Physical Sciences and Mathematics Commons^™

The Lippmann Equation And The Ideally Polarizable Electrode, Jean- Pierre Badiali, Jerry Goodisman

Chemistry - All Scholarship

The Lippmann equation for the ideally polarizable interface is normally derived by thermodynamics, using the Gibbs dividing surface. Therefore, the quantities appearing in the Lippmann equation can have no reference to the actual charge distribution in the interfacial region. For example, the quantity referred to as surface charge is actually a sum of surface excesses, rather than the integral of a true charge density. In this article we derive, by statistical mechanical methods, the Lippmann equation for a model at the molecular level, thus giving a precise physical definition to all quantities which appear. First, we derive the conditions for …

Analysis Of Rocks And Minerals By Attenuated Total Reflection With Atlas, Donald Franklin Anderson

University of the Pacific Theses and Dissertations

Routine non-destructive analyses of rocks and minerals in slab or powder form maybe practicable by the application of the technique of attenuated total reflection [ATR] in infrared [IR] spectrophotometry.

An atlas of spectra would serve the analytical chemist and geologist, who in turn would serve the miner, the lapidarist, and other groups interested in rocks and minerals.

No effort has been made to produce an atlas of spectra of rocks and minerals by ATR. No ATR spectra of rocks and minerals were found in the literature. The history of ATR indicates that it is still in its early stages of …

Methyl Proton Nmr Shifts Of Coordinated Methanol In A Series Of Co(Ch,0h),X2+ Compounds, J.R Vriesenga, Jerry Goodisman

Chemistry - All Scholarship

The isotropic contact NMR shifts of the coordinated cis and tram methanol methyl proton resonances of a series of Co(CH30H)5X2+ complexes were measured, where the ligand X was pyridine, /I- and a-picoline, DMF, DMSO, acetonitrile, and water. The question of how to separate the observed shifts into their respective Fermi contact and dipolar (pseudocontact) contributions was examined in detail with the result that a new procedure for carrying out the separation was proposed. The dipolar shifts for these complexes were found to vary widely, with the acetonitrile complex exhibiting the largest dipolar shift. For the DMSO and water complexes the …

The Role Of Mannosyl-Phosphoryl-Dihydropolyisoprenol In The Synthesis Of Mammalian Glycoproteins, John W. Baynes, An-Fei Hsu, Edward C. Heath

Faculty Publications

A mouse myeloma tumor was used as a model system to study the biochemical steps involved in the incorporation of mannose into glycoproteins. This tumor, MOPC-46B, synthesizes a K-type immunoglobulin light chain (K-46) which is a glycoprotein with a single oligosaccharide side chain containing mannose as one of its constituent sugars. MOPC-46B microsomal preparations contain enzymes which transfer mannose from the sugar nucleotide, GDPmannose, to endogenous lipid and protein acceptors. Formation of the mannolipid proceeds by the reversible transfer of mannose from GDP-mannose to an endogenous phospholipid. The mannolipid was purified and characterized by chemical methods and mass spectrometry as …

Photochemical Rearrangements Of 6/5 -Fused Cross-Conjugated Cyclohexadiensnes In Protic Solvents, Drury Caine, John T. Gupton, Ko Ming, William J. Powers Iii

Chemistry Faculty Publications

Irradiation of the ring A unsubstituted 6/5-fused cross-conjugated cyclohexadienone (1a) and its 2-methyl derivative (1b) in methanolic acetic acid yields, in addition to other products, novel tricyclononane derivatives which have been assigned the structures (3a) and (3b).

The Kinetics And Mechanism Of The Reaction Of Chromium(Ii) With Pentaaquodiiodomethyl Chromium(Iii) And Pentaaquomonoiodomethyl Chromium(Iii) Ions., Ronald Sinclair Nohr

University of the Pacific Theses and Dissertations

Transition metal ions, in low oxidation states, have gained increasing use as versatile reducing agents for a number of organic compounds. The ability of metal ion to act as reducing agents in organic reactions is frequently thought to be due to the formation of intermediates which contain an organic species bound to a metal, although the identy of these organo-metallic intermediates has been determined in relatively few cases.

The purpose of this research was to investigate the kinetics and mechanism of one such reaction: the reduction of iodoform to methane by chromium(II). Two air stable organochromium(III) intermediates were separated and …

The Preparation And Characterization Of The Palladium(Ii) And Platinum(Ii) Chelates Of Three Cyclic Tertiary Amino Acids., Floyd Michael Hogue

University of the Pacific Theses and Dissertations

The purpose of this study was to prenare and characterize the palladium (II) and platinum (II) chelates of 1-pyrrolidineacetic acid, 1-piperidineacetic acid, and hexahydro-1-azepineacetic acid.

The ligands were prepared by reacting the cyclic secondary arnines (pyrrolidine, piperidine, and hexahydroazepine) with sodium chloroacetate. The resulting cyclic tertiary amino acids were saponified and, finally, converted to the hydrochloride salts by neutralization with hydrochloric acid.

The chelates were prepared by adding 1.0 millimole of K₂PdC1₄ or K₂PtC1₄ to a solution made by dissolving 2.0 Millimoles of amino acid hydrochloride in 25 ml. of water. The pH was …

Formation And Kinetics Of Dissociation Of Some Pentaaquotrihalomethyl Chromium(Iii) Ions., Sher Khan Malik

University of the Pacific Theses and Dissertations

The present.study was an investigation of the formation and kinetic stability of store complexes contain.ir)ing a chromium-carbon bond in an aqueous medium. An orange-brown pentaaquotrifluoromethylchromium(III) ion was obtained by the reduction of trifluororrethyl iodide with Cr(II) and is the most inert of any organochrotnium(III) complex known. The initial aquation rates of trifluoromethylchromium(III) ion were described by the differential rate law -dln [(H₂O)₅CrCF₃²⁺]/dt = k_{o + k1(H⁺)}

The products of the initial reaction were hexaaquochromium (III), carbon monoxide and HF. The values of k_o and k₁ at …

Dipole Moments In Thomas-Fermi-Dirac And Thomas-Fermi Theories., Jerry Goodisman

Chemistry - All Scholarship

It is shown that the electronic contribution to the dipole moment, calculated from a solution to the Thomas—Fermi—Dirac or Thomas—Fermi equations, should be equal and opposite to the nuclear contribution. Thus, the Thomas—Fermi—Dirac and Thomas—Fermi theories predict vanishing dipole moments for all molecular systems.

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.

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 …

A Kinetic Study Pertaining To The Enzymatic Reduction Of Pyruvate By Lactate Dehydrogenase, Ronald Floyd Tienhaara

All Master's Theses

The reduction of pyruvate as catalyzed by lactate dehydrogenase has been studied by monitoring the oxidation of DPNH (diphosphopyridine nucleotide) at 340 nm. The kinetic investigation was carried out in phosphate buffer at 25° C. Since pyruvate exists in equilibrium with the enolized and hydrated forms, a kinetic analysis was devised to determine the nature of the true substrate for the enzymatic process. Also, a comparative study was made involving two isozymes of lactate dehydrogenase. The catalytic effectiveness of these isozymes was studied as a function of pH and substrate concentration.

A Kinetic Analysis Of The Iodination Of Pyruvic Acid And Pyruvate Esters, Mohamed M. Fahmi Hegazi

All Master's Theses

In the present work the relative rates of iodination of pyruvic acid and ethyl and methyl pyruvate have been compared at 25.0° C. These studies allow the determination of the respective free energies of activation for these processes. Measurements have also been carried out at various temperatures to determine the enthalpies and entropies of activation for the spontaneous and base catalysed iodinations of these pyruvate systems. The present thesis also includes a comparison of the solvent deuterium isotope effects associated with the spontaneous rate of iodination of pyruvic acid and the alkyl pyruvates. Also, the catalytic rate coefficients associated with …

Synthesis And Characterization Of Some Dioxane Complexes, James Donald Satterlee

All Master's Theses

The boron trifluoride, tin (IV) fluoride and titanium (IV) fluoride complexes with 1,4-dioxane have been prepared and studied using infrared techniques. The compositions of the complexes have been determined and correspond to the 1:1 adducts in the case of the tin and titanium compounds. The boron trifluoride adduct is a 2:1 (acid:base) adduct. Infrared spectra in the region 1300 cm.-1 to 550 cm.-1 are given and the effects of coordination upon the ligand vibrations are described.

Electron Densities For Homonuclear Diatomic Molecules From The Thomas-Fermi-Dirac Theory, Jerry Goodisman

Chemistry - All Scholarship

Electron densities are calculated from approximate solutions to the Thomas-Fermi-Dirac equation for homonuclear diatomic molecules. The accuracy of expectation values calculated from these densities is assessed. In general, one obtains fair agreement with self-consistent-field and experimental results, but this is insufficient when a property is a difference between electronic and nuclear contributions. An important example is the Hellmann-Feynman force on a nucleus, the net force necessarily being repulsive, as for closed-shell atoms. Forc and energy results for such a situation are compared with experiment. Finally, it is shown that a modified theory, previously applied to atoms, gives improvement in expectation …

Palladium(Ii) And Platinum(Ii) Complexes Of 2-Cyanophenyl Diphenylphosphine, David Harrison Payne

University of the Pacific Theses and Dissertations

There has been no successful chelation of any phosphorus-acetylenic or phosphorous-nitrile ligand. The objectives of this study were to synthesize such ligands and to study their chemistry and chelating tendencies. The best choice appeared to be the preparation of ortho-substituted triphenylphosphines similar to the chelating ligand allylphenyldiphenylphosphine. The Grignard reactions utilized in the preparation of the olefinic compound could not be used in most cases due to the high reactivity of the acetylene and nitrile function Bromobenzene and iodobenzene have been reacted with alkali metal phosphines under conditions that were probably too drastic for the acetylenic and nitrile functions. There …

Fluorescence Lifetimes And Quantum Efficiencies Of Some 1,10-Phenanthrolines, Paul John Tabakian

University of the Pacific Theses and Dissertations

Fluorescence properties of fourteen substituted 1,10-Phenanthrolines were determined using two different solvent systems. Hour different sets of experiments were performed in order to measure fluorescence lifetimes, quantum efficiencies, absorption and corrected fluorescence spectra, oscillator strengths, and Stoke’s shifts. Two of the phenanthrolines, the 5-Nitro-1,10-Phenanthroline and the 1,10-Phenanthroline-5,6-Dione, did not fluoresce.

A new equation was developed in order to extract the true fluorescence lifetimes τ from the observed fluorescence output f(t), and the lamp decay function I(t). This equation was [see PDF] where “A” was the weight factor or the normalization constant for the appropriate functions. A test of this equation …

Hellmann-Feynman Theorem In Thomas-Fermi And Related Theories, Jerry Goodisman

Chemistry - All Scholarship

The general Hellmann-Feynman theorem (derivative of energy with respect to a parameter = expectation value of derivative of Hamiltonian) is proved for theories in which the electron density is determined by making the energy functional stationary. Some simple applications are given.

The Enzymatic Oxidation Of Aldehydes By Xanthine Oxidase, Duane Beal Gregory

All Master's Theses

As early as sixty years ago, the existence of an enzyme from mammalian tissues which catalyzed the oxidation of xanthine and hypoxanthine was recognized. The name given the enzyme was derived from its earliest recognized action, hence xanthine oxidase. Although little is known about the biological functions of the enzyme, the high affinity shown for xanthine and hypoxanthine may indicate that these are the most significant substrates biologically.

High Pressure Spectral Chemistry Of Selected Organic Compounds, Frank William Linsley

Theses and Dissertations

The series of compounds indicated by the formular C_6H_5-(CH=CH)n-C_6H_5 change in color from white (colorless) to yellow to orange to red to deep red as n increases from 1 to 12. Stilbene is the first compound of this series (n=1). Under pressure, exerted by a diamond anvil press, stilbene can be seen to change color from white to yellow to red as increasing pressure is applied. Similar color changes are observed for the compounds where n=2,3, and 4 when subjected to similar pressure. This study records and reports the spectra versus pressure for these compounds.

Modified Quantum-Statistical Calculations For Atomic Electron Densities, Jerry Goodisman

Chemistry - All Scholarship

We attempt to overcome one of the shortcomings in the Thomas-Fermi and related theories for atoms by connecting a quantum-mechanical electron density for the region near the nucleus to a density given by a statistical model. The joining may be done in a nonarbitrary manner: All parameters are determined. It suffices to use a very crude and easily calculated approximation to the density to start with, so the calculation is quite easy. The resulting electron density is in much better agreement with reality than that from the unmodified theories.

Modified Weizsäcker Corrections In Thomas-Fermi Theories, Jerry Goodisman

Chemistry - All Scholarship

We consider theories in which a kinetic-energy correction (h2322m)[2] (=density) is added to the usual Thomas-Fermi term. A treatment based on the WKB method and expected to be valid for large r shows =1 here, as found experimentally. For small r, =1 is needed to give proper behavior of, but other arguments suggest that the Thomas-Fermi term be dropped here.

Acid-Base Catalysis Of The Enolization Of Acetone, Janet Louise Larson

Undergraduate Honors Theses

Measurements are reported on the rate of iodination of acetone at 25°c in arsenate, phosphate, and diethylmalonic acid buffers at a constant ionic strength of 0.2. Unlike earlier results which indicate that in acetic acid buffer the expression for the reaction velocity contains an appreciable kinetic term involving the product of the concentrations of acid and anion, it has been found from the present work that such a term is experimentally immeasurable for the above mentioned buffers. This finding coupled with the relatively powerful catalysis by the phosphate and arsenate dianions could imply the simultaneous participation of these species in …

The Isoelectronic Principle And The Accuracy Of Binding Energies In The Hückel Method, Jerry Goodisman

Chemistry - All Scholarship

In the Hükkel and other methods, binding energies are calculated by subtracting the sum of orbital electronic energies for the molecule from the sum of orbital electronic energies for the separated atoms, and not considering the internuclear repulsion. Since this last may be several orders of magnitude greater than the binding energy, reasonable results could not be obtained without an approximate cancellation with another neglected term. It is shown that such a cancellation is a consequence of the isoelectronic principle (invariance of binding energy to change in atomic number of constituent atom). Numerical examples are given.

Syntheses Via Modifications Of The Knorr-Paal Procedure :|Ba. Derivatives Of 2,6-Dioxa-10-Azatricyclo[5.2.1.0[Superscript 4,10]]Decane ; B. Highly Sterically Crowded 1,2,5-Trialkylpyrroles And Pyrrolidines, Weldron Severin Burnham

Theses and Dissertations

Earlier work in these laboratories on the heterotricyclic system 2,6-dioxa-10-azatricyclo[5.2.1.04,10]-decane, formed from 1,4-diketones and 2-amino-1,3-propanediols by a product-water-azeotroping procedure, was extended with the synthesis of analogous compounds, e.g., the 1,4,7-triethyl-, 1,7-dimethyl-4-isopropyl-1,7-diethyl-4-isopropyl-, 1,7-dimethyl-3- and 4-phenyl- compounds. The 1,7-dimethyl heterotricycle, the kinetically-controlled product, was accompanied by the thermodynamically-controlled product, 2-(2,5-dimethyl-1-pyrryl)-1,3-propanediol. The 1,7-diethyl heterotricycle was also accompanied by the isomeric pyrrole as were the 1,7-dimethyl-3- and 4-phenyl compounds. A scheme postulating a common intermediate is presented. The interesting analogous compounds, 1,7-dimethyl-2-oxa-6-thia-10-azatricyclo[5.2.1.04,10]decane, 1,4,7-trimethyl-2,6-dioxa-11-azatricyclo[5.3.1.04,11]undecane and 11-hydroxymethyl- and 11-methyl-9,13-dioxa-14- azatetracyclo[6.5.1.02,7 011,14]tetradeca-2,4,6-triene were also prepared. The syntheses in good yields of a considerable number of moderately to …

The Preparation And Determination Of Some Of The Properties Of The Dicarboxylic Amino Acid Chelates Of Platinum(Ii) And Palladium(Ii), Gordon Harold Williams

University of the Pacific Theses and Dissertations

It is surprising that no one has considered that coordination might have some effect on the strength of the acid group. It is the intent of this study to fill this gap in the knowledge of amino-acid chemistry.

At about the time this study began on the effect of chelation on the strength of the uncomplexed acid group, the next two higher homologs of these dicarboxylic amino acids became commercially available. It was, therefore, decided that the problem of this research should be expanded to include all four of the acidic amino acids.

The research problem was also defined to …

The Reaction Of Ethylenediamine With Cobalt (Ii) Perchlorate And Oxygen In Dilute Aqueous Solutions, Robert J. Karmy

All Master's Theses

Cobalt (II) perchlorate was reacted with ethylenediamine and molecular oxygen. Various mole ratios of ethylenediamine to cobalt (II) were oxygenated and studied by photometric, potentiometric, conductometric, magnetic susceptibility, freezing point depression, electron spin resonance and cobalt (II) extraction methods. The fact that the complex was brown in color, diamagnetic, contained ethylenediamine to cobalt to oxygen in a mole ratio of 4:2:1 was confirmed. The complex underwent elation to form a polymeric species with excess base. The complex could not be oxidized to a green paramagnetic complex by reacting it with sodium peroxydisulfate, potassium bromate, bromine or chlorine. Ammonia was added …

Preparation Of Phenylsulphur Chloride Tetrafluoride, Dennis T. Sauer

All Master's Theses

The reaction of C6H5SF3, CSF and C12 was studied under a variety of conditions. The reaction run in the presence of a trace of water yielded C6H5SO2F and C1C6H4SO2F. The reaction run in stainless steel at 170°C yielded an amber solid believed to be a polymer with the empirical formula C6H3.67SF2. Chlorination of a C6H5SF3-CSF mixture in monel at 220°C yielded a yellow liquid tentatively identified as a mixture of the new species C6H5SF4C1, FC6H4SF4C1 and C1C6H4SF4C1.

A Polarographic Study Of Substituent Effects In Nickel(Ii)-Complex Ions Of Pyridine And Pyridine Derivatives, Keith Edward Fester

University of the Pacific Theses and Dissertations

The electrochemical technique of polarography was used to study the complexions formed by Ni(II) ion and pyridine compounds. It was of interest to vary the substituent group on the pyridine ring in order to observe the effects on the nickel - nitrogen coordinate bonds.

Determination Of Flow Curves From Capillary Rise Rate Measurements, Richard Lehr Kissling

University of the Pacific Theses and Dissertations

The measurement of viscosity is a common and useful technique for investigating the mechanical behavior of many real fluids. Theoretical interpretations of viscosity measurements have been important in attempts to elucidate fundamental properties of the liquid state. Brush (6) and Bondi (3) give reviews of the current status of attempts to construct theories of liquid viscosity, and it is quite apparent from these reviews that the molecular theory of rheological phenomena is in its infancy.

In addition to the fundamental aspects of viscometry, there are many practical applications to which viscosity measurements are directed (25). One has only to scan …