Chemistry Commons^™

The Oxidative Decarboxylation Of Polyaminocarboxylic Acids - Ii. A Comparative Kinetic Study Of The Oxidation Of Nta, Edta, Cdta And Dtpa With Cerium(Iv) In Sulfuric Acid Media, Samir B. Hanna, Rita Hessley, William H. Webb, William R. Carroll

Chemistry Faculty Research & Creative Works

The rates of oxidation of four chelating agents, NTA, EDTA, CDTA, and DTPA with Ce(IV), in sulfuric acid media, were determined spectrophotometrically by a stopped-flow technique. The reductive ability is in the order CDTA > EDTA > DTPA > NTA. The influence of varying the acidity of the medium was studied, and in each case a maximum in the rate constant vs. [H+] plot was observed. A possible interpretation of the reactivities and the influence of acidity is advanced. © 1971 Springer-Verlag.

Mössbauer Studies Of Bifeo₃-Pbtio₃ Perovskite-Type Solid Solutions, C. M. Yagnik, Robert Gerson, William Joseph James

Physics Faculty Research & Creative Works

The Mössbauer spectra of the ferroelectric solid solutions (BiFeO₃)_x(PbTiO)1-x have been studied as a function of temperature, mainly between room temperature and 600°C, using ⁵⁷Fe in the solutions as an absorber. The quadrupole splitting increased and the isomer shift decreased between x = 0.05 and x = 0.70, a range in which the solutions are tetragonal and paramagnetic, and in which the unit cell volume increases with increasing x. The isomer shift, in particular, was primarily determined by the unit cell volume. Data are presented on the internal magnetic field of the antiferromagnetic …

Conversions From Cyclohexanol: An Undergraduate Laboratory Project, Samir B. Hanna, James T. Wrobleski, Joseph T. Bohanon, Billy W. Peace

Chemistry Faculty Research & Creative Works

No abstract provided.

Anodic Dissolution Of Beryllium In Anhydrous Media, William Joseph James, Martin E. Straumanis

Chemistry Faculty Research & Creative Works

No abstract provided.

The Effects Of Divalent Metal Ions On The Micellar Properties Of Sodium Dodecyl Sulfate, Michael U. Oko, Raymond L. Venable

Chemistry Faculty Research & Creative Works

Critical micelle concentrations and micellar molecular weights have been determined for sodium dodecyl sulfate in the presence of nitrates of copper, lead, zinc, and magnesium and critical micelle concentrations have been determined with sodium nitrate and silver nitrate as the added electrolytes. The thickness of the ionic atmosphere at the critical micelle concentration has been found to be 34.1 Å with no electrolyte present and 33.6 Å with 9.66 x 10-6 M sodium or silver nitrate and was found to increase upon addition of the 2:1 electrolytes. This is explained in terms of molecular and ionic interactions. Micellar molecular weights …

The Halogen And Uranium Content Of Sedimentary Rocks, Tektites, Impact Glasses, And Obsidians, Victor J. Becker Jr.

Masters Theses

"The iodine and uranium concentrations in sedimentary rocks were measured by irradiating the samples in a neutron flux, radiochemically separating iodine, and ß-counting the resulting activity. The values obtained for uranium are in good agreement with previous estimates of the uranium content in sedimentary rocks. The values obtained for iodine define a distribution pattern similar to that reported for chlorine and bromine, in contrast with the distribution pattern previously reported for iodine in sedimentary rocks. The concentrations of chlorine, bromine, iodine and uranium were determined in tektites, obsidians and impact glasses by neutron activation. The uranium content found in tektites …

Mass Fraction And The Isotopic Anomalies Of Xenon And Krypton In Ordinary Chondrites, Edward W. Hennecke

Masters Theses

"The abundance and isotopic composition of all noble gases are reported in the Wellman chondrite, and the abundance and isotopic composition of xenon and krypton are reported in the gases released by stepwise heating of the Tell and Scurry chondrites. Major changes in the isotopic composition of xenon result from the presence of radiogenic Xe¹²⁹ and from isotopic mass fractionation. The isotopic composition of trapped krypton in the different temperature fractions of the Tell and Scurry chondrites also shows the effect of isotopic fractionation, and there is a covariance in the isotopic composition of xenon with krypton in the manner …

A Measurement Of The Capture Coefficient And Of The Vapor Pressure Of Co₂ From 69ºk To 80ºk, Michel Louis Chouarain

Masters Theses

"The capture coefficient of CO₂ gas at 135ºK on a surface of CO₂ at temperatures between 69ºK and 80ºK is measured by means of quartz crystal microbalances. The vapor pressure of CO₂ is measured in the same range of temperature"--Abstract, page ii.

The Oxidative Decarboxylation Of Aminopolycarboxylic Acids With Cerium (Iv) In Sulfuric Acid, Rita Kathleen Hessley

Masters Theses

"The rates of oxidation of four chelating agents, NTA, EDTA CDTA, and DTPA with Ce(IV), in sulfuric acid media, were determined spectrophotometrically by a stopped-flow technique. The reductive ability is in the order CDTA>EDTA>DTPA>NTA. The influence of varying the acidity of the medium was studied, and in each case a maximum in the rate constant [H +] plot was observed. A possible interpretation of the reactivities and the influence of acidity is advanced"--Summary, page 1.

A Kinetic Study Of The Reductive Abilities Of Four Polyaminocarboxylic Acids (Edta, Cdta, Dtpa And Nta) Towards Cerium(Iv) In Perchloric Acid Media, Salem Ahmed Attiga

Masters Theses

"The reduction of Ce(IV) in HC10₄ solutions by four polyaminocarboxylic acids, which are commonly used as chelating agents, has been studied by the stopped-flow technique. The rates of reduction first increase with increasing acidity, reach maxima which are characteristic of the chelating agent and the medium, then progressively decrease with increasing the acid concentration in the media. At their maximum reactivities, trans-1,2-diaminocyclohexane tetraacetic acid (CDTA) shows the highest reductive ability; this is followed by ethylenedinitrilotetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and finally nitrilotriacetic acid (NTA). The observed maxima can be qualitatively explained in terms of a mechanism which involves unhydrolyzed …

The Thermal Accommodation Coefficients Of Helium, Neon, And Argon On Surfaces, Gerald Lee Zweerink

Doctoral Dissertations

"Measurements of the accommodation coefficients of helium, neon, and argon on an ice surface at 77ºK were accomplished; Measurements of the accommodation coefficients of helium and neon on a clean tungsten surface are also reported here; These data are compared with theoretical calculations of accommodation coefficients as well as with data from other experimental studies"--Abstract, pages iii-iv.

Some Metal Complexes Of Dihydroxycyclobutenedione, Stewart Michael Condren

Doctoral Dissertations

"This study involves an investigation of some of the physical and chemical properties of the trivalent metal squarate complexes of iron, vanadium, and indium in order to determine their structure. In this investigation studies were made of the infrared spectra, electronic spectra, x-ray diffraction powder photographs and diffractometer patterns, magnetic susceptibilities, and thermogravimetric patterns for the trihydrate, dihydrate, and anhydrous squarate complexes of vanadium(III) and iron (III) and the dihydrate squarate complex of indium(III). These studies suggest that the structures of the vanadium(III) and iron(III) squarate complexes are dimeric with hydroxyl bridges between the metal atoms. This is supported by …

Synthesis, X-Ray Characterization, Structural And Magnetic Studies Of A New Class Of Iso-Structural Bimo₃ Compounds, Joseph Donato Bucci

Doctoral Dissertations

"This dissertation consists of four sections. The first part is a temperature dependent X-ray study of the lattice parameters of BiFeo₃. The synthesis and subsequent X-ray characterization of BiCo₃, BiAlO₃, BiMnO₃ , BiScO₃, BiCo₁₋ₓFeₓO₃ , and BiAl₁₋ₓFeₓO₃ are reported in the second part. These compounds all crystallize in the body centered cubic (BCC) structure with a~10.2Å. Single crystal Precession and Weissenberg photographs confirmed the BCC structure. In part three, the results of the magnetic studies on BiCoO₃ and biAl.₉FE.₁ are presented. The magnetic data for BiCoO₃ are substantiated by X-ray thermal expansion studies. In the last part the compound BiCo.₉FE.₁O₃ …

Metal Salt Catalyzed Carbenoids, Billy W. Peace

Doctoral Dissertations

"The interaction of diazomalonic esters with olefins in the presence of homogeneous copper(I) and copper(II) catalyst has been examined as a function of olefin structure, solvent media, ionic strength, catalyst structure and catalyst concentration, using partial rate data. It has been possible to determine the fine mechanistic details of the cycloproponation, C-H insertion and "dimer" forming reactions. The initial step is displacement of a ligand from copper by diazo compound in a pre-equilibrium, loss of nitrogen in the rate determining step, return of the ligand, displacement of metal from the carbenoid by olefin, followed by collapse to products. Studies revealed …

Noble Gases Anomalies In Terrestrial Ores And Meteorites, B. Srinivasan

Doctoral Dissertations

"Analyses of the content and isotopic composition of xenon and krypton in terrestiral ores containing tellurium, selenium or iodine resulted in the following conclusions: 1. The double beta-decay half-life for ¹³⁰Te is 2.51 x 10²¹ years from analysis of tellurobismuthite from Boliden, Sweden and 2.83 x 10²¹ years from analysis of tellurides from Kalgoorlie, Australia. 2. The ratio of the double beta-decay half-life of ¹²⁸Te relative to that of ¹³⁰Te is ≥ 108 and ≥ 293 for Boliden tellurobismuthite and Kalgoorlie tellurides, respectively. 3. Selenium minerals and tellurium ores containing selenium exhibit ⁸²Kr excess attributed to the double beta-decay of …

Thermochemical Hydrogen-Deuterium Isotope Effects, Wayne C. Duer

Doctoral Dissertations

"The heats of solution at 25.0 ± 0. 1°C for each member of hydrogen-deuterium isotopic pairs (chloroform/chloroform-d, acetone/acetone-d₆, methanol/methanol-d₁, ethanol/ethanol-d₁, and water/heavy water) have been determined as a function of molality in a variety of solvents. The heats for most of the systems could be described as a linear function of average molality with an average deviation in fit of less than one per cent. Using these linear equations, heats of solution at infinite dilution were obtained by extrapolation to zero molality. The heats of solution at infinite dilution of the hydrogen containing compounds were subtracted from those of the …

The Semibullvalene Question: A Semi-Empirical Molecular Orbital And Bond Energy Approach, Shiow Yeh Lee

Masters Theses

"Semi-empirical molecular orbital calculations of the Extended Ruckel and MIND0/1 type have been performed on semibullvalene and the supposed transition state for its degenerate [3,3] sigmatropic rearrangement. The results have been coupled with bond energy calculations to ascertain whether semibullvalene is homo-aromatic or is undergoing a rearrangement of exceedingly low activation energy. A preponderance of the resulting data suggests that semibullvalene is homo-aromatic"--Abstract, page ii.

Theory Of Droplet Growth In Clouds. I. The Transient Stage Of The Boundary-Coupled Simultaneous Heat And Mass Transport In Cloud Formation, John C. Carstens, Joseph T. Zung

Physics Faculty Research & Creative Works

Two solutions to the system of equations describing the simultaneous heat and mass transport involved in the condensational growth of a droplet in a supersaturated atmosphere are presented. The first, valid for very short times, describes the transient stage of such growth; the second, valid for longer times, presupposes the establishment of a steady-state condition. The two are shown to be complementary for the cases examined. The equations examined satisfy the usual boundary conditions imposed on a drop in a concentric sphere as required by the cellular model for cloud formation. Hence our results can be immediately extended to the …

The Electrochemical Oxidation Of 1-Pentyne On Platinum And Gold, Michael Jensen Danielson

Doctoral Dissertations

"The anodic oxidation of 1-pentyne was studied at 70°C on Pt and Au electrodes in solutions of H₂SO₄, K₂SO₄, K₂CO₃, and KOH. Pt was studied in a pH range of 0.35 - 12.7 and Au in a range of 10.9 - 12.7. Reaction rates were measured as a function of potential, pH, temperature, and 1-pentyne partial pressure. The coulombic efficiencies for the oxidation to CO₂ were 77 percent in 1 N H₂SO₄ and 69 percent in 1 N KOH on Pt and 43 percent in 1 N KOH on Au. The kinetic parameters on Pt were [partial derivative]V/[partial derivative]log i …

Glory Scattering In Molecular Collisions: Formal Expressions For The Total Cross Section, Louis Biolsi

Chemistry Faculty Research & Creative Works

An Extended Distorted-Wave Treatment is Used to Obtain Formal Expressions for the Total Cross Section When Two Rigid Diatomic Molecules with Orbital and Nuclear-Spin Angular Momenta Collide. Explicit Expressions Are Obtained through Second Order, Including the Lowest-Order Inelastic Effects.

Mass Spectrometric Study Of "Anomalous" Water, Bernard Jean Bouy

Masters Theses

"Considerable interest has developed recently in a material called "polywater" or "anomalous water". This material has properties quite different from those normally associated with liquid water. The purpose of this study is to give some mass spectrometric observations of "polywater". The "polywater" samples were produced within silica capillaries. These capillaries were heated by means of a helical coil to vaporize the "polywater". The vapor was directed into the source of a mass spectrometer. The results of this study show that a significant portion of the "anomalous water" samples is composed of a polymer of dimethylsiloxane. To date, the observations are …

Identification Of Decomposition Products Of Tropyl Azide And Interaction Of Tropylium Ion With Nucleophiles, James Joseph Ward

Doctoral Dissertations

"An investigation of the structures of several of the products resulting from the decomposition of tropyl azide (I) and of the chemistry of related processes has been undertaken. Irradiation of samples of (I) in the vapor phase with low intensity UV G.E. Sun Lamps furnished a low melting white solid identified as tropyl troponimmonium azide (II). Earlier experiments of a similar nature reported to furnish (III) were not repeatable (Chem. Commun 276 (1967))...

Upon standing, solutions of (I) slowly formed troponimmonium azide (IV) in the cold (J. Chem. Soc. (D), 220 (1970)). The structures (II) and (IV) were confirmed by …

The Electrochemical Behavior Of The Lead-Thallium System In Acidic Sulfate Solutions, Pedro Juan Aragon

Doctoral Dissertations

"Although the literature involving the corrosion of pure lead in sulfuric acid solutions is extensive, such studies still constitute an active field of investigation and debate. Much of the effort expended on this subject is due to the need of a better understanding of the reaction in lead storage batteries as well as of the mode of electrocrystallization processes. The resistance of lead to attack by sulfuric acid renders it an important coating material in this media. It is also often used in electrochemical synthesis because of its overvoltage characteristics. Unfortunately its mechanical properties are poor, and many ways have …

The Ultraviolet Absorption Spectra Of Solutions Of 2, 4, 6-Trimethoxybenzoic Acid In Sulfuric Acid, Kathy Show-Shing Ho

Masters Theses

"Studies of the ultraviolet and proton magnetic resonance spectra of solutions of 2,4,6-tribromo-, trichloro-, trimethyl- and trinitro-benzoic acids dissolved in concentrated sulfuric acid by Dr. D. W. Beistel and his coworkers lead to the synthesis of the corresponding benzoate esters. In the present work the nature of ionic species formed in mixtures of sulfuric acid and 2,4,6-trimethoxybenzoic acid was examined, The spectral data suggest the presence of species similar to those assigned for the previous trisubstituted analogs, together with a species capable of fluorescence in the 2400 Å region. The reason of this unprecedented fluorescence has not been established"--Abstract, Page …

Metabolism Of 3-Iodotyrosine And 3,5-Diiodotyrosine By Thyroid Extracts, Shih-Ying Sun

Masters Theses

"A porcine thyroid enzyme was extracted from thyroid tissue by homogenization and differential centrifugation. The enzyme was capable of metabolizing both 3-iodotyrosine and 3,5-diiodotyrosine. All of the thyroid subcellular particles produced a fluorescent compound when incubated with these substrates. When the 1,000 x g sediment was supplemented with the 48,000 x g supernatant a second compound was formed. The compound was UV absorbing and has been identified as either 3-iodo-4-hydroxybenzaldehyde or 3,5-diiodo-4-hydroxybenzaldehyde depending upon which substrate was used. The 1,000 x g sediment was solubilized with 1% Conoco 1012-6 detergent. The activating factor in the 48,000 x g supernatant was …

Amino Acid Sequence Of An Iodotyrosyl-Containing Peptide Produced By Tryptic Digestion Of Thyroglobulin, Pai-Chun Chiang

Masters Theses

"Thyroglobulin was digested with trypsin. An iodotyrosyl-containing peptide was isolated from tryptic digests by a combination of electrophoresis and paper chromatography. The amino acid sequence of this peptide was determined by applying the Edman degradation and by using the proteolytic enzyme, carboxypeptidase A. The sequence of this peptide is: NH₂-Ala-Ile(Leu)-Ala-Ser-Phe-Gly-Asp-Tyr-Glu-Phe-COOH The importance of the position of the tyrosyl residue which is iodinated to form monoiodotyrosine (MIT) , diiodotyrosine (DIT) , and thyroxine (T₄) is considered in connection with the structure-activity relationship of the protein"--Abstract, page ii.

The Possible Correlation Of Carcinogenic Activity With Electronic Structure Of Benz(A)Anthracene, Patricia Joan Blair

Masters Theses

"The electronic structure of benz(a)anthracene based on the sigma and pi electrons was predicted by the modified intermediate neglect of differential overlap (MINDO) molecular orbital method and compared with the pi electronic structure determined by the Pople method. The crystalline molecular structure was used for both methods. The Pople calculation was also done on the aromatic molecular structure and a combination structure which assumed the bond lengths of the crystal structure and the bond angles of the aromatic structure. Chemical properties predicted by the MINDO and POPLE electronic structures were compared; the MINDO results provided the best agreement with experimental …

The Radial Distribution Curve Of "Anomalous" Water By X-Ray Diffraction, Jerome Dechelette

Masters Theses

"Amorphous and liquid samples, believed to be "anomalous" water were studied by X-ray diffraction. A diffusion ring, characteristic of liquids and glass was observed at Θ =10.5º. For purposes of comparison an X-ray diffraction pattern was obtained for pure water under nearly identical conditions. By means of a microdensitometer, X-ray intensity curves were prepared from the diffraction patterns and corrected for absorption and polarization. From the Fourier transform of the intensities, we obtained the radial distribution curves. The radial distribution curve for water, obtained in previous work, shows an initial peak at 2.9Å. This peak is due to the nearest …

The Anodic Oxidation Of Oxalic Acid On Au, Jean Louis Lucien Desmartin

Masters Theses

"The anodic oxidation of oxalic acid on Au has been studied at 25ºC in aqueous media. The reaction rate was measured as a function of potential, oxalic acid concentration, pH, and temperature in H₂SO₄-K₂SO₄ solutions. A change in the Tafel slope in going from the lower to the higher Tafel region is explained by an alteration of the reaction mechanism due to electrical interactions between adsorbed species and the anode. Further details of an oxidation sequence involving resonant forms of oxalic acid are proposed"--Abstract, page 1.

A Study Of The Oxygen Exchange Between Chromate Ion And Water, James Hsiao-Hsin Chiang

Masters Theses

"The kinetics of the isotopic exchange reaction between O¹⁸-enriched chromate ion and solvent water have been measured as a function of pH and chromate ion concentration. The exchange kinetics can be explained in terms of the dimerization equilibria HCrO_4̄ + Cr₂O[subscript 7 with double dash above] [double arrows] Cr₂O[subscript 7 with double dash above] + OH⁻ and 2HCrO_4̄ [double arrows] Cr₂O[subscript 7 with double dash above] + H₂O except at high pH, where it is independent of pH. Rate constants at 30ºC for the reactions of the dimerization equilibria and the first order reaction at the high pH …