Chemistry Commons^™

Enhanced Evaporation Of Water Droplets Due To Surface Contamination, Robert Bernard Hughes

Masters Theses

"Experimental evidence for enhanced evaporation of small (3-9 µ radius) water droplets are presented. Both "pure" droplets and droplets contaminated with surface active materials fell into air of known relative humidity (96-99 per cent) at an ambient temperature of 29.9C and evaporated. The rates of evaporation were determined by photographing the evaporating drops, measuring the distance a drop fell during a fixed time interval, and applying Stokes law. The contaminated droplets exhibited a rate of evaporation 1.8µ² sec⁻¹ faster than "pure" drops. This can be compared with rates for pure drops of 1.9 and 5.7µ² sec⁻¹ at 0.1 and 0.3C …

Substitution And Photolytic Rearrangements In Three-Member Ring Compounds, Joseph Terril Bohanon

Doctoral Dissertations

"An investigation into the substitution and photolytic rearrangements of 1,2,3-triphenylcyclopropenes was conducted. Triphenylcyclopropenyl t̲-butyl ether was found to undergo alkyl group exchange with refluxing methanol, ethanol, or 2-propanol to yield the corresponding 1,2,3-triphenylcyclopropenyl alkyl ether when a trace impurity of a 1,2,3-triphenylcyclopropenium halide is present to catalyse the reaction. This forms hydrogen halide with solvent. Upon standing for long periods of time, the 1,2,3-triphenylcyclopropenyl ethers were observed to partially rearrange to new products. A sample of 1,2,3-triphenylcyclopropenyl methyl ether was subjected to photolysis in hexane and yielded 3-methoxy-1,2-diphenylindene, 2,3- diphenylindenone, tolane, benzoic acid, 1,2,3-triphenylpropen-1-one and a polymer. Samples of 1,2,3-triphenylcyclopropene, …

The Reaction Of N-Sulfinylamines With Diazoalkanes, Harry R. Musser

Doctoral Dissertations

"The photochemical decomposition of diphenyldiazomethane in the presence on N-sulfinylamines leads to ketimines. By-products include tetraphenylethylene, benzophenone, thiobenzophenone, and benzophenone azine. This reaction is the first example of carbene addition to a non-carbon containing multiple bond system. Evidence indicates that the carbene adds to the N=S bond of the N-sulfinylamine to give the corresponding thiaziridine-S-oxide which spontaneously decomposes to give ketimine and SO. In the dark N-sulfinylaniline catalyzes the decomposition of diazoalkanes to carbenes. This decomposition presumably takes place through a thiatriazole-1-oxide intermediate. The carbene then reacts either with N-sulfinylaniline to form ketimine, after loss of SO, or with diazoalkane …

A Fundamental Investigation Of The Gas Phase Polymerization Of Styrene And Vinyl Type Monomers In A Low Power Inductively Coupled 4 Mhz Rf Plasma, L. F. Thompson

Doctoral Dissertations

"A study has been made on the plasma polymerization of styrene and vinyl type monomers in a cold, low power, inductively-coupled RF plasma. All vinyl type monomers yielded an insoluble, crosslinked film which was slightly colored. A kinetic study is reported for styrene. The effects of power level, bleed rate of monomer, pressure and reactor geometry on the rate of polymer formation are reported. A mechanism is postulated for plasma polymerization. It was found that the initiation step was the rate controlling step and that the reaction followed a cationic polymerization scheme. Both crosslinking and discoloration of the polymers occur …

Mössbauer Effect In The Ferroelectric Pbtio₃-Bifeo₃ Solid Solutions, C. M. Yagnik, James P. Canner, Robert Gerson, William Joseph James

Physics Faculty Research & Creative Works

The Mössbauer spectra of the system (PbTiO₃)_0.95(BiFeO₃)_0.05 have been studied from room temperature to 585°C. From the isomer-shift of 0.491±0.02 mmsec^-1 at room temperature, the ionicity is found to be 60% ± 20%. A discontinuity in the plot of isomer-shift versus temperature at T_c is observed. The quadrupole splitting at room temperature is 0.295 ± 0.02 mm/sec^-1. A dip in the Mössbauer fraction is observed at the Curie temperature.

The Oxidative Decarboxylation Of Polyaminocarboxylic Acids - I. A Study Of The Reaction Of Ethylenedinitrilotetraacetic Acid (Edta) With Cerium (Iv) In Acid Solution, Samir B. Hanna, S. Al-Hashimi, William H. Webb, William R. Carroll

Chemistry Faculty Research & Creative Works

The reaction between Ce(IV) and EDTA was followed titrimetrically and spectrophotometrically and was found to occur in stages. Four equivalents of Ce(IV) are reduced per mole of EDTA almost instantaneously at room temperature. With increasing temperature and reaction time an ultimate of about 14 equivalents of Ce (IV) is consumed per mole of EDTA. Carbon dioxide, formaldehyde, and other yet unidentified compounds are the products of oxidation of EDTA. The kinetics of the reaction in aqueous sulfuric acid was studied over the temperature range 11.7°-40°C by a spectrophotometric technique. The effects of the acidity of the medium and of added …

Das Problem Der Mononitrierung Von Durol, S. B. Hanna, E. Hunziker, T. Saito, H. Zollinger

Chemistry Faculty Research & Creative Works

In contrast to many previous investigations, reaction conditions were found under which the nitration of durene (nitrating ratio of 1:1) gives predominantly, and in high yield, mononitrodurene rather than the usually formed dinitrodurene (plus unreacted durene). The method consists in nitrating by nitronium phosphorohexafluoride in nitromethane as solvent in presence of two equivalents of water. With mixed acid (HNO₃ + H₂SO₄) in nitromethane and in acetonitrile durene forms also monoand no dinitrodurene; but under most conditions by‐products are formed. Some of the by‐products were identified. Some preliminary mechanistic results are reported: An addition complex of …

Semiempirical Determination Of The Hydrogen Bond Energy For Water Clusters In The Vapor Phase. I. General Theory And Application To The Dimer, Richard W. Bolandee, James L. Kassner, Joseph T. Zung

Physics Faculty Research & Creative Works

A simple semiempirical method is given for determining the hydrogen bond energy for water clusters in the vapor phase. This method is based on a general statistical-mechanical theory of clustering. The partition function for a system of clusters is used to determine the equilibrium distribution of clusters. In conjunction with available thermodynamic and spectroscopic data, the cluster equilibrium constants can be used to calculate the cluster potential energy and the hydrogen bond energy. Results for the water dimer agree quite well with other reported values obtained either by quantum-mechanical calculations or approximate thermodynamic estimates. A correct temperature dependence of the …

Modification Of The Devonshire Formula For The Thermal Accommodation Coefficient Of Helium On Tungsten, D. Vincent Roach, Robert E. Harris

Chemistry Faculty Research & Creative Works

The thermal accommodation coefficients (a.c.) of 3He and of 4He on clean tungsten were calculated using the Devonshire formula for temperatures between 70 and 600°K using "realistic" Morse potential parameters. The calculated a.c. values for 3He and 4He and the calculated ratios of the 4He to 3He values are compared with experimental data. The agreement is satisfactory if allowance is made for the error in the transition probability calculation used in the Devonshire formula.

Michael Reactions Part Iv Syntheses With Carboalkoxycarbenes, Frederick Ralph Carman

Masters Theses

"A preliminary investigation has been made involving syntheses with dicarboalkoxycarbenes for the purpose of developing new heterocyclic and alicyclic synthese employing functionalized carbenes. The ultimate goals were the development of a stereospecific synthesis of trans fused and angularly substituted ring systems suitable for conversion to natural products and the development of useful synthetic paths to the azabullvalene system. Although these ultimate goals were not realized, new and improved syntheses of alkyl substituted anisoles and diazomalonic esters, including the first reported synthesis of di-tert-butyl-diazomalonate were accomplished. The addition of dicarboalkoxycarbenes to di-, tri- and tetra- substituted ethylenes, tropilidene and 7-aza-tropilidenes by …

The Incorporation Of Oxygen-18 Into Oxindole Acid By Cells Of Hygrophorous Conicus, William Green Allen

Masters Theses

"To understand the mechanism of a biological oxidation in which oxygen is incorporated into a substrate, it is necessary to determine the origin of the incorporated oxygen. The objective of this investigation was to determine the origin of the oxygen atom incorporated into indoleacetic acid (IAA) by the IAA oxidase of Hygrophorous conicus through the use of oxygen-18. To determine the source of the oxygen atom incorporated into IAA it is necessary to incubate H. conicus cells with tryptamine or IAA in the presence of ¹⁸O₂ and H₂¹⁶O in one case and ¹⁶O₂ and H₂¹⁸O in another. An examination of …

Thermochemical Investigations Of The Methanol-Isopropanol System, Elmer Lee Taylor

Masters Theses

"Heats of solution and partial molar excess volumes at infinite dilution were determined for n-butanol, acetone, chloroform, and water in pure methanol, pure isopropanol, and several mixtures of the two at 25.0⁰C. The partial molar excess enthalpies of methanol and isopropanol were also determined and were combined to obtain integral heats of mixing. All heat data were obtained using a calorimeter of the heat-leak design, containing approximately 300 ml of solvent. Sample sizes ranged for 0.1 to 8 ml. Individual heat measurements were reproducible to 0.05 calories and reported values are considered to be accurate to 1% + 0.5 calorie …

Isotopic Anomalies Of Noble Gases In Natural Gas, Garry A. Bennett

Masters Theses

"This investigation of the abundance and isotopic composition of noble gases in helium-rich gas wells was undertaken in order to obtain new data which might be used to elucidate the origin of isotopic anomalies of noble gases in the atmosphere. Since noble gases are presently leaking to the atmosphere (Damon and Kulp, 1958a; Bieri et al., 1967-) the isotopic composition of the present atmosphere is not static. The direction of change, and ultimately the origin of anomalous noble gases, might therefore be discovered in studying the noble gases presently leaking from the earth. Since the two major noble gas isotopes …

Noble Gases: A Record Of The Early Solar System, E. C. Alexander

Doctoral Dissertations

"Analyses of the noble gases in samples of iron meteorites are presented which indicate the following: 1. The inclusions of iron meteorites contain noble gases with a wide range of isotopic compositions. 2. The noble gas concentration and isotopic anomalies arc often grossly inhomogeneously distributed within a given inclusion and vary from inclusion to inclusion in a meteorite. 3. Silicate inclusions appear to be the most promising samples for I-Xe and Pu-Xe dating. 4. Graphite and troilite in addition to the silicate inclusion contain significant radiogenic ¹²⁹Xe anomalies. 5. The total I-Xe (and in the case of Toluca silicates total …

The Effect Of Impurities On The Time Dependence Of The Surface Tension Of Aqueous Surfactant Systems, Elizabeth Ann Munson

Masters Theses

"In this study surface tension measurements were made on tetradecylpyridinium bromide (TPB) solutions both in water in solutions containing various concentrations of impurities. Three impurities were studied, dodecyl alcohol, decyl alcohol and dodecylpyridinium bromide. Surface tension vs. time plots were constructed and show a definite dependence on the concentration of the impurity added. As the concentration of the impurity increases the equilibrium surface tension decreases. The decrease in the equilibrium surface tension is also dependent upon the concentration of the tetradecylpyridinium bromide. As the concentration of the surfactant (TPB) increases the effect of the impurity is reduced"--Abstract, page i.

Geochemical Abundance Of Iodine, Jane Hanisch Bennett

Masters Theses

"The research reported herein includes unpublished iodine and uranium data on a group of United States Geological Survey standards and on a group of ultrabasic rocks. Data are also included for the major rock types, deep sea sediments, and for graphite and troilite inclusions in iron meteorites. Tellurium data for the troilite are also reported. Appendix I is a literature article (Bennett and Manuel, 1967a) on Canyon Diablo Graphite. Appendix II is a literature article (Bennett and Manuel, 1967b) on deep sea sediments. The results of this study show that most of the earlier estimates of the crustal abundance of …

Current Density-Anodic Potential Curves Of Single Crystal Gaas At Low Currents In Koh, Martin E. Straumanis, J. P. Krumme, William Joseph James

Materials Science and Engineering Faculty Research & Creative Works

Single p-type, GaAs crystals of high purity, Zn doped, were used to determine whether or not the inverse octahedral {111} faces show potential differences and various rates of anodic dissolution. The Ga{111}, As{111}, {110}, and {100} faces, were polished, etched, and etch-polished with concentrated H₂SO₄ + H₂O₂, and immersed in IN KOH. The Ga{111} faces were found to be the most noble with respect to rest and anodic dissolution potentials. The potential difference between the inverse {111} faces was as large as 0.14v for the rest and 0.123v for the dissolution potentials. The …

Dielectric Properties Of Solid Solutions Of Bifeo₃ With Pb(Ti, Zr)O₃ At High Temperature And High Frequency, Robert Travis Smith, Gary D. Achenbach, Robert Gerson, William Joseph James

Physics Faculty Research & Creative Works

Solid solutions of BiFeO₃ with PbTiO₃, PbTi_0.5Zr_0.5O₃, and PbZrO₃ were prepared. The crystallographic data on these solutions, which are basically perovskitic, are given. The dielectric constants of the materials were determined at a frequency of 0.53 GHz and at temperatures up to 800°C. Dielectric Curie points were found in solutions containing up to 90 mole % BiFeO₃. These results leave little doubt that BiFeO₃ is ferroelectric or antiferroelectric. The extrapolated Curie point for BiFeO₃ is above 850°C. BiFeO₃ appears more likely to be ferroelectric than …

Surface Interactions Between Nickel Ions And Sodium Dodecyl Sulfate, Ralph Edward Coleman

Masters Theses

"In this research the interaction of nickel ions with the surfactant sodium dodecyl sulfate at the liquid-air interface was studied. Surface tension measurements were performed on pure sodium dodecyl sulfate solutions, with and without the addition of nickel ions. Results of these measurements showed that the addition of nickel ions lowered the equilibrium surface tension values of pure sodium dodecyl sulfate solutions and shifted the critical micelle concentration to lower concentrations. The foam fractionation technique was used to determine if the nickel ions could be removed from surfactant solutions. It was found that the removal of nickel ions was influenced …

Endogenous Metabolism Of Polyporus Sulfureus. : Utilization Of Exogenous Carbohydrates And Fatty Acids, Shu-Mei Wang

Masters Theses

"A strain of Polyporus sulfureus from the collection at the University of Missouri at Rolla was used in this investigation. Organisms of this genus have been reported to produce eburicoic acid in good yield and this was confirmed for the organism used in this study by the isolation and identification of eburicoic acid from the mycelium. Growth studies of this organism showed that 4% malt extract is a better medium than synthetic media containing asparagine, nitrate or nitrate plus 0.5% yeast extract as nitrogen sources. An examination of the pH of the culture medium led to the conclusion that regardless …

A Study Of Solvent Effects On The Reaction Between P-Nitrobenzyl Chloride And Hydroxide Ion In Aqueous Dioxane Homogeneous Media, Ken K. Ho

Masters Theses

"The kinetics and activation parameters of the reaction between p̲, p̲' - dinitrostilbene quantitatively, have been studied in five aqueous dioxane solvent systems at five different temperatures between 20⁰ and 40⁰C. At any one temperature the second-order rate constants are minimum in the 30% dioxane solvent mixture, reach a maximum in the 50% dioxane systems, and fall off slightly in the 60% and 70% dioxane systems. The Arrhenius activation energies are highest in the 30% dioxane and lowest in the 70% dioxane systems. The free energies of activation change in the same direction but the magnitude of change is much …

A Kinetic Investigation Of The Reaction Of Ethylenedinitrilotetraacetic Acid (Edta) And Cerium (Iv) In Acid Solution, Sahmia K. Al-Hashimi

Masters Theses

"The reaction between Ce(IV) salt solutions and EDTA solution was followed titrimetrically and spectrophotometrically and found to occur in stages. Four equivalents of Ce(IV) are reduced per mole of EDTA almost instantaneously at room temperature or even lower. With increasing temperature and reaction time an ultimate of about 14 equivalents of Ce(IV) is consumer per mole of EDTA. Formaldehyde, carbon dioxide, and other unidentified compounds are the products of oxidation of EDTA with Ce(IV). The kinetics of the reaction in aqueous sulfuric acid (0.09 - 2.95 M̲) was studied over the temperature range 11.7-40⁰ by a spectrophotometric technique. In the …

A Study Of Succinic Dehydrogenase, Indole Acetic Acid Oxidase, Nitrate Reductase And Cytochrome C Reductase In Hygrophorus Conicus, Jagdish M. Mehta

Doctoral Dissertations

"The activity of the enzyme succinic dehydrogenase (succinate : phenazine methosulfate oxidoreductase, EC 1.3.99.1) of Hygrophorus conicus, a member of a class of fungi known as basidiomycetes, was found to be stimulated by nitrate. Two substances were tested as electron acceptors in the measurement of succinic dehydrogenase activity. Of the two substances tried, phenazine methosulfate and brilliant cresyl blue, the former was found to be the best. Nicotinamide adenine dinucleotide (NAD⁺) was a necessary cofactor for the enzyme and could be readily dissociated from the enzyme. The enzyme has the properties of a high molecular weight nucleo- or lipoprotein.

The …

Deuterium Isotope Effects On The Solvolysis Rates Of Cyclopentyl Brosylates And Tosylates, Jimmie D. Christen

Doctoral Dissertations

"The brosylates and tosylates of cyclopentanol and its 1-d₁, c̲i̲s̲-2-d₁, t̲r̲a̲n̲s̲-2-d₁, and 2,2,5,5-d₄ analogs have been synthesized and their solvolysis rates measured at 25° in 70% vol. ethanol-water. The solvoylsis reactions were monitored by a conductance method. The isotope effects, k_H/k_D, observed for the brosylates and tosylates of each of the isotopically substituted cyclopentyl alcohols are as follows: 1-d₁-brosylate (1.1869) and 1-3₁-tosylate (1l1836); c̲i̲s̲-2-d₁-brosylate (1.1533) and c̲i̲s̲-2-3₁-tosylate (1.1577); t̲r̲a̲n̲s̲-2-d₁-brosylate (1.1803) and t̲r̲a̲n̲s̲-2-d₁-tosylate (1.1765); 2,2,5,5-d₄-brosylate (1.8881) and 2,2,5,5-d₄-tosylate (1.8863). The closeness in magnitude of the isotope effects for the c̲i̲s̲- and t̲r̲a̲n̲s̲-isomers is important in that it …

Anodic Dissolution Of Zinc In Potassium Nitrate, Martin E. Straumanis, J. L. Reed, William Joseph James

Materials Science and Engineering Faculty Research & Creative Works

The apparent valence of pure zinc dissolving anodically in 3% KNO₃ was determined as a function of current density, temperature, and ultrasonic agitation. The apparent valence of zinc dissolving anodically at 24°C diminishes from 2.01 ± 0.01 at low current densities to 1.86 at about 50 ma and remains fairly constant up to about 80 ma cm−2. This valence is affected to some extent by the preparation, e.g., polishing of the electrode, but is independent of its structure (mono- or polycrystal). Ultrasonic vibrations do not influence the apparent valence at high current densities. In all cases a black film …

The Anodic Dissolution Of Cadmium, James W. Johnson, E. Deng, S. C. Lai, William Joseph James

Chemical and Biochemical Engineering Faculty Research & Creative Works

The anodic dissolution of cadmium has been studied in aqueous solutions containing Cl−, Br−, I−, Ac−, SO₄=, and NO3− ions. The normal valence (+2) was found in all solutions with the exception of NO₃−. The apparent valence (calculated) of cadmium ions in nitrate solutions varied from 1.2 to 2.0 and was found to be a function of NO₃− concentration, current density, and temperature. An anodic dissolution mechanism has been proposed involving local corrosion and disintegration of the anode which is consistent with the experimental results. © 1967, The Electrochemical Society, Inc. All rights reserved.

The Role Of The Doctor Of Engineering Degree In Graduate Education, Wouter Bosch, Robert E. Carlile

Chemistry Faculty Research & Creative Works

No abstract provided.

Noble Gases In The Earth And Its Atmosphere, Robert Anthony Canalas

Masters Theses

"Abundance of noble gases extracted from Fig Tree Shale exhibit a marked deviation from the gas content of eclogitic rocks purported to be mantle material. The abundances of the heavy noble gases in shale were found to exceed the highest known meteoritic values. The abundances of the lighter noble gases were found to be comparable to the abundances of these gases in typical chondrites.

Temperature gradient analyses show that excess heavy gases are released at low temperatures. This is interpreted to indicate a preferential adsorption of the heavy noble gases on fine-grained sediments when these gases were being released from …

Mechanisms Of Base-Catalyzed Reactions: Part Iii: The Acidities Of Some Hydroxylic Compounds In T-Butyl Alcohol., Charles Frederick Seger

Masters Theses

"The K_HA of water and five alcohols were determined in t̲-butyl alcohol employing sodium and potassium t̲-butoxides. The order of acidity is methanol>water>ethanol> 2-propanol~cyclohexanol>methanol. It was also shown that potassium t̲-butoxide was twice as strong a base as sodium t̲-butoxide. A spectrophotometric method was employed with p-nitroaniline as the indicator. Calculations were made employing the methods of Stearns and Wheland and of Hine and Hine"--Abstract, page iii.

Studies In Coprecipitation Of Trace Amounts Of Elements, Gerald Delano Schucker

Masters Theses

"A new approach to preconcentration of trace amounts of elements has been demonstrated whereby traces of metals tied up as chelates are coprecipitated on a column of solid organic material. Complete coprecipitation was found to occur within very narrow pH ranges, thereby allowing separation as well as concentration of the elements by careful adjustment of acidity and concentration of chelating agent. The separation is based on the difference in stability constants of the metal chelates. Preliminary studies with different physical forms of the carrier precipitate, indicate adsorptive processes could play a significant role in the mechanism of the column-coprecipitation process. …