Excited mercury–ammonia system. Part 1.—Kinetics of the attachment of NH3and ND3to Hg(63P0), and measurement of the emission rates

Abstract

Mixtures of NH₃ or ND₃ and Hg vapour were excited with flashes of the 2537 Å resonance radiation. By observing relaxation times for the decay of the HgNH^* ₃ emission at 3500 Å, rate coefficients were measured at 293 K for the following processes: Hg(6³P₀)+ NH₃(ND₃)→ Hg(6¹S₀)+ NH₃(ND₃)+hν(2), Hg(6³P₀)+ NH₃(ND₃)+ M → HgNH^* ₃(HgND*)+ M [M = N₂ or NH₃(ND₃)](3), HgNH^* ₃(HgND^* ₃)→ Hg(6¹S₀)+ NH₃(ND₃)+hν(4) The rate coefficient of reaction (3) was also recorded with high ammonia pressures by measuring the competitive rate of removal of Hg(6³P₀) by H₂. From a consideration of the relative magnitudes of the rate coefficients of (2) and (3), it is suggested that the emission rate of the mercury ammonia complex increases with increasing internal energy.