Physical Sciences and Mathematics Commons^™

A Mechanistic Study Of The Saponification Of Pivaloate Esters, Beni Brian Wolf

Honors Theses

The reactions of the esters of trimethyl acetic acid (pivalic acid) have been followed kinetically (Walrath 1977 and Watkins 1986) in the presence of alkali in a 3:1 ethyl cellosolve: water solvent at 64°C. Through the use of both optically active pivaloates and O18 as a tracer, the positions of bond fission during saponification for several pivolates have been determined. With the secondary butyl ester bimolecular attack on both the acyl- and the alkyl- carbon atom is observed in the presence of alkali. Partial racemization of the product secondary butyl alcohols suggests that for a saponification of secondary butyl pivaloates …

The Effects Of Hydrogen Bonding On The Spectral Properties Of 2'-Acetonaphthone, Kristine A. Loparo

Honors Theses

The effects of hydrogen bonding on the luminescent properties of 2'-acetonaphthone (2-AN) have been studied. Solvents of varying hydrogen bond donor abilities such as perfluorohexane(PFH), cyclohexane, ethanol, methanol, water, trifluoroethanol(TFE), and hexafluoroisopropanol(HFIP) have been used. An attempt is made to find a relationship between solvent hydrogen bond donor ability, the energy and efficiency of fluorescence emission and changes in 2-AN electronic absorption in these solvents. The 2-AN spectral properties have also been studied in mixed solvent systems where the molecule is dissolved in a nonpolar solvent, either PFH of cyclohexane, and one of the fluorinated alcohols (TFE or HFIP) is …

Conformational Energy Calculations Of Tyrocidine, Leslie Beth Shapiro

Honors Theses

The minimum energy conformation of the cyclic decapeptide tyrocidine was calculated using the Empirical Conformational Energy Program for Peptides (ECEPP). Half of the amino acid sequence of tyrocidine is identical to the amino acid sequence found in the cyclic decapeptide gramicidin-S. Hence this study focuses on the conformation of the decapeptide that is not contained in gramicidin-S. This study calculates the conformation of a tripeptide ASN-GLN-TYR without the consideration of the presence of a beta bend formation because there is a low probability that a beta bend exists in this location. Two of the lowest energy conformations found in this …

The Construction And Testing Of A System For Flash Photochemical Studies Of Organotransition Metal Compounds, Robin Lynn Miller

Honors Theses

The main objective of my research efforts was to construct a flash photolysis system which would enable one to carry out time-resolved studies of photoinitiated reactions of organometallic hydrides. Such a development involved two major tasks. First, it required establishing a functioning vacuum line. Organometallic complexes are extremely sensitive to oxygen and water. Therefore these contaminants must be removed if one is to have any success in studying their reactions. A vacuum line is the most efficient means for degassing both solvent and solute Second, it involved modifying our flash photolysis apparatus. Changes in the flash rig included upgrading the …

Development Of An Analytical Method For The Detection Of Specific Cations Using Flow Injection Analysis, John G. Cummings

Honors Theses

A general approach for the development of an analytical method for the detection of specific cations using flow injection analysis has been investigated. In this approach, an ionophore (I), which is selective for the cation (M+) of interest, is noncovalently immobilized on a controlled pore glass (CPG) surface. A column of tygon tubing is then filled with the 1-CPG phase and placed in the cell compartment of a spectrofluorometer. When an aqueous mobile phase containing M+ and 8-anilino+naphthalene sulfonic acid (ANS) is pumped through the column, the M+ reversibly binds to the immobilized I, and the resulting complex then forms …

Interfacial Adhesion Of Fiberglass Reinforced Thermoplastic Composites, David Gascoyne

Honors Theses

The use of reinforced plastics is vast. A proper understanding of these materials and their properties is Important. The interface of a reinforced plastic influences many of the materials mechanical properties. This study of fiber reinforced composites was conducted to better understand the interfacial interactions between XENOY and E-Glass fibers. The research consisted of studying the effects of processing temperature, long term hydrolytic attack, and coupling agents, on the interface.

Synthesis Of Allylic Organotin Compounds For The Preparation Of Homoallylic Alcohols, Deborah R. Hermance

Honors Theses

The addition of an allylic organotin compound to an aldehyde in the presence of a Lewis acid affords the erythro homoallylic alcohol. Organotin compounds containing optically active constituents such as menthyl and myrtanyl have been prepared. The myrtanyl compound was used in the preparation of an allylic organotin, cinnamyl trimyrtanyl tin, for future reaction with benzaldehyde. The objective is to obtain both enantio- and diastereoselectivity in the addition reaction.

Conformations Of Dna Oligomers, Daniel Edward Vaughn

Honors Theses

This work examines the conformations of various ollgonucleotides as a function of two environmental conditions, neighboring base combinations and surrounding media. The conformations were determined by molecular mechanical energy refinement using the internal minimization function of a program written by Ken Miller. The first condition examined was the effect of various neighboring base combinations on the conformation of the interior base. Our results indicate that the NH2 a,,lino groups are the primary factors in determining differences in conformations of various base pairs sequences. One way in which the NH2 amino groups are able to affect the conformation of the molecule …

Use Of Economic Instruments In Biodiversity Conservation Projects: The Sustainability Of Projects In The Ecuadorian Amazon, Amy Lyons

Honors Theses

Under what conditions do biodiversity conservation projects that use economic incentives promote the most significant and sustainable biodiversity protection? The study of how nations can best invest their resources to promote conservation while simultaneously encouraging a sustainable form of economic development has recently become a major focus for ecologically rich, less-developed countries. There have been many innovative and successful attempts at combining biodiversity protection with economic development, and others that have done more harm than good. Since there is no guaranteed recipe for a successful project, it is crucial to examine projects in detail to discern which type of project …

Fluoride As A Therapeutic Drug In Osteoporosis Treatment, Rita Priyadarshani Francis

Honors Theses

The use of fluoride as a therapeutic drug is not a novel idea. Studies dealing with the effects of fluoride on the skeletal system date back to the late 1960's. This paper will define osteoporosis, examine methods of detection, and will discuss various methods of treatment with emphasis on the use of fluoride supplements in the form of tablets or fluorinated drinking water.

Equilibrium Constant Determination For Bisulfite Addition To Aromatic Aldehydes, Daniel Y. Choi

Honors Theses

Equilibrium constants for bisulfite addition to benzaldehyde and its derivatives were determined by a spectrophotometric method developed by Kokesh and Hall. The concentration of the benzaldehyde derivative was monitored by UV as aliquots of a bisulfite solution are added to a buffered solution of the aldehyde. Additional data on ΔH° and ΔS° for the reactions were derived from the temperature variation of the equilibrium constants. For benzaldehyde, the reaction had an equilibrium constant at 25°C of 6.2 x 103 M-1, a ΔH° of -54.3 kJ/mol, and a ΔS° of -111 J/Mol·K. o-Tolualdehyde exhibited a lower Keq of 2.4 x 103 …

The Synthesis Of Homoallylic Alcohols Through Diasteriomeric Transition States, Jeffrey Lee Osofsky

Honors Theses

Theoretically, optically active homoallylic alcohols can be synthesized by reacting an optically active organotin with an aldehyde in the presence of a Lewis acid. It is expected that the chirality of the organotin will induce one diastereomeric transition state which will have a significantly reduced activation energy than the transition state of the other diastereomer. If the difference between the two activation energies is substantial enough, the transition state with the lower activation energy will be preferred over the other transition state. If the preference is absolute one completely pure alcohol enantiomer will be produced. If there is a preference, …

Making A Rainbow Workstation For A Chemistry Lab, John D. Bak

Honors Theses

Chemical kinetics is the study of how quickly and by what means chemical reactions proceed. Some reactions are so fast and complicated that data must be taken very quickly and then lengthy calculations must be done to get results. Computers speed these studies greatly. The system to he described uses a DEC-Rainbow microcomputer as a terminal for a workstation. The system may collect 8k of buffered data at a rate of 1MHz and then upload the data to a VAX for analysis using the same Rainbow u a graphics terminal. The program for data analysis, called KinSim, will then accept …

Chirality Transfer In The Synthesis Of Homoallylic Alcohols, Simon Paul Drew

Honors Theses

Previous studies on the reaction of the optically active organotin, diallylisopropylmyrtanyltin, to produce homoallylic alcohols, using boron trifluoride as a Lewis acid, produced racemic mixtures regardless of the aldehyde used.1 In this experiment bromine was attached to the tin atom in allylmyrtanylphenyltin bromide, letting tin become an internal Lewis acid. Benzaldehyde was reacted with this compound to see it a single optically active product could be synthesized. After the alcohol had been separated out using vacuum distillation, the optical rotation of the product was taken and showed no appreciable rotation; thus a racemic mixture was produced.

The Use Of Direct Current Argon Plasma Spectroscopy For Quantitative Analysis Of Geological Samples, Stephen N. Lipsky

Honors Theses

The focus of this project was the development of a process of analyzing geological samples which contain moderate amounts of silica. The main emphasis was put upon the reduction of the amount of "wet" chemistry and laboratory time involved in such analysis. Previous elemental analysis of such samples relied upon time consuming techniques such as combustion and precipitation reactions. Moreover, these analyses required the use of highly corrosive hydrofluoric acid (HF). This project utilized a DC Argon Plasma Spectrometer (DCP) for all elemental analyses. Furthermore, the only chemical required for the project was concentrated nitric acid. This project proposed that …

Synthesis Of 3, 6-Dimethyl-9, 10-Bis (Trimethylsilyl) Diimine: Structural Modification Of An Electrically Conductive Organic Solid, Cynthia A. Morphet

Honors Theses

The current, intense interest in non-classical electrical conductivity and superconductivity has stimulated an equally intense effort to synthesize new materials which exhibit enhanced electrical conductivities. This thesis reports such an effort. Previous work had resulted in the formation of planar aromatic compounds capable of acting as "synthetic metals", i.e.: of conducting an electrical charge. These efforts had focused on compounds utilizing heteroatoms from Group VIA. Efforts to synthesize analogous compounds utilizing heteroatoms from Group VA had been partially successful, but were hampered by solubility considerations. This research focuses on the synthetic procedure developed to produce an analog of one of …

Spectral Studies Of Pyrene Carboxylic Acids, Jeannie Haller

Honors Theses

The pKa and pKa* of 1-pyrenecarboxylic acid (PCA) in a 50% ethanol/water solvent were experimentally (letermined to be 4.3 and 5.2, respectively. The pK8 of pyrene acrylic acid (PAA) in the same solvent was experimentally determined to be 4.6. An excited state equilibrium was not reached at the buffer concentrations used for the pKa* analysis; therefore, a valid value for the pKa* can not be reported at this time, but taking both the experimental results and the calculated pK8.'s into account, it appears that the pKa* of PAA is in the range 6.6 < pKa* < 7.4. The fluorescence of PCA, PAA, and 1-anthroic acid (1-AA) were studied as a function of solvent. The fluorescence of PCA was solvent independent- small spectral shifts as well as the retention of structure were observed in solvents of varying polarity. The fluorescence of 1-AA and PAA exhibited a solvent dependence. The results of both the pKa analysis and the fluorescence studies indicate that the S0 and the S1 states of PCA have a similar geometry, but that the geometry of the S0 and the S1 states of PAA differ. The change in geometry may be the rotation of the carboxyl group from its nearly perpendicular position with the ring in the S0 state to a more coplanar position with the ring in the S1 state. The effects of hydrogen bonding in hexafluoroisopropanol on the spectral properties of PAA were studied, and the results of the studies indicate that PAA forms a hydrogen-bonded complex with hexafluoroisopropanol in both the ground and the excited states.

Determination Of The Kinetic And Thermodynamic Properties For Bisulfite Addition To: Acetophenone, 2-Chloroacetophenone And Trans-Cinnamaldehyde, Laurie Ann Le Tarte

Honors Theses

The equilibrium constants for bisulfite addition to acetophenone, 2-choloroacetophenone and trans-cinnamaldehyde were determined using an ultraviolet spectrophotometric method. The absorbance of the carbonyl compound was monitored as aliquots of a bisulfite solution were added to the reaction cell. By plotting 1/A versus [HSO3-], and dividing the slope by the intercept, it was possible to determine Keq. All determinations were made at pH 4.66 and ionic strength 1.0. By determining Keq at various temperatures it was also possible to determine ΔH° and ΔS°. The equilibrium constants for bisulfite addition to: acetophenone, 2-choloracetophenone and trans-cinnamaldehyde, were determined to be: 5.8 M-1, 53 …

Determination Of The Kinetic And Thermodynamic Properties For Bisulfite Addition To: Acetophenone, 2-Chloroacetophenone And Trans-Cinnamaldehyde, Laurie Ann Letarte

Honors Theses

The equilibrium constants for bisulfite addition to acetophenone, 2-choloroacetophenone and trans-cinnamaldehyde were determined using an ultraviolet spectrophotometric method. The absorbance of the carbonyl compound was monitored as aliquots of a bisulfite solution were added to the reaction cell. By plotting 1/A versus [HSO3-], and dividing the slope by the intercept, it was possible to determine Keq. All determinations were made at pH 4.66 and ionic strength 1.0. By determining Keq at various temperatures it was also possible to determine ΔH° and ΔS°. The equilibrium constants for bisulfite addition to: acetophenone, 2-choloracetophenone and trans-cinnamaldehyde, were determined to be: 5.8 M-1, 53 …

The Synthesis Of Homoallylic Alcohols Through Diasteriomeric Transition States, Jeffrey Lee Osofsky

Honors Theses

Theoretically, optically active homoallylic alcohols can be synthesized by reacting an optically active organotin with an aldehyde in the presence of a Lewis acid. It is expected that the chirality of the organotin will induce one diastereomeric transition state which will have a significantly reduced activation energy than the transition state of the other diastereomer. If the difference between the two activation energies is substantial enough, the transition state with the lower activation energy will be preferred over the other transition state. If the preference is absolute one completely pure alcohol enantiomer will be produced. If there is a preference, …

Rise To Power Of Senator Joseph R. Mccarthy: Reflections Of The Cold War Mccarthy Era In American Film, Scott Lainer

Honors Theses

The common bond between much of the film industry and Joseph McCarthy was insecurity and the drive for national approval. If one grasps the specific characteristics of McCarthy the man, and the methods of these politically "inspired" movies, we can to better place the period into context and acknowledge the fact that, if the citizenry is not aware, and is again caught by an ever-building wave of trickle down sentiment, the 1950s might not prove to be an isolated period in American history. Insecurity was not a fifties novelty. It still exists, and could potentially escalate anti-Communist policy and sentiment …

The Synthesis Of Phenyl Carbamate (From Urea, Phenol, And A Lewis Acid), Michael W. Barrett

Honors Theses

The synthesis of phenyl carbamate from urea, phenol, and Lewis acid was attempted with varied results being observed. The proposed reaction mechanism involves and Acyl-2 type reaction with a nucleophilic attack on urea by phenol. The Lewis acid is present to add carbocation character to the urea and to further complex with by-products, thus driving the reaction to completion. The solvents utilized were isopropyl alcohol, dichloromethane, and tetrahydrofuran. The reaction parameters were varied in an effort to successfully run a reaction mechanism. Phenyl carbamate was not isolated and what was observed of the reactions did not appear to follow the …

An Nmr Analysis Of The Hydrolysis Of Alpha-Bromopropionic Acid, Barbara A. Jensen

Honors Theses

The kinetics of hydrolysis of ∝-bromopropionic acid were investigated at 80° and a constant pH of 3.3. An average first order rate constant of 4.74x10-3 min-1 was determined. This hydrolysis reaction has been studied by several workers. It is unique in that the reaction proceeds through inversion reactions, the first involving the carboxylate ion. This paper covers the first study where the pH of the system was maintained constant. The design if an inexpensive pH-stat for this purpose is given. The experiment and/ or data lend themselves useful for treatment in physical chemistry where the students must gather data in …

The Triplet State Photophysics Of Phenanthrene, Roberta Susnow

Honors Theses

The first excited triplet state (TI state) of aromatic hydrocarbons such as phenanthrene acts as an intermediate in many chemical and photochemical reactions. The TI state is a metastable state and its lifetime can be measured in terms of its decay to the ground state. The duration of this decay is on the order of microseconds. Therefore, techniques for measuring the kinetics of fast reactions must be employed in the determination of the rate of the TI state decay, one such technique that is utilized in this research is flash photolysis. The rate of the Tl state decay is greatly …

Luminescence Probes For The Measurement Of Oxygen, Mary Katherine Carroll

Honors Theses

The goal of this project was to design an optical sensor for oxygen. One type of system suitable for oxygen detection in aqueous solutions is based on two distinct emission bands: one band oxygen-sensitive, the other insensitive to oxygen quenching. By taking the ratio of these bands, a quantitative measurement of the oxygen present could be obtained. This could be accomplished in a system where a fluorescing compound, through triplet state energy transfer, causes a lanthanide ion to luminesce. By choosing a compound which has a triplet energy near the excitation wavelength of terbium (III) or europium (III) and which …

Saponification Of Several Esters Of Pilvalic Acid, Kevin Thomas Watkins

Honors Theses

The base promoted hydrolysis, saponification, of several esters of pivalic acid (trimethyl acetic acid – C (CH3)3COOH) has been studied. Kinetic studies were performed and a possible mechanism for the reactions is proposed. The saponification of esters has been well studied. Ingold1 proposes three possible mechanisms for the reaction; Bac2, Bal1, and Bal2. The B stands for base promoted, the ac and al for acyl oxygen cleavage or alkyl oxygen cleavage, respectively, and the 1 or 2 for first or second order kinetics.

A Study Of Dislocations In Crystals Using The Technique Of Chemical Etching, Ramona R. Dennis

Honors Theses

The beauty of many of the crystalline solids has attracted man's attention from the earliest times. Eventually the science of crystallography developed from studies of their shapes. The word crystal sterns from the Greek word "krystallos" meaning "clear ice." The word was first applied to describe the clear quartz crystals found in the Swiss Alps. The crystals were thought to be formed from water under conditions of extreme cold.

The earliest recorded crystallographic observation was in 1597 by Andreas Libarius. He noticed that crystals of different substances often have characteristic shapes. He suggested that the salts in mineral water could …

Senior Honors Project, Kelly Dyksterhouse

Honors Theses

The Statistical Analysis Project is a computer program that interacts with a person to discover the type of statistical test that person should use. Essentially, this program is intended to assist students, faculty and researchers in choosing the correct statistical procedure to use in a particular situation. For example, there are many different types of tests a person can use to test the mean of data but each test is used in a different situation. This program will tell you which test to use based on the situation you give it. This project was started by Anika Forsblad in 1985.

A Preliminary Study On The Separation Of Bovine Plasma Albumin-Copper Ion Dimer And Trimer Reaction Products By Ion-Exchange Chromatography, James T. Miller

Honors Theses

When bovine plasma albumin is in the presence of copper metal ions at pH values below the isoelectric point, a dimerization reaction takes place between the protein molecules. The kinetics of this reaction have been previously studied by using light scattering techniques. These techniques involve monitoring the amount of light scattered as the dimerization reaction proceeds. As the amount of dimer present increases, more light is scattered due to increased molecular size in the solution. Accurate calculations of the rate of this reaction depend upon knowing the ratio of dimer to monomer concentrations at any given time. Unfortunately, evidence has …

Detection And Analysis Of Carbonyl Compounds In Rural Cloudwater, Steven Bart Bertman

Honors Theses

A new technique for aqueous determination of aldehydes and ketones was field tested along with a new technique for ambient air analysis. The work was done during the summer of 1984 on Whiteface Mountain in Wilmington, NY. Both techniques utilized carbonyl derivitization as their 2,4-dinitrophenyl hydrazones and subsequent analysis by reversed phase HPLC. Analysis of the blank levels for the ambient air method shows the levels found to be non-detectable. The aqueous method worked well. Formaldehyde, acetaldehyde, and acetone were the only species found in cloud water. They were generally present in concentrations between .5 uM and 4 uM. Little …