Physical Chemistry Commons^™

Measurement Of Proton Transfer Reaction Rates In A Microwave Cavity Discharge Flowing Afterglow, George M. Brooke Iv

Physics Theses & Dissertations

The reaction rate coefficients between the hydronium ion and the molecules ethene (C₂H₄), propene (C₃H₆), 1-butene (C₄H₈) and hydrogen sulfide (H₂S) were measured at 296 K. The measured reaction rates were compared to collision rates calculated using average dipole orientation (ADO) theory. Reaction efficiency depends primarily upon the proton affinity of the molecules. All the measurements were obtained using the newly developed microwave cavity discharge flowing afterglow (MCD-FA) apparatus. This device uses an Asmussen-type microwave cavity discharge ion source that is …

Argon Eximer Emission From High-Pressure Microdischarges In Mental Capillaries, R. Mohan Sankaran, Konstantinos P. Giapis, Mohamed Moselhy, Karl H. Schoenbach

Bioelectrics Publications

We report on argon excimer emission from high-pressure microdischarges formed inside metal capillaries with or without gas flow. Excimer emission intensity from a single tube increases linearly with gas pressure between 400 and 1000 Torr. Higher discharge current also results in initial intensity gains until gas heating causes saturation or intensity drop. Argon flow through the discharge intensifies emission perhaps by gas cooling. Emission intensity was found to be additive in prealigned dual microdischarges, suggesting that an array of microdischarges could produce a high-intensity excimer source.

Comparison Between The Ultraviolet Emission From Pulsed Microhollow Cathode Discharges In Xenon And Argon, Isfried Petzenhauser, Leopold D. Biborosch, Uwe Ernst, Klaus Frank, Karl H. Schoenbach

Bioelectrics Publications

We measured the dynamic I–V characteristics and vacuum ultraviolet (VUV) emission lines of the second continuum in xenon (170 nm) and argon (130.5 nm) from pulsed microhollow cathode discharges (MHCD). For pulse lengths between 1 and 100 μs the dynamic I–V characteristics are similar in both inert gases. Only the time variation of the VUV emission line at 170 nm for xenon can be related to the dimer excited states. In argon the energy transfer between the Ar*₂ dimers and the oxygen impurity atoms is responsible for a qualitatively different time behavior of the resonance line at 130.5 nm. …

Chemical Vapor Deposited Diamond Films For Self-Referencing Fiber Optic Raman Probes, Sacharia Albin, Jianli Zheng, Bing Xiao, John B. Cooper, Robert B. Jeffers, Sonia Antony

Chemistry & Biochemistry Faculty Publications

Diamond thin films grown by the microwave plasma enhances chemical vapor deposition (CVD) process have been investigated as an internal reference in fiber optic remote Raman sensing. The growth parameters have been optimized for diamond thin films on quarts substrates using a gas mixture of methane, carbon dioxide, and hydrogen. The resulting films exhibit essentially no Raman spectral background while exhibiting a strong Raman peak at 1332 cm^-¹. The films are used as an internal reference in the quantitative measurement of chemical concentration using remote fiber optic Raman sensing. Internal referencing is accomplished by normalizing all spectral intensities …

Stm And Electrochemical Investigation Of Homoepitaxial Boron-Doped Cvd Diamond Films, John B. Cooper, Jason A. Moulton, Sacharia Albin, Bing Xiao

Chemistry & Biochemistry Faculty Publications

Homoepitaxial growth of boron-doped CVD diamond films was carried out on (100) and (111) oriented substrates. Atomic resolution images were obtained for both (100) and (111) surfaces using scanning tunneling microscopy. STM images reveal the presence of a 2x1-monohydride reconstruction for the untreated (100) surface and a lxl reconstruction for the untreated (111) surface. No other atomically resolved reconstructions were observed under a wide range of growth conditions. Non-aqueous electrochemical investigations were carried out on the films exhibiting atomically resolved reconstructions. Evidence for potential-induced surface-reconstruction and surface chemical modification of the (100) 2xl-monohydride surface has been observed.

Boron-Doped Homoepitaxial Diamond (100) Film Investigated By Scanning Tunneling Microscopy, Bing Xiao, Weihai Fu, Sacharia Albin, Jason Moulton, John Cooper

Electrical & Computer Engineering Faculty Publications

Conducting epitaxial diamond films of high quality are essential for many diamond studies and diamond electronic device fabrication. We have grown boron-doped epitaxial diamond films on type Ila natural diamond (100) substrates by microwave plasma chemical vapor deposition. A gas mixture of H₂/CH₄ was used. Boron doping was done by placing solid sources of pure boron in the microwave plasma. Homoepitaxial films with atomic smoothness were achieved under the following growth conditions: substrate temperature 900 °C, gas pressure 40 Torr, and gas flow rates of H₂/CH₄ = 900/7.2 seem. The growth rate was 0.87 …

Fourier Transform Raman Spectroscopy For Process Control In The Petroleum Industry, Kent Lawson Wise

Chemistry & Biochemistry Theses & Dissertations

As early as 1950, Raman spectroscopy was proposed as a method to determine aromatics and olefins in hydrocarbon mixtures. Until recently, extensive use of Raman spectroscopy in the characterization of hydrocarbons has not been practical due to several limitations. One early limitation to Raman analysis was the absence of a high intensity and stable excitation source. This problem has been overcome with the advent of lasers. Another limitation was the presence of fluorescence in hydrocarbon fuels when excited by visible lasers. However, the development of Fourier-transform Raman spectrometers now allows Raman spectra to be collected using near-IR lasers (e.g …

Microhollow Cathode Discharge Excimer Lamps, Karl H. Schoenbach, Ahmed El-Habachi, Mohamed M. Moselhy, Wenhui Shi, Robert H. Stark

Bioelectrics Publications

Microhollow cathode discharges are high-pressure, nonequilibrium gas discharges between a hollow cathode and a planar or hollow anode with electrode dimensions in the 100 μm range. The large concentration of high-energy electrons, in combination with the high-gas density favors excimer formation. Excimer emission was observed in xenon and argon, at wavelengths of 128 and 172 nm, respectively, and in argon fluoride and xenon chloride, at 193 and 308 nm. The radiant emittance of the excimer radiation was found to increase monotonically with pressure. However, due to the decrease in source size with pressure, the efficiency (ratio of excimer radiant power …

Chemical Modification Of Cvd Diamond Electrodes, Robert Matthew Johnson

Chemistry & Biochemistry Theses & Dissertations

The micro-array behavior of boron doped CVD diamond thin film electrodes has been studied in acetonitrile containing two redox couples. The analytical technique employed in these studies was cyclic voltammetry. One system is 0.4 mM ferrocene containing 0.1 M tetrabutylammonium hexafluorophosphate (TBAH). This reversible redox system is not only well-known, but also involves only one electron transfer with no breakage/formation of chemical bonds, thus making it a simple system for analysis. The second test is 0.8 mM cobaltocenium hexafluorophosphate, with 0.4 mM ferrocene as an internal standard. Unlike ferrocene, which is neutral initially, cobaltocenium is positively charged, and is reduced …

Characterization Of Iron Oxides And Atmospheric Corrosion Of Steel, Sei Jin Oh

Physics Theses & Dissertations

The study of corrosion behavior was performed using three different analytical techniques, which provided information on the formation, development and layering of iron oxides on the corrosion products as a function of atmospheric conditions, exposure time and type of steel. In particular, the protective layer formed on weathering steel was investigated as a function of different amounts of alloying elements in the steel, atmospheric conditions and exposure times. Combined together, the results provided a better understanding of the atmospheric corrosion behavior of steel, and formed a part of database of the atmospheric corrosion characteristics.

Accurate characterization of the iron oxides …

Absolute-Convective Instabilities And Their Associated Wave Packets In A Compressible Reacting Mixing Layer, F. Q. Hu, T. L. Jackson, D. G. Lasseigne, C. E. Grosch

Mathematics & Statistics Faculty Publications

In this paper the transition from convective to absolute instability in a reacting compressible mixing layer with finite rate chemistry is examined. The reaction is assumed to be one step, irreversible, and of Arrhenius type. It is shown that absolute instability can exist for moderate heat release without backflow. The effects of the temperature ratio, heat release parameter, Zeldovich number, equivalence ratio, direction of propagation of the disturbances, and the Mach number on the transition value of the velocity ratio are given. The present results are compared to those obtained from the flame sheet model for the temperature using the …

Thermal Characterization Of Carbon Monoxide Oxidation Catalysts Using Thermogravimetric Analysts And Differential Scanning Calorimetry, Rene A. Bartgis

Chemistry & Biochemistry Theses & Dissertations

Catalysts composed of platinum and/or palladium on tin (IV) oxide supports, with and without silica gel, as well as catalysts composed of gold on manganese oxide, have been developed for the recombination of carbon monoxide and oxygen to form carbon dioxide for use in carbon dioxide lasers. A thermogravimetric method and a differential scanning calorimetric method have been developed for the thermal characterization of these catalysts. The mass loss data and the enthalpy changes determined as the catalysts lost water were then related to existing activity data for these catalysts. No relationship was found between the thermal data and the …

Reactions Of Aqueous Chlorine With Valine In Model Solutions And In Wastewater, Erika Forrer Mccormick

Chemistry & Biochemistry Theses & Dissertations

Solutions of the amino acid valine were chlorinated to seven chlorine-to-nitrogen mole (Cl/N) ratios and analyzed by high performance liquid chromatography, gas chromatography/mass spectroscopy, infrared spectroscopy, and nuclear magnetic resonance spectroscopy. The chlorination products found were N-chlorovaline, isobutyraldehyde, isobutyronitrile, and N-chloroisobutyraldimine. Their product distribution depends on the level of chlorination and pH. The main products identified at the lower CI/N mole ratios were N-chlorovaline and isobutyraldehyde, whereas at the higher CI/N mole ratios isobutyronitrile and N-chloroisobutyraldimine were identified as the main products. The concentration and the chlorination products of valine in municipal wastewater were also determined. The chlorination products of …

A Diffuse Reflectance Infrared Fourier Transform Spectroscopic Study Of Platinum/Tin (Iv) Oxide Low-Temperature Carbon Monoxide Oxidation Catalysts, Donna Sue Duarte

Chemistry & Biochemistry Theses & Dissertations

Platinum-coated tin(IV) oxide catalysts have been developed for the recombination of carbon monoxide and oxygen at 55°C and 1 atmosphere of pressure in closed-cycle carbon dioxide lasers. A diffuse reflectance infrared fourier transform spectroscopic (DRIFTS) study of four of these catalysts during 5% carbon monoxide pretreatment at temperatures of 30°C, 100°c, 125°c, and 150°C has been performed. Evidence for the development of surface carbonate, bicarbonate, and formate species during pretreatment has been found. Dehydroxylation of the surface and loss of a partially charged hydrogen-bonded hydroxyl species have also been found to result from elevated temperature pretreatment. The four catalysts have …

Hydrogen Sulfide And Radon In And Over The Western North Atlantic Ocean, T. W. Andreae, Gregory A. Cutter, N. Hussain, J. Radford-Knoery, M. O. Andreae

OES Faculty Publications

Atmospheric measurements of radon and hydrogen sulfide, and seawater measurements of total sulfide, free sulfide, and carbonyl sulfide, were made on a cruise in the western North Atlantic Ocean (October 24 to November 9, 1989). Measured values for ²²²Rn ranged from 3 to 70 pCi m⁻³, those for atmospheric hydrogen sulfide from 1 to 85 parts per trillion, and those for dissolved total and free sulfide in seawater from 33 to 930 pmol L⁻¹ and 0 to 73 pmol L⁻¹, respectively. A positive correlation between ²²²Rn and atmospheric H₂S was observed. …

Second Coefficient Of Viscosity In Air, Robert L. Ash, Allan J. Zuckerwar, Zhonquan Zheng

Mechanical & Aerospace Engineering Faculty Publications

Acoustic attenuation measurements in air were analyzed in order to estimate the second coefficient of viscosity. Data over a temperature range of 11 C to 50 C and at relative humidities between 6 percent and 91 percent were used. This analysis showed that the second coefficient of viscosity varied between 1900 and 20,000 times larger than the dynamic or first coefficient of viscosity over the temperature and humidity range of the data. In addition, the data showed that the molecular relaxation effects, which are responsible for the magnitude of the second coefficient of viscosity, place severe limits on the use …

Role Of Surface Morphology In Wafer Bonding, W.P. Maszara, B.L. Jiang, A. Yamada, G.A. Rozgonyi, H. Baumgart, A.J.R. De Kock

Electrical & Computer Engineering Faculty Publications

The strain patterns detected by x-ray topography in wafers bonded for silicon-on-insulator (SOI) technology were found related to the flatness nonuniformity of the original wafers. Local stresses due to the bonding process are estimated to be about 1×10⁸ dynes/cm². The stress is reduced about 100 times for the thin (0.5 μm) SOI films. Most of the wafer deformation occurs during room temperature mating of the wafers. The deformation is purely elastic even at 1200 °C. The magnitude of the stress appears insignificant for complimentary metal-oxide-semiconductor devices performance.

A Potentiometric Gaseous Hydrogen Sensor, Anne Guillory

Chemistry & Biochemistry Theses & Dissertations

The development of a potentiometric gaseous hydrogen sensor using a 75% palladium - 25% silver alloy as a selectively hydrogen permeable electrode is described. The sensor showed some promise when used with a molten base electrolyte. Other electrolytes are investigated at ambient and higher temperatures. Various cell designs including a platinum/silver-silver chloride sensor with a gel electrolyte are discussed.

The Reaction Of Organoboranes With N-Chloro-N-Sodiocarbamates: A Convenient Synthesis Of N-Alkylcarbamates, Nanette M. Wachter-Jurcsak

Chemistry & Biochemistry Theses & Dissertations

N-alkylcarbamic acid esters are used extensively as fungicides, herbicides and pesticides. Industrial methods of preparation employ highly toxic reagents in their synthesis. Convenient and safe alternative methods are necessary.

Organoboranes are electrophilic compounds which can be employed as a source of alkyl substituents. They have been shown to successfully transfer alkyl groups to the nitrogen of chloramines. N-Alkylation of carbamic acid esters by reacting the corresponding N-chloro-N-sodiocarbamate with a variety of trialkylboranes is described. The yields of the various N-substituted products are discussed.

Two synthetic methods were devised. Originally, an equivalent of the isolated N-chlorocarbamate salt was added to the …

A Pulse Gas Chromatographic Method For Determining The Dispersion And Surface Area Of Co Oxidation Catalysts, Susan Kay Ohorodnik

Chemistry & Biochemistry Theses & Dissertations

Catalysts composed of platinum and/or palladium on tin(IV) oxide supports with or without silica gel have been developed for the recombination of carbon monoxide and oxygen to form carbon dioxide for use in carbon dioxide lasers. A pulse gas chromatographic method has been developed to measure the chemisorption properties of the catalysts. From the chemisorption measurements, the active surface area and dispersion of the catalysts have been determined.

Evaluation Of The Function Exp (X2) Erfc (X) To Higher Precisions For Higher-Order Derivative Polarography Of Ce-Type Electrode Process, Myung-Hoon Kim, Veriti P. Smith, Tae-Kee Hong

Chemistry & Biochemistry Faculty Publications

The function exp(x2)erfc(x), which is often encountered in studies of electrode kinetics, is evaluated to an extended precision with 32 significant decimal digits in order to find theoretical relationships used in derivative polarography/voltammetry for a chemically-coupled electrode process. Computations with a lower precision are not successful. Evaluation of the function is accomplished by using three types of expansions for the function. Best ranges of arguments are selected for each equation for particular precisions for efficiencies. The method is successfully applied to calculate higher-order derivatives of the current-potential curves in all potential ranges for a reversible electron transfer reaction coupled with …

Low Pressure Gas Flow Analysis Through An Effusive Inlet Using Mass Spectrometry, David Robert Brown

Chemistry & Biochemistry Theses & Dissertations

A mass spectrometric method for analyzing flow past and through an effusive inlet designed for use on the tethered satellite and other entering vehicles is discussed. Source stream concentrations of species in a gaseous mixture are determined using a calibration of measured mass spectral intensities versus source stream pressure for standard gas mixtures and pure gases. Concentrations are shown to be accurate within experimental error. Theoretical explanations for observed mass discrimination effects as they relate to the various flow situations in the effusive inlet and the experimental apparatus are discussed.

Gas Permeation Measurements On Small Polymer Specimens, Karen S. Burns

Chemistry & Biochemistry Theses & Dissertations

Mass spectrometry was used to measure oxygen and nitrogen permeabilities while polarography was used to measure oxygen permeabilities for several contact lens materials. Applicable sample holders were designed and fabricated to accommodate curved and flat specimens with surface areas of 0.5 cm² and 1.0 cm² and thicknesses between 0.025 mm and 0.500 mm. A prepared standard was used to calibrate the mass spectrometric analyses.

The oxygen permeability values determined by mass spectrometry were significantly greater than those determined by polarography. This was attributed to the phase boundary phenomena and the limiting oxygen permeance of water inherent in the …

Mössbauer Spectroscopic Studies Of Hemoglobin And Its Isolated Subunits, G. R. Hoy, D. C. Cook, R. L. Berger, F. K. Friedman

Physics Faculty Publications

Samples of 90% enriched ⁵⁷Fe hemoglobin and its isolated subunits have been prepared. Mössbauer spectroscopic measurements have been made on three such samples. Sample one contained contributions of oxyhemoglobin, deoxyhemoglobin, and carbonmonoxyhemoglobin. This sample was studied from a temperature of 90 K down to 230 mK. Measurements were also made at 4.2 K using a small applied magnetic field of 1.0 T. In general, the measured quadrupole splittings and isomer shifts for each component agreed with previous measurements on single component samples in the literature, and thus demonstrated that chemically enriched hemoglobin has not been altered. The second and …

Nonadiabatic Theory Of Fine-Structure Branching Cross Sections For Na-He, Na-Ne, And Na-Ar Optical Collisions, Linda L. Vahala, P. S. Julienne, Mark D. Havey

Electrical & Computer Engineering Faculty Publications

The nonadiabatic close-coupled theory of atomic collisions in a radiation field is generalized to include electron spin and is used to consider the weak-field Na–rare-gas (RG) optical collision Na(²S_1/2)+RG+nhν μNa(²P_j)+RG+(n-1)hν. The effects of detuning and incident energy on the branching into the atomic Na 3p²P_3/2 and 3p²P_1/2 states are examined. The cross sections σ(j) are found to have a strong asymmetry between red and blue detuning as well as a complex threshold and resonance structure dependence on energy. A partial cross-section analysis …

Development Of An On-Line Computer System For Cyclic Voltammetry Studies, Tai-Lee Leo Huo

Chemistry & Biochemistry Theses & Dissertations

An Apple II Plus microcomputer was interfaced to a PAR 174A Polarographic Analyser, an HP 7O4OA X-Y recorder and a three-electrode system. This on-line computer system was applied to Cyclic Voltammetry (CV) studies. The interfacing involved both hardware and software development. Various hardware components were used to amplify and transmit the analog signal both going into the computer and coming from the computer. Software programs were written for staircase waveform generation, data acquisition, and plotting the voltammograms obtained.

A package was designed for CV experiments to be used by the students in the instrumental analysis laboratory. This package contains several …

Determination Of The Internal Rotational Energy Of Gaseous 1,2-Dichloroethane In An Argon Matrix Using Fourier Transform Spectroscopy, Susan Lynn Clarke

Chemistry & Biochemistry Theses & Dissertations

A sample cell and delivery system for rapid matrix isolation of gas mixtures at constant gas temperature was designed and evaluated. The rotational energy differences of 1,2-dichlorosthane and of its deuterium compound wars then determined to test this technique.

The rotational energy barriers calculated from Boltzman plots of ths gases at different temperatures were; 1.21 + 0.38 keel/mole, 1.33 + 0.70 Real/mole, and 1.12 + 0.45 kcal/mole for the CH2 wagging„ C-Cl stretching and CD₂ wagging modes respectively. These values were in good agreement with previously published values.

These results allowed evaluation of this apparatus and experimental design and …

Mass Spectrometric Studies Of Oxygen Isotope Exchange Reactions With Oxide Surfaces, Gayle J. Allen

Chemistry & Biochemistry Theses & Dissertations

Isotopic exchange reactions with the surface of amorphous silica and crystalline quartz were studied mass spectrometrically. A mixture of approximately 2%18_o2 in neon was used as the test gas, and was passed over the surface of the oxides. Measurements were taken as a function of temperature and residence time, for kinetic studies.

These studies clearly show a second order rate law for the surfaces examined. The rate constant on amorphous silica was 2.2xl0²L/mol/sec. The energy of activation was 35.3 kcal/mol and the frequency factor was l.35xl0⁹L/mol/sec. On the crystalline quartz the rate constant was 2.0xl0 …

A Study Of The Gas-Solid Reaction Between Hydrogen Sulfide And Mercury(I) Chloride; Development Of A Method For Determination Of Atmospheric Hydrogen Sulfide, Eric H. De Carlo

Chemistry & Biochemistry Theses & Dissertations

The possibility of measuring hydrogen sulfide indirectly by measuring the mercury evolved from the gas-solid reaction between hydrogen sulfide and mercury(I) chloride was studied. DMCS treated glass wool was coated with mercurous chloride and used as a conversion material. The response to hydrogen sulfide was studied as a function of concentration and temperature. The possible interference of other sulfur gases and water was examined.

The studies indicated that hydrogen sulfide could be determined at concentrations as low as 15 ppb. It was found that mercaptans would actively interfere with the hydrogen sulfide to mercury conversion, but that sulfur dioxide would …