Physical Sciences and Mathematics Commons^™

Biological And Chemical Evaluation Of The Aquatic Environment Of Selected Undeveloped Kentucky Lake Embayments, Marshall Gordon, Morgan E. Sisk

KWRRI Research Reports

This report describes research involving biological and chemical analysis of two undeveloped embayments on Kentucky Lake, namely Anderson and Vickers Bays. Field and laboratory studies were made to assess current biotic standing crops, limnological conditions, levels of inorganic and organic pollutants in the embayments.

The Effects Of Ultrasonic Vibration, Tension And Torsion On The Charge Acceptance Of The Alkaline Silver Electrode ; Ii. Potentiostatic Studies Of The Oxide Growth Rate Law For The Alkaline Silver Electrode ; Iii. The Determination Of Ionic Transport In Silver Oxide Using Radiotracer Techniques With Ag[Superscript 110m], Reed Harold Chase

Theses and Dissertations

The effect of ultrasonic vibration on the anodic oxidation of silver foil in KOH was studied. An increase in charging capacity of approximately 20% was found to be the result of cavitation erosion. Silver wire was exposed to tension and torsion during oxidation but no change in charge acceptance was caused by these stresses. The oxide growth rate on silver foil electrodes was compared to rate equations that have been proposed for other metals. Uhlig's equations for the growth of semiconductor oxides was found to describe most of the data. The data did not fit other rate equations. Determination of …

Voltammetric And Electrochemical Kinetic Studies Of The Halides And Halogens At A Platinum Rotating Ring-Disk Electrode In Anhydrous Acetic Acid, Donald Harrison Cranney

Theses and Dissertations

The electrochemical behavior of the iodine-iodide couple was investigated in both basic and neutral acetic acid solutions at a platinum rotating ring-disk electrode. Voltammetric curves were obtained and discussed. Various kinetic parameters were determined and by comparing to theoretical kinetic parameters a probable reaction mechanism was deduced. The mechanism that best fit experimental results is the following I- + S = I(S) + e- I(S) + I- = I2 + S + e (slow). The electrochemical behavior of bromine, bromide, and chloride was also investigated in the same media. Voltammetric curves were recorded and discussed with emphasis on the hysteresis …

A Study Of Selected Photo Fries Rearrangements, Elwood Lloyd Loveridge

Theses and Dissertations

The Fries rearrangement of phenyl esters is reviewed and compared to the reaction when light is the source of energy. The products are different due to different mechanism of reaction. Light energy causes either free radical or concerted reactions. The S-phenylthiol esters and anilides were studied also. Although many of the rearrangements are the same, we did not see any alkyl migration nor decarboxylation type reactions with either the sulfur or nitrogen compounds. Three papers have been published from this work: Bradshaw, J. S., Knudsen, R. D. and Loveridge, E. L., J. Org. Chem., 35, 1219 (1970); Bradshaw, J. S., …

Piezomodulated And Specular Reflection Spectra Of A Polydiacetylene Crystal, Craig J. Eckhardt, H. Muller, J. Tylicki, R.R. Chance

Craig J. Eckhardt Publications

A class of potential quasi-one-dimensional organic conductors is the monocrystalline polydiacetylenes. These polymers can be obtained as single crystals that have high structural perfection and a chain configuration that permits extensive π-electron delocalization. The poly-2, 4-hexadiyne-1, 6-diol-bis-(p-toluene sulfonate) (PTS) has been the most extensively studied system and interest centers upon the extent of delocalization along the two chains compromising the P2₁/c unit cell.

A Review Of The Limnology Of And Water Quality Standards For Lake Mead, Charles R. Goldman

Publications (WR)

1. The waters of Las Vegas Bay, a heavily utilized recreational resource, receive discharges from a variety of municipal and industrial waste sources. The U.S. Environmental Protection Agency has determined, on the basis of numerous studies, that the present water quality violates state and federal standards and constitutes a public nuisance. Consultants have advised the Sewage and Wastewater Advisory Committee that rapid abatement of the alleged pollution conditions can be achieved by an advanced wastewater treatment (AWT) plant.

2. The major problems in Las Vegas Bay are an objectionable water color, excessive turbidity, noxious odors, and oxygen depletion in certain …

Effect Of Glycosylation On The In Vivo Circulating Half-Life Of Ribonuclease, John W. Baynes, Finn Wold

Faculty Publications

The circulating half-lives of the four isozymes of bovine pancreatic ribonuclease (RNases A, B, C, and D) have been determined in normal and in nephrectomized rats. The isozymes differ only in their glycosyl content. While A contains no sugars, B has a simple oligosaccharide (GlcNAc, Man,+), and C and D each have a complex oligosaccharide (GlcNAc, Man,., Gal, Fuc NeuAc%, and GlcNAc, Mans Gal, Fuc NeuAc,, respectively) attached to Asn-34 of the polypeptide chain. All four isozymes were cleared rapidly in normal rats (t,,, = 2 to 3 min), as expected on the basis of the established role of the …

Statistical Mechanical Derivation Of The Lippmann Equation. The Dielectric Constant, Jerry Goodisman

Chemistry - All Scholarship

We consider the polarizable electrochemical interface with spherical symmetry, and show that the common assumption of an invariant dielectric constant violates the mechanical equilibrium condition, unless its value is that of vacuum. The polarizable particles must be taken into account explicitly, which we do by deriving distribution functions for interacting charged and polarizable particles, neglecting short-range forces and short-range correlations, Calculating the change in surface tension when the distributions change so as to keep constant the temperature and the pressure inside and outside the interface, we obtain the Lippmann equation.

Inelastic Cross Sections For Molecules Interacting Through Dipole And/Or Quadrupole Potentials, Louis Biolsi Jr.

Chemistry Faculty Research & Creative Works

Formal expressions for the lowest order inelastic contribution to the degeneracy averaged total cross section for both distinguishable and indistinguishable rigid diatomic molecules are obtained for molecules interacting through a multiple potential. Explicit expressions for the inleastic cross section are obtained for molecules interacting through permanent dipole-dipole, dipole-quadrupole, or quadrupole-quadrupole potentials. These results require the summation over only a single quantum number; the relative angular momentum quantum number. Thus, they are useful for analytic or numerical calculations.

A Comparison Of The Rough Sphere Rotational Diffusion Model With Experimental Results For Liquid Methyl Iodide, Scott Whittenburg

Chemistry Faculty Publications

No abstract provided.

A Comparison Of The Rough Sphere Rotational Diffusion Model With Experimental Results For Liquid Methyl Iodide, Dane R. Jones, Scott L. Whittenburg, C. H. Wang

Chemistry and Biochemistry Faculty Publications

No abstract available.

18th Annual Rocky Mountain Spectroscopy Conference

Rocky Mountain Conference on Magnetic Resonance

Final program and abstracts from the 18th annual meeting of the Rocky Mountain Spectroscopy Conference, sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Denver, Colorado, August 2-3, 1976.

Extraction Rate Study Of Ni(Iii) Oxinate & Separation Of Cu(Ii) & Ni(Ii) With Oxide Based On Differences In Rates Of Extraction, Somchai Taichilassunthorn

Masters Theses & Specialist Projects

This study was conducted with metal ion concentrations in the range of parts per million and used batch extraction techniques to study the non-equilibrium extraction of Cu(II) and Ni(II) oxinates. Contrary to other authors, atomic absorption was used exclusively for the analysis of phases.

The two main areas of investigation in this study were:

1. Kinetics study of extraction of Ni(II) oxinate.
2. Separation of Cu(II) and Ni(II) with oxine based on differences in rates of extraction.

It was the purpose of this work to study the extraction of Cu(II) and Ni(II) with oxine in chloroform. This particular pair of elements was …

An Fe (Iii) - Initiated Oxidase Reaction With Ferroxidase-Ii, Glenn Alexander Hegamyer

Master's Theses

A reaction involving iron as an intermediary electron carrier for the coupling of electron transfer from an endogenous substrate to ferroxidase-I has been proposed.

The enzymic nature of the reacti on has been established and studies with iron chelating agents have demonstrated the involvement of Fe(III). The kinetic parameters of ferroxidase-11 with Fe (lll) were found to be quite similar to those previously established for Fe(Il). The participation by the copper associated with ferroxi dase-11 was ascertained by use of the copper chelating agent, diethyl -di thio-carbamate .

A variety of substances normally found in blood were surveyed as possible …

The Effect Of Stabilizing Groups On The Extent Of Long-Range Π Electron Participation And The Effect Of The Negative Charge On The Chemical Shift Of Neighboring Protons In Carbanions, Atilla Tuncay

Dissertations

No abstract provided.

Esr Study Of Free Radicals In Irradiated Single Crystals Of Potassium Hydroxylamine Disulfonate, B. J. Wilson, Robert W. Holmberg

Faculty Publications

Two free radicals formed when single crystals of potassium hydroxylamine disulfonate are irradiated with gamma rays at 77degrees K were studied by ESR. The ESR spectra result from a predominant center (radical A) exhibiting large 14N and 1H hyperfine splittings and from lesser amounts of Fremy's radical [O-dotN(SO3)2-2]. The g and hyperfine tensors of these radicals have been evaluated and are discussed. Radical A, whose identity remains in doubt, may be regarded as the precursor to Fremy's radical; on warming its lines decay and those of Fremy's radical are formed. Lines from radical A decrease in strength and those of …

A Comparison Of Free Radical Detection Methods, Danny Kiang-Wah Pan

Theses and Dissertations

The methods used for free radical detection are chemical titration, spectrophotometry, Gouy magnetic measurements and NMR shift technique. The free radicals chosen for this study are Fremy' s salt (ON(SO_3 )K_2),2,2-diphenyl-1-picryl hydrazyl (DPPH) 3-carbamoyl-2,2,5,5-tetramethylpyrrolidin-1-yloxy (CTM-pyrrolidin), 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolin-1-yloxy (CTM-pyrrolin), 4-acetamido-2,2,6,6-tetramethylpiperidino-1- oxyl (ATMP) and galvinoxyl. The detectable range for each method is given. The NMR method is a fast and convenient method for the magnetic susceptibility determination of a sample in solution, with. accuracy up to ± 1%.

A Potentiometric Method, A Convenient And Rapid Technique For Determination Of The Thermodynamics Of Ionization Reactions For Water, Weak Acids, And Some Slightly Soluble Salts In Aqueous Organic Mixed Solvents, Charanai Panichajakul

Theses and Dissertations

A potentiometric method which is devised to be rapid and convenient for determining ionization constants for water, weak acids (or bases), and certain solids in mixed solvents is described. The method has been applied to the determination of ionization for water, acetic acid, benzoic acid, and phenol and the solubility product constant for silver chloride in mixtures of water with methanol, ethanol, acetone, tetrahydrofuran, and p-dioxane containing from 0 to 70 mass percent organic co-solvent at several temperatures between 10 and 40°C. Results are used to study the thermodynamics of ionization in each mixture which is discussed relative to various …

The Intermolecular Potential And Vibrational Relaxation Of The Ar-Co System, Gregory Allen Parker

Theses and Dissertations

The angle, distance and vibration dependence of the Ar-CO intermolecular potential is calculated using the electron gas model to obtain the short range interaction which is smoothly joined onto the long range van der Waals tail which is obtained from accurate C_6, C_7, and C_8 coefficients. Our calculated second interaction virial coefficients are compared with experiment and with a simple adjustment of the Ar-CO potential an excellent agreement is obtained. Our spherically averaged potential is also in excellent agreement with a spherical potential inferred from high energy scattering data. Simplified expressions for the scattering amplitude and differential cross section are …

Solid-Liquid Phase Equilibria In Systems Of (I) Para-Xylene, (Ii) Mesitylene, And (Iii) N,N-Dimethylformamide ; Excess Volume Determination In Systems Containing Cyclohexane ; Calculations Of Activities For The N-Hexane + Cyclohexane System, John F. Moellmer

Theses and Dissertations

Solid-liquid phase equilibria studies were used to investigate possible compolllld formation in solutions of (i) para-xylene, (ii) mesitylene, and (iii) N,N-dimethyl-formamide (DMF) with mono- and di- halobenzenes that were selected to give a wide range of acceptor properties. Solid 1:1 intermolecular compounds were identified from solutions of p-C_6H_4F_2 with mesitylene, p-C_6H_4Br_2 with p-xylene, and p-C_6H_4Cl_2 with p-xylene. The results suggest that compound formation occurs because of favorable geometry rather than a charge transfer process. A vibrating tube densimeter was used to determine, with high precision, the densities and subsequently excess volumes of mixing of the n-hexane plus cyclohexane system. Temperature …

The Addition Of Sf5br To Unsaturated Systems, Qui-Chee Wendy Wang

Dissertations and Theses

Addition reactions of pentafluorosulfur bromide with unsaturated substrates were studied and four new compounds containing the pentafluorosulfur group have been prepared.

The mechanism for these reactions seems to involve a radical addition pathway. In reaction with CH₂=CFC1, CF₃C≡CH and CH₃C≡CH the SF₅ radical attacks the carbon atoms carrying the most hydrogens. The reaction with CF₂=CHCl is interesting, as by analogy with other fluoroolefins, the SF₅ primary attack should occur.at the CHCl group, however, SF₅CF₂CHC1Br was found as the only product for this reaction. The reaction of …

A Facile One Step Synthesis Of Some New 2-Hydroxy-4,6-Bis Aryl S-Triazines And Related Compounds, Howard Steven Grossberg

Honors Theses

In the past few years the symmetrical triazines have developed extreme importance in biochemical research as well as importance in industrial applications. In our research we have developed a facile, one-step synthesis of a number of 2-hydroxy-4, 6-bis aryl symmetrical triazines based upon the addition of the anion of urea and an aromatic nitrile, with the aryl group including a number of halogenated benzenes, pyridine, or benzene itself. The structure of these compounds had been proved by microanalysis and by both infra-red and mass spectroscopy. The further versatility of the synthesis has also been explored, and by replacing the urea …

Effect Of Solvent Polarity On The Singlet-Triplet Energy Gap Of Methyl-2-Anthroate, William Gregg Hawkins

Honors Theses

Nonradiative processes cause the fluorescence quantum yield to be less than one. Elucidation of nonradiative decay mechanisms without knowing the location of triplet states is difficult. Determination of the fluorescence quantum yield (Øf) as a function of temperature can provide valuable information about relative location of triplet states and the nonradiative processes which result from having a triplet near the energy of the first excited singlet state. Methyl-2-anthroate is very sensitive to solvent polarity. The Øf values and S1 energies vary greatly, depending on the solvent environment. Temperature studies on Øf have indicated the intersystem crossing (ISC) to a nearby …

The Design, Development And Construction Of A Low Cost Multi-Purpose Computer/Interface System For On-Line Experimentation: Applications To Time Averaging Of Nmr Spectra And Other Chemical Instrumentation Problems, Steven A. Carr

Honors Theses

The project goal was the development of a low cost multipurpose microprocessor interfacing system that would be adaptable to a number of commonly encountered chemical instruments (such as NRM, GC, IR, and UV-VIS.) for the purpose of control, data acquisition processing. The Altair Microprocessor with 4K random access memory was constructed from kit form; it functions as the computer portion of the system. The digital to analog and analog to digital signal conversion elements as well as timing, control and other necessary logic functions are incorporated in the electronic interface portion of the system. The computer, interface, principles of time …

The Synthesis And Decomposition Of O-Substituted Phenylhydroxylamines, Helen Carol Kennicott

Honors Theses

0-(phenyl)hydroxylamine and its p-nitrated derivative were synthesized for use in a study of substitution reactions at an sp3 hybridized nitrogen atom. The 0-(phenyl)hydroxylamine was decomposed thermally in several nonnucleophilic solvents and in water, with base present. It is proposed that in organic solvents, the decomposition proceeds by a radical mechanism involving a solvent cage intermediate. Ammonia and aminophenols are the major products. In water, it appears that an SN1 reaction producing phenoxide may compete with the radical mechanism.

The Preparation And Kinetic Studies Of Two Sterically Hindered Gold (Iii) Complexes, James Forrest Stevens

Honors Theses

Previous studies indicate substitution of bromide ion for chloride ion in [Au(Et4dien~H)c.i] +occurs at a rate almost independent of the bromide ion concentration, while similar reactions with [Au(dien-H)Cl]+, [Au(Me2dien-H)c!]+ and [Au(Me4dien-H)c~+ show rates dependent on bromide ion concentration as usually encountered for square planar complexes. There is retardation of the reaction by steric and electronic effects with increased N-alkyl substitution of the triamine. It has also been postulated that substitution of [Au(Et2dien-H)cJ]+ proceeds via a ring-opening mechanism. The purpose of this research was to study further the effect of steric hindrance on rates of substitution of two additional gold(III) complexes. …

The Synthesis Of 2, 11-Dithiabenzo - [3.3] - Paracyclophane And An Octadeutero Derivative, Paul M. Begley

Honors Theses

The purpose of this work was the synthesis of 2, 11 -dithia-benzo- [3.3] -paracyclophane and its octadeutero derivative 2,11-dithia- 3,3, 5, 6, 8, 9, 10, 10-octa­deutero-benzo - [3.3] paracyclophane. A comparison of their nuclear magnetic resonance spectra as well as their mass spectra will unequivocably provide proof of their successful synthesis.

Ozone Complexes With Substituted Aromatic Compounds, David C. Eaton

Honors Theses

Ozone has been observed to complex with aromatic compounds at low temperatures. The ability of an aromatic system to complex with ozone appears to be due to the inductive effect of the substituent on the pi system. The experimental work was done in the solid phase at temperatures of -175° C to -186° C. Under these conditions all the substituted aromatics with electron withdrawing groups did not complex including benzene. The complexes are highly colored. To insure the reversibility of the pi complex, infrared spectra were taken of some of the aromatic species before and after complexing.

Photochemistry Of Beta-Methyl-Beta-Nitrostyrene And Its Derivatives, Mohammad Z. Kassaee

Masters Theses & Specialist Projects

o-CH₃, o-CH₃O, m-CH₃O and p-CF₃-β-methyl- β-nitrostyrene (compounds not previously reported) were synthesized using the method of Lappin¹³ and Robertson.¹⁴ These styrenes were irradiated in the U.V. region. The yield of corresponding oximes varied from 85 to 100% in aqueous ethanol. This variation in yield of the oximes was attributed to the effect of the substituent on the phenyl rings of the corresponding styrenes. Electron donating substituents promoted the nitro-nitrite rearrangement and electron-withdrawing groups inhibited this rearrangement. A mechanism is proposed for this reaction which unifies and includes ideas proposed by …

Some New Metallocenes, Larry Warfield

Masters Theses & Specialist Projects

The synthesis and characterization of some new metallocenes is discussed. These organometallic compounds contain some of the first reported pi-complexes between an aromatic ylid, triphenylphosphoniumcyclopentadienvlide. and some transition metals.

Also reported is the synthesis of some new mercury halide metallocenes involving dimethylsulfoniumcyclopentadienylide as the sigma bonded organic substrate.