Automated reaction mechanism generation : improving accuracy and broadening scope

Chemical kinetic modeling plays an important role in the study of reactive chemical systems. Thus, an automated means of constructing chemical kinetic models forms a useful tool in the engineering and science surrounding such systems. This document describes work to further develop one such tool, known as RMG (Reaction Mechanism Generator). Focus is placed on improving the accuracy of parameter estimation in the mechanism generation process and expanding the scope of applicability of the tool. In particular, effort has targeted the generation and use of explicit three-dimensional molecular structures for chemical species considered during reaction mechanism generation. This work has resulted in the generation of a software system integrated with RMG that can automatically generate and use such structures with quantum chemistry or force field codes to obtain more reliable thermochemistry estimates for cyclic structures without human intervention. Ultimately, the result of these updates is improved usefulness and reliability of the software system as a predictive tool. An application of the tool to the high temperature oxidation of JP-10, a jet fuel often used in military applications, is described. Using the newly refined RMG system, a detailed chemical kinetic model was constructed for this system. The resulting model represents a significant improvement upon existing work for JP- 10 oxidation by capturing detailed chemistry for this system. Simulations with this model have been found to produce results for ignition delay and product distribution that compare favorably with experimental results. The successful application of the refined RMG software system to this system demonstrates the practical utility of these updates.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemical Engineering.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2012

Author dc:creator

• Magoon, Gregory Russell

Advisor dc:contributor.advisor

• William H. Green.

• 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/1721.1/76484

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/76484