A quantitative explanation for the apparent anomalous temperature dependence of OH + HO2 = H2O + O2 through multi-scale modeling

Abstract

Kinetic models for complex chemical mechanisms are comprised of tens to thousands of reactions with rate constants informed by data from a wide variety of sources – rate constant measurements, global combustion experiments, and theoretical kinetics calculations. In order to integrate information from distinct data types in a self-consistent manner, a framework for combustion model development is presented that encapsulates behavior across a wide range of chemically relevant scales from fundamental molecular interactions to global combustion phenomena. The resulting kinetic model consists of a set of theoretical kinetics parameters (with constrained uncertainties), which are related through kinetics calculations to temperature/pressure/bath-gas-dependent rate constants (with propagated uncertainties), which in turn are related through physical models to combustion behavior (with propagated uncertainties). Direct incorporation of theory in combustion model development is expected to yield more reliable extrapolation of limited data to conditions outside the validation set, which is particularly useful for extrapolating to engine-relevant conditions where relatively limited data are available. Several key features of the approach are demonstrated for the H2O2 decomposition mechanism, where a number of its constituent reactions continue to have large uncertainties in their temperature and pressure dependence despite their relevance to high-pressure, low-temperature combustion of a variety of fuels. Here, we use the approach to provide a quantitative explanation for the apparent anomalous temperature dependence of OH+HO2=H2O+O2 – in a manner consistent with experimental data from the entire temperature range and ab initio transition-state theory within their associated uncertainties. Interestingly, we do find a rate minimum near 1200K, although the temperature dependence is substantially less pronounced than previously suggested.