Physical Sciences and Mathematics Commons^™

Advances In Synthetic Polymer Chemistry: New Polymer Types And New Directions, The Sixth Carl S. Marvel Symposium, Otto Vogl, Henry K. Hall

Emeritus Faculty Author Gallery

No abstract provided.

Polymer Science In Japan: The Hokuriku District And The Remaining Universities Of Japan, Otto Vogl, Kiichi Takemoto

Emeritus Faculty Author Gallery

No abstract provided.

Characterization Of Potassium Promoted & Unpromoted Fischer-Tropsch Catalysts, Steven Miller

Masters Theses & Specialist Projects

The technique of x-ray photoelectron spectroscopy (XPS) has been applied to characterize iron-manganese catalysts used in Fischer-Tropsch synthesis. The catalysts, which vary in composition from 10 FE/90 Mn, to 50 Fe/50 Mn are analyzed after being placed in a slurry reactor and having synthesis gas reacted over them. Changes, in catalyst composition are investigated further using in situ techniques. Additionally, 20 Fe/80 Mn catalysts containing potassium in the range of 0.1 wt.% to 1.3 wt.% are analyzed in the same manner. These studies have permitted the identification of some of the factors influencing activation and deactivation, product selectivity, and surface …

Redox Reaction Kinetics Between Cobalt(Ii)-4,4',4",4'"-Tetrasulfophthalocyanine & Iodine In Various Solvents, Byung-Soo Yu

Masters Theses & Specialist Projects

Analyses of the kinetic data obtained on the redox reaction between cobalt(II)-4,4',4",4"-tetrasulfophthalocyanine [Co(II)TSPC4^-] and iodine in the presence of air show three reactions in dimethylsulfoxide(DMS0), N,N-dimethylacetamide(DMA), and diethylene glycol(DEG) while there are two reactions in methanol(Me0H). Two of the three reactions in DMSO, DMA, and DEG are biphasic with one reaction in all of the solvents being too fast to be accurately measured on the Cary Model 14 spectrophotometer. When the reactant solutions are purged with argon for 40 minutes under identical conditions, the same biphasic reactions are observed in DMSO and DEG while only one of the …

Reductive Dechlorination Of Toxic Chlorocarbons, K. Grant Taylor

KWRRI Research Reports

The sodium hydride based reducing agents were prepared the method of Caubere (Angew. Chem. Int. Ed. Engl., 1983, 22, 599-613). Reagents were prepared containing nickel, iron and zinc metals. All were effective in dechlorinating 1,3-dichlorobenzene, 4-methoxy-chlorobenzene, and arochlor 1254. Most work focused on nickel based reagents, the most active. The nickel-based reducing agent used in THF at 65°C reduced to 200 ppm 1,3-dichlorobenzene (to benzene) and arochlor 1254 (to biphenyl) to below 0.2 ppm in less than 15 minutes. A two stage reduction reduced arochlor 1254 to below a detectable level as determined by gas chromatography using f.i.d. detector. Using …

Specialty Polymers -Present And Future, Otto Vogl, Roger Epton

Emeritus Faculty Author Gallery

No abstract provided.

Calculated Electronic Profiles For Liquid-Metal Surfaces, Jerry Goodisman

Chemistry - All Scholarship

The electronic density profile for a liquid-metal surface can be calculated by solving the self-consistent Lang-Kohn equations for the electronic wave functions. One requires a surface density profile for the ion cores, which enters the electrostatic and pseudopotential parts of the electronic Hamiltonian. We use oscillatory profiles, suggested by those found by molecular-dynamics simulations on a pseudoatom model. Calculating surface potentials and work functions, we obtain excellent agreement with experiment (within 0.2 eV). It is shown that use of either step-function ion profiles or a simple variational method leads to serious errors (12 eV) for these quantities.

Glycation Of Amino Groups In Protein, Nancy G. Watkins, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

Ribonuclease A has been used as a model protein for studying the specificity of glycation of amino groups in protein under physiological conditions (phosphate buffer, pH 7.4, 37 “C). Incubation of RNase with glucose led to an enhanced rate of inactivation of the enzyme relative to the rate of modification of lysine residues, suggesting preferential modification of active site lysine residues. Sites of glycation of RNase were identified by amino acid analysis of tryptic peptides isolated by reverse-phase high pressure liquid chromatography and phenylboronate affinity chromatography. Schiff base adducts were trapped with Na- BH&N and the a-amino group of Lys-1 …

Predicting The Self-Heating Potential Of Coal, Seyed Mohammad Fatemi-Badi

Masters Theses & Specialist Projects

Self-heating in coal has been studied for well over one hundred years, yet there is no accurate or reliable method for predicting the potential of certain coals to undergo self-heating. Fires caused by self-heating, and eventually spontaneous combustion, have occurred in the high wall of surface mines, in underground mines, in coal stockpiles, and on trains, barges and ships. Self-heating in coal is brought about through a complex interplay of conditions depending on the specific properties of the coal as well as many external factors involved in the mining and handling of coal.

In a study supported by the United …

Hydrogenation Of Nitro Compounds To Amines Using Polymer Bound Catalysts, Eduardo Baralt

Masters Theses & Specialist Projects

A polymer bound catalyst is a relatively new type of catalyst. The basis of polymer bound catalysis lies in the chemical attachment of a homogeneous catalyst to a solid support, in our case, polystyrene. Applications of polymer bound catalysts started in the late 1960’s, and have been used in several types of reactions. In some cases such a catalyst offers a series of advantages over the classical models of catalysis, homogeneous and heterogeneous.

The hydrogenation of various aromatic and aliphatic nitro compounds, such as nitro-benzene and 2-nitropropane, were performed successfully. The hydrogenation activity in most cases was high, and in …

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 …

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.

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 …

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.

Atomic Spectroscopy- The Short Course Organiser's Approach, Julian Tyson

Chemistry Department Faculty Publication Series

No abstract provided.

Flow Injection Analysis Techniques Of Method Development For Flame Atomic Absorption Spectrometry, Julian Tyson, C. E. Adeeyinwo, J. M. H. Appleton, S. R. Bysouth, A. B. Idris, L. L. Sarkissian

Chemistry Department Faculty Publication Series

The flow injection introduction of samples that would be difficult by conventional nebulisation owing to dissolved solid content, viscosity or quenching effects on flame reactions is demonstrated. The various ways of achieving sample dilution by control of volume injected, tube dimensions and flow-rate are discussed and a manifold described for producing solutions for calibration purposes and diluting off-range samples. The important characteristics of the nebuliser and instrument for flow injection work are evaluated. A simple manifold for investigating interference effects is described and its use illustrated for some well known effects. The possibilities of achieving pre-treatment by solvent extraction and …

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 …

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.

Comparison Of Proton Transfers In (S2h5)+ And (O2h5)+, L. Bigham, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

The energetics and electronic rearrangements associated with proton transfer between S atoms in (H₂S–H–SH₂)⁺ are calculated using ab initio molecular orbital methods and compared with similar data in the first‐row analog (H₂O–H–OH₂)⁺. The full potential energy surface of (S₂H₅)⁺, calculated as a function of the H‐bond length as well as the position of the proton, contains two equivalent minima separated by a small energy barrier, whereas the surface of (O₂H₅)⁺ contains a single minimum corresponding to a symmetric …

Interobserver Variability In The Assessment Of Neurologic History And Examination In The Stroke Data Bank, David Shinar, Cynthia R. Gross, Jay P. Mohr, Louis R. Caplan, Thomas R. Price, Philip A. Wolf, Daniel B. Hier, Carlos S. Kase, Irene G. Fishman, Christine L. Wolf, Selma C. Kunitz

Chemistry Faculty Research & Creative Works

Interobserver Reliability in Obtaining Neurologic Histories and Examinations Was Investigated among Neurologists Collaborating in the Stroke Data Bank (SDB). Seventeen In-Hospital Stroke Patients Were Examined by Six Neurologists Experienced in Stroke over the Course of Three Days. Patients Were Examined Twice a Day for Two Successive Days, with Each Patient Seen by Four Different Neurologists. Data Were Recorded on SDB Forms, According to Definitions and Procedures Established for the SDB. Percent Agreement and Κ Coefficients Were Calculated to Assess the Levels of Agreement for Each Item. Important Differences in Levels of Agreement Were Found among Items on Both Neurologic History …

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 …

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.

Structure Of A Solvated Nickel(Ii) Complex Of (S)-2'-(N-Benzylprolyl)Aminoacetophenone And (R)-Valine Schiff Base, C25H29N3Nio3.1/2c4H8O. Conformational Calculation Of Diastereomeric Complexes Of (R)-Valine And (S)-Valine, Sergey V. Lindeman, T. V. Timofeeva, V. I. Maleyev, Yuri N. Belokon, M. G. Ryzhov, V. M. Belikov, Yuri T. Struchkov

Chemistry Faculty Research and Publications

No abstract provided.

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.

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 …

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 …

Influence Of Basis Set On The Calculated Properties Of (H3n–Hcl), Z. Latajka, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

The structure of (H₃N–HCl) is investigated by ab initio calculations using a number of different basis sets ranging from minimal to split valence. The effects of including a diffuse sp shell and d orbitals on Cl are considered as well. The geometries of the complex and the isolated subunits are fully optimized. Minimal basis sets (STO‐3G, STO‐6G, and MINI‐1) lead to an overestimate of the interaction between the subunits. Addition of d functions produces only a marginal improvement. The 3‐21G, 3‐21+G, MIDI‐1, and LP‐31G split‐valence sets erroneously predict an ion pair …

Contribution Of Dispersion To The Properties Of H2s‐‐Hf And H2s‐‐Hcl, M. M. Szczesniak, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Ab initio calculations are carried out using a doubly polarized basis set. Dispersion, evaluated by second‐order Møller–Plesset perturbation theory (MP2), is found to have a profound influence on the stabilities and structures of the H‐bonded complexes. The contribution of dispersion to the H‐bond energies of H₂S‐‐HF and H₂S‐‐HCl is 44% and 69%, respectively, placing this attractive term second in magnitude only to electrostatics. Reductions of the intermolecular distance of 0.17 and 0.34 Å result from inclusion of correlation effects. Nevertheless, the influence of dispersion upon the angular characteristics of the …