Doctoral Dissertations

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Browsing Doctoral Dissertations by Department "Chemistry & Physics"
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    A 195Pt nuclear magnetic resonance spectroscopy study of the solvolysis of sodium hexachloroplatinate by dimethyl sulfoxide.
    (Middle Tennessee State University, 1991) Allbritten, Jeffery ; Chemistry & Physics
    Platinum-195 Fourier transform nuclear magnetic resonance spectroscopy was used to study the reaction of sodium hexachloroplatinate with dimethyl sulfoxide-dg in the mixed solvent dimethyl sulfoxide-dg: water, 1:2, V/V.
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    Differentiation of mistletoes on the basis of geographical origin using capillary gas chromatography and multivariate analysis.
    (Middle Tennessee State University, 1996) Looney, Michael ; Chemistry & Physics
    Multivariate statistical analysis of gas chromatographic data has been applied to the differentiation of species of mistletoe based on their geographic origin. Mistletoe plants were collected from 26 locations in Texas and 13 locations in Tennessee, Alabama, Georgia, and Florida. Hexane extractions were analyzed by split injection capillary gas chromatography. The column used was a Hewlett Packard capillary column Ultra 1, 25-meters long with an I. D. of 0.2 millimeters and a film thickness of 0.11 micrometers. The oven was programmed from {dollar}100\sp\circ\rm C{dollar} to {dollar}315\sp\circ\rm C{dollar} at a rate of {dollar}7.5\sp\circ\rm C{dollar} per minute and then held at {dollar}315\sp\circ\rm C{dollar} for 30 minutes.
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    Mechanism and kinetics of haloperoxidase-catalyzed bromination reaction.
    (Middle Tennessee State University, 1994) Yang, Zhen-ping ; Chemistry & Physics
    Haloperoxidase-catalyzed bromination of tyrosine was studied. Three haloperoxidases from different sources were used. When chloroperoxidase (CPO) was used as the enzyme, and when {dollar}\rm was H\sb2O\sb2{dollar} was present, the conversion of Br{dollar}\sp-{dollar} to Br{dollar}\sb3\sp-{dollar}/Br{dollar}\sb2{dollar} species was an enzyme-catalyzed reaction, and the enzyme, CPO, was irreversibly deactivated by the free molecular bromine formed in that reaction. It was observed that the above deactivation of CPO was associated with the irreversible destruction of CPO's heme structure. The minimum Br{dollar}\sb2{dollar}/CPO ratio to cause that deactivation was obtained. The actual bromination reaction was concluded to be a nonenzymatic reaction between Br{dollar}\sb2{dollar} and tyrosine, Also observed was the reaction between {dollar}\rm H\sb2O\sb2{dollar} and Br{dollar}\sb3\sp-{dollar}/Br{dollar}\sb2{dollar} species to produce O{dollar}\sb2{dollar} and Br{dollar}\sp-,{dollar} if the Br{dollar}\sp-{dollar}/{dollar}\rm H\sb2O\sb2{dollar} ratio was not high enough. The minimum Br{dollar}\sp-{dollar}/{dollar}\rm H\sb2O\sb2{dollar} ratio required to inhibit the production of O{dollar}\sb2{dollar} and Br{dollar}\sp-{dollar} was determined. Inhibition of this reaction would allow Br{dollar}\sb3\sp-{dollar}/Br{dollar}\sb2{dollar} to accumulate. The maximum Br{dollar}\sp-{dollar}/{dollar}\rm H\sb2O\sb2{dollar} ratio that would allow the production of O{dollar}\sb2{dollar} and Br{dollar}\sp-{dollar} was also determine. This would prevent the Br{dollar}\sb3\sp-{dollar}/Br{dollar}\sb2{dollar} species from accumulating.
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    Numerical analysis as applied to x-ray scattering curves.
    (Middle Tennessee State University, 1991) Jeffries, Thomas ; Chemistry & Physics
    Various numerical methods involving polynomials were employed for both interpolation and linear least-squares curve fitting of the atomic scattering factors of X-ray diffraction. This included use of Lagrangian and orthogonal Legendre polynomials, as well as cubic spline and Stineman interpolation.
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    OSHA compliance in the academic organic chemistry laboratory.
    (Middle Tennessee State University, 1995) Newhouse, Marlyn ; Chemistry & Physics
    The Federal Regulation, 29 CFR 1910.1450, "The Occupational Exposures to Hazardous Chemicals in Laboratories", applies to school science laboratories where chemicals are found. This may be a new finding to those who thought Occupational Safety and Health Act (OSHA) regulations only apply to industries and manufacturing.
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    The role of silica gel in the solid-phase-catalyzed friedel-crafts tert-butylation of hydroquinone.
    (Middle Tennessee State University, 1995) Davis, Arthur ; Chemistry & Physics
    The use of silica gel as an acidic catalyst for the Friedel-Crafts alkylation of hydroquinone with tert-butyl bromide affords 2,5-di-tert-butylhydroquinone in high yield and purity if sodium carbonate is also present. Drying the sodium carbonate in a furnace (275{dollar}\sp\circ{dollar}C) effectively stops this Friedel-Crafts alkylation. Hence, a trace amount of water serves a necessary role as cocatalyst. Isobutene and its olefinic dimers are formed in small amounts from tert-butyl bromide during the reaction; however, isobutene is not the source of the electrophilic intermediate in the Friedel-Crafts tert-butylation because the extent of alkylation in a closed reaction vessel is the same as that obtained when the stirred and heated reaction was conducted in an open system whose thermostated reflux condenser was kept at temperatures above the boiling point of isobutene.
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    A scanning electron microscopic examination of radiation-induced structural changes in potato tubers.
    (Middle Tennessee State University, 1991) Mitchell, Villa ; Chemistry & Physics
    Both chemical and scanning electron microscopic (SEM) analyses were done on potato tubers ("Superior" variety) before and after a sprout inhibiting dose (10 Krad) of radiation. The chemical analyses were run to detect any changes in the reducing and nonreducing sugar content as well as any changes in the starch concentration. A colorimetric method using 3,5-dinitrosalicylic acid was chosen to estimate the change in sugar and starch content. The results obtained indicate that radiation caused an increase in the reducing and nonreducing sugar (sucrose) content and a decrease in the amount of starch.
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    Selection and evaluation of experiments in instrumental analysis for schools with limited instrumental resources utilizing the inquiry oriented approach.
    (Middle Tennessee State University, 1996) Mauldin, Penny ; Chemistry & Physics
    The purpose of this study was to develop and evaluate a selection of experiments in instrumental analysis for schools with limited instrumental resources. The primary intent behind the selection of experiments was to develop them in such a manner that students would have the opportunity to acquire physical skills in working with laboratory instrumentation, study the scientific method, develop critical thinking, and initiate investigation in the chemical laboratory. Six experiments for ultraviolet/visible and gas chromatography were selected for field-testing and evaluation. The instrument chosen for the content analysis was the Laboratory Structure and Task Analysis (LAI) by Tamir, Lunetta, Novick, and Fuhrman. The LAI was designed as a tool to measure inquiry oriented laboratory curricula. Qualitative open-ended questions designed by the investigator were also included as part of the evaluation.
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    Synthesis and investigation of nickel (II) 4-substituted 2,6- dichlorophenolates.
    (Middle Tennessee State University, 1995) Mccorkle, David ; Chemistry & Physics
    Monodentate or bidentate ligands (L) of nitrogen and phosphorus were used in the synthesis of nickel(II) complexes of the type M({dollar}\rm OC\sb6H\sb2Cl\sb2X)\sb2(L)\sb{lcub}n{rcub}{dollar} (X = Cl, Br, H). Nuclear quadrupole resonance (NQR) spectroscopy was utilized to examine the secondary bonding of ortho-chlorines of 2,4,6-trichlorophenolate, 2,6-dichlorophenolate, and 4-bromo-2,6-dichlorophenolate ions to the nickel in the presence of various ligands. Trends in the strength of the M-Cl interaction as a function of M were explained by crystal field theory: they are largely determined by the octahedral site stabilization energy (OSSE) of the metal ion. Steric effects and strong ligand fields also play a role. Difficulties in forming complexes using both monodentate and bidentate phosphorus ligands may indicate only a small role for back bonding, while the presence of extra ligands capable of forming normal strength bonds to nickel(II) can prevent secondary bonding altogether. Secondary bonding in octahedral (N,N,N{dollar}\sp\prime{dollar}N{dollar}\sp\prime{dollar}-tetramethyl-1,2- ethanediamine)bis-(2,4,6-trichlorophenolato-O,Cl)nickel(II) and pentacoordinate tris(pyridine)bis(2,4,6-trichlorophenolato-O)nickel(II) is discussed.
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    Teaching spectroscopy through the use of computer simulation.
    (Middle Tennessee State University, 1991) Pfister, Karen ; Chemistry & Physics
    Spectral analysis of hydrocarbons is an important part of teaching organic chemistry. This field has depended heavily upon infrared spectroscopy (IR) and proton nuclear magnetic resonance spectroscopy ({dollar}\sp1{dollar}H NMR) with some emphasis placed on mass spectroscopy (mass spec) and carbon-13 nuclear magnetic resonance spectroscopy ({dollar}\sp{lcub}13{rcub}{dollar}C NMR). The main use of these concepts, while briefly covered during lecture, is in the identification of unknowns in qualitative organic laboratory sessions. The combination of "wet" qualitative chemical analysis and spectroscopic analysis of a compound makes positive identification of an unknown possible.