Physical Sciences and Mathematics Commons^™

Synergistic Effects In Bimetallic Hydrogenation Catalysts, Kathleen L. Mcintyre

Retrospective Theses and Dissertations

Mono and bimetallic catalysts of varying composition were prepared in order to examine any synergistic effect that may occur by mixing metals on a support. The test reactions were hydrogenation of 1, 3-butadiene and piperylene, a mixture of similar boiling 5-carbon olefins. Catalysts containing ruthenium and rhodium displayed some synergistic effects when supported on silica gel and 13X molecular sieves. The use of 5A molecular sieves as a support was used to examine the feasibility of selective hydrogenation as a separation tool for the piperylene mixture.

Photothermal Lens Aberration Effects In Two Laser Thermal Lens Spectrometry, Stephen E. Bialkowski

Stephen E. Bialkowski

A comparison of theories describing two laser photothermal lens signals is given. The aberrant nature of this lens is accounted for in a theory which treats the propagation of a monitor laser in terms of a phase shift in this laser beam wave front. The difference between theories are discussed in terms of the predicted signal strengths and temporal behavior. The aberrant theory results in smaller theoretical signal strengths and different functional relationships between signal and analyte level.

Preparation Of Methyl-Substituted Dienols By The Hydromethylation Of Ene-Yn-Ol Substrates With Titanium Tetrachloride And Trimethylaluminum, Terry James Zitzelberger

Dissertations, Theses, and Masters Projects

No abstract provided.

Interobserver Variability In The Assessment Of Neurologic History And Examination In The Stroke Data Bank, David Shinar, Cynthia R. Gross, Jay P. Mohr, Louis R. Caplan, Thomas R. Price, Philip A. Wolf, Daniel B. Hier, Carlos S. Kase, Irene G. Fishman, Christine L. Wolf, Selma C. Kunitz

Chemistry Faculty Research & Creative Works

Interobserver Reliability in Obtaining Neurologic Histories and Examinations Was Investigated among Neurologists Collaborating in the Stroke Data Bank (SDB). Seventeen In-Hospital Stroke Patients Were Examined by Six Neurologists Experienced in Stroke over the Course of Three Days. Patients Were Examined Twice a Day for Two Successive Days, with Each Patient Seen by Four Different Neurologists. Data Were Recorded on SDB Forms, According to Definitions and Procedures Established for the SDB. Percent Agreement and Κ Coefficients Were Calculated to Assess the Levels of Agreement for Each Item. Important Differences in Levels of Agreement Were Found among Items on Both Neurologic History …

The Determination Of Biological Activity And Biochemical Mode Of Action For The Oxadiazole And Diacylhdrazine Insecticides, Bonnie M. Gunn

Retrospective Theses and Dissertations

This report includes the determination of activity and possible mode of action for a group of potential new insecticides. The biological screening procedure was developed using Drosophila melanogaster as the test organism while Musca domestica was used for mode of action assays. The percent kill for each compound is based on the number of eggs placed on media containing the insecticide minus the number of adults enclosed as compared to the control media reared flies. Observations were made on all stages from eggs through adults to determine time of death and if any malformations were present. These observations aided in …

Attenuation Of Infrared Radiation By Diesel Fuel Generated Particle And Droplet Aerosols, Soodabeh Karimi

Retrospective Theses and Dissertations

The object of this project was to explore the absorbance and scattering properties of carbon particle smoke in the infrared and visible regions of the spectrum. Laboratory scale apparatus were developed to produce smoke in the form of carbon particles, droplet aerosols and combinations of the two. These smokes were made from diesel fuel and fog oil.

Trans Diequatorially Fused 3',3'-Diphenyl-2'-Morpholinone Derivatives Of 2-Amino-2-Deoxy-D-Glucose, Julian Guardado Puentes

University of the Pacific Theses and Dissertations

The chemistry of amino sugar compounds has been studied in the last years in connection with the study of natural products, and many of them have been isolated. ^57,17,18 Amino sugars play an important role in biochemistry, forming blocks of homo- and heteropolymers and complex molecules such as microbial polysaccharides, enzymes, gangliosides, glycoproteins, and antibiotics.

This research project had the purpose of preparing a derivative of 2-amino-2-deoxy-D-glucose, with a free hydroxyl group at the anomeric carbon, with the 4,6-positions blocked with the benzylidene cyclic acetal, and the 2,3-positions being blocked by a 3,3-diphenyl-2-morpholinone ring trans diequatorially fused to the amino …

Influence Of Basis Set On The Calculated Properties Of (H3n–Hcl), Z. Latajka, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

The structure of (H₃N–HCl) is investigated by ab initio calculations using a number of different basis sets ranging from minimal to split valence. The effects of including a diffuse sp shell and d orbitals on Cl are considered as well. The geometries of the complex and the isolated subunits are fully optimized. Minimal basis sets (STO‐3G, STO‐6G, and MINI‐1) lead to an overestimate of the interaction between the subunits. Addition of d functions produces only a marginal improvement. The 3‐21G, 3‐21+G, MIDI‐1, and LP‐31G split‐valence sets erroneously predict an ion pair …

Comparison Of Proton Transfers In (S2h5)+ And (O2h5)+, L. Bigham, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

The energetics and electronic rearrangements associated with proton transfer between S atoms in (H₂S–H–SH₂)⁺ are calculated using ab initio molecular orbital methods and compared with similar data in the first‐row analog (H₂O–H–OH₂)⁺. The full potential energy surface of (S₂H₅)⁺, calculated as a function of the H‐bond length as well as the position of the proton, contains two equivalent minima separated by a small energy barrier, whereas the surface of (O₂H₅)⁺ contains a single minimum corresponding to a symmetric …

Contribution Of Dispersion To The Properties Of H2s‐‐Hf And H2s‐‐Hcl, M. M. Szczesniak, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Ab initio calculations are carried out using a doubly polarized basis set. Dispersion, evaluated by second‐order Møller–Plesset perturbation theory (MP2), is found to have a profound influence on the stabilities and structures of the H‐bonded complexes. The contribution of dispersion to the H‐bond energies of H₂S‐‐HF and H₂S‐‐HCl is 44% and 69%, respectively, placing this attractive term second in magnitude only to electrostatics. Reductions of the intermolecular distance of 0.17 and 0.34 Å result from inclusion of correlation effects. Nevertheless, the influence of dispersion upon the angular characteristics of the …

Dilithiation Reactions Of N-Substituted Benzylamines, Richard Patrick Franks

Theses & Honors Papers

N-Cyclohexyl -2-methylbenzylamine was metalated with two equivalents of n-butyllithium activated with one equivalent of tetramethylethylenediamine (T.M.E.D.A.) , and the solvent system, time, and temperature were varied to establish a maximum yield . It was experimentally found that a thirty minute ice-water bath metalation in diethyl ether, followed by a fifteen minute condensation with benzophenone in refluxing diethyl ether gave the best yield with the benzophenone electrophile. The product was characterized by N.M.R. and found · to be 2- ( cyclohexylamino)-2-(2-toluyl ) -1 ,1-diphenylethanol (the benzylic adduct) in a 29% yield.

When N-cyclohexyl -2-methylbenzylamine was metalated for three hours in an …

Structure Of A Solvated Nickel(Ii) Complex Of (S)-2'-(N-Benzylprolyl)Aminoacetophenone And (R)-Valine Schiff Base, C25H29N3Nio3.1/2c4H8O. Conformational Calculation Of Diastereomeric Complexes Of (R)-Valine And (S)-Valine, Sergey V. Lindeman, T. V. Timofeeva, V. I. Maleyev, Yuri N. Belokon, M. G. Ryzhov, V. M. Belikov, Yuri T. Struchkov

Chemistry Faculty Research and Publications

No abstract provided.

Thermodynamics And Kinetics Of Aqueous Solution Of Liquid Hydrocarbon Mixtures (Solutes, Petroleum), David Robert. Burris

Dissertations, Theses, and Masters Projects

Two-phase systems of a liquid hydrocarbon mixture, containing medium molecular weight (C(,7)-C(,12)) aromatic and aliphatic hydrocarbons, and water were examined in both equilibrium and kinetic experiments. Knowledge of the aqueous solution behavior of liquid hydrocarbon mixtures is of importance in determining the fate of hydrocarbon components in such systems of an environmental or geologic nature. Solute concentrations were determined by solvent extraction followed by gas chromatography. The equilibrium solute concentration for a given component i (C(,i)) is related to the pure compound solubility (C(,i)('o)), mole fraction of component i in the hydrocarbon phase (x(,i(h))) and the activity coefficient of component …

Search For New Membrane Active Substances: Synthesis Of 3-Tropanols With Alkyl, Alkenyl And Alkenynyl Group At The Bridgehead, Ramalinga Murty Dharanipragada

Graduate Theses, Dissertations, and Problem Reports

In recent years, Witkop and coworkers have isolated several structurally unique alkaloids from the colombian frog belonging to the genera Dendrobates. These alkaloids, which occur in the defensive skin secretions of the frog have been found to be highly active venoms as well as mucosal tissue irritants towards both mammals and reptiles. Among them are three important alkaloids histrionicotoxin, isodihydrohistronicotoxin and octahydrohistronicotoxin.

The Irreversible Inhibition Of D-Amino Acid Oxidase With Trans-3-Bromoacrylic Acid And Four Others Halo-Vinylic Acids, Christopher D. Kontos

Dissertations, Theses, and Masters Projects

No abstract provided.

Acidic And Chemical Properties Of Molten Salt Hydrates, Stephen Keith Franzyshen

Dissertations, Theses, and Masters Projects

No abstract provided.

Thermodynamics Of Ion Association In Aqueous Fluoride Solutions. Determination Of Stability Constants For (Naf), (Mgf)+ And (Caf)+ Ion Pairs, Waldo Zamorano-Santander

Masters Theses

Stoichiometric ion-association constants were determined at several ionic strengths for (NaF) over the temperature range 15-40°C and for (MgF)⁺ and (CaF)⁺ over the temperature range 25-45°C using fluoride ion selective electrode measurements.

Thermodynamic association constants, K°, were obtained through extrapolation of the stoichiometric values to infinite dilution. Values of K° for (NaF) are 1.70, 2.16 and 2.54 at 15, 25 and 40°C, respectively. The K° values for (MgF)⁺ are 73.4, 88.0 and 98.2, and for (CaF)⁺ are 13.7, 17.5 and 21.9 at 25, 35 and 45°C., respectively.

The stoichiometric association constants for (NaF) can be reproduced …

Bimetallic Complexes Of Tungsten And Mercury, Zakariah Abdullah

Masters Theses

A tungsten-mercury bimetallic complex [(CO)₄W(PPh₂CH₂CH₂PPh₂)₂HgCl₂]_n has been synthesized from the reaction of trans-(CO)₄W(η¹-PPh₂CH₂CH₂PPh₂)₂ and HgCl₂. The value of n has not been determined due to the insolubility of the complex. The anologous reaction with HgI₂ gave an insoluble, uncharacterizable complex, which best corresponds to (CO)₄W(PPh₂CH₂CH₂PPh₂)₂Hg₂I₄.

The geometry about tungsten in [(CO)_{4 …}

Bimetallic Tungsten Carbonyl Complexes, Jin-Guu Wang

Masters Theses

Two heterobimetallic complexes, [(CO)₄W(PPh₂CH₂CH₂-PPh₂)₂MCl₂]_n ( M = Pd or Pt ), were prepared from the reaction of trans-W(CO)₄(ŋ¹-PPh₂CH₂CH₂PPh₂) ₂ with M(COD)Cl₂ (COD = cyclooctadiene). A trans arrangement about tungsten was found for both the palladium and platinum complexes. The square planar palladium center was shown to have a trans geometry in solution while a cis arrangement for the platinum moiety was observed. Far infrared studies indicated a mixture of cis and trans …

Evaluation Of Electrochemical Kinetic Parameters Using The Bond-Henderson-Oldham Global Analysis, Dennis Evans, Mark Anderson

Mark R. Anderson

No abstract is currently available.

Polymer Science And Technology In Universities In Sweden, Otto Vogl, Bengt Ranby

Otto Vogl

No abstract provided.

Second S.R. Romania-U.S.A. Seminar On Polymer Science, Otto Vogl, Viorica Dobrescu

Otto Vogl

No abstract provided.

The Application Of Multiderivative Infrared Spectroscopy To Iodine Number Determination, Jeffrey C. Lowry

Masters Theses

The Food and Drug Administration requires the disclosure of total unsaturation of commercial products as an indication of nutritional value. This unsaturation is a guide to the expected stability of food additives, such as edible oils and foods in which they are used. Unsaturation is typically evaluated as an iodine number, calculated for these additives based on their consumption of iodine through addition across the carbon-carbon double bonds. This titration method can typically take 45 minutes.

The investigation presented develops an alternative method for determining iodine numbers of some common oils using a computerized infrared spectophotometer. The analysis time, as …

Kinetics Of The Formation Of The Nickel(Ii) Complex With N, N' -Dimethylethylenediaminediacetic Acid And The Metal Exchange Reaction Between N,N'-Dimethylethylenediaminediacetatonickel(Ii) And Copper(Ii), Roger A. Karel

Masters Theses

The kinetics of the reaction of aquonickel (II) ion with N'N'-dimethlethylenediaminediacetic acid has been studied at 25°C and 0.1M iconic strength over a pH range of 6.0 to 9.3 using stopped-flow techniques. Formation reactions in all cases were first-order in Ni (II) and in ligand. The formation rate constant for the protonated and unprotonated species were evaluated and compared to their theoretical value. The rate-determining step is shown to be ring closure. A comparison of this system with other studies involving complexation of nickel (II) confirm the magnitude of the internal conjugate base effect and also shows a correlation between …

The Kinetics Of The Metal Exchange Reaction Between N-(2-Hydroxyethyl) Iminodiacetatonickelate (Il) And Copper(Ii), Craig R. Weed

Masters Theses

The reaction between copper(II) and N -(2-hydroxyethyl)iminodiacetatonickelate( II) (NiHEIDA) was studied between pH 4.0 and 5.6 over a 70 fold variation in copper concentration at an ionic strength of 1.25 and a temperature of 25° C. The reaction order in both NiHEIDA and Cu(U) is first. The reaction rate is pH sensitive and a hydrogen dependent pathway as w ell as copper dependent and copper and hydrogen independent pathways were found.

Evidence is given for a stepwise mechanism for the unwrapping of HEIDA from its nickel complex, follow ed by copper attack to give a dinuclear intermediate, which then breaks …

Heterocyclic Syntheses Utilizing Aryl Cyanates, Joseph Eugene Drumm

Masters Theses

No abstract provided.

A Proposal To Fertilize The Overton Arm And Gregg Basin Areas Of Lake Mead, Larry J. Paulson

Publications (WR)

Several limnological studies have been conducted in Lake Mead during the past decade. The recent studies clearly show that most of Lake Mead is deficient in nutrients, especially phosphorus, and very low in productivity. The reservoir-wide average total phosphorus concentration for 1981 - 1982 was only 9 mg/m³. This is below levels found In most oligotrophic lakes and reservoirs. Algal biomass, as measured by chlorophyll-a, averaged only 1.5 mg/m³. That also places Lake Mead in the oligotrophic range. Transparency, as measured by a Secchi disc, averaged 9-5 m in Lake Mead during 1981-1982. That far exceeds …

Iupac 6th International Symposium On Cationic Polymerization And Related Processes, Otto Vogl, Etienne Schacht

Otto Vogl

No abstract provided.

Polymer Science In Academy Institutes In Northern China (North Of The Yangtze): Part Ii: Changchun, Otto Vogl, B. Huang

Otto Vogl

No abstract provided.

Theoretical Study Of Silylene Insertion Into N-H, O-H, F-H, P-H, S-H, And Cl-H Bonds, Krishnan Raghavachari, Jayaraman Chandrasekhar, Mark S. Gordon, Ken Dykema

Mark S. Gordon

The potential energy surfaces for the insertion reactions of silylene into NH3, Hp, HF, PH3, H2S, and HCl have been characterized in detail by using ab initio molecular orbital theory, including electron correlation and zero-point corrections. All the interactions involve the initial formation of a donor-acceptor complex followed by a proton shift via an unsymmetrical high-energy transition state. The binding energies of the complexes as well as the rearrangement barriers for the hydrogen migration of these complexes to give the normal valent compounds have been calculated in all cases. The complex between SiH2 and NH3 exists in a deep minimum …