Quantification of fire gases by FTIR: Experimental characterisation of calibration systems

Abstract: Gaseous fire effluents contain a mixture of components, some of which are present in toxicologically significant proportions, together with water vapour and particulate matter, representing a significant challenge to the analyst. The most useful information is obtained from fire gases at about 180°C where water and most organic species are volatile. Despite this, it is often necessary to sample and measure fire effluents for prediction of fire toxicity, estimation of the environmental impact of fires, and to understand their behaviour. Gas phase Fourier Transform Infrared (FTIR) spectroscopy has the potential to measure almost all volatiles on a continuous basis during fire. This paper considers the key parameters, which must be carefully measured and controlled in order to obtain reliable calibration data. It evaluates a number of techniques designed for calibrating an FTIR spectrometer for use in fire gas analysis with conclusions on the best system for use for each species and for specific fire tests or experimental scenarios. As few molecules in the gas phase infrared spectrum obey the Beer-Lambert law, a full set of infrared spectra at different concentrations must be obtained for each target analyte, for the actual spectrophotometer—gas cell configuration in use. In some cases, stable standard mixtures are available, and these only have to be quantitatively diluted. In other cases reactive gases such as hydrogen halides must be generated quantitatively in situ, or vapours must be generated from volatile liquids under controlled conditions, in order to obtain calibration spectra. In each case, care must be taken in the design of the sampling line and calibration system, paying particular attention to the temperature, pressure and gas flow. Gas phase FTIR is a powerful analytical tool, but requires a significant investment in time and equipment before quantitative analysis can be undertaken. Unless care is taken to ensure constant temperature and pressure in the sample lines and gas cell, significant errors will result. [Copyright &y& Elsevier]