Issue 10 Volume 41 May 16, 2003

This report discusses high energy density matter: polyhedral oligomeric silsesquioxanes (POSS), non-linear optical
materials. Also, theoretical methods and benchmarks are discussed: ab initio electronic structure theory, nuclear-electronic
orbital approach, and centroid molecular dynamics.
DTIC
Molecular Dynamics; Rocket Propellants
20030034908 Lawrence Livermore National Lab., Livermore, CA
Kinetic Study of the Combustion of Phosphorus Containing Species
Glaude, P. A.; Curran, H. J.; Pitz, W. J.; Westbrook, C. K.; Oct. 22, 1999; 20 pp.; In English
Report No.(s): DE2002-791455; No Copyright; Avail: Department of Energy Information Bridge
The combustion of organophosphorus compounds is of great interest for the incineration of chemical warfare agent and
their use in flame inhibition as halon replacement. The thermochemical data of these species and the reactions involved at high
temperature are not well known, despite some recent experimental studies. With BAC-MP4 ab initio estimations as a basis
and semi-empirical estimations for many new compounds, the thermochemistry of organophosphorus compounds is studied.
New group additivity values are proposed for enthalpies of formation at 298K, entropies and heat capacities of species
involving pentavalent phosphorus bonded to carbon, hydrogen, oxygen, fluorine, nitrogen and sulfur atoms. The kinetic of
unimolecular elimination is investigated by modeling pyrolysis experiments of DEMP, TEP and DIMP. A new combustion
mechanism is described and applied to the modeling of DMMP reaction in a H2/O2, flame.
NTIS
Combustion; Phosphorus Compounds; Oxidation-Reduction Reactions; Reaction Kinetics; Organic Compounds
20030037012 Lawrence Livermore National Lab., Livermore, CA
Prediction of Carbon Monoxide and Hydrocarbon Emissions in Isooctane HCCI Engine Combustion Using Multi-Zone
Simulations
Flowers, D. L.; Aceves, S. M.; Martinez-Fias, J.; Dibble, R. W.; May 02, 2002; 30 pp.; In English
Report No.(s): DE2002-15002362; UCRL-JC-148209; No Copyright; Avail: Department of Energy Information Bridge
Homogeneous Charge Compression Ignitions (HCCI) engines show promise as an alternative to Diesel engines, yet
research remains: development of practical HCCI engines will be aided greatly by accurate modeling tools. A novel detailed
chemical kinetic model that incorporates information from a computational fluid mechanics code has been developed to
simulate HCCI combustion. This model very accurately predicts many aspects of the HCCI combustion process.
High-resolution computational grids can be used for the fluid mechanics portion of the simulation, but the chemical kinetics
portion of the simulation can be reduced to a handful of computational zones (for all previous work 10 zones have been used).
While overall this model has demonstrated a very good predictive capability for HCCI combustion, previous simulations using
this model have tended to underpredict carbon monoxide emissions by an order of magnitude. A factor in the underprediction
of carbon monoxide may be that all previous simulations have been conducted with 10 chemical kinetic zones. The chemistry
that results in carbon monoxide emissions is very sensitive to small changes in temperature within the engine. The resolution
in temperature is determined directly by the number of zones. This paper investigates how the number of zones (i.e.
temperature resolution) affects the model’s prediction of hydrocarbon and carbon monoxide emissions in an HCCI engine.
Simulations with 10, 20, and 40 chemical kinetic zones have been conducted using a detailed chemical kinetic mechanism
(859 species, 3606 reactions) to simulate an isooctane fueled HCCI engine. The results show that 10-zones are adequate to
resolve the hydrocarbon emissions, but a greater numbers of zones are required to resolve carbon monoxide emissions. Results
are also presented that explore spatial sources of the exhaust emissions within the HCCI engine combustion chamber.
NTIS
Carbon Monoxide; Hydrocarbons; Prediction Analysis Techniques; Emission; Combustion Chambers
20030037020 National Renewable Energy Lab., Golden, CO
Issues associated with the Use of Higher Ethanol Blends (E17-E24)
Hammel-Smith, C.; Fang, J.; Powers, M.; Aabakken, J.; Oct. 2002; In English
Report No.(s): DE2002-15000996; No Copyright; Avail: National Technical Information Service (NTIS)
This report reviews the issues associated with utilizing higher ethanol blends (E17-E24), and is intended to advise the
Department of Energy (DOE) on factors that might encourage or constrain the integration of such blends into the marketplace.
Subjects include technical vehicle issues, emissions and emissions testing, infrastructure, market issues, and regulatory and
policy considerations. These subjects are examined in relation to both the changes needed to accommodate higher ethanol
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