Abstract
Ion chemistry with temperature evolution in weakly ionized plasma is important in plasma-assisted combustion and plasma-assisted catalysis, fuel reforming, and material synthesis due to its contribution to plasma generation and state transition. In this study, the kinetic roles of ionic reactions in nanosecond discharge (NSD) plasma-assisted temperature-dependent decomposition and oxidation of methane are investigated by integrated studies of experimental measurements and mathematical simulations. A detailed plasma chemistry mechanism governing the decomposition and oxidation processes in a He/CH4/O2 combustible mixture is proposed and studied by including a set of electron impact reactions, reactions involving excited species, and ionic reactions. A zero-dimensional model incorporating the plasma kinetics solver ZDPlasKin and the combustion chemical kinetics solver CHEMKIN is used to calculate the time evolution of the ion density. Uncertainty analysis of ionic reactions on key species generation is conducted by using different referenced data, and insignificant sensitivity is found. The numerical model is consistent with experimental data for methane consumption and generation of major species including CO, CO2, and H2. By modeling the temporal evolution of key ions, it is observed that O2+ presents the largest concentration in the discharge stage, followed by CH4+, CH3+, and CH2+, which is in accordance with the traditional ion chemistry in hydrocarbon flames and agrees well with molecular-beam mass spectrometer investigations. The path flux shows that the concentrations of key species, including electrons, O, OH, H, O(1D), O2(a1Δg), O2+, CH3+, and CH4+, change within 1–2 orders of magnitude and that the transition from a homogeneous state to a contracted/constricted state does not occur. The path flux and sensitivity analysis reveal the significant roles of cations in the stimulation of active radical generation, including CH, O, OH, and O(1D), thus accelerating methane oxidation. This work provides a deep insight into the ion chemistry of temperature-dependent plasma-assisted CH4 oxidation.
Transition-State Expansion: A Quantitative Model for Counterion Effects in Ionic Reactions
