Physical Sciences and Mathematics Commons^™

Thermodynamic Equilibrium Formation Constants And Molal Concentrations Of The Complexed Mercury-Containing Species Of Mercuric Chloride In Added Hydrochloric Acid And Methanol-Water Solvent Mixtures, Karl Jennings Walker

Theses and Dissertations

Saturated solutions of mercuric chloride in different methanol-water and hydrochloric acid solvent mixtures were equilibrated at 25.00 ± 0.01°C. Total mercury and free chloride concentrations were determined by analytical procedures and the data were analyzed with the aid of the computer. Tabulated below are the results of this study: [--see thesis for table--]

Reactions Of N₂F₄ And Sf₆ With H₂ Induced By Co₂ Laser Pulses And By Electrical Discharge, John Leslie Lyman

Theses and Dissertations

A high power pulsed CO_2 laser was used to induce reactions in gas mixtures containing either N_2F_4 or SF_6. The rate of laser induced dissociation of N_2F_4 to NF_2 was as much as 1000 times faster than the thermal rate, and the rate law was of lower order than the thermal, bimolecular rate law. Explosion threshold and induction time data were obtained for butene stabilized mixtures of N_2F_4 and H_2. HF laser gain was observed during the first few microseconds of CO_2 laser pulse, but it was strongly quenched by the explosion. The laser driven reaction of SF_6 with H_2 …

Development Of Standard Procedures For Determination Of [Delta]G° (K), [Delta]H° And [Delta]S° Values Via Potentiometric And Calorimetric Titration Techniques, Jack Hugh Ruckman

Theses and Dissertations

Standard computer techniques were developed for computation of ΔG° values from potentiometric titration data and ΔH° values from calorimetric titration data. The procedures developed can be used for any systems having the general equations HA = W^+ + A^- ; H_2A = 2H^+ + A^2- ; and H_3A = 3H^+ + A^3-, where the proton ionizations may be consecutive or simultaneous. The thermodynamic values ΔG°(K), ΔH° and ΔS° were determined for the ionization of protons from the protonated compounds methionine (-NH_3^+ group only), phosphoethanalomine and phosphoserine. The compounds studied were selected because they contain one, two and three ionizable protons …

The Photolysis Of Propane At 123.6 Nm, James H. Vorachek, Robert D. Koob

Office of the Provost Scholarship

Propane has been photolyzed at 123.6 nm, in the presence and absence of O₂, at pressures from 2–380 Torr. All products except ethane exhibit a pressure dependence which is attributed to secondary dissociation of the primary fragments, H₂, CH₄, C₂H₄, and C₃H₆. It is assumed that the range of energies carried by these fragments is broad enough that some will not dissociate even at low pressures while others of the same species cannot be stabilized even at high pressures. An internally consistent analysis rationalizes the entire …

An External Goniometer For Orientation Of A Cryostat, N.C. Lockhart, L.F. Nichols, Craig J. Eckhardt

Craig J. Eckhardt Publications

An economical two-circle orienting external goniometer has been designed and fabricated for an Andonian liquid helium Dewar. The Dewar can be tilted ±30° from the vertical in two perpendicular directions. The geometrical center of the Dewar's optical cavity moves a maximum of 1 mm when the cryostat is tilted the full 30°. The basic design involves the rotation of two concentric cylinders riding on bearing surfaces. Two chain belts and gear boxes are used as drive mechanisms.

Radiative And Predissociative Lifetimes Of The A ²Σ+ State Of Oh, Richard Orlin Sutherland, Richard A. Anderson

Chemistry Faculty Research & Creative Works

Lifetime measurements have been made on the A 2Σ+ state of OH by the delayed coincidence technique in conjunction with an interrupted rf discharge through water vapor. Lifetimes are reported for rotational states up to K=29 and K=20 in the ν=0 and ν=1 vibrational levels, respectively, and on the unresolved levels of ν=2. A predissociation, previously predicted from relative intensity measurements, resulting from a curve crossing by the repulsive 4Σ− state, was observed for the rotational states above K=23 of ν=0, for those above K=14 of ν=1, and for all those of ν=2. These lifetime data are discussed qualitatively in …

Ferroxidase-Ii: A Blood Serum Lipo-Protein, Christine Shih Ming Sung

Master's Theses

Ferroxidase-II was definitely identified as a lipoprotein. Cholesterol and phospholipids remained tightly associated with the ferroxidase-II protein following extensive purification. Quantitative analysis showed that it is a high-density lipoprotein. Thin-layer chromatographic analyses indicated that phosphatidylcholine accounts for the majority of the bound phospholipid with lysophosphatidyl choline and sphingomyel in accounting for the remaining phospholipid.

Treatment of purified ferroxidase-II with phospholipase C or A resulted in a loss of ferroxidase activity which paralleled the hydrolysis of phospholipid. Phospholipid D treatment also resulted in the loss of ferroxidase activity, yet the loss was not as great as with other phospholipases. A lipid-depleted …

A Pycnometer Of Improved Design, Richard Moore

Journal of the Minnesota Academy of Science

The density of a solution must be known to laboratory medicine , biochemistry, and physical chemistry. Knowledge of the density may permit calculation of solution concentration, solute molecular weight, solute partial, or specific volume , for example. Therefore, the determination of the density of a solution is a measurement which must be made with precision, accuracy, and sensitivity. This report describes a pycnometer which permits making such measurements.

Synthesis And Chemistry Of Thione-Iron Carbonyl Complexes, Albert Shil-Kwan Chan

Graduate Dissertations and Theses

The first examples of sulfur-donor ligand ortho-metallated complexes were obtained in good to excellent yields by reaction of various thiobenzophenones and a thiobenzoate with diiron enneacarbonyl in benzene at room temperature. The known trinuclear complex S₂Fe₃(CO)₉ was a by-product of these reactions, and complexes of the type (Ar₂C)S₂Fe₂(CO)₆ were formed in several instances. The structures of these complexes were established on the basis of microanalytical and spectral data as well as by reductive cleavage experiments. Oxidative or photolytic cleavage of the ortho-metallated complexes provides a convenient …

Pmr Spectra Of The 4-Alkylnitrobenzenes, Donald W. Beistel, Hsin-Liang Chen

Chemistry Faculty Research & Creative Works

Evidence of first-order alkyl-ring proton coupling is reported for the 4-alkylnitrobenzenes. Typical coupling constants of 0.7 Hz and 0.3 Hz were found for α-alkyl coupling with the ortho and meta ring protons, respectively, when the alkyl function was methyl, ethyl, and isopropyl. No β-alkyl coupling with ring protons was observed for the ethyl, isopropyl, or t -butyl groups, suggesting that the magnitude of the coupling constant is vanishingly small.

A Computer-Oriented Course In Chemical Spectroscopy, D. (Donald) W. Beistel

Chemistry Faculty Research & Creative Works

No abstract provided.

The Synthesis And Spectroscopic Properties Of Vanadium(Iii) Squarate Trihydrate, S. M. Condren, Hector O. Mcdonald

Chemistry Faculty Research & Creative Works

Vanadium(III) squarate trihydrate has been prepared; and the infrared, X-ray diffraction, and electronic spectra of the complex indicate that the central metal atom is in a slightly distorted octahedral field. A thermogravimetric study has shown that the complex loses three water molecules upon heating. A hydroxy-bridged, dimeric structure has been proposed from these data. © 1973, American Chemical Society. All rights reserved.

Final Report On Interrelationships Between Chemical, Physical And Biological Conditions Of The Waters Of Las Vegas Bay Of Lake Mead, James E. Deacon, Richard W. Tew

Publications (WR)

This program was a status study of the interaction between Las Vegas Wash, an enriched stream, and Las Vegas Bay, a wedge shaped arm of one of the world's deeper reservoirs. The program centered primarily on identification and counting of planktonic algae from several points in Las Vegas Bay. Additional work on nutrient enrichment of water samples was conducted to aid in interpretation of algal distribution related to nutrient input. Examination of a variety of physical, chemical, and biological parameters, both at many surface points in the bay, as well as in vertical profile, was also accomplished and further aided …

A Study Of Bisimines Of Tetramethyl-1,3-Cyclobutanedione, Edward Albert Schmidt

Electronic Theses and Dissertations

It was the purpose, therefore, of this work, to investigate the preparation, properties, and reactions of bisimines of 2,2,4,4- tetramethyl-1,3-cyclobutanedione, to determine the chemical effects of carbon π-bonded to nitrogen. Certain of these effects are compared to carbon π-bonded to oxygen in a structurally similar environment.

The Primary Structure Of Nifungin, Marvin Lee Withrow

Electronic Theses and Dissertations

The primary structure of the antifungal peptide nifungin was studied. Amino acid analysis of nifungin before and after performic acid oxidation revealed 51 amino acids and the presence of an unidentified ninhydrin positive material. The unidentified material constituted approximately ten per cent of nifungin by weight. It contains nitrogen but, as reported by others (2), did not contain phosphate or reducing sugars. It was not hydrolyzed into smaller compounds by strong mineral acids. Carboxyl terminal analysis was conducted utilizing carboxy-peptidase A and B on both the oxidized and unoxidized nifungin. Tyrosine appeared to be released most rapidly followed by lysine, …

A Study Of The Pulse-Height Response Of Silicon Surface-Barrier Detectors To High-Energy Heavy Ions, Gregory Dan Smith

Doctoral Dissertations

"The pulse-height defect (PHD) of high-energy heavy ions in silicon surface-barrier detectors can be divided into three components: (1) energy loss in the gold-surface layer, (2) a nuclear-stopping defect, and (3) a defect due to recombination of electron-hole pairs in the plasma created by the heavy ion. The plasma recombination portion of the PHD was the subject of this study using the variation of the PHD with (1) the angle of incidence of incoming heavy ions, and (2) changes in the detector bias. The Tandem Van de Graaff accelerator at Argonne National Laboratory was used to produce scattered beam ions …

Photochemical Rearrangements Of 6/5 -Fused Cross-Conjugated Cyclohexadiensnes In Protic Solvents, Drury Caine, John T. Gupton, Ko Ming, William J. Powers Iii

Chemistry Faculty Publications

Irradiation of the ring A unsubstituted 6/5-fused cross-conjugated cyclohexadienone (1a) and its 2-methyl derivative (1b) in methanolic acetic acid yields, in addition to other products, novel tricyclononane derivatives which have been assigned the structures (3a) and (3b).

Polarographic Trace Analysis Of Copper, Lead And Cadmium, Donald Paul Jepson

University of the Pacific Theses and Dissertations

The area of study for this project was the development of an accurate, reliable, and inexpensive method of trace analysis for copper, cadmium, and lead in foods. AT this time, the Association of Official Analytical Chemists Manual, eleventh edition, (4) has only official and recognized methods of analysis for copper (25.023), cadmium (25.018), and lead (25.041). In general, these procedures are long and tedious. The digestions involved often require many hours and are quite dangerous due to leakage of metallic and organometallic fumes from the digestion apparatus. The official methods of analysis for these elements require a very large outlay …

A Crystalline Fragment Of The Double Helix: The Structure Of The Dinucleoside Phosphate Guanylyl-3',5'-Cytidine, Roberta Ogilvie Day, Nadrian C. Seeman, John M. Rosenberg, Alexander Rich

Chemistry Department: Faculty Publications

The sodium silt of guanylyl-3',5'-cytidine crystallizes in a monoclinic unit cell with one molecule in the asymmetric unit. Each molecule is related to another molecule by a 2-fold rotation axis which results in the formation of an antiparallel; right-handed .double helix with complementary hydrogen bonding between the guanine and cytosine residues. The crystal is heavily hydrated with 36 water molecules in the unit cell. The geometry of this crystalline double helix is. very similar to those which have been derived from studies of fiber x-ray diffraction patterns of double-stranded RNA; even though the latter do not yield data at atomic …

Formation And Kinetics Of Dissociation Of Some Pentaaquotrihalomethyl Chromium(Iii) Ions., Sher Khan Malik

University of the Pacific Theses and Dissertations

The present.study was an investigation of the formation and kinetic stability of store complexes contain.ir)ing a chromium-carbon bond in an aqueous medium. An orange-brown pentaaquotrifluoromethylchromium(III) ion was obtained by the reduction of trifluororrethyl iodide with Cr(II) and is the most inert of any organochrotnium(III) complex known. The initial aquation rates of trifluoromethylchromium(III) ion were described by the differential rate law -dln [(H₂O)₅CrCF₃²⁺]/dt = k_{o + k1(H⁺)}

The products of the initial reaction were hexaaquochromium (III), carbon monoxide and HF. The values of k_o and k₁ at …

The Consideration Of Some Aspects Of Two Methods Used To Study Ion Association, Richard Karl Gard

Masters Theses

An investigation was made into the possibility of determining thermodynamic ion association equilibrium constants for salts important in the study of seawater using spectrophotometry and ion selective electrodes. Calcium sulfate was used as the test salt. The success of the spectrophotometric method was found to depend upon the choice of a suitable indicator and refinement of the proper instrumental techniques. The indicators investigated were 1-(2'-hydroxy-1'-benzeneazo)-2-hydroxynaphthalene, 1-(2'-hydroxy-5'-chloro-1'-benzeneazo)-2-hydroxynaphthalene, and ammonium purpurate (murexide). Ammonium purpurate was found to be the most suitable indicator. Spectra of these three indicators and their calcium complexes at pH 10 are included in the paper. The ion selective …

The Isolation And Purification Of A Fluorescent Compound From Pseudomonas, Thomas M. Davey

Masters Theses

Fluorescence in certain land snails has been found to arise from a bacteria carried by the snails. The bacteria, a genus of Pseudomonas, produce a pigment complex in iron-deficient media. The pigment complex consists of both fluorescent and non-fluorescent pigments. One of the fluorescent compounds was isolated and purified by paper chromatography using several different solvent systems.

Absorption and fluorescent spectra of the compound at a number of pH values were measured and the changes with pH of both the intensity and the color of the fluorescence were observed. The purified compound was ninhydrin negative but after acid hydrolysis …

Computer Investigation Of The Variation Of Conductivity With Concentration, Larry Macpeers Shadwick

Masters Theses

Computer programs were developed tor the conductance equations of R. M. Fuoss and L. Onsager as well as for the conductance equations of T. J. Murphy and E. G. D. Cohen. These programs were used to calculate values from selected conductance measurements. The resulting values were compared with values produced by other computer programs using the equations of Fuoss and Onsager as well as the equations of E. Pitts. The comparisons demonstrated the equations of Murphy and Cohen to be the equal of or superior to the other equations for the majority of cases. The equations of Pitta were superior …

A Comparison Of The Effects Of Aspirin, Sodium Salicylate, And Acetate On Cells In Vitro, Roger Scott Barron

University of the Pacific Theses and Dissertations

Salicylic acid and its concern have long been used for the management of pain, fever, and inflammation. Of this group, acetyl-salicylic acid, or aspirin (ASA) has proved to be the most potent in each case. Although hydrolysis, the first step in biotransformation of aspirin takes place very rapidly, many workers feel that the greater effectiveness is due to a unique action of the intact molecule; however, others disagree. In this study, the effects of aspirin and in vitro were compared in order to obtain a greater amount of information relating to the problem.

The Kinetics And Mechanism Of The Reaction Of Chromium(Ii) With Pentaaquodiiodomethyl Chromium(Iii) And Pentaaquomonoiodomethyl Chromium(Iii) Ions., Ronald Sinclair Nohr

University of the Pacific Theses and Dissertations

Transition metal ions, in low oxidation states, have gained increasing use as versatile reducing agents for a number of organic compounds. The ability of metal ion to act as reducing agents in organic reactions is frequently thought to be due to the formation of intermediates which contain an organic species bound to a metal, although the identy of these organo-metallic intermediates has been determined in relatively few cases.

The purpose of this research was to investigate the kinetics and mechanism of one such reaction: the reduction of iodoform to methane by chromium(II). Two air stable organochromium(III) intermediates were separated and …

The Preparation And Characterization Of The Palladium(Ii) And Platinum(Ii) Chelates Of Three Cyclic Tertiary Amino Acids., Floyd Michael Hogue

University of the Pacific Theses and Dissertations

The purpose of this study was to prenare and characterize the palladium (II) and platinum (II) chelates of 1-pyrrolidineacetic acid, 1-piperidineacetic acid, and hexahydro-1-azepineacetic acid.

The ligands were prepared by reacting the cyclic secondary arnines (pyrrolidine, piperidine, and hexahydroazepine) with sodium chloroacetate. The resulting cyclic tertiary amino acids were saponified and, finally, converted to the hydrochloride salts by neutralization with hydrochloric acid.

The chelates were prepared by adding 1.0 millimole of K₂PdC1₄ or K₂PtC1₄ to a solution made by dissolving 2.0 Millimoles of amino acid hydrochloride in 25 ml. of water. The pH was …

Mechanistic Studies Of Cobalt Super Nucleophiles, Audrey Yeh Ku

Masters Theses

A study was initiated on the hypothesis, by Ugi and co-workers, that cyclopropyl, cyclobutyl, and cyclopentyl electrophiles might undergo nucleophilic substitution reactions with retention of configuration.

A simple, high yield synthesis of both cis and trans-2-phenylcyclopropyl chlorides from styrene and chloroform is described. Reaction of each of these alkylating agents with the very nucleophilic cobaloxime super-nucleophile ultimately gave peroxy compounds which appear to arise from insertion of oxygen into the carbon-cobalt bond.

Neither trans-2-phenylcyclopentyl tosylate nor trans-2-phenylcyclohexyl tosylate would alkylate low valent cobaloximes under standard conditions.

A partial synthesis of the 2-phenylcyclobutyl tosylate is described along with suggestions for future …

The Conductance Of Some Polyvalent Electrolytes, Jack Lee Worthington

Masters Theses

A new compound, 1,3,5-triphenylbenzene-4' ,4",4"'-trisulfonic acid, was synthesized by treating triphenylbenzene in 1,2-dichloroethane with chlorosulfonic acid. The reaction appears to be quantitative. Conductance measurements were then made on the sodium, potassium, and lanthanum salts of this new acid and of 1,3,5-benzenetrisulfonic acid.

The choice of these acids was based on two factors: 1) the desire to prepare a 3-3 symmetrical unassociated electrolyte which would allow the determination of a more reliable equivalent ionic conductance value for La³⁺ and 2) an interest in using the Murphy-Cohen equation to determine solute parameters such as association constants if association is present.

Conductance …

Oxidation Of Thin Silver Films By Ozone And Atomic Oxygen, Lawrence R. Thorne

Undergraduate Honors Capstone Projects

Recently, thin silver film detectors have been used to determine atomic oxygen profiles in the 70-100 km region of the upper atmosphere. The detectors' sensitivity to atomic oxygen is the result of the formation of silver oxide(s) which cause their electrical resistance to increase. A common procedure to calibrate and to make these detectors more sensitive is to cycle them through a series of three or more oxidations and reductions. This paper indicates that this cycling makes silver films more sensitive to ozone, causing them to be usable only at heights greater than 38 km. Also reported herein are experimentally …

Some Aspects Of Mercury Accumulation By The Purple Shore Crab Hemigrapsus Nudus Dana (Crustacea: Decapoda), Ralph Gene Swanson

University of the Pacific Theses and Dissertations

The present study has attempted to investigate some of the more basic questions concerning the toxicity and accumulation of mercury in the purple shore crab, Hemigrapsus nudus. This rocky intertidal denizen is found in abundance along the entire Pacific coast of the United States from Sitka, Alaska, to the Gulf of California where it dominates the mid-tide pool region. Local specimens were collected just north of the Pacific Marine Stations, Dillon Beach, Marin County, California. The animal is hearty and can be kept in a state of good health for long periods of time in the laboratory with minimum care …