Publications

Inference of H2O2 thermal decomposition rate parameters from experimental statistics

Casey, Tiernan A.; Khalil, Mohammad K.; Najm, H.N.

The thermal decomposition of H2O2 is an important process in hydrocarbon combustion playing a particularly crucial role in providing a source of radicals at high pressure where it controls the 3rd explosion limit in the H2-O2 system, and also as a branching reaction in intermediatetemperature hydrocarbon oxidation. As such, understanding the uncertainty in the rate expression for this reaction is crucial for predictive combustion computations. Raw experimental measurement data, and its associated noise and uncertainty, is typically unreported in most investigations of elementary reaction rates, making the direct derivation of the joint uncertainty structure of the parameters in rate expressions difficult. To overcome this, we employ a statistical inference procedure, relying on maximum entropy and approximate Bayesian computation methods, and using a two-level nested Markov Chain Monte Carlo algorithm, to arrive at a posterior density on rate parameters for a selected case of laser absorption measurements in a shock tube study, subject to the constraints imposed by the reported experimental statistics. The procedure constructs a set of H2O2 concentration decay profiles consistent with these reported statistics. These consistent data sets are then used to determine the joint posterior density on the rate parameters through straightforward Bayesian inference. Broadly, the method also provides a framework for the replication and comparison of missing data from different experiments, based on reported statistics, for the generation of consensus rate expressions.