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Department:
Department of Chemistry
Degree Level:
Master's
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UNT Theses and Dissertations
Electrochemical Depostion of Bismuth on Ruthenium and Ruthenium Oxide Surfaces
Date: May 2012
Creator: Taylor, Daniel M.
Description: Cyclic voltammetry experiments were performed to compare the electrodeposition characteristics of bismuth on ruthenium. Two types of electrodes were used for comparison: a Ru shot electrode (polycrystalline) and a thin film of radio-frequency sputtered Ru on a Ti/Si(100) support. Experiments were performed in 1mM Bi(NO3)3/0.5M H2SO4 with switching potentials between -0.25 and 0.55V (vs. KCl sat. Ag/AgCl) and a 20mV/s scan rate. Grazing incidence x-ray diffraction (GIXRD) determined the freshly prepared thin film electrode was hexagonally close-packed. After thermally oxidizing at 600°C for 20 minutes, the thin film adopts the tetragonal structure consistent with RuO2. a hydrated oxide film (RuOx?(H2O)y) was made by holding 1.3V on the surface of the film in H2SO4 for 60 seconds and was determined to be amorphous. Underpotential deposition of Bi was observed on the metallic surfaces and the electrochemically oxidized surface; it was not observed on the thermal oxide.
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Experimental Determination of L, Ostwald Solubility Solute Descriptor for Illegal Drugs By Gas Chromatography and Analysis By the Abraham Model
Date: May 2012
Creator: Wang, Zhouxing
Description: The experiment successfully established the mathematical correlations between the logarithm of retention time of illegal drugs with GC system and the solute descriptor L from the Abraham model. the experiment used the method of Gas Chromatography to analyze the samples of illegal drugs and obtain the retention time of each one. Using the Abraham model to calculate and analyze the sorption coefficient of illegal drugs is an effective way to estimate the drugs. Comparison of the experimental data and calculated data shows that the Abraham linear free energy relationship (LFER) model predicts retention behavior reasonably well for most compounds. It can calculate the solute descriptors of illegal drugs from the retention time of GC system. However, the illegal drugs chosen for this experiment were not all ideal for GC analysis. HPLC is the optimal instrument and will be used for future work. HPLC analysis of the illegal drug compounds will allow for the determination of all the solute descriptors allowing one to predict the illegal drugs behavior in various Abraham biological and medical equations. the results can be applied to predict the properties in biological and medical research which the data is difficult to measure. the Abraham model will predict ...
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Permallink:digital.library.unt.edu/ark:/67531/metadc115179/
Incorporating Electrochemistry and X-ray Diffraction Experiments Into an Undergraduate Instrumental Analysis Course
Access: Use of this item is restricted to the UNT Community.
Date: May 2012
Creator: Molina, Cathy
Description: Experiments were designed for an undergraduate instrumental analysis laboratory course, two in X-ray diffraction and two in electrochemistry. Those techniques were chosen due their underrepresentation in the Journal of Chemical Education. Paint samples (experiment 1) and pennies (experiment 2) were characterized using x-ray diffraction to teach students how to identify different metals and compounds in a sample. in the third experiment, copper from a penny was used to perform stripping analyses at different deposition times. As the deposition time increases, the current of the stripping peak also increases. the area under the stripping peak gives the number of coulombs passed, which allows students to calculate the mass of copper deposited on the electrode surface. the fourth experiment was on the effects of variable scan rates on a chemical system. This type of experiment gives valuable mechanistic information about the chemical system being studied.
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Permallink:digital.library.unt.edu/ark:/67531/metadc115123/
Electrochemical Quartz Crystal Microbalance Study Of Bismuth Underpotential Deposition On Ruthenium And On Electrochemically Formed Ruthenium Oxide
Date: December 2011
Creator: Lin, Po-Fu
Description: Kinetics and thermodynamics of bismuth (Bi) underpotential deposition (UPD) on ruthenium (Ru) and on electrochemically formed Ru oxide are studied using electrochemical quartz crystal microbalance technique. The Bi UPD and Bi bulk deposition are observed both on Ru and on electrochemically formed Ru oxide electrodes. The anodic peak potential of Bi UPD shifts slightly to positive potential as the scan rate increases. The peak current ratio (IAnode/ICathode) of Bi UPD and Bi bulk increases as the scan rate increases. Bi monolayer coverage calculated from mass (MLMass) and from charge (MLCharge) with scan rates dependent are compared both in Bi UPD region and in Bi bulk region. Stability and oxidation time effects are also investigated. Bi UPD on Ru and on electrochemically formed Ru oxide are quasi-reversible, scan rate independent, oxidation time dependent, and have higher plating efficiency on Ru. However, Bi bulk deposition on Ru and on electrochemically formed Ru oxide are quasi-reversible, scan rate dependent, oxidation time independent, and have higher plating efficiency on electrochemically formed Ru oxide. Both Bi UPD adatoms and Bi bulk are unstable in 0.5M H2SO4.
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Permallink:digital.library.unt.edu/ark:/67531/metadc103354/
Boron Nitride by Atomic Layer Deposition: A Template for Graphene Growth
Date: August 2011
Creator: Zhou, Mi
Description: The growth of single and multilayer BN films on several substrates was investigated. A typical atomic layer deposition (ALD) process was demonstrated on Si(111) substrate with a growth rate of 1.1 Å/cycle which showed good agreement with the literature value and a near stoichiometric B/N ratio. Boron nitride films were also deposited by ALD on Cu poly crystal and Cu(111) single crystal substrates for the first time, and a growth rate of ~1ML/ALD cycle was obtained with a B/N ratio of ~2. The realization of a h-BN/Cu heterojunction was the first step towards a graphene/h-BN/Cu structure which has potential application in gateable interconnects.
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Molecular Structure Analyses of Asymmetric Hydrocarbon Liquid Compounds in the Gas Phase Using Chirped-pulse Fourier Transform Microwave Spectroscopy: Acyl Chlorides and Perfluorinated Acyl Chlorides
Date: August 2011
Creator: Powoski, Robert A.
Description: Examinations of the effects of (a.) alkyl carbon chain length and (b.) perfluorination of acyl chlorides; propionyl chloride, butyryl chloride, valeroyl chloride, and perfluorinated acyl chlorides; perfluoropropionyl chloride and perfluorobutyryl chloride, are reported and compared using CP-FTMW spectroscopy. All of these molecules are already published in various journals except for valeroyl chloride. The chapters are organized by molecule alkyl chain length and include some background theory. Conformational stability, internal rotation, helicity, and ionic character of the C-Cl bond via the nuclear electric quadrupole coupling constant (χzz) are analyzed. Results show syn, syn-anti/syn-gauche, and syn-anti-anti/syn-gauche-anti stable conformations. Internal rotation was only seen in propionyl chloride. Helicity was not observed. (χzz) was observed to be inert to alkyl chain length, ~ 60 MHz and ~ 65 MHz for the nonfluorinated and fluorinated acyl chlorides. Partial fluorination and varying functional groups are recommended.
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Permallink:digital.library.unt.edu/ark:/67531/metadc103374/
Kinetic Investigation of the Gas Phase Atomic Sulfur and Nitrogen Dioxide Reaction
Date: May 2011
Creator: Thompson, Kristopher Michael
Description: The kinetics of the reaction of atomic sulfur and nitrogen dioxide have been investigated over the temperature range 298 to 650 K and pressures from 14 - 405 mbar using the laser flash photolysis - resonance fluorescence technique. The overall bimolecular rate expression k (T) = (1.88 ± 0.49) x10-11 exp-(4.14 ± 0.10 kJ mol-1)/RT cm3 molecule-1 s-1 is derived. Ab initio calculations were performed at the CCSD(T)/CBS level of theory and a potential energy surface has been derived. RRKM theory calculations were performed on the system. It is found that an initially formed SNO2 is vibrationally excited and the rate of collisional stabilization is slower than the rate of dissociation to SO + NO products by a factor of 100 - 1000, under the experimental conditions.
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Permallink:digital.library.unt.edu/ark:/67531/metadc68055/
Synthesis and Characterization of Copper Releasing Polymer Nanoparticles
Date: May 2011
Creator: Harris, Alesha N.
Description: Polymeric nanoparticles were synthesized and loaded with Cu²⁺ to explore the therapeutic potential for catically active transition metal ions and complexes other than cisplatin. Two types of nanoparticles were synthesized to show the potential for polymer based vectors. Copper loading and release were characterized via inductively coupled plasma mass spectrometry (ICP MS), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), and elemental analysis. Results demonstrated that Cu could be loaded to the nano-sized carriers in an aqueous environment, and that the release was pH-dependent. The toxicity of these particles was measured in HeLa cells where significant toxicity was observed in vitro via dosing of high Cu-loaded nanoparticles. No significant toxicity was observed in cells dosed with Cu-free nanoparticles.
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Permallink:digital.library.unt.edu/ark:/67531/metadc67990/
Chirped-Pulse Fourier Transform Microwave Spectroscopy of Fluoroiodoacetonitrile and Chloropentafluoroacetone
Date: December 2010
Creator: Kadiwar, Gautam
Description: This work focuses on finding the complete iodine and nitrogen nuclear electric quadrupole coupling tensors for fluoroiodoacetonitrile using chirped-pulse Fourier transform microwave spectroscopy. Fluoroiodoacetonitrile contains two hyperfine nuclei, iodine (I=5/2) and nitrogen (I=1) and the spectra were observed with great resolution. A total of 499 transitions were observed for this molecule. The a, b and c rotational constants were obtained. A study of chloropentafluoroacetone was also done using chirped-pulse Fourier transform microwave spectroscopy. The two chlorine isotopes for this molecule, Cl-35 and Cl-37 were observed and 326 and 170 transitions were recorded, respectively.
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Permallink:digital.library.unt.edu/ark:/67531/metadc84230/
Forensic Science Applications Utilizing Nanomanipulation-Coupled to Nanospray Ionization-Mass Spectrometry for the Analysis of Ultra-Trace Illicit Drugs
Date: December 2010
Creator: Wallace, Nicole
Description: Presented in this thesis are two methods that are coupled to the instrumentation for the recovery and analysis of ultra-trace illicit drug residues. The electrostatic dust lifting process is coupled with nanomanipulation-nanospray ionization to retrieve drug particles off of hard surfaces for analysis. For the second method, drug residues from fingerprint impressions are extracted followed by analysis. The methodology of these hyphenated techniques toward forensic science applications is applied as to explore limits of detection, sensitivity, and selectivity of analytes as well as immediacy and efficiency of analysis. The application of nanomanipulation-coupled to nanospray ionization-mass spectrometry toward forensic science based applications is considered as future improvements to trace and ultra-trace analysis.
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Permallink:digital.library.unt.edu/ark:/67531/metadc33209/