Major and minor minerals have been separated from
three L-6 chondritic meteorites (Alfianello, Colby (Wisconsin),
and Leedey). Olivine, hypersthene, diopside, feldspar,
troilite, chromite, phosphate minerals, and metallic
minerals were analyzed for major, minor and trace elements
using instrumental neutron activation analysis and radiochemical
neutron activation analysis techniques. Concentrations
df the...
A continuous amperometric monitor for aqueous sulfite solutions
has been developed employing the electro-oxidation of sulfur (IV)
in 0. 1 M sulfuric acid at a glassy carbon test electrode. The monitor
employs a hydrodynamic flow cell, in which the solution stream
enters the cell through an orifice impinging on the...
A mechanism for filiform corrosion of aluminum is proposed
based on experimental evidence and the known aqueous chemistry of
the trivalent aluminum ion. Experimental methods utilized include
autoradiographs with Cl³⁶; pH paper determination of the filiform
head pH; activator concentration and activation period as they affect
filiform growth.
The pH...
Part 1
The pyrolysis of cis-1-trimethylsiloxy-1-cyclopr opyl-3-cyclononene in the temperature range 285-350° is described. Instead
of siloxy-Cope rearrangement, undesired desiloxylation took place.
Part 2
Gas-phase pyrolytic rearrangement of 2-phenyl-1-trimethylsiloxy-1-vinylcyclononane was investigated in a static system
in the temperature range 213-330°. It was discovered that
three major products resulted: cis- and...
A quadratic programming method was developed for the statistical
analysis of gas chromatographic data. The method was applied to
three types of flavor extracts, peppermint, hops and brewed tea. The
brewed tea data had to be abandoned because of the singularity of its
coveriance matrix. In all cases tried the...
The reaction between 4- chloro- 6- methoxy- 5-nitropyrimidine
and methylamine was investigated. The reaction product was identified
as 4-methoxy-6-methylamino-5-nitropyrimidine from synthesis
of the product via 4-chloro-6-methylamino-5-nitropyrimidine.
The product was the result of displacement of chloro substituent with methylamine. The reaction occured under mild condition (e. g. 15-20
C. in dioxane)....
A double-beam photometer was designed and built employing photon counting to give a direct digital readout. It was evaluated as an analytical instrument with special emphasis on pulse recovery time, pulse interaction and instrument settings. An equation is developed to explain pulse interaction in event counting systems.
The simultaneous diffusion of Ca 2+ and Sr 2+ ions in purified
single crystals of KC1 and NaC1 was studied over the temperature
ranges from 451°C to 669°C in KC1 and from 448°C to 683°C in NaCl.
A radioactive tracer technique was used in two types of measurements:
diffusion from...
Nine Ca-Al-rich inclusions and one olivine inclusion
from Allende meteorite were studied for Ti, Al, Fe, Mg, Ca,
Na, Cl, K, Sc, V, Cr, Mn, Co, Ni, Zn,Hf, W, Ir, Au, Ta,
and Re -via INAA (instrumental neutron activation analysis)
and REE, Ba, Sr via RNAA (radiochemical NAA). The inclusions...
The yields from the oxidation of 4-methylpyrimidine with potassium permanganate were found to increase from 25 to 92 percent by the addition of small amount of potassium hydroxide to the reaction mixture. Pyrimidine-4-carboxylic acid decarboxylates in hot aqueous solution to yield pyrimidine and carbon dioxide. The rate is that decarboxylation...
The photolysis of the aqueous thymine system has been investigated
at 214 nm, 229 nm and 254 nm at room temperature. Products
of photolysis have been identified as hydrogen peroxide, 6-hydroxy-5-
hydroperoxy thymine and tentatively 5-hydroxy-6-hydroperoxy thymine.
These together with thymine loss, were determined quantitatively
under a variety of conditions....
Sequential alkylation of Hagemann's ester with methyl and
methallyl halides has been studied. Treatment of Hagemann's ester
with methyl iodide and sodium ethoxide gave a mixture of 21 and 25
in a ratio of 4:1. Alkylation of 21 with methallyl chloride and potassium
t-butoxide afforded a mixture of 37 and...
Eight layered gabbro samples from two layered complexes, two
xenoliths, one basalt from a hot brine area and a standard basalt rock
(BCR-1) were analyzed by RNAA (radiochemical neutron activation
analysis) for 14 trace elements, Au, Ni, Co, Ag, Sb, Se, Zn, In, T1,
Rb, Cs, U, Ba and Sr....
AT-cut piezoelectric quartz crystals coated with low vapor
pressure materials are evaluated as digital transducers in completely
digital detection systems for monitoring gas streams. Mathematical
relations describing the detectors are developed and tested. Specific
application is made to monitoring gaseous sulfur compounds commonly
found in stack effluents of pulp mills....
Several approaches to the synthesis of methymycin were
investigated. Segment A (39), containing functionality corresponding
to C-9, 10, and 11 of methynolide was made in
six steps from propionaldehyde in an overall yield of 37%.
Oxidation of 34 with silver nitrate gave 35 which, upon hydroxylation
with hydrogen peroxide, gave...
Several approaches to the synthesis of penicillin from 2-iminothioazolidine
50, from 2-thiothiazolidine 66 and by photocyclization of
77 and 78 were investigated. 2-Iminothiazolidine 50 was prepared
from dibromoester 45 by the action of benzylamine followed by treatment
of aziridine 46 with potassium or ammonium thiocyanate. Attempted
introduction of a two-carbon...
An approach to the generation of polyketides was investigated,
which involved ozonolysis of 6, 7 cyclopenteno -1> 4, 5, 8 -tetrahydromethoxy-
3-methylnaphthalene (26), to produce what is believed to be
polyketide 27. Compound 26 was formed by the following sequence:
Die ls -Alder addition of 1, 2 -dim.ethylenecyclopentane and 2...
The atmospheric trace element abundances associated with
several major sources of air pollution in Western Oregon, such as the
paper industry, the metallurgical processing industry, the plywood
industry and agricultural field burning have been measured by instrumental
neutron activation analysis (INAA). Air samples were collected
directly from industrial stacks and...
The tosylhydrazones of exo-3-deuteriocamphor and 2- deuterio-2,4-dimethy1-3-pentanone were treated with Nbromosuccinimide (NBS) and pyruvic acid to regenerate the parent ketones. The ketones from the pyruvic acid cleavage show a significant loss of deuterium. The ketones from the NBS cleavage show no loss of deuterium, indicating that stereochemical integrity at. C[subscript...
The reaction of cyclodeca-1,215triene with mercuric salts
gave only rearranged hydrocarbon, tricyclo[4.4.0.0²'⁴]deca-5ene
in acetic acid. Other catalysts [Rh(CO)₂C1]₂ and AgC10₄ gave
the same rearranged hydrocarbon. The isomerization is proposed
to proceed through a "metalcomplexed" carbenoid intermediate.
The reaction of bicyclo[7.1.0 ]deca-213diene gave
oxymercurated products.
Basalts of both Eocene and Miocene age from several groups
along the Oregon and Washington coasts have been analyzed for some
major, minor, and trace elements using instrumental neutron activation analysis (INAA). The rare earth element (REE) patterns observed
in these samples are used for comparisons within the groups studied...
The analysis of 64 rock samples from Saudi Arabia and three
samples from the axial trough of the Red Sea has been done.
Instrumental neutron activation analysis (INAA) was the analytical
tool used for the analysis of at least 18 and as many as 24 elements
in these 67 rock...
A systematic study of the elution of magnesium and calcium from
Dowex 50 X 8 resin using α-hydroxyisobutyric acid (α-HIBA) at
various pH values and concentrations, indicated that the difference in
the equilibrium distribution coefficients of these two elements was
large enough for a good separation. This fact was applied...
A classification of stationary liquids by infrared spectroscopy to evaluate the polarity was made using the solvent effect technique. The infrared C-Cl absorption frequency shift was measured for solutions of 1-chlorohexane dissolved in each stationary phase. These frequency shifts were correlated to the relative retention times of 1-octene/n-octane, trans-2-octene/n-octane and...
A critical study of the cold vapor atomic absorption and fluorescence instrumentation for the analysis of mercury is described. Some of the important modifications involve the reduction vessel, absorption cell, fluorescence cell, and radiation source. The new modified systems have much greater calibration sensitivities and lower detection limits than those...
Intramolecular cyclization of organometallic compounds represents
a promising tool for synthesis. The reaction involves exothermic
consumption of intramolecular double bonds via insertion
into a carbon metal sigma bond. This represents an intramolecular
example of the reaction type responsible for metal catalyzed polymerization
of olefins.
Organolithium reagents were found to cyclize...
All attempted synthesis of perfluoroalkyl boron bonded groups
have resulted in the formation of boron-fluorine bonds from the
probable decomposition by α-fluorine transfer. The substance alkali
metal di-n- butylborate (I) has been identified as the potassium derivative
by its reaction with di-n-butylboron chloride and isolation of
potassium chloride. The reaction...
The design and construction of a chemiluminescence
photometer is described. The design is based on a discrete
sample system which has a number of advantages over
the previously described flow cell system and centrifugal
analyzer. The advantages include simple and inexpensive
equipment, small sample size, versatile electronic readout
system, and...
The design, construction and operation of a fluorometric reaction
rate instrument is described. The instrument is designed for simple
operation with maximum versatility. Advantages and modes of
operation of the system are discussed in detail. The instrument is
used for the kinetics-based determination of trace levels of Ag and Al....
The application of lucigenin chemiluminescence for the determination
of trace concentrations of Co(II) is described. This method
is based on the enhancing effect that Co(II) has on the reaction of
lucigenin and hydrogen peroxide in a basic solution. The chemiluminescence
signal from a Co(II) enhanced lucigenin reaction, which is in...
The study of diffusion coefficients of n-alkanes and other organic compounds in silicones is undertaken by gas-liquid chromatography. About 0. 3% of stationary phase is coated on glass bead support so that the only significant source of peak spreading is due to slow liquid phase mass transfer. Diffusion coefficients are...
Diffusion of short chain n-alkanes was found to be faster in the
polydimethylsilicone elastomer SE-30 than in the polydimethylsilicone
oil SF-96-2000. The opposite was true for the longer chain n-alkanes
suggesting that choice of stationary phase for gas chromatography
would depend on the chain length of sample components. The dependence...
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 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...
Investigations of plasma production by a pulsed dye laser
microprobe were made. Comparisons between a Q- switched and a
pulsed dye laser system were made on the intensity of the continuum
produced by atmospheric breakdown. The dye laser system was
foundtominimize the production of the continuum which in turn
allowed...
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...
A new pulse method for measuring differential double layer
capacitances has been developed in this work. The technique is based
on the determination of the cell time constant which, for an ideally
polarized test electrode-solution interface, is composed of the double
layer capacitance and solution resistance. By applying small step...
High-precision instrumental neutron activation analysis has
been used to determine Al, Na, Mn, Sc, Cr, Fe, Co, and Ni in a
suite of more than 500 chondrules from 26 distinct meteorites. These
meteorite specimens represent the H, L, LL and C chemical classes
and most of the petrologic types. In...
Ninety basalt samples from eight locations in central Oregon
and one location in the Willamette Valley were analyzed for Si and Al.
Fourteen basaltic rock specimens (> 1 kg each) from four buttes in the
Willamette Valley were sampled and analyzed for Si, Al, Fe, Na, K,
Mn, Cr, Co,...
The silicate phases of 11 pallasites were analyzed instrumentally
to determine the concentrations of some major, minor, and
trace elements. The silicate phases were found to contain about
98% olivine with 1 to 2% accessory minerals such as lawrencite,
schreibersite, troilite, chromite, and farringtonite present. The
trace element concentrations, except...
Fluorescence of adenine, guanine, thymine, cytosine, and uracil
has been detected at room temperature in neutral aqueous solution
using a digital signal accumulation technique and right angle fluorescence
detection from solutions with absorbances between 0. 4 and 0. 7.
The quantum yields are respectively 2.6 x 10⁻⁴, 3.0 x 10⁻⁴,...
The relative rates of hydrogen abstraction from o-xylene,
o-diethylbenzene and a series of four benzocycloalkenes by trichloromethyl
radical were determined at 70°. The strain energies of the
hydrocarbons and the corresponding radicals were calculated. A good
correlation between the log of the relative rates and the calculated
changes in strain...
Six polycyclic aliphatic hydrocarbons were reacted with the
trichloromethyl radical photolytically generated from bromotrichloromethane
at 40°. Relative rates of reaction were correlated
with a computer analysis of the change in strain energy in going
from the ground state to the intermediate. A good correlation between
the log of the relative...
A new x-ray source capable of operating at up to 80
watts has been designed and developed, and put to use with
the Oregon State University Cylindrical Electrostatic
Analyzer. The new source produces over four times the
photoelectron intensity of its predecessor, from gaseous
samples, and accommodates a wider selection...
The relative rates of hydrogen abstraction from a series of 13
arylmethanes by the trichloromethyl radical were determined at 70°.
The attacking radical was generated from bromotrichloromethane us
ing benzoyl peroxide as the initiator. The solvent was benzenebromotrichloromethane.
An excellent correlation, with a coefficient
of 0.977, was obtained when the...
The atmospheric trace element abundances associated with "indoor"
and '"outdoor" air particulate have been measured for university chemistry
laboratories, typical homes, modern office buildings, hospital and
automobile repair garages in a rural setting (Corvallis, Oregon) and
modern office buildings in an urban setting (Portland, Oregon). Samples
of atmospheric particulate matter...
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...
The relative rates of hydrogen abstraction from 1-phenylalkanes and a,w-diphenylalkanes using N-bromosuccinimide and bromotrichloromethane were determined at 70°C. In both cases the reactions were photoinitiated. Only benzylic bromination was observed. The 1-phenylalkanes reacted with both reagents to give rates largely independent of substrate. Similarly, the rate of the reaction between...
The infrared absorption spectrum from 3200 cm⁻¹ to 4025
cm⁻¹ of thin crystals of ⁶LiOH (99%⁶Li.) is presented and compared
to the spectrum of [superscript]NLiOH (93%⁷Li). A shift in only one of the band
pairs supports the lattice combinations model and assists in making
assignments for the major features of...
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...
A multielement spectrometer has been developed for the simultaneous determination of four elements by atomic absorption (AA) or atomic fluorescence (AF). The spectrometer is based on a multiple exit slit monochromator and uses a mirrored funnel to direct light from the various exit slits to a single photomultiplier. There are...
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...
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...