Co-laser photoacoustic spectroscopy of gases and vapours for trace gas analysis

Abstract This comprehensive study reviews the sensitive and selective detection of trace gases by laser photoacoustic spectroscopy. A computer controlled CO-laser photoacoustic system is presented. The wavelength range between 5.0 and 6.5 μm is of great interest because it coincides with specific absorption bands of various gases and vapours of environmental concern. However, since water-vapour, which is present in most samples, absorbs rather strongly in this wavelength region, its contribution to the total absorption has to be determined with high accuracy. For this purpose, we developed a dual-beam setup with sample- and reference cell. The novel design of these resonant photoacoustic cells is based on a new matrix formalism with distributed acoustic impedances and sources. Our photoacoustic system is calibrated with certified gas mixtures and vapours. In total, the absorption cross sections of 18 gases and vapours have been derived for all CO-laser lines. In addition to the absorption, the relaxation time of vibrationally excited nitric oxide (NO) could be deduced by measuring the phase shift of the photoacoustic signal for a sample of nitrogen containing traces of NO and water-vapour. The main application concerns the detection of multiple components in gas mixtures, particularly in exhaust gases. The high sensitivity achieved permits the detection of trace gases at ppbv concentrations. The problem of interfering absorptions occurring for multicomponent mixtures is studied in detail. We discuss measurements and results on exhausts of various vehicles. The photoacoustic spectra of the exhaust samples are analyzed on the basis of the calibration spectra with the aid of an iterative mathematical procedure. The individual concentrations of 12 of the most important components including nitric oxide, olefines, aromatic hydrocarbons and aldehydes could be derived. In particular, the selective detection of the different isomers of xylene is emphasized.

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