Nonequilibrium effects in thermal plasma chemistry

Numerical calculations have been performed to assess the potential significance of nonequilibrium effects on chemical reactivity in thermal plasmas The calculations consider situations in which the electron temperature and/or the electron density are elevated above their equilibrium values corresponding to the local gas temperature. Such nonequilibrium may occur in the plasma torch itself or could be purposefully imposed by a controlled hybrid discharge in a downstream reactor region so as to augment reactivity over a longer residence time. The calculations account for finite ionization/recombination rates of atomic and molecular species, electron-impact dissociation, dissociative recombination, dissociative attachment, and predissociation effects, as well as thermal reactions between neutral chemical species. As an example of the possible nonequilibrium enhancement of molecular decomposition, initial consideration has focused on the dissociation rates of diatomic species where heavy particle reaction rates and cross sections can be reasonably estimated. The results show that for O₂ or H₂ in argon at moderate temperatures, electron-temperature elevation can give rise to a notable enhancement of the dissociation rate, in comparison with the equilibrium case. Depending on the situation, it is found that either relatively energetic electron-impact dissociation or dissociative attachment (for O₂) can dominate the enhanced dissociation rate—which can be more than a factor of 2 greater than in the absence of a discharge. Similar effects would be expected for the decomposition of more complicated molecules.