Digital Commons Network^™

Spectroscopic Studies Of Hydrophobic Association Of Merocyanine Dyes In Cationic And Anionic Micelles, Sayed Sadiq Shah

University of the Pacific Theses and Dissertations

Merocyanine dyes exhibit interesting changes in absorption spectra with changes in solvent polarity. For example solutions of 1-methyl-4- (oxocyclohexadienylidene) ethylidene -1,4-dihydropyridine (MOED) are yellow, red, violet, or blue, in water, ethanol, acetone or pyridine respectively.¹ More striking effects are observed when aqueous solutions are diluted with various proportions of the organic co-solvents such as pyridine. The color varies across the whole spectrum from golden yellow to blue.These characteristic properties of merocyanine dyes in various organic solvents have been extensively studied and correlations between [see PDF file for formula]_max and solvent polarity have been determined. In this work the …

Kinetics And Stoichiometry Of The Aquation Reaction Of Pentaaquodihalomethyl Chromium(Iii) Ions, Mohammad Javaid Akhtar

University of the Pacific Theses and Dissertations

This study was designed to provide information about the mechanisms of pentaaquodihalomethyl chromium(III) ions (halo chloro, bromo and iodo).

...

Mechanisms based on carbonium ion, carbeno and carbenoid type intermediates are proposed. A mechanism based on the nucleophillic attack (S_N2) of water on the carbon center leading to a metal-formyl type intermediate is suggested as best fitting all the criteria observed in these studies.

(see PDF file for additional Abstract as it includes formulas)

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

University of the Pacific Theses and Dissertations

No abstract provided.

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

Chemistry Faculty Research and Publications

No abstract provided.

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 …

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 …

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 …

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.

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

Department of Chemistry: 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 …

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.

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 …

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.

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.

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.

Isoviscosity Curves In The Analysis Of The Pressure--Temperature Dependence Of Liquid Viscosity., Gayle Nathaniel King

University of the Pacific Theses and Dissertations

The temperature and pressure dependence of liquid viscosity has been extensively discussed in the chemistry, physics, and engineering literature for over half a century. Thus far, theoretical ab initio calculations of temperature and pressure effects on viscosity have been unsuccessful. Therefore there have been numerous attempts to relate fundamental properties of liquid state models with experimental viscosity, temperature, pressure, and density (η,T, P, ρ) data. This work has resulted in many semi-empirical equations expressing η as functions of temperature, pressure, volume, density, chain length, molecular weight, degrees of freedom, etc.

Synthesis And Characterization Of Pentaaquo-4-Pyridylchromium (Iii) Ion, Danny Alan Biggs

University of the Pacific Theses and Dissertations

4-bromopyridine hydrochloride is a compound which has a relatively high formal charge on the 4 carbon. Molecular orbital calculations on pyridine show a +0.18 charge on the 4 position, a +0.15 charge on the 2 position, and a +0.05 charge on the 3 position with the nitrogen holding a -0.59 charge.¹² And in aqueous acidic solutions, and added +1 charge would be distributed throughout the aromatic ring of the resulting pyridinium ion, thus increasing all charges. Benzene would show all carbons being identical having relative charges of zero each on the scale used for pyridine. As a result of …

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.

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 …

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., …

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 …

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, Dane R. Jones, Scott L. Whittenburg, C. H. Wang

Chemistry and Biochemistry Faculty Publications

No abstract available.

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

Chemistry Faculty Publications

No abstract provided.

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.

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 …