Measurement of the absorption cross-sections of sulfur compounds in the 180-270 nm region considering nonlinear effects

• Published in: Physical chemistry chemical physics : PCCP Vol. 26; no. 23; pp. 16821 - 16828
• Main Authors: Gao, Jie, Wu, Yongqi, Zhao, Shuo, Zhu, Rui, Li, Mu, Qin, Wanyi, Zhang, Yucun, Zhang, Yungang
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 12.06.2024
• Subjects: Absorption cross sections; Absorption spectra; Absorption spectroscopy; Photolysis; Room temperature; Spectrum analysis; Sulfur; Sulfur compounds; Sulfur dioxide
• ISSN: 1463-9076; 1463-9084; 1463-9084
• DOI: 10.1039/d3cp05881f

Sulfur compounds (SO 2 , CS 2 , H 2 S and OCS) are common toxic pollutants in the atmospheric environment, and the absorption spectroscopy technique can indeed help to realize online monitoring of their concentrations. However, nonlinear effects that occur during absorption spectroscopy measurements have a serious impact on the measurement of the absorption cross-sections (ACSs) of sulfur compounds, leading to serious deviations in both the substance absorption properties and concentrations obtained based on ACS analysis. In this paper, the maximum effective ACSs of sulfur compounds in the linear region are obtained by considering the influence of nonlinear effects and eliminating interference factors such as oxygen and photolysis. In addition, the nonlinear effects are found to be greatly attenuated in spectra with broad band absorption characteristics by comparing the oscillatory absorption spectra before and after the differential treatment and by comparing the change in the oscillatory ACS with the broad band ACS. The experimental results show that the effective ACSs of SO 2 , CS 2 , H 2 S, and OCS with a resolution of 0.23 nm are 14.15 × 10 −18 cm 2 per molecule, 5.61 × 10 −16 cm 2 per molecule, 7.09 × 10 −18 cm 2 per molecule, and 3.20 × 10 −19 cm 2 per molecule, respectively. So far, it is the largest ACS obtained at room temperature and atmospheric pressure, which is of great significance for online measurement of sulfur compounds. The ACS obtained from intensity is not constant at finite resolution and is subject to non-linearities. Therefore, it is important to obtain an effective ACS in the low concentration range in order to monitor the concentration of sulfur compounds.