Chemistry Commons^™

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 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 …

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 …

Heterocyclic Syntheses Utilizing Aryl Cyanates, Joseph Eugene Drumm

Masters Theses

No abstract provided.

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 …

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 …

Naphthalene-2,3-Dialdehyde: A Synthon To 7,9-Polymethylene-8h-Cyclohepta[B]Naphthalene-8-One And A Study Of Their Aromaticity, Edward O. Crapps

Dissertations

This report describes the synthesis of naphthalene-2,3-dialdehyde, and an analytical method for determining its purity by thin layer chromatography. Subsequently, the dialdehyde was condensed with various cyclic ketones to generate a series of polymethylene bridged naphthotropones. It was found that planarity and aromaticity increase with the size of the methylene bridge, although, the bridge must contain six or more methylene groups for the latter to be true. The claim for aromaticity is supported by NMR and IR data, which indicates the positive charge for a perchlorate cation salt is delocalized over the naphthalene and tropone ring system. Furthermore, from the …

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.

Cationic And Anionic Micellar Catalyzed Hydrolysis Of Hydroxamic Acids, Douglas Eugene Conran

Masters Theses

The hydrolysis of octanohydroxamic and N-methyloctanohydroxamic acids in the presence of cationic and anionic micelles was investigated. Rate constants were determined for the hydrolyses in cetyltrimethylammonium bromide (ctab), the cationic surfactant, with 0.1111 N NaOH and in sodium 1-dodecanesulfonate, the anionic surfactant, with 0.09270 N HC1 at 50.01 + 0.11°C. The acid hydrolysis and the base hydrolysis of N-methyloctanobydroxamic acid followed the standard model for micellar catalysis.

A Microprocessor Controlled Pulsed Hollow Cathode Lamp For An Atomic Absorption Spectrometer, James B. Schilling

Masters Theses

A Jarrell-Ash Atomic Absorption/Flame Emission 82-360 Spectrometer was interfaced to a Heathkit ETA-3400 microprocessor. The microprocessor is used to pulse the hollow cathode lamp from a "steady" current to a "peak " current during the opening of the chopper. The current from the photomultiplier-tube is converted to a proportional voltage which is supplied to a sample-and-hold circuit. A successive approximation routine is used to convert the voltage to a representative digital value. Digital values are obtained for the "blank" and "sample" and are used to calculate percent absorption values. The system can also be used to obtain emission values.

The …

Kinetics And Mechanism Of Acylation Of Amines With 2-Naphthoyl Azide, Abraham L. Faburada

Dissertations

The reaction of 2-naphthoyl azide with primary and secondary amines in protic and aprotic solvents follows second-order kinetics. The effect of increasing solvent polarity is shown to increase the rate of reaction. For amines of similar basicity, the rate of reaction decreases with increasing steric hindrance on the amine. The changes in free energy and entropy of activation for n-butylamine and cyclohexylamine are in accord with steric requirements of amines. For amines of similar steric hindrance, the rate of reaction increases with increasing amine basicity. The mechanism of addition-elimination involving the formation of a tetrahedral intermediate is consistent with the …

Kinetics Of Ternary Complex Formation Reactions Of The Nickel(Ii) Complexes Of Ethylenediaminediacetate And Triethylenetetramine With Bidentate Donors, Lawrence H. Kolopajlo

Dissertations

The stopped-flow technique was used to measure rate constants for ternary complex formation involving both NiEDDA and Ni(trien)('2+), and bidentate donors. The reactions of both NiEDDA and Ni(trien)('2+) with bipy, phen, en, and sar were studied. In addition the reaction of NiEDDA and gly was studied. The reactions were of the first-order with respect to either nickel complex, and with respect to enH('+), bipy, and phen. The reactions involving phen and bipy were independent of pH and were reversible. The formation rate constants for the systems containing diamine reactants are as follows:

(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI)

For …

Determination Of Organophosphorus Compounds By Hplc With Post-Column Photochemical Degradation Followed By The Formation Of Reduced Heieropolymolybdate, Stephen R. Priebe

Dissertations

A novel method for the determination of organophosphorus (OP) compounds by HPLC with post-column photochemical and chemical derivatization reactions has been developed. The OP compounds eluted from the column were photochemically degraded to orthophosphate by the use of a 450 W xenon lamp in conjunction with an auxiliary photodegradation reagent. The photodegradation reaction was studied extensively by means of batch irradiations with triethylphosphate as a model compound. The effects of the initial concentrations of triethylphosphate and ammonium peroxydisulfate, and of varying the pH of the reaction medium were determined. A survey of potential interferences was performed. Copper(II) ion was found …

Micellarly Catalyzed Reaction Of Substituted Benzohydroxamic Acids, Nop Utrapiromsuk

Dissertations

The rate constants for hydrolysis of ten derivatives of benzohydroxamic acid, namely, p-H, p-CH(,3), m-CH(,3), p-CH(,3)CH(,2), p-OCH(,3), p-NO(,2), p-Cl, and m-Cl, in 0.160 and 0.158 M HCl at 67.9-68.2(DEGREES)C without and with sodium 1-dodecanesulfonate were determined. There is a good linear correlation between log k(,w) and the Hammett substituent constants, (sigma), for all para and meta derivatives where k(,w) is the rate constant in the bulk aqeous phase. In the presence of micelles all the compounds, except the meta-nitro derivative, followed the standard pseudophase model of micellar catalysis. However, correlations of log k(,m) or log K/N, where k(,m) is the …

Stereochemistry And Circular Dichorism Of Some Cobalt(Iii) Complexes With Ethylenediamine-N, N’-Diacetic Acid And N, N'-Dimethylethylenediamine-N ,N'-Diacetic Acid, Godfrey Chinenye Mbah

Dissertations

Two series of complexes trans-{Co(LL')EDDA}('+) and trans-{Co(LL')DMEDDA}('+), LL' = Meen, 2-Mepn, udmeen, sdmeen, R-dmepn were prepared. EDDA was reacted with cobalt(II) carbonate and the resulting solution combined with the diamine of choice. For the DMEDDA complexes the ligand DMEDDA was first prepared by adding neutralized chloroacetic acid to sdmeen and precipitating out the ligand as the barium salt. The DMEDDA complexes were prepared by reacting the barium salt first with cobalt(II) sulfate and then with the diamines listed above except udmeen. The DMEDDA complexes with R-pn were also prepared. For both series the oxidation of the Co(II) to Co(III) was …

A Column For The High Pressure Liquid Chromatography Of Some Potentially Hazardous Metal Ions, Stephen R. Friebe

Masters Theses

No abstract provided.

Analysis Of Mixtures Of Chlorine, Chlorine Dioxide And Chlorite, Ying-Chien Chu

Masters Theses

No abstract provided.

Kinetic Study Of The Formation Of Mixed Ligand Complexes Formed From Triethylenetetramine Nickel (Ii) And Bidentate Ligands, Burtrand Insung Lee

Masters Theses

No abstract provided.

Preparation And Properties Of Benzotropones And Benzohomotropones, Robert E. Suder

Dissertations

No abstract provided.

Photon Counting System For The Determination Of Creatine Phosphokinase, Steven E. Dueball

Masters Theses

No abstract provided.

Structural Effects On Micellar Catalyzed Reaction Of Hydroxamic Acids, Nop Utrapiromsuk

Masters Theses

Introduction

For many years scientists have tried to find a model which resembles a biological system, so that they can use this model for studying biological systems in human and in living organisms. Micelle systems provide the environment to mimic enzyme systems to some degree.¹

Soaps and detergents generate micelles. Soaps and detergents have been used as cleansing agents for a long time. Their cleansing properties are related to micelle formation. Actually, soap is simply a mixture of sodium salts of long chain fatty acids, R-COO^- Na⁺, and some detergents are general sodium salts of straight …

The Unexpected Preferential Formation Of 1-Alkyl-1-Phenyl-2–Propanones On Monoalkylation Of The 1-Phenyl-2-Propanone Dianion, Jack M. Hinkley

Masters Theses

No abstract provided.

The Effects Of Electron-Donating And Electron-Withdrawing Groups On The Alkylation Sites Of Para-Substituted Phenylacetones, Abraham L. Faburada

Masters Theses

The dianions of phenylacetone and its para-substituted derivatives were generated using potassium hydride and n-butyl lithium in tetrahydrofuran. Methyl, ethyl, and n-butyl iodides were used to alkylate the dianions. The results of alkulation indicated that C₁ is preferentially attacked by the less active ethyl and n-butyl iodides. The results further show that terminal alkylation is enhanced by electron-donating groups at the para-position of the phenyl ring. The results are rationalized in terms of the difference in electron density at C₁ and at C₃ in the dianion, on the basis of resonance theory. The regio-selectivity of alkylation as …

The Analysis Of N-Methylscopolamine Bromide By High Speed Ion Pair Partition Chromatography, John L. Nappier

Masters Theses

No abstract provided.

The Response Of The Micro-Adsorption Detector To Inorganic Anions, Maria E. Munera

Masters Theses

No abstract provided.

Determination Of The Rate Of Formation Of Hcn, Mitchell Hull

Honors Theses

Nitric oxide is a major air pollutant arising from fossil fuel combustion, yet the fuel contribution to its formulation is uncertain. Since, in combustion, fossil fuels undergo disintegration before oxidation takes place, the study of the pyrolsis of a model constituent of fossil fuels can shed light on NO formation. The rate of inert pyrolytic disappearance of pyridine and the rate of formation of the principal Nitrogen-containing pyrolytic product, HCN, was studied in an inert atmosphere. The rate constant for the formation of HCN and its temperature dependence were determined.

The Preparation And Study Of Some Bridged Tropones, Sultan T. Abu-Orabi

Masters Theses

No abstract provided.

Proximity Effects. Kinetics, Mechanisms And Reactivity Correlations For The Acidic And Alkaline Hydrolysis Of Ortho-Substituted-N-Methylbenzohydroxamic Acids, Irl E. Ward

Dissertations

No abstract provided.

Studies Toward The Total Synthesis Of A Colchicine Analog, Jacob Shya Tou

Masters Theses

No abstract provided.

Side-Chain Metalations Of Certain Dimethylpyridines By Means Of Organoalkali Metal Reagents, Stephen Bendzunas

Masters Theses

No abstract provided.