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Synthesis And Studies Of A Carbon-13 Labelled Chemical Carcinogen, Robert E. Royer

Chemistry and Chemical Biology ETDs

Derivatives of 6-methylbenzo[a]pyrene enriched to 90% carbon-13 at the methyl carbon were synthesized. Reactions of the carcinogen, 6-chloromethylbenzo[a]pyrene, with nucleophiles under solvolytic conditions were studied kinetically and, using labelled 6-chloromethylbenzo[a]pyrene, the reaction products were studied by CMR. The purpose was to characterize the selectivity of the benzo[a]pyrenyl- 6-methyl carbonium ion in its reactions with some simple nucleophiles and with nucleosides and other nucleic acid components.

Although the solvolysis of 6-chloromethylbenzo[a]pyrene in aqueous/organic solution is first order, information about the course of the reaction can be obtained, under certain circumstances, from rate constants. Thus, if the rate of solvolysis is slowed …

Photochemical Studies Of Hydroxo-Bridged Complexes Of Chromium (Iii), Ronald Raymond Ruminski

Chemistry and Chemical Biology ETDs

The acid solution and solid state photolysis in both visible and ultraviolet regions of the spectrum for µ-hydro­xo-bis[pentaamminechromium(III)] chloride, and the solution photolysis in the visible and 1 traviolet region of the spectrum for µ-hydroxo-bis[pentaarnrninechr rnium(III)] perchlorate, have been studied. The ultraviolet irradiation of µ-hydroxo-bis[pentaamminechromium(III)] chloride in HCl and CHlO₄ produces a redox photoproduct identified as HCrO₄^-, although the rate of production of HCrO₄^- in HClO₄ is slower than in HCl. Photochemical cleavage of the hydroxo-bridge occurs in the ultraviolet photolysis of µ -hydroxo-bis[pentaanuninechromium(III)] chloride and is 1.9 times faster than the corresponding …

Observation Of Davydov Splitting In Pts Polydiacetylene Crystal Spectra, Hans Muller, Craig J. Eckhardt

Craig J. Eckhardt Publications

The electronic spectra of polydiacetylene crystals have often been typified by poly-2, 4-hexadiyne-1, 6-diol-bis-(p-toluene sulfonate) (PTS). The spectra of crystals of this polydiacetylene have been unique in that they have displayed a pronounced “doubling” of the 300 K spectral bands at temperature below 170 K. The reflection bands are also observed to undergo a continuous red shift with continued decrease of temperature. The reflection band observed at lowest energy at 300 K is resolved at 77 K into two clearly separated bands at 15,700 cm^-1 (Ib) and 16,050 cm^-1(IIb). A recent study by modulated piezoreflection …

Erratum: A Comparison Of The Rough Sphere Rotational Diffusion Model With Experimental Results For Liquid Methyl Iodide, Scott Whittenburg

Chemistry Faculty Publications

No abstract provided.

The Effects Of Various Pyrolysis Conditions On The Release Of Products From Green River Oil Shale, Georgia Thomas Fritz

Chemistry and Chemical Biology ETDs

The fusion of oil shales with eutectic mixtures of inorganic salts was studied with the objective of finding a chemical means of releasing the organic material either at a lower temperature or with a lower empirical activation energy (E_a). Experimental techniques by which the pyrolysis of oil shale was studied were thermogravimetry (TG), evolved gas detection (EGD), and pyrolysis/thin-layer chromatography (TLC). The following fused salts were investigated (ratios in mo1%): LiCO₃/Na₂co₃/K2CO3, 43.5/31.5/25.0; KSCN/NaSCN, 73.75/26.25; KSCN/­NaSCN, 70/30; Na₂SO₄/K₂SO₄/ZnSO₄, 29.1/30.2/40.7; NaCl/Na₂CO_{3 …}

The Chemistry Of Sf₅Br And Sf₅Cf=Cf₂ - Addition Reactions, Robin J. Debuhr

Dissertations and Theses

Addition reactions of pentafluorosulfur bromide (SF₅Br) with fluoroolefins were studied. Three new adducts were prepared, SF₅CHFCHC1Br, SF₅CH₂CH(CF₃)Br, SF₅CHFCFC1Br. SF₅Br and CFC1=CHC1 yielded a small amount of product but attempts to add SF₅Br to CF₂₌FCOF were unsuccessful.

The mechanism for these addition reactions seems to involve a free radical addition pathway. Steric factors seem to be important in determining whether SF₅Br will add to fluoroolefins.

The new compounds, SF₅CF(CF₃)COF and SF₅CF(CF₃ )CONH₂ have …

Determination Of The Rate Of Formation Of Hcn, Mitchell Hull

Honors Theses

Nitric oxide is a major air pollutant arising from fossil fuel combustion, yet the fuel contribution to its formulation is uncertain. Since, in combustion, fossil fuels undergo disintegration before oxidation takes place, the study of the pyrolsis of a model constituent of fossil fuels can shed light on NO formation. The rate of inert pyrolytic disappearance of pyridine and the rate of formation of the principal Nitrogen-containing pyrolytic product, HCN, was studied in an inert atmosphere. The rate constant for the formation of HCN and its temperature dependence were determined.

Thermochromism In A Polydiacetylene Crystal, R.R. Chance, R.H. Baughman, H. Muller, Craig J. Eckhardt

Craig J. Eckhardt Publications

Specular reflection spectra are reported for a thermochromic polydiacetylene crystal, ETCD [substituent group – (CH₂)₄OCONHC₂H₅] over the temperature range 23–130°C. A reversible thermochromic phase change occurs at ~120°C and is accompanied by a 2750 cm^-1 blue shift in the reflection spectra. Evidence is presented which strongly suggests that the dramatic change in optical properties of ETCD at the phase transition is due to an acetylene to butatriene transformation in the bonding sequence of the polydiacetylene backbone.

4th Annual Umr-Dnr Conference On Energy -- Entire Proceedings, University Of Missouri--Rolla

UMR-MEC Conference on Energy / UMR-DNR Conference on Energy

No abstract provided.

Erratum: Light Scattering Studies Of Transverse Sound Wave And Molecular Motion In Benzonitrile, Scott Whittenburg

Chemistry Faculty Publications

No abstract provided.

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 …

An Electrochemical Investigation Of The Effects Of Antiaromaticity And Determination Of The Increased Antiaromatic Destabilization Of Cyclobutenedione Upon Reduction, Reuben D. Rieke, C. Kenneth White, Lee D. Rhyne, Mark S. Gordon, John F. W. Mcomie, Niegel P. Hacker

Mark S. Gordon

Electrochemical studies were carried out on a series of cyclic 1,2-diones under nonaqueous conditions. From thereduction potentials and Hucke! molecular orbital calculations, the increase in antiaromatic destabilization of cyclobutenedione upon reduction is estimated to be at least 14 kcal/mol. The EPR spectrum of the radical anion of naphtho[b ]cyclobutadienoquinone is presented. Also, INDO calculations were carried out on several of the diones and the results are consistent with the experimental observations.

High Spin-Low Spin Crossover And Antiferromagnetic Interactions In Tris(1-Pyrrolidinecarbodithioato)Iron(Iii) And The 4-Morpholine (Fem) And Dibutyl Analogs, Effect Of Recrystallization Solvent, And Crystal Structure Of Fem·Nitrobenzene, Edward J. Cukauskas, Bascom Sine Deaver, Ekkehard Sinn

Chemistry Faculty Research & Creative Works

High sensitivity magnetic susceptibility determinations, especially in the range 1.2-4.2 K on pure and dilute tris(pyrrolidinecarbodithioato)iron(III) (FeP) in its high spin form, show that a maximum at about 2 K is caused by antiferromagnetic interactions. The analogous chromium(III) complex does not exhibit significant antiferromagnetism compared to that of the iron complex, and it is likely that the upper e electrons possessed by the iron and not by the chromium are responsible for the bulk of the antiferromagnetism. As the iron atoms are about 9 Å apart in discrete molecules, the antiferromagnetic interactions presumably occur between unpaired spins delocalized on to …

19th Annual Conference On Analytical Chemistry

Rocky Mountain Conference on Magnetic Resonance

Program and abstracts from the 19th annual meeting of the Conference on Analytical Chemistry, co-sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy and the Rocky Mountain Chromatography Discussion Group. Held in Denver, Colorado, August 1-3, 1977.

Proximity Effects. Kinetics, Mechanisms And Reactivity Correlations For The Acidic And Alkaline Hydrolysis Of Ortho-Substituted-N-Methylbenzohydroxamic Acids, Irl E. Ward

Dissertations

No abstract provided.

High Pressure Liquid Chromatographic Methods For The Separations Of Derivatized Alpha-Keto Acids And Thiamine Phosphate Esters, Bruce Clark Hemming

Theses and Dissertations

Improved methods have been developed for separation of a-keto acid derivatives and for thiamine and its phosphate esters. Linear gradient reverse phase chromatography using ion-pair formation provides baseline resolution for a seven-component homologous series of a-keto acid dinitrophenylhydrazones having increasing carbon chain lengths. Branched-chain keto acids can also be separated. Aldehyde derivatives were examined as possible interfering compounds. Peak identification in biological material was confirmed for pyruvate by an enzymic peak shift technique. Monitoring near 365 nm permits low nanogram detection. Preliminary studies of keto acids in biological material illustrate the method's applicability. The same system with slight changes separates …

The Synthesis Of Novel Macrocyclic Multidentate Compounds From Dioxodioic Acids (1), R. Elliott Asay

Theses and Dissertations

A series of novel macrocyclic multidentate crown compounds have been prepared from a series of dioxodioic acids. The dioxodioic acids were prepared by treating various oligoethylene glycols or amines with maleic, succinic, citraconic, and glutaric anhydrides. The crown compounds were then synthesized from the dioxodioic acid chlorides obtained from the diacids and various oligoethylene glycols or ethylene diamine.

A Photochemical Study Of S-Triazolo[4,3-B] Pyridazine And 3-Diazo-4-Oxo-3,4-Dihydroquinoline, John Timothy Carlock

Theses and Dissertations

When subjected to ultraviolet radiation in the presence of an alkene, s-triazolo[4,3-b]pyridazine (STP) undergoes an unusual 3 + 2 photocycloaddition wherein the alkene adds to the 1 and 8 positions of STP with concommitant N4-N5 bond cleavage yielding 5,6-disubstituted-6,7-dihydro-7-methylene (and 7-cyanomethyl)-5H-pyrrolo[1,2-b]-s-triazoles. Amides and esters of indole-3-carboxylic acid have been synthesized by a novel reaction employing the ultraviolet irradiation of 3-diazo-4-oxo-3,4-dihydroquinoline (QDA) in the presence of amines or alcohols respectively. QDA, when irradiated, is postulated to undergo an internal Wolff Rearrangement to Indole-3-ketene which can add any amine or alcohol to form the corresponding amide or ester in modest to good …

Real-Time Computer Optimized Scanning Potential Coulometry For Multi-Component Trace Analysis, Norman W. Petty

Theses and Dissertations

The instrumentation and methodology for real-time computer controlled scanning potential coulometry for multi-component trace analysis is described. The sensitivity limit was determined to be 10^-8 F for electrochemically reversible constituents. The sensitivity limit could be extended if measures were taken to compensate for the periodic signal found on the electrolysis current. Non-linear least squares curve fitting methods accurately resolved iron-platinum and silver-iron interferences to give accurate determinations for iron and silver. The resolving capability of this method was tested using theoretically generated scanning potential coulograms. The computer resolved sample constituents with a 1 to 100 concentration ratio and a formal …

The Preparation And Study Of Some Bridged Tropones, Sultan T. Abu-Orabi

Masters Theses

No abstract provided.

Determination Of Mercury By Photoacoustic Spectroscopy, Robert Allen Cary

Dissertations and Theses

A new detector for atomic spectroscopy was developed based on the photoacoustic principle. A simple system was constructed based on this detector and applied to the trace analysis of mercury. The detection limit was found to be about 0.2 μg/1 of mercury with a one milliliter sample.

Determination Of Size Distributions In Heterodisperse Systems Of Homogeneous, Non-Absorbing Spheres From Angular Light Scattering Extrema, Werner Bergman

Wayne State University Dissertations

No abstract provided.

Characterization Of Trace Iron Species In Natural Water, James Robert Johnson

Dissertations and Theses

The distribution and speciation of trace metals in natural waters is only slightly, at best, understood. Interactions with organic substances can effectively distribute the metals throughout many ill-defined physical and chemical. To better comprehend the complexity of metal-organic interactions this work focused on the delineation of trace iron species present in a natural system. The separation of Fe(II) and Fe(III) was successfully accomplished using a variation of an ion exchange method involving resin-loaded filter paper. The quantitation of the various iron species was determined using linear scan voltammetry and atomic absorption. The total iron concentration, determined as the sum of …

Comparisons Between Oriented Film And Solution Tertiary Structure Of Various Nucleic Acids, Douglas R. C. Priore

Chemistry and Chemical Biology ETDs

It was desired to help establish whether or not the tertiary structure of a biomolecule is the same in a cry­stal (or an oriented film) as it is in solution. Generally it is accepted that the structures in these diverse environ­ments are similar, if not identical. By comparing the extinction coefficients obtained from oriented film data to those obtained from solution data it was hoped that this question might further be resolved. To this end an electric dichroism instrument built in our lab was used to measure the dichroic signal so as to calculate, with the help of the ultraviolet …

Light Scattering Studies Of Transverse Sound Wave And Molecular Motion In Benzonitrile, Scott Whittenburg

Chemistry Faculty Publications

The zero-frequency shear wave dip appearing in the depolarized Rayleigh spectrum in benzonitrile has been studied as a function of concentration and temperature. The solution study was carried out at constant viscosity equal to the viscosity of liquid benzonitrile at each temperature. The result indicates that the presence of shear wave fine structure does not depend on the collective orientational fluctuations. The orientational and vibrational relaxation times of benzonitrile were measured at various concentrations and temperatures. The orientational relaxation times show no concentration dependence at any temperature, suggesting that the pair correlation is negligible at all concentrations. The orientational relaxation …

Light Scattering Studies Of Transverse Sound Wave And Molecular Motion In Benzonitrile, Scott L. Whittenburg, C. H. Wang

Chemistry and Biochemistry Faculty Publications

The zero‐frequency shear wave dip appearing in the depolarized Rayleigh spectrum in benzonitrile has been studied as a function of concentration and temperature. The solution study was carried out at constant viscosity equal to the viscosity of liquid benzonitrile at each temperature. The result indicates that the presence of shear wave fine structure does not depend on the collective orientational fluctuations. The orientational and vibrational relaxation times of benzonitrile were measured at various concentrations and temperatures. The orientational relaxation times show no concentration dependence at any temperature, suggesting that the pair correlation is negligible at all concentrations. The orientational relaxation …

Metal-Ion Oxidative Decarboxylations. 10. Substituent Effects In The Cerium(Iv)-Benzilic Acids Reaction, Samir B. Hanna, Sezai A. Sarac

Chemistry Faculty Research & Creative Works

The rates of oxidation by cerium (IV) of several substituted benzylic acids (unsubstituted, 2,2′-dichloro, 4,4′-dichloro, 4,4′-dimethyl, 4,4′-dimethoxy, and 4,4′-dinitro) to the corresponding benzophenones have been studied spectrophotometrically in aqueous H₂SO₄, aqueous HClO₄-HOAc, and acetonitrile. The rates are much slower in H₂SO₄ than in the other two media, probably because of heavy sulfato complexation of cerium(IV). The px as of the various acids were determined potentiometrically. The Hammett p values in acetonitrile and HClO₄-HOAc media, derived from correlations with several sets of σ constants and with the newly determined pK …

The Effect Of Solvent Polarity On The S1-T2 Energy Gap In 9- And 2-Substituted Anthracene Derivatives In Aromatic And Non-Aromatic Solvents, John S. Facci

Honors Theses

Fluorescence quantum yields, fluorescence lifetimes, energies and intersystem crossing activation energies were measured for methyl-2-anthroate and methyl-9-anthroate in various polar, non-polar and aromatic solvents.

The Decomposition Of Phenyl-Benzoyl-Diazamethane And Its Relevance To Alkyne Ozonolysis, Joy A . Sawyer

Honors Theses

The thermal or photolytic decomposition of diazo compounds is known to produce a carbonyloxide in the presence of oxygen. Analogously, ∝-diazoketones should produce acyl carbonyloxides. This intermediate is identical to one proposed for the ozonolysis of alkynes and its substantiation is the purpose of this study. By examining the products of the thermal, copper catalyzed phenylbenzoyldiazomethane decomposition, one should be able to determine the intermediate’s presence. Benzoic anhydride, benzil and methyl diphenyl-acetate have been identified as products and tetraphenylglycolide is also thought to be present. Methyl diphenyl-acetate is the result of Wolff rearrangement, while the other three are proposed to …

Mechanisms Of Saponification Of Sterically Hindered Esters By Optical Activity And Kinetic Studies, George A. Walrath

Honors Theses

This thesis presents methods for preparation of sterically hindered organic acid esters. The secondary- and tertiary-butyl esters of 2,2’ dimethylpropanoic acid (pivalic acid, neo-pentanoic acid, or trimethyacetic acid) were prepared by suggested methods. The best method proved to be that suggested by Bochkova, Proskuryakov, Pirozhkoc and Eidus, where the esters of neo-acids are prepared through their respective acid chlorides. In the case studies in this thesis, the acid chloride of neopentanoic acid (pivaloyl chloride) was reacted with secondary or tertiary-butyl alcohol. Kinetic studies of the saponification of secondary-butyl pivaloate were made at various temperatures, and from the data obtained, the …