Physical Sciences and Mathematics Commons^™

Light Scattering Studies Of Rotational And Vibrational Relaxations Of Acetonitrile In Carbon Tetrachloride, Scott Whittenburg

Chemistry Faculty Publications

The rotational and vibrational relaxation times of acetonitrile-carbon tetrachloride solutions were investigated as a function of concentration. viscosity, and temperature using depolarized Rayleigh and Raman scattering. Using a Fabry-Perot interferometer and single frequency laser source, we have shown that reliable results for the single particle orientational correlation times (T,) for -CH3CN can be obtained by carrying out a concentration dependent depolarized Rayleigh scattering study. Raman scattering was shown to yield inconsistent results for T. in CH3CN. At constant viscosity, it was found that the Rayleigh scattering relaxation time (TRay) of CH3CN in CCI. does not change with CH3CN concentration, indicating …

Photochemistry Of Alpha, Beta-Unsaturated Nitro Compounds, Charles Elmore

Masters Theses & Specialist Projects

A total of twelve α ,β - unsaturated nitro compounds of the form

Ar-C=C-NO₂

| |

H R

(where Ar=phenyl, o-methylphenyl, mesityl, α - naphthyl, and β - naphthyl; R=hydrogen, methyl, ethyl, and phenyl) were prepared and irradiated with ultraviolet light. When the corresponding α - oximinoketone was formed, it was recovered and identified. Six of the α , β - unsaturated nitro compounds and one α - oximinoketone had not been previously reported. Yields of irradiation products were determined and a kinetic study performed on these.

The effect of substituents size at the β - position of α …

Computer Simulation Of The Rotational Spectrum Of A Symmetric Top Molecule, W. Scott Wells

Masters Theses & Specialist Projects

Given the proper equations and the appropriate set of selection rules, a computer can be programmed to simulate the spectrum of a molecule. This study deals with the rotational spectrum of a symmetric top molecule. The program itself was written in several subroutine blocks. By doing this the computing time was reduced by 70% over similar programs.

The program can be used to simulate the spectrum of a molecule if the transition polarization type and the rotational constants are known. However, if the type of transition polarization or constants is unknown, the program can be used as a tool for …

Chromium(Iii) Tartrates, Gerald Lynn Robbins

Chemistry and Chemical Biology ETDs

The binuclear tartrate-bridged complexes [Cr ₂ (tartH) ₂ (L)₂ ] and Na [ Cr₂ (tart) (tartH) (L)₂]("tart" = C₄H₂O₆^4-, "tartH" = C₄H₃O₆^3- and "L"= 1,10-phenanthroline or 2,2'-bipyridyl) have been synthesized where each complex contains either two optically active or two meso bridging ligands. A discussion of the number of isomers and symmetries of these complexes is presented, as well as a complete description of the syntheses of the complexes and their sodium salts.

Kinetics And Mechanism Of The Solvolysis Of The Cis- And Trans-5, 5-Dimethyl-1, 3-Cyclohexanediol Bis-P-Toluenesulfonate In Aqueous Pyridine, Louis Frederick Holzknecht

Morehead State Theses and Dissertations

A thesis presented to the faculty of the Sciences and Mathematics School at Morehead State University in partial fulfillment of the requirements for the Degree of Master of Science in Chemistry by Louis Frederick Holzknecht on April 5, 1977.

Side-Chain Metalations Of Certain Dimethylpyridines By Means Of Organoalkali Metal Reagents, Stephen Bendzunas

Masters Theses

No abstract provided.

Studies Toward The Total Synthesis Of A Colchicine Analog, Jacob Shya Tou

Masters Theses

No abstract provided.

Unusual Alkylations Of The 1,1-Diphenyl-2-Propanone Dianion, Ruth E. Tenbrink

Masters Theses

No abstract provided.

The Synthesis And Study Of The Enolate Monoanion Of 2, 4-Di-P-Anisylbicyclo(3.2.1)Oct-6-En-3-One, Phillip D. Reynhout

Masters Theses

No abstract provided.

The Synthesis And Physical Properties Of Some 1-Methyl And 2-Methyl Bridged Cycloheptapyrazolones, Gary R. Larson

Masters Theses

No abstract provided.

The Dependence Of The Apparent Pk Of Ion Exchange Celluloses Of Ionic Strength, Paul Cyril Gillespie

Theses and Dissertations

Diethylaminoethyl cellulose was titrated with acid and base in various concentrations of NaCl. The pK values were determined from titration curves using a graphical technique. Two titratable groups were observed from the acid titration curve, a major and a minor group. The minor group, which represented 20% of the acid titration, was barely detectable in the base titration curve and had a salt-independent pK of 6.0. The pK of the major group was strongly salt-dependent and was approximately a linear function of log N NaCl. An equilibrium shift caused by the counter ion may explain the salt dependence. Hydrogen bonding …

A Comparison Of Various Pattern Recognition Techniques, Larry Wood

Masters Theses & Specialist Projects

A comparison of the reliability of three pattern recognition classifiers has been made using data having a great amount of variation. The basic concepts of the Linear Learning Machine, the K Nearest Neighbor Classifier, and the Potential Function Classifier are presented. Prediction of whether a student would pass or fail freshmen Chemistry 120 was made, based on various test results. The Linear Learning Machine was found to be an unworkable classifier for this kind of data. Both the Potential Function Classifier and the K Nearest Neighbor classifier were acceptable with the Potential Function Classifier being generally a better classifier.

Intermolecular Potential Surfaces From Electron Gas Methods. Ii. Angle And Distance Dependence Of The A’ And A” Ar–No(X^2ii) Interactions, Glen C. Nielson, Gregory A. Parker, Russell T. Pack

Faculty Publications

Angle dependent intermolecular potential energy surfaces for the two states (2A’ and 2A”) that arise from the interaction of ground (X^2II) state NO with Ar are calculated using the electron gas model to obtain the short range interactions. The average and difference of the two interaction energies are fit to analytic forms convenient for use in scattering calculations and joined smoothly onto the long range van der Waals potential previously determined. The results, which appear to be of useful accuracy, and the applicability of the electron gas model to such open shell–closed shell interactions are discussed.

Petroleum Hydrocarbons From Effluents: Detection In Marine Environment, John T. Tanacredi Ph.D.

Faculty Works: CERCOM (1977-2016)

The marine environment has become the primary disposa ground for an increasing quantity of petroleum wastes. Mushrooming demands for petroleum products and the lack of economic incentive to recycle waste oil will increase the concentrations of detrimental petroleum hydrocarbons in the marine environment

Although a continuous, low-level discharge of waste petroleum hydrocarbons into the marine environment may not be as dramatic as a major oil spill, the consequences could be more devastating over an extended period. As noted by Blumer, earlier interpretations of the environmental effects of oil must not be reevaluated in the light of recent evidence of its …

Conformational Analysis Of 1-Tertiarybutyl-1, 4-Dihydronaphthalene A Turnover From Srni To Sni Mechanism, Su-Jen Huang

Masters Theses & Specialist Projects

The cyclohexadiene porition of 1-tertiarybutyl-1, 4-dihydronaphthalene exists in a puckered rather than planar conformation at room temperature, with approximately equal populations of the isomer with the t-butyl group “axial” and “equatorial.” Analysis of chemical shifts and coupling constants was aided by use of a LAOCOON III program.

Excited States And Photochemistry Of Saturated Molecules, Patrick M. Saatzer, Robert D. Koob, Mark S. Gordon

Office of the Provost Scholarship

The molecular structures and bond energies in the low-lying excited states of n-alkanes from methane to n-pentane are investigated using the semi-empirical INDO method with configuration interaction. In general the calculated geometries and bond energies are consistent with the known threshold photochemistry of these molecules, the only exception being the prediction of vicinal (rather than geminal) elimination of H₂ in ethane. It appears that INDO overestimates the amount of angular distortion in these excited states.

Kinetics Of The Alkaline Tetramer Dimer Dissociation In Liganded Human Hemoglobin: A Laser Light-Scattering Stopped-Flow Study, D. P. Flamig, L. J. Parkhurst

Chemistry Department: Faculty Publications

The first-order dissociation of tetrameric HbCO to the dimer has been studied over the pH range 10.30-11.57 in a light-scattering stopped-flow apparatus using argon-ion laser excitation. The first-order dissociation rate constant varies from 0.25 sec^-1 to 24.0 sec^-1 over this pH interval. A semilogarithmic plot of k versus pH has a slope of 2.56 at pH 11.07, the midpoint. The pH dependence of the dissociation of the tetramer is consistent with progressive titration of α₁-α₂ and β₁-β₂ salt bridges. At pH 10.66, the dissociation rates of HbO₂, HbCO, methemoglobin, and …

Catalytic Fluorination Of Dichloromethane With Hydrofluoric Acid, Michael O. Myers

Retrospective Theses and Dissertations

The catalytic, vapor-phase fluorination of dichloromethane to chlorofluoromethane with 38% hydrofluoric acid was investigated as a model system for possible direct utilization of hydrofluoric acid in the production of fluorocarbons and chlorofluorocarbons. Catalysts consisting of Cr or Ni supported on alumina and Ni, Cr, Ag, Co, La, Sn, Hg(I), Hg(II), Cu, Fe, Ru, Zn, Na, or Ca supported on activated charcoal were utilized at various reaction temperatures and reactor residence times. Alumina-supported catalysts were found to have low activities for fluorination in comparison to catalysts utilizing anhydrous HF reported in the patent literature. The low activities were attributed to low …

Proton Shift Additivity And Substituent Interaction Parameters, Donald W. Beistel, Gary Chappell, W. Daniel Edwards

Chemistry Faculty Research & Creative Works

The 4-substituted acetophenone family is characterized and its shifts are correlated with those of nine families of 1, 4-disubstituted benzenes reported previously. Then a simple mathematical model is derived to account for the proton magnetic resonance shifts within families of 1, 4-disubstituted benzenes. The model suggests that the substituents interact by σ-bond polarization. The polarization model rationalizes shift additivity and is consistent with the qualitative relationship between the number of valence electrons on a substituent and its capacity to induce shifts. © 1977, American Chemical Society. All rights reserved.

Erratum: The Internal Chemical Shift - A Key To Bonding In Aromatic Molecules. 2. Substituent Effects On Carbon-13 Magnetic Resonance Spectra Of The 1,4-Disubstituted Benzenes (Journal Of Physical Chemistry (1976) 80, (2024)), D. (Donald) W. Beistel, W. Dan Edwards

Chemistry Faculty Research & Creative Works

No abstract provided.

The Liquid Phase Oxidation Of 1,3-Pentadiene, Carl B. Reaves

Retrospective Theses and Dissertations

The liquid phase autoxidation of 1,3-pentadiene to 2,4-pentadienoic acid utilizing gaseous oxygen at atmospheric pressure was investigated as a possible route for direct utilization of piperylene obtained during the cracking of naptha to ethylene. Catalyst system consisting of cobalt, manganese, and iron salts promoted by sodium, potassium and hydrogen bromides, were used under a variety of condition of catalyst concentration, temperature, oxygen flow and piperylene purity. Under all conditions studied, a large number of oxidation products were formed. Maximum yields of 2,4-pentadienoic acid were obtained using a cobalt acetate bromide catalyst at 85°C.

The Liquid Phase Conversion Of Carbon Dioxide To Hydrocarbons Over Ruthenium Catalyst Systems, Mohammad M. Akbarnejad

Retrospective Theses and Dissertations

The purpose of this research project was to evaluate the feasibility of producing hydrocarbons by liquid phase hydrogenation of carbon dioxide. Initial studies dealt with the evaluation of ruthenium (III) chloride over a wide range of reaction conditions. High conversions were observed and were found to vary with catalyst concentration, temperature and time. Conversion of carbon dioxide reached 73% after twenty-four hours at a catalyst concentration of 0.75g/mole of CO2 feed. The hydrogen to carbon dioxide ratio was found to have a significant effect on product distribution and amount of methane produced. For example, low ratios of H2/CO2 gave large …

A 13C-Nmr Study Of Cis-Ti(Ac Ac)2Cl2, Daniel T. Haworth, Charles A. Wilkie

Chemistry Faculty Research and Publications

No abstract provided.

Process For The Production Of 2-Alkyl Or 2-Cycloalkyl-4-Methyl-6-Hydroxypyrimidines, J. Thomas Blackwell, John T. Gupton, Jim B. Narbors

Chemistry Faculty Publications

Production of 2-alkyl or 2-cycloalkyl-4-methyl-6-hydroxy pyrimidines by sequentially reacting without isolation of any intermediates in an organic solvent (1) diketene and ammonia to produce .beta.-aminocrotonamide and (2) .beta.-aminocrotonamide, after water removal therefrom, a lower alkanoic or cycloalkanoic acid ester and an alkali metal alkoxide.

Process For The Production Of 2-Alkyl Or 2-Cycloalkyl-4-Methyl-6-Hydroxypyrimidines, John T. Gupton, Alex M. Jelenevsky, Teruko U. Miyazaki, Harris E. Petree

Chemistry Faculty Publications

Production of 2-alkyl or 2-cycloalkyl-4-methyl-6-hydroxy pyrimidines by first reacting diketene and lower alkanoic or cycloalkanoic acid amides in the presence of catalytic amounts of Lewis bases or Lewis or Bronsted acids, followed by treating the N-acetoacetyl (lower) alkanoic or cycloalkanoic acid amide intermediates with ammonia in the presence of acid catalysts.

Quantitative Analysis Of Thin Films By Dc Arc Optical Emission Spectroscopy, Arnold W. Hogrefe

Retrospective Theses and Dissertations

The use of DC arc optical emission spectroscopy (OES) for quantitative analysis of thin films deposited on graphite electrodes was investigated as a process control tool. Three binary systems were evaluated: nickel-chromium, phosphorous-silicon, and silicon-aluminum. Sampling by direct deposition onto graphite electrodes placed in the deposition chamber with product runs proved to be a rapid, representative, and non-disruptive technique. Standard electrodes were prepared for each system either by evaporation of solutions of known concentration onto the tips of electrodes or by weighing out powdered standards of the appropriate concentrations. Standard curves were then prepared by burning multiple sets of standard …

Catecholborane Reductions Of Ditosylhydrozones To The Corresponding Methylene Derivatives, Dominic T.C. Yang, Michael C.W. Yang, George W. Kabalka, J. H. Chandler

Journal of the Arkansas Academy of Science

The smooth deoxygenation of diketones via the Catecholborane reduction of the corresponding ditosylhydrzaones is described. The reductions occur under mild conditions and are suitable for sensitive compounds.

Trans Diequatorially Fused Blocking Groups For Glucopyranose Derivatives, Basharat Ali Khan

University of the Pacific Theses and Dissertations

No abstract provided.

Stability Constants Of Naco3-, Naso4- And Kco3- In Water At 25°C, Frank Dennis Blum

Masters Theses

A new method for determining ion association constants in aqueous solutions using ion selective electrodes has been developed. This method has been applied to the NaCO₃^-, NaSO₄^- and KCO₃^- ion pairs at 25°C. Association constants for NaCO₃^- and NaSO₄^- were determined at various ionic strengths and extrapolated to zero ionic strength to yield 2.2 ± 0.2 for NaCO₃^- and 5.3 ± 0.4 for NaSO₄^-. Values for the association constants at an ionic strength near sea water (I=0.70) were calculated to be 1.7 ± 0.1 …

Reactions Of 1-Bromo-2-(P-Tolyl)Cyclopropane With Nucleophiles In The Presence Of Crown Ether, Gerald Mccomas

Masters Theses

Reactions of 1-bromo-2-(p-tolyl)cyclopropane with potassium acetate in the presence of crown ether in various solvents (DMSO, t-butanol, and toluene) have been examined. No cyclopropyl products were observed, only ring-opened p-methylsinnamyl acetates. The trans 1-bromo-2-(p-tolyl)cyclopropane isomer reacts about 3.8 times faster than the cis isomer in DMSO, but only about 1.5 times faster in t-butanol, seemingly related to solvation factors in the transition state. Although stability studies indicated that p-methylcinnamyl bromide might be an intermediate, the rate of formation of this compound in the absence of potassium acetate was much lower than rate of product formation even in the presence of …