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The transfer of neutral molecules, ions and ionic species from water to ethylene glycol and to propylene carbonate; descriptors for pyridinium cations

Description: Article on the transfer of neutral molecules, ions and ionic species from water to ethylene glycol and to propylene carbonate and descriptors for pyridinium cations.
Date: June 29, 2010
Creator: Abraham, M. H. (Michael H.) & Acree, William E. (William Eugene)
Partner: UNT College of Arts and Sciences

A Well-Defined, Silica-Supported Tungsten Imido Alkylidene OlefinMetathesis Catalyst

Description: The reaction of [W(=NAr)(=CHtBu)(CH2tBu)2](1; Ar =2,6-iPrC6H3) with a silica partially dehydroxylated at 700oC, SiO2-(700),gives syn-[(_SiO)W(=NAr)(=CHtBu)(CH2tBu)](2) as a major surface species,which was fully characterized by mass balance analysis, IR, NMR, EXAFS,and DFT periodic calculations. Similarly, complex 1 reacts with[(c-C5H9)7Si7O12SiOH]to give [(SiO)W(=NAr)(=CHtBu)(CH2tBu)](2m), whichshows similar spectroscopic properties. Surface complex 2 is a highlyactive propene metathesis catalyst, which can achieve a TON of 16000within 100 h, with only a slow deactivation.
Date: June 13, 2006
Creator: Rhers, Bochra; Salameh, Alain; Baudouin, Anne; Quadrelli, ElsjeA.; Taoufik, Mostafa; Coperet, Christophe et al.
Partner: UNT Libraries Government Documents Department

Final Project Report Project 10749- 2007-2009

Description: This is the final report for the DOE Project 10749- for the FY2007 - FY2009 period. This report is non-proprietary, and will be submitted to DOE as a final project report. The report covers activities under the DOE Project inside CRADA 269 (Project 53231) as well as project activites outside of that CRADA (Project 56662). This is the final report that is summarized from the non-proprietary quarterlies submitted to DOE over the past 2.5 years, which in turn are summaries from the proprietary technical reporting to UOP.
Date: May 11, 2009
Creator: Zacher, Alan H.; Holladay, Johnathan E.; Frye, J. G.; Brown, Heather M.; Santosa, Daniel M. & Oberg, Aaron A.
Partner: UNT Libraries Government Documents Department

Issues involved with non-characterized control of methanotrophic bacteria

Description: Methane-utilizing bacteria, methanotrophs, have application as biocatalysts in the commodity chemical production, waste treatment and environmental remediation industries. Methanotrophs have the ability to oxidize many chemical compounds into more desired products, such as the production of propylene oxide. Methanotrophs can also degrade toxic compounds such as trichloroethylene. However, there are many physical, chemical and biological problems associated with the continuous oxidation of chemicals. These include, low mass transfer of methane, oxygen and propylene; toxicity of substrates and degradation products, and competition between the growth substrate, i.e., methane and chemical feed stock, e.g., propylene for the biocatalyst. To supervise methanotrophic bioprocesses, an intelligent control system must accommodate any biological limitations, e.g., toxicity, and mitigate the impact of the physical and chemical limitations, e.g., mass transfer of methane and the solubility of propylene. The intelligent control system must have the capability to assess the current conditions and metabolic state of the bacteria; recognize and diagnose instrument faults; and select and maintain sets of parameters that will result in high production and growth.
Date: May 11, 1998
Creator: Stoner, D.L.; Tolle, C.R.; Noah, K.S.; Davis, D.A.; Miller, K.S. & Fife, D.J.
Partner: UNT Libraries Government Documents Department


Description: In the last annual reports, we reported Cu-exchanged pillared clays as superior selective catalytic reduction (SCR) catalysts. During the past year we explored the possibilities with MCM-41, a new class of molecular sieve. In this report, Rh exchanged Al-MCM-41 is studied for the SCR of NO by C{sub 3}H{sub 6} in the presence of excess oxygen. It shows a high activity in converting NO to N{sub 2} and N{sub 2}O at low temperatures. In situ FT-IR studies indicate that Rh-NO{sup +} species (1910-1898 cm{sup {minus}1}) is formed on the Rh-Al-MCM-41 catalyst in flowing NO/He, NO+O{sub 2}/He and NO+C{sub 3}H{sub 6}+O{sub 2}/He at 100-350 C. This species is quite active in reacting with propylene and/or propylene adspecies (e.g., {pi}-C{sub 3}H{sub 5}, polyene, etc.) at 250 C in the presence/absence of oxygen, leading to the formation of the isocyanate species (Rh-NCO, at 2174 cm{sup {minus}1}), CO and CO{sub 2}. Rh-NCO is also detected under reaction conditions. A possible reaction pathway for reduction of NO by C{sub 3}H{sub 6} is proposed. In the SCR reaction, Rh-NO{sup +} and propylene adspecies react to generate the Rh-NCO species, then Rh-NCO reacts with O{sub 2}, NO and NO{sub 2} to produce N{sub 2}, N{sub 2}O and CO{sub 2}. Rh-NO{sup +} and Rh-NCO species are two main intermediates for the SCR reaction on Rh-Al-MCM-41 catalyst.
Date: March 31, 1999
Creator: Yang, R. T. & Long, R.Q.
Partner: UNT Libraries Government Documents Department

Infrared absorption measurements of the kinetics of Cl atom reactions with C{sub 3}H{sub n} (n=4,6) unsaturated hydrocarbons between 300-850 K

Description: The reaction of chlorine (Cl) atoms with the unsaturated C{sub 3}H{sub n} where n=4,6, hydrocarbons propylene, allene, and methyl acetylene have been uninvestigated as a function of temperature and pressure.
Date: August 1, 1997
Creator: Farrell, J.T.; Pilgrim, J.S. & Taatjes, C.A.
Partner: UNT Libraries Government Documents Department


Description: The nonionic superbase P(MeNCH{sub 2}CH{sub 2}){sub 3}N (A) efficiently desulfurizes trisulfides to disulfides and monosulfides, disulfides to monosulfides, and propylene sulfide to propene. S=P(MeNCH{sub 2}CH{sub 2}){sub 3}N (B) was formed as the sulfur acceptor. P(NMe{sub 2}){sub 3} was a much poorer desulfurizing agent than A under the same reaction conditions. Thiocyanates and triphenylphosphine sulfide were also desulfurized with A, but N-(phenylthio)phthalimide formed [A-SP]{sup +} phthalimide in quantitative yield.
Date: August 31, 1998
Creator: Verkade, John G.
Partner: UNT Libraries Government Documents Department

SISGR: Linking Ion Solvation and Lithium Battery Electrolyte Properties

Description: The solvation and phase behavior of the model battery electrolyte salt lithium trifluoromethanesulfonate (LiCF3SO3) in commonly used organic solvents; ethylene carbonate (EC), gamma-butyrolactone (GBL), and propylene carbonate (PC) was explored. Data from differential scanning calorimetry (DSC), Raman spectroscopy, and X-ray diffraction were correlated to provide insight into the solvation states present within a sample mixture. Data from DSC analyses allowed the construction of phase diagrams for each solvent system. Raman spectroscopy enabled the determination of specific solvation states present within a solvent-“salt mixture, and X-ray diffraction data provided exact information concerning the structure of a solvates that could be isolated Thermal analysis of the various solvent-salt mixtures revealed the phase behavior of the model electrolytes was strongly dependent on solvent symmetry. The point groups of the solvents were (in order from high to low symmetry): C2V for EC, CS for GBL, and C1 for PC(R). The low symmetry solvents exhibited a crystallinity gap that increased as solvent symmetry decreased; no gap was observed for EC-LiTf, while a crystallinity gap was observed spanning 0.15 to 0.3 mole fraction for GBL-LiTf, and 0.1 to 0.33 mole fraction for PC(R)-LiTf mixtures. Raman analysis demonstrated the dominance of aggregated species in almost all solvent compositions. The AGG and CIP solvates represent the majority of the species in solutions for the more concentrated mixtures, and only in very dilute compositions does the SSIP solvate exist in significant amounts. Thus, the poor charge transport characteristics of CIP and AGG account for the low conductivity and transport properties of LiTf and explain why is a poor choice as a source of Li+ ions in a Li-ion battery.
Date: March 14, 2013
Creator: Trulove, Paul C & Foley, Matthew P
Partner: UNT Libraries Government Documents Department

UV-Raman spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption studies of model and bulk heterogeneous catalysts

Description: X-ray photoelectron spectroscopy (XPS) and Temperature Programmed Desorption (TPD) have been used to investigate the surface structure of model heterogeneous catalysts in ultra-high vacuum (UHV). UV-Raman spectroscopy has been used to probe the structure of bulk model catalysts in ambient and reaction conditions. The structural information obtained through UV-Raman spectroscopy has been correlated with both the UHV surface analysis and reaction results. The present day propylene and ethylene polymerization catalysts (Ziegler-Natta catalysts) are prepared by deposition of TiCl{sub 4} and a Al(Et){sub 3} co-catalyst on a microporous Mg-ethoxide support that is prepared from MgCl{sub 2} and ethanol. A model thin film catalyst is prepared by depositing metallic Mg on a Au foil in a UHV chamber in a background of TiCl{sub 4} in the gas phase. XPS results indicate that the Mg is completely oxidized to MgCl{sub 2} by TiCl{sub 4} resulting in a thin film of MgCl{sub 2}/TiCl{sub x}, where x = 2, 3, and 4. To prepare an active catalyst, the thin film of MgCl{sub 2}/TiCl{sub x} on Au foil is enclosed in a high pressure cell contained within the UHV chamber and exposed to {approx}1 Torr of Al(Et){sub 3}.
Date: August 19, 2002
Creator: Tewell, Craig R.
Partner: UNT Libraries Government Documents Department

Toxicity Data to Determine Refrigerant Concentration Limits

Description: This report reviews toxicity data, identifies sources for them, and presents resulting exposure limits for refrigerants for consideration by qualified parties in developing safety guides, standards, codes, and regulations. It outlines a method to calculate an acute toxicity exposure limit (ATEL) and from it a recommended refrigerant concentration limit (RCL) for emergency exposures. The report focuses on acute toxicity with particular attention to lethality, cardiac sensitization, anesthetic and central nervous system effects, and other escape-impairing effects. It addresses R-11, R-12, R-22, R-23, R-113, R-114, R-116, R-123, R-124, R-125, R-134, R-134a, R-E134, R-141b, R-142b, R-143a, R-152a, R-218, R-227ea, R-236fa, R-245ca, R-245fa, R-290, R-500, R-502, R-600a, R-717, and R-744. It summarizes additional data for R-14, R-115, R-170 (ethane), R-C318, R-600 (n-butane), and R-1270 (propylene) to enable calculation of limits for blends incorporating them. The report summarizes the data a nd related safety information, including classifications and flammability data. It also presents a series of tables with proposed ATEL and RCL concentrations-in dimensionless form and the latter also in both metric (SI) and inch-pound (IP) units of measure-for both the cited refrigerants and 66 zerotropic and azeotropic blends. They include common refrigerants, such as R-404A, R-407C, R-410A, and R-507A, as well as others in commercial or developmental status. Appendices provide profiles for the cited single-compound refrigerants and for R-500 and R-502 as well as narrative toxicity summaries for common refrigerants. The report includes an extensive set of references.
Date: September 30, 2000
Creator: Calm, James M.
Partner: UNT Libraries Government Documents Department

Improved Modeling of Transition Metals, Applications to Catalysis and Technetium Chemistry

Description: There is considerable impetus for identification of aqueous OM catalysts as water is the ultimate ''green'' solvent. In collaboration with researchers at Ames Lab, we investigated effective fragment and Monte Carlo techniques for aqueous-phase hydroformylation (HyF). The Rh of the HyF catalyst is weakly aquated, in contrast to the hydride of the Rh-H bond. As the insertion of the olefin C=C into Rh-H determines the linear-to-branched aldehyde ratio, it is reasonable to infer that solvent plays an important role in regiochemistry. Studies on aqueous-phase organometallic catalysis were complemented in studies of the gas-phase reaction. A Rh-carbonyl-phosphine catalyst was investigated. Two of the most important implications of this research include (a) pseudorotation among five-coordinate intermediates is significant in HyF, and (b) CO insertion is the rate-determining step. The latter is in contrast to experimental deductions, highlighting the need for more accurate modeling. To this end, we undertook studies of (a) experimentally relevant PR{sub 3} co-ligands (PMe{sub 3}, PPh{sub 3}, P(p-PhSO{sub 3{sup -}}){sub 3}, etc.), and (b) HyF of propene. For the propylene research, simulations indicated that the linear: branched aldehyde ratio (linear is more desirable) is determined by thermodynamic discrimination of two distinct pathways. Other projects include a theory-experiment study of C-H activation by early transition metal systems, which establishes that weakly-bound adducts play a key role in activity selectivity. By extension, more selective catalysts for functionalization of methane (major component of natural gas) will require better understanding of these adducts, which are greatly affected by steric interactions with the ligands. In the de novo design of Tc complexes, we constructed (and are now testing) a coupled quantum mechanics-molecular mechanics protocol. Initial research shows it to be capable of accurately predicting structure ''from scratch.'' Challenges include conformational, geometric, coordination, spin, and particularly linkage (e.g., Tc-SCN versus Tc-NCS) isomerism. In general, our ...
Date: March 5, 2004
Creator: Cundari, T. R.
Partner: UNT Libraries Government Documents Department

Preparation of 1-C14-Propene-1 and the Mechanism of PermanganateOxidation of Propene

Description: 1-C{sup 14}-propene has been prepared. The migration of the double bond under a variety of experimental conditions in the preparation of propene has been investigated. The mechanism of the permanganate oxidation of the labeled propene has been examined; it has been found to proceed by several paths, the relative importance of which depends upon the experimental conditions, especially the pH.
Date: December 10, 1947
Creator: Fries, B.A. & Calvin, M.
Partner: UNT Libraries Government Documents Department


Description: Samples of ethylene propylene diene monomer (EPDM) elastomer were exposed to tritium gas in closed containers initially at 101 kPa (1 atmosphere) pressure and ambient temperature for about one week. Tritium exposure effects on the samples were characterized by dynamic mechanical analysis (DMA) and radiolysis products were characterized by measuring the total final pressure and composition in the exposure containers at the end of exposure period. There was no effect of one week tritium exposure on the glass transition temperature, Tg, of the samples tested. Impurity gases produced in the closed containers included HT and lesser amounts of H{sub 2}, DTO, and CT{sub 4}. The total pressure remained the same during exposure.
Date: August 13, 2007
Creator: Clark, E & Gregory Staack, G
Partner: UNT Libraries Government Documents Department

Theoretical studies of pentene cracking on zeolites: C-C beta-scission processes

Description: The nature of the molecular species involved in the cracking of hydrocarbons into smaller fragments over zeolite catalysts has been studied extensively, as the advent of zeolites such as faujasite to carry out these transformations more selectively has revolutionized the petroleum refining technology. While the nature of the acid-catalyzed process involving proposed carbocationic species has been proposed for nearly fifty years, there have been extensive studies involving heterogeneous processes and analogs with solution superacid chemistry to elucidate these mechanisms more clearly and to attempt to detect the intermediates involved in these reactions. Also in recent years there have been an increasing number of theoretical studies on the nature of the acid sites in zeolites, the interactions of these acid sites with adsorbates including hydrocarbons, and on simple reactions of hydrocarbon species using model systems to represent the zeolite. In this study the authors report the results of ab initio and density functional studies on one aspect--the beta-scission C-C bond-breaking step--that arises in the cracking process of alkanes and alkenes. The authors focus on the species arising from pentene adsorption on an acid site and the subsequent cracking of this C{sub 5} species as an illustration of the carbon-carbon bond-breaking step. In these studies they employ a simple three-T-site to represent the immediate vicinity of the acid site in faujasite comprised of the Si-O-Al-OH-O-Si skeleton with the unsatisfied bonds terminated by hydrogens. They study the reaction of the 2-pentyl cation undergoing beta-scission in the gas phase to form propene and the ethyl cation and the corresponding reaction on the zeolite cluster. The structures of the reactants, products and transition states are determined using ab initio electronic structure techniques.
Date: April 1, 1997
Creator: Hay, P.J.; Redondo, A. & Guo, Y.
Partner: UNT Libraries Government Documents Department

Prompt non-tire rubber recycling : final report for phases 1 and 2.

Description: This report summarizes an assessment conducted by Environmental Technologies Alternatives, Inc., under a subcontract to Argonne National Laboratory. The project was conducted in two phases. An assessment of alternative technologies for recycling of prompt non-tire rubber was conducted in the first phase, and an experimental program focusing on a new technology called the catalytic Regeneration Process offered the greatest opportunity for recovery of high-value recyclable rubber material. An experimental and large-scale test program was undertaken to further delineate the economic potential as an essential step leading to commercial deployment and to determine the course of continued development of the technology by the private sector. The experimental program defined process-operating conditions for the technology and verified the degree of devulcanisation achievable for two rubber compounds: ethylene-propylene-nonconjugated-diene monomer (EPDM) and neoprene. To determine product acceptance, samples of devulcanized EPDM and neoprene were prepared and used in factory trials for the production of automotive moldings (EPDM) and fiber-filled belting (neoprene). The factory trials indicated that the physical properties of the products were acceptable in both cases. The appearance of molded and calendared surface finishes was acceptable, while that of extruded finishes was unsatisfactory. The fiber-filled neoprene belting application offers the greatest economic potential. Process costs were estimated at $0.34/lb for neoprene waste rubber relative to a value of $0.57/lb. The results of the experimental program led to the decision to continue development of this technology is being planned, subject to the availability of about $3 million in financing from private-sector investors. The ability to recycle non-tire rubber scrap could conserve as much as 90,000 Btu/lb, thus yielding an estimated energy savings potential of about 0.25 quad/yr.
Date: June 25, 1999
Creator: Smith, F. G. & Daniels, E. J.
Partner: UNT Libraries Government Documents Department

Energy Efficient Catalytic Reaction and Production of Cumene

Description: Alkylation reactions of benzene with propylene using zeolites were studied for their affinity for cumene production. The current process for the production of cumene involves heating corrosive acid catalysts, cooling, transporting, and distillation. This study focused on the reaction of products in a static one-pot vessel using non-corrosive zeolite catalysts, working towards a more efficient one-step process with a potentially large energy savings. A series of experiments were conducted to find the best reaction conditions yielding the highest production of cumene. The experiments looked at cumene formation amounts in two different reaction vessels that had different physical traits. Different zeolites, temperatures, mixing speeds, and amounts of reactants were also investigated to find their affects on the amount of cumene produced. Quantitative analysis of product mixture was performed by gas chromatography. Mass spectroscopy was also utilized to observe the gas phase components during the alkylation process.
Date: December 1, 2001
Partner: UNT Libraries Government Documents Department

Comparison of advanced distillation control methods. Third annual report

Description: Detailed dynamic simulations of three industrial distillation columns (a propylene/propane splitter, a xylene/toluene column, and a depropanizer) have been used to study the issue of configuration selection for diagonal PI dual composition controls, feedforward from a feed composition analyzer, and decouplers. Auto Tune Variation (ATV) identification with on-line detuning for setpoint changes was used for tuning the diagonal proportional integral (PI) composition controls. In addition, robustness tests were conducted by inducting reboiler duty upsets. For single composition control, the (L, V) configuration was found to be best. For dual composition control, the optimum configuration changes from one column to another. Moreover, the use of analysis tools, such as RGA, appears to be of little value in identifying the optimum configuration for dual composition control. Using feedforward from a feed composition analyzer and using decouplers are shown to offer significant advantages for certain specific cases.
Date: July 1, 1997
Creator: Riggs, J.B.
Partner: UNT Libraries Government Documents Department

Carbons for lithium ion cells prepared using sepiolite as an inorganic template.

Description: Carbon anodes for Li ion cells have been prepared by the in situ polymerization of olefins such as propylene and ethylene in the channels of sepiolite clay mineral. Upon dissolution of the inorganic framework, a disordered carbon was obtained. The carbon was tested as anode in coin cells, yielding a reversible capacity of 633 mAh/g, 1.70 times higher than the capacity delivered by graphitic carbon, assuming 100% efficiency. The coulombic efficiency was higher than 90%.
Date: December 9, 1998
Creator: Sandi, G.
Partner: UNT Libraries Government Documents Department

Exploring old and new benzene formation pathways in low-pressure premixed flames of aliphatic fuels

Description: A modeling study of benzene and phenyl radical formation is performed for three low-pressure premixed laminar flat flames having an unsaturated C{sub 2} or C{sub 3} hydrocarbon fuel (acetylene, ethylene, and propene). Predictions using three published detailed elementary-step chemical kinetics mechanisms are tested against MBMS species profile data for all three flames. The differences between the three mechanisms predictive capabilities are explored, with an emphasis on benzene formation pathways. A new chemical kinetics mechanism is created combining features of all three published mechanisms. Included in the mechanism are several novel benzene formation reactions involving combinations of radicals such as C{sub 2}H+C{sub 4}H{sub 5}, and C{sub 5}H{sub 3}+CH{sub 3}. Reactions forming fulvene (a benzene isomer) are included, such as C{sub 3}H{sub 3}+C{sub 3}H{sub 5},as well as fulvene-to-benzene reactions. Predictions using the new mechanism show virtually all of the benzene and phenyl radical to be formed by reactions of either C{sub 3}H{sub 3}+C{sub 3}H{sub 3} or C{sub 3}H{sub 3}+C{sub 3}H{sub 5}, with the relative importance being strongly dependent upon the fuel. C{sub 5}H{sub 3}+CH{sub 3} plays a minor role in fulvene formation in the acetylene flame. The C{sub 2}H{sub x}+C{sub 4}H{sub 4} reactions do not contribute noticeably to benzene or phenyl radical formation in these flames, sometimes being a major decomposition channel for either fulvene or phenyl radical. The formation pathways for C{sub 3}H{sub 3} and C{sub 3}H{sub 5}are delineated for the three flames; while the key reactions differ from flame to flame, CH{sub 2}+C{sub 2}H{sub 2} {Longleftrightarrow} C{sub 3}H{sub 3}+H is important for all three flames.
Date: December 13, 2000
Creator: Pope, Christopher J. & Miller, James A.
Partner: UNT Libraries Government Documents Department