Physical Sciences and Mathematics Commons^™

Solvents For Use In The Extractive Distillation Of Piperylene Concentrate, Abdulhadi Sagga

Retrospective Theses and Dissertations

This report describes an evaluation of the effectiveness of different solvents and solvent-organometallic compound mixtures for use in the extractive distillation of a piperylene mixture, consisting of five carbon olefins and diolefins obtained as a byproduct from an ethylene feedstock production plant. The most effective solvent is judged to be the one which gives the best separation of the lowest boiling and highest boiling points of the key components in the mixture. In this study twenty solvents and solvent mixtures were tested. Acetonitrile was found to be the most effective solvent and nitromethane the next most effective.

Determination Of N,N'-Diphenylguanidine In Biological Tissues And Fluids Using High Pressure Liquid Chromatography, Edward Sidney Hunter Iii

Chemistry & Biochemistry Theses & Dissertations

N,N'-Diphenylguanidine (DPG) is a potentially toxic compound used in the vulcanization of rubber products. Distribution of DPG in hybrid mice (C57BL/6J interbred with DAB₂) was determined following intraperitoneal injection. Urine, fecal material, whole blood and tissues were collected at various times after administration of DPG and the extracts analyzed for DPG by high pressure liquid chromatography. Recovery of DPG from spiked urine and whole blood exceed 90%, however, the recovery of DPG from spiked tissue samples was approximately 70%.

DPG concentration in whole blood reached a maximum within ten minutes and rapidly decreased through 180 minutes after administration …

Ab Initio Studies Of Abstraction Reactions Xhn + Hydrogen (H2) → Xhn+1 + Hydrogen (H) (X = Carbon, Nitrogen, Silicon, Or Phosphorus), Mark S. Gordon, David R. Gano, Jerry A. Boatz

Mark S. Gordon

The abstraction reactions CH3 + H2 --+ CH4 + H, SiH3 + H2 --+ SiH4 + H, NH2 + H2 --+ NH3 + H, and PH2 + H2--+ PH3 + H have been studied with a variety of methods, including MCSCF, POL-CI, UMP2, and UMP3. In agreement with the observed thermochemistry, abstraction by methyl radical is found to proceed more easily than by silyl, and the reverse of the last reaction occurs with a very small ( ~ 5.6 kcal/mol) barrier. POL-CI appears to be a consistently reliable approach for this type of reaction.

Electrical Properties Of Plasma-Polymerized Thin Organic Films, Maciej Gazicki, H. Yasuda

Chemistry Faculty Research & Creative Works

The electrical properties of plasma-polymerized films are summarized and compared to those of conventional polymers. Particular attention is devoted to the dielectric relaxation, dielectric breakdown, electric conductivity and photoconductivity, and their control via control of the plasma parameters. © 1983 Plenum Publishing Corporation.

25th Rocky Mountain Conference

Rocky Mountain Conference on Magnetic Resonance

Abstracts and meeting program from the 25th annual meeting of the Rocky Mountain Conference, co-sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy and the Rocky Mountain Chromatography Discussion Group. Held in Denver, Colorado, August 14-17, 1983.

Nonenzymatic Glucosylation And Glucose-Dependent Cross-Linking Of Protein, Albert S. Eble, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

A model system using RNase A has been established for studying the nonenzymatic glucosylation and glucose-dependent cross-linking of protein (Maillard reaction) under physiological conditions in vitro. The rate of glucosylation of RNase was first order in glucose. Glucosylation was accompanied by a comparable decrease in primary amino groups in the protein and lysine recoverable by amino acid analysis. Analysis of glucosylation reaction mixtures by sodium dodecyl sulfate-polyacrylamide gel electrophoresis in the presence of mercaptoethanol revealed the time-dependent formation of RNase dimer and trimer. The polymerization reaction was mixed order with respect to glucose concentration, but was approximately first order with …

Generalized Response Of Chemiluminescence Analyzers, A. A. Mehrabzadeh, Robert J. O'Brien, Thomas M. Hard

Chemistry Faculty Publications and Presentations

The mass flow and chemical kinetic equations for a gaseous chemiluminescence (CL) analyzer are formulated and solved. The resultant equation can be used to predict the absolute response of the analyzer as a function of the sample flow rate, the sample gas pressure, the chamber pressure, the chamber volume, the mass flow rate and mole fraction of the reagent gas, and the rate constants of the relevant chemical processes. Thus, the equation allows optimization of these parameters. It is shown that for varying sample pressure the analyzer can be used to measure either concentration or mole fraction and that interfering …

A Microprocessor Controlled Pulsed Hollow Cathode Lamp For An Atomic Absorption Spectrometer, James B. Schilling

Masters Theses

A Jarrell-Ash Atomic Absorption/Flame Emission 82-360 Spectrometer was interfaced to a Heathkit ETA-3400 microprocessor. The microprocessor is used to pulse the hollow cathode lamp from a "steady" current to a "peak " current during the opening of the chopper. The current from the photomultiplier-tube is converted to a proportional voltage which is supplied to a sample-and-hold circuit. A successive approximation routine is used to convert the voltage to a representative digital value. Digital values are obtained for the "blank" and "sample" and are used to calculate percent absorption values. The system can also be used to obtain emission values.

The …

Transport Properties Of Ground State Nitrogen Atoms, James C. Rainwater, Louis Biolsi Jr., Kevin J. Biolsi, Paul M. Holland

Chemistry Faculty Research & Creative Works

Transport properties of dilute monatomic gases depend on the two body atom-atom interaction potential. When two ground state (⁴S) nitrogen atoms interact, they can follow any of four potential energy curves corresponding to the N₂ molecule; the X ¹Σ⁺_g, A³Σ⁺_u, ⁵Σ⁺_g, and ⁷Σ⁺_u curves. Transport collision integrals for the ¹Σ⁺_g and ³Σ⁺_u states have been calculated by representing the potentials for these states with the Hulburt-Hirschfelder potential. The⁵Σ⁺_g state has a …

Analytical Pyrolysis Of Eastern Shales, Kenneth Naples

Masters Theses & Specialist Projects

The effects of pyrolysis interval, ceiling temperature, heating rate and mesh size on both the pyrolysis yield and relative product distribution for two eastern oil shales (Sunbury and Cleveland) were studied. An extension of the technique of analytical pyrolysis (pyrolysis-gas chromatography) was used. This extension employed a Chemical Data System (C.D.S.) Model 382 Extended Pyroprobe and a C.D.S. Model 310 Concentrator which enabled the pyrolysis products to be collected into a trap system. After completion of a predetermined heating interval, the trap was pulse heated to 250°C and the high and low volatile components were back-flushed into the injection port …

The Metal In The Polarisable Interface Coupling With The Solvent Phase, Jerry Goodisman, Jean Paul Badiali, Martin Luc Rosinberg

Chemistry - All Scholarship

A quantum mechanical treatment of the conduction electrons of a metal in a polarisable interface shows that they can make an appreciable contribution to the electrical capacitance. Results for six metals are given, showing how differences in metal properties account qualitatively for experimentally observed differences in interfacial capacities, when the solvent is replaced by a dielectric film. To justify the neglect of solvent structure when metal properties are treated, the coupling between metal and solvent is discussed for orientable point solvent dipoles, and for a representation of the solvent polarisation by a pair of charged planes. The electron profile affects …

The Binding Of Ribosomal Protein Si To Si-Depleted 30s And 70s Ribosomes. A Fluorescence Anisotropy Study Of The Effects Of Mg2+, Dixie J. Goss, Lawrence J. Parkhurst, Arkesh M. Mehta, Albert J. Wahba

Lawrence Parkhurst Publications

We have determined the equilibrium constants for the binding of AEDANS-labelled Si to Sl-depleted 30S and 70S ribosomes. For “tight” ribosomes, the association of S1 increases with the sixth power of Mg²⁺ concentration, but for 30S subunits and "loose" ribosomes, there is virtually no dependence of the association on Mg²⁺ over the same concentration range, 2-1O mM in Mg²⁺. The binding of S1 to 70S ribosomes at 10 mM Mg is stabilized by 2 kcal/mol compared to the binding to 30S subunits. When intact Si binds to tight ribosomes, the fluorescence anisotropy is that for virtually …

Are The Silacyclopentadienyl Anion And The Silacyclopropenyl Cation Aromatic?, Mark S. Gordon, Philip Boudjouk, Freidun Anwari

Mark S. Gordon

Stabilization energies attributable to aromaticity in the silacyclopentadienyl anion and the silacyclopropenyl cation were found to be small in the former and absent in the latter when calculated from bond-separation reactions employing 3-21G and ST0-2G basis sets. The silacyclopentadienyl anion is approximately 25% as aromatic as the all-carbon analogue whereas silabenzene is more than 80% as aromatic as benzene. The introduction of diffuse functions into the basis sets has only a small effect on these results. The silacyclopropenyl cation is actually destabilized but strain is probably a key factor in the comparison. Also found was that the ST0-2G basis set …

Gamma-Gamma Angular Correlation Studies For 142ce, A. Wolf, C. Chung, W. B. Walters, R. L. Gill, M. Shmid, R. E. Chrien, Graham F. Peaslee

Faculty Publications

Gamma-gamma angular correlations for several cascades in 142Ce were measured using a four-detector system. In a recent publication the level at 1219 keV was assigned 22+ in contradiction to a previous assignment of 41+. This makes 142Ce completely different from any known nucleus in the same region. It is shown, however, that this level is, in fact, completely consistent with 4+ and is in agreement with systematics.

Soil Degradation Of H-Coal Liquid & Various Aromatic Compounds, Kevin Wilson

Masters Theses & Specialist Projects

The common bacterial genera Pseudomonas and Acinetobacter are ubiquitous in most soils and are capable of degrading a large number of chemical compounds. While the degradative pathways of several individual aromatic compounds are known, the degradative pathways of many other aromatic compounds have not yet been elucidated. In addition, very little work has been done on the microbial degradation of coal liquids in the environment.

Previous work at Western Kentucky University has shown that decomposition of Ashland Oil Company's liquified coal can indeed be accomplished by the above bacterial genera in an enriched liquid media. The topic of this thesis …

The Products Of The Gas Phase Ozonolysis Of Tetramethylethylene, Anthony R. Deangelo

Honors Theses

The products of the ozonolysis of tetramethylethylene (TME) in the gas phase was studied. Reactions were run at concentrations between 10 and 400ppm TME and lower concentrations of ozone. The reactions were run at room temperature and atmospheric pressure. Gaseous products were studies by gas chromatography, mass spectrometry and HPLC analysis, the latter using 2, 4-dinitrophenylhydrazine derivatives of carbonyl products. Ozone concentrations and the determination of possible peroxidic products was accomplished by measuring the absorbance of a buffered KI solution (352 nm) after reaction with a known volume of gas. The possibility of acetone/ ozone and TME/ peroxides reactions were …

Fluorescence Quenching Of Peptidyl Tryptophan By External Quenchers, Richard Dennin

Honors Theses

Fluorescence quenching data have been collected on several small peptides (1-4) residues which contain tryptophan. These data have been analyzed by a variety of methods. The classical Stern-Volmer equation is utilized to obtain Stern-Volmer plots of fluorescence quenching data. Substantial upward curvature is observed in the Stern-Volmer plots of all the peptides studied. Data were also analyzed via the modified Stern-Volmer static quenching model. Although this model could explain the deviation from simple Stern-Volmer behavior found in SV plots, the parameters used by the model were often physically “unrealistic”: Therefore, another form of data analysis was used. The newly proposed …

Sterically Hindered Esters: Mechanisms Of Saponification, Frederick F. Fenter

Honors Theses

This paper discusses the mechanisms of base catalyzed hydrolysis of the secondary-butyl ester of 2, 2-dimethyl-propanoic acid (secondary-butyl pivaloate). Kinetic studies were carried out at 53° and near neutral hydroxide ion concentrations, but due to the slow velocity of reaction, no conclusions concerning the order of the kinetics of hydrolysis could be drawn. Also discussed is a scheme for an experiment involving the utilization of 018 enriched water in the saponification reaction of secondary-butyl pivolate under similar conditions of pH and temperature. The purpose of this experiment is to determine the site of oxygen cleavage during the hydrolysis. The analysis …

Determination Of Aldehydes And Ketones In The Gas Phase, Clyde A. Kelly

Honors Theses

A recently developed method for the quantitative detection of carbonyl compounds in ambient air was investigated, specifically in order to further standardize and improve the process. The method involves drawing a gas phase sample of carbonyl compounds through impingers containing a 2, 4-Dinitrophenylhydrazine solution is then injected directly into the hplc for separation on a reversed phase column and quantitative determination by UV absorption at 254 nm and 360 nm simultaneously. The critical feature of the method (based upon a standard analytical derivatization reaction) is the use of the acetonitrile solvent. This allows for direct injection of the sampling solution …

Cationic Copolymerization Of Styrene And Beta-Pinene: The Effect Of Solvent On Monomer Reactivity Ratios, George Yusun Paik

Honors Theses

Copolymers of styrene and B- pinene were synthesized at 30 degrees Celcius in methylene dichloride, carbon tetrachloride, and nitrobenzene. NMR analysis was used to determine the mole percent of styrene and B-pinene in the copolymer. These data were used to calculate monomer reactivity ratios in the three different solvents. It was also found that the styrene reactivity ratio increased when solvents with low dielectric constants were used. The B-pinene reactivity ratio also increased as the dielectric constant of the solvent increased. Pyrolysis and gas chromatography indicated that copolymerization may not have occurred in nitrobenzene and carbon tetrachloride if the mole …

Syntheses And Fluorescence Properties Of Sterically-Hindered Esters Of 9-Anthroic Acid, Richard Leslie Dubs

Honors Theses

For over a decade, Professor Thomas C. Werner and his students have been studying the unusual florescence properties of methyl-9-anthroate. In the ground state of this ester, the carboxyl group lies perpendicular to the anthracene rings due to steric inhibition by the peri hydrogens. Werner has postulated that, upon excitation, the carboxyl group rotates to form a planar configuration with the anthracene rings, and that this rotation is the cause of the unusual spectral properties. In our work, we have attempted to prove or disprove this hypothesis. We have chosen to synthesize analogues of methyl-9-anthroate in which carboxyl group rotation …

The Apple Ii, Daniel M. Laby

Honors Theses

The apple II+ microcomputer was interfaced to an Aminco-Morrow stopped-flow Apparatus. This interface package can be broken into two parts; the hardware, or electrical connections necessary to link the two instruments, and secondly, the software, or programs written to control the interface package. A circuit was constructed as part of the interface hardware. This circuit consisted of several operational amplifiers connected in such a way as to transform the output voltage of the stopped-flow into one acceptable by the Apple computer. The software for this interface package is extensive. Programs were written that allowed the user to initialize the correct …

Dmf Extractability As A Predictor Of Plasticity In Bituminous Coals, Jana Whitt

Masters Theses & Specialist Projects

Plasticity is a phenomenon of certain coals that is not completely understood. Some bituminous coals go through a softening and swelling state upon heating before they re-solidify. It is this softening and swelling state that is labeled as the "plastic state" of the coal. Concurrent with the plastic state of the coal, thermal decomposition of the coal takes place. Several low molecular weight gases are also evolved. These occur at a temperature of approximately 450° C.

The plasticity of a coal is a good indication of the coking ability of a coal. Plastic coals tend to give higher yields in …

The Combined Effect Of Cu And Zn On Selenastrum Capricornutum, Helmer Colonia-Roque

Dissertations and Theses

It has been demonstrated that the toxicity of heavy metals depends on their chemical speciation and can be related to their free ion activities, rather than the total metal concentrations. The objective of this study was to determine the effect of combined free ions of zinc and copper on the toxicity to the green alga Selenastrum capricornutum. This alga was grown in a defined medium, under controlled laboratory conditions, with a varying range of zinc and copper concentrations. The growth rate of the alga was inhibited at pZn = 5.93 or at pCu = 7.24. The results suggest that …

Cow Brain Glutaminase: Purification And Influence Of Phosphate And Borate Ions On Its Activity And Molecular Weight, Mahnaz Badamchian

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

An efficient and simple purification procedure for cow brain glutaminase (L- glutamine amidohydrolase, EC 3.5.1.2) is described. The main steps consisted of acetone extraction and French press treatment in the presence of phosphate ions, precipitation of nucleic acids and lipids by 0.08 % protamine·S04 and high speed centrifugation (300,000xg), ammonium sulfate fractionation, and gel filtration on Sepharose 4B first as the low molecular weight and then as the aggregated form. The yield was 22% and the final preparation had a specific activity of 142 μmoles/min/mg. The purification was more than 8000-fold over crude brain homogenate. The enzyme showed one strong …

Photochemical Energy Storage (Photosensitized Isomerization Of Norbornadiene To Quadricyclane By Copper(I) Complexes), Dennis J. Fife

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

This research has focused on the sensitized photoisomerization step of a solar energy storage system based on the interconversion of norbornadiene (NBD) and quadricyclane (Q). Sensitizers studied in the photoisomerization were arylphosphine complexes of copper(I) halides [(Ph₃P)₃CuX, (MePh₂P)₃CuX, (DIPHOS)CuCl; X = Cl, Br, I and DIPHOS = Ph₂P(CH₂)₂PPh₂]. The lowest electronic excited state of the complexes can be an effective triplet energy sensitizer as evidenced by a maximum quantum yield of 1.0 with (MePh₂P)₃CuX. The sensitization mechanism of the L …

Cell-Mediated Immunity Of The Dog Lung And Effects Of Inhaled 239puo2 Or Pulmonary Tumors, Jennifer Baker Galvin

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Cell-mediated immunity (CMI) in the lung has not been well characterized due to the lack of applicable tests. A major objective was to define pulmonary CMI serially in immunized and control lung lobes using the leukocyte procoagulant (LPCA) assay in young adult dogs. This was compared to a standard, but less reproducible CMI assay, macrophage migration inhibition facet (MIF). The CMI response, as measured by the LPCA assay, peaked in the blood 7 days after lung immunization. The pulmonary CMI response measured with cells obtained by bronchial lavage from the immunized and control lung lobes peaked at 9 to 12 …

Studies In Peptide Synthesis Towards The Lanthionine Analog Of Des-N-Tetramethyl Triostin A, Ganesh Devdas Kini

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Studies have been carried out towards the synthesis of bicyclic octadidepsipeptide lanthionine 4, an analog of des-N-tetramethyl triostin A. Starting with a symmetrical lanthionine unit 5 (R₁, R₃ = Me; R₂, R₄ = t-butyloxycarbonyl), synthesized from the corresponding cystine by contraction with hexaethylphosphorus triamide, linear octadidepsipeptides 29 and 32 were synthesized.

Attempted cyclizations of 29 and 32 to the bicyclic octapeptide were unsuccessful.

The failure of the symmetrical approach to 4 prompted the synthesis of an unsymmetrical lanthionine unit with appropriate compatible protecting groups. Attempts to synthesize unsymmetrical lanthionines by nucleophilic displacement on …

Analytical Pyrolysis Of Eastern Oil Shales, Lizbeth Sturgeon

Masters Theses & Specialist Projects

The Sunbury shale and the Cleveland member of the Ohio shale were studied utilizing the technique of analytical pyrolysis (pyrolysis gas chromatography). The effects of ceiling temperature, heating rate, and pyrolysis interval on the pyrolysis yield and relative product distribution for these eastern oil shales were observed. Carefully monitored pyrolysis of the shale allows separation of high and low volatile components and measurement of the relative peak areas in the pyrogram provides the yield of the high and low volatile fractions. Linear temperature ramps of 5000, 2000, and 100°C per second were employed. Ceiling temperatures of 450°C to 950°C and …

Kinetic & Spectral Studies Of Copper(Ii)-4,4',4",4'"-Tetrasulfophthalocyanine In Aqueous Solution, Stephen Scholl

Masters Theses & Specialist Projects

The monomer-dimer equilibrium of CuTSPC^4- was examined by spectral methods in aqueous solution over a total dye concentration of 2 x 10^-8M to 8 x 10^-7M at 24°C. The value obtained for the dimerization constant, KD,was 1.1 x 10⁷M^-1 which is smaller than literature values. However, the discrepancy is not appreciable considering the differences in the methods used and the experimental conditions of the different solutions. Spectral measurements of the dimerization constant were made at only one temperature since the spectral changes were quite small when the temperature was varied. This observation …