12 Matching Results

Search Results

Advanced search parameters have been applied.

Modeling and Experimental Investigation of Methylcyclohexane Ignition in a Rapid Compression Machine

Description: A new mechanism for the oxidation of methylcyclohexane has been developed. The mechanism combined a newly-developed low temperature mechanism with a previously developed high temperature mechanism. Predictions from the chemical kinetic model have been compared to experimentally measured ignition delay times from a rapid compression machine. Predicted ignition delay times using the initial estimates of the methylcyclohexyl peroxy radical isomerization rate constants were much longer than those measured at low temperatures. The initial estimates of isomerization rate constants were modified based on the experimental findings of Gulati and Walker that indicate a much slower rate of isomerization. Predictions using the modified rate constants for isomerizations yielded faster ignition at lower temperatures that greatly improved the agreement between model predictions and the experimental data. These findings point to much slower isomerization rates for methylcyclohexyl peroxy radicals than previously expected.
Date: October 13, 2005
Creator: Pitz, W J; Naik, C V; Mhaold?in, T N; Curran, H J; Orme, J P; Simmie, J M et al.
Partner: UNT Libraries Government Documents Department

Analysis of Hydroperoxides in solid Polyethylene by NMR and EPR Spectroscopy

Description: The authors have shown that the hydroperoxide species in {gamma}-irradiated {sup 13}C-polyethylene can be directly observed by {sup 13}C MAS NMR spectroscopy. The experiment was performed without the need for special sample preparation such as chemical derivatization or dissolution. Annealing experiments were employed to study the thermal decomposition of the hydroperoxide species and to measure an activation energy of 98 kJ/mol. EPR spectroscopy suggests that residual polyenyl and alkylperoxy radicals are predominantly trapped in interracial or crystalline regions, while the peroxy radicals observed after UV-photolysis of hydroperoxides are in amorphous regions.
Date: June 12, 2000
Partner: UNT Libraries Government Documents Department

Pentan isomers compound flame front structure

Description: The fuels (hexane, pentane, diethyl ether) and conditions investigated in this study are relevant to engine knock in spark- ignition engines. A review is provided of the field of low temperature hydrocarbon oxidation. Studies were made of radical and stable intermediate distribution in the front of cool flames: Maximum concentrations of H atoms and peroxy radicals were observed in the luminous zone of the cool flame front. Peroxy radicals appear before the luminous zone at 430 K due to diffusion. H atoms were found in cool flames of butane and hexane. H atoms diffuses from the luminous zone to the side of the fresh mixture, and they penetrate into the fresh mixture to a small depth. Extension of action sphear of peroxy radicals in the fresh mixture is much greater than that of H atoms due to their small activity and high concentrations.
Date: August 13, 1995
Creator: Mansurov, Z. A.; Mironenko, A. W.; Bodikov, D. U. & Rachmetkaliev, K. N.
Partner: UNT Libraries Government Documents Department

Reaction of Phenyl Radical with O2: Thermodynamic Properties, Important Reaction Paths and Kinetics

Description: The Phenyl + O{sub 2} association results in a chemically activated phenyl-peroxy radical which can dissociate to phenoxy radical + O, undergo intramolecular addition of the peroxy radical to several unsaturated carbon sites or react back to phenyl + O{sub 2}. The intramolecular addition channels further react through several paths to ring opening (unsaturated + carbonyl moieties) as well as cyclopentadieny radical + CO{sub 2}. Enthalpy ({Delta}H{sub f(298)}{sup o}), Entropy (S{sub 298}), and heat capacities Cp(T) for species in the decomposition of the ring are evaluated using density functional and ab initio calculations and by comparisons to vinyl + O{sub 2} data of Mebel et al, and phenyl + O{sub 2} data of Hadad et al. Isodesmic reaction analysis is used to estimate enthalpy values of the intermediates and well depths of the adducts. High Pressure limit kinetic parameters are obtained from the calculation results using canonical Transition State Theory. Quantum RRK analysis is utilized to obtain k(E) and modified strong collision or master equation analysis is used for evaluation of pressure fall-off in this complex bimolecular, chemical activation, reaction system. Uncertainty in key barriers is discussed, resulting variations in important reaction product ratios are illustrated, and changes in these branching ratios are evaluated with a detailed reaction mechanism.
Date: April 12, 2001
Creator: Bozzelli, J; Sebbar, N; Pitz, W & Bockhorn, H
Partner: UNT Libraries Government Documents Department

Application of natural radionuclides for determination of tropospheric ozone and aerosol transport.

Description: Natural radionuclides have been proposed for use in assessing the transport of ozone and aerosols in the troposphere. For example, {sup 7}Be is known to be produced in the upper troposphere and lower stratosphere by interactions with cosmogenic particles. Beryllium-7 has a 53.28-day half-life and is a gamma emitter that attaches itself to fine particles in the atmosphere once it is formed. Indeed, in tropospheric aerosol samples TBe is typically found in association with aerosol particles that are 0.3 {micro}m in diameter. Some investigators have asserted that ozone from aloft can be transported into rural and urban regions during stratospheric/tropospheric folding events, leading to increased background levels of ozone. During the Texas 2000 Air Quality study, aerosol samples with a 2.5-{micro}m cutoff were collected during 12-hour cycles (day/night) for a 30-day period at the Deer Park, Texas, field site in August-September 2000. To monitor {sup 7}Be levels, high-volume samples were collected on glass fiber filters on Julian dates 225-259. Sample collection was at a field site near a city park, away from any nearby traffic. This site is under routine operation by the Texas Natural Resource Conservation Commission. Instruments operated at this same site during the study period included an ozone monitor (Dasibi), a nitrogen oxides instrument (API), a CO instrument (API), a nephelometer, a UV-B meter (Richardson-Berger), and a multifilter rotating shadow band radiometer (MFRSR, Yankee Environmental Systems). In addition, we made modified fast-response NO{sub 2} and peroxyacetyl nitrate (PAN) measurements by using a fast gas chromatography with luminol detection, to be described at this meeting (3). The results for {sup 7}Be (mBq m{sup {minus}3})are compared in Figure 1 with the maximum and average ozone values (ppb) observed at the site to identify potential correlations. In Figure 2, all of the {sup 7}Be data are plotted against the maximum ...
Date: December 6, 2000
Creator: Gaffney, J. S.; Marley, N. A.; Drayton, P. J. & Orlandini, K. A.
Partner: UNT Libraries Government Documents Department

Pulse radiolytic studies of electron transfer processes and applications to solar photochemistry. Progress report, [March 1992--March 1993]

Description: Electron transfer and other reactions of various short-lived intermediates have been studied by pulse radiolysis and laser flash photolysis. Highlights of results during the past year are summarized under two main sections: Metalloporphyrin electron transfer and associated reactions, and solvent effects on reactions of inorganic radicals and organic peroxyl radicals.
Date: April 1, 1993
Creator: Neta, P.
Partner: UNT Libraries Government Documents Department

Tropospheric chemistry of natural hydrocarbons, aldehydes, and peroxy radicals: Their connections to sulfuric acid production and climate effects

Description: Recent work has shown that natural hydrocarbon emissions can significantly affect the levels of urban and regional tropospheric ozone. We report on the reactivities of these biogenic trace gases, particularly isoprene, focusing on their importance in the production of aldehydes and peroxy radicals, leading to increased levels of hydrogen over regional forests. Hydrogen peroxide can lead to the wet oxidation of sulfur dioxide to acidic sulfate in aerosols, fogs, and clouds. In turn, acidic sulfate can act to as a light scattering aerosol and a source of cloud condensation nuclei (CCN), potentially leading to global cooling. Aerosol sulfate and other dissolved organic and inorganic compounds can also play important roles as a greenhouse species in the lower troposphere.
Date: May 1, 1993
Creator: Gaffney, J. S. & Marley, N. A.
Partner: UNT Libraries Government Documents Department

Decay of peroxy radicals of methanol and isopropanol in the presence of copper ions and superoxide dismutase. Progress report, December 1, 1978--November 30, 1979

Description: The decay of the peroxy radicals produced from methanol and isopropanol was followed in the presence and in the absence of Cu/sup 2 +/ ions, and the enzyme Superoxide Dismutase. The results indicate that both Cu/sup 2 +/ and Superoxide do not affect the decay of the alcohol peroxy radicals. They catalyze the decay of O/sup -//sub 2/ radicals which are formed from the alcoholic peroxy radicals, and which absorb light at the same wavelengths region as these radicals. This catalysis enables the resolution of the decay of the alcoholic peroxy radicals, without the interference of absorption changes originating in the decay of HO/sub 2/ and O/sup -//sub 2/ radicals.
Date: January 1, 1979
Creator: Ilan, Y A; Ilan, Y & Czapski, G
Partner: UNT Libraries Government Documents Department

Reaction mechanisms in the radiolysis of peptides, polypeptides and proteins

Description: The purpose of this review is to bring together and to correlate the wide variety of experimental studies that provide information on the reaction products and reaction mechanisms involved in the radiolysis of peptides, polypeptides and proteins (including chromosomal proteins) in both aqueous and solid-state systems. The comparative radiation chemistry of these systems is developed in terms of specific reactions of the peptide main-chain and the aliphatic, aromatic-unsaturated and sulfur-containing side-chains. Information obtained with the various experimental techniques of product analysis, competition kinetics, spin-trapping, pulse radiolysis and ESR spectroscopy is included. 147 refs.
Date: January 1, 1985
Creator: Garrison, W.M.
Partner: UNT Libraries Government Documents Department