Physical Sciences and Mathematics Commons^™

Detection And Quantification Of Atmospheric Carbonyl Compounds, Peter Gerard Schulam

Honors Theses

Ambient air aldehyde analysis was performed in Schenectady, NY. The Technique, as prescribed by Kuntz et. Al. (7), entailed the trapping of the volatile aldehydes as their 2,4-dinitrophenylhydrazone derivatives in an acetonitrile solution. The derivatives were then separated on a reversed phase HPLC column and detexted by UV absorption at 254 and 360 nm., simultaneously. The air in Schenectady was found to contain formaedehyde and acetaldehyde at concentrations which ranged from .70 to 30.5 ppb and below that of detection to 1.6 ppb, respectively. Formaldehyde's daily average in Schenectady was 7.6 ppb. The formaldehyde and acetaldehyde levels at Whiteface Mtn. …

Electrochemical Studies Of Antimony(Iii) And Antimony(V) In Molten Mixtures Of Aluminum Chloride And Butylpyridinium Chloride, Dhia A. Habboush, Robert A. Osteryoung

Chemistry & Physics Faculty Publications

Electrochemical studies of Sb, Sb(III), and Sb(V) have been camed out in molten mixtures of AlC13 and N-1-butylpyridinium chloride (BuPyCl) at 40 OC, as a function of melt composition. Analysis of measurements in the acidic melts indicates SbC12+ as the dominant species. The reduction of this species on glassy carbon exhibits irreversible behavior. In the basic melts, SbC14- and SbC1,- are believed to be the dominant species. The reduction of Sb(II1) to Sb on glassy carbon also showed irreversible behavior while its oxidation to Sb(W revealed a quasi-reversible behavior. No Sb(II1) oxidation was observed in the acidic melts.

Quantitative Evaluation Of Substituent Effects On Stabilization Energies Of Strained And Unsaturated Molecules, Tyler Arthur Stevenson

Theses

Thermodynamic stabilization energies are presented for a series of monosubstituted vinyl, cyclopropyl, ethynyl, and phenyl compounds. The energies are calculated using ab initio molecular orbital calculations at the 4-31G level, and also with published experimental heat of formation data. Correlation analyses are then attempted with the dual substituent parameter approach with the stabilization energies. The analyses are also attempted with a triple-parameter approach using Topsom's theoretically calculated X, F, and Ro constants. Among the findings are the facts that π-donating substituents correlate well, while π-accepting substituents do not. Indications of the relative sensitivities of hydrocarbon frameworks to substituent electrostatic and …

Synthesis Of Cyclobutenyl Ketals, Atef Z. Boulos

Theses

A series of dialkoxy derivatives of N,N'-di-tert-butyl-2-butylamino-3,3-dichloro-4-dichloromethylene cyclobutenyl carboxamidinum chloride, were prepared by dissolving either Na+ or K+ alkoxide in the appropriate alcohol, or by treatment with potassium hydroxide in the appropriate alcohols. Thus, the dimethoxy, diethoxy, di-isopropoxy, di-n-butoxy, di-tertbutoxy derivatives were obtained.

Derivatives Of Trifluorovinylsulfur Pentafluoride And F-(Tert-Butyl) Hypochlorite, Jo Ann Marie Canich

Dissertations and Theses

Trifluorovinylsulfur pentafluoride dimerizes to (SF₅CFCF₂)₂ in the presence of cesium fluoride. Two derivatives of trifluorovinylsulfur pentafluoride, SF₅CF(CF₃)C(O)F and SF₅CF(CF₃)C(O)NH₂, were used to prepare the new compounds, SF₅CF(CF₃)CO₂H and SF₅CF(CF₃)CN, respectively. The first was prepared by reacting the SF₅-acid fluoride with water, while the second involved the abstraction of water from the SF₅-amide using P₄O₁₀. The attempted preparation of a bis-pentafluorosulfur ketone and a pentafluorosulfur containing acid anhydride …

Photoaffinity Labeling Of The Antimycin Binding Site In Rhodopseudomonas Sphaeroides, Emily Wilson

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The purpose of this study was to identify the site of interaction of antimycin with the ubiquinone-cytochrome b-c1 oxidoreductase in the photosynthetic bacteria, Rhodopseudomonas sphaeroides. To accomplish this goal, three areas of research were undertaken: the synthesis of a radiolabeled, photoaffinity analog of antimycin, identification of the inhibitory characteristics of this analog, and the photoaffinity labeling of the antimycin binding site. All three areas were accomplished.

The major finding of this study was the identification of an 11,000 dalton polypeptide as the predominantly labeled protein. Although this polypeptide was not exclusively labeled, it was consistently labeled and showed competition …

H2o2-Tfa-H2so4 Oxidation Of Coal & Coal Model Compounds, Darrell Pierce

Masters Theses & Specialist Projects

The Deno coal oxidation technique was investigated as a tool for the characterization of the aliphatic components of coal. This technique was applied to three high sulfur Kentucky coals:(1) No. 789673, (2) KCER 4002-Elkhorn No. 2, (3) KCER 7122-Ky. No. 12 and a low sulfur coal from Alpha Resources, Inc. Model compound investigations on toluene, ethyl benzene, propyl benzene, bibenzyl, indan and tetralin were also conducted. Different addition modes were investigated using ethyl benzene and diphenylmethane. The stability of the expected aliphatic acid products in the oxidation reagent were also investigated.

The data indicated the following:

1. Pyrite present in high …

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Desulfurization Of Coal Using Carboxylic Acids & Peracids, Dwight Watson

Masters Theses & Specialist Projects

Bituminous coals were desulfurized by leaching in a 325 ml, agitated, autoclave with hot, dilute solutions of carboxylic acids, buffered carboxylic acids, carboxylic salts, and carboxylic salt:alkali combinations. The partial pressure of oxygen was not increased as it was found not to increase the amount of organic sulfur removal. The effect of increasing carboxylic size and decree of desulfurization was studied. Among the carboxylic acids studied, formic acid removed the greatest amount of organic sulfur;and iso-valeric acid removed the greatest percentage of pyritic sulfur. It was found that there is a direct correlation between the amount of organic sulfur removal …

The Low-Temperature Pyrolysis Of A Nitrated North Dakota Lignite, Dennis Spears

Masters Theses & Specialist Projects

Low-temperature pyrolysis is the thermal degradation of coal in an inert atmosphere at temperatures below 700°C. Coal pyrolysis is well-studied, being a complex mix of many reactions. Pyrolysis is affected by changes in many different process variables, such as temperature, pressure and heating rate. Low-temperature pyrolysis is an old and well-studied process.

Chemical pretreatments have been used to beneficiate conversion processes, inducln pyrolysis. Nitration has not been one of them. Pyrolyzing a nitrated coal would, hopefully, rapidly devolatilize the coal and break up the matrix into more commercially usable products. The nitration procedure developed by The Standard Oil Company minimizes …

Spontaneous Heating Of Coal & Electrochemical Measurements Of Corrosion Rates, Bihan Naderi

Masters Theses & Specialist Projects

A new and relatively fast method for measuring the susceptibility of coal to spontaneous heating was studied in this work.

This method is based on the ability of coal to adsorb iron(III) from aqueous solutions. The more iron taken up by the coal, the more susceptible the coal is to spontaneous heating. The relationship holds for most of the coals being analyzed during this research project and for other succeeding ones.

The experimental procedures used and results obtained are discussed. A brief literature survey of other applied methods which have been studied, including a description of many factors affecting the …

Non-Matrix Corrected Organic Sulfur Determination In Coal By Energy Dispersive X-Ray Spectroscopy, Carol Clark

Masters Theses & Specialist Projects

A method for non-matrix corrected organic sulfur analysis by energy dispersive X-ray spectroscopy has been developed using petroleum coke standards. This technique capitalizes on the fact that when a substance is excited by an electron beam it will emit photons of electromagnetic radiation in the X-ray range. The emitted X-rays are characteristic of the excited elements in the substance. Typically, electron beam microanalysis is a rapid, nondestructive analytical technique to quantitatively measure organic sulfur in coal. The results show good correlation to ASTM values for numerous well characterized bituminous coals with a wide range in total and pyritic sulfur content. …

Corrosion Of Carbon Steel In Synthetic Coal Liquid Wash Waters, Keith Evans

Masters Theses & Specialist Projects

The Potentiodynamic corrosion measuring technique is an electrochemical analytical method which measures corrosion rates of a metal exposed to a corrosive environment.

The corrosion characteristics of carbon steel A1044 in aqueous solutions of aniline hydrochloride,simulating a coal liquid wash water, were determined by this method. The effects of solution velocity and oxygen concentration on the system were also determined.

A bimodal corrosion rate effect was observed in deaerated solutions of 1000 and 5000 ppm chloride as aniline hydrochloride. This effect was interpreted to be the result of the formation of a film on the surface of the specimen.

Theoretical Studies Of Cyclic C2si2h4 Molecules, Thomas A. Holme, Mark S. Gordon, Satoshi Yabushita, Michael W. Schmidt

Mark S. Gordon

Thirteen cyclic C2Si2H4 isomers, including disilatetrahedrane and the disilacyclobutadienes, have been studied by using ab initio quantum mechanics. At the MP3/6-31G* / /3-21G level of computation, the silyl-substituted silacyclopropenylidene is found to be the most stable. Disilatetrahedrane is quite high on the energy surface, and the two possible planar 1,2-disilacyclobutadienes do not represent minima on this surface. Planar 1,3-disilacyclobutadiene is a stable structure and exhibits significant diradical character.

The Synthesis And Characterization Of Some Transition Metal Complexes Prom Mixtures Of Poly Pyrazolyl Borates, Robert Matthew Alway

Masters Theses

This is a report of the synthesis and separation of transition metal complexes of hydrotris(1-pyrazolyl)- borate and hydrotris(3,5-dimethyl-l-pyrazolyl)borate. These complexes contain a central metal ion and two tridentate ligands, one hydrotris(1-pyrazolyl)borate and one hydrotris(3,5-dimethyl-l-pyrazolyl)borate. Mass spectrometry proved to be an extremely useful technique for identifying products. Many mass spectra are included and discussed extensively.

Complexes containing hydrobis(pyrazole)(3,5-dimethyl -1-pyrazolyl)borate and hydrobis(3,5-dimethyl-l-pyrazole) (pyrazolyl)borate also were synthesised and mass spectra obtained.

Investigation Of Matrix Effects On The Furnace Atomic Absorption Signals Of Chromium, Nickel And Selenium, Susan Marie Viet

Chemistry & Biochemistry Theses & Dissertations

The flameless atomic absorption signals of chromium, nickel and selenium are subject to matrix interferences arising from inorganic salts and anions commonly found in urine. The effects of such salts on the atomic absorption signals were investigated using Polarized Zeeman Effect background correction in conjunction with a detector/readout system capable of resolving absorbance signals in 18 msec readings. Both optical temperature control and current temperature control were employed for each analysis. Peak area, peak height, peak shape and appearance time were compared for matrix-free standards and matrix-containing standards.

The influence of the inorganic salts on the metal analyses was found …

Theoretical Studies Of Polyvinyl-Substituted Carbenium And Silylenium Ions, Thanh Truong, Mark S. Gordon, Philip Boudjouk

Mark S. Gordon

Ab initio (ST0-2G and 3-21G) calculations have been performed to analyze the ability of one, two, and three vinyl groups to stabilize the CH3 + and SiH3 + ions. Vinyl groups appear to be quite effective at stabilizing the positive charge on the silylenium ion, and successive vinylization preferentially stabilizes the silicon relative to the carbon ion.

Preparation And Characterization Of Composite Hollow Fiber Reverse Osmosis Membranes By Plasma Polymerization. 2. Reproducibility Of The Plasma Polymerization Process And Durability Of The Resulting Coated Membrane, Y. Matsuzawa, H. Yasuda

Chemistry Faculty Research & Creative Works

The reproducibility of the plasma polymerization process was examined in a semicontinuous coating of hollow fibers, 6 fibers in lengths of approximately 12-15 m, by evaluating the performance of reverse osmosis membranes. The uniformity of the coating along the length of hollow fibers, as well as the reproducibility of the process, was found to be satisfactory when electrodes were conditioned in the actual conditions of plasma polymerization to be employed and plasma polymerization conditions were carefully controlled. The durability of the coated hollow fibers was then investigated in the following test media: hot water, low pH, high pH, and 0.1% …

Preparation And Characterization Of Composite Hollow Fiber Reverse Osmosis Membranes By Plasma Polymerization. 1. Design Of Plasma Reactor And Operational Parameters, P. J. Heffernan, K. Yanaglhara, Y. Matsuzawa, E. E. Hennecke, E. W. Hellmuth, H. Yasuda

Chemistry Faculty Research & Creative Works

Composite hollow fiber reverse osmosis membranes were prepared by depositing a thin layer (10-50 nm) of plasma polymers on hollow fibers with porous walls (made of polysulfone). The coating was carried out in a semicontinuous manner with six strands of substrate fibers. Operational parameters which influence reverse osmosis characteristics of composite membranes were investigated. © 1984, American Chemical Society. All rights reserved.

Magnetic Phase Diagram And Spin Glass Behavior Of Fe₁₋ₓmnₓcl₂·2h₂O, Gary C. Defotis, Christoph Pohl, Spencer A. Pugh, Ekkehard Sinn

Chemistry Faculty Research & Creative Works

The magnetic phase diagram of Fe_1-xMn_xCl₂·2H₂O has been determined. A tetracritical point appears to be present at x ≊ 0.74 and T≊2.8 K. The upper paramagnetic-antiferromagnetic phase boundaries exhibit an unusually rapid descent, and the mixed ordered region below the tetracritical point is quite small. Moreover, regions exhibiting spin glass character also occur in the diagram. The unusually complex behavior is presumably due to the unique constitution of this system: A mixture of two antiferromagnets with different periodicities, competing orthogonal spin anisotropics, competing ferromagnetic and antiferromagnetic near neighbor intrachain exchange interactions, and …

Theoretical Study Of Methylsilanone And Five Of Its Isomers, Mark S. Gordon, Clayton George

Mark S. Gordon

By use of 3-21G SCF geometries and relative energies from MP3/6-31G* wave functions, methylsilanone has been found to be the most stable of the six isomers investigated. The relative stabilities of methylsilanone and silylformaldehyde are rationalized by the metathesis reaction H 2Si0 + C2H4 .... H 2CO + H 2CSiH4. This reaction is used to suggest that the C=O bond is about 10 kcaljmol stronger than Si=O.

Structure, Bonding, And Internal Rotation In Phosphine Oxide (H3po), Hydroxyphosphine (H2poh), And Hydroxyfluorophosphine (Hfpoh), Michael W. Schmidt, Satoshi Yabushita, Mark S. Gordon

Mark S. Gordon

The fundamental nature of the PO bond is reexamined by using ab initio (3-21G* and 6-31G*) wave functions and energy-localized orbitals. The bond is best described as a dative single bond augmented by 71' back-donation from the oxygen lone pairs. The isomerization pathway from H3PO to H2POH is followed by using the intrinsic reaction coordinate and localized orbitals. The latter, more stable, isomer has two forms, cis and trans, which are nearly equal in energy. The internal rotation barriers in this molecule and in HFPOH are examined with a Fourier analysis and compared with their nitrogen analogues. The major differences …

Las Vegas Wash Multispectral Scanner Survey, T. H. Mace, M. V. Olsen, Environmental Protection Agency

Publications (WR)

At the request of the U.S. Bureau of Reclamation, Boulder City, Nevada, the U.S. Environmental Protection Agency's Environmental Monitoring Systems Laboratory at Las Vegas collected multispectral scanner imagery of Las Vegas Wash on October 1, 1982.

A combined maximum likelihood classification and editing procedure was used to classify the multispectral scanner imagery into 12 categories of land cover. The classification identified four categories of marsh vegetation, one category of riparian, two categories of mixed scrub, and two desert categories. Turbid water and cultivated land formed an "other" category. Area tabulations were formed by georeferencing the classification to the Universal Transverse …

Hydrogeochemical Aspects Of Surface Mine Reclamation In The Northern Great Plains, Gerald H. Groenewold, Robert D. Koob

Office of the Provost Scholarship

Studies of several coal-mining sites in western North Dakota have resulted in the development of a hydrogeochemical model which accounts for the observed chemical characteristics of subsurface water in undisturbed settings. Critical hydrogeochemical processes include sulfide oxidation, gypsum precipitation and dissolution, carbonate mineral dissolution and cation exchange.

In the semi-arid climate of western North Dakota, the near-surface several meters of the landscape is constantly subjected to alternate wetting/drying. This mechanism is the key to hydrogeochemical evolution of both pore water in the rooting zone and subsurface water that eventually reaches the water table.

Recent refinements in the hydrogeochemical model have …

Comparison Of Three Methods For Sampling Fishes And Macroinvertebrates In A Vegetated Wetland, B. J. Freeman, H. S. Greening, J. Douglas Oliver

Faculty Publications and Presentations

Three methods of sampling fishes, two seining methods and a drop trap method, were evaluated in heavily vegetated freshwater habitats. The portable drop trap method, which utilized a 1 x 1 m-sq. trap, collected significantly more macroinvertebrates and fish per unit area than did the seining methods. The meter square drop trap offered the additional advantages of a greater number of animals per unit effort and an integrated sample of vegetation, macroinvertebrates and fish in a given area. A 90% (s.d.= 7.4%) recovery of tagged fishes released into the traps in different habitats showed the m2 drop trap to be …

The Synthesis And Characterization Of Some Fluoride Perovskites, An Undergraduate Experiment In Solid State Chemistry, Richard H. Langley, Colleen K. Schmitz, Maureen B. Langley

Faculty Publications

In light of the increasing importance of solid state chemistry, an experiment dealing with at least some aspects of this rapidly expanding area should he included in advanced chemistry laboratories. Herein is described one of the experiments that we have developed to meet this need. This experiment was designed for a senior level integrated chemistry lab taken by all our chemistry majors. Normally six to eight hours are needed to complete this experiment. This experiment deals with the synthesis and characterization of a perovskite. Perovskites were chosen because compounds with this structure are important in solid state technology, and since …

Nmr Measurements On Intercalated 3r-Tas2.Ix (I=Nh3 And N2h4), N. H. Handly, Juana Vivó Acrivos

Faculty Publications, Chemistry

No abstract provided.

Some Plant Leaves Have Orientation-Dependent Epr And Nmr Spectra, Douglas C. Mccain, Ted C. Selig, University Of Illinois At Urbana-Champaign, John L. Markey

Chemistry Department: Faculty Publications

Proton nuclear magnetic resonance (¹H NMR) spectra of leaves from 50 plant species were obtained at a spectrometer frequency of 470 MHz. Water present in leaf samples gives rise to characteristic spectral patterns. Most species show only one broad ¹H NMR peak; however, the leaves of some plants display complex, orientation-dependent spectra in which a common three-line pattern is discerned. The pattern varies with the angle between the leaf surface and the external magnetic field. Proton relaxation measurements show the presence of at least two water compartments in the leaves. The compartments are responsible for different components …

Carbon Monoxide-Driven Reduction Of Ferric Heme And Heme Proteins, D. Bickar, C. Bonaventura, J. Bonaventura

Chemistry: Faculty Publications

Oxidized cytochrome c oxidase in a carbon monoxide atmosphere slowly becomes reduced as shown by changes in its visible spectra and its reactivity toward oxygen. The 'autoreduction' of cytochrome c oxidase by this procedure has been used to prepare mixed valence hybrids. We have found that this process is a general phenomenon for oxygen-binding heme proteins, and even for isolated hemin in basic aqueous solution. This reductive reaction may have physiological significance. It also explains why oxygen-binding heme proteins become oxidized much more slowly and appear to be more stable when they are kept under a CO atmosphere. Oxidized α …

Modeling Of Laboratory Scale Batch Distillations With A Desktop Computer, Dale F. Johnson

Retrospective Theses and Dissertations

A program has been written that simulates the operation of a batch distillation process. The program has been implemented on a Hewlett-Packard 9845T minicomputer and will be used as an instructional aid in a graduate level chemistry course. The program is very user interactive and is capable of using the final conditions from one run as the initial values of the next simulation. The batch simulation is achieved by using a tray-by-tray algorithm and is equipped with three integration techniques; the Euler, the Modified Euler and the 4th order Runge-Kutta methods. The program has the capability for studying the effect …

Evaluation Of Sugar Cane Bagasse And Rice Straw As Process Substrates For The Production Of Ethyl Alcohol, Douglas B. Rivers, Gisella M. Zanin, George H. Emert

Journal of the Arkansas Academy of Science

No abstract provided.