Physical Sciences and Mathematics Commons^™

Electrocapillary Studies Of Reversible Charge Transfer V(Iii)/V(Ii) Electrode, Mohammad Ali Akhtar

University of the Pacific Theses and Dissertations

Electrocapillary equation for an ideal polarized electrode based on Gibb's adsorption equation is appropriately recast into experimentally measurable quantities in order to apply it to a reversible charge transfer electrode.

To calculate the various parameters of the equation developed, experimental details were worked out. For the measurement of Current-time relationship of a single drop, a fast response potentiostat was built by using transistorized chopped stabilized operational amplifiers and precision components in the circuitry with proper compensation for IR-drop in the cell and the electrical double layer capacity. The analysis of I-t curves was done by taking into account the composite …

Measurement Of Fluorescence Lifetimes Of Biologically Significant Compounds, Irene Adele Petz

University of the Pacific Theses and Dissertations

The purpose of this research was to measure fluorescence decay-times of several biologically significant compounds. Although various equations are available which permit one to calculate fluorescence lifetimes from spectral data, ample evidence exists which indicates such calculations are at considerable variance with experimental results.

A Modern Philosopher's Stone, Grant Gill Smith

Faculty Honor Lectures

Alchemists, the forerunners of chemists, for more than a millennium sought the "Philosopher's Stone"-the transmuting agent that could change imperfect base metals such as lead and tin to the noble metals, gold and silver, and also serve as the Elixir of Life to heal the infirmities of man and prolong his existence on earth.

Where alchemy failed, chemistry, in little more than a century, has succeeded in finding the "Philosopher's Stone," for it is now not only possible to transmute one metal into another and heal many of man's infirmities, but scarcely a facet of man's life has not been …

Palladium And Platinum Complexes Of Substituted Cycloolefins, Gerald Brady Mccauley

University of the Pacific Theses and Dissertations

Much of the fundamental work on complexation of cycloolefins by platinum metals has been laid down by several workers and ranges from complexes of butadiene those of cyclododecatriene. The work here was chiefly a continuation of research on cycloolefin complexes which appear in papers by Kuljian and Frye (30,31,44). Most of this work on the complexes of cyclic seven, eight, and twelve carbon ligands was repeated here to insure a more complete laboratory background and for verification of previously reported literature data on these compounds. These compounds were used a s basis for comparison to original compounds developed in the …

A Polarographic Study Of Selected Metal Complex Ions Of Several P-Tosyl Amino Acids, Joseph Martin Reyes

University of the Pacific Theses and Dissertations

A polarographic study of the complexes of selected metal ions and the p-Tosyl derivatives of the amino acids; glycine, glutamic acid and lysine has been made to determine their coordination number, formula, dissociation constant and free energy of formation.

A Comparative Study Of Inductive Influence On The Hydrolysis Of Beta-Thioglucopyranosides By Beta-Thioglucosidase And Beta-Glucosidase, Robert W. Miller Jr.

All Master's Theses

A series of phenyl-D-thioglucopyranosides were prepared and characterized in order to determine the absolute specificity of the .B-thioglucosidase and B-glucosidese enzyme systems toward the th1oglucosidic bond. The specificity of B-glucosidase of almond emulsin toward oxygen linkage seems to be absolute, since no hydrolysis was observed by this enzyme system toward the phenyl-D-thioglucopyranosides. The P-th1oglucosidase system was found to hydrolyze only two of the thioglucopyranosides. It was apparent that only where the electron-attracting substituents in the phenyl group were strong enough to greatly weaken the strength of the sulfur linkage, as in the case of the nitro group, would there be …

Ternary Phase Diagram Determinations Concerning Potassium Electrolyte Influence On Aqueous Solutions Of Dioxane Or Tetrahydrofuran, John Albert Mcnaney

University of the Pacific Theses and Dissertations

For the graphical representation of the mutual, partial solubilities of a·ternary system, a diagram is generally employed which is based upon the equilateral triangle, whose properties are especially felicitous for this-purpose.

In this study, the phase diagrams for the following systems were determined: potassium acetate-water-dioxane, potassium acetate-water-tetrahydrofuran, potassium benzoate-water-dioxane, potassium benzoate-watertetrahydrofuran, potassium chloride-water-tetrahydrofuran, and potassium hydroxide-water-dioxane.

The systems, potassium acetate-water-dioxane and potassium hydroxidewater-dioxane, were investigated at 25° and 85°. This study indicates that they are, to a slight degree, temperature dependent. When these systems were plotted on a mole-percentage basis, it was found that both potassium compounds have about the …

Scaling In Carbon Monoxide And Nitrogen, Jerry Goodisman

Chemistry - All Scholarship

No abstract provided.

Refinements In The Isomer Distribution And Relative Rate Of Sulfonation Of Toluene And Hydrochlorination Of Olefins With Stannic Chloride Catalyst, David George Guillot

Theses and Dissertations

The sulfonation of toluene at -12.5° C. with sulfur trioxide in liquid sulfur dioxide was found to give 10.03 ± 0.20 % ortho, 0.73 ± 0.20 % meta and 89.24 ± 0.20 % para isomers. This isomer distribution was determined by isotope dilution analysis using sulfur-35 enriched sulfur trioxide. After dilution of aliquots of the neutralized sulfonation mixture with pure sodium salts of each of the isomers prepared from the corresponding toluidines, the isomers were converted to the p-toluidine salts, purified by recrystallization, and counted by liquid scintillation counting. The relative rate of sulfonation of toluene compared to benzene was …

Capillary Behavior Of Viscous Liquids, Marvin De Young

University of the Pacific Theses and Dissertations

A major problem confronting every investigator who works with synthetic organic chemistry is that of the crystallization of the products obtained. This problem necessitates extensive attention both on the experimental and on the theoretical level. In order to gain an understanding of the behavior of substances in the liquid state, so as to be better able to manipulate them in procedures intended to induce crystallization from complex mixtures, considerable attention has been given to various models of the liquid state. An understanding of the nature of pure liquids would seem to be an essential prelude to any attempt to understand …

Scaling In Isoelectronic Molecules, Jerry Goodisman

Chemistry - All Scholarship

A modification of a scaling method introduced for atoms by Ellison enables one to use expectation values calculated for one molecule in calculations of the energy of a second molecule isoelectronic to the first. In going from Hz to Hez2+t,h e results are only fair, but in going from LiF to BeO, the results are suffeciently good to allow prediction of equilibrium distance and several expectation values as well as energy. The dipole moment is a notable exception, which reveals one basic dissimilarity between the two molecules, the ionic character. LiF dissociates to ions, Be0 to neutral atoms, causing our …

Hydrogenation Of 4-Methylcinnoline, William E. Maycock

Theses and Dissertations

The rapid expansion of knowledge of cinnoline chemistry since 1941 has not included the hydrocinnolines. Not one catalytic hydrogenation of a fully aromatic cinnoline had been reported. This thesis is an effort to enlarge knowledge of this particular area of cinnoline chemistry. The work is a natural outgrowth of that done at Brigham Young University on decahydroquinoxaline, both the cis- and trans- isomers having been prepared and characterized. 4-Methylcinnoline, prepared by the method of Jacobs, et.al., was hydrogenated in neutral and acidic ethanolic solutions at 2000-3000 psig. hydrogen pressure and 100-266°. The catalysts used were 5% palladium on alumina, ruthenium …

A Graphical Method Of Estimating Heat Capacities Of Hydrocarbons, Pu-Ying Liu

Masters Theses

"Heat capacity arises because the individual particles comprising a substance are able to move and thus take up kinetic energy and usually also potential energy as the temperature rises. In many substances electrons do not absorb energy until very high temperatures are reached. Thus most heat capacity effects are interpreted in terms of the motion of the atoms neglecting electronic transitions. The total internal energy of a material is, therefore, equal to the sum of the energies due to translational and rotational motion of the molecules and to the vibrational motion of the atoms making up the molecules...The objective of …

The Binary Halides Of Molybdenum(Iv) And Tungsten(Iv) And The Oxochlorides Of Tungsten(Vi), Edward Roy Epperson

University of the Pacific Theses and Dissertations

It was the purpose of this study to investigate the reaction of molybdenum and tungsten dioxides with carbon tetrachloride and bromoform (via the method of Knox and Tyree) to produce anhydrous molybdenum and tungsten tetrachlorides and bromides and to determine whether the method is a reliable one for the synthesis of these compounds. Out of this grew an investigation into the preparation of the oxochlorides of tungsten(VI) using the same preparative technique.

The results of this study are here set forth. An attempt is made to systematize the published material on the synthesis and properties of the binary halides of …

Polarography Of Selected Metal Ions In Anhydrous Aliphatic Diamines, Frederick William Foss Jr.

University of the Pacific Theses and Dissertations

A search of the literature revealed that no study has sought to measure and compare the polarographic solvent properties of the anhydrous aliphatic diamines. In fact, there has been no reported instance of the use of anhydrous 1,3-propanediamine or 1,4-butanediamine in any electro- chemical system.

Some Spectrophotometric Studies Of Molecular Complexes For Phenanthrene, Anthracene, Pyrene, Chrysene, And Benzanthracene With Iodine Monochloride, Joe Boyd Coacher

University of the Pacific Theses and Dissertations

The principal purpose of the present study was to prove the existence of the weak interaction between the halogenoid iodine monochloride and the condensed polycyclic aromatic hydrocarbons, phenanthrene, anthracene pyrene, chrysene, and benzanthracene (see Figure 1).

Polarography As A Measure Of Ionic Environment, James Wilburne Larsen

University of the Pacific Theses and Dissertations

The present work is a polarographic study of the alkali metals and selected first row transition metals in DMSO (dimethylsulfoxide) with tetraethylammonium perchlorate as a supporting electrolyte. DMSO was chosen as a solvent because of its interesting solvent and complexing properties. Tetraethylammonium perchlorate was chosen as a supporting electrolyte because of its lack of complex forming tendencies and because of the wide range of voltages available for polarographic investigation before the supporting electrolyte ions react electrochemically.

One of the problems, particularly in nonaqueous polarography, is the low conductivity of the solutions leading to high cell resistance. As current flows through …

Anomers Of D-Galactosamine Benzoates, Robert Stanley Strong

University of the Pacific Theses and Dissertations

D-Galactosamine has been known as one of the rarer amino sugars, occurring widely distributed in small concentrations in living organisms. The biological importance of D-galactosamine and its derivatives was thought to justify a study of the chemical properties of this group of compounds. As a result of this study the reactions of D-galactosamine have been found to differ more than previously thought from those of D-glucosamine, the more common amino sugar

For this investigation D-galactosamine hydrochloride was isolated from chondroitin sulfate, a polysaccharide obtained from the cartilaginous tissues of animals. This was changed by appropriate reactions to the 1,3,4,6-tetra-0-benzoyl-N-carbobenzoxy-α-β-D-galactosamine (III). …

The Transition Metal Complexes Of Anthranilic Acid And Its Derivatives, Jesse Smith Decker

University of the Pacific Theses and Dissertations

Part of this investigation was undertaken to determine the effects of functional group substitution on the ring - as well as on the -NH₂ radical - on the formation of metal complexes with the first transition series in the periodic classification of the elements.

The outline of the investigation in this report is as follows: (1) To mind methods for the preparation of the complexes.; (2) To examine the relative ease of formation, and the relative solubility of such chelates in common laboratory reagents.; (3) To determine the relative stabilities by relative molar conductance measurements.; (4) To discover relative …

Studies In The Behavior Of Certain Cyclic Olefins Toward Divalent Platinum And Palladium, Ernest Sam Juljian

University of the Pacific Theses and Dissertations

The initial program of study for consideration was the extension of cyclooctatetraene complexation to other metals of the transition group. Compounds of (COT) with iron, cobalt, chromium, molybdenum, and tungsten which have been reported in the literature involve carbonyl ligands simultaneously as (COT)M(CO)_x with x = 2,3----; only Ag(I) as AgN03 adducts are known. Rhodium (I) is said to form an unstable dimer while ruthenium (I) forms a polymer. (COT)Pt(II) chloride, bromide and iodide have been reported but only the iodide has been studied; only (COT)PdCl₂ has been reported recently. It was further conceived that substituted (COT) would …

I. Preparation And Properties Of Alkyl And Aryl Substituted Thioquinazolines And Sulfoxides ; Ii. An Investigation Of The Quinazoline 3-Oxide--1,4-Benzodiazepine 4-Oxide Rearrangement, Marvin C. J. Kuchar

Theses and Dissertations

I. The quinazolines, a branch of the benzodiazine class of aromatic nitrogen hetercycles, do not occur to any great extent in naturally occurring compounds. The discovery of the antimalarial febrifugine and its structure elucidation led to the preparation and investigation of a host of new quinazolines in the search for new and more effective antimalarials. Most of the present body of information governing the quinazolines arose out of these synthetic studies. The present study has been accomplished with a four-fold purpose in mind: (1) to investigate the susceptibility of chloroquinazolines to nucleophilic displacement reactions by thiols or their salts, (2) …

Molecular Addition Compounds :|Bi. Systems Of P-Dioxane With Alkyl Halides, Anisole, And Silicon Tetrachloride ; Ii. Titanium Tetrachloride Chargetransfer Complexes Of Benzene, P-Xylene, And Pseudocumene, Nolan F. Mangelson

Theses and Dissertations

Freezing-point diagrams were detennined tor a number or p-dioxane systems. The system, p-dioxane:carbon tetrachloride, was found to contain a 1:2 complex with a congruent melting point of 255.71 °K. This confirmed work reported in the literature. Solid solutions in the region between 0.0000 and 0.4796 mole fraction of p-dioxane were found in the present study. The system, p-dioxane:chloroform, was found to contain a 1:2 complex with a congruent melting point of 215.65 °K. It was determined that no other complexes formed in the solid state. This information resolved contradicting reports in the literature. The system, p-dioxane:dichloromethane, was found to contain …

Directive Effects In The Sulfonation Of Toluene ; Synthesis And Attempted Rearrangement Of Some Anilinoketones ; The Kinetics And Mechanism Of The Addition Of Bromine To Cyclohexene In Dichloromethane. Solution, John Joseph Duvall

Theses and Dissertations

The pure sodium salts of the toluenesulfonic acids were prepared by one of two ways. Both methods started with diazotization of the toluidine. In the first method, the diazonium solution was treated with sulfur dioxide and copper powder, and the resulting sulfinic acid was oxidized to the sulfonic acid with potassium permanganate. In the second method, the diazonium solution was treated with cuprous chloride and sulfur dioxide to give the sulfonyl chloride which was hydrolyzed to the sulfonate. Toluene was sulfonated by SO3 (enriched with S-35) in refluxing SO2 solution. The isotope dilution technique was used to determine the isomer …

Determination Of Thallium(Iii) Using The Dead-Stop End Point, Richard Blount Williams

University of the Pacific Theses and Dissertations

An accurate and fairly rapid method of analysis of thallium solutions is desirable in order to facilitate further investigation of the chemistry of thallium. The dead-stop titration method which has been successfully applied to other metals of Group 3b, will not be applied to the quantitative determination of the thallium (III) ion in aqueous solution.

High Frequency Titrations In Liquid Ammonia, Jack Charles Hileman

University of the Pacific Theses and Dissertations

An extensive literature has been established on the use of high frequency conductometric methods in chemical analysis and research. The fact that the instruments respond to chemical changes without having electrodes immersed in the reacting solutions has attracted the attention of many investigators. Until the last few years, practically all of the investigations were concerned with aqueous solutions, with the exception of measurements of dielectric constants.

There seemed no logical reason for not extending the use of the high frequency instruments to the study of Bronsted acid-base reactions, organic syntheses, rates of reaction, and the other commonly studied aspects of …

Hydroxy Derivatives Of Benzalthiophenone, John M. Newey

University of the Pacific Theses and Dissertations

It is the purpose of this work to prepare a series of these chalcones containing the thiophene ring.

The compounds were prepared by the condensation of a series of benzaldehydes with acetylthiophene dissolved in dry ethylacetate and saturated with dry HCl. The benzaldehyde compounds were benzaldehyde, m-hydroxybenzaldehyde, o-hydroxybenzaldehyde, O-p-dihydroxybenzaldehyde and vanillin. To prevent the oxidation of the hydroxy groups of the benzaldehydes, the compounds were benzolated with benzoylchloride. The condensed products were debenzoylated with NaOH solution in an atmosphere of nitrogen to prevent oxidation during the debenzoylation process.

High Temperature Adsorption Studies On Solid Adsorbents, Julian Joseph Hamerski

University of the Pacific Theses and Dissertations

It has been found that there exist certain crystalline aluminosilicates which provide regular net-works of channels with diameters no bigger than those of molecules. Such crystals can act as sieves (thus the name "molecular sieves" now marketed by the Linde Air Products Company) and bring about a separation of molecular species by occluding small molecules while not adsorbing larger molecules or molecules with shapes that do not "fit."

The aluminosilicates were termed zeolites first by Baron Cronstedt (1) some 200 years ago. He observed that certain mineral crystals, when heated, appeared to melt and to boil at the same time. …

Kinetic Investigation Of The Hydrochlorination Of Olefins In Aprotic Solvents And Sulfonation Of Idobenzene And The Selectivity Relation, Thomas Glen Davies

Theses and Dissertations

Kinetic investigation of the hydrochlorination of cyclohexene and cis-2-butene in n-heptane with SnCl4 as catalyst shows that the reaction is second order with respect to both olefin and catalyst. The specific rate constants at 25° , 0° and -23.8°C and the activation parameters were determined. Investigation of the Ga2Cl6 catalyzed hydrochlorination of cyclohexene and cis-2-butene in dichloromethane indicates that alkylation and polymerization compete with the hydrochlorination reaction in the presence of the solvent. The relative reaction rates and the isomer distribution for the sulfonation of iodobenzene by S35O3 have been determined in refluxing SO2 at -10°C. The reaction resulted in …

Sulfonation Of Chlorobenzene And The Selectivity Relation ; Bromine Addition To Cyclohexene In Dichloromethane ; Thorpe's Synthesis Of The Caged Acid, 4-Methyltricyclo[1.1.0.0[Superscript 2-4]] Butane-1,2,3-Tricarboxylic Acid, John A. Gurney

Theses and Dissertations

Aromatic sulfonation and some substitution reactions of chlorobenzene show deviations in the selectivity relation. A determination of chlorobenzene sulfonation provided the following rate ratio relative to benzene and partial rate factors: 1.0, [---] of 0.064 , mf 1.7 and pf 4. 2. Our work, Olah's nitration, Ferguson's bromination and Stock's chlorination define a new relation that can be express by adding an entropy term (A) to the selectivity relation. We determined the rate of bromine-cyclohexene addition in dichloro-methane at 0° to provide a basis for a systematic variation of solvents at low temperature. An unusual zero-order reaction was encountered. The …

Dissertation In Organic Chemistry. Part I, The Fate Of The Anilino Moiety In The Rearrangement Of Α-Anilonoketones. Part Ii, Partial Rate Factors For Sulfonation Of Bromebenzene With Sulfur Trioxide. Part Iii., Preliminary Survey On The Effect Of High Pressure On Ferrocene And Cycloöctatetraene, Jerold Carter Robertson

Theses and Dissertations

Part I. The rearrangement of α-anilinoketones was studied in an effort to determine the mode of movement of the nitrogen moiety. A crossover experiment was carried out with an equimolar mixture of 2-(4- bromoanilino)-1-(4-bromophenyl)-2-(4-methoxyphenyl) ethanone and 2-(4-chloroanilino)-1-(4-chlorophenyl) -2-(4-methoxyphenyl)ethanone with γ- picoline hydrobromide as the catalyst. The reaction product was analysed by means of a mass spectrograph. The results of the analysis indicate a crossover of the nitrogen moiety during rearrangement. This indicates that the nitrogen moiety moves in an intermolecular manner during the rearrangement. Part II. The isomer distribution from the sulfonation of bromobenzene with sulfur trioxide was determined by …