Further Developments in Multi-Scale Combustion Models
M.P. Burke,1* S.J. Klippenstein,1 L.B. Harding,1 C.F. Goldsmith,2 A.W. Jasper,3
L. Sheps, 3 O. Welz, 3 J. Zádor, 3 H. Huang, 3 C.A. Taatjes 3
1
Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA
Department of Inorganic Chemistry, Fritz Haber Institute, Berlin, 14195, Germany
3
Combustion Research Facility, Sandia National Laboratories, MS 9055, Livermore, CA 94551-0969, USA
* mpburke@anl.gov
3
As the power of scientific computing continues to grow, detailed models for complex chemicaltransport phenomena play a more significant role in the design process of advanced energy
conversion devices (e.g. Ref. 1). As a result, there have been substantial research efforts devoted
to the construction and further development of detailed chemical models for conventional and
alternative fuels. However, given the enormous range of temperature/pressure/bath-gas
conditions of potential interest, kinetic models are often applied at conditions far outside their
validation set, resulting in frequent deficiencies in model performance. We have developed a
multi-scale approach2 to combustion model formulation that directly incorporates kinetic theory
as a means to ensure a physically meaningful kinetic model and to provide reliable extrapolation
to engine-relevant conditions. This modeling technique integrates information from a wide
variety of sources – rate constant measurements, global combustion experiments, and ab initio
theoretical kinetics calculations. The resulting kinetic model consists of a set of theoretical
kinetics parameters (with constrained uncertainties) that can be related through kinetics
calculations to rate constants (with propagated uncertainties) that can in turn be related through
physical models to combustion behavior (with propagated uncertainties). A paper2 to be
presented at this meeting reveals results from application of this approach to the H2O2
decomposition system – yielding an optimized model that is consistent with ab initio calculations
and raw experimental data for OH + HO2 = H2O + O2 across the entire temperature range,
including those that had previously indicated a peculiar, deep rate minimum near 1000 K. The
present poster highlights further developments in multi-scale combustion modeling, such as
comparison of optimized theoretical kinetics parameters with high-level ab initio electronic
structure calculations and application of the technique to low-temperature propyl oxidation as a
test bed for reaction systems containing multiple potential-energy wells.
References
(1) Hwang, W. Dec, J. Sjöberg, M. Combust. Flame 154 (2008) 387–409.
(2) M.P. Burke, S.J. Klippenstein, L.B. Harding, “A Quantitative Explanation for the Apparent
Anomalous Temperature Dependence of OH + HO2 = H2O + O2 through Multi-Scale Modeling,”
Proc. Comb. Inst. (2012) accepted.
This work was supported by a Director’s Postdoctoral Fellowship from Argonne National Lab and by the U.S.
Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and
Biosciences, under Contract Nos. DE-AC02-06CH11357 and DE-AC04-94-AL85000, and the U.S. Department of
Energy, in part under the Argonne-Sandia Consortium on High-Pressure Combustion Chemistry, (ANL FWP #
59044; SNL FWP # 014544). Sandia is a multi-program laboratory operated by Sandia Corporation, a Lockheed
Martin Company, for the National Nuclear Security Administration under contract DE-AC04-94-AL85000.