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Donor Properties Of Dimethylsulfoniumcyclopentadienylide And Tetramethylenesulfoniumcyclopentadienylide In Metal Complexes ; Part Ii. The Attempted Preparation Of Boron Tricyanide, Gary Scott Barney

Theses and Dissertations

Part I.--Complexes of dimethylsulfoniumcyclopentadientylide and tetramethylenesulfoniumcyclopentadienylide with metal ions were studied in order to determine the coordination site on the ylids. Infrared spectra indicate that the ylids are coordinated through the cyclopentadienyl ring in all complexes except for the Hg(CN)2 complexes. Coordination-of the HgI2, CdI2, ZnCl2, and AgNO3 complexes is through the number one position on the ring as suggested by NMR data. Infrared and NMR data strongly indicate that the ylids in the Hg(CN)2 complexes are coordinated through sulfur. Part II.--The only method given in the chemical literature for the preparation of boron tricyanide could not be duplicated in …

A Dialyzable Phospholipid Renin Inhibitor, Donna L. Webber

Senior Scholar Papers

Crude renin preparations from steer kidneys were incubated with Cd2+ and with Zn2+ elevation of renin activity resulted in both preparations. Analyses of each preparation against Tris-saline, and finally EDTA, removed the cations; however, renin activity remained elevated. An indirect activation of Renin by Cd2+ and, to a lesser extent, Zn2+, was thus demonstrated. Removal of the cations by Tris-saline and DTA-dialyses was suspected to involve the loss by dialysis of a renin inhibitor. An isolation technique for a proposed phospholipid renin inhibitor similar to bovine phosphatidylserine, reported by another laboratory, was thought to be unnecessarily arduous due to the …

A Study Of Substituent Effects In Selected Aromatic Systems By Nuclear Magnetic Resonance Spectroscopy, Carol K. Haas

Chemistry Honors Papers

This 53 page thesis builds upon previous work investigating substituent effects on nuclear magnetic resonance spectroscopy parameters.

The Photochemical Reduction Of Octacyanomolybdate(V) Ion In Aqueous Solutions, Gordon W. Gray

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The photochemical reactions occurring in aqueous solutions of octacyanomolybdate(V) ion, Mo(CN)₈^3-, during irradiation with light of 365 and 436 nm wavelengths were studied. The quantum yields and reaction products were determined for neutral, unbuffered solutions as well as solutions buffered at pH 4.0, 7.0, and 9.0.

The results of these studies showed that the Mo(CN)₈^3- ion is rapidly reduced by light to a Mo(IV) complex. In neutral or acidic media, the initial photoreduction product was found to be the red heptacyanoaquomolybdate(IV) ion, Mo(CN)₇(H₂O)^3-. Photolysis in basic solution gave the …

Magnesium Ion Inhibition Of Calcium Carbonate Precipitation And Its Relation To Water Quality, John J. Hassett

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The effect of Mg⁺⁺ ion on the solubility of calcium carbonate was determined using P. K. Weyls "carbonate saturometer."

The amount of calcium carbonate precipitated or dissolved was measured for five series of waters when equilibrated with solid carbonate.

It was found that the effect of Mg⁺⁺ ion on solubility depend upon the nature of the solid phase: surface area, coprecipitated Mg⁺⁺, minerology, etc.

Pure low area calcite showed an increase in solubility which could be explained by ion-pair formation, while its other carbonates departed from this behavior.

The Stepwise Nature Of The Unwrapping And Transfer Of Ethylenediaminediacetate From Nickel(Ii) To Copper(Ii), Robert Swann

Masters Theses

No abstract provided.

Asymptotic Evaluation Of Wkb Matrix Elements. Ii. Use Of Langer's Uniform Asymptotic Wavefunctions, Wesley D. Smith, Russell T. Pack

Faculty Publications

An improvement in a previous procedure for the analytic asymptotic evaluation of integrals arising in the quantum-mechanical theory of inelastic molecular collisions is presented. The integrals are evaluated using Langer's uniform asymptotic wavefunctions and the higher-order saddle-point or steepest-descents method. It is found that the Langer functions give no better results than WKB functions, but the higher-order steepest-descents corrections produce a marked improvement. The result is a simple method for evaluating a large class of integrals with an error of 0.1%-2.1%.

The Synthesis Of Some New Azabenzo[A]Pyrene And Monomethyl Azabenzo[A]Pyrene Derivatives, Richard E. Phillips

Chemistry and Chemical Biology ETDs

The synthesis of six new azabenzo[a]pyrenes was undertaken in order that the carcinogenic and carcinostatic properties of these com­pounds might be tested. The compounds thus synthesized were 4-aza­ benzo[a]pyrene (1), 5-methyl-4-azabenzo[a]pyrene (2), 12-azabenzo[a]­pyrene (3), 11-methyl-12-azabenzo [a]pyrene (4),5 -azabenzo [a]pyrene (5), and 4-methy1-5-azabenzo[a]pyrene (6).

Compounds 1 and 2 were prepared from the intermediate 4-keto-1,2,3,4-tctrahydrochrysene. The azine from this ketone was dehydro­genated and the resulting aromatic amine was both formylated and acetylated. The amides were cyclized with polyphosphoric acid in a Bischler-Napieralski cyclodchydration giving fair yields of 1 and 2. The synthesis of compounds 3 and 4 was carried out in a …

Paths Of Energy Degradation In Transition Metal Complexes, James N. Demas

Chemistry and Chemical Biology ETDs

To elucidate the paths and rates of energy degradation in transition-metal complexes following photoexcitation, a comprehensive experimental study was carried out on a total of fourteen complexes of Ru(II), Os(II), Ir(III), and Rh(III). Photoluminescence lifetimes, spectra, wavelength dependences of the quantum yields, and absolute quantum yields were determined. The complexes all contained organic ligands—pyridine, 2, 2’bypyridine, 2, 2’ 2”-terpyridine, and 1, 10-phenanthroline. The ruthenium, osmium, and iridium complexes all exhibited charge transfer (CT) phosphorescences with quantum yields of 1-60% and lifetimes of 0.6-11 µsec in an alcoholic glass at 77°K. The rhodium complexes gave d-d* phosphorescences with yields in the …

The Crystal Structure Of P-Azoxyanisole, W. R. Krigbaum, Yozo Chatani, Patrick G. Barber

Chemistry & Physics Faculty Publications

The stable crystalline form ofp-azoxyanisole is assigned to space group P21/a (C~h) with four molecules in the unit cell having parameters a= 15-776, b= 8.112, e= 11-018 A and b'= 114"57 °. The crystal structure was refined by full-matrix least-squares to a final R value of 0.091 using 2507 reflections measured with a manually operated single-crystal diffractometer. The molecules are arranged in the unit cell with their long axes approximately perpendicular to the (100) plane. The angle between the normals to the two benzene rings is 22.6 °, and the -N=N- bond conformation departs from the planar trans position by …

Modified Quantum-Statistical Calculations For Atomic Electron Densities, Jerry Goodisman

Chemistry - All Scholarship

We attempt to overcome one of the shortcomings in the Thomas-Fermi and related theories for atoms by connecting a quantum-mechanical electron density for the region near the nucleus to a density given by a statistical model. The joining may be done in a nonarbitrary manner: All parameters are determined. It suffices to use a very crude and easily calculated approximation to the density to start with, so the calculation is quite easy. The resulting electron density is in much better agreement with reality than that from the unmodified theories.

Modified Weizsäcker Corrections In Thomas-Fermi Theories, Jerry Goodisman

Chemistry - All Scholarship

We consider theories in which a kinetic-energy correction (h2322m)[2] (=density) is added to the usual Thomas-Fermi term. A treatment based on the WKB method and expected to be valid for large r shows =1 here, as found experimentally. For small r, =1 is needed to give proper behavior of, but other arguments suggest that the Thomas-Fermi term be dropped here.

The Control Of Algae, G R W Meadly

Journal of the Department of Agriculture, Western Australia, Series 4

CONDITIONS in areas of still, stored water in Western Australia can easily become ideal for the development of algae and control measures may become necessary in farm dams and swimming pools.

Acid-Base Catalysis Of The Enolization Of Acetone, Janet Louise Larson

Undergraduate Honors Theses

Measurements are reported on the rate of iodination of acetone at 25°c in arsenate, phosphate, and diethylmalonic acid buffers at a constant ionic strength of 0.2. Unlike earlier results which indicate that in acetic acid buffer the expression for the reaction velocity contains an appreciable kinetic term involving the product of the concentrations of acid and anion, it has been found from the present work that such a term is experimentally immeasurable for the above mentioned buffers. This finding coupled with the relatively powerful catalysis by the phosphate and arsenate dianions could imply the simultaneous participation of these species in …

Superphosphate Deficiency Raises Pasture Oestrogens, H G. Neil, T. Marshall

Journal of the Department of Agriculture, Western Australia, Series 4

A recent field experiment on established pastures at Esperance Downs Research Station has demonstrated a relationship between superphosphate application, pasture oestrogens and oestrogenic response in sheep.

Results of the experiment indicate that on phosphate deficient soils carrying oestrogenic clovers, the levels of oestrogenic materials in the pasture are increased if superphosphate applications are below those recommended for healthy pasture growth.

Undergraduate Research Program In Chemistry At Philander Smith College, James O. Wear

Journal of the Arkansas Academy of Science

No abstract provided.

Theory Of Droplet Growth In Clouds. I. The Transient Stage Of The Boundary-Coupled Simultaneous Heat And Mass Transport In Cloud Formation, John C. Carstens, Joseph T. Zung

Physics Faculty Research & Creative Works

Two solutions to the system of equations describing the simultaneous heat and mass transport involved in the condensational growth of a droplet in a supersaturated atmosphere are presented. The first, valid for very short times, describes the transient stage of such growth; the second, valid for longer times, presupposes the establishment of a steady-state condition. The two are shown to be complementary for the cases examined. The equations examined satisfy the usual boundary conditions imposed on a drop in a concentric sphere as required by the cellular model for cloud formation. Hence our results can be immediately extended to the …

Analysis Of Solutions For Surface Active Agents, Henry H. Bauer

KWRRI Research Reports

The objective of this study was to obtain a better understanding of the behavior of surfactants in aqueous solutions at electrodes. With this understanding it should be possible to design electrochemical methods for the detection, identification, and quantitative determination of such substances. This study was concerned primarily with the influence of extraneous salts on the behavior of surface active agents when these are examined by the electrochemical technique known as tensammetry.

The tensammetric method consists essentially of the measurement of the electrical impedance of an electrochemical cell. This impedance is characteristically increased in the presence of surfactants at those potentials …

The Dipole Moment Of Cis- And Trans- Chloroiodoethylene, Ashvin Gajendralal Gajjar

Masters Theses

No abstract provided.

Apparatus For Dielectric Constant Measurements And Measurements For Water-Methanol Mixtures, James O. Wear

Journal of the Arkansas Academy of Science

A system for measuring dielectric constants has been constructed using a Sargent Oscillometer and an air bath for temperature control. The design and construction of the air bath as well as the temperature control achieved with it are described. The overall performance of the system including a computer program for forming the calculations is described. The system is one that requires calibration using two or more standard solvents and is good for both conducting and non-conducting liquids. Data are presented for water-methanol mixtures at 25 degrees with several points near pure methanol and also near pure water

A Study Of The Esterification Of 2,2,4,4-Tetramethyl-1,3-Cyclobutanediol, Lewis Metzler Naylor

Dissertations and Theses @ UNI

The purpose of this research was to prepare, identify, and characterize 2,2,4,4-tetramethyl-1,.3-cyclobutanediol bischloroacetate using 2,2,4,4-tetramethyl-1,3-cyclobutanediol and monochloroacetic acid as starting materials. The synthesis of this diester has not been reported previously.

Catalyzed and uncatalyzed reactions were attempted, with the uncatalyzed having, in general, the better yield. The diester, trans-2,2,4,4-tetrametbyl-1,3-cyclobutanediol bischloroacetate (mp, 103.5-104; n²², 1.516-1.520), was isolated from a mixture of the isomers. The trans configuration of the diester was confirmed by comparing known nuclear magnetic resonance spectra to that of the diester. Infrared spectroscopy was used to confirm functional groups. Standard analytical techniques were used to determine chloride …

Sheep : Experimental Basis For Urea Feeding Recommendations, Department Of Agriculture, Western Australia

Journal of the Department of Agriculture, Western Australia, Series 4

Recent scientific reviews have concluded that in spite of the great number of experimental observations recorded throughout the world there is no evidence yet to prove that urea can be used profitably for sheep on low quality roughages in genuine grazing conditions.

An experiment is in progress at Merredin Research Station this season, especially designed to demonstrate a response to urea by sheep grazing wheat stubbles, if such a response is possible.

Studies Of Rare Earth Acid Oxalates, Kenneth Clinton Pyles

Masters Theses

No abstract provided.

The Preparation Of Coordination Compounds Of Rhodium Iii And Some Substituted Pyridines, Campbell John Mcrobbie

University of the Pacific Theses and Dissertations

The purpose of this study, then, is to prepare and characterize the complexes produced by the reaction of these ligards with rhodium III chloride. Of particular interest will be the mode of bonding of the ligand to the metal ion. For the first two groups, the potential exists for bonding to the metal from different parts of the ligand molecule. Bridging and chelation are also possibilities. Examination of the infrared spectrum of each complex should produce information as to the position of bonding. For one complex of the aminopyridines an N.M.R. spectrum will be examined.

Magnetic Solid-Phase Extraction Of Trace Cobalt(Ii) On Iron Oxide-Hexagonal Boron Nitride In Water And Food Samples, Mustafa Soylak, Ali Mohammednour Ali Mohammed, Furkan Uzcan

Turkish Journal of Chemistry

Determination of trace cobalt(II) (Co(II)) in real samples remains challenging because of its very low concentration and strong matrix interferences. In this study, a simple and green magnetic solid-phase extraction (mSPE) method was developed for the selective separation and preconcentration of Co(II) ions using a newly designed iron oxide/hexagonal boron nitride (IOhBN) nanocomposite. The material was synthesized through a one-step, surfactant-free coprecipitation process, combining the high surface area, stability, and layered structure of hBN with the magnetic and reactive features of Fe₃O₄ nanoparticles. This hybrid structure provided abundant active sites and rapid magnetic separability, enabling efficient extraction within 5 min …

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 …

Thermochemical Hydrogen-Deuterium Isotope Effects, Wayne C. Duer

Doctoral Dissertations

"The heats of solution at 25.0 ± 0. 1°C for each member of hydrogen-deuterium isotopic pairs (chloroform/chloroform-d, acetone/acetone-d₆, methanol/methanol-d₁, ethanol/ethanol-d₁, and water/heavy water) have been determined as a function of molality in a variety of solvents. The heats for most of the systems could be described as a linear function of average molality with an average deviation in fit of less than one per cent. Using these linear equations, heats of solution at infinite dilution were obtained by extrapolation to zero molality. The heats of solution at infinite dilution of the hydrogen containing compounds were subtracted from those of the …

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 …

Identification Of Decomposition Products Of Tropyl Azide And Interaction Of Tropylium Ion With Nucleophiles, James Joseph Ward

Doctoral Dissertations

"An investigation of the structures of several of the products resulting from the decomposition of tropyl azide (I) and of the chemistry of related processes has been undertaken. Irradiation of samples of (I) in the vapor phase with low intensity UV G.E. Sun Lamps furnished a low melting white solid identified as tropyl troponimmonium azide (II). Earlier experiments of a similar nature reported to furnish (III) were not repeatable (Chem. Commun 276 (1967))...

Upon standing, solutions of (I) slowly formed troponimmonium azide (IV) in the cold (J. Chem. Soc. (D), 220 (1970)). The structures (II) and (IV) were confirmed by …