Dual-Beam Photothermal Spectroscopy Employing a Mach-Zehnder Interferometer and an External Cavity Quantum Cascade Laser for Detection of Water Traces in Organic Solvents.

We report on a mid-infrared (mid-IR) photothermal spectrometer for liquid-phase samples for the detection of water in organic solvents, such as ethanol or chloroform, and in complex mixtures, such as jet fuel. The spectrometer is based on a Mach-Zehnder interferometer (MZI) employing a He-Ne laser, a mini-flow cell with two embedded channels placed in the interferometer's arms, and a tunable external cavity quantum cascade laser (EC-QCL) for selective analyte excitation in a collinear arrangement. In this study, the bending vibration of water in the spectral range 1565-1725 cm-1 is targeted. The interferometer is locked to its quadrature point (QP) for most stable and automated operation. It provides a linear response with respect to the water content in the studied solvents and photothermal analyte spectra, which are in good agreement with FTIR absorbance spectra. The method is calibrated and validated against coulometric Karl Fischer (KF) titration, showing comparable performance and sensitivity. Limits of detection (LODs) for water detection in the single-digit ppm range were obtained for chloroform and jet fuel due to their low background absorption, whereas lower sensitivity has been observed for water detection in ethanol due to pronounced background absorption from the solvent. In contrast to KF titration, which requires toxic reagents and produces waste, the developed method works reagent-free. It can be applied in an online format in the chemical industry as well as for fuel quality control, being industrial applications where traces of water need to be accurately determined, preferably in real-time. It thus holds great promise as a green alternative to the offline KF titration method, which is the current standard method for this application.