Sequential Collinear Photofragmentation and Atomic Absorption Spectroscopy for Online Laser Monitoring of Triatomic Metal Species.

Industrial chemical processes are struggling with adverse effects, such as corrosion and deposition, caused by gaseous alkali and heavy metal species. Mitigation of these problems requires novel monitoring concepts that provide information on gas-phase chemistry. However, selective optical online monitoring of the most problematic diatomic and triatomic species is challenging due to overlapping spectral features. In this work, a selective, all-optical, in situ gas-phase monitoring technique for triatomic molecules containing metallic atoms was developed and demonstrated with detection of PbCl2. Sequential collinear photofragmentation and atomic absorption spectroscopy (CPFAAS) enables determination of the triatomic PbCl2 concentration through detection of released Pb atoms after two consecutive photofragmentation processes. Absorption cross-sections of PbCl2, PbCl, and Pb were determined experimentally in a laboratory-scale reactor to enable calibration-free quantitative determination of the precursor molecule concentration in an arbitrary environment. Limit of detection for PbCl2 in the laboratory reactor was determined to be 0.25 ppm. Furthermore, the method was introduced for in situ monitoring of PbCl2 concentration in a 120 MWth power plant using demolition wood as its main fuel. In addition to industrial applications, the method can provide information on chemical reaction kinetics of the intermediate species that can be utilized in reaction simulations.