Compensation of composition variation-induced sensitivity changes in gas phase photoacoustics

Abstract

Infrared photoacoustic (PA) spectroscopy is a widely used technique to monitor trace gas concentration changes during industrial processes where the bulk composition may vary considerably. However, the PA signal is prone to changes in bulk composition, leading to relative uncertainties in measurements of up to 10%, due to the complex dependence of the sensitivity of a PA system (S) on the thermal and acoustic properties of the gas sample. A novel calibration and concentration calculation method is proposed to keep the relative accuracy of the PA measurements in the few percentages range even in case of large-scale composition variations. The main novelty of the proposed method is that it tackles the complex dependence of the PA system's sensitivity in a way that while it varies the resonance frequency of the calibration gas, it keeps the heat capacity ratio of calibration gases at a constant value. We prove that it determines the analyte’s concentration with relative accuracy of about 1 %, even when the composition of the gas varies drastically. It rigorously compensates for the frequency and heat capacity ratio dependence of S and for the dependence of the half-width of the resonance curve of the PA cell on the thermal and acoustic properties of the gas. Although the reported demonstration measurements are executed in a relatively simple gas mixture, the proposed method has widespread applicability in high-precision monitoring.