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Co-Oxidative Depolymerization of CoalRosencrans, Renae 01 May 1985 (has links)
In contrast to current coal conversion technology, cooxidative depolymerization of coal is a novel approach to coal liquefaction in that the reactions are carried out under relatively mild conditions. This free radical process utilizes air or oxygen and a suitable co-oxidant (solvent) which acts as a radical and hydrogen transfer agent throughout the coal matrix. Ideally, co-oxidation would lead to the formation of hydroperoxide groups at the reactive bridging sites in the coal matrix, which upon decomposition would lead to C-C bond scission.
The effects of several variables on co-oxidation and subsequent post-treatment were investigated. Up to 49% conversion to DMF soluble products was achieved. Further enhancement of solubility is believed to be limited by the failure of hydroperoxide decomposition to lead to C-C bond scission.
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Analysis of Forms of Sulfur in CoalRuba, Gary 01 August 1987 (has links)
Methods for the determination of sulfur forms are reviewed. Each method is compared to the ASTM D 2492 standard method when data are available. The extraction of pyrites with dilute nitric acid is reviewed in detail because of its relationship to data presented in this thesis.
A new technique for the analysis of organic sulfur was developed in response to a need by the coal community for an accurate and inexpensive method. In this method nitric acid extraction is used to remove the inorganic sulfur forms and the residual coal is then analyzed for organic sulfur. Organic sulfur values obtained by this direct method show good agreement with the sulfur content in "supercleaned" coal which has had almost all mineral matter removed by physical methods. The precision of the direct analysis method Is better than that experienced when using ASTM D 2492.
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Ultraviolet Stimulated Thermoluminescent Response Characteristics of Aluminum OxideRyan, Edward, III 01 December 1976 (has links)
This investigation has demonstrated that some aluminum oxide crystals have high sensitivity and are well suited for detecting and measuring ultraviolet radiation rates significantly less than .01 µW/cm2.
The thermoluminescent glow curve, linearity of response, and fading of the crystals were determined. An action spectrum was performed to determine the relative sensitivities of several crystals in a range of wavelengths from 230 nm to 546 nm.
The sensitivity of the crystals was found to decrease as a function of exposure. \n explanation for the decrease in sensitivity due to the presence of high temperature traps is presented.
This investigation has demonstrated that certain aluminum oxide crystals exhibit ultraviolet response characteristics necessary to meet the criteria set forth by the Occupational Safety and Health Administration for the detection and measurement of low levels of ultraviolet radiation.
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Kinetic & Spectral Studies of Copper(II)-4,4',4",4'"-Tetrasulfophthalocyanine in Aqueous SolutionScholl, Stephen 01 May 1983 (has links)
The monomer-dimer equilibrium of CuTSPC4- was examined by spectral methods in aqueous solution over a total dye concentration of 2 x 10-8M to 8 x 10-7M at 24°C. The value obtained for the dimerization constant, KD,was 1.1 x 107M-1 which is smaller than literature values. However, the discrepancy is not appreciable considering the differences in the methods used and the experimental conditions of the different solutions. Spectral measurements of the dimerization constant were made at only one temperature since the spectral changes were quite small when the temperature was varied. This observation is consistent with the small heat of reaction associated with the dimerization process which has been reported in the literature for this system. A comparison of the dimerization constant of CuTSPC4- with other cations shows the following trend:
Cu2+ ≥ Ni2+ > H+ > Zn2+ ᷈ Vo2+ > Fe3+ > Co2+
The larger dimerization constants of CuTSPC4- and NiTSPC4- compared to the other tetrasulfonated phthalocyanines is attributed to the lack of axial ligand binding to these metals which enhances the dimerization process. Ligand binding studies made here and elsewhere on the CuTSPC4- and NiTSPC4- systems showed no evidence of ligand binding unlike the FeTSPC3- and CoTSPC4- systems where various ligands have been found to bind at the axial positions of these metals.
Kinetic measurements on the monomer-dimer equilibrium of CuTSPC4- in aqueous solution were made on the stopped-flow apparatus at 24°C using a total dye concentration range of 1 x 10-6 M to 1 x 10-5M. The rate constants for the formation and dissociation of the CuTSPC4- dimer are 3.24 x 106M-1s-1 and 0.27 s-1 , respectively. Activation parameters could not be obtained due to the small spectral changes which occur at different temperatures and hence cannot be measured on the stopped-flow apparatus. The kinetic data show that the formation and dissociation rate constants of CuTSPC4- in aqueous solution is similar to those of NiTSPC4- and VOTSPC4- systems. All these tetrasulfonated metallophthalocyanine systems show no evidence of ligand binding to the central metal ion and have similar dimerization constants. On the other hand the lower dimerization constant of CuTSPC4- relative to these systems can be attributed to the smaller rate constant associated with the formation of the dimer. The presence of axial ligands on the central metal ion is believed to inhibit the formation of the dimer in CoTSPC4-.
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Determination of the Time Delay in the Arrival of Jovian Signals at Opposite Ends of a Long Baseline Fringe Synthesis InterferometerScott, Roger 01 July 1970 (has links)
In order to determine the size of the decametric sources, the technique of long baseline radio interferometry is being employed. The University of Florida at Gainesville is a pioneer in this field. In 1964, T. D. Carr introduced the procedure of recording the signals received at each end of an interferometer on magnetic tape and comparing the re-corded signals at a later time. This eliminated the necessity for transmission lines over the length of the baseline, allowing greater separation to attain higher resolution.
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Behavior of Chlorine & Sulfur During Coal Pyrolysis & CombustionShao, Dakang 01 December 1992 (has links)
The behavior of chlorine and sulfur in Illinois coals and during pyrolysis and combustion their forms in the coals were evaluated by combined Thermogravimetry/Fourier Transform Infrared Spectroscopy/ Ion Chromatography (TG/FTIR/IC) techniques. It was found that more than 90% of chlorine in Illinois coals was liberated as HC1 gas during pyrolysis and combustion in the temperature range of approximately 3000 - 600°C, with the amount reaching the maximum around 440°C. Similarity of the HC1 and NH3 release profiles during pyrolysis of IBC-109 indicates that the forms of chlorine in coal is associated closely with the forms of nitrogen, and that the chlorine may be bonded to the basic nitrogen-sites on the inner walls of coal micropores.
Approximately more than 60% of the total sulfur in the coals was evolved mainly as SO2 and COS in the 250°C-750°C range during combustion. Except for SO2 and COS, H2S was a major gaseous sulfur-containing product observed during coal pyrolysis. The release rates of the gaseous sulfur species reached several peaks at some points within the temperature ranges during pyrolysis and combustion, and these peaks were due to the emissions of several types of the sulfur in different forms present in the coals.
The effect of chlorine removal from high chlorine Illinois coal on its reactivity was also investigated by TG/FTIR/IC techniques. The weight loss behavior of the leached coals was significantly different from that of the raw coal (IBC-109) during combustion. The release profiles of gaseous chlorine (HCl) and sulfur species (SO2 and COS) of the leached coals are significantly different from those of the raw coal.
The effect of the addition of CaCO3 and Ca(OH)2 on the behavior of chlorine and sulfur during combustion of high chlorine and medium sulfur Illinois coal was investigated by TG/FTIR/IC techniques. Thermogravimetry showed no significant difference in weight loss between IBC-109 and its sorbent mixtures, Coal-CaCO3 and Coal-Ca(OH)2. However, addition of 5% Ca(OH)2 or 6% CaCO3 to IBC-109, may not only reduce emission of chlorine by about 48% or 20%, but also reduce emission of total sulfur by about 68% or 52% during combustion.
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Determination of Energy Levels & Oscillator Strengths of 2% Nd:Y2O3Shao, Kung-Chuan 01 December 1979 (has links)
The absorption spectrum of 2% Nd:Y2O3 has been obtained at room termperature. It has been used to determine the crystalline energy levels.
Through counting the number of Stark components, degeneracies have been determined for oscillator strength calculations.
Overlapping absorption lines were analyzed into their components.
Oscillator strengths have been measured for those well-identified and analyzed transitions in the variable and near ultraviolet regions of the 2% Nd:Y2O3 absorption spectrum.
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Development of HPLC-EC Methodology & Its Use in the Determination of the Daily Pattern of Brain Octopamine Levels in Leucophaea MaderaeSiddiqui, Maya 01 May 1992 (has links)
A solid phase extraction technique was developed to aid in removing interfering substances from the cockroach brain extract. Quantitative analysis of octopamine was subsequently achieved by HPLC with amperometric electrochemical detection. The procedure affords 80 to 100 percent recovery of octopamine. The presence of octopamine in brain extract was confirmed by GC-MS.
The daily pattern of brain octopamine levels in cockroach Leucophaea maderae was investigated using the HPLC-EC assay procedure. It was concluded that the concentration of brain octopamine in the cockroach L. maderae does not exhibit daily rhythm.
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An Analysis of a New Partizan Game Using Combinatorial TechniquesSnodgrass, James, III 01 July 1979 (has links)
John Horton Conway's combinatorial game theory was applied to a new partizan game with a complete analysis as the result. Mathematical values were assigned to the countably infinite number of positions in the game. Direct computation of the first eight values and extension via the Principle of Mathematical Induction made the assignments possible.
Examination of these values (which repeat with period 2) shows that the game, played on a strip of squares, can be won by the first player if the strip is of odd length and can be won by the second player if the strip is of even length. Further examination of the values leads to a completely general symmetry strategy for the first and second player wins in the appropriate cases.
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The Low-Temperature Pyrolysis of a Nitrated North Dakota LigniteSpears, Dennis 01 May 1984 (has links)
Low-temperature pyrolysis is the thermal degradation of coal in an inert atmosphere at temperatures below 700°C. Coal pyrolysis is well-studied, being a complex mix of many reactions. Pyrolysis is affected by changes in many different process variables, such as temperature, pressure and heating rate. Low-temperature pyrolysis is an old and well-studied process.
Chemical pretreatments have been used to beneficiate conversion processes, inducln pyrolysis. Nitration has not been one of them. Pyrolyzing a nitrated coal would, hopefully, rapidly devolatilize the coal and break up the matrix into more commercially usable products. The nitration procedure developed by The Standard Oil Company minimizes oxidation of the coal, reducing the adverse affects of such a treatment.
Lignite, both untreated and nitrated at two different levels, was pyrolyzed at temperatures of 250, 425 and 600°C, helium pressures of 0, 500, and 1000 psig, with sample masses of about 1, 3, and 5 grams. Residence times of 0.5, 1.5 and 2.5 hours were used. The yields of volatiles (gas), oils,asphaltenes, preasphaltenes, and char were monitored. The char was subjected to elemental analysis, and the pyrolysis gas was analyzed by gas chromatography.
Nitration does not appear to improve lignite lowtemperature pyrolysis substantially. Nitrated and untreated lignites the char nitrogen content is hydrogen content of the char not cause the expected rapid produce similar char and oil yields. After nitration raised substantially, and the is decreased. Nitration does devolatilization, nor does it substantially improve the quality of the off-gas. Nitration does de-ash and desulfurize the coal.
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