Chemistry Commons^™

The Survival Of Mesophilic And Thermophilic Bacteria Subjected To Uv Irradiation, Sajida A. Shaikh

Masters Theses

Survival curves were determined for the mesophile, Bacillus licheniformis and the thermophile, Bacillus stearothermophilus after subjecting the cells to ultraviolet irradiation. Cells were grown at 37°C for the mesophile and at 55°C for the thermophile.

At low UV exposure times, the thermophile was more resistant to UV irradiation (had a better survival rate) than was the case for the mesophile. At higher exposure times, the situation was reversed, the mesophile having a greater survival rate than the thermophile.

The effect of changes in the temperature during irradiation was also determined. Thermophiles were greatly affected by changes in temperature while the …

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 …

Thermodynamics Of Ion Association In Aqueous Fluoride Solutions. Determination Of Stability Constants For (Naf), (Mgf)+ And (Caf)+ Ion Pairs, Waldo Zamorano-Santander

Masters Theses

Stoichiometric ion-association constants were determined at several ionic strengths for (NaF) over the temperature range 15-40°C and for (MgF)⁺ and (CaF)⁺ over the temperature range 25-45°C using fluoride ion selective electrode measurements.

Thermodynamic association constants, K°, were obtained through extrapolation of the stoichiometric values to infinite dilution. Values of K° for (NaF) are 1.70, 2.16 and 2.54 at 15, 25 and 40°C, respectively. The K° values for (MgF)⁺ are 73.4, 88.0 and 98.2, and for (CaF)⁺ are 13.7, 17.5 and 21.9 at 25, 35 and 45°C., respectively.

The stoichiometric association constants for (NaF) can be reproduced …

Bimetallic Complexes Of Tungsten And Mercury, Zakariah Abdullah

Masters Theses

A tungsten-mercury bimetallic complex [(CO)₄W(PPh₂CH₂CH₂PPh₂)₂HgCl₂]_n has been synthesized from the reaction of trans-(CO)₄W(η¹-PPh₂CH₂CH₂PPh₂)₂ and HgCl₂. The value of n has not been determined due to the insolubility of the complex. The anologous reaction with HgI₂ gave an insoluble, uncharacterizable complex, which best corresponds to (CO)₄W(PPh₂CH₂CH₂PPh₂)₂Hg₂I₄.

The geometry about tungsten in [(CO)_{4 …}

Bimetallic Tungsten Carbonyl Complexes, Jin-Guu Wang

Masters Theses

Two heterobimetallic complexes, [(CO)₄W(PPh₂CH₂CH₂-PPh₂)₂MCl₂]_n ( M = Pd or Pt ), were prepared from the reaction of trans-W(CO)₄(ŋ¹-PPh₂CH₂CH₂PPh₂) ₂ with M(COD)Cl₂ (COD = cyclooctadiene). A trans arrangement about tungsten was found for both the palladium and platinum complexes. The square planar palladium center was shown to have a trans geometry in solution while a cis arrangement for the platinum moiety was observed. Far infrared studies indicated a mixture of cis and trans …

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 …

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 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 …

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. …

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 …

Synthesis And Reactions Of Aromatic Ethers As Model Compounds For Coal, James Nicolas Ong Sy

Masters Theses

o-Anisic acid and o-ethoxybenzoic acid were reacted with pyridine hydriodide in pyridine at 115° for 3 days to yield 81% and 18% salicylic acid respectively. o-Anisic acid with KI in pyridine at 115° for 3 days gave 58% salicylic acid while o-anisic acid with LiI·3H₂O in pyridine at 85° for 3 days gave 54% salicylic acid. p-Anisic acid and o-phenoxybenzoic acid did not undergo cleavage reactions with pyridine hydriodide under similar conditions.

Beta-methylnaphthyl beta-naphthyl ether(I) or alpha-methylnaphthyl alpha-naphthyl ether(II) with pyridine hydriodide in pyridine at 100-115° for 3 days showed no cleavage. Ether I …

Preparation And Characterization Of Tertiary Phosphine Carbonyl Ruthenium (0) Complexes, Joann C. Bady

Masters Theses

Dichlorocarbonyltris(triphenylphosphine)ruthenium (II), Ru(CO)(Cl)₂(Ph₃P)₃, was prepared by modification of a procedure reported to yield the dimer, (Ru(CO)(Cl)₂(Ph₃P)₂)₂. Dissolution of Ru(CO)(Cl)₂(Ph₃P)₃ in acetonitrile resulted in loss of triphenylphosphine and dimer formation.

Metathesis of Ru(CO)(Cl)₂(Ph₃P)₃ in hexane with excess tertiary phosphine yielded complexes of the type Ru(CO)(Cl)₂-(R₂R′P)₃ where R₂R′P is Ph₂MeP or PhMe₂P. ¹H and ³¹p nmr spectra of these materials showed that two phosphines are …

A Study Of The Electroless Plating Of Sn Onto A Die-Cast Aluminum Alloy, Ann-Tinn Shen

Masters Theses

"A tin layer was immersion plated onto a zinc-silicon containing aluminum alloy by using a potassium stannate solution. Conventional aluminum pretreatment was used before immersion plating.

Effects of immersion time with immersion tin thickness and Al-Sn adhesion were studied. Conditions of subsequent Sn-Pb electroplating on Sn plated aluminum samples were investigated.

SEM (scanning electron microscope) and x-ray energy dispersion studies were extensively used on samples of each stage"--Abstract, page ii.

Analysis Of The Surface Polysaccharides Of R. Trifolii Su843 And Its Sym Plasmid Alterated Mutants, Jauh-Lin Duh

Masters Theses

The Rhizobium trifolii polysaccharides from SU843 and mutants--HC843(pBR1AN), HC843, 8002--in which the sym plasmid is replaced, absent, or mutated by transposon Tn5 were isolated. The surface polysaccharides of genetically altered mutants were compared quantitatively and qualitatively with one another and with the parent strain. The interpretation of these results is discussed in relation to the function of Rhizobium surface polysaccharides in the symbiotic process. The symbiotic ability of SU843 and mutant strains is as follows: (a) SU843, nod⁺, fix⁺; (b) mutant 8002, roa⁺ (still attaches to root hair), hac^-, nod^-; (c) …

Internal Rotation Effects And Nuclear Hyperfine Structure In The Microwave Spectrum Of Propyne-Hf, Roger E. Bumgarner

Masters Theses

The microwave spectrum of the weakly bound propyne-HF/DF complex in the region between 6 and 16 GHz was analyzed. The spectrum was characteristic of a distorted T-shaped asymmetric top exhibiting torsional splitting caused by a low barrier to internal rotation of the methyl top relative to the propyne-HF frame. Deuterium substitution of HF confirms that the acid proton of HF is located between the F atom and the propyne triple bond. The spectroscopic constants given below are consistent with the fluorine atom being displaced toward the methyl group from a line perpendicular to and bisecting the propyne triple bond, suggesting …

Cleavage And Deoxygenation Of Phenolic Ethers, Derhsing Luu

Masters Theses

Dibromotriphenylphosphorane (DTP) in acetonitrile at 50°C was found to cleave ß-naphthylmethyl phenyl ether in preference to ß-naphthyl benzyl ether, 62% and 30% cleavage, respectively. Reaction of ß-naphthyl benzyl ether in dichloromethane at reflux produced 67% cleavage.

The quasiphosphonium complexes obtained by reaction of phenolic compounds with DTP were found to be reduced by several reducing reagents to give the corresponding aromatic hydrocarbons. Reaction of p-cresol with DTP, followed by lithium aluminum hydride reduction gave 38% toluene; sodium naphthalide reduction in THF gave 32% toluene; sodium in liquid ammonia reduction gave 12% toluene; sodium naphthalide reduction in DMF gave 15% toluene. …

A Laser Interferometric Study Of Electric Field Effects On Methane-Oxygen Flame Plasmas, Mark D. Prairie

Masters Theses

A laser interferometer is developed to study the refractive index field, aerodynamic structure, and three dimensional temperature profile of a methane-oxygen flame system under the influence of D.C. electric fields. A combined graphical-numerical method is used to transform the observed interference patterns into radial temperature distributions. The results indicate that the electric field exerts a marked influence on the flame stability, geometry, and charged particle flow. Experimental evidence shows that these effects are most apparent under fuel rich conditions. It is suggested an electric field may change the concentration gradients of reacting species, leading to an altered course of fuel …

A Comparison Of The Surface Polysaccharides From Rhizobium Japonicum Strains I110ars And 61a76str, And The Isolation Of Soybean Root Proteins Responsible For The Binding Of Eps From R. Japonicum Strain I110ars, Richard F. Koehler

Masters Theses

The surface polysaccharides of Rhizobium are implicated in the symbiotic process. The composition of the surface polysaccharides from two strains of Rhizobium japonicum, I110 ARS and 61A76 str, have been compared. Five polysaccharide fractions are obtained from the I110 ARS strain. They are the EPS (extracellular polysaccharide), CPS-1 and CPS-2 (capsular polysaccharide fractions), LPS (lipopolysaccharide) and Phe (polysaccharide found in the phenol layer from the phenol/water extraction). These polysaccharide fractions have identical sugar compositions. Four polysaccharide fractions are obtained from the 61A76 str strain. These are the EPS, CPS-1, SmPS (small molecular weight polysaccharide), and Phe. Each of these …

Controlling The Number Of Metal Sites To Which A Poly(Tertiary Phosphine) Coordinates To Group 6 Metal Carbonyls, Nestor Paul Hansen

Masters Theses

The compounds trisdiphenylphosphine(tricarbonyl) metal and trisdiphenylvinylphosphine(tricarbonyl) metal of molybdenum and tungsten were prepared. These compounds were allowed to react with diphenylvinylphosphine and diphenylphosphine, respectively, in the presence of azobis(2-methyipropio)nitrile or potassium t-butoxide to yield the complex containing bis(diphenylphosphino) ethane as a chelated ligand.

The tris-substituted compounds showed a large degree of lability which prevented the isolation of the desired, (OC)₃M(Ph₂PCH₂CH₂PPh₂)₃, compound which contains three ditertiary phosphines acting as monodentate ligands.

Coordinated diphenylphosphine and diphenylvinylphosphine pentacarbonyl compounds of chromium, molybdenum and tungsten were prepared and allowed to react in …

The Interaction Of R. Leguminosarum 128c53 With Pea Root Proteins And A Comparison Of The Surface Polysaccharide With A Mutant Defective In Nodulation, Ru-Po Lee

Masters Theses

The Rhizobium extracellular polysaccharides (EPS) and lipopolysaccharides (LPS) are implicated in the symbiotic process. The interaction between host root protein fractions and symbiont EPS-polyacrylamide affinity support has been investigated. Ten percent root protein fractions had been observed to bind to the affinity support. The compositions of the polysaccharides from the parent R. leguminosarum and its Exo^-1 mutant have also been compared. The Exo^-1 mutant produces diminished amount of EPS and does not nodulate the host pea roots. Five kinds of polysaccharides from the parent were obtained: EPS, capsule polysaccharides (CPS I) washed from the bacteria with saline solution, …

A Comparison Of The Surface Polysaccharides Of Rhizobium Trifolii Su843 With Its Genetically Altered Mutant, 8002, Which Is Defective At Root Hair Curling (Hac-), Elroy Alfredo Turnbull

Masters Theses

Bacteria of the genus Rhizobium are capable of forming a complex nitrogen fixing (fix⁺) symbiotic association with leguminous plants. The surface polysaccharides are believed to be essential in the symbiotic process. The surface polysaccharides of a genetically altered Rhizobium trifolii mutant, 8002--which does not cause root hair curling (HAC^-), forms no nodules (Nod^-) nor fixes nitrogen (Fix^-)--is compared with its parent, SU843, which causes root hair curling (HAC⁺), forms nodules (Nod⁺), and fixes nitrogen (Fix⁺). Three types of surface polysaccharides--extracellular polysaccharide(s) (EPS), capsular polysaccharide(s) (CPS), and …

Pyridine Hydrogen Iodide As An Ether Cleaving Agent In Coal Chemistry, Agnes Mei-Ying Chen

Masters Theses

Reactions of several phenyl ethers and an ester with pyridine hydrogen iodide were examined under various conditions as model studies for the recently reported molecular weight reduction of a fraction of Illinois No. 6 coal by hydrogen iodide in pyridine at 50°.

No ether or ester cleavage was observed at 60-80° in pyridine, acetonitrile, ethanol or the absence of solvent. Sealed tube reactions at 210° resulted in cleavage to phenol plus various hydrocarbon and alkyl halide products. Pyridine and benzyl phenyl ether at 210° produced no cleavage in the absence of hydrogen iodide.

Syntheses of crystalline pyridine hydrogen iodide and …

Spectroscopic Studies Of Pre-Mixed Hydrocarbon Flame Plasmas, Tsao-Chin C. Huang

Masters Theses

This thesis contains two different studies.

Chapter 1, "Infrared Emission Spectrum of the Hydroxyl Radical.", is in collaboration with Dr. Giles L. Henderson and Mr. Chun-Sheng Ko. This chapter has been submitted and accepted for publication by the Journal of Chemical Education.

In this chapter, we describe a rather novel physical chemistry experiment in which ab initio potential parameters for the OH radical are compared with those obtained from the ir emission spectrum of an oxy-acetylene welding torch.

Chapter 2, "A Preliminary Spectroscopic Study of Field-Induced Ion Movements in Flame Gases.", describes the effects of longitudinal electric fields on CH …

Controlling The Number Of Metal Sites To Which A Polytertiary Phosphine Coordinates In Tungsten Carbonyls, Rodney D. Borger

Masters Theses

Judiciously selected coordinated fragments of Ph₂PCH₂CH₂PPhCH₂-CH₂PPh₂ [(OC)₅WPPh₂H, (OC)₅WPPh₂CH=CH₂ and (OC)₅WPPh(CH=CH₂)₂] were used to construct its five possible nonchelated pentacarbonyltungsten complexes. These are the trimetallic (OC)₅WPPh[CH₂CH₂PPh₂W(CO)₅]₂ and the two pairs of constitutional isomers, (OC)₅WPPh[CH₂CH₂PPh₂]₂ and (OC)₅WPPh₂CH₂CH₂PPhCH₂CH₂PPh₂, and PPh[CH₂CH_{2 …}