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  Partner: UNT Libraries
 Degree Discipline: Chemistry
 Collection: UNT Theses and Dissertations
Synthesis of Gold Complexes From Diphosphine Ligands and Screening Reactions of Heterocyclic Acetylacetonato (Acac) Ligands with Transitional Metal Complexes

Synthesis of Gold Complexes From Diphosphine Ligands and Screening Reactions of Heterocyclic Acetylacetonato (Acac) Ligands with Transitional Metal Complexes

Date: August 2015
Creator: Nyamwihura, Rogers
Description: Syntheses of diphosphine gold (I) complexes from gold THT and two ligands, 4, 5-bis (diphenylphosphino)-4-cyclopenten-1, 3-dione (BPCD) and 2,3-bis(diphenylphosphino)-N-phenylmaleimide (BPPM), were done separately. The reactions happened under ice conditions followed by room temperature conditions and produced two diphosphine gold (I) complexes in moderated yield. Spectroscopic results including nuclear magnetic resonance (NMR) and X-ray crystallography were used to study and determine the structures of the products formed. Moreover, X-rays of all newly synthesized diphosphine gold (I) complexes were compared with the known X-ray structures of other phosphine and diphosphine gold (I) complexes. There were direct resemblances in terms of bond length and angle between these new diphosphine gold (I) complex structures and those already published. For instance, the bond lengths and angles from the newly prepared diphosphine gold (I) complexes were similar to those already published. Where there were some deviations in bond angles and length between the newly synthesized structures and those already published, appropriate explanation was given to explain the deviation. Heterocyclic ligands bearing acetylacetonate (ACAC) side arm(s) were prepared from ethyl malonyl chloride and the heterocyclic compounds 8-hydroxylquinoline, Syn-2-peridoxyaldoxime, quinoxalinol and 2, 6-dipyridinylmethanol. The products (heterocyclic ACAC ligands) from these reactions were screened with transition metal carbonyl compounds ...
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Applications of Single Reference Methods to Multi-Reference Problems

Applications of Single Reference Methods to Multi-Reference Problems

Date: May 2015
Creator: Jeffrey, Chris C.
Description: Density functional theory is an efficient and useful method of solving single-reference computational chemistry problems, however it struggles with multi-reference systems. Modifications have been developed in order to improve the capabilities of density functional theory. In this work, density functional theory has been successfully applied to solve multi-reference systems with large amounts of non-dynamical correlation by use of modifications. It has also been successfully applied for geometry optimizations for lanthanide trifluorides.
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Computational Studies of C–h/c–c Manipulation Utilizing Transition Metal Complexes

Computational Studies of C–h/c–c Manipulation Utilizing Transition Metal Complexes

Date: May 2015
Creator: Pardue, Daniel B.
Description: Density Functional Theory (DFT) is an effective tool for studying diverse metal systems. Presented herein are studies of a variety of metal systems, which can be applied to accomplish transformations that are currently difficult/impossible to achieve. The specific topics studied utilizing DFT include: 1) C–H bond activation via an Earth-abundant transition metal complex, 2) C–H bond deprotonation via an alkali metal superbase, 3) and amination/aziridination reactions utilizing a CuI reagent. Using DFT, the transformation to methanol (CH3OH) from methane (CH4) was examined. The transition metal systems studied for this transformation included a model FeII complex. This first-row transition metal is an economical, Earth-abundant metal. The ligand set for this transformation includes a carbonyl ligand in one set of complexes as well as a phosphite ligand in another. The 3d Fe metal shows the ability to convert alkyls/aryls to their oxidized counterpart in an energetically favorable manner. Also, “superbasic” alkali metal amides were investigated to perform C—H bond cleavage. Toluene was the substrate of interest with Cs chosen to be the metal of interest because of the highly electropositive nature of this alkali metal. These highly electrophilic Cs metal systems allow for very favorable C—H bond scission with a toluene substrate. ...
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Quantitative Chemical Analysis of the Soils of Erath County, Texas

Quantitative Chemical Analysis of the Soils of Erath County, Texas

Date: June 1938
Creator: Barnes, Benjamin F.
Description: A chemical analysis of representative samples of Windthorst sand, Denton sand, and Denton clay has been made, and this analysis shows that their composition has a strict correlation with respect to their geological origins. The analyses of the different soils have shown the Windthorst sand to be highly deficient in all of the essential elements, whereas the Denton sand is deficient in only one; namely, phosphorus. The analysis of the Denton clay showed it to be highly fertile. From the consideration of the pH and the lime content, it has been determined to some extent what crops will grow in each of the soils.
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A Study of the Quantitative Determination of Nitrogen

A Study of the Quantitative Determination of Nitrogen

Date: June 1938
Creator: Willard, John Gordon
Description: The purpose of this paper is to investigate the Kjeldahl method of nitrogen determination.
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Studies of L-Asparaginase from Lactobacillus Plantarum

Studies of L-Asparaginase from Lactobacillus Plantarum

Date: May 1979
Creator: Nalepka, Edward R.
Description: This study is concerned with the regulation of Lasparaginase (LA) in the cell-free crude extracts from Lactobacillus plantarum (ATCC8014). A previously reported finding that adenosine triphosphate (ATP) inhibits the action of LA in crude extracts was confirmed. The study was extended to include the mono-, di-, and triphosphates of adenosine, guanosine, cytidine, and uridine. These compounds were also shown to inhibit LA activity. These andother studies revealed that LA appears to be an allosteric type enzyme exhibiting positive homotropism with respect to substrate and heterotropism with respect to the nucleotides tested. The regulation of LA activity by high energy compounds, when coupled with asparagine synthetaseL suggests a relationship between amide synthesis-amide degradation and the energy levels of the cell.
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The Correlation Between Carbon-Proton and Proton-Proton Coupling Constants

The Correlation Between Carbon-Proton and Proton-Proton Coupling Constants

Date: December 1975
Creator: Seiwell, Ruth R.
Description: The correlation between the carbon-proton and proton-proton coupling constants have been studied in various 13 systems. Isocrotonic acid-carboxyl-3C, crotonic acid- 13 13 carboxyl-3C, and 5-norbornene-2-carboxylic acid-carboxyl-3C- 1,5,6,7,7-hexachloro were synthesized and their carbonproton coupling constants were analyzed. Nmr studies showed the magnitudes of the carbon-proton coupling constants to correlate well with analogous protonproton coupling constants, although the values of the couplings were larger than expected. The geminal olefinic couplings were considerably larger than all other couplings, but they were self-consistent. The signs of the carbon-proton coupling constants also were in agreement without exception with the signs of analogous proton-proton coupling constants.
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Magnetic Properties of Metal(II) Schiff Base Complexes

Magnetic Properties of Metal(II) Schiff Base Complexes

Date: May 1976
Creator: Hines, Mary Katherine
Description: Ligands prepared from various combinations of aldehydes and ketones with the appropriate aminealcohol were complexed with cupric acetate monohydrate. The complexes with O,NO or N,N,O donor atoms were synthesized to study the influences of the ligand on molecular structure, spin-spin interaction, and on the value of the exchange integral. The magnetic data indicated that of the eight Cu(II) complexes discussed, two behaved differently from known analogous compounds. Cu (benzoylacetone :ethanolamine) was compared to Cu(acac:ethanolamine), and Cu(pyrr:oaminophenol) was compared to Cu(acac:o-aminophenol). Each pair of complexes was postulated to have the same molecular structure. The synthesis and characterization of Mn(pyrr:oaminophenol) 2H2 is also discussed. The following physical data were collected and discussed: elemental analysis, melting point, molecular weight, infrared spectra, electronic spectra, and magnetic susceptibility.
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Chemical Cleavage of Human Phosphoglucose Isomerase at Cysteine

Chemical Cleavage of Human Phosphoglucose Isomerase at Cysteine

Date: December 1975
Creator: Conn, Worth R.
Description: The present study has resulted in the development of a procedure for the specific chemical fragmentation of human phosphoglucose isomerase into a minimal number of peptides. A two-cycle procedure for cleaving the protein with 2-nitro-5- thiocyanobenzoic acid results in four primary peptides and three overlap peptides. The peptides can be readily separated on the basis of their size by using sodium dodecyl sulfate polyacrylamide gel electrophoresis. Preliminary peptide alignments have been considered, and amino acid analyses have been performed. End-terminal analyses of the enzyme revealed a carboxyl terminal sequence of Asp-Val-Gln and a blocked amino terminus. The cysteine cleavage procedure provides an excellent method for the identification and location of specific genetic mutations of human phosphoglucose isomerase.
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Denaturation, Renaturation and Other Structural Studies on Phosphoglucose Isomerases

Denaturation, Renaturation and Other Structural Studies on Phosphoglucose Isomerases

Date: December 1975
Creator: Young, Clint D.
Description: Structural properties of phosphoglucose isomerases isolated from a variety of species have been compared by peptide fingerprinting, predicted amino acid sequence homologies and by denaturation and renaturation studies. The enzymes are more readily denatured in guanidinium chloride than in urea, and the isomerase isolated from yeast is more stable toward acid pH than the rabbit muscle enzyme. The rates of guanidinium chloride-induced denaturation are markedly increased by ionic strength and decreased by substrates, competitive inhibitors or glycerol. The enzyme can be renatured, but only in the presence of glycerol. The renaturation process is dependent on protein concentration and temperature and provides a method for the formation of mixed species heterodimers.
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Copper (II) Complexes with Deprotonated N-(2-hydroxyethyl)ethylenediamine

Copper (II) Complexes with Deprotonated N-(2-hydroxyethyl)ethylenediamine

Date: December 1975
Creator: Miller, Toney G.
Description: This thesis reports the synthesis and characterization of two new copper(II) halide complexes with deprotonated N-(2-hydroxyethyl)ethylenediamine behaving as a bidentate. The magnetic properties of the new copper(II) complexes were studied from room temperature to liquid nitrogen temperatures. The magnetic data show that both complexes exhibit antiferromagnetic interactions with a singlet ground state and a thermally accessible triplet excited state. Magnetic data and infrared spectra indicate the complexes are halogenbridged. Deprotonation at an amine nitrogen is based on the presence of a hydroxyl stretching band in the infrared spectra. Electronic spectra and infrared spectra indicate the complexes are square planar. Elemental analyses, infrared spectra, electronic spectra, electron spin resonance spectra, and magnetic data are reported and discussed.
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The Electronic Spectrum of (-)-S-(pS)-2,5,3',6'-Tetrahydro-2.2-Paracyclophane-2-Carboxylic Acid

The Electronic Spectrum of (-)-S-(pS)-2,5,3',6'-Tetrahydro-2.2-Paracyclophane-2-Carboxylic Acid

Date: May 1980
Creator: Hall, Lindsey
Description: A new, efficient route was used in the synthesis of [2.2]-paracyclophane-2-carboxylic acid. The acid as then resolved and the Birch reduction performed yielding one enantiomer of tetrahydro-[2.2]-paracyclophane-2-carboxylic acid. The ultraviolet spectrum of tetrahydro-[2.2]-paracyclophane- 2-carboxylic acid in isopenthane shows one absorption at 206 nm (Emax = 5,271). There are three bands observed in the circular dichroism spectrum in isopentane at 236 nm ([] = 1.8 X 104), 201 nm ([0] = -16 X 104) and a positive band indicated below 180 nm but not observed. The bands were assigned and possible reasons for the occurrence of a mr'r* transition at unexpectedly long wavelengths are discussed.
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The Chlorination of Amino Acid in Municipal Waste Effluents

The Chlorination of Amino Acid in Municipal Waste Effluents

Date: July 1977
Creator: Burleson, Jimmie L.
Description: In model reaction systems to test amino acids in chlorinated waste effluents, several amino acids were chlorinated at high chlorine doses. (2000-4000 mg/1). Amino acids present in municipal waste effluents before and after chlorination were concentrated and purified using cation exchange and Chelex resins. After concentration and cleanup of the samples, the amino acids were derivatized by esterification of the acid functional groups and acylation of the amine groups. Identification and quantification of the amino acids and chlorination products was carried out by gas chromatography/mass spectrometry, using a digital computer data system. Analysis of the waste products revealed the presence of new carbon-chlorine bonded derivatives of the amino acid tyrosine when the effluents were treated with heavy doses of chlorine.
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The Determination of Organic-Bound Chlorine Levels in Municipal Wastewaters After Treatment with Heavy Chlorine Doses

The Determination of Organic-Bound Chlorine Levels in Municipal Wastewaters After Treatment with Heavy Chlorine Doses

Date: May 1976
Creator: Smith, Garmon B.
Description: The development of an analytical method for the determination of total organic-bound chlorine (TOCl) produced during the chlorination of municipal wastewater effluents is presented. Sewage effluent from the Denton, Texas municipal treatment plant was chlorinated at high chlorine doses (1000 - 4000 ppm), as well as typical treatment levels. Chlororganics present in the wastewater, before and after chlorination, were concentrated by adsorption on Amberlite XAD-2 macroreticular resin, followed by elution with diethyl ether. After concentration, the extracts were analyzed for TOC1 by microcoulometry. Analysis of wastewater extracts revealed the production of substantial amounts of new chlorinated organics when effluents were treated with chlorine. The method shows good precision and estimated accuracy is favorable.
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Regulation of Pyridine Nucleotide Metabolism in Saccharomyces cerevisiae

Regulation of Pyridine Nucleotide Metabolism in Saccharomyces cerevisiae

Date: May 1976
Creator: Ting, Haung-yu
Description: The levels of total nicotinamide adenine dinucleotide (NAD) and nicotinamide adenine dinucleotide phosphate (NADP), and their redox states were determined as the function of growth in S. cerevisiae. Cells growing in a medium containing 0.8% glucose exhibit two phases of exponential growth, utilizing glucose and ethanol, respectively. The NAD pool is 50% reduced during both stages of growth while the NADP pool is 67% reduced in glucose growth and 48% reduced in ethanol growth. The NAD/NADP ratio is constant during growth on glucose and a two-fold increase in the NAD/NADP ratio occurs upon exhaustion of glucose. The increased ratio is maintained during growth on ethanol. This alteration in the regulation of the relative levels of NAD and NADP may be due to a change in the regulation of NAD kinase and/or NADP phosphatase activities. These changes may be related to the redox state of the NADP pool.
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Structure, Energetics and Reactions of Bisketenes: An Ab Initio and Density Functional Theory Study

Structure, Energetics and Reactions of Bisketenes: An Ab Initio and Density Functional Theory Study

Date: December 1997
Creator: Palmer, Prem
Description: The effect of varying substituents on structure and energies of bisketenes was studied using ab initio methods. Effect of substituents on ring closing reaction of bisketenes to the corresponding cyclobutenediones was also studied using ab initio methods. One or two of the following substituents were used to study the effect of varying substituents: BH2, CH3, NH2, OH, F, AlH2, SiH3, PH2, SH, Cl. Studies were done at the Hartree-Fock (HF), Møller-Plesset (MP2), and Density Functional Theory (B3LYP) levels of theory using the 6-31G* basis set.
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Reduction Pathways in Cyclopentadienyl Rhenium Dicarbonyl Dibromide Deriviatives and Indenyl Rhenium Tricarbonyl: Synthesis, Structure, and Reactivity of Anionic Cyclopentadienyl Rhenium Complexes. Ring Attack vs. Metal-Halogen Exchange

Reduction Pathways in Cyclopentadienyl Rhenium Dicarbonyl Dibromide Deriviatives and Indenyl Rhenium Tricarbonyl: Synthesis, Structure, and Reactivity of Anionic Cyclopentadienyl Rhenium Complexes. Ring Attack vs. Metal-Halogen Exchange

Date: December 1989
Creator: Lee, Sang Woo, 1952-
Description: The reactions of diagonal and lateral Cp'Re(CO)2Br2 (where Cp' = n5-C5H5, n5-C5Me5) and (n5-CgH7)Re(CO)3 with reducing agents have been examined. Hydride reduction at -78 °C is observed to occur at the Cp ring in both CpRe(CO)2Br2 isomers, affording a thermally unstable [(n4 -C5Hg)Re(CO)2Br2]- complex. The product of hydride ring attack has been characterized by low-temperature IR and 1H NMR measurements in addition to 13C NOE and heteronuclear 2D NMR measurements. Reaction of lateral CpRe(CO)2Br2 with either MeLi or PhLi affords both Cp-ring attack and metalhalogen exchange, [CpRe(CO)2Br]- (1) while t-BuLi reacts exclusively via metal-halogen exchange. diag-CpRe(CO)2Br2 reacts with the above lithium reagents to yield the same metal-halogen exchange anion. Analogous reactions using diag- and lat-Cp*Re(CO)2Br2 (where Cp* = n5-CgMe5) afford only the corresponding rhenium metal-halogen exchange anion, [Cp*Re(CO)2Br] (2). The molecular structures of 1-[Li/15-Crown-5] and 2-PPP were established by X-ray crystallography. 1-[Li/15-Crown-5] crystallizes in the monoclinic space group P21 with a = 10.860(4) A, b = 13.116(5) A, c = 7.417(3) A, B = 105.26(3)0, V = 1018.7(3) A3 , and Z = 2. 2-PPP crystallizes in the orthorhombic space group Pbca with a = 20.646(5) A, b = 17.690(5) A, c = 17.553(3) A, and z = 8. Solution ...
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Thermal and Flash Photolysis Studies of Ligand-Exchange Reactions of Substituted Metal Carbonyl Complexes of Cr and Mo

Thermal and Flash Photolysis Studies of Ligand-Exchange Reactions of Substituted Metal Carbonyl Complexes of Cr and Mo

Date: May 1989
Creator: Awad, Hani H. (Hani Hanna)
Description: Thermal and flash photolysis studies of ligand-substitution reactions of cis-(pip)(L)M(CO)_4 by L' (pip = piperidine; L, L' = CO, phosphines, phosphites; M = Cr, Mo) implicate square-pyramidal [(L)M(CO)_4], in which L occupies a coordination site in the equatorial plane, as the reactive species. In chlorobenzene (= CB) solvent, the predominant species formed after flash photolysis and a steady-state intermediate for the thermal reaction is cis—[(CB)(L)M(CO)_4], for which rates of CB-dissociation increase with increasing steric demands of coordinated L. Rates of CB-dissociation from trans-[(CB)(L)M(CO)_4] intermediates, formed after photolysis but not thermally, exhibit no observable dependence on the steric properties of the coordinated L.
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Kinetics Studies of Substituted Tungsten Carbonyl Complexes

Kinetics Studies of Substituted Tungsten Carbonyl Complexes

Date: August 1989
Creator: Wang, I-Hsiung, 1950-
Description: Thermal reactions and flash photolysis are used to study the olefin bond-migration promoted by tungsten carbonyls. Substitution of piperidine (pip) by 2- allylphenyldiphenylphosphine (adpp) in the cis-(pip)(η^1- adpp)W(CO)-4 complex was investigated, and no olefin bond-migration was observed. This suggests that a vacant coordinated site adjacent to the coordinated olefin is an essential requirement for olefin bond rearrangement. The rates of olefin attack on the photogenerated coordinatively unsaturated species, cis-[(CB)(η^1-ol- P)W(CO)-4] (CB = chlorobenzene, p-ol = Ph-2P(CH-2)-3CH=CH-2; n = 1-4) were measured. Kinetics data obtained both in pure CB and in CB/cyclohexane mixtures support a dissociative mechanism in which the W-CB bond is broken in the transition state. In contrast to results observed in studies of other related systems, no olefin bond-migration is noted. This observation is attributed to P-W coordination at all stages of the reaction, which precludes formation of a reactive intermediate containing a vacant coordination site adjacent to a P-ol bond.
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Studies of Nitrogen-containing Compounds Having Pyrethroid-like Bioactivity

Studies of Nitrogen-containing Compounds Having Pyrethroid-like Bioactivity

Date: August 1989
Creator: Lee, Jimmy Jing-Ming, 1955-
Description: During recent years most of the successful developments in pyrethroids have been primarily concerned with structural or compositional variations. As a part of our continuing interest in pyrethroid insecticides, nitrogen-containing compounds having pyrethroid-like structures were synthesized. Seven prolinate compounds, N-(substituted)-phenyl-prolinates and N-carbobenzoxy-prolinates were coupled with known pyrethroid alcohols. These structural variations which "locked in" a specific conformation between the nitrogen and chiral a-carbon in the acid moiety of fluvalinate were studied to determine the influence of certain conformations on insecticidal toxicity. The toxicity data for the prolinate compounds showed intermediate mortality against nonresistant cockroaches. It was concluded that the conformation imposed by the proline ring portion of the esters was probably close to the favored conformation for interaction of fluvalinate-like pyrethroids with the insect receptor site. A second series of nitrogen-containing compounds, twenty-five carbamate esters resulting from the condensation of N-isopropyl-(substituted)-anilines and N-alkyl-(substituted)-benzylamines with appropriate pyrethroid alcohols were studied for insecticidal activity. These studies were conducted on pyrethroid-susceptible houseflies. Some of the carbamate esters exhibited high toxicity when synergized by piperonyl butoxide. For example, the toxicity ( LD 50 ) of O-a-cyano-3-phenoxyfaenzyl-N-a,a-dimethyl-4-bromo-benzyl carbamate was 0.012 ug/g, which is significantly greater than that reported for the potent pyrethroid, fenvalerate. Correlations of ...
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Thermal Reactions of Four-Membered Rings Containing Silicon or Germanium

Thermal Reactions of Four-Membered Rings Containing Silicon or Germanium

Date: December 1988
Creator: Namavari, Mohammad, 1950-
Description: The synthesis of E- and Z-1,1,2,3-tetramethylsilacyclobutanes is described. Pyrolysis of either isomer at 398.2 °C provides the same products but in different amounts: propene, E- and Z-2-butene, allylethyldimethylsilane, dimethylpropylsilane, the respective geometric isomers, 1,1,2,3,3-pentamethyl-1,3-disilacyclobutane, 1,1, l-ethyldimethyl-2,2,2-vinyldimethyl-disilane and E- and Z-1,1,2,3,3,4-hexamethyl-1,3-disilacyclobutane. Mechanisms involving di- and trimethylsilenes are described for disilane formation and rate constants of the elementary steps for the fragmentation reactions are reported. Photochemically generated dimethylsilylene in the hydrocarbon solution inserts into the cyclic Ge-C or Si-C bonds of 1,1-dimethylgerma- or silacyclobutane to produce 1-germa-2-sila- or 1,2-disilacyclopentane. The relative reactivities of 1,1-dimethylgerma- and silacyclobutanes toward the dimethylsilylene have been determined. The carbenoid resulting from the cuprous chloride catalyzed decomposition of diazomethane at 25 °C in cyclohexane reacts with 1,1-dimethylgermacyclobutane to give, surprisingly 1,1,5,5-tetramethyl-1,5-digermacyclooctane as the major product. The reactions of the carbenoid with 1,1-dimethylsilacyclobutane are described. The kinetics of gas phase thermal decomposition of 1,1-dimethylgermacyclobutane has been studied over the temperature range, 684 - 751 K at pressures near 14 Torr. The Arrhenius parameters for the formation of ethylene are k_1 (s^-1) = 10^(14.6 ± 0.3) exp (62.7 ± 2.9 kcal mol^-1/RT) and those for the formation of propene and cyclopropane are k_2 (s^-1) = 10^(14.0 ± 0.1 ) exp ...
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Intramolecular [2+2] Cycloadditions of Phenoxyketenes and Intermolecular [2+2] Cycloadditions of Aminoketenes

Intramolecular [2+2] Cycloadditions of Phenoxyketenes and Intermolecular [2+2] Cycloadditions of Aminoketenes

Date: May 1989
Creator: Gu, Yi Qi
Description: One objective of this study was to explore the intramolecular [2+2] cycloadditions of phenoxyketenes to carbonyl groups with isoflavones and benzofurans as target compounds. The other objective was to investigate the eyeloaddition reactions of rarely studied aminoketenes. The conversion of 2-(carboxyalkoxy)benzils to the corresponding phenoxyketenes leads to an intramolecular [2+2] cycloaddition to ultimately yield isoflavones and/or 3-aroylbenzofurans. The product distributions are dependent upon the substitution pattern in the original benzil acids. The initial cycloaddition products, β-lactones, are isolated in some instances while some β-lactones spontaneously underwent decarboxylation and could not be isolated. The ketene intermediate was demonstrated in the intramolecular reaction of benzil acids or ketoacids with sodium acetate and acetic anhydride. It is suggested that sodium acetate and acetic anhydride could serve as a source for the generation of ketenes directly from certain organic acids. The treatment of ketoacids with acetic anhydride and sodium acetate provides a simpler procedure to prepare benzofurans than going through the acid chloride with subsequent triethylamine dehydrochlorination to give the ketenes. N-Ary1-N-alkylaminoketenes were prepared for the first time from the corresponding glycine derivatives by using p-toluenesulfonyl chloride and triethylamine. These aminoketenes underwent in situ cycloadditions with cyclopentadiene, cycloheptene and cyclooctenes to yield only the ...
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Pyrolysis Capillary Chromatography of Refuse-Derived Fuel and Aquatic Fulvic Acids

Pyrolysis Capillary Chromatography of Refuse-Derived Fuel and Aquatic Fulvic Acids

Date: December 1989
Creator: Haj-Mahmoud, Qasem M. (Qasem Mohammed)
Description: Pyrolysis-capillary gas chromatography combined with FID, ECD and MS detection were used to characterize refuse-derived fuel and aquatic fulvic acids. Different pyrolysis methods and programs were evaluated. Pyrolysis temperatures of 700-800°C produced the strongest signal for organics present in RDF and fulvic acid. Cellulose and fatty acids pyrolyzates were identifiable by GC-MS following preparative pyrolysis fractionation. At organic chloride content of 0.023%, only three halogenated compounds were detected in the GC-MS of the fractions. None of the priority pollutants were detected at lower detection limit of 0.72 to 24 mg/ kg RDF. Selective solvent extraction improves the reproduciblities of the technique and allows the detection of polymeric structures. Pyrograms of polyvinyl chloride and regular typing paper showed some common peaks that are present in the RDF pyrogram. About 65% of the peaks in the RDF pyrogram might be of paper origin. The organic chloride content of the RDF was evaluated by ion chromatography of the trapped pyrolyzates in 2% NaOH trap and it was found to be 221 mg Cl/ kg dry RDF. Pyrolysis conditions and temperature programs for FA were systematically evaluated. Samples included purified FA, methylated FA and HPLC separated fractions. Characteristic pyrograms were developed. Profiles of benzene, ...
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Molecular Dynamics in the Liquid Phase by FT-NMR, FT-IR and Laser Raman Lineshape Analysis

Molecular Dynamics in the Liquid Phase by FT-NMR, FT-IR and Laser Raman Lineshape Analysis

Date: August 1988
Creator: Chen, Fu-Tseng Andy
Description: Nuclear magnetic resonance (NMR) provides a convenient probe for the study of molecular reorientation in liquids because nuclear spin-lattice relaxation times are dependent upon the details of molecular motion. The combined application of Raman and Infrared (IR) lineshape analysis can furnish more complete information to characterize the anisotropic rotation of molecules. Presented here are the studies of NMR relaxation times, together with Raman/IR Mneshape analysis of the solvent and temperature dependence of rotational diffusion in 1,3,5-tribromobenzene and 1,3,5-trifluorobenzene. In these experiments, it was found that the rotational diffusion constants calculated from Perrin's stick model were two to three times smaller than the measured values of D, and D,,. Similarly, rotational diffusion constants predicted by the Hu-Zwanzig slip model were too large by a factor of 2. Application of the newer Hynes-Kapral-Weinberg model furnished rotational diffusion constants that were in reasonable agreement with the experimental results. The vibrational peak frequencies and relaxation times of the isotropic Raman spectra of the υ1 modes of CD2Br2 and CHBr3 were studied in solution. The frequency shifts in non-interactive solvents were explained well on the basis of solution variations in the dispersion energy. In Lewis bases, the displacements were in some, but not all, cases ...
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