Chemistry Commons^™

Absolute-Convective Instabilities And Their Associated Wave Packets In A Compressible Reacting Mixing Layer, F. Q. Hu, T. L. Jackson, D. G. Lasseigne, C. E. Grosch

Mathematics & Statistics Faculty Publications

In this paper the transition from convective to absolute instability in a reacting compressible mixing layer with finite rate chemistry is examined. The reaction is assumed to be one step, irreversible, and of Arrhenius type. It is shown that absolute instability can exist for moderate heat release without backflow. The effects of the temperature ratio, heat release parameter, Zeldovich number, equivalence ratio, direction of propagation of the disturbances, and the Mach number on the transition value of the velocity ratio are given. The present results are compared to those obtained from the flame sheet model for the temperature using the …

Interferences Of N-Chloroorganic Compounds In Free Chlorine Determination, Sushma H. Gandhi

Chemistry & Biochemistry Theses & Dissertations

Various N-chlorinated organic compounds give positive responses to the analytical methods used to determine free chlorine. The present work quantifies interferences due to N-chloroisoleucine, N-chloropiperidine and N-chloro-2-methylbutyraldiminein the free chlorine determination by amperometry. These N-chloroorganic compounds were also studied for the recovery in response by the indicator electrode in amperometric titrimetry. The total chlorine content of the chloroaldimines derived from the chlorination of the amino acids, alanine, glutamic acid, glycine, isoleucine, leucine, phenylalanine, serine, valine, and those of dipeptides, alanylvaline and glycylleucine, was determined by amperometry and DPD-FAS titrimetry. The two methods were compared and evaluated with respect to recovery …

Investigation Of Alignment Dynamics In Mg-Ne And Mg-Ar Two-Photon Fractional Collisions, David Allen Olsgaard

Physics Theses & Dissertations

A new technique is used to observe the dynamics of electronic alignment in a dissociating collision complex. The technique requires the absorption of two optical photons during a single binary collision. Two exciting light fields are tuned into the wings of the 3s¹s₀-3p₁ and 3p¹p₁-5s¹s₀ resonances of Mg where strong collisions with rare gas atoms induce transitions between corresponding molecular states. The alignment produced in the intermediate state by the first excitation is probed by the second laser as a function of relative linear laser polarization and laser …

Biodegradation Of Crude Oil By Marine Higher Fungi, Brian J. Dyer

Biological Sciences Theses & Dissertations

Four experiments were performed to determine the ability of marine higher fungi to grow in and degrade crude oil. Eight species, previously determined to be hydrocarbonoclastic, were grown in artificial sea water medium (ASM) and southern Louisiana crude oil. The dry mycelial weights were measured and consumption of crude oil was measured gravimetrically. The two species with the best growth, Corollospora maritima and Zalerion maritimum, were grown in ASM containing crude oil spiked with three known hydrocarbons. To this was added glucose (0.15%) and incubated 49 days to test for possible cometabolism of hydrocarbons. Hydrocarbons remaining in the growth …

Thermal Characterization Of Carbon Monoxide Oxidation Catalysts Using Thermogravimetric Analysts And Differential Scanning Calorimetry, Rene A. Bartgis

Chemistry & Biochemistry Theses & Dissertations

Catalysts composed of platinum and/or palladium on tin (IV) oxide supports, with and without silica gel, as well as catalysts composed of gold on manganese oxide, have been developed for the recombination of carbon monoxide and oxygen to form carbon dioxide for use in carbon dioxide lasers. A thermogravimetric method and a differential scanning calorimetric method have been developed for the thermal characterization of these catalysts. The mass loss data and the enthalpy changes determined as the catalysts lost water were then related to existing activity data for these catalysts. No relationship was found between the thermal data and the …

Reactions Of Aqueous Chlorine With Valine In Model Solutions And In Wastewater, Erika Forrer Mccormick

Chemistry & Biochemistry Theses & Dissertations

Solutions of the amino acid valine were chlorinated to seven chlorine-to-nitrogen mole (Cl/N) ratios and analyzed by high performance liquid chromatography, gas chromatography/mass spectroscopy, infrared spectroscopy, and nuclear magnetic resonance spectroscopy. The chlorination products found were N-chlorovaline, isobutyraldehyde, isobutyronitrile, and N-chloroisobutyraldimine. Their product distribution depends on the level of chlorination and pH. The main products identified at the lower CI/N mole ratios were N-chlorovaline and isobutyraldehyde, whereas at the higher CI/N mole ratios isobutyronitrile and N-chloroisobutyraldimine were identified as the main products. The concentration and the chlorination products of valine in municipal wastewater were also determined. The chlorination products of …

A Diffuse Reflectance Infrared Fourier Transform Spectroscopic Study Of Platinum/Tin (Iv) Oxide Low-Temperature Carbon Monoxide Oxidation Catalysts, Donna Sue Duarte

Chemistry & Biochemistry Theses & Dissertations

Platinum-coated tin(IV) oxide catalysts have been developed for the recombination of carbon monoxide and oxygen at 55°C and 1 atmosphere of pressure in closed-cycle carbon dioxide lasers. A diffuse reflectance infrared fourier transform spectroscopic (DRIFTS) study of four of these catalysts during 5% carbon monoxide pretreatment at temperatures of 30°C, 100°c, 125°c, and 150°C has been performed. Evidence for the development of surface carbonate, bicarbonate, and formate species during pretreatment has been found. Dehydroxylation of the surface and loss of a partially charged hydrogen-bonded hydroxyl species have also been found to result from elevated temperature pretreatment. The four catalysts have …

Stable N-Chloraldimines And Other Chlorination Products Of Phenylalanine In Model Solutions And In A Wastewater, Barbara L. Conyers

Chemistry & Biochemistry Theses & Dissertations

Model solutions of the amino acid phenylalanine were chlorinated to seven Cl/N mole ratios. The by-products were characterized using gas chromatography, high performance liquid chromatography, GC/MS, infrared spectroscopy, and nuclear magnetic resonance spectroscopy. At the lower Cl/N ratios N-chlorophenylalanine and phenylacetaldehyde were identified as the main products while phenylacetonitrile and N-chlorophenylacetaldimine were the major products at Cl/N ratios of 2.0 and beyond. The concentration of phenylalanine in a municipal wastewater was determined. Using a radiotracer the chlorination products of phenylalanine in the wastewater at the 7 Cl/N ratios were identified as those seen in the model solutions. The distribution of …

A Study Of The Reactions Of P-Dipiperidino Benzene And Its Synthesis From 1,4-Dicyano-1,4-Dipiperidinocyclohexane, Ilias Konstantinos Dorziotis

Chemistry & Biochemistry Theses & Dissertations

Following a classical synthesis of PCP² Williams attempted to prepare l,4-diphenyl-1,4-dipiperidino cyclohexane 4¹ . This approach involved the preparation of 1,4- dicyano-1,4-dipiperidinocyclohexane 7 and the subsequent decyanation of the compound with phenylmagnesium bromide to produce 4. This attempt failed, however, as only the monophenylated product, 8, was thought to be obtained. This product had unique reactivity, producing a blue intermediate upon treatment with halogen in both aqueous and non aqueous media. The same intermediate was produced upon irradiation of a chloroform solution of this product with sunlight or UV light in a UV chamber, with the …

Analytical Modeling And Simulation For Investigation Of A Digital Gas Filter Correlation Radiometer, Catherine P. Mcgowan

Electrical & Computer Engineering Theses & Dissertations

This thesis investigates a digital gas filter correlation radiometer called the Tropospheric Radiometer for Atmospheric Chemistry and Environmental Research (TRACER), which will be used to remotely measure carbon monoxide at three levels in the troposphere. The nadir-viewing radiometer measures the differential absorption of radiation through the atmosphere at 4.67@m and 2.33pm wavelengths. This thesis develops an analytical model of the TRACER measurement process to evaluate the effect of varying certain system parameters on the measurement. The independent sampling criterion and the response of linear systems to random signals are explained. A parametric simulation model is also developed to evaluate the …

Second Coefficient Of Viscosity In Air, Robert L. Ash, Allan J. Zuckerwar, Zhonquan Zheng

Mechanical & Aerospace Engineering Faculty Publications

Acoustic attenuation measurements in air were analyzed in order to estimate the second coefficient of viscosity. Data over a temperature range of 11 C to 50 C and at relative humidities between 6 percent and 91 percent were used. This analysis showed that the second coefficient of viscosity varied between 1900 and 20,000 times larger than the dynamic or first coefficient of viscosity over the temperature and humidity range of the data. In addition, the data showed that the molecular relaxation effects, which are responsible for the magnitude of the second coefficient of viscosity, place severe limits on the use …

Activator-Inhibitor Control Of Tissue Growth, John A. Adam

Mathematics & Statistics Faculty Publications

This note develops a simple model for the competition between activator and inhibitor control mechanisms in one-dimensional tissue growth. The pedagogic usefulness of such a model is that it is easily accessible to undergraduate applied mathematicians and is suggestive of behavior known to occur in more realistic biological systems (e.g., some types of cancer). The limitations of the model are obvious and can provide a basis for discussion of the applicability of complementary levels of description in mathematical modeling.

Role Of Surface Morphology In Wafer Bonding, W.P. Maszara, B.L. Jiang, A. Yamada, G.A. Rozgonyi, H. Baumgart, A.J.R. De Kock

Electrical & Computer Engineering Faculty Publications

The strain patterns detected by x-ray topography in wafers bonded for silicon-on-insulator (SOI) technology were found related to the flatness nonuniformity of the original wafers. Local stresses due to the bonding process are estimated to be about 1×10⁸ dynes/cm². The stress is reduced about 100 times for the thin (0.5 μm) SOI films. Most of the wafer deformation occurs during room temperature mating of the wafers. The deformation is purely elastic even at 1200 °C. The magnitude of the stress appears insignificant for complimentary metal-oxide-semiconductor devices performance.

Hydrogen Sulfide And Radon In And Over The Western North Atlantic Ocean, T. W. Andreae, Gregory A. Cutter, N. Hussain, J. Radford-Knoery, M. O. Andreae

OES Faculty Publications

Atmospheric measurements of radon and hydrogen sulfide, and seawater measurements of total sulfide, free sulfide, and carbonyl sulfide, were made on a cruise in the western North Atlantic Ocean (October 24 to November 9, 1989). Measured values for ²²²Rn ranged from 3 to 70 pCi m⁻³, those for atmospheric hydrogen sulfide from 1 to 85 parts per trillion, and those for dissolved total and free sulfide in seawater from 33 to 930 pmol L⁻¹ and 0 to 73 pmol L⁻¹, respectively. A positive correlation between ²²²Rn and atmospheric H₂S was observed. …

Trace Elements In Estuarine And Coastal Waters: U.S. Studies From 1986-1990, Gregory A. Cutter

OES Faculty Publications

The use of specialized analytical techniques, field studies, controlled laboratory experiments, and geochemical modeling have allowed U.S. investigators to expand our understanding of trace element cycling in coastal waters and estuaries. Considerable emphasis has been placed on quantifying the flux of trace elements within and through the coastal zone. In addition, substantial progress has been made in identifying the chemical speciation of many trace elements, providing a linkage between the geochemical and biochemical behavior of these elements. Another significant advance has been the use of trace elements as tracers of geochemical processes and water masses in the coastal environment.

A Potentiometric Gaseous Hydrogen Sensor, Anne Guillory

Chemistry & Biochemistry Theses & Dissertations

The development of a potentiometric gaseous hydrogen sensor using a 75% palladium - 25% silver alloy as a selectively hydrogen permeable electrode is described. The sensor showed some promise when used with a molten base electrolyte. Other electrolytes are investigated at ambient and higher temperatures. Various cell designs including a platinum/silver-silver chloride sensor with a gel electrolyte are discussed.

The Role Of The Voltage Gradient In The Agarose Gel Electrophoresis Of Dna, David Wheeler

Theses and Dissertations in Biomedical Sciences

In Part I of this dissertation, empirical equations for predicting DNA mobility during agarose gel electrophoresis (AGE) from voltage gradient are developed from the data of McDonnel (36) for electrophoresis in a 1.6% agarose gel. These equations represented the data well for DNA between 2 and 10 kilobase pairs (KBp) in length. A computer program, called GELSIM, which incorporates these equations is described in Part II. GELSIM was designed to allow researchers to analyze electrophoresis data by predicting the effect on DNA migration of altering the voltage of electrophoresis. In this way, electrophoretic banding patterns produced using different voltages could …

The Reaction Of Organoboranes With N-Chloro-N-Sodiocarbamates: A Convenient Synthesis Of N-Alkylcarbamates, Nanette M. Wachter-Jurcsak

Chemistry & Biochemistry Theses & Dissertations

N-alkylcarbamic acid esters are used extensively as fungicides, herbicides and pesticides. Industrial methods of preparation employ highly toxic reagents in their synthesis. Convenient and safe alternative methods are necessary.

Organoboranes are electrophilic compounds which can be employed as a source of alkyl substituents. They have been shown to successfully transfer alkyl groups to the nitrogen of chloramines. N-Alkylation of carbamic acid esters by reacting the corresponding N-chloro-N-sodiocarbamate with a variety of trialkylboranes is described. The yields of the various N-substituted products are discussed.

Two synthetic methods were devised. Originally, an equivalent of the isolated N-chlorocarbamate salt was added to the …

A Pulse Gas Chromatographic Method For Determining The Dispersion And Surface Area Of Co Oxidation Catalysts, Susan Kay Ohorodnik

Chemistry & Biochemistry Theses & Dissertations

Catalysts composed of platinum and/or palladium on tin(IV) oxide supports with or without silica gel have been developed for the recombination of carbon monoxide and oxygen to form carbon dioxide for use in carbon dioxide lasers. A pulse gas chromatographic method has been developed to measure the chemisorption properties of the catalysts. From the chemisorption measurements, the active surface area and dispersion of the catalysts have been determined.

Evaluation Of The Function Exp (X2) Erfc (X) To Higher Precisions For Higher-Order Derivative Polarography Of Ce-Type Electrode Process, Myung-Hoon Kim, Veriti P. Smith, Tae-Kee Hong

Chemistry & Biochemistry Faculty Publications

The function exp(x2)erfc(x), which is often encountered in studies of electrode kinetics, is evaluated to an extended precision with 32 significant decimal digits in order to find theoretical relationships used in derivative polarography/voltammetry for a chemically-coupled electrode process. Computations with a lower precision are not successful. Evaluation of the function is accomplished by using three types of expansions for the function. Best ranges of arguments are selected for each equation for particular precisions for efficiencies. The method is successfully applied to calculate higher-order derivatives of the current-potential curves in all potential ranges for a reversible electron transfer reaction coupled with …

Identification And Quantitation Of Volatile Amines In Marine Sediments, Chuen Mei Huang

Chemistry & Biochemistry Theses & Dissertations

Pore waters which were taken from sediments of the Chesapeake Bay were analyzed to determine the presence of volatile amines. A purge-and-trap technique was used to concentrate the amines. Then, following derivatization with heptaflourobutyric anhydride, the HFBA-amines were analyzed by gas chromatography with electron capture detection and with mass spectrometric detection. One secondary amine, diethylamine with a concentration of 0.3-0.6 uM, was found in a total of three pore water samples from cores collected on two different dates. A primary amine, sec-butylamine with a concentration of O. 05 AIM, was also found in one of these same samples. Another primary …

Mounting Sex Pheromone: A Novel Pheromone Responsible For Mate Recognition In The Ixodidae, Jgc Hamilton

Theses and Dissertations in Biomedical Sciences

Cholesterol oleate was demonstrated to be the cuticular contact sex pheromone of Dermacentor variabilis. This pheromone which has been termed the Mounting Sex Pheromone (MSP) was also demonstrated to be present on the surface of D. andersoni, Amblyomma maculatum and A. americanum. This contact sex pheromone enables males excited and attracted by 2,6-dichlorophenol to identify the female as a potential mating partner. The MSP is the second in the series of three sex pheromones guiding the hierarchy of behavioral responses which constitute tick courtship behavior. Tests with D. variabilis and D. andersoni showed that this pheromone …

Simultaneous Determination Of 3-Methoxy-4-Hydroxyphenyl-Glycol, Homovanillic Acid, And 5-Hydroxyindoleacetic Acid In Plasma By High Performance Liquid Chromatography, Yung-Te Tseng

Chemistry & Biochemistry Theses & Dissertations

A rapid, reliable, and sensitive method for simultaneous determination of 3-methoxy-4-hydroxyphenylglycol (MHPG), Homovanillic acid (HVA), and 5-hydroxyindoleacetic acid (5- HIAA) in plasma is described. The method is based on high performance liquid chromatography with electrochemical detection. Samples were filtered with Amicon Centrifree micropartition systems and extracted with organic solvent before chromatography. Chromatographic separation of sample components was achieved isocratically in a C18 reverse-phase column. Quantitation was performed by measuring the peak height ratios of the sample components to an internal standard. Analytical recoveries ranged from 50.78 (SD 4.2%) to 67.94 (SD 3.28). Within-run coefficient of variations (CVs) ranged from 3.78 …

Permanganate Colorimetric Rapid Method For Chemical Oxygen Demand In Seawater, Myung Zoon Czae, Taekee Hong, Myung Hoon Kim

Chemistry & Biochemistry Faculty Publications

No abstract provided.

Sulfide In Surface Waters Of The Western Atlantic Ocean, Gregory A. Cutter, Christian F. Krahforst

OES Faculty Publications

Using newly developed techniques, some preliminary data on hydrogen sulfide in surface waters of the western Atlantic have been obtained. Concentrations of total sulfide range from <0.1 to 1.1 nmol/L, and vary on a diel basis. At these concentrations, sulfide may affect the cycling of several trace metals via the formation of stable complexes. Production of sulfide in oxygenated seawater may occur through the hydrolysis of carbonyl sulfide or by sulfate reduction within macroscopic particles in the water column. Removal mechanisms can include oxidation, complexation with particulate trace metals, and metal sulfide precipitation. However, the temporal and spatial distributions suggest a complex set of processes governing the behavior of sulfide in the surface ocean.

The Synthesis And Evaluation Of 5-Phenyloxazolidines As Potential Cardiovascular Drugs, Tammy C. Wang

Chemistry & Biochemistry Theses & Dissertations

Drugs such as adrenoceptor antagonists and certain centrally acting agents are known to lower blood pressure and thus serve as clinically useful antihypertensive agents. Norepinephrine 4, a natural ∝-adrenoceptor agonist, is the major agent associated with increased blood pressure in the periphery. Based on a careful structure-activity comparison, a series of substituted oxazolidines, 20, 21, 22 and 23, have been designed as possible antihypertensive candidates. Specifically, 22 and 23 have been synthesized to serve as potential norepinephrine antagonists.

Preliminary evaluation of these compounds indicated that they were not antihypertensive in nature. The more active compound, 23, …

Optimization Of The Tungstic Acid Denuder Technique For The Measurement Of Atmospheric Ammonia, Patricia Diane Roberts

Chemistry & Biochemistry Theses & Dissertations

Measurement of - atmospheric ammonia with the tungstic acid denuder technique is discussed. Characterization of denuder tubes for manual sampling in terms of, repeatability, reliability and the development of ammonia blank signals was determined. Field testing of the manual sampling apparatus was performed at ground test sites and in a biomass burn smoke plume. Ammonia emissions from biomass burning are discussed.

Use Of 52Cr For The Quantitative Determination Of Red Cell Volume, Claude Michael Hanbury

Chemistry & Biochemistry Theses & Dissertations

Chromium-52 has recently been suggested for use as a new agent to label red cells for the in vivo quantitation of red cell volume (1). In this paper, the development and validation of a routine ⁵²cr labeling procedure is described.

The accuracy, precision, and detection limits of chromium analysis by Zeeman effect atomic absorption spectroscopy was evaluated in the concentration range of 1 - 10 ug Cr/L.

Red cell chromium uptake was evaluated as a function of time, temperature, and concentration. Red cells labeled with a 2.5 mg/L chromium solution for 30 minutes at room temperature exhibited optimal label …

Low Pressure Gas Flow Analysis Through An Effusive Inlet Using Mass Spectrometry, David Robert Brown

Chemistry & Biochemistry Theses & Dissertations

A mass spectrometric method for analyzing flow past and through an effusive inlet designed for use on the tethered satellite and other entering vehicles is discussed. Source stream concentrations of species in a gaseous mixture are determined using a calibration of measured mass spectral intensities versus source stream pressure for standard gas mixtures and pure gases. Concentrations are shown to be accurate within experimental error. Theoretical explanations for observed mass discrimination effects as they relate to the various flow situations in the effusive inlet and the experimental apparatus are discussed.

Reactions Of Aqueous Chlorine In The Gastric Fluid Of The Rat, Michael Gary Nickelsen

Chemistry & Biochemistry Theses & Dissertations

Gastric fluid was recovered from Sprague-Dawley rats that had been fasted for 24 hr or 48 hr and administered 4 mL deionized water. The protein, carbohydrate and chloride ion content of the gastric fluid was determined.

When gastric fluid is chlorinated with radiolabeled chlorine to concentrations between 323 and 375 mg/L, analyzed by high performance chromatography followed by liquid scintillation counting, as much as 59% of the radiolabeled chlorine was associated with organic components of the gastric fluid.

Model studies with the aromatic amino acids and the protein pepsin showed the formation of chlorinated analogs. Two chlorinated amino acid derivatives …