NH3 absorption line study and application near 1084.6 cm-1

Ammonia (NH3) holds significant importance as an industrial product, ambient trace pollutant, and a promising zero-carbon energy carrier, underscoring the critical need for accurate quantification in various applications. In this study, a mid-infrared quantum cascade laser (Mid-IR QCL) based tunable diode laser absorption spectroscopy (TDLAS) spectrometer was developed. It was coupled with two reactors, namely a gas cell and a shock tube and operated in three modes: low- and high-frequency (140 Hz and 10 kHz) scan modes and fixed-wavelength mode, tailored to the specific needs of each experimental scenario. The primary objects were NH3 line parameters measurement and absolute NH3 quantification. With the 140 Hz low-frequency scan mode, NH3-Ar pressure broadening coefficients of six transition lines near 1084.6 cm-1 were measured in a gas cell at 295 K and 1-11 mbar for the first time. These coefficients were subsequently employed to quantify the initial NH3 mole fraction in shock tube experiments, considering the substantial adsorption effect of NH3. Using the high-frequency scan mode (10 kHz), spectrally resolved NH3 absorption cross-sections were obtained in a shock tube across a pressure range of 1.46-3.25 bar and a temperature range of 1000-1800 K. This data, acquired for the first time, significantly contributes to the understanding of NH3 behavior in high-temperature environments. Additionally, potential interference from high-temperature water absorption near 1084.6 cm-1 was thoroughly examined. The high-temperature water absorption cross-section was measured over a pressure range of 0.99-3.02 bar and a temperature range of 1322-2905 K, utilizing a near-infrared water laser. Leveraging these comprehensive datasets, the study quantified the NH3 mole fraction during the NH3 oxidation process in the shock tube, employing the fixed-wavelength mode to achieve high time resolution. The quantified NH3 mole fraction was then compared to predictions from eleven recent chemical kinetic mechanisms, demonstrating the utility of the developed spectrometer in validating these mechanisms.