Physical Sciences and Mathematics Commons^™

Catechol Effected Dissolution Of Silicate Minerals, James Maurice Kelley

Dissertations and Theses

The chemical properties of guanidinium tris(catecholato)siliconate, [(H₂N)₂C=NH₂]₂[Si(C₆H₄O₂)₃]·XH₂O (0 < X < 1), precipitated from an ammoniacal solution of silica and catechol by adding guanidinium hydrochloride, (H₂N)₂C=NH·HC1, were studied, and infrared, nmr, x-ray powder diffraction, and analytical data were gathered.

This same compound was, upon addition of' (H₂N)₂C=NH·HC1, isolated from 0.25, M aqueous catechol solutions buffered at pH 10 and containing the silicate minerals albite, andradite, muscovite, pyrophyllite, talc, and wollastonite, and also from unbuffered catechol solutions containing wollastonite and andradite.

It is concluded from this work that the formation of an anionic catechol-silicon complex, Si(C₆H₄O₂)₃²⁻, is largely responsible for the dissolution of the minerals mentioned above. From this conclusion, it is proposed that naturally occurring members of the class of organic compounds to which catechol belongs, the aromatic v̲i̲̲c̲-diols, may play …

On The Mechanism Of Low-Temperature Termolecular Atomic Recombination, Russell T. Pack, Richard L. Snow, Wesley D. Smith

Faculty Publications

A simple theory of gas-phase termolecular atomic recombination kinetics is presented which treats the bound-complex (BC) mechanism in a fashion which parallels the Roberts, Bernstein, and Curtiss resonance theory of the energy-transfer (ET) mechanism. The ET rate constant has a low temperature maximum, but the BC rate constant does not. The contributions of the two mechanisms to the low-temperature recombination of hydrogen atoms, with He, Ar, and H2 as third bodies, are estimated and compared. The presence (absence) of a low-temperature maximum in the observable total rate constant is determined by absence (presence) of bound vibrational levels of the hydrogen-third …

Isopiestic Studies Of Some Aqueous Electrolyte Solutions At 80°C, John T. Moore

Faculty Publications

No abstract provided.

The Interpretation Of Lanthanide-Induced Shifts In 1h Nuclear Magnetic Resonance Spectra, Jerry Goodisman, R. S. Matthews

Chemistry - All Scholarship

Owing to the present accuracy of the data and various other factors, it is easy to obtain agreement with experimental results for lanthanide-induced shifts in ¹H n.m.r. spectra; some considerations in the formulation of such models which have been ignored previously are discussed.

Birch Reduction Of Benzamide, N-Substituted Benzamides And Biphenylene, Luther Dickson

University of the Pacific Theses and Dissertations

The Birch reduction of benzamide with sodium and absolute ethanol. 95% ethanol, or tert-butanol in liquid ammonia gave 1,4-dihydrobenzamide in varying amounts. The amide group was not reduced. The two most important variables encountered were the alcohol used and whether or not ammonium chloride was added after the reduction was completed. Without this addition of ammonium chloride, little or no 1,4-dihydrobenzamide was present after workup, while with its addition some 1,4-dihydrobenzamide formed whether the proton source was absolute ethanol, 95% ethanol, or tert-butanol. The highest yield was obtained with tert-butanol with ammonium chloride being added. Addition of ammonium chloride apparently …

Studies On The Mechanism Of Action Of Nerve Growth Factor., D. (Daniel) B. Hier, B. G. Arnason, M. Young

Chemistry Faculty Research & Creative Works

No abstract provided.

An Aircraft, Aerosol Sampling Program: Some Preliminary Results, J. F. Stampfer

Chemistry Faculty Research & Creative Works

An aircraft sampling program to determine the vertical and size distributions of that part of the atmospheric aerosol with radius greater than 0.25 μ is described. The feasibility of using a single engine aircraft and a light scattering particle analyzer, for this work, is shown. Examples of the data are given and preliminary conclusions are drawn about the normal size distribution, effect of lapse rate on the vertical aerosol concentration gradient, effect of relative humidity on the size distribution, and the possibility of producing high concentrations of giant particles aloft. © 1972.

The Study Of The Isomerization Of Trans-3-Acetoxy-2-Bromocyclooctene, Virginia Hill Lewis

University of the Pacific Theses and Dissertations

The isomerization of trans-3-acetoxy-2-bromocyclooctene (trans-1) to cis-3-acetoxy-2-bromocyclooctene (cis-1) was studied, trans-3- Methoxy-2-bromocyclooctene (trans-2) was used as a model compound for comparison. The rate of isomerization of both compounds increased tremendously with iodine (free radical catalysis) and decresed tremendously in the presence of hydroquinone (free radical inhibitor). This showed that the isomerizations of trans-1 and trans-2 are free radical catalyzed. It was anticipated that acetoxyl participation in trans-1, by stabilizing the free radical intermediate, would cause the rate of rearrangement of trans-1 to be much greater than the rate of rearrangement of trans-2. However, trans-1 iscented only about four times faster …

Structural And Magnetic Properties Of [(Ch₃)₃Nh] Cucl₃2h₂O, D. B. Losee, J. N. Mcelearney, A. Siegel, Richard Lewis Carlin, A. A. Khan, J. P. Roux, William Joseph James

Chemistry Faculty Research & Creative Works

The crystal structure at room temperature and the low-temperature heat capacity and magnetic susceptibilities of single crystals of [(CH3)3 NH]CuCl3 2H2O are reported. The monoclinic crystals belong to the space group P21c with a=7.479(10), b=7.864(11), c=16.730(23), =91.98(3)°, and Z=4. The structure consists of chains of edge-sharing [CuCl4(OH2)2] octahedra running along the a axis. Each copper atom is coordinated in a square plane by two water molecules and two chlorine atoms, with two more chlorine atoms at a longer distance. The susceptibility data can be fitted adequately between 1.5 and 20°K by a CurieWeiss law [ga=2.080.01, gb=2.020.01; gc=2.110.01; a=(0.380.03)°K, b=(0.360.03)°K, c=(0.410.03)°K], …

The Identification Of Barbiturates By Attenuated Total Reflectance, Robert Lewis

University of the Pacific Theses and Dissertations

The use of Attenuated Total Reflectance as an analytical technique in infrared spectroscopy has become increasingly important in the past few years. ATR (Attenuated Total Reflectance) is a relatively new analytical method. Producing spectra of compounds by this method requires no solvent for dissolving the sample and no salts for making pellets. The only requirements for spectra production, similar in quality to those produced by conventional methods, are that there is enough sample to cover both sides of the reflector be similar. The index of the sample is fixed; therefore, the index of the reflector is controlled by selecting a …

The Mechanism Of The Reaction Of Lead(Iv) Acetate, Thallium(Iii) Acetate And Mercury(Ii) Acetate With Ketones, Su Hsiung Tsung

Masters Theses

No abstract provided.

The Hemoglobin Of Tubifex Tubifex, Lalitchandra Vrajlal Vora

Masters Theses

The hemoglobin of Tubifex tubifex is found in solution in the blood of the worm in cells as in vertebrates. The binding of oxygen to the hemoglobin can be followed spectrophotometrically. A peak of absorbtion at 540 nm is fairly constant under different condition, while a peak at 575 nm disappears from the spectrum when oxygen is removed. The hemoglobin contains heme, non-heme iron and protein.

Binding of oxygen to the hemoglobin was found to be dependent on the concentration of the hemoglobin, at low concentrations (4.16 x 10^-6 M), oxygen could not be removed from the hemoglobin. Only …

The Conductance Of Some Non-Rigid Bolaform Electrolytes, William Terry Schmidt

Masters Theses

Bolaform electrolytes are those which contain two or more charges separated by an inert framework. These are intermediate in structure between simple electrolytes and polyelectrolytes. Since these are similar to both synthetic and biological electrolytes, this investigation has been undertaken to determine some of their properties in solution.

The sodium and magnesium salts of ethane, propane, butane, pentane, hexane and decane α,ω-disulfonates were prepared. Each acid was prepared by refluxing the α,ω-dibromide of the desired salt with sodium sulfite. The sodium and magnesium salts were prepared by ion-exchange techniques.

The conductance of each salt was determined in methanol utilizing the …

Equilibrium And Kinetic Study Of The Substitution Reactions Of Pentacarbonylaminetungsten (O) With Triphenylphosphine, William O. Bailey

Masters Theses

A kinetic and equilibrium study of the reaction of triphenylphosphine (PPh₃) with pentacarbonylaminetungsten (O) [(CO)₅WNH₂C₆H₅] has been reported previously. Equilibrium constants for the reaction (CO)₅WNH₂C₆H₅ + PPh₃ = (CO)₅W[P(C₆H₅)₃] + C₆H₅NH₂ in toluene were reported to be 17.1, 49.2 and 65.7 respectively. In addition, the entropy change (ΔS) for the reaction was found to be 86±5 cal mol^-1 deg^-1.

In this study the above reaction was …

Birch Reduction Of Benzenesulfonamide, N,N-Dimethylbenzenesulfonamide, N,N-Diisobutylbenzenesulfonamide, And 2-Mesitylenesulfonamide, Vishnubhai V. Patel

University of the Pacific Theses and Dissertations

It has been previously shown that benzenesulfonamide gives thiophenol and diphenyldisulfide upon Birch reduction. The sulfonamide group is easily reduced. Probably the electron deficient sulfur atom in sulfonamide can accommodate an electron easily.

The present study involved the Birch reduction of benzenesulfonamide, N,N-dimethylbenzenesulfonamide, N,N-diisobutylbenzenesulfonamide and 2-mesitylenesulfonamide.

Dipeptide Complexes Of Palladium(Ii) And Platinum(Ii), Lewis Enos Nance

University of the Pacific Theses and Dissertations

Due to recent interest in the role of heavy metals in enzymes. oxygen-carrying molecules. and anticarcinogenic compounds, the study of metal-protein bonding has assumed a new importance. Studies have been made utilizing platinum compounds as anticarcinogenic agents in several different types of cancerous activity. No study of the mechanism by which Pd(II) and Pt(II) compounds exhibit anticarcinogenic properties has been made to date.

The purpose of this research was to investigate the nature of bonding of Pd(II) and Pt(II) with various dipeptides, which were chosen in this study as a basic unit of protein-like material. These compounds have the advantage …

The Thermal Rearrangement Of Triarylacetonitrile Oxides., Leslie Wayne Gibbs

University of the Pacific Theses and Dissertations

This research is a detailed study of the rearrangement of triarylacetonitrile oxides to the corresponding triarylmethylisocyanates. The kinetics of the rearrangement of triphenylacetonitrlle oxide was followed by infrared absorption spectroscopy using the peak due to the N-0 stretching (1307cm^-1). A study, both, using the differential method (i.e., a plot of the logs of the initial slopes vs. the log of the concentration) and a check of the integrated forms of the rate expressions to determine which gave a constant value for the rate constant showed that the reaction is first order.

From measurements of the rate constant, k, …

Spectrophotometric And Microbiological Determination Of The Stability Of Sodium Ampicillin As Affected By Ph, Enrico Frank Raffanti

University of the Pacific Theses and Dissertations

The specific purpose of this investigation was to determine the effect of pH on the stability of ampicillin sodium for injection. Then, to correlate this information, a pH profile may be established to predict chemical stability with ampicillin sodium alone or when other drugs may be included in the admixture. With a pH profile the pharmacist could predict the length of time after which more than a 10 percent loss of activity would occur. Stability measurements were to be accomplished through a microbiological assay after adding ampicillin sodium to different buffer solutions. At the end of four hours, eight hours, …

Glucose-6-Phosphate Hydrolysis By A Soluble Fraction From Brassica Nigre, Edwrd Pak-Tung Lau

All Master's Theses

Glucose-6-P occupies a strategic crossroad position in a variety of carbohydrate metabolic pathways. This hexosephosphate ester may serve as a substrate for glycogen synthesis (1), glycolysis (2), or oxidation through the pentose shunt. This ester may also undergo hydrolysis to form glucose (3). The last process is the terminal reaction in glucose synthesis from gluconeogenesis and glycogenolysis and is catalyzed by glucose6-phosphatase.

Reactions Of Trichloro(Beta-Diketonato)Titanium(Iv) Complexes With Alcohols In The Presence Of Pyridine, William R. C. Munsey

Dissertations, Theses, and Masters Projects

No abstract provided.

Kinetics Of The Cope Rearrangement Of 3,4-Diphenylhexa-1,5-Diene, Harlan Albert Jerome Berg

Dissertations and Theses

Kinetics investigations of the thermal Cope rearrangement of meso-and d1-3,4-diphenylhexa-1,5-dienes were undertaken in order to gain information about the transition states for these reactions by determining the appropriate enthalpies and entropies of activation. Of particular interest were the activation parameters for the meso compounds' rearrangement as it represents the only known example in which both four-and six-centered transition states are of comparable energy.

Kinetics of the dl isomers' rearrangement in the temperature range 90-110⁰were determined using 5 X 10¯⁵M solutions of the olefin in heptane contained within sealed Pyrex ampules. Extents of reaction were determined from UV absorbance measurements at …

Reaction Of Aqueous Catechol Solutions With Minerals, Boonthong Poocharoen

Dissertations and Theses

The effectiveness of catechol, an aromatic vic-diol, in dissolving silicate minerals was studied. A synthetic amorphous magnesium trisilicate, Mg₂Si₃O₈∙5H₂O, as well as the minerals olivine, sepiolite, diopside, augite, and enstatite were used to react with catechol in slightly acidic, basic, and neutral solutions. It was found, depending on the solvent used, that 33-52, 8-17, 14-30, 5-11, 3-6, and 0.5-1 % of the minerals dissolved, respectively.

The reaction with Mg₂Si₃0₈·5H₂0 resulted in the formation of crystals of magnesium tris (catecholato) siliconate nonahydrate Mg[Si(Cat)₃]∙9H₂0. Dehydration of the crystals at room temperature resulted in the loss of 6 moles of water to form …

A Study Of Some Complexometric Titrations In Nonaqueous Solvents, Ngo The Hung

Masters Theses

"Complexometric titrations of calcium, zinc and lead with polyaminocarboxylic acids: ethylenediaminetetraacetic acid (EDTA), 1,2-diaminocyclohexanetetraacetic acid (DCTA), ethyleneglycol-bis(2-aminoethylether)tetraacetic acid (EGTA) and tetraethylenepentamine (tetren) have been investigated and compared in the following organic solvents: methanol, dimethyl formamide, dimethyl sulfoxide and methyl ethyl ketone. Various end point detection methods have been used: direct visual titration with metallochromic indicators and instrumental detection by photometry, potentiometry (mercury electrode and lead ion selective electrode) and amperometry. Calcium, zinc and lead can be determined up to trace levels (ppm) under specific conditions. A concrete application of this thesis is the determination of zinc or calcium in a …

On The Mechanism Of The Diels-Alder Reaction--Dimerization Of Trans-Phenylbutadiene, Michael Ward Mcnicholas

Dissertations and Theses

The Diels-Alder dimerization of trans-1-substituted butadienes is expected to yield a cyclohexene adduct with the substituents in the 3 and 4 positions cis to one another. This prediction is based on past observations of other Diels-Alder additions. The cis-isomer is the only one consistent with a two-stage mechanism proposed by Woodward and Katz.

In the case of trans-phenylbutadiene, the expected adduct is cis-3-phenyl 1-4-(trans-styry1) cyclohexene. Alder, Haydn and Vogt, however, reported that the corresponding trans-isomer is the dimerization product. There is reason to believe that the observation of the trans-isomer may have been the result of product isomerization during purification. …

Substituent Effects On The Magnetic Resonance Spectra Of 1, 4-Disubstituted Benzenes, Holger Er-Chah Chen

Doctoral Dissertations

"The Nuclear Magnetic Resonance spectra of five complete series of para-substituted benzenes have been investigated: the benzoic acids, benzonitriles, benzoyl chlorides, methyl benzoates and nitrobenzenes. Precise values of aromatic proton chemical shifts and coupling constants were obtained from LAOCOON3 computer analyses of the spectra. Using the relative internal chemical shift technique of Beachell and Beistel, excellent linear correlations among all five series were found. All substituents gave proton shifts which lay on the least-squares line, so it is concluded that all substituents are well behaved. Using the correlation plots the chemical shifts of the aromatic ring protons can be predicted …

Condensation And Sublimation Of Carbon Dioxide And Water Molecules At Cryogenic Temperatures, Victor Cazcarra

Doctoral Dissertations

"Measurements of the condensation coefficient of CO₂ and H₂O have been made using a molecular beam and quartz crystal microbalances. The dependence of the condensation coefficient on variables such as population density on the substrate, temperature of the substrate, molecular beam intensity and temperature of the molecular beam, was investigated. The results are explained using heterogeneous nucleation theory for low density population, and a new approach for high density population is presented. The rate of sublimation of these two gases was measured directly. The results are reported in terms of vapor pressure in the range 10⁻⁹ to 10⁻⁴ Torr. The …

Selected First Row Transition Metal Coordination Compounds Of 2-(N-Aminomethyl)-3-Quinuclidinone Chelates, Richard Cecil Dickinson

Doctoral Dissertations

"As part of a project directed towards elucidating the characteristics of ligands which coordinate to give complexes having tetrahedral structures, a study of chelates containing the bulky quinuclidine group has been made. With 2-(N-morpholinylmethyl)-3-quinuclidinone (MQN), complexes having the general formula M(MQN)X₂ were prepared where the metal ion was Co(II), Ni(II), Fe(II), Cu(II), and Mn(II). The ligands 2-(N-piperidinylmethyl)-3-quinuclidinone (PQN) and 2-(N-dimethylaminomethyl)-3-quinuclidinone (DQN) were prepared along with the analogous cobalt(II) chloride complexes. The series of complexes Co(MQN)X₂ where X = Cl, Br, or I were prepared, and magnetic susceptibilities and spectral data obtained. They have room temperature magnetic moments in the range …

The Utilization Of High Sensitivity Noble Gas Mass Spectrometry In The Detection Of Iodine-129 And Plutonium-244, Mervet S. Boulos

Doctoral Dissertations

"Mass spectrometric analysis of the xenon isotopes in natural gas wells demonstrates that radioactive isotopes of element number 53 (I) and element number 94 (Pu) were present at the time of the Earth's formation. Evidence for the now extinct nuclide¹²⁹I (t_1/2 = 17 x 10⁶ years) was found in CO₂ -rich gas while evidence for the now extinct ²⁴⁴Pu (t_1/2 = 82 x 10⁶ years) was discovered in other natural gas wells. The amounts of ¹²⁹I in thyroids was measured by combining neutron activation analysis with noble gas mass spectrometry. The current …

Studies Of Neutron Capture Produced Rare Gas Isotopes In Rocks And Minerals Containing Chlorine, Selenium And Tellurium, David E. Sinclair

Masters Theses

"Noble gas mass spectrometry was used to study rare nuclear processes in terrestrial rocks and minerals. An excess of ³⁶Ar was detected in a chlorine-rich rock. The excess ³⁶Ar has been produced in rocks near the earth's surface due to capture of cosmic-ray-produced neutrons on ³⁵Cl. Measurement of ³⁶Ar formed by the ³⁵Cl(n, γ)³⁶Cl(β^-)³⁶Ar process makes possible a new method for determining the surface residence time of chlorine-rich minerals

Excess ⁸²Kr and excess ⁸³Kr were detected in selenium-rich ores. The excess ⁸²Kr results from double beta …

Purification And Inhibition Study Of Xanthine Oxidase, Porn Paul Israngkun Na Ayudthaya

All Master's Theses

The paper describes a new and improved method of isolating and purifying xanthine oxidase and includes inhibition studies involving a number of reagents which are structurally related to the substrate or to other inhibitors of xanthine oxidase. The inhibitors studied are classified as to type, and inhibitor constants are reported.