Physical Sciences and Mathematics Commons^™

Analytical Pyrolysis Of Thai Lignites, Naowarat Poolasap

Masters Theses & Specialist Projects

Samples of four different Thai lignites were utilized to study the effects of ceiling temperature and heating rate on the overall yield and product distribution by the technique of analytical pyrolysis (pyrolysis-gas chromatography). Ceiling temperatures of 450°, 550°, 650°, 750°, 850°, and 950°C, a heating rate of 500°C/sec and pyrolysis intervals of 20 seconds were investigated. The results were reported in terms of percentage high-volatile product and low-volatile product fraction, weight-loss (% by weight), and total yield (counts per milligram). One sample which showed the highest sensitivity to changing ceiling temperature was selected to study the effect of heating rate …

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 …

The G-Factor Of The 7/2+ 1264.4 Kev Level In 97zr, Z. Berant, R. L. Gill, M. H. Rafailovich, R. E. Chrien, J. C. Hill, F. K. Wohn, R. F. Petry, C. Chung, Graham F. Peaslee, M. Mohsen

Faculty Publications

The g-factor of the level in 97Zr has been measured using the time-differential perturbed angular correlation method. The resultant g-factor, g=+0.39(4) is consistent with the simple shell model prediction for a if neutron, assuming gs=gsfree. This is in contrastrast to the measured in 115Sn, 121Te, 125,127Xe where consistency is obtained with theoretical calculation by assuming gs≈0.7 gsfree and is seen as another confirmation of quasi-shell closure at 96Zr.

Determination Of The Equilibrium Constant For The Acetaldehyde-Bisulfite Addition Compound, Mark B. Richard

Honors Theses

Synthesis of the addition compounds of formaldehyde, acetaldehyde, acetone, and propionaldehyde with sodium bisulfite was achieved using the method of Stewart and Donnally. Recognition of a water comtamination led to a method for determining purity using the integrations from NMR spectrometry. An equilibrium constant for the acetaldehyde-bisulfite addition compound was determined using the method of Dasgupta. A value of 6.3 x 10-5 was determined at a ph of 4.7. This value correlates well in magnitude when compared to the value of 1.56 x 10-5 for the formaldehyde-bisulfite addition compound at pH 5.0 determined by Dasgupta and also with Stewart and …

The Syntheses Of Benzo-(2.2)-Paracyclophane, 2, 15-Dithia-(3.3)-Napthalenophane, And Hexamethylbenzene Dichloride, David Gene Barrett

Honors Theses

The purpose of this study was the preparation by a novel approach of benzo-(2.2)-paracyclophane. Also synthesized were the syn-and anti-isomers of 2,15-dithia (3.3)- napthalenophane. The results of these syntheses are supported by spectral studies. In preparation for future study of the ruthenium complexes of these cyclophanes, hexamethylbenzeruthenium dichloride was also synthesized.

Detection And Analysis Of Carbonyl Compounds In Rural Cloudwater, Steven Bart Bertman

Honors Theses

A new technique for aqueous determination of aldehydes and ketones was field tested along with a new technique for ambient air analysis. The work was done during the summer of 1984 on Whiteface Mountain in Wilmington, NY. Both techniques utilized carbonyl derivitization as their 2,4-dinitrophenyl hydrazones and subsequent analysis by reversed phase HPLC. Analysis of the blank levels for the ambient air method shows the levels found to be non-detectable. The aqueous method worked well. Formaldehyde, acetaldehyde, and acetone were the only species found in cloud water. They were generally present in concentrations between .5 uM and 4 uM. Little …

A Study Of Chemiluminescence Via Flash Photolysis, Craig Lawrence Shalmi

Honors Theses

We are interested in understanding the mechanistic details of photo-initiated chemiluminescent reactions. Currently, we are examining reactions which lead to luminescent from electronically excited nitric oxide. Stedman has reported observing NO gamma-band emission in the thermal reaction of hydrazoic acid, HN3 with O(3P). The rate constant for the production of NO* is low and, consequently, the emission intensity is weak. We are endeavoring to generate excited NO from HN3 and O(1D), the later produced in the flash photolysis of ozone. It is hoped that a greater population of NO* will be produced yielding a greater chemiluminescent intensity. By observing the …

Reaction Of Atomic Hydrogen With Chloroform In A Discharge Flow Reactor, Wan-Kuen Jo

Theses

The reactions of atomic hydrogen with chloroform were studied in a tubular flow reactor both in a 4 cm i.d. and 2.6 i.d. discharge flow reactor at pressure of 2.22 to 2.82 mmHg and room temperature using GC and GC/MS for analysis of the reaction. The hydrogen atom concentration at the reaction flame was measured by Chemiluminescence titration with nitrogen dioxide. The hydrogen concentrations are in the 2.48 x 10⁺¹⁴ to 4.83 x 10⁺¹⁴ atoms/cc range at six different hydrogen flow rates. Evidence was found for the formation of atomic carbon intermediate in the reaction, but methane was …

The Intrinsic Reaction Coordinate And The Rotational Barrier In Silaethylene, Michael W. Schmidt, Mark S. Gordon, Michel Dupuis

Mark S. Gordon

The intrinsic reaction coordinate (IRC) is a minimum-energy pathway connecting reactants to products via the transition state. An improved algorithm for the determination of an IRC is presented. The method is illustrated for the rotation of the silicon-carbon double bond in silaethylene. This IRC shows all coordinates vary smoothly during the rotation from the planar to twisted structures, except for a slight pyramidalization at carbon. The rotational barrier is found to be about 37 kcaljmol, in good agreement with experimental estimates.

Glass Formation And High Conductivity In The Ternary System Silver Iodide + Silver Arsenate (Ag3aso4) + Silver Metaphosphate (Agpo3): Host To Glassy .Alpha.-Silver Iodide?, Steve W. Martin, Alberto Schiraldi

Steve W. Martin

Wide regions of glass formation have been found in the ternary system xAgI + yAg,As04 + (1 - x - y)AgPO,. Glasses containing up to 75 mol 7% AgI can be formed in sections greater than 2 cm thick without signs of devitrification. Glass transition temperatures as high as 175 OC for glasses containing - 10 mol % AgI fall to -45 OC at the highest AgI content. An equivalent ratio of Ag1:N is defined and it is found that, for all glass-forming compositions, the electrical data as expressed in the Arrhenius form, u = A exp(-E,,/RT), log (./(a cm)-’), …

Co-Oxidative Depolymerization Of Coal, Renae Rosencrans

Masters Theses & Specialist Projects

In contrast to current coal conversion technology, cooxidative depolymerization of coal is a novel approach to coal liquefaction in that the reactions are carried out under relatively mild conditions. This free radical process utilizes air or oxygen and a suitable co-oxidant (solvent) which acts as a radical and hydrogen transfer agent throughout the coal matrix. Ideally, co-oxidation would lead to the formation of hydroperoxide groups at the reactive bridging sites in the coal matrix, which upon decomposition would lead to C-C bond scission.

The effects of several variables on co-oxidation and subsequent post-treatment were investigated. Up to 49% conversion to …

Electronic Structure Of The Phosphoryl And Thiophosphoryl Bonds, Michael W. Schmidt, Mark S. Gordon

Mark S. Gordon

.The pho~phoryl bond is presented as a. resonan~e hybrid between singly and triply bound structures. The types of electromcally excited states and a number of their potential surfaces can be understood within the confines of a singly bound model: However, a detailed analysis of the electronic distribution within the ground state shows significant contribution from the tnpl~ bound structure. In fact, increasing the electronegativity of the ligands at phosphorus increases the contribution of t~e tnp~y bound structure, so that the. PO bond order approaches that of a double bond. The thiophosphoryl bond may be VIewed m much the same manner …

Reactivity Of Some Nitrogen-Containing Compounds At Supercritical Water Conditions, David M. Tiffany

Masters Theses

The use of water at cuperctirical conditions to remove nitrogen from several nitrogen-containing compounds was studied with the purpose of exploring the use of supercritical water as a method of removing nitrogen from the extraction products of coal. Quinoline and isoquinolone were the primary model compounds used with benzonitrile and carbazole also being examined briefly. Reaction conditions varied in temperature (350-500°C), pressure (3500-5200 psi), and water density (0.170-.0.426g/cc). The major products formed by isoquinoline were benzene, toluene, ethylbenzene, and o-xylene as well as nonvolatile tar and char. Quinoline produced aniline and toluidine in addition to those obtained from isoquinoline. Most …

The Synthesis And Evaluation Of A New Analog Of Phencyclidine (Pcp), William H. Johnson Jr.

Chemistry & Biochemistry Theses & Dissertations

Based on an interpretation of the literature of phencyclidine (PCP) together with an examination of the relevant models or prototype structures, this research has attempted to design and synthesize a rigid analog of the phencyclidine structure. The parent ring systems suggested for this study were the 1-arnino and 2-arninornethyltetralins, 10 and, 12.

Several organic compounds, based on this design, have been prepared by classical examples of reductive alkylation reactions of the corresponding 2-hydroxyciethylene-1-tetralones, 11, and by the condensation and subsequent reductive alkylation of the 1-arninotetralin, 9. These arninomethyltetralones, 28, 29 and 30, together with an example of a substituted 1-arninotetralin, …

Molecular And Electronic Structures Of Metallaspiropentanes, Mark S. Gordon, Philip Boudjouk

Mark S. Gordon

Recent efforts in this laboratory have concentrated on synthesizing metallaspiropentane compounds (I) with M = C, Si, Ge, Sn, Ni, and Zn. To date, the molecule with M = Si and R = methyl has been successfully prepared, 1 while attempts to synthesize the corresponding carbon compound have not reached fruition. This paper presents initial ab initio calculations on the species with M = C and Si and with R = H. Geometries for all species were calculated with the

Piezomodulated Raman Spectroscopy Of Molecular Crystals: An Experimental Method For Study Of The Anharmonic Properties Of Solids, T. Luty, Craig J. Eckhardt

Craig J. Eckhardt Publications

Consideration of phonon-phonon coupling induced by strain serves as impetus for developing a theoretical structure for piezomodulated Raman spectroscopy which can be used for experimental realization of the coupling. The direct relation of the coupling constant to generalized stress Gruneisen parameters is shown. These describe the crystal's anharmonic properties such as the thermal expansivity and the temperature dependence of the phonon energies. Numerical calculations are performed for anthracene crystal which exemplify the use of the stress Gruneisen parameters as sensitive measures of anisotropy of intermolecular interactions. Further development shows how the measurement can be used to determine these parameters and …

G-Factor Measurements Of 41+ States In The N=82 Isotones 136xe And 138ba, Z. Berant, A. Wolf, John C. Hill, F. K. Wohn, R. L. Gill, H. Mach, M. Rafailovich, H. Kruse, B. H. Wildenthal, Graham F. Peaslee, A. Aprahamian, J. Goulden, C. Chung

Faculty Publications

The g factors for the 4+1 states in Xe136 and Ba138 were measured using the method of time-integral perturbed angular correlation. The levels of interest were populated by the decay of mass-separated I136 and Cs138. g factors of 0.80±0.15 and 0.80±0.14 were measured for the 4+1 states in Xe136 and Ba138, respectively. The above results, along with those for the g factors in the 4+1 state in Ce140 and the 6+1 states in Te134 and Ba138, are well described by a shell-model calculation in which the effective elemental proton g factors are g’l=1.12 and g’s=4.12.

Predictors Of Grades In General Chemistry For Allied Health Students, Chris Craney, R. Armstrong

Chris L. Craney

Study searching for an effective predictor of student performance in the first term of a full-year general chemistry sequence for allied health students.

Electrochemical Reduction Of 1,1,4,4-Tetraphenylbutatriene In Dimethylformamid, Dennis Peters, Mark Anderson, Tsu-Yu Chen

Mark R. Anderson

No abstract is currently available.

Vibrational Predissociation In Linear Hydrogen-Bonded Complexes, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

Dr. Shannon Lieb's contribution to Volume 95 of the Proceedings of the Indiana Academy of Science.

Solvent Influence On Atomic Spectra: The Effect Of Finite Size, Randall W. Hall, Peter G. Wolynes

Collected Faculty and Staff Scholarship

Time dependent Hartree theory is used to determine the solvent effect on atomic spectra for a given solvent configuration. Configuration averaging is performed as in the mean spherical approximation, resulting in an upper bound to the polarizability. Comparisons are made with previous, more approximate theories, including path integral treatments. It is found that deviations from previous theories can be significant in certain regimes.

I. The Use Of Polyethers As Phase Transfer Catalysts For The Fluoroalkoxylation Of Halogenated Aromatic And Heteroaromatic Systems Ii. The Grignard Addition And Sodium Cyanoborohydride Reduction Of Arylchloropropeniminium Salts, Martin A.M. Moebus

Retrospective Theses and Dissertations

This research addresses two distinct areas of synthetic organic chemistry: the use of phase transfer catalysts for the fluoroalkoxylation of activated haloaromatic and haloheteroaromatic systems, as well as the Grignard addition and sodium cyanoborohydride reduction of aryl chloropropeniminium salts. In Part I of this research, a number of macrocyclic- and linear polytethers were studied as phase transfer catalysts in the nucleophilic aromatic substitution of haloaromitc systems. The most effective catalyst was determined to be poly(ethylene glycol)-8000 and the reaction conditions were optimized for this catalyst. Subsequently isomer reactivity, effects of activating groups, effects of leaving groups, and nucleophiles were studied …

The Examination Of The Adsorption Capabilities Of The "Magic" Black Rocks Of The Little Missouri River, Denise Leverett

Honors Theses

It has been seen that manganese oxides precipitate from aqueous solution as they pass downstream from cold water release reservoirs. This precipitation is visible in the form of black coatings on gravels in the river or stream bed. These oxide coatings not only cause the further oxidation and precipitation of manganese ions but also have the capacity for adsorbing trace metals from the system. The amount of metal adsorbed varies with the element. This study not only addresses the various elements which may be adsorbed but also the rates at which adsorption occurs and the factors which affect those rates.

Removal Of Colloidal Silica In Simulated Seawater By A Dynamic Multi-Short-Circuited Galvanic Cell, Jan E. Osterholm, Paul W. Kramer, Hlrotsugu K. Yasuda

Chemistry Faculty Research & Creative Works

A dynamic multi-short-circuited galvanic cell (MSCGC) with Pt-AI electrodes has been used to study the removal of colloidal silica from seawater as a pretreatment step for the desalination of seawater by use of reverse osmosis. The rate of silica removal is observed to be affected by the flow rate of the solution through the cell and the dissolved oxygen content of the solution as well as by the nature of the aluminum electrode surface and the number of contact points (short circuits) between the aluminum and platinum. The total silica content is reduced by 95 % by use of this …

Chapter 3 Coatings And Surface Modification Using Low Pressure Non-Equilibrium Plasmas, Harold F. Winters, Robert P.H. Chang, C. J. Mogab, John Evans, John A. Thornton, Hirotsugu Yasuda

Chemistry Faculty Research & Creative Works

No abstract provided.

Dynamic Structure Of N-Hexadecane Solubilized In A Nonionic Surfactant Bilayer Measured By Deuteron Magnetic Resonance, Anthony J.I. Ward, Stig Friberg, David W. Larsen, Shankar B. Rananavare

Chemistry Faculty Research & Creative Works

A 2H NMR study was made of the order parameters of n-hexadecane molecules solubilized up to 55% (w/w) in a lyotropic lamellar liquid crystal of tetra ethylene glycol n-dodecyl ether and water for a range of compositions of varying water and hydrocarbon content. The NMR data supported a model with only a small amount of penetration of the hydrocarbon between the amphiphilic molecules and a rapid exchange on the 2H NMR time scale between the penetrated segments and the nonpenetrating molecules which latter are essentially isotropic. © 1985, American Chemical Society. All rights reserved.

Racial Differences In The Distribution Of Posterior Circulation Occlusive Disease, Philip B. Gorelick, Louis R. Caplan, Daniel B. Hier, Dushyant Patel, Patricia Langenberg, Michael S. Pessin, Jose Biller, David Kornack

Chemistry Faculty Research & Creative Works

We Compared Clinical and Arteriographic Features in 27 White and 24 Black Patients with Symptomatic Posterior Circulation Occlusive Disease. the Degree of Arterial Stenosis Was Measured Independently by Two Examiners at 12 Sites within the Vertebrobasilar Territory. Racial Comparisons Were Made based Upon the Distribution of Extra- and Intracranial Occlusive Lesions and Symptomatic Sites of the Lesions. White Patients Had Significantly More Angina Pectoris, More Lesions of the Origin of the Left Vertebral Artery and More High-Grade Lesions of the Extracranial Vertebral Arteries. Black Patients Had Significantly Higher Mean Diastolic Blood Pressure, More Diabetes Mellitus, More Lesions of the Distal …

Kinetics Of Reduction Of Cytochrome C Oxidase By Dithionite And The Effect Of Hydrogen Peroxide, M. Brunori, D. Bickar, J. Bonaventura, C. Bonaventura

Chemistry: Faculty Publications

The reduction of cytochrome c oxidase by dithionite was reinvestigated with a flow-flash technique and with varied enzyme preparations. Since cytochrome a3 may be defined as the heme in oxidase which can form a photolabile CO adduct in the reduced state, it is possible to follow the time course of cytochrome a3 reduction by monitoring the onset of photosensitivity. The onset of photosensitivity and the overall rate of heme reduction were compared for Yonetani and Hartzell-Beinert preparations of cytochrome c oxidase and for the enzyme isolated from blue marlin and hammer-head shark. For all of these preparations the faster phase …

Chemical Studies On Oxomolybdenum(Vi,Iv) Complexes As Bioinorganic Models For The Molybdenum Oxidases, James Thomas Lyon Iii

Theses and Dissertations

The synthesis, characterization, and chemical properties of Mo(VI)o₂(5-X-SSP) and Mo(VI)o₂(5-X-SSE), (5-X- SSP²- = 2-((5-X-salicylidene)amino)benzenethiolate; 5-X- SSE^2- = 2-((5-X-salicylidene)amino)ethanethiolate; X = Br, Cl, H, CH₃O), which contain tridentate (ONS) Schiff base ligands is described. The chemical properties of these molybdenum complexes are compared with those which possess tridentate (ONO) Schiff base ligands. Cyclic voltammetry was used to obtain cathodic reduction potentials (E_PC) for the quasi-reversible reduction of the cis-dioxomolybdenum (VI) complexes. Although the reductions are quasi-reversible, trends are observed in E_PC both within series and when different series are …

Plasma Polymerization Investigated By The Substrate Temperature Dependence., H. Yasuda, Cheng Wang

Chemistry Faculty Research & Creative Works

In the reported experiments, plasma polymerization of tetrafluoroethylene (TFE), perfluoro-2-butyl-tetrahydrofuran (PFBTHF), ethylene, and styrene were investigated in various combinations of monomer flow rates and discharge wattages for the substrate temperature range of minus 50 to 80 degree C. The polymer deposition rates can be generally expressed by k//o equals Ae** minus **b**t, where k//o is the specific deposition rate given by k//o equals (deposition rate)/(mass flow rate of monomer), A is the preexponential factor representing the extrapolated value of k//o at zero absolute temperature, and b is the temperature-dependence coefficient. It was found that the value of b is not …