Neutral and ion chemistry in low pressure dc plasmas of H2/N2 mixtures: routes for the efficient production of NH3 and NH4

• Published in: Physical chemistry chemical physics : PCCP 2011-01, Vol.13 (43), p.19561-19572
• Main Authors: CARRASCO, Esther, JIMENEZ-REDONDO, Miguel, TANARRO, Isabel, HERRERO, Victor J
• Format: Article
• Language: English
• Subjects: Chemistry; Density; Direct current; Electron temperature; Exact sciences and technology; General and physical chemistry; Hydrogenation; Low pressure; Plasmas; Reactors; Stress concentration
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/c1cp22284h

The chemistry in low pressure (0.8-8 Pa) plasmas of H(2) + 10% N(2) mixtures has been experimentally investigated in a hollow cathode dc reactor using electrical probes for the estimation of electron temperatures and densities, and mass spectrometry to determine the concentration of ions and stable neutral species. The analysis of the measurements by means of a kinetic model has allowed the identification of the main physicochemical mechanisms responsible for the observed distributions of neutrals and ions and for their evolution with discharge pressure. The chemistry of neutral species is dominated by the formation of appreciable amounts of NH(3) at the metallic walls of the reactor through the successive hydrogenation of atomic nitrogen and nitrogen containing radicals. Both Eley-Rideal and Langmuir-Hinshelwood mechanisms are needed in the chain of hydrogenation steps in order to account satisfactorily for the observed ammonia concentrations, which, in the steady state, are found to reach values ~30-70% of those of N(2). The ionic composition of the plasma, which is entirely due to gas-phase processes, is the result of a competition between direct electron impact dissociation, more relevant for high electron temperatures (lower pressures), and ion-molecule chemistry that prevails for the lower electron temperatures (higher pressures). At the lowest pressure, products from the protonation of the precursor molecules (H(3)(+), N(2)H(+) and NH(4)(+)) and others from direct ionization (H(2)(+) and NH(3)(+)) are found in comparable amounts. At the higher pressures, the ionic distribution is largely dominated by ammonium. It is found that collisions of H(3)(+), NH(3)(+) and N(2)H(+) with the minor neutral component NH(3) are to a great extent responsible for the final prevalence of NH(4)(+).