The redox potentials of [Fe(CpSMe2)2]2+ (CpSMe2= dimethysulfoniumcyclopentadienflide), [Ni(CpSMe2)2]2+, [Co(CpSMe2)2]2+, [Mn(CpSMe2)2]2+, (CpPPh3)HgBr2 (CpPPh3= triphenylphosphoniumcyclopentadienylide), (CpPPh3)HgCl2, and MoPC (PC = phthalocyanine) were examined using cyclic voltammetry (CV). The experimentation was carried out in a temperature controlled environment. With the exception of the mercury and molybdenum complexes, the solvent system consisted of 15 milliliter mixture of acetonitrile and water. Due to the solubility problems of the mercury bromide complex, dimethylformamide (DMF) was used as the solvent. Pure acetonitirile was used for the mercury chloride and molybdenum complexes. The emphasis of this research was directed towards the iron complex. Its complimentary pure metallocene FeCp2(Cp = cyclopentadiene) is well characterized, thereby permitting a comparison of the two complexes. The iron sulfonium ylide complex was found to have lower redox potentials. This supports the anticipated effect of the added dimethylsulfonium (SMe2) group.

The application of anodic stripping voltammetry (ASV) to the determination of several trace metals in coal ash was studied. An ashing and ash digestion method was developed which limited the total salt and acid concentration of the analyte solutions, a necessary step for routine analysis. The simultaneous determination of cadmium, copper, lead, and zinc in eight Pennsylvania State University Coal Bank Samples and in the National Bureau of Standards SRM 1632a coal sample were made. Chromium was separated from the prepared coal ash solutions and determined independently in the form of chromate(VI). All values determined by ASV methods were in good agreement with those determined by auomic absorption spectrophotometry. There was also good agreement between the anodic stripping voltammetry values and those reported for the NBS 1632a coal sample, and most of the values reported for the Pennsylvania State University coal samples.

Oxidation of heavy metal sulfides is a thermodynamically spontaneous process. Because of this, metal sulfides in the presence of oxygen are not stable. Currently there are over 100 streams and rivers, within the U.S., contaminated with heavy metal mine drainage; therefore an approved method of restoration is necessary. Precipitation of heavy metals as sulfides using H2S as a reductant has been favorably reviewed as a restorative technique to clean up mining areas. However, using this technique on the laboratory scale does not prove to be a viable answer and shows strong pH dependence. In the past three years the ILI (Instrumentation and Laboratory Improvement) has awarded funding to over 50 institutions, in the U.S., for the purchase of GC/MS. Therefore, there is a great need for laboratory experiments to properly train students in this field in American universities. A strong theoretical treatment for sophomore-level students is presented within this thesis and from this, three experiments have been developed in order to educate young professionals seeking a career in the field of chemistry.

A new and relatively fast method for measuring the susceptibility of coal to spontaneous heating was studied in this work. This method is based on the ability of coal to adsorb iron(III) from aqueous solutions. The more iron taken up by the coal, the more susceptible the coal is to spontaneous heating. The relationship holds for most of the coals being analyzed during this research project and for other succeeding ones. The experimental procedures used and results obtained are discussed. A brief literature survey of other applied methods which have been studied, including a description of many factors affecting the spontaneous combustion of coal, is presented.

The effects of pyrolysis interval, ceiling temperature, heating rate and mesh size on both the pyrolysis yield and relative product distribution for two eastern oil shales (Sunbury and Cleveland) were studied. An extension of the technique of analytical pyrolysis (pyrolysis-gas chromatography) was used. This extension employed a Chemical Data System (C.D.S.) Model 382 Extended Pyroprobe and a C.D.S. Model 310 Concentrator which enabled the pyrolysis products to be collected into a trap system. After completion of a predetermined heating interval, the trap was pulse heated to 250°C and the high and low volatile components were back-flushed into the injection port of a Varian Model 3700 Gas Chromatograph and separated into the low and high molecular weight fractions respectively. Measurements of relative peak areas of the pyrogram gave the yield of the respective fractions. Samples were repeatedly pulsed to obtain intervals of up to 120 seconds at ceiling temperatures of 750° C for both shales and a cefling temperature of 550°C for the Cleveland shale. Ceiling temperatures of 550°C, 650°C, and 750°C, with an interval of 20 seconds were investigated for the Sunbury Shale only to test the concentrator system. Ramps of 10° C/min, 120°C/min, 300°C/min, 100°C/sec, and a nonlinear ramp of 600°C/sec were employed for both the Sunbury and Cleveland shales at a ceiling temperature of 500°C for an interval of 60 minutes. The 10°C/min ramp is a close approximation of the Fischer Assay conditions. Mesh sizes of -30, 30/60, 60/100, -100 were studied for the Cleveland shale only. Data was collected for each mesh size at a ceiling temperature of 650° C and an interval of 20 seconds. Carbon-hydrogen-nitrogen and thermogravimetric analyses were also performed on the spent shale. The results of the above investigation may be summarized as follows: At lower ceiling temperatures, the heating interval has to be increased in order to maintain optimum yields of product. As the ceiling temperature increases, the overall product yield increases. There is a shift in product distribution towards the high volatile fraction (lower molecular weights) with higher rates of heating and higher ceiling temperature. The optimum heating rate for the eastern oil shales studied appears to be between 120° and 300°C per minute. These experiments suggest that pyrolysis of smaller mesh samples results in a slight yield enhancement. It is also probable that the finer mesh shales are also more susceptible to oxidative aging.

A. Cyclization of ethylene oxide in the presence of transition metal salts was studied. Several reactions with different catalysts were tried and some of these reactions produced compounds which show only one sharp singlet in their NMR spectra. These products were also soluble in benzene. The solubility of potassium permanganate in this mixture suggests the presence of cyclic polyethers. In spite of the above observations, all attempts to liberate cyclic ethers from their metal complexes were unsuccessful. B. In the second project, the stereochemistry of 1,4-ditertiarybuty1- 1,4-dihydronaphthalene was elucidated using 1H and 13C NMR. For this purpose, other naphthalene and anthracene systems were used as model compounds. For cases in which no model systems were available, the angular dependence of coupling constants was used to estimate the coupling constants. The LAOCOON III computer program was implemented to produce the observed spectrum. It was determined that the dihydrobenzene ring in this molecule is nearly planar.

Polymer-supported and polymeric quinones were synthesized and evaluated in their ability to dehydrogenate ethylbenzene in the vapor phase. The polymeric quinones were found to be more useful agents for dehydrogenation than the polymer-supported quinones, probably due to the higher concentration of quinone per given mass of polymer. The factors that affected the yield of styrene using the polymeric quinone were the nature of the polymer, the space velocity in the column, and the reaction temperature. The space velocity was evaluated by holding constant the flow rate of the carrier gas and varying the concentration of ethylbenzene in the gas stream. The best yields were obtained by introducing 0.25 ml of reactant into the column every ten minutes. Using this process the yield of styrene varied from 2.73% at 200°C to 6.90% at 250°C. Both nitrogen and air were used as the carrier gas in this process, and there was no significant difference in the yield of styrene. However, the ability of air to re-oxidize the quinone or its tendency to form undesirable oxidation by-products was not evaluated. The effect on the ease of vapor-phase dehydrogenation of adding an electron-donating or an electron-withdrawing substituent to ethylbenzene was evaluated. The electrondonating substituent appeared to have little effect upon the dehydrogenation, but the electron-withdrawing substituent had a negative effect.

The Deno coal oxidation technique was investigated as a tool for the characterization of the aliphatic components of coal. This technique was applied to three high sulfur Kentucky coals:(1) No. 789673, (2) KCER 4002-Elkhorn No. 2, (3) KCER 7122-Ky. No. 12 and a low sulfur coal from Alpha Resources, Inc. Model compound investigations on toluene, ethyl benzene, propyl benzene, bibenzyl, indan and tetralin were also conducted. Different addition modes were investigated using ethyl benzene and diphenylmethane. The stability of the expected aliphatic acid products in the oxidation reagent were also investigated. The data indicated the following: Pyrite present in high sulfur coals catalyzes the decomposition of the oxidizing reagent. Complete oxidation of both coals and model compounds to CO2 and H20 was occurring. The expected aliphatic acid products were not stable in the oxidizing reagent.

Samples of four different Thai lignites were utilized to study the effects of ceiling temperature and heating rate on the overall yield and product distribution by the technique of analytical pyrolysis (pyrolysis-gas chromatography). Ceiling temperatures of 450°, 550°, 650°, 750°, 850°, and 950°C, a heating rate of 500°C/sec and pyrolysis intervals of 20 seconds were investigated. The results were reported in terms of percentage high-volatile product and low-volatile product fraction, weight-loss (% by weight), and total yield (counts per milligram). One sample which showed the highest sensitivity to changing ceiling temperature was selected to study the effect of heating rate on overall yield and product distribution. Heating rates of 500°C/sec and 100°C/sec (for an interval of 20 seconds) and 500°C/sec for one minute and 300°C/min for two minutes were employed in the study, at a ceiling temperature of 750°C. The results of the above investigation may be summarized as follows: All four samples are lignite A (rank) but give different pyrograms as a result of differences in maceral concentrations and chemical structure of each of the coals. The total yield, high-volatile product, and weight-loss increase with increasing ceiling temperatures. Heating rates in the range studied have no significant effect on the total yield and product distribution. High -volatile product yield increases with increasing pyrolysis interval because of secondary cracking reactions but the overall product yield remains essentially constant.

Numerous studies have been made in recent years on electron transfer reactions of transition metal complexes which proceed by either an inner- or an outer-sphere mechanism. However, except for the Fe(II)/ Fe(III) isotopic electron exchange system, few of the studies have been conducted in other than aqueous media. This study was undertaken to examine solvent effects on redox reactions of transition metal complexes which proceed by an outer-sphere mechanism. During this study, the electron exchange rate between the bis(2,2',2"-tripyridyl)cobalt(II) complex and the tris(2,2'-dipyridyl) cobalt(III) complex was measured in a number of nonaqueous solvents. Rate measurements were made at three or more temperatures in order to determine the activation parameters. The free energy drive for the electron transfer reaction in each solvent was evaluated from the equilibrium constant which was deternined by either spectral or kinetic methods. In the case of water, a third method was used to determine the equilibrium constant which involved measurements of the redox couple of each reactant. The results of this kinetic study are discussed in terms of the theoretical predictions of Marcus.