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Heterocyclic Syntheses Utilizing Aryl Cyanates, Joseph Eugene Drumm

Masters Theses

No abstract provided.

The Application Of Multiderivative Infrared Spectroscopy To Iodine Number Determination, Jeffrey C. Lowry

Masters Theses

The Food and Drug Administration requires the disclosure of total unsaturation of commercial products as an indication of nutritional value. This unsaturation is a guide to the expected stability of food additives, such as edible oils and foods in which they are used. Unsaturation is typically evaluated as an iodine number, calculated for these additives based on their consumption of iodine through addition across the carbon-carbon double bonds. This titration method can typically take 45 minutes.

The investigation presented develops an alternative method for determining iodine numbers of some common oils using a computerized infrared spectophotometer. The analysis time, as …

Kinetics Of The Formation Of The Nickel(Ii) Complex With N, N' -Dimethylethylenediaminediacetic Acid And The Metal Exchange Reaction Between N,N'-Dimethylethylenediaminediacetatonickel(Ii) And Copper(Ii), Roger A. Karel

Masters Theses

The kinetics of the reaction of aquonickel (II) ion with N'N'-dimethlethylenediaminediacetic acid has been studied at 25°C and 0.1M iconic strength over a pH range of 6.0 to 9.3 using stopped-flow techniques. Formation reactions in all cases were first-order in Ni (II) and in ligand. The formation rate constant for the protonated and unprotonated species were evaluated and compared to their theoretical value. The rate-determining step is shown to be ring closure. A comparison of this system with other studies involving complexation of nickel (II) confirm the magnitude of the internal conjugate base effect and also shows a correlation between …

The Kinetics Of The Metal Exchange Reaction Between N-(2-Hydroxyethyl) Iminodiacetatonickelate (Il) And Copper(Ii), Craig R. Weed

Masters Theses

The reaction between copper(II) and N -(2-hydroxyethyl)iminodiacetatonickelate( II) (NiHEIDA) was studied between pH 4.0 and 5.6 over a 70 fold variation in copper concentration at an ionic strength of 1.25 and a temperature of 25° C. The reaction order in both NiHEIDA and Cu(U) is first. The reaction rate is pH sensitive and a hydrogen dependent pathway as w ell as copper dependent and copper and hydrogen independent pathways were found.

Evidence is given for a stepwise mechanism for the unwrapping of HEIDA from its nickel complex, follow ed by copper attack to give a dinuclear intermediate, which then breaks …

I. A Temperature Dependent Nmr Study Of 6,6-Dicarbethoxy-5,5-Dideuteodi-Benzo--[A,C]-[L, 3]-Cycloheptadiene Ii. The Synthesis Of Four Deuterated Analogs Of 6, 6-Dicarbethoxydibenzo-[A,C]-[1,3]-Cycloheptadiene, Patrick F. Jonas

Masters Theses

The kinetics of conformational interchange of 6,6-dicarbethoxydi-benzo- a,c - 1,3 -cyloheptadiene and its 5,5-dideuterated analog were studied using variable temperature NMR techniques. The free energy of activation for conformational interchange of the parent compound was found to be 9.02 kcal mol^-1 and that of the 5,5-dideuterated analog to be 9.42 kcal mol^-1. Values of the entropy of activation were found to be -19.91 e. u. and -18.12 e. u. respectively. The spectra were recorded on a Nicolet NMC-360 wide bore spectrometer and the data collected treated as an AB spin system.

The 4,8-dideutero, 4,5,5,8-tetradeutero and 5,5,7,7-tetradeutero analogs …

The Synthesis And Characterization Of Some Transition Metal Complexes Prom Mixtures Of Poly Pyrazolyl Borates, Robert Matthew Alway

Masters Theses

This is a report of the synthesis and separation of transition metal complexes of hydrotris(1-pyrazolyl)- borate and hydrotris(3,5-dimethyl-l-pyrazolyl)borate. These complexes contain a central metal ion and two tridentate ligands, one hydrotris(1-pyrazolyl)borate and one hydrotris(3,5-dimethyl-l-pyrazolyl)borate. Mass spectrometry proved to be an extremely useful technique for identifying products. Many mass spectra are included and discussed extensively.

Complexes containing hydrobis(pyrazole)(3,5-dimethyl -1-pyrazolyl)borate and hydrobis(3,5-dimethyl-l-pyrazole) (pyrazolyl)borate also were synthesised and mass spectra obtained.

The Purification And Partial Characterization Of The Surface Polysaccharides From Three Fast-Growing Rhizobium Japonicum Strains, Madhav P. Yadav

Masters Theses

The fast-growing strains of R. japonicum were originally isolated from China. They are acid-producing Rhizobia and are capable of nodulating soybeans. These isolates share a common host-specificity (Peking soybean) with the slow-growing R. japonicum strains even though their biochemical properties are more closely related to other fast-growing Rhizobium species. The surface polysaccharides from three fast-growing R. japonicum strains--USDA201, USDA205, and HC205--were isolated and partially characterized. Strain HC205 is a nod⁻ mutant of USDA205 which lacks the symbiotic plasmid. These surface polysaccharides consist of extracellular, capsular and lipopolysaccharides (EPSs, CPSs and LPSs). The EPSs from all three strains are very similar …

A Study Of Oxygen Functional Groups In Illinois Coal Fractions, Kenneth R. Osborne

Masters Theses

Ferric chloride/acetic anhydride reacted with butyl phenyl ether in acetonitrile at 80° to give a 75.6% yield of p-butoxyacetophenone. Reactions with benzyl aryl ethers gave 30% cleavage. The reaction of benzyl phenyl ether gave 10.3% p-benzyloxyacetophenone as well as cleavage product. Reaction of a pyridine soluble, toluene insoluble fraction (preasphaltene) of an Illinois No. 6 coal with ferric chloride/acetic anhydride in acetonitrile gave a product 94% insoluble in pyridine. The insolubility was ascribed to condensation reactions.

Phenols were measured in coals, preasphaltenes and preasphaltene derivatives by acetylation with acetic anhydride in pyridine. Suggestions for improvement in the method were presented. …

The Intermolecular Force Field Of Acetylene-Hcl: The Normal Coordinate And Centrifugal Distortion Analysis Of Two Weakly Bound Rigid Rods, Rebecca S. Lee

Masters Theses

In order to determine the intermolecular force field of C₂H₂⋅⋅HCl, a normal coordinate analysis appropriate for two weakly bound rigid rods is developed. An exact centrifugal distortion analysis is then carried out on the microwave spectrum of this "T''-shaped hydrogen-bonded π complex. The distortion constants and published matrix-isolated vibrational frequencies are employed in the normal coordinate analysis to obtain the intermolecular force field and refinements in the structural parameters. The following van der Waals force field is found to reproduce the existing spectroscopic constants of C₂H₂⋅⋅H³⁵Cl … . This study …