Physical Sciences and Mathematics Commons^™

The Response Of The Micro-Adsorption Detector To Inorganic Anions, Maria E. Munera

Masters Theses

No abstract provided.

Structural Effects On Micellar Catalyzed Reaction Of Hydroxamic Acids, Nop Utrapiromsuk

Masters Theses

Introduction

For many years scientists have tried to find a model which resembles a biological system, so that they can use this model for studying biological systems in human and in living organisms. Micelle systems provide the environment to mimic enzyme systems to some degree.¹

Soaps and detergents generate micelles. Soaps and detergents have been used as cleansing agents for a long time. Their cleansing properties are related to micelle formation. Actually, soap is simply a mixture of sodium salts of long chain fatty acids, R-COO^- Na⁺, and some detergents are general sodium salts of straight …

The Effects Of Electron-Donating And Electron-Withdrawing Groups On The Alkylation Sites Of Para-Substituted Phenylacetones, Abraham L. Faburada

Masters Theses

The dianions of phenylacetone and its para-substituted derivatives were generated using potassium hydride and n-butyl lithium in tetrahydrofuran. Methyl, ethyl, and n-butyl iodides were used to alkylate the dianions. The results of alkulation indicated that C₁ is preferentially attacked by the less active ethyl and n-butyl iodides. The results further show that terminal alkylation is enhanced by electron-donating groups at the para-position of the phenyl ring. The results are rationalized in terms of the difference in electron density at C₁ and at C₃ in the dianion, on the basis of resonance theory. The regio-selectivity of alkylation as …

The Unexpected Preferential Formation Of 1-Alkyl-1-Phenyl-2–Propanones On Monoalkylation Of The 1-Phenyl-2-Propanone Dianion, Jack M. Hinkley

Masters Theses

No abstract provided.

Redox Study Of Cobalt(Ii)-Cobalt(Iii) Polypyridyl, Larry Long

Masters Theses & Specialist Projects

The rate of reduction of [Co(dipy)₃]³⁺ by [Co(tripy)₂]²⁺ has been examined in six nonaqueous solvents and water. The kinetic results in these solvents were compared with those obtained in nine other solvents where the same reaction was investigated. Activation parameters were obtained over a temperature range of 5° to 50°C with the ionic strength at 0.0027 or 0.0046 M. The slowest rate of electron transfer was found in acetonitrile while the fastest occurred in acetophenone, the solvent of lowest dielectric constant. A linear correlation between ln k and the reciprocal dielectric constant of the …

Thermodynamics Of The Lanthanide Trifluorides. I. The Heat Capacity Of Lanthanum Trifluoride, Laf₃ From 5 To 350°K And Enthalpies From 298 To 1477°K, William G. Lyon, Darrell W. Osborne, Howard E. Flotow, Fernande Grandjean, Ward N. Hubbard, Gerald K. Johnson

Chemistry Faculty Research & Creative Works

The heat capacity of a sample of LaF₃ was determined in the temperature range 5-350°K by aneroid adiabatic calorimetry and the enthalpy from 298.15 to 1477°K by drop calorimetry. The heat capacity at constant pressure C°_p(298.15°K), the entropy S°(298.15°K), the enthalpy [H°(298.15°K)-H°(0)] and the Planck function -[G°(298.15°K)-H°(0)]/298.15°K; were found to be (90.29±0.09) J °K^-1·mole^-1, (106.98±0.11) J °K^-1·mole^-1, (16717±17) J mole^-1, and (50.91±0.05) J °K ^-1·mole^-1. The thermal functions from the present research were extended up to the melting temperature (1766°K) by combination with previously …

The Design And Construction Of A Nitrogen Laser And Its Use To Pump A Tunable Dye Laser To Measure The Multiphoton Ionization Spectrum Of Molecular Iodine, James Kintigh

Masters Theses & Specialist Projects

A nitrogen laser was constructed for use in multiphoton ionization studies. The short pulse duration and highly intense pulse make the nitrogen laser ideal for pumping a dye laser.

By using the nitrogen laser to pump a tunable dye laser, the multiphoton ionization spectrum for molecular iodine vapor was obtained for the visible spectrum between 23,188 cm^-1 (430 nm) and 16, 304 cm^-1 (615 nm) using pulsed electronics and a parallel plate ionization chamber. The ionization occurs in this region upon the absorption of four or five photons. The ionization appears to take place via a three-step process. …

The Kinetics Of Solvent Reorientation In Hydroxylated Solvents From The Exciting-Wavelength Dependence Of Chromophore Emission Spectra, John Milton, Robert M. Purkey, William C. Galley

WM Keck Science Faculty Papers

The disappearance of the exciting-wavelength dependence of the phosphorescence spectra of polar, aromatic chromophores in supercooled glycol–water mixtures is utilized to monitor the kinetics of solvent reorientation. Reorientation times in the nanosecond to second range are obtained for (3:2 v/v) glycerol–water and (1:1 v/v) ethylene glycol–water at 140–240 °K. The results suggest that the process is one involving a cluster of solvent molecules and in which the chromophore plays a relatively passive role. Steady-state data and direct measurements of phosphorescence shifts as a function of time indicate that the solvent reorientation process is nonexponential in nature. The decay function derived …

A Study Of The Acid Etch Pretreatment Used With The Nuva-Seal" Dental Process, Judith Ann Komoroski

Honors Theses

Nuva-Seal, a bisphenol-A-glycidyl-methacrylate polymer, is applied to the occlusal surface of teeth to prevent tooth decay. Before application of the sealant, the enamel surface is etched for one minute by a 50 percent by weight solution of phosphoric acid containing seven percent by weight of zinc oxide. This treatment renders the tooth surface more porous and surface active to insure a strong bond between tooth and sealant. Past studies at Union College have shown that the etching treatment removes much of the enamel from the tooth. In the current work the amount of tooth removed by acid etching was determined …

The Decomposition Of Azibenzil In The Presence Of Oxygen, Nancy C. Westby

Honors Theses

The ozonolysis of acetylenes is thought to proceed through the formation of ∝-carbonyl carbonyl oxide intermediates. This reaction has been shown to parallel the effect of molecular oxygen on ketocarbenes. Azibenzil, a diazo-ketone, will decompose to a ketocarbene by the action of heat, light or catalyst. The ketocarbene may decompose by two pathways: Wolff rearrangement and non-rearrangement. The Wolff rearrangement route will produce methyldiphenylacetate (upon addition of methanol), benzophenone, tetraphenylglycolide and possibly other high molecular weight polymeric species. The non-rearrangement pathway will presumably produce ∝-carbonyl carbonyl oxides which will decompose under varying circumstances to produce benzyl, benzoic anhydride, benzophenone, tetraphenylglycolide …

The Addition Of Singlet Oxygen To N, N-Diethyl-1-Propynylamine, Kenneth S. Zimmerman

Honors Theses

The addition of singlet oxygen to N, N-diethyl-1-pro-pynylamine produced 60-75% yields of N, N-diethyl pyruvamide and various carbon dioxide contamination products under several conditions. Products under several conditions. Product formation was independent of solvent and photosensitizer and was shown to proceed via a singlet oxygen addition mechanism with no free radical involvement. The water addition product was also demonstrated to be N, N-diethyl propanamide. A dioxetene intermediate is suggested as the precursor of N, N-diethyl pyruvamide.

The Preparation And Kinetics Of A Sterically Hindered Gold (Iii) Complex, Michael R. Golden

Honors Theses

The alkyl substituted gold (III) complex [Au(1, 4, 7-Me3dien)Cl] (PF6)2 [where 1, 4, 7-Me3dien respresents (CH3) HNCH2CH2N(CH3)CH2CH2NH(CH3)] has been synthesized. The cation of this compound differs from previously synthesized gold (III) complexes of similar structure since it can form a conjugate base only by loss of hydrogen from a terminal nitrogen. Aqueous solution chemistry studies of this ion reveals that the Cl- is hydrolyzed before loss of a proton from the ligand which is the reverse of the sequence observed with previously studied ions. Monobromo substitution rates are found to be slower than for the complex with no alkyl substitution …

Reactions Of Diazoketones With Neighboring Carbon-To-Carbon Double Bonds, Robert James Perry

Honors Theses

It was hoped that the carbon-carbon double bond in an unsaturated diazoketone would act as a nucleophile in an intramolecular attack to give a ring closure. Experimental results indicate that the double bond did participate, but in such a manner so as to give only substituted products, rather than cyclic ones. We suggest a diazonium salt intermediate in the initial formation of these substituted products. Polymerization and oxonium formation after reactopm with a Lewis acid solvent account for the polymers formed and some of the substituted products.

Magnetic Properties Of Linear Chain Systems: Metamagnetism Of Single Crystal Co(Pyridine)₂Ci₂, Simon N. Foner, Richard B. Frankel, William Michael Reiff, Herbert Wong, Gary J. Long

Chemistry Faculty Research & Creative Works

The metamagnetic behavior of the low temperature properties of single crystal Co(pyridine)₂Cl₂ is discussed. At 1.25 K oriented single crystals exhibit a two-step metamagnetic transition at applied fields ~0.8 and 1.6 kG along the b-axis, a single transition at ~0.7 kG for applied fields along the a* axis, and a single transition at ~4.2 kG for an applied field along the c axis. Just above the transition fields a moment of 2µ_B/Co atom is measured for B₀ parallel to the a* axis or b axis, and 0.4µ_B/Co atom is measured for the …

Co2 Laser Induced Decomposition Of Freon 113, Richard S. Herrick

Honors Theses

Irradiations were made on CCl2FCClF2, Freon 113, to see if the resulting decomposition was photochemical in nature. The irradiation source was Molectron 250, continuous wave, infrared laser operating in the single line mode. The wavelength of irradiation was varied over the range 9.473 µ to 9.734 µ. The pressure except one (in which the cell window broke). Relative rates of reaction were calculated for a constant power absorbed by the sample of 7.8 ± 4W. These relative rates were plotted against the irradiation wavelength. This was superimposed on a plot of the IR band for Freon 113 which was irradiated …

Synthesis Of Crown Ethers & Stereochemistry Of 1, 4-Ditertiarybutyl-1, 4-Dihydronaphthalene, Abdolreza-H-Hossein Nejad

Masters Theses & Specialist Projects

A. Cyclization of ethylene oxide in the presence of transition metal salts was studied. Several reactions with different catalysts were tried and some of these reactions produced compounds which show only one sharp singlet in their NMR spectra. These products were also soluble in benzene. The solubility of potassium permanganate in this mixture suggests the presence of cyclic polyethers. In spite of the above observations, all attempts to liberate cyclic ethers from their metal complexes were unsuccessful.

B. In the second project, the stereochemistry of 1,4-ditertiarybuty1- 1,4-dihydronaphthalene was elucidated using ¹H and ¹³C NMR. For this purpose, other …

Crown Ethers : Applications In Inorganic Synthesis, Robert L. Sundberg

Senior Scholar Papers

The ability of macroheterocyclic compounds to complex with ionic species has led to the synthesis and investigation of many multidentate macroheterocyclic species. The most stable complexes are formed between macrocyclic polyetheral ligands (crown ethers) with alkali or alkaline earth metal iona. There is an excellent correlation of the stability of these complexes with the size of the cation and the site of the cavity in the macrocyclic ligand. Additional factors, such as the basicity of the ligand and the solvating ability of the solvent, also play important roles in the stabilization of the complex. The stability of such complexes has …

The Investigation Of 3,4- Dipheny1-3- Cyclobutene-1, 2-Dione As A Precursor To A Bis-Ketene, John Dana Myers

Master's Theses

The purpose of this research is to investigate the use of 3, 4-diphenyl-3-cyclobutene-1, 2-dione as a synthetic precursor to bis-ketenes and ultimately examine the chemical behavior of this relatively unknown system. We intend to investigate some of the chemical behavior of bis-phenylketene produced by the well-documented photochemical ring opening of 3, 4-diphenyl-3-cyclobutene-1, 2-dione. Specifically the use of alkenes a chemical traps for the bis-ketene will be investigated. These reactions will be compared and contrasted to the behavior of the ketenes and vinyl ketenes.

Coordination Chemistry Of Bidentate Difluorophosphines, Darrell Lynn Gallup

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The reactions of 1, 2–bis(difluorophosphino)cyclohexane, PF₂C₆H₁₀PF₂, with hexacarbonyls of Cr(O), Mo(O), and W(O) have been extensively investigated. The hexacarbonyls react, either under photolytic or thermolytic conditions, to produce carbon monoxide and oily mixtures of products of the general formulations, [M(CO)₄(PF₂C₆H₁₀PF₂C)]_x, where x varies apparently from 1 – 4. The higher values of x, corresponding to species involving bridging ligands, are more common to the photolysis rather than the thermolysis reactions. Photolysis reactions of Mo(Co)₆ with increasing amounts of the …

Studies Toward The Synthesis Of A- And B- Mercapto Alanine Derivatives, And Of A,B- And B, B- Dimercapto Alanine Derivatives, Aldean James Kolar

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

A convenient, economical, large scale synthesis of N-acetyldehydro-alanine (a-acetamidoacrylic acid) and its methyl ester was developed via a sequence of N-chlorination-dehydrochlorination. The method was extended to the synthesis of the corresponding N-benzoyl, N-phenylacetyl and N-benzyloxycarbonyl derivatives.

The conversion of a-methoxy-N-acetyl alanine derivatives to the corresponding a-mercapto alanine derivatives, using zinc chloride and an appropriate mercaptan, was investigated. Methyl a-methoxy-N-acetyl-D, L-alaninate was successfully converted to the a-acetylthio derivative, in 24% yield; however, a 90% yield could be obtained by treatment of the dehydroalanine derivative with hydrogen chloride gas in neat thiolacetic acid.

A facile conversion of the a-acetylthio derivative to the …

The Photochemistry Of Alpha, Beta-Unsaturated Nitro Compounds, Liang-Wuen Chang

Masters Theses & Specialist Projects

1-(9-Anthry1)-2-nitropropene and 1-(3-pyridy1)-2-nitropropene were prepared and irradiated with ultraviolet light.

Irradiation of 1-(9-anthry1)-2-nitropropene, in which the ethylene group was twisted out of the plane of the aromatic ring and the resonance stabilization between the ethylene group and the aromatic ring was limited , gave only cis-trans isomerization.

Irradiation of 1-(3-pyridy1)-2-nitropropene gave an oxime. The effect of added HC1 on the reactivity of 1-(3-pyridy1)-2-nitropropene showed that the rate for the formation of oximinoketone was decreasing., while irradiation of 1-phenyl-2-nitropropene with HC1 showed that the rate for the formation of oximinoketone was increasing.

From these observation, steric factors and resonance factors are …

Removal Of Nitrogen & Sulfur From Coal-Derived Liquids & Identification Of Nitrogen & Sulfur Compounds In Coal-Derived Liquids, Tay-Yean Lin

Masters Theses & Specialist Projects

Since all the nitrogen compounds that have been identified in coal-derived liquids in the past have been basic in character, the effect of an acid-wash on the nitrogen content of coal-derived liquids was examined. Because sulfuric acid is the cheapest of the commerical strong acids, it was the natural choice, and its use was examined in detail. The greater the concentration of the sulfuric acid used, the greater the amount of nitrogen removed. :he sulfur compounds in coal-derived liquids were not removed noticeably by extraction with sulfuric acid. Column chromatography is a possible technique for removal of nitrogen compounds. The …

Second-Row Molecular Orbital Calculations. 5. A Minimal Basis Indo For Sodium-Chlorine, Mark S. Gordon, Mark D. Bjorke, Fred J. Marsh, Michael S. Korth

Mark S. Gordon

An INDO method is developed for molecules containing Na-CJ. Using only valences and p orbitals, the parametrization is carried out in the spirit of the approach originally taken by Pople and co-workers. The reliability of the method is tested by calculating geometries, dipole moments, and internal rotation barriers for approximately 100 molecules. The improvement in predictive ability relative to previous parametrizations is considerable. Predicted geometries are nearly as good as those for ST03G. Dipole moments of molecules containing Si and Clare in excellent agreement with experiment, while for P and S the agreement is only fair.

Erratum: Light Scattering Studies Of Rotational And Vibrational Relaxations Of Acetonitrile In Carbon Tetrachloride, Scott Whittenburg

Chemistry Faculty Publications

No abstract provided.

Comparative Enzymology Of Glyoxalase I, Christina Margaret Schimandle

Chemistry and Chemical Biology ETDs

The role of the metal ion in rat erythrocyte glyoxalase I was evaluated. The apoenzyme was formed by dialysis against an EDTA-imidazole buffer. Fluorescence studies of the Mg⁺⁺- and Mn⁺⁺-dansylated glyoxalase I's suggest that the metal ion is near the active site of the enzyme and participates in the catalytic reaction. Stereochemical studies of the conversion of methylglyoxal to S-lactoylglutathione with Mg⁺⁺, Mn⁺⁺, Co⁺⁺ and Ni⁺⁺-glyoxalase I's show that the 0-lactate of S-lactoylglutathione (97±1.5%) is formed. This result suggests that the reaction mechanism is the same with a change …

Freezing Points Of Aqueous Alcohols: Free Energy Of Interaction Of The Choh, Ch₂, Conh And C[Double Bond]C Functional Groups In Dilute Aqueous Solutions, B. Y. Okamoto, R. H. Wood, Peter T. Thompson

Chemistry & Biochemistry Faculty Works

The freezing temperatures of dilute aqueous solutions of methanol, ethanol, 2-propanol, butanol, t-butanol, cyclohexanol and ethylene glycol were measured over the concentration range 0.1 to 1 mol kg–1. Osmotic coefficients at 0°C were calculated. The limiting pairwise interaction coefficients of the alcohols, plus a variety of polyhydroxy compounds and carbohydrates, were calculated at 25°C from the available data and then correlated using the additivity principle of Savage and Wood. This correlation approximates effective free energies of CH2 and CHOH group interactions with themselves and with each other. Literature data were used to estimate interactions between CONH and C[double bond]C groups. …

Rapidly Converging Activity Expansions For Representing The Thermodynamic Properties Of Fluid Systems: Gases, Non-Electrolyte Solutions, Weak And Strong Electrolyte Solutions, R. H. Wood, T. H. Lilley, Peter T. Thompson

Chemistry & Biochemistry Faculty Works

For dilute gases and non-electrolyte solutions in the McMillan–Mayer standard state, an activity expansion due to Mayer has great advantages over the normal concentration expansion (virial equation) for strongly associating species. For weakly interacting systems, both approaches are suitable. The activity expansion eliminates the need to differentiate between strong “chemical” interactions and weak “physical” interactions since the same equation is used in each situation. The equation has been modified to represent electrolyte solutions in the McMillan–Mayer standard state by requiring that it be consistent with the Debye–Hückel and higher order limiting laws for strong electrolytes and that it be equivalent …

New Header Treatment Aids Weevil Control, J H. Moulden

Journal of the Department of Agriculture, Western Australia, Series 4

A new insecticide formulation supplied in high pressure cylinders simplifies weevil control in headers.

Excited States And Photochemistry Of Saturated Molecules. Ix. Vertical Excited States Of Silane, Mark S. Gordon

Mark S. Gordon

The vertical excited states of silane are investigated using ten different basis sets to systematically compare the effects of (a) Rydberg functions, (b) diffuse d functions, (c) valence d functions, and (d) a split valence shell. Wavefunctions are generated using all singly excited configurations, excluding inner shells. The low‐lying singlet states are dominated by excitations into the diffuse orbitals, while low‐lying triplets have significant valence character. Valence d functions have a minor effect on excitation energies if an adequate valence s p basis set is used. The main effect of Rydbergd functions is to introduce additional Rydberg states below the …

Thermodynamics And Statistical Mechanics Of The Ideally Polarisable Electrode Gibbs Isotherm And Surface Tension, Jean-Pierre Badiali, Jerry Goodisman

Chemistry - All Scholarship

A definition of the ideally polarisable electrode which allows a general statistical mechanical treatment is given, comparisons with the usual thermodynamic approach being made. It is shown that, with this definition, the system behaves as a pure capacitance to an imposed alternating potential of sufficiently low frequency. The equilibrium states of the system are described by the grand canonical distribution. Thermodynamic functions, given in terms of the grand canonical partition function, can be computed in molecular terms: In particular, general expressions for the surface tension and the pressure are obtained, and compared to those proposed by various authors. The separation …