectra, especially ultraviolet spectra, of hydrazones with their structure has resulted in considerable confusion because of the variations in spectra obtained from apparently the same basic chromophore.

Dissertation In Organic Chemistry. Part I, The Fate Of The Anilino Moiety In The Rearrangement Of Α-Anilonoketones. Part Ii, Partial Rate Factors For Sulfonation Of Bromebenzene With Sulfur Trioxide. Part Iii., Preliminary Survey On The Effect Of High Pressure On Ferrocene And Cycloöctatetraene, Jerold Carter Robertson

Theses and Dissertations

Part I. The rearrangement of α-anilinoketones was studied in an effort to determine the mode of movement of the nitrogen moiety. A crossover experiment was carried out with an equimolar mixture of 2-(4- bromoanilino)-1-(4-bromophenyl)-2-(4-methoxyphenyl) ethanone and 2-(4-chloroanilino)-1-(4-chlorophenyl) -2-(4-methoxyphenyl)ethanone with γ- picoline hydrobromide as the catalyst. The reaction product was analysed by means of a mass spectrograph. The results of the analysis indicate a crossover of the nitrogen moiety during rearrangement. This indicates that the nitrogen moiety moves in an intermolecular manner during the rearrangement. Part II. The isomer distribution from the sulfonation of bromobenzene with sulfur trioxide was determined by …

The Analysis Of Seed Oils Of Six Tropical Plant Species By Gas Chromatography, Justin C. Hamer

Chemistry and Chemical Biology ETDs

Several factors influenced the choice of tropical plant seeds studied in this research. Among these factors were: (1) an early interest in the chemistry of natural products; (2) the legends surrounding the use of certain plants by native herb "doctors," and (3) the ready availability of the materials at the beginning of this investigation, which was started in Cuba.

A Spectroscopic Study Of Some Rare Earth Complexes, Richard M. Alire

Chemistry and Chemical Biology ETDs

The phenomenon of intramolecular energy transfer was studied using anthranilate, 8-hydroxyquinolate, 2-methyl-8-hydroxyquinolate, and salicylaldehyde rare earth chelates. Line emission characteristic of the rare earth ion was observed whenever the lowest triplet (measured) of the complex was higher in energy than the emitting (resonance) level of the rare earth trivalent ion. The path of energy transfer from the organic portion of the chelate to the rare earth ion was verified as going via the lowest or a nearby triplet state of the complex.

The Synthesis And Analysis Of Kau(Cn)4.3/2 H2o And Its Proposed Separation From Kau(Cn)2.2h2o, George Edgar Hartwell

Honors Theses

The increasing use of radioactive tracers in chemistry has lead to many investigations of the rate of exchange between two different oxidation states of a single element in solution. These studies lead to a more basic understanding of the structure of certain ions and their chemical reactions. Other methods of identification open for investigation include polarography and the use of conductance measurements, since the equivalence conductances differ significantly.

Studies In Photoexcited Ketone Systems, Robert Michele Heimlich

Honors Theses

The photochemical reduction of benzophenone to benzopinacol has been known since the early part of this century when it was first discovered by Ciamician and Silber (4). The reaction is used today as a convenient preparation of benzopinacol. Benzophenone dissolved in isopropyl alcohol is placed in bright sun light and allowed to stand. After several hours the first crystals of benzopinacol begin to separate and within a few days the reaction is complete (13). The reaction proceeds through a photoexcited state of benzophenone. The excited intermediate abstracts hydrogen from the solvent (isopropyl alcohol) to form the diphenylhydroxymethyl radical and a …

Electromigration In A Cation Exchange Resin, Barton Stephen Solomon

Honors Theses

The purpose of this research was to investigate the phenomenon of electromigration of ions in a cation exchange resin. When a potential is applied across a solution of ions in series with an ion exchange resin column, the cations will migrate through the resin column, the cations will migrate through the resin toward the cathode and the anions will migrate toward the anode. The cations as they migrate through the resign should form bands because of their different ionic mobilities and their different exchange rates on the resin. The object of these experiments was to design and build the apparatus …

Catalyzed Reactions Of Organosiliconhydrides With Α, Β Unsaturated Ketones, Robert P. Desieno

Honors Theses

The addition of organosiliconhydrides to olefins has been of laboratory and industrial importance for twenty-five years. Literally hundreds of examples may be cited describing reactions of organosilicon­hydrides with a wide spectrum of olefinic compounds. These reactions have been conducted in either the catalyzed or uncatalyzed state. While the reactions may be forced under the influence of heat and pressure, they are more economically and practically carried out in the presence of catalysts. Catalysts encompass a wide variety of materials including peroxides, tertiary bases, metals, metal salts, U.V light, and gamma radiation.

Attempts In The Synthesis Of T-Alkylhydrazines, Richard A. Evans

Masters Theses

Introduction

Interest in t-alkyhydrazines has developed from the recent preparation of azoacetates (5) by the leadtetra-acetate oxidation of hydrazones

High Temperature Vaporization Behavior And Thermodynamic Properties Of Hafnium Diboride, Milton C. Krupka

Chemistry and Chemical Biology ETDs

Vaporization of hafnium diboride has been studied in a tungsten effusion cell over the temperature range 2175 degrees K. to 2500 degrees K. A low-melting eutectic at 2520 degrees K. prevented the use of the effusion cell technique at higher temperatures.

The Kinetics Of The Exchange Of Chlorine Atoms Between Hydrogen Chloride And Benzyl Chlorides, Warren Bruce

Chemistry and Chemical Biology ETDs

The study of the rates of chemical reactions in solutions has received a great deal of attention, primarily because of the relative ease with which such investigations can be persued; however, the great number of publications can never obscure the truth that a rigorous treatment of molecular processes in solutions is not available. The approach to the problem has been through extensions of theories which have their origins in descriptions of gaseous systems, and, with few exceptions, these extensions are firmly grounded on the techniques of classical thermodynamics. Hopefully, future advances in the calculation of the partition functions of molecules …

Kinetics Of The Reaction Of Isatoic Anhydride With Low Molecular Weight Alcohols, William Mast

Chemistry Honors Papers

This 22 page thesis studies the kinetics of the reaction of isatoic anhydride with low-molecular-weight alcohols by a colorimetric method.

Molybdenum Chelates Of 8-Hydroxyquinoline-5-Sulfonic Acid, Ellis Ray Peterson

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Man has had an intense interest in the role of enzymes in biological reactions for many years. The basic question -- how enzymes are able to function so efficiently -- remains as yet largely unanswered.

Only in recent years has it been discovered that molybdenum is essential for certain biological processes. For example, traces of molybdenum added to certain soils have resulted in spectacular plant growth (1). Four enzymes are known to contain molybdenum: nitrate reductase (2), hydrogenase (3), xanthine oxidase (4), and aldehyde oxidase (5). In each of these enzymes riboflavin is also present as the coenzyme FAD (flavin …

Complexing Of Sugars And Polyhydroxy Alcohols With Molybdenum (Vi), Su Chin Kiang

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Molybdenum is very important in the life processes of both plants and animals. It acts as a catalyst in promoting and controlling many biological reactions in living cells, but exactly what it does and how it functions are not well understood. In the past because of the obvious complexity of the reactions concerned and the extremely minute quantities of molybdenum involved, its presence was long undetected. Lately, molybdenum has drawn special attention on account of its effects on metabolic processes, particularly of plants. In this regard, molybdenum has been shown to be present in four enzymes: nitrate reductase (JJ), xanthine …

An Investigation Of Coulometric Methods Of Analysis Of 1,1-Dimethylhydrazine, David M. Creighton

Theses and Dissertations

The oxidation of 1,1-dimethylhydrazine by bromine has been studied using a coulometric method of bromine generation, and a dual intermediate system of bromide and cupric ions in solution. The system allowed over-generation of bromine and back-titration by cupric ion. The results of the investigation showed that the mechanism of oxidation is not fixed, but is a function of the concentration of bromine in the solution at any time. Additional studies have been recommended, whereby the mechanisms of the reactions may be determined.

A Study Of The Reactions In The Formation Of Sulfoacetic Acid And Of The Preparation Of Pure Crystalline Sulfoacetic Acid, Barbara Jean Eichel

Chemistry Honors Papers

This 15 page thesis attempts to explain the difficulty in obtaining crystalline solids from sulfoacetic acid.

The Effect Of Chelates On Phosphorus Availability And Mobility, Salah Ahmed Tahoun

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Soil-phosphorus relations and plant-phosphorus relations have attracted the interest of many investigators since Liebig introduced his famous theory about the importance of the mineral matters to the plant in 1840. It was soon realized that phosphorus nutrition was a problem not easily solved for two reasons. 1. The added phosphorus fertilizers, soon after soil application are converted by some reactions in the soil to complex compounds far less soluble, consequently less available to the plant. Conclusions about this process led to controversial debates until it was discovered that a general statement covering all soils was impossible since the reactions involved …

Mass Spectra Correlations And The Appearance Potentials Of The Major Tobacco Alkaloids, William Frederick Kuhn

Master's Theses

The main objectives of this investigation were three­ fold: (1) to design and fabricate a heated inlet system for the mass spectrometer; (2) to obtain the mass spectra of the major tobacco alkaloids under normal operating conditions; and ( 3) to determine the ionization potentials of the alkaloids as well as the appearance potentials of some of the major fragment ions derived from the alkaloids.

The mass spectrometer is designed to analyze only materials in the vapor state . Since some materials do not exert sufficient vapor pressure at room temperature under reduced pressure to be analyzed directly, it is …

Characterization And Determination Of Aldehydes By The Ultraviolet Spectral Changes Resulting From Acetal Formation, Edwin Patrick Crowell

Master's Theses

Aldehydes are a very important group of organic compounds because they have been round to contribute t the flavor and odor of many foods and plants . To the organic chemist, aldehydes are important because of their reactivity and interesting chemistry.

Because aldehydes are so prevalent in natural products and because they have . wide use in industrial and synthetic chemistry, their analytical chemistry is extensive . Despite this, there is still a need for rapid, simple, and general procedure for characterization or aldehydes that is not subject to extensive interferences.

The primary purpose of this study was to develop …

The Synthesis And Medicinal Chemical Study Of Some Pyridazones, Winnifred M. Osner

Chemistry and Chemical Biology ETDs

An examination of the literature revealed that the majority of pyridazines prepared were substituted in the three and six positions. Therefore, it appeared appropriate to prepare four and five substituted pyridazines.

Low Temperature Infrared Cell And Its Application In Isoprene And Nitrogen Dioxide Reaction Studies, Gunars Vilcins

Master's Theses

The purpose of this research was to explore the application of low temperature infrared spectroscopy to the study of several chemical problems. In particular the following items were investigated:

1. The design, manufacture, and operation of a low temperature optical cell suitable for infrared spectroscopic studies or gas-solid samples at liquid nitrogen temperature (-196°c) and above.

2. The recording and study of the infrared spectra or nitrogen dioxide and isoprene at 25°c and at lower temperatures.

3. A preliminary study of the reaction between nitrogen dioxide and isoprene at various temperatures using infrared techniques.

In recent years infrared studies have …

A Laboratory-Centered General Chemistry Course For College Freshmen, Alexander Vavoulis

University of the Pacific Theses and Dissertations

In order to give the laboratory-centered course a trial run and to compare it with a lecture-centered course it seemed necessary to the author that both courses should be taught and compared. The latter gave rise to the following hypotheses:

1. Students in a laboratory-centered general chemistry course show more favorable attitudes toward chemistry than do students in a lecture-centered course.
2. Students in a laboratory-centered course show as good a subject-matter mastery as students in a lecture-centered course.

A New Approach To General Chemistry Laboratory In College (With) A Laboratory Manual For General Chemistry, Constantine G. Vlassis

University of the Pacific Theses and Dissertations

Statement of the problem. This study was carried out to determine: (1) what advantages a laboratory-centered general chemistry course might have over the conventional laboratory course, and (2) whether improved understanding of laboratory work leads to better learning of chemistry. The four following questions were raised in connection with the study or this problem:

1. What is the need for a laboratory-centered course?
2. What has been done in the past to meet this need?
3. Can students learn chemistry more effectively in a laboratory-centered course as compared to the conventional course?
4. Is a laboratory-centered course to be preferred over the conventional course …

Studies Involving Modification Of The Megregian Method Of Fluoride Determination And Application To Fluoride Balance Studies In Infants, Gene R. Wright

Masters Theses

Introduction

At the request of Dr. Frederick Margolis, M.D., and in association with The Upjohn Company, this research problem was initiated as a participation in the investigation of whether or not fluoride ingested as a constituent of the Upjohn 47-M liquid vitamin preparation is retained in an infant's body to the same extent as is fluoride ingested as the sodium salt by itself--either in solution or in tablet form. The retention patterns may be studied indirectly by measuring the amounts of fluoride excreted in the urine and in the feces during each of a series of equal time intervals after …

The Reaction Of N-Magnesium Halides On Nitriles In The Synthesis Of Amidines, Robert Bauer

Masters Theses

Introduction

Compounds of the amidine class have long been of interest because of their therapeutic and pharmacological properties. Members of this class of compounds have been shown to be effective in combating pathological conditions ranging from virus (11), bacterial (12), and protozoal infections (7) to diseases of the circulatory system (6), neoplasms (5) and hyperglucemia (21), Since many basic nitrogen compounds have been of interest in cancer chemotherapy, such as a variety of amino alcohols shown by the Upjohn Company to have anti-tumoral activity, it was felt that additional investigations into the use of amidines and amino amidines in this …

The Dielectric Strength Of Some Anti-Corrosive Paints, George Albert Chappell Iii

Masters Theses

"Corrosion has been one of the costly problems to industry because each year losses due to corrosion are in excess of six billion dollars. Corrosion is caused by the tendency of all metals to become oxidized and return to their natural state. Oxidation may be suppressed by restraining the flow of electrons from the system, thereby inhibiting corrosion.

One effective means to prevent rusting is by applying a barrier of paint between the system and the corrosive atmosphere. Not all paints, however, are equally effective as corrosion inhibitors. At present, the only effective means of determining the corrosion resistant ability …

The Separation Of Germanium From Lead, Cadmium, And Zinc By Ion Exchange, Myra Sue Anderson

Masters Theses

"The object of this study was to investigate the ion exchange behavior of germanium in order to find a quantitative separation method applicable to the analysis of germanium in zinc ores.

Germanium had been predicted and described as eka-silicon by Mendeleeff, and was discovered by Winkler in 1886. The importance of the metal has increased very much since World War II because of its use as a semiconductor in diodes and transistors.

All commercial scale germanium is now produced as a by-product of base metal processing. Although the United States Bureau of Mines is conducting a program for the recovery …

A Study Of The Colloidal Properties Of Zirconium And Promethium By Electrodialysis And Liquid-Liquid Extraction, James N. Click

Masters Theses

"The purpose of this investigation was to study the solution chemistry of zirconium by investigating the colloidal behavior of natural zirconium and zirconium-95, utilizing electrodialysis and liquid-liquid extraction techniques. Also incorporated into this study was the investigation of optimum conditions for the extraction of the natural zirconium and zirconium-95 with thenoyl trifluoracetone. A limited amount of work was done on the colloidal nature of promethium-147"--Introduction, pages 2-3.