A 2 to 55 micron spectrum was obtained for sulfur in its three thermodynamic phases and at three temperatures covering a range of 320%. A temperature analysis was performed in order to identify the three infrared active fundamental vibrations in the Sg molecule. The analysis indicates that the infrared fundamentals are the observed bands located at 41.6 μ and 52.3 μ, which is in good agreement with the assignment of Scott, Mcullough and Kruse. Less conclusive results were found for the identification of third infrared fundamental. Intermolecular coupling in the crystal was found to have a pronounced effect on its infrared transmission spectrum. A Raman active fundamental of S_s was observed at 46.7 μ in the infrared spectra of both the crystal and liquid sulfur specimens. The identification of this band as a Raman fundamental of S_g was made from an analysis of the free S_g molecule in solution where this band did not appear. Further evidence of the strong intermolecular forces present in the crystal showed up as a shift in wavelength of the 52.3 μ band in solution to 50.6 μ in the solid state. A large number of overtone or combination bands not previously observed were found around the low frequency infrared fundamental. The extensive data collected in this experiment provided a check to the work of Scott, McCullough and Kruse. Splitting was observed in absorption bands at 41.6 μ and 52.3 μ where no splitting was seen for the 21.5 μ band. These observations seem to contradict Scott’s assignment as this assignment designated the 21.5 μ and 52.3 μ fundamentals as degenerate and the 41.6 μ infrared fundamental as non-degenerate. The bands occurring at 41.6 μ and 50.6 μ in the crystal were so intense as to seemingly rule out its application to infrared systems below 55 microns. / M. S.

The bolling film coefficients of sulfur dioxide were obtained from. experiments with an electrically heated wire submerged in a pool of sulfur dioxide liquid. A three-inch 15 Gage Nichrome V wire served as heating element in the boiling process. Electric power consumed by the wire was equal to the amount of heat transferred. Both temperatures of the wire surface and the liquid were recorded by thermocouples for the computation of the boiling film coefficients. The boiling curves of sulfur dioxide in the nucleate boiling region were obtained and plotted for pressures of 50, 60, 70, and 80 psig. The data for plotting the boiling curves are given in detail. A plot of heat flux versus the temperature difference between the boiling liquid sulfur dioxide and the surface of the heating element at different pressures is also presented. Comparisons were made with the limited information available for this boiling region. / Master of Science

Land application of anaerobically stabilized biosolids is a beneficial method of handling the solid residuals from a wastewater treatment plant. One of the main issues that restrict land application of biosolids is nuisance odors associated with biosolids. Despite its importance, few studies have been done to enhance our knowledge of odor causing processes. This study was conducted to evaluate the effects of some factors that have been thought to be linked to odor generation from biosolids. The first part of this study has looked at the role of metals, iron and aluminum in particular, in determining the odor causing processes. The results showed that iron correlated well with headspace organic sulfur odor. In general, as the iron content of sludge increased greater amounts of odorous sulfur gases were produced from dewatered biosolids cakes. Aluminum did not show any relationship with organic sulfur odors. Parameters commonly used for assessing the performance of anaerobic digesters (volatile solids reduction (VSR), residual biological activity (RBA) and effluent volatile fatty acid (VFA) content) also showed no correlation with odors. The second part of the study focused on determining the impact of anaerobic digester solids retention time (SRT) on the odor generation from dewatered biosolids cakes and also on elucidating the nature and impact of the various Extracellular Polymeric Substances (EPS) fractions on odors. The results showed that odors decreased with an increase in the anaerobic digester SRT. VSR and RBA correlated with odors; however, as only one type of sludge was assessed, the conclusions about any relationship may not be universal. The results also showed that sulfur gas generation was a function of EPS material bound to iron, again showing that iron plays an important role in odor generation from dewatered sludge cakes. The third part of the study looked at the effects of advanced digestion processes on odor generation. Digested sludge from acid/gas and temperature phased anaerobic digestion systems were analyzed in the lab. The results show that both acid/gas system and temperature phased digestion had a positive impact on odor generation from dewatered biosolids cake. Comparison of sludge from pancake shaped and egg shaped digesters showed that egg shaped digester was more efficient with regard to odor reduction. / Master of Science

The scope of supercritical fluid chromatography continues to enlarge. The use of open tublar and packed columns, nearly universal detectors and the introduction of new mobile phases make it more important. In this work sulfur hexafluoride is evaluated as a mobile phase for supercritical fluid chromatography. The separation of a model aromatic hydrocarbon mixture using different packed columns and operational parameters with UV as a detector is presented. The chromatographic properties of supercritical sulfur hexafluoride and supercritical carbon dioxide are compared under corresponding chromatographic parameters. / Master of Science

It was the intent of this investigation to determine boiling film coefficients of SO₂ in a temperature range not previously investigated. Further, a practical method of circulating liquid SO₂ and reclaiming SO₂ vapor without a compressor or pump was attained. For the range investigated the boiling film coefficients decreased with an increase in temperature difference between the boiIing SO₂ liquid and the surface of the heater. This occurred in the regime of partial nucleate boiling. Favorable comparisons were made with the limited information available for this bolling regime. It was found that the controlling film coefficient was on the steam side of the test evaporator. This was due to the comparatively large values obtained for SO₂ bolling film coefficients. Within the limits of this investigation, the overall heat transfer coefficient may be taken as approximately equal to the steam film coefficient. Much more work needs to be done in the regime of partial nucleate boiling as the available literature is far from complete. / Master of Science

No description available.

The object of this paper is to determine the optimum concentration of sulfur dioxide to be used in the commercial dehydration of the sweet potato by this process. Attention has been given to two aspects of the problem, (1) the effect of sulfur dioxide upon the extraction of water from the sweet potato by mechanical means, and (2) the effect of sulfur dioxide upon the stability of the carotene in the sweet potato over a period of several months.

Lithium-sulfur (Li-S) batteries are faced with practical drawbacks of poor cycle life and low charge efficiency which hinder their advancements. Those drawbacks are primarily caused by the intrinsic issues of the cathodes (sulfur) and the anodes (Li metal). In attempt to resolve the issues found on the cathodes, this work discusses the method to prepare a binder-free three-dimensional carbon nanotubes-sulfur (3D CNTs-S) composite cathode by a facile and a scalable approach. Here, the 3D structure of CNTs serves as a conducting network to accommodate high loading amounts of active sulfur material. The efficient electron pathway and the short Li ions (Li+) diffusion length provided by the 3D CNTs offset the insulating properties of sulfur. As a result, high areal and specific capacities of 8.8 mAh cm−2 and 1068 mAh g−1, respectively, with the sulfur loading of 8.33 mg cm−2 are demonstrated; furthermore, the cells operated at a current density of 1.4 mA cm−2 (0.1 C) for up to 150 cycles. To address the issues existing on the anode part of Li-S batteries, this work also covers the novel approach to protect a Li metal anode with a thin layer of two-dimensional molybdenum disulfide (MoS2). With the protective layer of MoS2 preventing the growth of Li dendrites, stable Li electrodeposition is realized at the current density of 10 mA cm−2; also, the MoS2 protected anode demonstrates over 300% longer cycle life than the unprotected counterpart. Moreover, the MoS2 layer prevents polysulfides from corroding the anode while facilitating a reversible utilization of active materials without decomposing the electrolyte. Therefore, the MoS2 protected anode enables a stable cycle life of over 500 cycles at 0.5 C with the high sulfur loading amount of ~7 mg cm−2 (~67 wt% S content in cathode) under the low electrolyte/sulfur (E/S) ratio of 6 μL mg−1. This translates to the specific energy and power densities of ~550 Wh kg-1 and ~300 W kg−1, respectively. Additionally, such values far exceed the electrochemical performance of the current Li-ion batteries. Therefore, the synergetic effect of utilizing the 3D CNT-S cathode and the MoS2 protected Li anode will allow the Li-S batteries to become applicable for the transportation and the large-scale energy grid applications.

Lithium-sulfur batteries (LSBs) demonstrate a potential to be the next-generation energy storage systems due to the high theoretical capacity and energy density of sulfur cathode, in addition to low-cost natural abundance, and environmentally benign characteristics of sulfur. However, the insulating nature of sulfur requires an efficient conductive and porous host material such as three-dimensional carbon nanotubes (3D CNTs) to provide efficient electron pathways and short Li-ions diffusion lengths. Therefore, the first part of this dissertation elucidates the facile and scalable approach to synthesizing free-standing 3D CNTs with varying morphologies and studying the parameters critical to high-performance CNT-sulfur (CNT-S) cathodes in LSBs. The optimized 3D CNT-S cathode in the LSB demonstrated high areal and specific capacities of 8.7 mAh cm-2 and 1387 mAh g-1 at 1.4 mA cm-2 of current density (0.1C), respectively, with a high sulfur loading amount of 6.27 mg cm-2. Additionally, LSBs with an efficient lithium polysulfide (LiPS) conversion at a very low electrolyte-to-sulfur (E:S) ratio is critical to achieving the energy density greater than 500 Wh kg-1; however, the mechanism of LiPS conversion under a low E:S ratio has yet to be well studied and understood. Therefore, in the second part of this dissertation, catalyst and solid-state electrolyte (SSE) assisted CNT-S cathodes are examined in real-time, employing in-situ Raman spectroscopy to understand further their role in enhancing LiPS conversion and sulfur utilization. This work revealed that the dual ionic and metallic phases of the catalyst, in coordination with SSE and CNTs, form a tri-junction in the cathode, enabling a typical solid-liquid-solid conversion facilitating a complete conversion of sulfur and its utilization, exhibiting superior capacity, cyclability, and energy density even at a low E:S ratio of 2. Furthermore, electrochemical and in-situ experiments from this work confirm that at an E:S ratio of 2, the cathode is in ~100% SSE state, suggesting the LiPS conversion in SSE cathode structure is highly effective and meaningful for developing high-performance LSBs for commercial applications.

Foram preparadas algumas 2-sulfinil-3,6-dimetil-1,4-benzoquinonas racêmicas (contendo substituintes p-tolila, terc-butila, iso-butila e iso-propila ligados ao enxofre) e estudadas as suas reações de Diels-Alder com ciclopentadieno, sob condições térmicas e catalíticas. Com estes estudos foi constatada a habilidade destas quinonas em gerar majoritariamente certos tipos de adutos, dependendo das condições utilizadas. Na ausência de catalisadores, formaram-se principalmente os adutos resultantes da aproximação do ciclopentadieno sobre a dupla C-C não sulfinilada, pela face da quinona para a qual não está voltado o par de elétrons do enxofre, quando a ligação C-S se encontra na conformação s-cis. O uso de BF3.Et2O provocou uma inversão da face atacada, mas manteve a quimiosseletividade observada na ausência deste catalisador. Já, pelo emprego de ZnBr2, houve preferência do ataque do ciclopentadieno sobre a dupla C-C da quinona sulfinilada. As conclusões de tal estudo permitiram selecionar as condições a serem utilizadas para a obtenção de certos adutos com vistas a serem estes depois empregados para a síntese de um precursor enantiopuro do hirsuteno. Os trabalhos prosseguiram com ensaios para se determinar a melhor forma de obtenção de tal precursor: i) fotoisomerização a compostos gaiola seguida de dessulfurização ou ii) remoção do enxofre do aduto de Diels-Alder e fotociclização do produto dessulfurizado. A reação de fotociclização do aduto de Diels-Alder formado pela reação do dieno sobre a dupla sulfinilada da quinona gerou o compostogaiola dessulfurizado e também um novo aduto, cuja estrutura supõe-se ser a de uma enodiona hidroxilada, mas de configuração trans entre os anéis. Pela rota dessulfurizante ii), o mesmo composto foi obtido quando se empregou o hidreto de tributilestanho/AIBN, também ao lado do compostogaiola. As melhores condições para a obtenção de um precursor do hirsuteno enantiopuro foram estabelecidas como sendo aquelas que seguem a rota ii), isto é, dessulfurização do aduto de Diels-Alder resultante do ataque do ciclopentadieno sobre a dupla não sulfinilada, em condições catalíticas (BF3Et2O), quando o grupo sulfinila ligado à quinona está com a configuração S e contém um substituinte isso-propila, seguida de fotociclização do aduto sem enxofre. / Some racemic 2-tolyl- or 2-alkylsulfinyl-3,6-dimethyl-1,4-benzoquinones (alkyl is terc-butyl or iso-butyl or iso-propyl) were prepared and submitted to the Diels-Alder reactions with cyclopentadiene, under thermal or catalytic conditions. It was verified that the sulfinyl group is able to control the chemo- and diasterofaciaselectivity, giving rise to different adducts, depending on the reactions conditions. In the absence of catalyst, the above mentioned quinones underwent cycloaddition mainly on the non-sulfinylated quinoidic C-C double bond. The resulting adducts arised from the approach of diene from the more hindered face of the quinone, ie that one where the lone pair at sulfur is not located on, when the C-S bond is in a s-cis conformation. The use of BF3.Et2O diverted the cycloaddition to the other face, but kept the same chemoselectivity. When ZnBr2 was employed, the chemoselectivity was reversed, being the sulfinylated C-C double bond preferentially attacked by cyclopentadiene. The conclusions which arised from this study allowed the selection of the best set of conditions for obtaining the structurally more adequate sulfinyl-Diels-Alder adducts for the synthesis of enantiomerically pure hirsutene. Two pathways were assayed in order to transform the sulfinylated Diels-Alder adducts into a structurally closely related precursor of hirsutene: i) photoisomerization of the above mentioned Diels-Alder adducts followed by desulfurization of the resulting cage-compounds or ii) removal of the sulfurated moiety from the sulfinyl-Diels-Alder adducts followed by photocyclization. Irradiation of the Diels-Alder adduct containing a sulfinyl group at the ring junction led to the desired sulfur-free cage-compound in amixture with other product. The proposed structure for this new compound is based on a Diels-Alder adduct with a trans configuration, with an hydroxyl group linked to the enedionic system. This same compound was obtained, in amixture with the sulfur-free Diels-Alder adduct, when route ii) was tested using tributyltin hydride/AIBN as desulfurizating agent. In summary, the best conditions for the synthesis of an enantiomerically pure precursor of hirsutene is desulfurization of the Diels-Alder adduct resulting from the BF3.Et2O catalysed cycloaddition between the cyclopentadiene and 2-(SS)-iso-propylsulfinyl-3,6-dimethyl-1,4-benzoquinone, followed by photoisomerization of the sulfur-free product.