Kinetic mechanism of molecular energy transfer and chemical reactions in low-temperature air-fuel plasmas

This work describes the kinetic mechanism of coupled molecular energy transfer and chemical reactions in low-temperature air, H-2-air and hydrocarbon-air plasmas sustained by nanosecond pulse discharges (single-pulse or repetitive pulse burst). The model incorporates electron impact processes, state-specific N-2 vibrational energy transfer, reactions of excited electronic species of N-2, O-2, N and O, and 'conventional' chemical reactions (Konnov mechanism). Effects of diffusion and conduction heat transfer, energy coupled to the cathode layer and gasdynamic compression/expansion are incorporated as quasi-zero-dimensional corrections. The model is exercised using a combination of freeware (Bolsig+) and commercial software (ChemKin-Pro). The model predictions are validated using time-resolved measurements of temperature and N-2 vibrational level populations in nanosecond pulse discharges in air in plane-to-plane and sphere-to-sphere geometry; temperature and OH number density after nanosecond pulse burst discharges in lean H-2-air, CH4-air and C2H4-air mixtures; and temperature after the nanosecond pulse discharge burst during plasma-assisted ignition of lean H-2-mixtures, showing good agreement with the data. The model predictions for OH number density in lean C3H8-air mixtures differ from the experimental results, over-predicting its absolute value and failing to predict transient OH rise and decay after the discharge burst. The agreement with the data for C3H8-air is improved considerably if a different conventional hydrocarbon chemistry reaction set (LLNL methane-n-butane flame mechanism) is used. The results of mechanism validation demonstrate its applicability for analysis of plasma chemical oxidation and ignition of low-temperature H-2-air, CH4-air and C2H4-air mixtures using nanosecond pulse discharges. Kinetic modelling of low-temperature plasma excited propane-air mixtures demonstrates the need for development of a more accurate 'conventional' chemistry mechanism.