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Thermal Decomposition Kinetics Of Iodine‐Doped Polyacetylene In Vacuum, J. ‐E Osterholm, H. Yasuda, L. L. Levenson

Physics Faculty Research & Creative Works

The thermal stability of iodine‐doped polyacetylene films, (CHIy)x, has been studied by means of electrical conductivity measurements, measurements on weight loss, and mass spectrometric analysis of desorbing species. When heated between room temperature and 125°C in vacuum, these films proved to be of poor thermal stability, being unstable at temperatures above 20°C. During the thermal treatments, molecular iodine desorbs from the films, resulting in an appreciable dopant weight loss with accompanying decrease in the electrical conductivity. The decomposition process does not follow simple kinetics. Copyright © 1983 John Wiley & Sons, Inc.

Evaluation Of A New Silicone-Methane Polymer Contact Lens, Jeffrey E. Koziol, Gholam A. Peyman, Hirotsuga Yasuda

Chemistry Faculty Research & Creative Works

A new gas permeable contact lens is produced using a solid silicone core and a plasma polymer surface. This surface is hydrophilic and impermeable to macromolecules. The surface characteristics of this lens were compared with the surface characteristics of available silicone contact lenses. We found that in contrast to our lens, the silicone contact lenses lost their hydrophilic surface with time. In addition, they are permeable to lipid dyes, eg, Sudan red. © 1983 Arch Ophthalmol All rights reserved.

Intermolecular Interactions For Phosphatidyl Choline And Phosphatidyl Ethanolamine, Tony Flaim, Stig Friberg, Patricia L.M. Plummer

Chemistry Faculty Research & Creative Works

Intermolecular interaction between pairs of methylphosphocholine (MPC) and methylphosphoethanolamine were calculated using an extended CNDO/2 program. Experimentally determined conformations were used for the ethanolamine and choline groups. In the methylphosphocholine the major interaction was intramolecular, involving the phosphate ester-choline groups, while in the ethanolamine the maximum attraction was intermolecular between the ethanolamine and the phophate ester of a neighboring molecule(s). © 1983.

Metal Ion Oxidative Decarboxylations. 13.¹ Kinetics And Mechanisms Of The Oxidation Of N-Benzyliminodiacetic Acid With Cerium(Iv) In Acidic Perchlorate And Acidic Sulfate Media2, Samir B. Hanna, Marilyn E. Moehlenkamp

Chemistry Faculty Research & Creative Works

The Ce(IV)-mediated decarboxylation of N-benzyliminodiacetic acid (BIDA) produces benzaldehyde, formaldehyde, dimethylamine, benzylmethylamine, and N-benzylglycine in acidic perchlorate and acidic sulfate media. Spectrophotometric evidence of an intermediate Ce(IV)-BIDA complex is given. The data may be interpreted in terms of a mechanism which involves sequential reactions, the first of which is a reversible reaction: BIDA + Ce(IV) (k1) ⇄ (k-1) complex (k2) → products. The rapid complex formation is followed by a slower oxidative decomposition to give a free radical capable of inducing free-radical polymerization. The free radical reacts rapidly with another Ce(IV) to give an iminium ion which undergoes either hydrolysis …

Analysis Of Clay Minerals, Other Silicate And Nonsilicate Minerals, And The Grading Of Chrysotile Asbestos By Attenuated Total Reflection Infrared Spectrophotometry (With Atlas), Ashraf Muhammad Chaudhry

University of the Pacific Theses and Dissertations

This study of ATR-IR involved taking spectra of various silicate minerals in powder samples, finding similarities and differences in nature, and locating various bands and intensities of absorption bands for identification and classification purposes. This study is limited to 4000-300 cm^-1 with major emphasis on absorptions in the 2000-300 cm^-1 region.

The Theory And Synthesis Of [2.2.2] Propellane, Theodore Mark Prociv

Dissertations, Theses, and Capstone Projects

INDO calculations indicated that the triplet state of dimethylene cyclohexane could rearrange to gometrically relaxed triplets which should collapse preferentially to the ground state [2.2.2] Propellane. A mercury sensitized photolysis of the dimethylene cyclohexane did in fact result in detectable quantities of the propellane, trapped as 1,4 dibromobicyclo octane. Synthesis of 1,4 dibromobicyclo octane and 1,1,6,6 tetradeuterodimethylene-cyclohexane are presented in the dissertation. Included in the dissertation are the results of INDO calculations of various propellane isomers having nitrogens and borons in the bridgehead positions.

Xanes In (Tmtsef)2re04: Polarization Dependence Of The Se K-Edge, Juana Acrivos

Faculty Publications, Chemistry

We have measured XANES (X-ray Absorption Near Edge Spectra) near the Re Li(i=l,II,III) edges in (TMTTF)2Re04 and (TMTSeF)2Re04 and the Se K edge in the latter compound. An important dependence of the XANES at the Se K edge on the polarization of the incident beam with respect to the crystal axes was observed, whose interpretation can give information on the symmetry of the unoccupied conduction band states. The positions of the Re L edges were compared with those in several .inorganic compounds containing Re in various oxidation states, and were found to be, within experimental error, the same as those …

Kinetic And Spectral Studies Of Cobalt (Ii) -4, 4’, 4’’, 4’’’ –Tetrasulfophthalocyanine With Sodium Cyanide In Aqueous Solution, Pablo J. Diaz Cruz

Masters Theses & Specialist Projects

Kinetic studies of the cobalt (II)-4, 4’, 4’’, 4’’’-tetrasulfophtalocyanine and cyanide system were performed under argon and in air over temperature ranges of 294-314°K and 294-324°K, respectively. Two reactions were detected under argon. One was quite rapid and was followed on the stopped-flow apparatus. The results are consistent with the perturbation of a monomer-dimer equilibrium. The second reaction was slow enough to be followed spectrophotometrically on the Cary Model 14 spectrophotometer. The second order rate constant of 0.11 M^-1 sec^-1 at 294°K has been attributed to the rate of substitution of the second cyanide addition to a dye-cyanide …

Oxidation Activity Of Catalyst 3-7a Toward Formaldehyde, Hydrogen Cyanide, And Some Alkane Gases, John Kawas

Masters Theses & Specialist Projects

The activity of Catalyst 3-7A toward the oxidation of formaldehyde, hydrogen cyanide, methane, propane, and isobutene was examined at temperatures between 25°C and 400°C. The catalyst consists of palladium(II) and copper (II) salts impregnated on an alumina support. The oxidation measurements were made primarily with gas chromatographs, although form aldehyde and hydrogen cyanide were also examined using the colorimetric fushsin method and Liebig titrations, respectively. Catalyst 3-7A demonstrated appreciable activity toward the oxidation of all gases studied except formaldehyde where there was no evidence of oxidation. The latter result is quite unexpected since aldehydes are more easily oxidized than alkanes. …

Calculated Electrocapillary Curve For A Molten Salt, Jerry Goodisman, S Amokrane

Chemistry - All Scholarship

If bulk properties of simple molten salts may be reasonably well understood in terms of the primitive model, the situation with respect to surface properties is less satisfactory. It has been shown that a simple model for the distributions at the free surface of a molten salt can give surface tension and surface energy in reasonable accord with experiment, provided that a factor guaranteeing local electroneutrality is introduced. In this model, properties are given in terms of bulk-salt distribution functions, for which the primitive model is used. The present work extends this model to the electrocapillary curve, i.e., variation of …

Kinetics Of Ternary Complex Formation Reactions Of The Nickel(Ii) Complexes Of Ethylenediaminediacetate And Triethylenetetramine With Bidentate Donors, Lawrence H. Kolopajlo

Dissertations

The stopped-flow technique was used to measure rate constants for ternary complex formation involving both NiEDDA and Ni(trien)('2+), and bidentate donors. The reactions of both NiEDDA and Ni(trien)('2+) with bipy, phen, en, and sar were studied. In addition the reaction of NiEDDA and gly was studied. The reactions were of the first-order with respect to either nickel complex, and with respect to enH('+), bipy, and phen. The reactions involving phen and bipy were independent of pH and were reversible. The formation rate constants for the systems containing diamine reactants are as follows:

(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI)

For …

Determination Of Organophosphorus Compounds By Hplc With Post-Column Photochemical Degradation Followed By The Formation Of Reduced Heieropolymolybdate, Stephen R. Priebe

Dissertations

A novel method for the determination of organophosphorus (OP) compounds by HPLC with post-column photochemical and chemical derivatization reactions has been developed. The OP compounds eluted from the column were photochemically degraded to orthophosphate by the use of a 450 W xenon lamp in conjunction with an auxiliary photodegradation reagent. The photodegradation reaction was studied extensively by means of batch irradiations with triethylphosphate as a model compound. The effects of the initial concentrations of triethylphosphate and ammonium peroxydisulfate, and of varying the pH of the reaction medium were determined. A survey of potential interferences was performed. Copper(II) ion was found …

Spermidine-Condensed Phi X174 Dna Cleavage By Micrococcal Nuclease: Torus Cleavage Model And Evidence For Unidirectional Circumferential Dna Wrapping., Kenneth A. Marx, Thomas C. Reynolds

Dartmouth Scholarship

Spermidine-condensed phi X174 replicative form (RF) II DNA was digested with micrococcal nuclease to yield seven identifiable DNA bands forming an arithmetic fragment-length series. The DNA monomer unit length was found to be 780 +/- 80 base pairs. This result is most consistent with a proposed model for micrococcal nuclease cleavage of a DNA torus organized by the unidirectional, circumferential wrapping of B-geometry DNA. By a topological consideration, the blunt-end-rod-fusion model for torus formation [Eickbush, T. H. & Moudrianakis, E. N. (1978) Cell 13, 295-306] is shown to be inconsistent with our empirical solution results. We propose a continuous, circumferential …

Self‐Consistent Molecular Orbital Methods. Xxiii. A Polarization‐Type Basis Set For Second‐Row Elements, Michelle M. Francl, William J. Pietro, Warren J. Hehre, J Stephen Binkley, Mark S. Gordon, Douglas J. Defrees, John A. Pople

Chemistry Faculty Research and Scholarship

The 6‐31G* and 6‐31G** basis sets previously introduced for first‐row atoms have been extended through the second‐row of the periodic table. Equilibrium geometries for one‐heavy‐atom hydrides calculated for the two‐basis sets and using Hartree–Fock wave functions are in good agreement both with each other and with the experimental data. HF/6‐31G* structures, obtained for two‐heavy‐atom hydrides and for a variety of hypervalent second‐row molecules, are also in excellent accord with experimental equilibrium geometries. No large deviations between calculated and experimental single bond lengths have been noted, in contrast to previous work on analogous first‐row compounds, where limiting Hartree–Fock distances were in …

Separation Of Piperylene Concentrate Via Metathesis Catalysis, Donald R. Allred

Retrospective Theses and Dissertations

Diolefin metathesis, using a Re2O7 catalyst, failed to show a reactivity difference due to conjugation of double bonds. However, the same system allows reaction of pentadiene while not affecting cyclopentene yielding a successful reaction ΓÇô separation scheme for a piperylene concentrate mixture.

Excluded-Volume Effect On Quasi-Elastic Light Scattering By Flexible Macromolecules, Genzo Tanaka, Walter H. Stockmayer

Dartmouth Scholarship

First-order perturbation expressions are developed for the first cumulant (initial time derivative) of the dynamic structure factor observable by photon-correlation measurements of the light scattered by flexible chain molecules in solution. A dimensionless coefficient C, which measures the initial departure of the first cumulant from proportionality to the square of the scattering vector, is found to be only slightly altered by excluded-volume effects.

Isolation And Characterization Of The Serum Ferroxidase Inhibitor, Melissa Page Calisch

Master's Theses

strong evidence suggests that the serum ferroxidases (ceruloplasmin andferroxidase II) promote the formation of Fe-III transferrin and thereby stimulate the turnover of iron from tissue stores. Ceruloplasmin is the major ferroxidase in human serum; whereas, ferroxidase II accotmts for an increased proportion of the activity in less highly developed animals. A large fold increase in total ferroxidase II activity was observed when both human and rabbit sera were subjected to gel-filtration on sephadex G-200. This indicated that whole serum might contain a potent inhibitor of ferroxidase II. Such an inhibitor has been isolated and purified to homogeneity by a combination …

24th Rocky Mountain Conference

Rocky Mountain Conference on Magnetic Resonance

Abstracts and meeting program from the 24th annual meeting of the Rocky Mountain Conference, co-sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy and the Rocky Mountain Chromatography Discussion Group. Held in Denver, Colorado, August 1-5, 1982.

Micellarly Catalyzed Reaction Of Substituted Benzohydroxamic Acids, Nop Utrapiromsuk

Dissertations

The rate constants for hydrolysis of ten derivatives of benzohydroxamic acid, namely, p-H, p-CH(,3), m-CH(,3), p-CH(,3)CH(,2), p-OCH(,3), p-NO(,2), p-Cl, and m-Cl, in 0.160 and 0.158 M HCl at 67.9-68.2(DEGREES)C without and with sodium 1-dodecanesulfonate were determined. There is a good linear correlation between log k(,w) and the Hammett substituent constants, (sigma), for all para and meta derivatives where k(,w) is the rate constant in the bulk aqeous phase. In the presence of micelles all the compounds, except the meta-nitro derivative, followed the standard pseudophase model of micellar catalysis. However, correlations of log k(,m) or log K/N, where k(,m) is the …

An Investigation Of Cadmium And Sulfur Reactions In Dimethylsulfoxide, Howard W. Hogle

Dissertations and Theses

The study of the reaction of cadmium and sulfur in dimethylsulfoxide (DMSO) is presented. Specifically, the reaction of dissolved molecular sulfur in DMSO at temperatures greater than 90°C with freshly precipitated metallic cadmium is followed by UV-visible spectrometry, atomic absorption spectrometry, and Raman spectrometry. Evidence for the formation of a new cadmium-sulfur species and S₃^- is discussed. In a second reaction, an equilibrium sodium polysulfide solution in DMSO is titrated with a solution of cadmium ion at room temperature and the reaction progress is followed by means of UV-visible spectrometry. A calculation of the average number of polysulfide …

Hydroxide Binding Equilibrium In Hemerythrin, John David Mccallum

Dissertations and Theses

The measurement of the equilibrium constant and the thermodynamic parameters of the binding of hydroxide ions to the active site of hemerythrin, an invertebrate iron containing protein, was done by a new difference spectroscopic method. The method enables accurate measurements of equilibrium constants without accurate knowledge of molar absorptivities or protein concentrations and is novel in that it takes the difference between the two equilibrium mixtures, thus enabling the measurement of equilibrium constants when it is not convenient or possible to produce either substance as a pure reference material.

The Kinetics Of Oxidation Of Various Organic Substrates By Potassium Ferrate, Ronald Lee Bartzatt

Department of Chemistry: Dissertations, Theses, and Student Research

Potassium ferrate is a strong oxidizing agent and highly soluble in water. These properties may allow it to oxidize a wide variety of aqueous organic compounds to simpler organic compounds. The kinetics and final products of typical ferrate oxidations must be studied before conclusions about its efficiency can be drawn.

The ferrate oxidation of diethylsulfide and 2,2-thiodiethanol were studied in a pH range of 8.90 to 9.90. Their plots of Log k_s versus pH are essentially parallel and show mixed-order characteristics. The order of dependence of diethylsulfide on [H⁺] is 0.708. The order of dependence of 2,2-thiodiethanol …

Analysis Of Organic N-Chloramines In Chlorinated Drinking Water, John Po Wen Yang

Chemistry & Biochemistry Theses & Dissertations

This thesis describes the development of a sensitive method for the separation and quantitation of organic N-chloramines in chlorinated tap water. 5-Dimethylaminonaphthalene- l-sulfinic acid has been synthesized and characterized. It yields highly fluorescent dansyl derivatives on reaction with N-chloramines. Conditions of the derivatization were optimized for the detection of N-chloropiperidine at concentrations in aqueous solution of 10^-7 M. The technique gives a quantity of derivative which is proportional to the concentration of chloramine present over the range examined (10^-7 M to 10^-4 M). High pressure liquid chromatographic separation of dansyl derivatives of amines and amino acids has …

Binary Collision Dynamics And Numerical Evaluation Of Dilute Gas Transport Properties For Potentials With Multiple Extrema, James C. Rainwater, Paul M. Holland, Louis Biolsi

Chemistry Faculty Research & Creative Works

Prediction of gaseous transport properties requires calculation of Chapman-Enskog collision integrals which depend on all possible binary collision trajectories. The interparticle potential is required as input, and for a variety of applications involving monatomic gases the Hulburt-Hirschfelder potential is useful since it is determined entirely from spectroscopic information and can accomodate the long-range maxima and minima found in many systems. Hulburt-Hirschfelder potentials are classified into five distinct types according to their qualitative binary collision dynamics, which in general can be quite complex and can exhibit “double orbiting”, i.e., a pair of orbiting impact parameters for a single energy of collision. …

Development Of An On-Line Computer System For Enzyme Kinetics Studies, Jacqueline R. Thweatt

Chemistry & Biochemistry Theses & Dissertations

The PDP-11/10 minicomputer was interfaced to the Beckman 25 ultraviolet/visible spectrophotometer and this on-line computer system was applied to enzyme kinetics studies. This interface involved hardware equipment to locate, amplify, and transmit the analog signal to an analog-to-digital converter, and software to acquire and store the digital data. Data processing programs were used to calculate kinetic parameters and statistical information from the acquired data.

The Varian Cary 219 ultraviolet/visible spectrophotometer can be readily interfaced to the Apple II Plus microcomputer by hardware equipment which can be purchased from the manufacturer. Various software may also be purchased for use in enzyme …

Development, Verification And Use Of Methods To Model Chemical And Thermal Processes For Lakes Mead And Powell, John Eric Edinger, Edward M. Buchak, Joseph S. Norton, Bureau Of Reclamation

Publications (WR)

Analysis and development of carbonate-bicarbonate chemical subroutine.

Investigation Of The Role Of Phenols In Oxidative Degradation Of Coal-Derived Naphthas, Jeffrey Macke

Masters Theses & Specialist Projects

The oxidative instability of coal liquids is a possible problem for the utilization of these alternate fuels. Past experience with both petroleum and coal-derived distillates indicates that heteroatomic species are intimately involved in such degradation. However, the exact nature of the chemistry is, in many cases, unclear. The goal of this work is to study the role of phenols in the chemistry of oxidative degradation of naphthas from a variety of current conversion processes. The effects of exposure to oxygen, metal surfaces, and metal salts have been investigated in order to identify the major routes leading to gum formation.

Coal-derived …

Initiation Of Protein Synthesis In Eukaryotes. Nature Of Ternary Complex Dissociation Factor., John Siekierka, Asis Datta, Ljubica Mauser, Severo Ochoa

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

Excessive concentrations of the eukaryotic initiation factor 2(eIF-2).stimulating protein, a factor that catalyzes the formation of binary (GTP.eIF-2) and ternary (GTP.eIF-2.initiator methionyl-tRNA) initiation complexes at physiological Mg2+ concentrations, can cause ternary complex dissociation when the Mg2+ concentration is raised from 0.5 to 5.0 mM. Stimulation of ternary complex formation and dissociation have similar (a) pH optima, (b) metal ion specificity, and (c) sensitivity to phosphorylation of the eIF-2 alpha subunit. The results suggest that ternary complex dissociation is an artifact with no physiological significance.

Trace Analysis Of Uranium By Laser Induced Fluorescence Excitation ( Life ), R. Kenneth Marcus

Theses & Honors Papers

No abstract provided.

The Impact Of Solid State Science In Our Society, Juana Acrivos

Faculty Publications, Chemistry

No abstract provided.