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Ua66/7/2 Newsletter, Wku Chemistry

WKU Archives Records

Newsletter created by and about the WKU Chemistry department.

Acidities In Ethanol/Water Solvents;The Pka Of Hf., Raymond M. Merrill

Chemistry and Chemical Biology ETDs

The acidity of hydrofluoric acid in mixed ethanol/ water solvent systems was studied by determining the pKa of HF in a number of different ethanol concentrations. The effect of changing temperature on the acidity of HF in these media was also examined.

The pKa's were determined using a lanthanum fluoride membrane Fluoride Specific Ion Electrode and a glass pH electrode versus the same reference electrode. The method eliminates the need to determine liquid junction potentials. By determining the pKa for HF in each ethanol/water mixture, at a number of different temperatures, thermodynamic parameters, such as free energy, enthalpy, entropy, and …

The Effect Of Stereoelectronic Control And Long Range Interaction On The Stability Of Bicyclic Enolate Anions, Edwin M. Van Dam

Dissertations

No abstract provided.

Distribution Of Mass And Charge In The Spontaneous Fission Of ²⁴⁴Cm, K. F. Flynn, B. Srinivasan, Oliver Manuel, Lawrence Elgin Glendenin

Chemistry Faculty Research & Creative Works

The distribution of mass and charge in the spontaneous fission of ²⁴⁴Cm has been investigated by radiochemical and mass spectrometric determination of the fission yields for 40 mass chains and 2 shielded nuclides (independent yields). The mass distribution is highly asymmetric with a relative probability of asymmetric-to-symmetric fission (peak-to-valley ratio) of greater than 5700. The average masses of the light and heavy groups are 103.1 and 138.7, respectively. The characteristics of the mass distribution, as well as the division of nuclear charge indicated by the independent yields of the two shielded nuclides, are consistent with the systematics established from …

On Improved Wkb (Uniform Asymptotic) Quantum Conditions, Dunham Corrections, The Langer Modification, And Rkr Potentials, Russell T. Pack

Faculty Publications

An improvement to the WKB quantum condition for the rotation-vibration levels of diatomic molecules, known empirically to give RKR potentials of increased accuracy and to account for the Dunham correction Y00, is derived using uniform asymptotic methods. The role of the Langer transformation in this problem is also discussed.

Observation Of Excitons In A Molecular Liquid: Specular Reflection Spectrum Of Α -Methylnaphthalene, Craig J. Eckhardt, Leo F. Nichols

Craig J. Eckhardt Publications

The normal-incidence specular-reflection spectrum of liquid α-methylnaphthalene was obtained for the wavelength region from 215 to 400 nm. Comparison of the Kramers-Kronig transform of the reflection spectrum with the absorption spectrum of α-methylnaphthalene is cyclohexane shows the bands of the neat-liquid spectrum shift to lower energy and display significant broadening. These effects support the existence of excitons in molecular liquids.

Dipole Moments In Thomas-Fermi-Dirac And Thomas-Fermi Theories., Jerry Goodisman

Chemistry - All Scholarship

It is shown that the electronic contribution to the dipole moment, calculated from a solution to the Thomas—Fermi—Dirac or Thomas—Fermi equations, should be equal and opposite to the nuclear contribution. Thus, the Thomas—Fermi—Dirac and Thomas—Fermi theories predict vanishing dipole moments for all molecular systems.

Magnetic Nonequivalence In Higher Alkyl Groups, Philip Anthony Reitano

Masters Theses

The phenomenon of magnetic nonequivalence has been growing in recent years. Unequal populations of the various conformers in such molecules are normally accepted as the cause of nonequivalence, but nuclei which are stereochemically nonequivalent are not necessarily magnetically nonequivalent. This nonequivalence has been demonstrated for molecules of the type ABDC⁸CHR₁R₂, where R + H, F, and Me. Although in principle the effect is quite general this has not been previously observed in "freely rotating" systems for groups larger than methyl. The role of steric factors, the size of the substituents and the distances between …

Principles Of Control Theory As Applied To A Thermostat, Joseph Peter Stidham

Master's Theses

The recent development of solid state electronics has opened new possibilities in instrumentation design. One development has been the availability of compact, low cost, high gain, D. C. amplifiers which can be used in the design and construction of sensitive laboratory instruments (11). Using these amplifiers a thermostat capable of precise control can be constructed and its performance compared with the performance expected by an analysis of the closed loop control equations.

The Wittig Reaction With Carbohydrates And The Addition Of Benzenesulfonyl Azides To Indoles, George R. Wellman

Dissertations

No abstract provided.

Kinetics Of The Formation Of Nickel(Ii) Complexes With N,N’-Dibenzylethylenediamine And N,N’-Bis(2-Picolyl)Ethylenediamine, Zahid Amjad

Masters Theses

No abstract provided.

The Reactions Of Sodium Naphthalenide With Carbonyl Compounds And Esters, Manhar Vora

Masters Theses & Specialist Projects

The purpose of this investigation was to study the reactions of sodium naphthalenide with various carbonyl and acyl compounds. J. W. Stinnett, Jr. investigated aspects of the reactions of carbonyl compounds and that study was expanded. The major emphasis, however, was to extend the investigation to the reactions of esters. With regard to the reactions of esters, it was thought that sodium naphthalenide might provide a synthetic advantage, as compared to the sodium metal solutions, in the reduction of the acyl compounds to their corresponding acyloins.

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

Masters Theses

No abstract provided.

The Dimetalation And Subsequent Functionalization Of 1,3-Dimethylnaphthalene By Means Of Amylsodium In The Presence Of Certain Tertiary Amines, Atilla Tuncay

Masters Theses

I. Introduction

It is well known that the hydrogen atoms of a methyl group directly attached to an aromatic system are sufficiently acidic to be abstracted by suitable bases to generate the corresponding α-anion.^1,2 These monoanions have frequently served as suitable intermediates for the formation of a large variety of a-condensation products in good to excellent yields² On the other hand, attempts to obtain α,α-dianions from various dimethylaromatic systems have met with limited success.² Due to the lack of sufficiently strong bases, dimetalation products were obtained only in poor yields even at high temperatures and prolonged reaction …

14th Annual Rocky Mountain Spectroscopy Conference

Rocky Mountain Conference on Magnetic Resonance

Program and abstracts from the 14th annual meeting of the Rocky Mountain Spectroscopy Conference, sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Denver, Colorado, July 31 - August 1, 1972.

Relation Of Aromatic Substitution Patterns To Nmr Shifts Produced Tris - (1,1,1,2,2,3,3 - Heptafluoro - 7,7, Dimethyl - 4,6 - Octanedione) Europium (Iii), Roy R. Reeves

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 Roy R. Reeves on July 27, 1972.

Relation Of Shift Magnitude Of Alkyl Substituents To Aromatic Substitution Patterns, Michael E. Evans

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 by Michael E. Evans on July 27, 1972.

A Correlation Of The Idealized Heat Of Vaporization To Molecular Weight, Harold Earl Bennett

Master's Theses

Using the Clausius-Clapeyron equation as a base, many investigators have tried to develop variations to better describe both ideal and non-ideal systems. The literature is abundant with correlations of vapor pressure to temperature and associated correlations of latent heats of vaporization to molecular characteristics; often molecular weight or carbon number.

The Synthesis And Characterization Of The 2,2'-Bisacylazide Of 3,3'-Bipyridine, Magdy Adly Guirguis El-Fayoumy

Chemistry & Biochemistry Theses & Dissertations

The primary objective of this research has been the synthesis and characterization of a new heterocyclic diacylazide, the 2,2'-bisacylazide of 3,3'-bipyridine 19. This heterocyclic diacylazide has been successfully synthesized from the phenanthrolin-5,6-dione 14, and examined with regard to its.thermal and photolytic decomposition.

Thermal decomposition of this disacylazide seems to go by a double-barreled Curtius rearrangement leading to a series of pyridonaphthyridinone (20) compounds such as 22 and 29.

An initial study of the photolysis of this bisacylazide has been initiated to examine the possible formation of nitrene-type intermediates.

Synthesis Of Derivatives Of Pyrido [3,4-D]Pyridazines, Diane (D'Ottavio) Martin

Chemistry and Chemical Biology ETDs

The current interest in the biological activity of certain 1 ,4-disubstituted pyrido[2 ,3-d]pyridazines prompted the investigation of various derivatives of the isomeric pyrido[3,4-d]pyridazine ring system. Thus, 1,4 ­ dichloro[3,4-d]pyridazine was treated with thiourea and the intermediate thiouronium salt hydrolyzed to give pyrido[3, 4-d]pyridazine-1,4(2H,3H)-dithione which was subsequently alkylated to give 1,4-bis(alkylthio)pyrido­[3,4-d]pyridazines. On the other hand, 1,4-bis(arylthio)­pyrido[3,4-d]pyridazines were prepared by the reaction of 1,4-dichloropyrido[3,4-d]pyridazine with various substituted thiophenols. Furthermore, treatment of 1,4-dichloropyrido[3,4-d]­pyridazine with a variety of substituted anilines gave the corresponding 1,4-disubstituted aniline derivatives, whereas reaction with alkylamines afforded only the 1(4)-chloro-4(1)-alkylaminopyrido[3,4-d]pyridazines. When 1-chloropyrido[3,4-d]pyridazine-4(3H)-one or 4-chloropyrido[3,4-d]pyridazine-1(2H)-one was treated with hydrazine, the corresponding …

Cationic Copolymerization Of B-Pinene And Styrene, Charles Peter Snyder

Honors Theses

Cationic polymerizations are the least understood of all polymerization reactions. Perhaps even less understood are copolymerizations using cationic catalysts. Very little can be found in the literature concerning B-pinene and styrene copolymers. This work was done to shed some light on this interesting subject.

Attempted Synthesis Of Diethyl 7-Dimethylsilabicyclo 2.2.1 Hepta-2,5-Dione-1,4-Dioate, David Kenneth Tart

Honors Theses

An attempt was made to synthesize diethyl 7-dimethylsilabicyclo [2.2.1) hepta-2,5-dione-l,4-dioate by reacting dimethyldichlorosilane with the dianion of 1,4-dicarbethoxy- 2,5-cyclohexadione. The products formed in the reaction were silicones and 0-silylated polymeric materials. If any of the desired product was formed, it was not detected.

Synthesis Of C14-Labeled Bis (P-Chlorophenyl) Acetic Acid (Dda), William Michael Silver

Honors Theses

The past three decade has seen the widespread use of DDT as an insecticide. As a persistent insecticide, its use has prompted a great amount of research into the fate of DDT in living organisms. A large number of metabolites of DDT has been found and many identified, although not all of the metabolites were found in all of the experimental bacterium, insects, or mammals.

Photochemical Solvolysis Of Optically Active 3,5-Dimethoxy-Α-D-Benzyl Acetate, Peter Jerry Frank

Honors Theses

The purpose of this work was the stereochemical study of the photochemical solvolytic reaction of 3,5-dimethoxybenzoic acid, optically active 3,5-dimethoxy-α-d-benzyl alcohol was prepared. The specific rotation of the alcohol was compared to the alcohol produced from the photochemical solvolytic reaction of 3,5-dimethoxy-α-d-benzyl acetate.

The Preparation And Kinetics Of Sterically Hindered Gold (Iii) Complexes, David Luther Fant

Honors Theses

The purpose of this research was to prepare and study complexes with steric hindrance greater than that of the dien complex but less than that of the Et4dien complex.

Synthetic Approaches To Certain Acenapthalene Drivatives, Douglas Jeffrey Binder

Honors Theses

The purpose of this investigation is the synthesis of bis- acenaphth- (1, 2a)- acenaphthene. The experimental procedures used generally follow those of previous workers. The use of 1, 8- dibromonaphthalene is necessary throughout the synthesis. The preparation used follows that of letsinger, after a preferred synthesis of 8- bromo- 1- naphthotic acid. The latter compound reacted via a modified Hunsdiecker reaction to yield 1, 8- dibromo- naphthalene. Other approaches tried never seemed to result in improved yields, or were successful. Besides this approach to 1, 8- dibromonaphthalene, an attempt to circumvent its need has been made by running a dilute …

1-3 Dipolar Cycloadditions Of Nitrile Ylides, Steven Paul Braff

Honors Theses

1-3 dipolar cycloaddition is the union of a 1-3 dipole, a-b-c, with a system containing a multiple bond, d-e, to form a five membered ring. In this scheme, center c contains an electron sextet, and concommitant positive charge, while center c contains an unshared pair of electrons and is the anionic center of the dipole. In the cycloaddition reaction, the 1-3 dipole and the multiple bond system (called the dipolarophile), collapse to form a five membered ring with loss of all formal charges. All together, eighteen 1-3 dipolar systems have been mentioned. The synthetic potential with respect to heterocyclic adducts …

The Developement [Sic] Of Phosphorometric, Fluorometric And Absorption Analyses For The Measurement Of Carbamates And Carbamic Acids As An Explanation Of Carbon Dioxide Transport In Blood, Edward Theodore Gray

Honors Theses

Phosphorometric, flourometric, and absorption analyses have been developed for the measurement of amino acids, carbamic acids, and carbamates. The absorption analysis may be done in any solvent while the other two methods are limited to non-re-emitting solvents. Water is not excluded in any of the analyses. A carbamate or carbamic acid can be detected even in the presence of amino acids as low as 0.5%, with an overall accuracy of ± 0.3)%. Tentative assignments have been made for the n, π* direct triplet excitation bands for the carbonyls of glycine and its carbamic acid, acetyl chloride, ethyl acetate, and acetamide. …

Some Aspects Of Quantum Mechanics In Chemical Theory, Thomas Freeman Babson

Honors Theses

The physics of microscopic phenomena is called quantum mechanics. When quantum mechanics is extended to the macroscopic scale, the classical macroscopic physics results. Atomic interactions such as the formation of bonds between atoms falls into the range of physics described by quantum mechanics. Because of the interest of a chemist in such interatomic effects, it seems reasonable that a chemist would be interested in quantum mechanics because it is the physics governing these effects. The point of this thesis is to present some of those aspects of quantum mechanics that are directly applicable to molecular systems and that can aid …

An Acid Alkylation Of 8-Hydroxyquinoline, James D. Searcy

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 by James D. Searcy on May 11, 1972.