A detailed kinetic submechanism for OH[formula omitted] chemiluminescence in hydrogen combustion revisited. Part 1

Abstract

In this series of two papers, we present a novel physically sound kinetic submechanism aimed at modeling the formation and decay of chemiluminescent (electronically excited) OH∗ molecules in the ignition and combustion of hydrogen and hydrogen-based mixtures over a wide range of thermodynamic parameters and mixture compositions. The present part of this series describes the preparatory stages of the work, such as the aggregation of the data set for the OH∗ chemiluminescent emission (including the OH∗ emission profiles obtained in our shock-tube experiments), the choice of the basic kinetic model of hydrogen oxidation, and, importantly, quantum chemical calculations and theoretical estimates for the rate constant of the nonadiabatic preassociation reaction H + O + M ⇆ OH∗ + M, recognized as a major source of excited OH∗ molecules in hydrogen-air flames. These rate constant estimates are carried out in a wide range of temperatures (200–4000 K) and pressures (10−3−100 bar). It is shown that the rate constant of this key reaction exhibits distinct non-Arrhenius temperature behavior and, moreover, has a complex fall-off pressure dependence, with the transition from a third to a second-order, high-pressure regime occurring at pressures about 10 atm. The obtained dependence on temperature and pressure is in excellent agreement with the known experimental data and can be recommended (as part of the appropriate reaction mechanisms) for further kinetic modeling of OH∗ chemiluminescence accompanying the high-temperature oxidation of hydrogen and other fuels.Novelty and Significance StatementAlthough ultraviolet OH∗ chemiluminescence as an optical signature of the combustion process and the underlying chemistry is known to provide unique capabilities for combustion diagnostics, the development of the detailed reaction mechanisms intended for quantitative interpretation of the OH∗ emission measurements has now almost stagnated. Indeed, existing kinetic models contain a discouragingly small number of elementary processes and, apparently, do not account for the full variety of possible reaction pathways of OH∗ formation and depletion. Therefore, in this serial work, we have revised the current ideas about the kinetics of OH∗ production and consumption during ignition and combustion and focused first on the OH∗ kinetics in a reacting H2/O2/Ar/N2 mixture. The fundamentally significant and novel results of this Part of the present series are (i) the rate constant of the nonadiabatic preassociation reaction H + O + M ⇆ OH∗ + M (the primary source of OH∗ in hydrogen combustion), theoretically obtained for the first time as a function of temperature and pressure, and (ii) the OH∗ emission profiles obtained in our shock-tube experiments. The other aspects described here, such as the aggregation of the literature-based data set for the post-shock OH∗ chemiluminescent emission and the choice of the basic kinetic model of hydrogen oxidation, are also of interest and relevance.