Quantitative capillary Raman spectroscopy measurements are described, in which improved speed and sensitivity for atmospheric trace gas analysis and real-time monitoring of catalytic hydrogen-exchange reactions were demonstrated.
ARTICLE accepted for publicationT.M. James et al -Raman trace gas and process monitoring using metal-coated hollow glass fibres Results on using capillary Raman spectroscopy as an approach for improving the speed, sensitivity and limit of detection for quantitative analysis of gases are reported. Specifically, its potential for trace component identification and rapid process control has been explored. Using a metal-lined hollow glass capillary configuration, its Raman signal was found to be two orders of magnitude larger than that from a conventional 90° Raman implementation. However, the actual improvement in the signal-to-noise ratio and thus the limit of detection was markedly lower, due to an increase in the fluorescence background generated in optical components in the laser beam path and the capillary body itself. Using careful, systematic suppression strategies, the signal-tonoise ratio of our capillary setup increased by a further factor of 3-4, now yielding detection limits for trace gases well below the 100 ppm level. In a "dynamic" measurement series the time evolution of catalytic gas mixing of H 2 and D 2 , to form HD, has been recorded, in which sub-mbar detection limits in sub-second recording times were achieved.