Review of Kinetics of elementary reactions in low- temperature autoignition chemistry Paper by: Judit Zádor, Craig A. Taatjes, and Ravi X. Fernandes Tyler Strickland

Overview Background Reactions involved in low temperature combustion Experimental methods Theoretical methods Requirements for progress Landmark findings Conclusion

Chain propagation reactions can be segregated into three categories Abstraction (internal or external) Functional group is replaced to a different bond Addition Functional group is added to the substrate Substitution and metathesis Functional group is replaced by another Propene + OH to ethane + CH2OH

Reaction schematic for low temperature combustion

Experimental data can be retrieved in three methods High level Overreaching mechanism data collection HCCI, compression machine Classical kinetics Analysis of stable species after controlled reaction Time-resolved kinetics Dynamic reaction tracking Laser photolysis/synchrotron photoionization mass spectrometry (PIMS)

Modeling elementary reactions is based on 4 pillars

Synergy between modeling and experiments is required for effective and efficient advancement The flexibility and insight of theoretical modeling is absolutely required Branching fraction can be determined by 1kcal/mol QOOH radicals have never been experimentally observed Said models must be validated using available experimental data The elementary reaction of vinyl with O 2 has had 3 independent models with 3 different results This is not a novel concept and successful execution of this has been preformed in many disciplines

Identified advances in the field Formally direct pathways have been identified Ignorance contributes to difficulties in mechanisms such as those of Lawrence Livermore (LLNL) Some relations can be used to characterize untested reactions Larger oxygenated molecules can be related to alkanes Alcohols have lower energy pathways to OH production (thermal decomposition)

More work has to be done Novel fuels are typically oxygenated New combustion strategies for volumetric ignition Pressure dependence of reactions is very unknown QOOH species needs to be experimentally substantiated

Thanks for your attention. Questions? Fun facts Judit Zádor, Craig A. Taatjes, and Ravi X. Fernandes cited 519 sources Capitol ‘C’ used 2055 times ‘H’ used 2010 times (it was published in 2010; coincidence?) ‘O’ used 2356 times ‘N’ used 198 times