Preparatory Study for Detection of Nickel in Industrial Flue Gas by Excimer Laser-Induced Fragmentation Fluorescence Spectroscopy

Abstract

The purpose of this work is to survey possibilities for detecting molecular nickel species in industrial flue gas using excimer laser-induced fragmentation fluorescence (ELIF), in particular to establish suitable detection schemes and to obtain a sensitivity estimate for Ni detection. Investigations were conducted in a heated laboratory cell under defined conditions of temperature and pressure, using NiCl₂ as the precursor molecule. An ArF excimer laser (193 nm) was used for excitation and Ni atomic emission spectra were recorded in the range 300 to 550 nm. The dependence of ELIF signal on laser fluence was quadratic in the range of laser intensities investigated, as expected for a two-photon excitation process. The temporal behavior of the ELIF signals gave lifetimes significantly longer than the known natural lifetimes. This result and the energetics of the system suggest a Ni* production mechanism involving the formation of Ni+ and subsequent ion–electron recombination. The temperature dependence of the ELIF signal, determined in the range 773 to 1223 K, was found to follow the vapor-pressure curve (Antoine equation) known from the literature. Finally, quenching effects were investigated by measuring ELIF signals and lifetimes in nitrogen or air up to 1 atm. On the basis of the results so far, detection limits for Ni in practical combustion applications in the range of tens of ppb should be achievable, which will be sufficient for regulatory measurements in incinerators and power plants.