The reaction of NH3 with Hg(P-3(0))

A modification of the rotating sector method has been used to study the mercury-photosensitized luminescence of ammonia. At low ammonia pressures the intensity of the modulated luminescence decreases rapidly with increasing frequency of modulation, showing that a slow process must intervene between the rapid quenching of Hg(P-3(1)) by NH3 and the rapid emission of radiation by the excited Hg center dot NH3 complex, It is postulated that the initial quenching step results in the formation of metastable Hg(P-3(0)) and that the slow process is the reaction of this species with NH3. From the variation of emission intensity with modulation frequency the rate of the slow step is found to be 4.3 x 10(-13) cm(9)molecule(-1)sec(-1).