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Pulsed laser photofragment emission for detection of mercuric chloride

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Abstract

The viability of pulsed laser photofragment emission (PFE) is evaluated for the in situ measurement of vapor-phase mercuric chloride (HgCl2) concentration in combustion flue gas. Dispersed emissions from both the Hg(6P13) and HgCl(BΣ+2) photoproducts are presented, and the dependence of the HgCl2 PFE signal originating from Hg(6P13) on the collisional environment is examined for buffer-gas mixtures of N 2, O 2, and CO2. Integrated PFE intensity measurements as a function of buffer gas pressure support the assumption that the primary effect of the relevant flue gas constituents is to quench emission from Hg(6P13). The quenching rate constants for PFE from HgCl2 were measured to be 1.37(±0.16)×105Torr1s1 for N 2, 9.35(±0.25)×106Torr1s1 for O 2, and 1.49(±0.29)×106Torr1s1 for CO2. These values are in good accord with literature values for the quenching of Hg(6P13). The emission cross section for Hg(6P13) generated by photodissociation of HgCl2 in 760  Torr N 2 is found to be 1.0(±0.2)×1025m 2 by comparing the PFE signal to N 2 Raman scattering.

© 2006 Optical Society of America

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