A survey of the methods of purification of KC1, for use in
preparing single crystals by growth from the melt, was made. Two
methods, fractional recrystallization and ion exchange, were used.
The purity of the salt and crystals grown from the same salt were
compared with the findings of other...
I. Lithium alkyl and aryl monosubstituted cyclooctatetraenide
dianions (Li₂ C₈H₇-R; R = methyl, n- butyl, sec- butyl, tert- butyl,
phenyl and benzyl) were synthesized by the reaction of the appropriate
organolithium reagent with cyclooctatetraene in diethyl ether or
tetrahydrofuran. The reaction occurred cleanly and with good yield
of lithium monosubstituted...
A series of compounds, 7-8 and 20-25, were tested as competitive inhibitors of 2,5-dihydroxyacetanilide epoxidase I (DHAE I) and DHAE II. A Hammett plot was constructed for each enzyme to determine the effect of electron density on inhibition. DHAE I gave a linear, highly correlated plot (r²=0.91) that signifies the...
A three part study involving aspects of radical properties of various
aromatic species was accomplished.
Experiments to ascertain the importance of geometric and electronic
effects on the intramolecular transfer of a pi-complexed radical to a terminal double bond
was performed. Several 4-aryl-1-butenes were reacted in competition with 1-undecene
with a...
The dielectric relaxation of V₂ 0₅ was investigated using the method of Davidson and Cole. By means of an Argand diagram, deviation from an exact Debye dielectric was established. This was done with the parameter β. For a Debye dielectric β= 1. The largest value of β for V₂O₅ was...
The photochemical reaction between O⁻ ions and F centers
was investigated. The activation energy was determined by the
Arrhenius law to be 0.10 + 0.04 eV for temperature below 180°K.
The diffusion of alpha centers towards the oxide ion was eliminated
as the rate limiting step and the low trapping...
The incorporation of europium and dysprosium in potassium
chloride crystals was investigated. The crystals were prepared by
the Kyropoulos method from melts containing the rare-earth chlorides.
The concentration of these rare-earth ions in the crystals was determined
by neutron-activation analysis. The distribution coefficient of
europium and dysprosium between the molten...
Direct current conductivity measurements on KC1:O[superscript]= crystals
were used to determine an enthalpy of 0.42 ev for the dissociation for
anion-vacancy-oxide ion complex.
The entropy of dissociation was
found to be approximately -4x 10⁻⁴ev deg⁻¹. The intrinsic "activation" energy was found to be 1.91 ev as compared to 1.95 ev,...
The dc conductivity of single crystals of vanadium pentoxide
was measured in the three crystallographic directions. The temperature
range examined was -165°C to +25°C. The activation energy
of the conduction process was isotropic and found to be .56 ev. The
conductivity was anisotropic.
Measurements of the Hall effect were attempted...
The hydroxide ion as a substitutional defect in KC1 can be photo-dissociated
at liquid nitrogen temperature by ultraviolet light. The
photochemistry of this system was investigated by EPR and optical absorption
methods. Theoretical calculations were also performed in an
investigation of the KC1:OH system.
The bleaching behavior of photochemically colored...
When the dc conductivities of various pure KC1 crystals were
compared it was found that crystals grown under an HC1 atmosphere,
from salt purified by ion exchange, exhibited lower knee temperatures
than any of the crystals studied. These knee temperatures
were found to be approximately 350°C. From this the total...
Vanadium pentoxide single crystals were grown from the melt.
These crystals were made the cathode in an electrolytic cell and the
polarization and recovery of the electrode were studied under a
variety of experimental conditions.
A study of the electrode potential versus that of the standard
hydrogen electrode as a...
Vanadium pentoxide electrodes were prepared by melting
the powdered oxide around a platinum foil in a pyrex tube. The
electrode was discharged, and the discharge product was studied,
but not identified, by means of chemical and x-ray diffraction analysis.
A study was made of the relationship between the electrode
potential...
Theoretical studies and experimental results are presented for the rotational motion of molecule's in crystalline solids. The group theory is solved for molecules of any symmetry matrix isolated at a site in a crystal field of any symmetry. As the potential terrier to rotation of the molecule relative to the...
Optimization of the galvanovoltammetric determination of dissolved
chlorine in a flowing stream was achieved through the use of
an analog computational device and improvements in the design of the
galvanovoltammetric cell and accompanying electronic circuitry. An
analysis system, applicable to industrial use over a range of flow
rates and dissolved...
The first part of this thesis describes a study of the
characteristics of oxidation of a 1:2 iron(III):thiolate system in
methanolic solution and in water. This system was investigated as a
potential analog for the cysteine- and cysteamine-dioxygenase catalyzed
0₂-oxidation of cysteine and cysteamine, respectively, to the
corresponding sulfinic acids....
The satellite structure ("shake-up") present in the X-ray
photoelectron spectra of several planar molecules containing
double bonds has been investigated in the gas phase.
This set consists of three five-membered heterocyclic
molecules, ethylene and two of its fluorinated analogs, and
benzene with three of its fluorinated analogs. In addition,
core...
The relative influences of trans-Pacific and regional atmospheric transport on measured concentrations of polycyclic aromatic hydrocarbons (PAHs), PAH derivatives [Nitro- (NPAH) and Oxy-(OPAH)], organic carbon (OC), and Particulate Matter (PM) less than 2.5 μm in diameter (PM₂.₅) were investigated in the Pacific Northwest, USA in 2010-2011. Ambient high volume PM₂.₅...
A high-spectral resolution laser-excited molecular fluorescence
system was developed that utilizes a pulsed supersonic expansion to
simplify the fluorescence excitation spectra of large, gas-phase
aromatic molecules diluted in an excess of a monatomic gas. A
microcomputer was used to control and synchronize the instrumental
components, which included a Chromatix CMX-4...
An important aspect in device technology is the
processing of GaAs to produce highly-resolved etch
patterns on the substrate. This is done typically on the
GaAs(100) surface. Recently, a number of methods, all
using chlorinated vapor reactants, have been applied to
fabrication of GaAs devices. In spite of these
technological...
An instrument was developed which performs analysis of the
oxygen content of air by means of a commercial polarographic oxygen
electrode. The oxygen analyzer is part of a portable instrument
which converts the current from the oxygen electrode into a pulse
whose width is proportional to the oxygen concentration. This...
The cocondensation reactions of molybdenum trioxide vapor with
tetraalkoxysilanes, trimethylalkoxysilanes, and hexamethyldisiloxane
at -196°C were investigated. The products from the metal vapor
reactions of tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane
were characterized as molybdenum(VI)dioxodialkoxy compounds. The isolated compounds were found to be polymeric in the
solid state by bridging through alkoxide groups....
To determine the impact of emerging environmental contaminants on human and environmental health, quantitative analytical methods are required. Analysis of emerging contaminants is hampered by their widely varying physical-chemical properties. Therefore quantitative analytical methods must be developed to determine the behavior of emerging contaminants in environmental systems.
A quantitative analytical...
My work has focused on investigating synthetic organic reactions using applied computational methods. Non-covalent interactions are critical to catalysis, mechanism, and stereoselectivity, with the most prominent interaction for isothioureas being the S···O contact between the catalyst sulfur atom and the oxygen of the acyl group. A comprehensive joint experimental and...
Two nonlinear optical experiments are presented in which the third-order electronic susceptibility of molecules is used to generate Raman signals. The first one uses a single 532 nm beam from a Nd:YAG laser to produce Stimulated Raman Scattering in benzene and deuterated benzene. With a simple experimental set-up, stimulated emission...
The investigation
of impurity effects on the properties of alkali
halide crystals has often been difficult because of the variation of procedures used in various experiments.
The purpose of this work is to
develop a self consistent method of measuring the IV dipole polarization properties of single crystals while eliminating...
The techniques of coherent anti-Stokes Raman spectroscopy (CARS)
and inverse Raman spectroscopy (IRS) are used to examine carbon dioxide
aggregation in a supersonic jet expansion. To promote the formation of
small clusters, a BMW injector valve is modified to permit its use as a
pulsed nozzle at very cold temperatures....
Polybenzimidazoles were synthesized from 3, 3', 4, 4'-tetraminobiphenyl
(diaminobenzidine, or DAB) with orthoesters, carboxylic acid derivatives (an ester and
an acid) and with m-benzenedialdehyde. The products were of low molecular weight,
as evidenced by low inherent viscosity, except in the case of the dialdehyde plus DAB.
The product of that...
The target fragment production cross sections, angular
distributions, and range distributions have been measured for the
interaction of 12-16 A MeV³² S with ¹⁶⁵Ho. The fragment isobaric
yield distribution and the moving frame angular distributions have
been deduced from the data. Symmetry properties of the moving frame
angular distributions have...
Applications of several methods of coherent nonlinear Raman Spectroscopy have been made in this thesis research. The theory and potential of one of these, Photoacoustic Raman Spectroscopy (PARS), is discussed in chapter two. Experimental results are presented which illustrate the sensitivity of this method and establish sampling conditions for maximum...
Both oxy-Cope and siloxy-Cope rearrangements involve
(1, 3) and (3, 3) sigrnatropic shifts. Both the concerted mechanism,
and the stepwise mechanism via a diradical intermediate are possible.
In a cyclic system such as cis-l-vinylcyclooct-3-en-l-ol, the thermal
rearrangement takes place preferably through a diradical intermediate.
At high temperature, the reaction also...
The (±) 8,9:13,14-diseco-norestradiol, a large ring hormone
analog, and its related derivatives, were prepared by a ring expansion
approach. The key step of this approach is the establishment of the
benzocyclododecenone system via the Caubere reaction. This step
not only provides a favorable ring size, it also sets the necessary...
The CARS apparatus at OSU was modified to permit studies in the 0-500 cm⁻¹ spectral region. The new low frequency capabilities were then used to study molecular clusters formed in free expansion jets of carbon dioxide. A strong cluster band was observed at 73 cm⁻¹, with a weaker shoulder at...
Levels of activity of glucose-6-phosphate- , 6-phosphogluconate- , and isocitric- dehydrogenase were measured in the
soluble and particulate fractions of heart, brain and liver at
several ages throughout the development of the chick embryo.
Compared to isocitric dehydrogenase, levels of glucosesphosphate-
, and 6-phosphogluconate- dehydrogenase are generally
low. This suggests...
The thermal and anionic rearrangements of substituted 1-vinyltrans-
cyclotridec-3-en-l-ol compounds have been studied to determine
what effects substituents would have on the sigmatropic shift when
placed on the two positions of the 1-vinyl group.
For the thermal rearrangements, the a-substituted vinyl-trans-cyclotridecenols
gave both the [3,3] and [1,3] shift products of...
Due to its importance, the phenomenon of hydrogen
bonding has been the subject of much research over the
years. Among the different techniques used to study
hydrogen bonded systems, vibrational spectroscopy is
perhaps the most sensitive because of the striking
changes induced in molecular spectra by the formation of
hydrogen...
The work presented in this thesis deals with the mechanisms by which a vibrationally excited diatomic molecule gives up its energy to a host monatomic lattice at low temperature. The vibrational lifetimes (v"=1) of the metal oxides Ba0 and A10 in their ground electronic states are studied using pulsed dual...
The infrared absorption spectra (40-800 cm⁻¹) of the trifluorides
of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Tb, Ho, Er, Tm, and Yb isolated
in solid argon, krypton and nitrogen matrices have been obtained. For
PrF₃ the symmetric and asymmetric stretching modes were observed;
PrF₃ is accordingly assigned a...
A new experimental apparatus was built at Oregon State University to perform high resolution stimulated Raman spectroscopy in a pulsed molecular jet at state densities of the order of 10¹¹ cm⁻³. The technique uses a stimulated Raman step to first populate a vibrational/rotational level and then a resonantly enhanced multiphoton...