Physical Sciences and Mathematics Commons^™

Determination Of Wavelength Dependent Quantum Yields For Iron (Iii) Photoreduction In Well Defined Chloride Media, J. Catherine Kneece

Honors Theses

The quantum yields for iron (lII) photoreduction in sodium chloride and sodium perchlorate media were measured as a function of wavelength. The experiments were conducted using natural levels of total iron, less than 300 nM. The results indicate that three species are photochemically active in these media, Fe(OH)+2, FeCl2+and FeCl2+. The quantum yields for (OH)+2 are 0.22 at 300 run and 0.076 at 340 nm. The quantum yields for FeCl+ are 0.048 at 300 run and 0.038 at 340 nm. The quantum yields for FeCl2+ are 0.088 at 300 nm and 0.051 at 340 nm. The data presented suggests that …

Alternatives To Nitroprusside As Hypotensive Agents, Timothy Casey Mccullough

Honors Theses

The drug sodium pentacyanonitrosylferrate(2-)dihydrate, more commonly known as nitroprusside or nipride (Fig. 1), is a common vasodilating agent given clinically to patients with hypertension.12.22 Nitroprusside is effective in emergency rooms as it quickly reduces high blood pressure, but dosages are limited because of fear that cyanide could be released also. Nitroprusside is effective because the vasodilating agent nitric oxide, NO, is released. Nitric oxide is also recognized as an important biochemical messenger molecule.22 Our research involves a search for different species that could introduce nitric oxide into the body without cyanide. Transition metal complexes involving ruthenium, iron, and cobalt that …

A Computational And Experimental Investigation Of The Pinacol Coupling And Rearrangement Reactions, Ryan Sullivan

Honors Theses

This project was developed from previous reports concerned with the pinacol coupling and rearrangement methodologies. It is hoped that the results and conclusions of this study may provide someone in the future a chance to gain a more complete view of this material. Analysis of the pinacol coupling reaction shows that the yields of the pinacol products are not statistical for the asymmetric cycloalkanone systems. Also, the yields of the 5-7 and 6-7 systems plotted versus ab initio gas phase calculations of HOMG-LUMO gaps showed r values at or near 1.00. This correlation is excellent and offers an example of …

Dynamics Of Poly(Vinyl Acetate) In Bulk And On Silica, Frank D. Blum, Gu Xu, Minghua Liang, Charles G. Wade

Chemistry Faculty Research & Creative Works

Quadrupole echo deuterium NMR has been used to probe the dynamics of poly(vinyl acetate-d3) in bulk and at saturation coverage (from toluene) on silica at the solid-air interface. In bulk and at lower temperatures, the deuterium powder pattern of the labeled methyl group was found to be consistent with fast threefold jumps with a small asymmetry due to the interaction of the methyl deuteron with the carbonyl oxygen. This apparent asymmetry was a result either of a distortion in the C-C-D bond angle or a reduction of the axial symmetry of the electric field gradient along the C-D bond vector. …

1,1′-Diacetyl-2,2′-Biimidazole, Paula M. Secondo, Colin A. Hester, Harvest L. Collier, Russell G. Baughman, A. W. Cordes

Chemistry Faculty Research & Creative Works

A crystallographic twofold rotation axis passes through the C-C bond joining the imidazole rings of the title compound, C₁₀H₁₀N₄O₂. the molecule crystallizes in a cis disposition. the planar acetyl group is twisted by 5.0 (3)° with respect to the imidazole ring and the two imidazole rings are tilted by 60.53 (5)° in relation to one another.

Rotating Disk Ion Selective Electrodes, John Cassidy, David Mullen, Karen Casey, Patrick Cullen

Articles

A simulation was undertaken to predict the transient potential response following a concentration step at a rotating disk electrode comprised of an ion selective layer. A basis for this simulation was that the potential response would be independent of rotation rate since the diffusion layer is larger than the double layer at the electrode. In practice it was found that the potential response does vary with rotation rate. The response was such that the apparent concentration of the analyte in solution decreased with increased rotation rate. The reason for this behavior is due to the disruption of the double layer …

A New High Pressure Sapphire Nuclear Magnetic Resonance Cell, Shi Bai, Craig M. Taylor, Charles L. Mayne, Ronald J. Pugmire, David M. Grant

Faculty Publications

A new version of a single-crystal sapphire high pressure nuclear magnetic resonance (NMR) cell is described that is capable of controlling the sample pressure independent of the temperature. A movable piston inside the cell adjusts and controls the sample pressure from ambient conditions to 200 atm within plus or minus 0.3 atm. The linewidth at half-height for a 13C spectrum of carbon dioxide at 15degrees C and 57.8 atm is found to be 0.5 Hz. The carbon dioxide gas/liquid phase transition is clearly observed by measuring 13C chemical shifts as the sample pressure approaches equilibrium. The time required for this …

Highly Reactive Zerovalent Metals From Metal Cyanides, Reuben D. Rieke

Chemistry Department: Faculty Publications

Novel zerovalent metal species and organometallic reagents are disclosed. The zerovalent metal species are directly produced by reaction of a reducing agent on a metal cyanide salt. Preferably, the zerovalent metal species are directly produced by reaction of an alkali metal reducing agent with a metal cyanide salt. The organometallic reagent results from the reaction of the zerovalent metal species and an organic compound having one or more stable anionic leaving groups.

Flash Pyrolysis Of Anthropogenic And Natural Organic Matter In Polluted Sediments, Sami T. Abdel Bagi, Michael A. Kruge, Gary L. Salmon

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

INTRODUCTION - Combustion products along with spilled petroleum and industrial chemicals contribute to environmental degradation by contaminating soils and sediments. Such anthropogenic organic matter (OM), if preserved in sediments, can serve an archival function, documenting the local, history of industrial pollution. Christensen and Zhang (1993) determined the sources of polycyclic aromatic hydrocarbons (P AH) to Lake Michigan from sedimentary records, finding that coal combustion was a major source for PAHs in these sediments. Bodzek and Luks-Betlej (1993) reported that atmospheric deposition is the main source of PAH in soils of the heavily industrialized Upper Silesia region of Poland. Smith and …

Interactions Among The Stationary Phase, The Mobile Phase, And The Solute In Liquid Chromatographic Systems, Zengbiao Li

Theses and Dissertations

Interactions among the stationary phase, the mobile phase, and the solute in liquid chromatography' have been studied. A strong dependence of the stationary phase properties on the mobile phase composition may arise from their interactions.

The solvatochromic comparison method, which can give estimates for the dipolarity-polarizability, the hydrogen-bonding acidity, and the hydrogen-bonding basicity of a solvent, represented by the solvatochromic parameters π⁺, α and β, respectively, was used to study the surface properties of silica in the presence of n-hexane-chloroform or n-hexane-ethyl ether mixtures. A high dipolarity- polarizability, a high hydrogen-bonding acidity, and a low hydrogen-bonding basicity …

The Investigation Of Aluminum Sulfate-Potassium Chloride Solid Phase Reaction, İ. Ayhan Şengi̇l

Turkish Journal of Chemistry

It was found that aluminum sulfate reacts with potassium chloride to produce K_{2}SO_{4}, Al_{2}O_{3}, and Cl_{2} in the solid phase at 700 ^{\circ}C. This reaction was investigated with thermal analysis under air and nitrogen atmosphere. By changing temperature and time parameters, the actual yield of conversion in question was examined analytically and the optimum temperature and time were found for the reaction. The rate expression of the solid phase reaction was also investigated and the rate equation was obtained.

Analysis Of Retention In Supercritical Fluid Chromatography And Its Relation To Solubility, Z. Şermin Gönenç, Uğur Akman, Aydın K. Sunol

Turkish Journal of Chemistry

The effects of temperature, pressure and supercritical fluid density on the solubility-retention relationship of solutes in supercritical fluid chromatography are investigated. New retention data for naphthalene, phenanthrene, benzoic acid and 2-methoxy-naphthalene is obtained as a function of pressure at different temperatures. The bulk of the data is taken near the critical region of the mobile gas where the anomalities are expected. This data is used to compare two approaches for thermodynamic modeling of pressure dependence of solute retention. In these approaches, mobile-phase partial molar volumes of the solutes are determined either from bulk solubility data or from infinite-dilution fugacity coefficients. …

Quantum-Chemical Investigations On The Functionalized 1h-Pyrimidines, İsmail Yildirim, Makbule Tezcan, Yahya Güzel, Emin Saripinar, Yunus Akçamur

Turkish Journal of Chemistry

Conformational analysis and quantum-chemical calculations were carried out by means of the methods MMP2 and SCF MO LCAO in the CNDO/2 and MNDO approximation for the series of compounds being functionalized 1H- pyrimidines. The analysis of the electron density distribution depending on the substituents' nature was done on the basis of the data obtained.

Investigation Of Acid Sites On V_{2}O_{5}/Tio_{2}(A) Catalysts By Ftir With Adsorption Of Pyridine, Ahmet Akbaş, Holger Mi̇tzel, Dieter Höni̇ce

Turkish Journal of Chemistry

The V_{2}O_{5}/TiO_{2}(A) catalysts were prepared by the grafting and their Br\"{o}nsted and Lewis acid sites were investigated with pyridine adsorption by using FTIR Spectroscopy. The results obtained showed that monolayer or less coverage of the surface of the support, TiO_{2}(A), took place up to V_{2}O_{5} content of 11.88 \%. When V_{2}O_{5} amount was higher then 11.88 \%, the support was covered as multilayer. Pyridine adsorption studies showed that the number of the Lewis acid sites of the V_{2}O_{5}/TiO_{2}(A) catalysts decreased with increasing of V_{2} O_{5} amount. The number of the Br\"{o}nsted acid sites increased with increasing V_{2}O_{5} content, reached a …

Transmission Electron Microscopy (Tem) Study Of Polycrystalline Ru:Ag/Alumina Supported Catalyst System., S. Tajammul Hussain

Turkish Journal of Chemistry

Transmission Electron Microscopy (TEM) was used to characterize bimetallic Ru/Ag Catalyst samples dispersed on a high surface area Alumina support. The addition of Ag increases the metal dispersion but no consistent trend is observed. Ag forms crystallites of various shape and sizes, some of them are present in the close vicinity of Ru but not forming Ru:Ag bimetallics. A part of Ag crystallites cover the Ru surface hence blocking Ru emission. These irregular shaped crystallites are possibly responsible for the increase in metal dispersion. Particles below 2.5 nm were Ag particles, between 2.5 to 5.0 nm were Ru:Ag mixed crystallites …

Poly (D,L-Lactic Acid) Homopolymers: Synthesis And Characterization, Xu Kaitian, Ahmet Kozluca, Emir B. Denkbaş, Erhan Pi̇şki̇n

Turkish Journal of Chemistry

In this study, poly(D,L-lactic acid or D,L-lactide) (PDLLA) homopolymers were synthesized with different molecular weights. Low molecular weight PDLLAs (MW_n: 500-2300) were synthesized by direct polycondensation of DL-lactic acid without using any catalyst, while high molecular weight PDLLAs ( MW_n: 8x10^3-150x10^3) were produced by ring-opening polymerization of DL-lactide with stannous chloride as catalyst (initiator). Average molecular weights of PDLLAs were determined by end-group analysis, by viscosimetric measurements and by HPLC. PDLLA homopolymers were characterized by FTIR, NMR and DSC. In the production of PDLLAs by direct polymerization, molecular weights of the PDLLAs increased with the increase in the polymerization time …

Crystal Structure Of Tris(2-Hydroxyethyl)Ammonium Bromide, Veysel T. Yilmaz, Hasan İçbudak, Halis Ölmez, R. Alan Howie

Turkish Journal of Chemistry

The crystal structure of tris(2-hydroxyethyl)ammonium bromide, [HN(CH_{2}CH_{2}OH)_{3}]Br, was determined as rhombohedral by single crystal X-ray diffractometer. The final R value was found to be 0.032 for 576 observed reflections. The crystal consists of layers of hydrogen-bonded cations, [HN(CH_{2}CH_{2}OH)_{3}]^{+} and anions, Br^{-}. Within a layer every cation donates and every anion accepts three hydrogen bonds. In the cation, trifurcated intramolecular hydrogen bonds are formed due to the surrounding of the hydrogen atom bonded to the N atom by the 2-hydroxyethyl groups.

A Kinetic Study Of Homogeneous Bulk Polymerization Of Ethyl Methacrylate Initiated By Benzoyl Peroxide And An N, N^{\Prime} -Dimethylaniline Redox Pair, Serap Şenel, Belma Işik-Yürüksoy, Olgun Güven

Turkish Journal of Chemistry

The homogenous bulk polymerization of ethyl methacrylate (EMA) was studied using benzoyl peroxide (BPO) and an N,N^{\prime}-dimethylaniline (DMA) redox pair with the dilatometric method. The half-order dependence of the polymerization rate upon both the BPO and DMA concentrations was obtained. The overall activation energy of the polymerization was found to be between 32.3-55.3 kJ/mole for different initial molar ratios of the redox pair. A retaring effect was observed at lower polymerization temperatures for low concentrations of BPO. The formation of reddish colored polymers at higher DMA concentrations was explained by the adsorption of adduct formed between DMA radicals.

The Effects Of Polyacrylic Acid/Polypyrrole Composite Coating On Photocorrosion And Photoactivity Of Pyrite Electrodes, A. Sezai Saraç, Belkıs Ustamehmetoğlu, Esma Sezer, Candan Erbi̇l

Turkish Journal of Chemistry

Electrically conducting polyacrylic acid (PAA)/Polypyrrole (PPy) composite films were prepared by electrochemical polymerization of pyrrole on PAA which was electrocheimically adsorbed on natural and synthetic pyrite ( FeS_{2}) electrodes. The application of such polymer coating on pyrite, which is one of the semiconducting materials for solar applications, shows almost total protection against corrosion and can improve the photoactive character of the electrode. Addition of Ce(IV) ammonium nitrate into this system improved the photoactivity of the PAA/PPy composite. The composite polymer has higher photoconductivity than the pure PPy, because of the doping effect of anions on the PPA/PPy composite.

The Effect Of Metal Loading On The Adsorption Parameters Of Carbon Dioxide On Coprecipitated Nickel-Alumina Catalysts, A. Erhan Aksoylu, A. Nilgün Akin, S. Gönenç Sunol, Z. İlsen Önsan

Turkish Journal of Chemistry

A coprecipitation method has been developed and modified for the preparation of nickel-alumina catalysts having metal loadings in the 0-25 wt\% Ni range. The effect of metal loading on CO_{2} adsorption was investigated under isothermal chromatographic conditions using an elution technique in the temperature range 483-533 K. Average enthalpies of adsorption were determined using the isosteres obtained from the experimental adsorption isotherms. The isotherms were also fitted to the Langmuir equation for the evaluation of adsorption equilibrium coefficients, Gibbs free energies, average adsorption enthalpies and entropies. Keywords: nickel-alumina, coprecipitated nickel-alumina, CO_{2} adsorption

Validity Of A Linear Estimator For The Total \Pi-Electron Energy Of Alternant Hydrocarbons, Lemi Türker

Turkish Journal of Chemistry

The validity of a linear topological estimator formula which possesses a slope k such that 0

The Mechanism Of The Photoprotolytic Reactions Of Some Oxyazomethine Compounds, Lubov Efimovna Zelt'ser, Milan B. Bastic, Ljubinka V. Rajakovic

Turkish Journal of Chemistry

The kinetic spectral study of the photoprotolytic reactions of oxyazomethine molecules was performed. It was established that the deprotonation reactions of oxyazomethines proceed with the participation of electronically excited molecules and are characterized by parameters which differ to basic state reactions.

Distribution Of Ce (Iv) Species In Hno_{3}-Hcio_{4} Media And Determination Of Stability Constants Of The Nitrato Complexes, Seval Bayülken, A. Sezai Saraç

Turkish Journal of Chemistry

In this paper, the distribution of cerium (IV) species depending on the charges of nitric acid-perchloric acid concentration at constant ionic strength (I=1.0) was investigated. Cerium (IV), being a strong oxidant, was utilized for investigating the oxidation kinetics of some amino acids. Knowing the distribution of cerium (IV) species is beneficial for better understanding this type of kinetics. Distribution of cerium (IV) species in aqueous media was studied by measuring the total optical absorbance of cerium (IV) species in different nitric acid-perchloric acid mixture solutions. The stability constants (K_{1} and K_{2}) of the nitrato cerium complexes were determined spectrophotometrically from …

Automation Of Dipole Moment Measurements Using Microprocessor Controlled System, Nil Tarim, Hakan Kuntman, Ayten Kuntman

Turkish Journal of Chemistry

A microprocessor controlled instrument that can be used in physical chemistry research laboratories has been designed and constructed. The intended use is the measurement of the dipole moment and determination of the temperature dependency of the dipole moment for polar substances, especially for macromolecules. Measurement techniques with conventional dipolmeters require fine adjustments and measurements which seem to be very tedious and time consuming. Provided automation enables very frequent measurements with a step of 1^{\circ}C and disallows any user-oriented error. The dielectric constant measurement is performed within an accuracy limit of less than \pm 0.001. Furthermore, the equipment designed provides the …

Enantioselective Synthesis Of 4-Hydroxy-3-(3-Oxo-1-Phenyl Butyl)- 2h-1-Benzopyran-2-One (Warfarin), Ayhan S. Demi̇r, Cihangir Tanyeli, Volkan Gülbeyaz, Hülya Akgün

Turkish Journal of Chemistry

Oral anticoagulant Warfarin (4-hydroxy-3-(3-oxo-1-phenyl butyl)-2H-1- benzopyran-2-one) is synthesized in optically active form starting from 4- hydroxycoumarin via formation of optically active enamines followed by Michael addition reaction with benzyliden acetone at low temperature. Different amines gave 17-68\% ee and the chemical yield was 22-71\%, depending on the reaction conditions and the structure of chiral amines.

The Determination Of Some Heavy Metal Cations By Tlc/Photodensitometry, Şahin Savaşçi, Mehmet Akçay

Turkish Journal of Chemistry

The samples having complex matrices were analyzed for some heavy metal cations by using a thin layer chromatography/photodensitometry (TLC/PD) system. The rock samples were dissolved by suitable methods. Nickel, Cobalt and Copper were dedected and analyzed by photodensitometric comparison of corresponding spots of samples with those of standards. The results of the same samples and standards were compared with those obtained by atomic absorption measurements. Our results are comparable with the results of flame atomic absorption measurements. The precision of TLC method was calculated to be 9.4\% as relative standard deviations depending on 17 replicate measurements. The accuracy of TLC …

Molecular Structure Of 2'-Hydroxy-3'-Methoxy-5'-Allyl -4-Methylazobenzene, Veysel T. Yilmaz, Selami Şasmaz, İsmail E. Gümrükçüoğlu, R. Alan Howie

Turkish Journal of Chemistry

2'-hydroxy-3'-methoxy-5'-allyl-4-methylazobenzene was synthesized in two steps: 4-methylbenzenediazonium chloride was prepared by the reaction of 4- methylaniline, HCL and NaNO_{2}, and was then reacted with eugenol to give 2'-hydroxy-3'-methoxy-5'-allyl-4-methylazobenzene. The molecular structure was identified by UV/VIS, IR, ^{1}H-NMR and elemental analysis. The crystal structure was determined as monoclinic by single crystal X-ray diffraction technique. The final R values was found to be 0. 078 for 1065 observed reflections. The structure consists of isolated molecules with van der Waals contacts and the molecule is essentially planar in the solid state. There is a strong intramolecular hydrogen bond in which the hydroxyl group …

Synthesis Of Some Pyrazolo-Pyridazine Compounds, Adem Önal, Yunus Akçamur, Behzat Altural

Turkish Journal of Chemistry

Addition of {\bf 1} to two moles of phenylhydrazine gives 1,2,4,6- tetraphenyl-(2,3-d)-pyrazolo-5,6-pyridazine-7-one {\bf 4} isomer compound 1, 2,3,5-tetraphenyl-(2,3-d) pyrazolo-5,6-pyridazine-7-one {\bf 5} of {\bf 4} was synthesized by the reaction of {\bf 2} with phenylhydrazine. 3,4- Diphenyl-(2,3-d)-pyrazolo-(1H,6H)-pyridazine-7-one {\bf 6} was also obtained in two different ways. Reaction of {\bf 1} and 4-benzoyl-5 phenyl- furan-2,3-dione {\bf 3} with hydrazinium hydrate furnished compound {\bf 6}. The structures of {\bf 4,5} and {\bf 6} were determined by the ^{13} C- NMR, IR spectra and elemental analysis. These new isomer and condensed compounds synthesized in this study are important for heterocyclic chemistry.

A New Prodelphinine Type Alkaloid From, Ali H. Meri̇çli̇, Filiz Meri̇çli̇, Hans Becker, Ayhan Ulubelen

Turkish Journal of Chemistry

In a previous study we have isolated five known and a new diterpenoid alkaloids from the aerial parts of {\it Aconitum nasutum}. In the present paper the structure of a new and rather rare diterpenoid alkaloid aconasutine was determined by using 1D and 2D NMR techniques.

Cycloaddition Reactions Of Dichloroketene To Allyl Ethers, Hülya Şenöz, Süleyman Yildirir

Turkish Journal of Chemistry

Allyl ethers reacted with dichloroketene by [2+2] Cycloaddition to produce 2,2-dichlorocyclobutanones structure of products were determined by IR, NMR, GC MS tecniques.