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 Department: Department of Chemistry
 Collection: UNT Theses and Dissertations
Mercury-Sensitized Photochemical Reactions of Isopropyl Alcohol

Mercury-Sensitized Photochemical Reactions of Isopropyl Alcohol

Date: May 1959
Creator: Armstrong, Andrew Thurman
Description: This thesis describes the reactions of mercury-sensitized isopropyl alcohol when bombarded with 2537 Angstrom radiation.
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The Reactions and Emission Spectra of Propylene in Electrodeless Discharge

The Reactions and Emission Spectra of Propylene in Electrodeless Discharge

Date: May 1959
Creator: Armstrong, Andrew Thurman
Description: This thesis describes the reactions and emission spectra of propylene under radio frequency energy radiation.
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A Study of the Reduction Products of N-(4-Nitrophenacyl)-4-(1-Hexyl)pyridinium Bromide

A Study of the Reduction Products of N-(4-Nitrophenacyl)-4-(1-Hexyl)pyridinium Bromide

Date: 1950
Creator: Arnwine, Bennie C.
Description: Because of the structural analogies between these compounds and several other physiologically active compounds, such as chloroamphenicol, 4,4'-diaminodiphenyl sulfone, and 2,2-bis-(p-aminophenyl)-1,1,1-trichloroethane, a more complete study of the reduction products and the sequence of catalytic reduction of N-(4-nitrophenacyl)-4-(1-hexyl)pyridinium bromide was made in this investigation.
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Interfacial Electrochemistry of Metal Nanoparticles Formation on Diamond and Copper Electroplating on Ruthenium Surface

Interfacial Electrochemistry of Metal Nanoparticles Formation on Diamond and Copper Electroplating on Ruthenium Surface

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Date: May 2003
Creator: Arunagiri, Tiruchirapalli Natarajan
Description: An extremely facile and novel method called spontaneous deposition, to deposit noble metal nanoparticles on a most stable form of carbon (C) i.e. diamond is presented. Nanometer sized particles of such metals as platinum (Pt), palladium (Pd), gold (Au), copper (Cu) and silver (Ag) could be deposited on boron-doped (B-doped) polycrystalline diamond films grown on silicon (Si) substrates, by simply immersing the diamond/Si sample in hydrofluoric acid (HF) solution containing ions of the corresponding metal. The electrons for the reduction of metal ions came from the Si back substrate. The diamond/Si interfacial ohmic contact was of paramount importance to the observation of the spontaneous deposition process. The metal/diamond (M/C) surfaces were investigated using Raman spectroscopy, scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS) and x-ray diffractometry (XRD). The morphology (i.e. size and distribution) of metal nanoparticles deposits could be controlled by adjusting the metal ion concentration, HF concentration and deposition time. XRD data indicate the presence of textured and strained crystal lattices of Pd for different Pd/C morphologies, which seem to influence the electrocatalytic oxidation of formaldehyde (HCHO). The sensitivity of electrocatalytic reactions to surface crystal structure implies that M/C could be fabricated for specific electrocatalytic applications. The research also ...
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Sensitization of Lanthanides and Organic-Based Phosphorescence via Energy Transfer and Heavy-Atom Effects

Sensitization of Lanthanides and Organic-Based Phosphorescence via Energy Transfer and Heavy-Atom Effects

Date: May 2010
Creator: Arvapally, Ravi K.
Description: The major topics discussed are the phosphorescence sensitization in the lanthanides via energy transfer and in the organics by heavy atom effects. The f-f transitions in lanthanides are parity forbidden and have weak molar extinction coefficients. Upon complexation with the ligand, ttrpy (4'-p-Tolyl-[2,2':6',2"]-terpyridine) the absorption takes place through the ligand and the excitation is transferred to the lanthanides, which in turn emit. This process is known as "sensitized luminescence." Bright red emission from europium and bright green emission from terbium complexes were observed. There is ongoing work on the making of OLEDs with neutral complexes of lanthanide hexafluoroacetyl acetonate/ttrpy, studied in this dissertation. Attempts to observe analogous energy transfer from the inorganic donor complexes of Au(I) thiocyanates were unsuccessful due to poor overlap of the emissions of these systems with the absorptions of Eu(III) and Tb(III). Photophysics of silver-aromatic complexes deals with the enhancement of phosphorescence in the aromatics. The heavy atom effect of the silver is responsible for this enhancement in phosphorescence. Aromatics such as naphthalene, perylene, anthracene and pyrene were involved in this study. Stern Volmer plots were studied by performing the quenching studies. The quenchers employed were both heavy metals such as silver and thallium and lighter ...
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The Synthesis and Testing of Differential Herbicides

The Synthesis and Testing of Differential Herbicides

Date: 1948
Creator: Ashmore, James
Description: This investigation was limited to the preparation of substituted phenoxyacetic acids and related compounds. The types of substances prepared for testing can, in general, be placed in three groups. These are: aryloxyacetic acids, arylmercaptoacetic acids, and those acids containing the thiophene nucleus.
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Studies of spin alignment in ferrocenylsilane compounds and in regiospecific oxidation reactions of 1,9-dimethylpentacyclo [5.4.0.02,6.03,10.05,9]undecane-8,11-dione.

Studies of spin alignment in ferrocenylsilane compounds and in regiospecific oxidation reactions of 1,9-dimethylpentacyclo [5.4.0.02,6.03,10.05,9]undecane-8,11-dione.

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Date: August 2006
Creator: Atim, Silvia
Description: Part I. The syntheses of a series of stable ferrocenylsilane compounds and their corresponding polyradical cations are reported. Electron spin properties of these molecules were investigated by cyclic voltammetry, ESR, and magnetic susceptibility measurements. All the compounds presented, showed significant electronic communication (>100 mV) between the redox centers by CV. Part II. Baeyer-Villiger oxidation of (1,9-dimethyl-PCU-8,11-dione) was performed using m-chloroperoxybenzoic acid in 1:2 molar ratios. The product obtained was the corresponding dilactone 113. The structure of the reaction products was established unequivocally via single crystal X-ray diffraction methods. The reaction of the 1,9-dimethyl-PCU-8,11-dione with 1:1 molar ratio of m-chloroperoxybenzoic acid produced again the dilactone 113, and not the expected monolactone 114. Ceric ammonium nitrate (CAN) promoted oxidation reaction of 1,9-dimethyl-PCU-8,11-dione afforded a mixture of dimethylated lactones, which indicated unique reaction mechanism pathways. These individual isomers, 115 and 116, have been isolated from these mixtures via column chromatography by using silica gel as adsorbent followed by fractional recrystallization of individual chromatography fractions. Structures of these pure products have been established unequivocally by application of single crystal X-ray crystallographic methods.
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Thermal and Flash Photolysis Studies of Ligand-Exchange Reactions of Substituted Metal Carbonyl Complexes of Cr and Mo

Thermal and Flash Photolysis Studies of Ligand-Exchange Reactions of Substituted Metal Carbonyl Complexes of Cr and Mo

Date: May 1989
Creator: Awad, Hani H. (Hani Hanna)
Description: Thermal and flash photolysis studies of ligand-substitution reactions of cis-(pip)(L)M(CO)_4 by L' (pip = piperidine; L, L' = CO, phosphines, phosphites; M = Cr, Mo) implicate square-pyramidal [(L)M(CO)_4], in which L occupies a coordination site in the equatorial plane, as the reactive species. In chlorobenzene (= CB) solvent, the predominant species formed after flash photolysis and a steady-state intermediate for the thermal reaction is cis—[(CB)(L)M(CO)_4], for which rates of CB-dissociation increase with increasing steric demands of coordinated L. Rates of CB-dissociation from trans-[(CB)(L)M(CO)_4] intermediates, formed after photolysis but not thermally, exhibit no observable dependence on the steric properties of the coordinated L.
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Kinetics of Sulfur: Experimental Study of the Reaction of Atomic Sulfur with Acetylene and Theoretical Study of the Cn + So Potential Energy Surface

Kinetics of Sulfur: Experimental Study of the Reaction of Atomic Sulfur with Acetylene and Theoretical Study of the Cn + So Potential Energy Surface

Date: May 2013
Creator: Ayling, Sean A.
Description: The kinetics of the reaction of atomic sulfur with acetylene (S (3P) + C2H2) were investigated experimentally via the flash photolysis resonance fluorescence method, and the theoretical potential energy surface for the reaction CN + SO was modeled via the density functional and configuration interaction computational methods. Sulfur is of interest in modern chemistry due to its relevance in combustion and atmospheric chemistry, in the Claus process, in soot and diamond-film formation and in astrochemistry. Experimental conditions ranged from 295 – 1015 K and 10 – 400 Torr of argon. Pressure-dependence was shown at all experimental temperatures. The room temperature high-pressure limit second order rate constant was (2.10 ± 0.08) × 10-13 cm3 molecule-1 s-1. The Arrhenius plot of the high-pressure limit rate constants gave an Ea of (11.34 ± 0.03) kJ mol-1 and a pre-exponential factor of (2.14 ± 0.19) × 10-11 cm3 molecule-1 s-1. S (3P) + C2H2 is likely an adduct forming reaction due to pressure-dependence (also supported by a statistical mechanics analysis) which involves intersystem crossing. The potential energy surface for CN + SO was calculated at the B3LYP/6-311G(d) level and refined at the QCISD/6-311G(d) level. The PES was compared to that of the analogous reaction ...
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N-Heterocyclic Carbenes of the Late Transition Metals: A Computational and Structural Database Study

N-Heterocyclic Carbenes of the Late Transition Metals: A Computational and Structural Database Study

Date: May 2005
Creator: Baba, Eduard
Description: A computational chemistry analysis combined with a crystallographic database study of the bonding in late transition metal N-heterocyclic carbene (NHC) complexes is reported. The results illustrate a metal-carbon bond for these complexes, approximately 4% shorter than that of a M-C single bond found in metal alkyl complexes. As a consequence of this result, two hypotheses are investigated. The first hypothesis explores the possibility of multiple-bond character in the metal-carbon linkage of the NHC complex, and the second, considers the change in the hybridization of the carbenoid carbon to incorporate more p character. The latter hypothesis is supported by the results. Analysis of these complexes using the natural bond orbital method evinces NHC ligands possessing trans influence.
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Hydantoin Derivatives as Anticonvulsants. I. 5-Cyclohexylalkyl-5-(2-Thienyl)Hydantoins

Hydantoin Derivatives as Anticonvulsants. I. 5-Cyclohexylalkyl-5-(2-Thienyl)Hydantoins

Date: 1949
Creator: Baker, Andy Albert
Description: The study herein described represents a continuation of the work on 5-(2-thienyl)-5-substituted hydantoins which has been in progress in the laboratories of the North Texas State College for the past several years. It has for its purpose the study of the effect of lengthening the carbon chain connecting a cyclohexyl radical to 5-(2-thienyl)hydantoin in the 5- position.
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Studies in the Hydantoin Series. II. 5-(3-Pyridyl)hydantoin and Its Derivatives

Studies in the Hydantoin Series. II. 5-(3-Pyridyl)hydantoin and Its Derivatives

Date: 1957
Creator: Banta, Marion Calvin
Description: It is the purpose of this investigation to study the chemistry of 5-(3-pyridyl)hydantoin and to compare its properties with those of 5-phenylhydantoin.
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Modeling the chemical and photophysical properties of gold complexes.

Modeling the chemical and photophysical properties of gold complexes.

Date: August 2004
Creator: Barakat, Khaldoon A.
Description: Various gold complexes were computationally investigated, to probe their photophysical, geometric, and bonding properties. The geometry of AuI complexes (ground state singlet) is very sensitive to the electronic nature of the ligands: σ-donors gave a two-coordinate, linear shape; however, σ-acceptors yielded a three-coordinate, trigonal planar geometry. Doublet AuIIL3 complexes distort to T-shape, and are thus ground state models of the corresponding triplet AuIL3. The disproportionation of AuIIL3 to AuIL3 and AuIIIL3 is endothermic for all ligands investigated, however, σ-donors are better experimental targets for AuII complexes. For dimeric AuI complexes, only one gold center in the optimized triplet exciton displays a Jahn-Teller distortion, and the Au---Au distance is reduced versus the ground state distance (i.e., two reasons for large Stokes' shifts).
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Quantitative Chemical Analysis of the Soils of Erath County, Texas

Quantitative Chemical Analysis of the Soils of Erath County, Texas

Date: June 1938
Creator: Barnes, Benjamin F.
Description: A chemical analysis of representative samples of Windthorst sand, Denton sand, and Denton clay has been made, and this analysis shows that their composition has a strict correlation with respect to their geological origins. The analyses of the different soils have shown the Windthorst sand to be highly deficient in all of the essential elements, whereas the Denton sand is deficient in only one; namely, phosphorus. The analysis of the Denton clay showed it to be highly fertile. From the consideration of the pH and the lime content, it has been determined to some extent what crops will grow in each of the soils.
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Infrared Studies of Anions of Barbituric Acids

Infrared Studies of Anions of Barbituric Acids

Date: August 1960
Creator: Barnhart, Richard Lee
Description: As long ago as 1881, it was realized that a functional group of atoms in a molecule would cause an absorption band to appear at a particular frequency in the infrared spectrum of the molecule. In more recent years, the concept of characteristic group frequencies has become firmly established and has resulted in the present widespread use of infrared spectroscopy. There appear to have been relatively few studies of infrared absorption of organic acids as compared with their salts.
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The Stereochemistry of Silenes and Alpha-Lithio Silanes

The Stereochemistry of Silenes and Alpha-Lithio Silanes

Date: May 1987
Creator: Bates, Tim Frank
Description: When E- or Z-l-methyl-l-phenyl-2-neopentylsilene was generated by the retro-Diels-Alder vacuum-sealed tube thermolysis of its corresponding anthracene adduct, in the presence of various alkoxysilanes, only one diastereomeric adduct was formed in each case, showing that the reactions are stereospecific. An x-ray crystal structure of the methoxytriphenylsilane adduct of the E-silene confirmed its relative configuration as (R,S) or (S,R). This demonstrated that the addition of alkoxysilanes to silenes is stereospecific and syn. The relative configurations of similar alkoxysilane and alkoxystannane adducts to E- and Z-l-methyl-l-phenyl-2-neopentylsilene were assigned based on a combination of xray structures and *3C NMR data. A strong, nonbonded oxygen-metal interaction is apparent in all of those compounds studied. Treatment of the alkoxystannane adducts with alkyl lithium reagents results in tin-lithium exchange in some cases. The results indicate that the resulting <x-lithio alkoxysilanes are not configurationally stable in either THF or hydrocarbon solvents. The reaction of tert butyl lithium with a-trimethylsilylvinylmethylphenylchlorosilane in hydrocarbon solvents yields E- and Z-l-methyl-l-phenyl-2-neopentyl-2-trimethylsilylsilene. In the absence of any traps these silenes undergo a novel tert butyl lithium catalyzed rearrangement to 2-phenyl-3-trimethylsilyl-5,5-dimethyl-2-silahex-3-ene. These silenes were also trapped as their [4+2] cycloadducts with anthracene. The Z-isomer of the anthracene adduct was separated and its stereochemistry confirmed by ...
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Stereoisomerism of Dimethyl Muconate

Stereoisomerism of Dimethyl Muconate

Date: 1950
Creator: Bearden, Robert Gene
Description: The acid which is analogous to the next member of the diphenylpolyenes, 1,4-diphenylbutadiene, is muconic acid. This acid has been chosen to be investigated in an effort to isolate all the stereoisomers of a set containing more than two isomers.
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Comparison of Homework Systems (Four Web-Based) used in First-Semester General Chemistry

Comparison of Homework Systems (Four Web-Based) used in First-Semester General Chemistry

Date: May 2009
Creator: Belland, Joshua
Description: Web-based homework systems are becoming more common in general chemistry as instructors face ever-increasing enrollment. Yet providing meaningful feedback on assignments remains of the utmost importance. Chemistry instructors consider completion of homework integral to students' success in chemistry, yet only a few studies have compared the use of Web-based systems to the traditional paper-and-pencil homework within general chemistry. This study compares the traditional homework system to four different Web-based systems. Data from eight, semester classes consisting of a diagnostic pre-test, final semester grades, and the number of successful and unsuccessful students are analyzed. Statistically significant results suggest a chemistry instructor should carefully consider options when selecting a homework system.
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Acceptor-sensitizers for Nanostructured Oxide Semiconductor in Excitonic Solar Cells

Acceptor-sensitizers for Nanostructured Oxide Semiconductor in Excitonic Solar Cells

Date: August 2014
Creator: Berhe, Seare Ahferom
Description: Organic dyes are examined in photoelectrochemical systems wherein they engage in thermal (rather than photoexcited) electron donation into metal oxide semiconductors. These studies are intended to elucidate fundamental parameters of electron transfer in photoelectrochemical cells. Development of novel methods for the structure/property tuning of electroactive dyes and the preparation of nanostructured semiconductors have also been discovered in the course of the presented work. Acceptor sensitized polymer oxide solar cell devices were assembled and the impact of the acceptor dyes were studied. The optoelectronic tuning of boron-chelated azadipyrromethene dyes has been explored by the substitution of carbon substituents in place of fluoride atoms at boron. Stability of singlet exited state and level of reduction potential of these series of aza-BODIPY coumpounds were studied in order to employ them as electron-accepting sensitizers in solid state dye sensitized solar cells.
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A Fractionation Column for the Separation of Products of the Alkylation of Isobutane and Isobutene

A Fractionation Column for the Separation of Products of the Alkylation of Isobutane and Isobutene

Date: 1941
Creator: Berry, Quinton
Description: This thesis describes a fractionation column method of separating isobutane and isobutene to isolate isooctane.
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Soft Landing Ion Mobility Mass Spectrometry: History, Instrumentation and an Ambient Pressure Application

Soft Landing Ion Mobility Mass Spectrometry: History, Instrumentation and an Ambient Pressure Application

Date: December 2010
Creator: Birdwell, David
Description: Preparative mass spectrometry is an important method for the synthesis of new materials. Recently, soft landing mass spectrometry has been used to land ions on surfaces to coat or otherwise alter them. Commercial soft landing instruments do not yet exist, and the physical phenomenon of soft landing has not yet been fully described. For future ion mobility soft landing research, the theory of ion mobility, ion optics and soft landing is discussed, and 2 soft landing instruments have been built and described, along with proof of concept experiments for both instruments. Simulations of the process of ion mobility and ion optics for use in these instruments, as well as some preliminary results for the optics are included. Surfaces described include copper on mica and iron on silicon. Self assembly of soft landed ions is observed on the surfaces. The instruments constructed will be useful for future soft landing research, and soft landing can be used for future materials research with special attention focused on the self-assembly of the landed ions.
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Surface Chemical Deposition of Advanced Electronic Materials

Surface Chemical Deposition of Advanced Electronic Materials

Date: December 2010
Creator: Bjelkevig, Cameron
Description: The focus of this work was to examine the direct plating of Cu on Ru diffusion barriers for use in interconnect technology and the substrate mediated growth of graphene on boron nitride for use in advanced electronic applications. The electrodeposition of Cu on Ru(0001) and polycrystalline substrates (with and without pretreatment in an iodine containing solution) has been studied by cyclic voltammetry (CV), current-time transient measurements (CTT), in situ electrochemical atomic force microscopy (EC-AFM), and X-ray photoelectron spectroscopy (XPS). The EC-AFM data show that at potentials near the OPD/UPD threshold, Cu crystallites exhibit pronounced growth anisotropy, with lateral dimensions greatly exceeding vertical dimensions. XPS measurements confirmed the presence and stability of adsorbed I on the Ru surface following pre-treatment in a KI/H2SO4 solution and following polarization to at least &#8722;200 mV vs. Ag/AgCl. CV data of samples pre-reduced in I-containing electrolyte exhibited a narrow Cu deposition peak in the overpotential region and a UPD peak. The kinetics of the electrodeposited Cu films was investigated by CTT measurements and applied to theoretical models of nucleation. The data indicated that a protective I adlayer may be deposited on an air-exposed Ru electrode as the oxide surface is electrochemically reduced, and that this ...
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A Qualitative Analysis of the Products of the Reaction Between Chlorosulfonic Acid and 2, 2, 4-Trimethylpentane

A Qualitative Analysis of the Products of the Reaction Between Chlorosulfonic Acid and 2, 2, 4-Trimethylpentane

Date: 1941
Creator: Black, Harry
Description: This study was made in an attempt to analyze qualitatively the reaction products formed when chlorosulfonic acid reacts with 2, 2, 4-trimethylpentane.
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Photophysical properties of pyrene, 2,7 diazapyrene and 1,3-bis(β-naphthyl)propane.

Photophysical properties of pyrene, 2,7 diazapyrene and 1,3-bis(β-naphthyl)propane.

Date: August 2007
Creator: Boateng, Stephen
Description: The luminescence properties of Van Der Waals' dimers and clusters of pyrene and diazapyrene have been investigated. Excimers, dimeric species which are associative in an excited electronic state and dissociative in their ground state, have long been established and play an important role in many areas of photochemistry. My work here focuses on the luminescence and absorption properties of ground state dimers/aggregates, which are less understood, and allows further characterization of the ground state and excited state association of these aromatic molecules.
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