Physical Sciences and Mathematics Commons^™

Mott G-Ratios In Rbx(Nh3)1-X And Oxidation State Of Rubidium Compounds From Xas, Juana Vivó Acrivos, K. Hathaway, A. Robertson, M. P. Klein, A. Thompson

Faculty Publications, Chemistry

The x-ray absorption spectra (XAS) of Rb metal, Rh,("JH,J, ,, 2H-NbSe2Rb111x and RbBr near the Rb K-edge have been used to ascertain that the oxidation state V of rubidium dissolved in ammonia and intt:rcalated in the layer compound is in the range 0 < V < I. Theobservededge shifts with temperature for semimctals are explainedin terms of the population of band states, and the ratio of the density states near the mobility edge over that calculated for a free electron model, i.e. the Mott ratio g, is ascertained using a semiempirical relation developed for the x-ray absorbance from Is levels to empty states ncar the mobility edge.

Effect Of Solvent On Properties Of The Liquid Metal Surface, J. P. Badiali, M. I. Rosinberg, Jerry Goodisman

Chemistry - All Scholarship

We calculate the difference in the surface potentials between the free surface of a liquid metal and the same metal in an ideally polarizable interface at the point of zero charge. This difference, δXm, is due to the deformation of the electronic cloud of the metal by the solvent molecules. The simple model used for the free (metal-metal vapor) surface yields qualitatively correct work functions for a number of metals (Hg, Cd, In, Zn, Pb, Ga, A1). Two simple ways to model the metal-solvent interaction are proposed and calculations of δXm made for each. One, the dielectric film model, considers …

Effects Of N2h4 On The Transition Temperature In The Anisotropic Superconductor Tase3, K. Yamaya, T. H. Geballe, Juana Vivó Acrivos, J. Code

Juana Vivó Acrivos

No abstract provided.

Mott G-Ratios In Rbx(Nh3)1-X And Oxidation State Of Rubidium Compounds From Xas, Juana Vivó Acrivos, K. Hathaway, A. Robertson, M. P. Klein, A. Thompson

Juana Vivó Acrivos

The x-ray absorption spectra (XAS) of Rb metal, Rh,("JH,J, ,, 2H-NbSe2Rb111x and RbBr near the Rb K-edge have been used to ascertain that the oxidation state V of rubidium dissolved in ammonia and intt:rcalated in the layer compound is in the range 0 < V < I. Theobservededge shifts with temperature for semimctals are explainedin terms of the population of band states, and the ratio of the density states near the mobility edge over that calculated for a free electron model, i.e. the Mott ratio g, is ascertained using a semiempirical relation developed for the x-ray absorbance from Is levels to empty states ncar the mobility edge.

Glow Discharge Polymerization., H. Yasuda

Chemistry Faculty Research & Creative Works

In this review-paper the author summarizes some important aspects of ″polymer formation″ in the glow discharge polymerization or plasma polymerization, rather than presenting a bibliographical review of work. It is shown that glow discharge polymerization can be visualized as a process consisting of three discharge processes. These are (1) controlled discharge of monomer, (2) electric discharge (glow discharge), and (3) glow discharge polymerization of the monomer. Before the electric discharge is initiated, a steady-state flow of the monomer is generally established. During this controlled discharge of the monomer (without electric discharge), adsorption of the monomer onto the solid surfaces in …

The Initial And Terminating Stage Of Glow Discharge Polymerization Investigated By Thickness Monitor, N. Inagaki, H. Yasuda

Chemistry Faculty Research & Creative Works

An attempt to discuss the initial stage and terminating stage of glow discharge polymerization was made by selecting the monomer system of styrene and acetylene, which differ in their condensability, and a certain polymerization procedure. Results indicate the important aspects of the initial and terminating stages of glow discharge polymerization. These aspects may not play a significant role in the study of bulk properties of plasma‐polymerized polymers or in the study of polymer deposition rate. However, the initial stage effect might influence the adhesion of the polymer. The terminating stage effect might influence the surface characteristics of glow discharge‐polymerized polymers. …

Distribution Of Polymer Deposition In Glow Discharge Polymerization In A Capacitively Coupled System, N. Inagaki, H. Yasuda

Chemistry Faculty Research & Creative Works

The manner by which polymers created by plasma uniformly deposit onto substrates was sought. By rotating the substrate placed midway between electrodes, completely uniform distribution of polymer deposition was accomplished, and the deviation of the polymer deposition in a radius direction of the rotating substrate was within experimental errors. Materials of the substrate on which the polymer deposited had no influence on uniformity of polymer deposition, but the electrical circuit of power source, i.e., grounding an electrode, markedly disturbed the uniformity. Thickness of polymers deposited on the substrate was linearly proportional to reaction time. Surface energies of deposited polymers prepared …

The Effect Of Plasma-Deposited Polymers On The Nucleate Boiling Behavior Of Copper Heat Transfer Surfaces, T. Hinrichs, E. Hennecke, H. Yasuda

Chemistry Faculty Research & Creative Works

The effect of plasma deposited polymers on the nucleate boiling behavior of copper heat transfer surfaces, using water as the boiling liquid, was determined. The monomers used were tetrafluoroethylene (TFE) and methane. It was found that an 18 nm thick coating of TFE enhanced the nucleate boiling, while a 150 nm thick coating reduced the nucleate boiling. Both 15 nm and 150 nm thick coatings of methane reduced the nucleate boiling, with the effect being more pronounced with the thicker coating. A surface energy effect is postulated to explain the enhanced boiling observed. © 1981.

The Structure Of Lamellar Lyotropic Liquid Crystals From Lecithin And Alkanediols, Magda A. El-Nokaly, Larry D. Ford, Stig Friberg, David W. Larsen

Chemistry Faculty Research & Creative Works

Lamellar liquid crystals from lecithin and alkane diols were studied to determine the composition range of stability and geometrical dimensions using low-angle X-ray scattering. An estimation of the dislocation pattern was made from the optical pattern in polarized light. The ethylene glycol gave the widest range of stability for the lamellar structure, the range being reduced toward heptane diol, the longest member to give liquid crystals. The interlayer spacing was reduced with increasing chain length of the diol and the dislocation pattern remained identical. © 1981.

Collisional Depolarization Of State Selected (J,M J ) Bao A 1Σ+ Measured By Optical–Optical Double Resonance, Stuart J. Silvers, Richard A. Gottscho, Robert W. Field

Chemistry Publications

The optical–optical double resonance (OODR) technique is used to investigate the change in magnetic quantum number (M) a state selected molecule undergoes on collision with other molecules. A first linearly polarized dye laser prepares A  ¹Σ⁺BaO(v = 1) in the J = 1, M = 0 sublevel. The extent of collisional transfer to other M sublevels of both J = 1 and J = 2 is then probed by a second polarized dye laser which induces fluorescence from the C  ¹Σ⁺ state. Elastic collisions (ΔJ = 0) between BaO (A …

Conduction Band Symmetry In Ta Chalcogenides From Ta L Edge X-Ray Absorption Spectroscopy (Xas), Juana Vivó Acrivos, S.S. P. Parkin, J. Code, J. Reynolds, K. Hathaway, H. Kurasaki, E. Marseglia

Juana Vivó Acrivos

No abstract provided.

Similarity In Phase Diagrams Between Ionic And Nonionic Surfactant Solutions At Constant Temperature, K. Shinoda, H. Kunieda, N. Obi, Stig Friberg

Chemistry Faculty Research & Creative Works

No abstract provided.

Adhesion Of Glow Discharge Polymers To Metals And Polymers, N. Inagaki, H. Yasuda

Chemistry Faculty Research & Creative Works

Adhesion of glow discharge polymers to metals and polymers in an adhesive joint was measured by lap‐shear test and immersion in hot water of 70°C for an extended time. A glow discharge polymer was deposited onto polymers [polyethylene and poly(tetrafluoroethylene)] and metals (aluminum and stainless steel) prior to when the polymer and metal were joined. It is found that the lap‐shear strength is enhanced by coating the surfaces of these substrates with plasma film produced from methane, ethylene, and acetylene, and that deterioration of the adhesive bonding part, when immersed in hot water of 70°C, is strongly dependent on the …

A Quantitative Test Of Unimolecular Rate Theory In The Multi‐Photon Dissociation Of Cf2Cfcl, John C. Stephenson, Stephen E. Bialkowski, David S. King, Everet Thiele, James Stone, Myron F. Goodman

Stephen E. Bialkowski

We have measured the distribution of total energy in reaction products for the CO₂ laser‐induced MPD: CF₂CFCl→CF₂+CFC1. From a separate study of MPD rates as a function of laser intensity and inert buffer gas pressure, reliable estimates of the radiative pumping rates are known for this reaction. These results, when analyzed together, allow us to extract a unimolecular A factor from the MPD data. The determined value A = 3×10¹⁶ sec⁻¹ agrees well with estimates based on independent thermal data.

Method For Direct Preparation For 1,2,4-Triazole From Hydrazine And Formamide, Harris E. Petree, Joseph R. Pociask, John T. Gupton

Chemistry Faculty Publications

Process for the preparation of 1,2,4-triazole comprises contacting hydrazine or its aqueous solutions with at least about 2.5 moles of formamide at a temperature of 140° to 210° C. and then recovering the resultant 1,2,4- triazole in yields of 92-98% with 94-98% purity. The formamide is maintained in an excess over about the 2.5 molar amount consumed in the reaction with the hydrazine. Recovery steps for isolating the 1,2,4-triazole are disclosed.

Sodium Accumulation In Serpentine And Non-Serpentine Populations Of The Milkweed Asclepias Fascicularis, Paul N. Thomas

University of the Pacific Theses and Dissertations

Because Asclepias fascicularis is found on both serpentine and non-serpentine soils in California and because it was reported to accumulate sodium, this study was initiated to establish the degree of accumulation of this ion in these two soil types. Two other species, Asclepias speciosa Torr. and Asclepias cordifolia (Benth.) Jeps. were included to determine if this characteristic of accumulation occurs in other members of this genus.

Proton Transfers In Hydrogen‐Bonded Systems. Vi. Electronic Redistributions In (N2h7)+ And (O2h5)+, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Electronic rearrangements accompanying transfer of the central proton between the two XH_n units of (H₃NHNH₃)⁺ and (H₂OHOH₂)⁺ are studied using ab initio molecular orbital methods. Electron density difference maps are calculated by subtracting the density of the equilibrium structure (X–H‐‐‐X) from that of the midpoint geometry (X‐‐H‐‐X) using the split‐valence 4‐31G basis set. Some of the features revealed by the maps are common to both systems while others indicate significant differences between nitrogen and oxygen. Decomposition of the total electron density into …

A Matrix Isolation Study Of The Reactions Of Oxygen(Singlet-D) With The Chlorofluoromethanes Fluorotrichloromethane, Dichlorodifluoromethane And Chlorotrifluoromethane, Richard Thomason Burke

University of the Pacific Theses and Dissertations

We have studied the reactions of O(¹D) with CC1₃F, CC1₂F₂ and CC1F₃ in CO₂, SF₆ and N₂O matrices, and in neat mixtures. Photolysis of cryogenic mixtures of ozone and the chlorofluoromethanes in various matrix hosts resulted in production of O(¹D) which migrated through the matrix to react with the Freon molecules. Products were detected by infrared spectroscopy of the matrix deposits, with assignments confirmed by comparison of ¹⁶O and ¹⁸O absorption bands with literature values. Evidence for oxygen atom insertion into a C-C1 …

The Acid-Catalyzed Hydration Of Phenylallene, Gary Wayne Long

Dissertations, Theses, and Masters Projects

No abstract provided.

Interpretation Of Gc-Ms Data By Reverse Search And Relative Retention Indices, Christopher Hein

Dissertations, Theses, and Masters Projects

No abstract provided.

Isolation And Characterization Of Frullanolide From Frullania Franciscana (Howe), Marshall Stuart Sass

Dissertations and Theses

Investigation of the ether extract of the liverwort Frullania franciscana (Howe) resulted in the isolation of the sesquiterpene lactone frullanolide. The separation techniques of thin-layer chromatography, dry column chromatography, and liquid column chromatography were evaluated. Only liquid column chromatography was found useful. Fractions from alumina liquid column separations had infrared spectra which resembled the published spectrum of frullanolide. The identity of the compound obtained from F. franciscana (Howe) was established after extensive purification by comparison of its infrared and nuclear magnetic resonance spectra with published spectra of frullanolide.

Spectroscopic Studies Of Pre-Mixed Hydrocarbon Flame Plasmas, Tsao-Chin C. Huang

Masters Theses

This thesis contains two different studies.

Chapter 1, "Infrared Emission Spectrum of the Hydroxyl Radical.", is in collaboration with Dr. Giles L. Henderson and Mr. Chun-Sheng Ko. This chapter has been submitted and accepted for publication by the Journal of Chemical Education.

In this chapter, we describe a rather novel physical chemistry experiment in which ab initio potential parameters for the OH radical are compared with those obtained from the ir emission spectrum of an oxy-acetylene welding torch.

Chapter 2, "A Preliminary Spectroscopic Study of Field-Induced Ion Movements in Flame Gases.", describes the effects of longitudinal electric fields on CH …

Pyridine Hydrogen Iodide As An Ether Cleaving Agent In Coal Chemistry, Agnes Mei-Ying Chen

Masters Theses

Reactions of several phenyl ethers and an ester with pyridine hydrogen iodide were examined under various conditions as model studies for the recently reported molecular weight reduction of a fraction of Illinois No. 6 coal by hydrogen iodide in pyridine at 50°.

No ether or ester cleavage was observed at 60-80° in pyridine, acetonitrile, ethanol or the absence of solvent. Sealed tube reactions at 210° resulted in cleavage to phenol plus various hydrocarbon and alkyl halide products. Pyridine and benzyl phenyl ether at 210° produced no cleavage in the absence of hydrogen iodide.

Syntheses of crystalline pyridine hydrogen iodide and …

Controlling The Number Of Metal Sites To Which A Polytertiary Phosphine Coordinates In Tungsten Carbonyls, Rodney D. Borger

Masters Theses

Judiciously selected coordinated fragments of Ph₂PCH₂CH₂PPhCH₂-CH₂PPh₂ [(OC)₅WPPh₂H, (OC)₅WPPh₂CH=CH₂ and (OC)₅WPPh(CH=CH₂)₂] were used to construct its five possible nonchelated pentacarbonyltungsten complexes. These are the trimetallic (OC)₅WPPh[CH₂CH₂PPh₂W(CO)₅]₂ and the two pairs of constitutional isomers, (OC)₅WPPh[CH₂CH₂PPh₂]₂ and (OC)₅WPPh₂CH₂CH₂PPhCH₂CH₂PPh₂, and PPh[CH₂CH_{2 …}

Analysis Of Coal Fractions Using Dibromotriphenyl-Phosphorane: A Selective Ether Cleaving Reagent, Michael L. Ballard

Masters Theses

Dibromotriphenylphosphorane (DTP), in acetonitrile at 40°C, was found to cleave benzyl phenyl ether in preference to di-alkyl or other aryl alkyl ethers. Competition between 10 mmoles benzyl phenyl ether and 10 mmoles di-n-octyl ether for 0.92 mmole of DTP gave 48% cleavage of benzyl phenyl ether and 1.3% cleavage of di-n-octyl ether based on DTP. Reaction of benzyl phenyl ether and di-n-octyl ether separately with DTP at 40°C produced 80% and 8% cleavage, respectively. Reactions of DTP with diphenyl ether, butyl phenyl ether, phenyl cyclohexyl ether and benzyl benzoate at 40°C produced less than 3% cleavage in all cases.

Reaction …

Cis Labilization: A Study Of The Reactions Of Group 6 Pentacarbonyl Phosphido Anions, Matthew J. Madigan

Masters Theses

The synthesis of cis-(OC)₄M(PPh₂H)L (M=Cr,Mo,W; L=PPh₃,PPh₂Et,PPhEt₂,PEt₃) can be achieved by treating (OC)₅MPPh₂H with potassium tert-butoxide in the presence of L. […] The products are easily isolated and are not contaminated with trans isomers. Obtained as a minor product is [(OC)₄MPPh₂]₂.

The reaction of (OC)₅WPPh₂H with potassium tert-butoxide generates [(OC)₅WPPh₂]^- which reacts with (OC)₅WPPh₂H to give [(OC)₅WPPh₂W(CO)₅] …

Neutron Activation Analysis Of Nuclides From Stellar And Man-Induced Nuclear Reactions, Lawrence Lee Oliver

Doctoral Dissertations

"Neutron activation and γ-counting were used to determine the relative abundances of six stable tellurium isotopes in the acid-etched residues of the Allende meteorite. The results were correlated with the isotopic compositions of xenon and the elemental abundances of helium and neon in similarly prepared residues. Nucleosynthesis appears to be the only viable explanation for the anomalous isotopic and elemental compositions observed in these residues. Our results suggest that the solar system condensed from an isotopically and chemically zoned nebula that was produced by the explosion of a supernova, concentric with the present sun.

A combination of neutron activation and …

Ring Strain In Cyclopropane, Cyclopropene, Silacyclopropane, And Silacyclopropene, Mark S. Gordon

Mark S. Gordon

The strain energy in four three-membered rings is calculated by using the appropriate isodesmic reactions. Calculations with and without d functions on the heavy atoms indicate that while these polarization functions tend to reduce ring strain, the addition of d orbitals has little effect on the predicted trends. While introduciton of unsaturation drastically increases the strain in the carbon system (cyclopropane---. cyclopropene), this is not the case for silicon (silacyclopropane--+ silacyclopropene). As a result cyclopropane and cyclopropene are predicted to be the least and most strained rings, respectively.

Centers Of Polymer Research; Polymer Science In Silesia, Poland:Gliwice, Zabrze, Otto Vogl, W. Pradellok

Otto Vogl

No abstract provided.

Thermal Decomposition Kinetics Of Asf5-Doped Polyacetylene In Vacuum, T. Inoue, J. E. Osterholm, H. Yasuda, L. L. Levenson

Physics Faculty Research & Creative Works

Electrical conductivity measurements, mass spectra of desorbing species, and ESCA surface analysis are reported for AsF5-doped polyacetylene heated between 50 and 130°C in vacuum. All measurements indicate first-order decomposition kinetics with activation energies between 13 and 20 kcal mole-1. Decomposition leads to the desorption of AsF3 and F2. Metallic arsenic remains in the polyacetylene as a decomposition by-product.