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Synthesis, structure, and reactivity of high oxidation state silver fluorides and related compounds

Description: This thesis has been largely concerned with defining the oxidizing power of Ag(III) and Ag(II) in anhydrous hydrogen fluoride (aHF) solution. Emphasis was on cationic species, since in a cation the electronegativity of a given oxidation state is greatest. Cationic Ag(III) solv has a short half life at ordinary temperatures, oxidizing the solvent to elemental fluorine with formation of Ag(II). Salts of such a cation have not yet been preparable, but solutions which must contain such a species have proved to be effective and powerful oxidizers. In presence of PtF{sub 6}{sup {minus}}, RuF{sub 6}{sup {minus}}, or RhF{sub 6}{sup {minus}}, Ag(III) solv effectively oxidizes the anions to release the neutral hexafluorides. Such reactivity ranks cationic Ag(III) as the most powerfully oxidizing chemical agent known as far. Unlike its trivalent relative Ag (II) solv is thermodynamically stable in acid aHF. Nevertheless, it oxidizes IrF{sub 6}{sup {minus}} to IrF{sub 6} at room temperature, placing its oxidizing potential not more than 2 eV below that of cationic Ag(III). Range of Ag{sup 2+} (MF{sub 6}{sup {minus}}){sub 2} salts attainable in aHF has been explored. An anion must be stable with respect to electron loss to Ag{sup 2+}. The anion must also be a poor F{sup {minus}} donor; otherwise, either AgF{sup +} salts or AgF{sub 2} are generated.
Date: May 1, 1995
Creator: Lucier, G.M.
Partner: UNT Libraries Government Documents Department

Technical Report on Grant

Description: This research project employed a combination of laboratory, field and modeling activities to explore the fate of reactive species in the atmosphere. Our work focused particularly on the behavior of hydroperoxides and their precursors, hydroperoxy radicals. Initially, we pursed the study of these species to elucidate the role they play in the formation of photochemical smog. In recent years, we have extended our studies to the role of these oxidants in forming aerosol particles, due the potential of the latter to influence climate by changing the radiative properties of the atmosphere.
Date: November 21, 2006
Creator: Weinstein-Lloyd, Judith B.
Partner: UNT Libraries Government Documents Department

The concept of delayed nucleation in nanocrystal growthdemonstrated for the case of iron oxide nanodisks

Description: A comprehensive study of iron oxide nanocrystal growth through non-hydrolitic, surfactant-mediated thermal reaction of iron pentacarbonyl and an oxidizer has been conducted, which includes size control, anisotropic shape evolution, and crystallographic phase transition of monodisperse iron oxide colloidal nanocrystals. The reaction was monitored by in situ UV-Vis spectroscopy taking advantage of the color change accompanying the iron oxide colloid formation allowing measurement of the induction time for nucleation. Features of the synthesis such as the size control and reproducibility are related to the occurrence of the observed delayed nucleation process. As a separate source of iron and oxygen is adopted, phase control could also be achieved by sequential injections of oxidizer.
Date: September 9, 2005
Creator: Casula, Maria F.; Jun, Young-wook; Zaziski, David J.; Chan, EmoryM.; Corrias, Anna & Alivisatos, Paul A.
Partner: UNT Libraries Government Documents Department

Dilute oxygen combustion. Phase I report

Description: A novel burner, in which fuel (natural gas) and oxidant (oxygen or air) are separately injected into a furnace, shows promise for achieving very low nitrogen oxide(s) (NO{sub x}) emissions for commercial furnace applications. The dilute oxygen combustion (DOC) burner achieves very low NO{sub x} through in-furnace dilution of the oxidant stream prior to combustion, resulting in low flame temperatures, thus inhibiting thermal NO{sub x} production. The results of a fundamental and applied research effort on the development of the DOC burner are presented. In addition, the results of a market survey detailing the potential commercial impact of the DOC system are disclosed. The fundamental aspects of the burner development project involved examining the flame characteristics of a natural gas turbulent jet in a high-temperature ({approximately}1366 K) oxidant (7-27% O{sub 2} vol. wet). Specifically, the mass entrainment rate, the flame lift-off height, the velocity field and major species field of the jet were evaluated as a function of surrounding-gas temperature and composition. The measured entrainment rate of the fuel jet decreased with increasing oxygen content in the surrounding high-temperature oxidant, and was well represented by the d{sup +} scaling correlation found in the literature. The measured flame lift-off height decreased with increasing oxygen content and increasing temperature of the surrounding gas. An increase in surrounding-gas oxygen content and/or temperature inhibited the velocity decay within the jet periphery as a function of axial distance as compared to isothermal turbulent jets. However, the velocity measurements were only broadly represented by the d{sup +} scaling correlation. Several DOC burner configurations were tested in a laboratory-scale furnace at a nominal firing rate of 185 kW ({approximately}0.63 MMBtu/h). The flue gas composition was recorded as a function of furnace nitrogen content, furnace temperature, burner geometric arrangement, firing rate, and fuel injection velocity. NO{sub x} emissions ...
Date: October 1, 1997
Partner: UNT Libraries Government Documents Department


Description: This project was an extension of previous research to improve the applicability of ozonation and will help address the petroleum-industry problem of treating produced water containing soluble organics. The goal of this project was to maximize oxidation of hexane-extractable organics during a single-pass operation. The project investigated: (1) oxidant production by electrochemical and sonochemical methods, (2) increasing the mass transfer rate in the reactor by forming microbubbles during ozone injection into the produced water, and (3) using ultraviolet irradiation to enhance the reaction if needed. Several types of methodologies for treatment of soluble organics in synthetic and actual produced waters have been performed. The technologies tested may be categorized as follows: (1) Destruction via sonochemical oxidation at different pH, salt concentration, ultraviolet irradiation, and ferrous iron concentrations. (2) Destruction via ozonation at different pH, salt concentration, hydrogen peroxide concentrations, ultraviolet irradiation, temperature, and reactor configurations.
Date: March 14, 2002
Creator: Klasson, KT
Partner: UNT Libraries Government Documents Department

Laboratory Evaluation of In Situ Chemical Oxidation for Groundwater Remediation, Test Area North, Operable Unit 1-07B, Idaho National Engineering and Environmental Laboratory, Volume One - Main Text and Appendices A and B

Description: The laboratory investigation was performed to evaluate the feasibility of utilizing in situ chemical oxidation for remediating the secondary source of groundwater contaminants at the Idaho National Engineering and Environmental Laboratory (INEEL) Test Area North (TAN) Site. The study involved trichloroethene (TCE) contaminated media (groundwater, soil, and sludge) from TAN. The effectiveness of the selected oxidant, potassium permanganate (KMn0(sub4)), was evaluated at multiple oxidant and contaminant concentrations. Experiments were performed to determine the oxidant demand of each medium and the rate of TCE oxidation. The experiments were performed under highly controlled conditions (gas-tight reactors, constant 12C temperature). Multiple parameter were monitored over time including MN0(sub 4) and TCE concentrations and pH.
Date: April 1, 1999
Creator: Cline, S.R.; Denton, D.L.; Giaquinto, J.M.; McCracken, M.K. & Starr, R.C.
Partner: UNT Libraries Government Documents Department

Reaction chemistry of cerium

Description: It is truly ironic that a synthetic organic chemist likely has far greater knowledge of the reaction chemistry of cerium(IV) than an inorganic colleague. Cerium(IV) reagents have long since been employed as oxidants in effecting a wide variety of organic transformations. Conversely, prior to the late 1980s, the number of well characterized cerium(IV) complexes did not extend past a handful of known species. Though in many other areas, interest in the molecular chemistry of the 4f-elements has undergone an explosive growth over the last twenty years, the chemistry of cerium(IV) has for the most part been overlooked. This report describes reactions of cerium complexes and structure.
Date: January 1, 1997
Partner: UNT Libraries Government Documents Department

Mixing and chemical reaction in an idealized swirl chamber

Description: A vorticity-based, low-Mach-number model for simulating combustion in closed chambers is constructed. Numerical scheme is based on a mixed finite-difference pseudo-spectral discretization of the governing equations. Discrete evolution equations are integrated in time using a predictor-corrector scheme, while discrete elliptic systems are inverted with the help of fast-Poisson solver. Scheme is applied to analyze mixing and combustion in an idealized swirl cavity, which consists of the annular space between a spinning inner cylinder and a stationary reaction. To this end, we assume that the oxidizer and fuel are initially separated by a thin mixed region, and carefully control mixing levels by varying the duration of the swirl-driven mixing period. The mixture is then ignited along the boundary of the inner cylinder. When pre-mixing is complete, an axisymmetric flame front is established, and the reactants are consumed as the front propagates radially outwards. When the charge is partially mixed, combustion in the early stages predominantly occurs within a non-uniform premixed front. As this non-uniform front approaches the outer cylinder, a transition to a distributed combustion regime occurs. Following the transition, the remaining fuel burns at a slow rate within non-premixed flames which wrap around the inner cylinder. Results show that the mixing time has substantial effects on the pressure rise within the cavity and on the evolution of the burnt fraction, and that these effects become more pronounced as the Damkoehler number increases.
Date: January 1996
Creator: Knio, O. M.; Worlikar, A. S. & Najm, H. N.
Partner: UNT Libraries Government Documents Department

Destruction of VX by aqueous-phase oxidation using peroxydisulfate (direct chemical oxidation)

Description: Chemical warfare agents may be completely destroyed (converted to H{sub 2}O, CO{sub 2}, salts) by oxidation at 90--100 C using acidified ammonium peroxydisulfate, with recycle of NH{sub 4}SO{sub 4} byproduct. The process requires no toxic or expended catalysts and produces no secondary wastes other than the precipitated inorganic content of the agents. To determine oxidative capability of peroxydisulfate at low reductant contents, we measured rate data for oxidation of 20 diverse compounds with diverse functional groups; 4 of these have bonds similar to those found in VX, HD, and GB. On an equivalence basis, integral first-order rate constants for 100 C oxidation are 0.012{plus_minus}0.005 min{sup {minus}1} for di-isopropyl-methyl-phosphonate, methyl phosphonic acid, triethylamine, and 2,2{prime}-thiodiethanol at low initial concentrations of 50 ppM(as carbon) and pH 1.5. To provide scale-up equations for a bulk chemical agent destruction process, we measured time-dependent oxidation of bulk model chemicals at high concentrations (0.5 N) and developed and tested a quantitative model. A practical process for bulk VX destruction would begin with chemical detoxification by existing techniques (eg, hydrolysis or mild oxidation using oxone), followed by mineralization of the largely detoxified products by peroxydisulfate. Secondary wastes would be avoided by use of commercial electrolysis equipment to regenerate the oxidant. Reagent requirements, mass balance and scaleup parameters are given for VX destruction, using peroxydisulfate alone, or supplemented with hydrogen peroxide. For the use of 2.5 N peroxydisulfate as the oxidant, a 1 m{sup 3} digester will process about 200 kg (as C) per day. The process may be extended to total destruction of HD and hydrolysis products of G agents.
Date: October 11, 1995
Creator: Cooper, J.F.; Krueger, R. & Farmer, J.C.
Partner: UNT Libraries Government Documents Department


Description: As part of the 1999 NARSTO Northeast Oxidant and Particulate Study (NE-OPS) field campaign, the DOE G-1 aircraft sampled trace gases and aerosols in and around the Philadelphia metropolitan area. Twenty research flights were conducted between July 25 and August 11. The overall goals of these flights were to obtain a mechanistic understanding of O{sub 3} production; to characterize the spatial and temporal behavior of photo-oxidants and aerosols; and to study the evolution of aerosol size distributions, including the process of new particle formation. Within the NE-OPS program, other groups provided additional trace gas, aerosol, and meteorological observations using aircraft, balloon, remote sensing, and surface based instruments (Phillbrick et al., 2000). In this article we provide an overview of the G-1 observations related to O{sub 3} production, focusing on the vertical distribution of pollutants. Ozone production rates are calculated using a box model that is constrained by observed trace gas concentrations. Highest O{sub 3} concentrations were observed on July 31, which we present as a case study. On that day, O{sub 3} concentrations above the 1-hour 120 ppb standard were observed downwind of Philadelphia and also in the plume of a single industrial facility located on the Delaware River south of the city.
Date: October 1, 2001
Partner: UNT Libraries Government Documents Department

A method and apparatus for destroying hazardous organics and other combustible materials in a subcritical/supercritical reactor

Description: A waste destruction method is described using a reactor vessel to combust and destroy organic and combustible waste, including the steps of introducing a supply of waste into the reactor vessel, introducing a supply of an oxidant into the reactor vessel to mix with the waste forming a waste and oxidant mixture, introducing a supply of water into the reactor vessel to mix with the waste and oxidant mixture forming a waste, water and oxidant mixture, reciprocatingly compressing the waste, water and oxidant mixture forming a compressed mixture, igniting the compressed mixture forming a exhaust gas, and venting the exhaust gas into the surrounding atmosphere.
Date: December 1, 1997
Creator: Janikowski, Stuart K.
Partner: UNT Libraries Government Documents Department

Methods to reduce CO{sub 2} release to the atmosphere.

Description: The U.S. anthropogenic emission of CO{sub 2} is over 5.5 billion tons a year. Over 1/3 of it is emitted by power plants, and 90% of all power plant emissions is released by coal fired units. Figure 1 shows the amount of coal used and the amount of electricity generated from coal over a several year period. Burning one lb of coal produces about 2.1 lbs of CO{sub 2} and about 1 kWh of electricity, or a 1000 MW coal-fired plant emits over 1000 tons of CO{sub 2} per hour. Therefore, power plants are good candidates for reducing CO{sub 2} emissions. Emissions can be reduced by conserving energy, fuel and oxidant treatment prior to combustion, using fuels with higher H/C ratios, and by capturing the CO{sub 2}.
Date: April 10, 1998
Creator: Jody, B. J.
Partner: UNT Libraries Government Documents Department

Selective Oxidation of Benzene to Phenol. Final Report

Description: Direct catalytic oxidation of commodity aromatics to phenolic compounds was studied by a team from Akzo Nobel Chemicals, Argonne National Lab., and Northwestern University. Results did not exceed previously published performance. The object of the project was to selectively oxidize benzene to phenol using a conventional oxidant.
Date: September 30, 2000
Creator: Sherif, F.; Kung, H. & Marshall, C.
Partner: UNT Libraries Government Documents Department

Replacing chemicals in recycle mills with mechanical alternatives

Description: A high-intensity spark fired underwater decomposes a small amount of the water into hydroxyl radicals, which are strong oxidants. These are able to oxidize contaminants such as glue and wood pitch that enter paper recycling mills as a part of the incoming furnish and cost the industry several hundred million dollars. The sparking technique is safe, inexpensive, and is capable of treating large volumes of water, which makes it attractive for mill applications. Several mill trials were run. Sparking caused a decrease in the tack of the deposits in one case. Lower bleach use occurred in two other mills; sparking reduced the degree of ink reattachment to fiber. The payback for either application is attractive. Sparking induced deposition of contaminants in another mill, which is a positive development--if it can be controlled. The technique is also able to degas water and to oxidize odor-causing sulfur compounds. Although one unit has been purchased by a mill, second-order effects caused by the technology needs to be defined further before the technology can be broadly applied.
Date: July 1, 2002
Creator: Technology, Institute of Paper Science
Partner: UNT Libraries Government Documents Department

Performance of a New Lightweight Reciprocating Pump

Description: A new four-chamber piston pump design has been fabricated and tested. The small-scale propellant pump is intended to be powered by gas at elevated temperatures, e.g. in a gas-generator cycle rocket propulsion system. Two key features are combined for the first time: leak-tight liquid-cooled seals, and a high throughput per unit hardware mass. Measured performance curves quantify flows, pressures, leakage, volumetric efficiency, and tank pressure requirements. A pair of 300-gram pumps operating with significant margin could deliver fuel and oxidizer at 5 MPa to a compact lightweight 1000-N engine, while tank pressure remains at 0.35 MPa. Pump weight is well below one percent of thrust, as is typical for launch vehicle engines. Applications include small upper stages, aggressive maneuvers in space, and miniature launch vehicles for Mars ascent.
Date: June 9, 2005
Creator: Whitehead, J C
Partner: UNT Libraries Government Documents Department

Propagation studies of metastable intermolecular composites (MIC).

Description: Thermite materials are attractive energetic materials because the reactions are highly exothermic, have high energy densities, and high temperatures of combustion. However, the application of thermite materials has been limited because of the relative slow release of energy compared to other energetic materials. Engineered nano-scale composite energetic materials, such as Al/MoO{sub 3}, show promise for additional energetic material applications because they can react very rapidly. The composite material studied in this work consists of tailored, ultra-fine grain (30-200 nm diameter) aluminum particles that dramatically increase energy release rates of these thermite materials. These reactant clusters of fuel and oxidizer particles are in nearly atomic scale proximity to each other but are constrained from reaction until triggered. Despite the growing importance of nano-scale energetic materials, even the most basic combustion characteristics of these materials have not been thoroughly studied. This paper reports initial studies of the ignition and combustion of metastable intermolecular composites (MIC) materials. The goals were lo obtain an improved understanding of flame propagation mechanisms and combustion behaviors associated with nano-structured energetic materials. Information on issues such as reaction rate and behavior as a function of composition (mixture ratio), initial static charge, and particle size are essential and will allow scientists to design applications incorporating the benefits of these compounds. The materials have been characterized, specifically focusing on particle size, shape, distribution and morphology.
Date: January 1, 2002
Creator: Son, S. F. (Steven F.); Busse, J. R. (James R.); Asay, B. W. (Blaine W.); Peterson, P. D. (Paul D.); Mang, J. T. (Joseph T.); Bockmon, B. (Bryan) et al.
Partner: UNT Libraries Government Documents Department

Improving the Performance of Lithium Manganese Phosphate Through Divalent Cation Substitution

Description: Highly crystalline samples of LiMnPO{sub 4} and its analogs with partial substitution of Mn by divalent Mg, Cu, Zn, and Ni were prepared by hydrothermal synthesis and characterized by x-ray diffraction and infrared spectroscopy. Chemical oxidation produced two-phase mixtures of the initial phases LiMn{sub (1-y)}M{sub y}PO{sub 4} and the delithiated forms, Li{sub y}Mn{sub (1-y)}M{sub y}PO{sub 4}, all with the olivine structure. The extent of oxidation depended upon the quantity of oxidizing agent used and on the identity of the substituent ions. Mg, Ni and Cu were found to increase the level of delithation relative to that in pure LiMnPO{sub 4}. Mg was also shown to reduce the tendency of the oxidized phase to absorb water.
Date: March 3, 2008
Creator: Chen, Guoying & Richardson, Thomas J.
Partner: UNT Libraries Government Documents Department

Decontamination Options for Drinking Water Contaminated with Bacillus anthracis Spores

Description: Five parameters were evaluated with surrogates of Bacillus anthracis spores to determine effective decontamination options for use in a contaminated drinking water supply. The parameters were: (1) type of Bacillus spore surrogate (B. thuringiensis or B. atrophaeus); (2) spore concentration in suspension (10{sup 2} to 10{sup 6} spores/ml); (3) chemical characteristics of decontaminant [sodium dicholor-s-triazinetrione dihydrate (Dichlor), hydrogen peroxide, potassium peroxymonosulfate (Oxone), sodium hypochlorite, and VirkonS{reg_sign}]; (4) decontaminant concentration (0.01% to 5%); and (5) decontaminant exposure time (10 min to 24 hr). Results from 162 suspension tests with appropriate controls are reported. Hydrogen peroxide at a concentration of 5%, and Dichlor and sodium hypochlorite at a concentration of 2%, were effective at spore inactivation regardless of spore type tested, spore exposure time, or spore concentration evaluated. This is the first reported study of Dichlor as an effective decontaminant for B. anthracis spore surrogates. Dichlor's desirable characteristics of high oxidation potential, high level of free chlorine, and more neutral pH than that of other oxidizers evaluated appear to make it an excellent alternative. All three oxidizers were effective against B. atrophaeus spores in meeting EPA's biocide standard of greater than a 6 log kill after a 10-minute exposure time and at lower concentrations than typically reported for biocide use. Solutions of 5% VirkonS{reg_sign} and Oxone were less effective decontaminants than other options evaluated in this study and did not meet the EPA's efficacy standard for biocides. Differences in methods and procedures reported by other investigators make quantitative comparisons among studies difficult.
Date: February 16, 2010
Creator: Raber, E & Burklund, A
Partner: UNT Libraries Government Documents Department

Novel Graphite Salts and Their Electrical Conductivities

Description: A set of novel first stage graphite salts of general formula C{sub 8}{sup +}MF{sub 6}{sup -} has been prepared (M = Os, Ir, As). Single crystal X-ray diffraction studies indicate that these salts are hexagonal with a {approx} 4.9 and c {approx} 8.1 {angstrom}. The unit cell volume indicates that the anions are closely packed in the galleries. Platinum hexafluoride, which is the most powerful oxidizer of the third transition series, forms a first stage compound, which analytical, structural, and magnetic studies establish as C{sub 12}{sup 2+}PtF{sub 6}{sup 2-}. In this salt the anions are not close packed, but the electron withdrawal from the graphite planes is greater than for the C{sub 8}{sup +}MF{sub 6}{sup -} series. The variation in the electrical conductivity (in the a-b plane), as a function of composition, has been investigated with the OsF{sub 6}, IrF{sub 6}, PtF{sub 6} and AsF{sub 5} intercalates. For OsF{sub 6} and IrF{sub 6}, the conductance per plane of graphite is found to be a maximum at approximately C{sub 24}MF{sub 6} (second stage); the conductivity being an order of magnitude greater than that of the parent material. Intercalation beyond C{sub 24}MF{sub 6} leads to a marked decrease in conductivity. C{sub 8}MF{sub 6} is comparable in conductivity with the parent graphite. This behavior contrasts with the graphite/AsF{sub 5} system in which a steady increase in conductance per graphite plane with increasing AsF{sub 5} content is observed. For the PtF{sub 6} system, the second as well as the first stage materials are poorly conducting.
Date: February 1, 1980
Creator: Bartlett, N.; McCarron, E. M.; McQuillan, B. W. & Thompson, T. E.
Partner: UNT Libraries Government Documents Department

Supercritical water oxidation data acquisition testing. Final report, Volume I

Description: This report discusses the phase one testing of a data acquisition system for a supercritical water waste oxidation system. The system is designed to destroy a wide range of organic materials in mixed wastes. The design and testing of the MODAR Oxidizer is discussed. An analysis of the optimized runs is included.
Date: November 1, 1996
Partner: UNT Libraries Government Documents Department

Final Report: Fiscal Year 1997 demonstration of omnivorous non-thermal mixed waste treatment: Direct chemical oxidation of organic solids and liquids using peroxydisulfate

Description: Direct Chemical Oxidation (DCO) is a non-thermal, ambient pressure, aqueous-based technology for the oxidative destruction of the organic components of hazardous or mixed waste streams. The process has been developed for applications in waste treatment, chemical demilitarization and decontamination at LLNL since 1992. The process uses solutions of the peroxydisulfate ion (typically sodium or ammonium salts) to completely mineralize the organics to carbon dioxide and water. The expended oxidant may be electrolytically regenerated to minimize secondary waste. The paper briefly describes: free radical and secondary oxidant formation; electrochemical regeneration; offgas stream; and throughput.
Date: January 1, 1998
Creator: Cooper, J.F.
Partner: UNT Libraries Government Documents Department