A study of the relative rates of the alkyl hydrogen abstraction
from a series of meta and para substituted t-butylbenzenes by the
chlorine atom at 70°C has been carried out. Application of the
Hammett equation yielded a ρ value of -0.44 for the para compounds.
Possible explanations for the non-linearity...
Thermal analysis was used to investigate the following seven
systems: H₂S-B₂F₄, SOF₂-B₂F₄, COC1₂-B₂F₄, SF₄-B₂F₄, Xe-BF₃, NF₃-BF₃, and NF₃-BC1₃. In two of the seven systems
compound formation was observed.
In the system, H₂S-B₂F₄ the compounds H₂S[superscript .]B₂F₄ and
2H₂S[superscript .]B₂F₄ are formed. The compound H₂S[superscript .]B₂F₄ has a melting
point of...
For a number of reasons, miniaturization of chromatographic columns has been a general trend over the past three decades. Methods designed to enhance selectivity and efficiency can offer improved separation power and speed, expanding on the advantages of miniaturized columns. This dissertation describes novel approaches in this direction, focusing on...
The core-electron ionization potentials for mono- and
di(trifluoromethyl)benzene, for chlorofluoromethanes and for
chlorine have been measured in order to give information on
the electron distribution in these molecules and to investigate
differences between the inductive effect of fluorine
and that of CF3. For trifluoromethylbenzene the measured
ionization potentials in eV...
The concept of reducing laboratory operations into microfluidic devices has been an attractive area of research for several decades. Due to several advantages of porous-media microfluidic devices including low mass, portability, power-free fluid transport, and the ability to store dried reagents in the porous structures, these devices show great promise...
The carbon is photoelectron spectrum of CO₂ has been measured with very high photon energy resolution. The natural lifetime of the carbon is hole state has been determined from a series of spectra taken at photon energies of 308, 320, and 330 eV. The measured values of the lifetimes show...
Three areas of liquid state theory are considered.
First, Monte Carlo computer simulation of a two-dimensional hard
disk fluid with an imbedded ellipse was undertaken to determine how a
non-spherical molecule affects intermolecular ordering. The
elliptical molecule (with axial ratios of 2, 5 and 10) altered the
isotropic distribution of...
This research emphasized fundamental physical and electrochemical
studies of systems based on the room temperature fused salt, triethyl-ammonium
dichlorocuprate(I). Such systems, which must be maintained
under a protective atmosphere, were also used in some preliminary
battery studies.
Spectra of dark green solutions of copper (II) chloride in
triethylammonium dichlorocuprate(I) obey...
The photoelectron spectra of a series of halogenated
molecules have been investigated in the gas phase. Both
core-ionization energies and Auger kinetic energies were
measured to probe the nature of the interaction that holds
a core electron to the molecule.
It was found that satellite structure (shake) could be
used...
The variegated aqueous chemistries of metal cations are applied to the design and synthesis of non-toxic solution precursors suitable for additive printing of large-area oxide electronics. Polycondensation behaviors of aqueous Al+3 and PO4 +3 are manipulated in the deposition of atomically smooth amorphous aluminum oxide phosphate (AlPO) dielectric films. AlPO...
Solid state luminescent sulfides are prepared as powders in order to elucidate the relationship between structure and light emission. While the sulfides studied in this dissertation are known phosphors, materials are investigated in a variety of new ways. Elementary properties and structures of MgS are reviewed, and preparation of MgS...
We have developed a compact micro total analysis system (μTAS) to serve as a platform for in-situ spectrophotometric water quality monitoring. Individual fluidic, optical, and electrical components were designed, developed, and characterized. These components were combined in both an integrated (single lithographic “chip-based” platform) and a modular manner. The microfluidic...
The atmospheric trace element abundances associated with slash
burning have been measured by instrumental neutron activation analysis
(INAA). On site ground level samples were collected during the slash
burning season using high volume samplers and a cascade impactor. In
addition to the air samples, soil, wood and ashed wood samples...
In this dissertation, I present electronic spectra of a few polycyclic aromatic hydrocarbons (PAHs): tetracene, pentacene, pyrene, benzo[g,h,i]perylene and benzo[a]pyrene using resonantly enhanced multiphoton ionization (REMPI) and zero kinetic energy (ZEKE) photoelectron spectroscopy. The work of tetracene and pentacene also combine a laser desorption source with a ZEKE spectrometer, demonstrating...
Used Nuclear Fuel (UNF) contains transuranic (TRU) elements and numerous fission products as a result of the uranium fission process and neutron activation that occur in commercial light water power reactors. Recent environmental and nuclear proliferation concerns have spawned the development of advanced reprocessing techniques to close the nuclear fuel...
A specially designed gas chromatograph with both TCD and FID has
been tested for the measurement of the diffusion coefficients of methane and propane in helium. Knox's arrested elution technique(⁴) was used and yielded a value of 0.6431 cm²/sec averaged with the value
obtained by Yang and Hawkes(⁷). Values of...
An all-glass gas chromatograph was developed for the analysis
of corrosive metal halides. Included in the apparatus is a new liquid
sampling system designed for fast repetitive sampling of corrosive
liquids in an inert atmosphere. A flame photometer detector was developed
to permit the detection of corrosive solutes in the...
This thesis describes a Mossbauer effect and electron
paramagnetic resonance study of iron (III) tetraphenylporphyrinatobenzenethiolate
benzene thiol, an analog compound
for bacterial cytochrome P-450. The compound is unusual in
that it provides a model for the two ferric reaction states
of cytochrome P-450. The iron in the model compound exhibits...
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....
The velocity of sound in gases was measured, using an ultrasonic
wave train as a diffraction grating. The fundamental problems
involved in the optical technique are discussed. An apparatus utilizing
an objective lens of focal length 1.5 m and aperture f/20 was constructed
and used at an ultrasonic frequency close...
This dissertation presents a study of structure-property relationships within 3d/4d metal oxides containing precious metals through detailed structure refinements using high-resolution neutron and X-ray diffraction data along with exploration of the resultant properties.
Oxides of 4d or 5d transition metals tend to show new topological phases due to significant spin-orbit...
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....
In situ reduction of hydrido-tris-(3,5-dimethylpyrazolyl)borato(trioxo) rhenium(V) with triphenylphosphine or triethylphosphite leads to a reactive rhenium(V) species that catalytically deoxygenates epoxides at 75-105°C. The reaction is stereospecific, except for trans- and cis-butene oxide which formed minor amounts of the opposite isomer. A variety of different functional groups were tolerated and even...
A comparative study was made on the effect of urea denaturation
of bovine serum albumin (BSA), polyglycyl BSA and poly-L-phenylalanyl
BSA. The denaturation process was followed by ultraviolet
spectrophotometry and optical rotation.
A blue shift in the absorption maximum at 278 mμ was observed
in urea denatured proteins, In 7M...
Normal adult rats absorbed and metabolized C¹⁴-labeled acetate
rapidly. The greatest percentage of the administered radioactivity
was recovered in the expired CO₂, however small amounts of radioactivity
were also found in the urine and feces. There were two rates
of C¹⁴O₂ elimination in normal adult rats. The small amount of...
In order to examine some possible tyrosyl interactions, poly-tyrosyl lysozyme and poly-O-methyltyrosyl lysozyme were prepared and their solubilities were compared. Both derivatives exhibited
similar pH dependent solubilities, showing a minimum solubility at
about pH 8. Their solubilities varied with temperature, having a
positive enthalpy of solution. The effect of a...
White muscle disease or muscular dystrophy of sheep is a selenium
responsive malady common to many areas with an inherent natural
deficiency of selenium in the forage. The disease can be prevented in
lambs by adding trace amounts (approximately 0.1 ppm) of selenium to
the otherwise selenium deficient, forage fed...