Integrated pressure-dependence in automated mechanism generation : a new tool for building gas-phase kinetic models

A host of vital, current, and developing technologies, such as pyrolysis, thermal cracking, partial oxidation, and high-efficiency combustion engines, involve complex, gas-phase chemical mechanisms with hundreds of species and thousands of reactions. Building complete, explicit chemical models by-hand for these systems is exceedingly difficult. The bias and intuition of the developers figure strongly in the resultant mechanism, causing important but unanticipated pathways to be ignored, and useless pathways to be included. Thus many chemists and engineers have tried artificial intelligence software tools, or "automated mechanism generators", to build large chemical mechanisms systematically. These tools employ graph-theory algebra, and "rate rules" - estimates of rate constants for classes of reactions - to construct automatically all the possibly important reactions and species for a given set of conditions. All of these tools have been severely hampered by their inability to capture the effects of pressure-dependence and falloff - even though these effects are important in almost every gas-phase system of interest to engineers and designers. Pressure-dependent reactions cannot be included using simple rate rules. Until now they presented an unresolved quandary for automated mechanism generators. This work presents the first automated method for including pressure-dependent reactions generally and systematically, on-the-fly, in computerized mechanism generation.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemical Engineering.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2003

Author dc:creator

• Matheu, David M. (David Michael), 1974-

Advisor dc:contributor.advisor

• William H. Green, Jr.

• Chemical Engineering.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/29294

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/29294