Conventional absorption spectroscopy (CAS) with a blank reference has only a slight capacity to detect high concentrations at characteristic wavelengths owing to the corresponding large molar absorption coefficient (ε) on the scale of 10 or 10 cm M. To monitor concentrated analytes as high as the molar range in a plating bath and on a chemical production line, we propose a new approach using sideband differential absorption spectroscopy (SDAS). SDAS is obtained by subtracting the absorption spectra of the samples, A(λ,C), from that of a reference containing a concentrated standard analyte, A(λ,C>C), resulting in concave spectra with peaks at the sideband of conventional spectra with generally low ε values on the scale of 100 cm M or less. The negative absorbance changes linearly with the sample concentration at a certain peak wavelength, obeying Lambert-Beer's law. In this work, SDAS was obtained and verified using inorganic and organic substances, such as chromate potassium, rhodamine B, and paracetamol.

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The direct qualitative identification of pure liquids in laboratories and in security checks is generally performed by the detection of the refractive index or the permittivity. However, refractive indices are strongly influenced by temperature, while the permittivities of some organics are difficult to differentiate. On the other hand, the quantitative monitoring of samples with high concentration in plating baths and in chemical production lines are generally performed via a “Sampling–Dilution–Analysis” approach because of significant deviations from the linear range at high concentration, which makes the real-time monitoring of concentrated samples difficult. Here, we propose a self-reference analysis (SRA) method to directly analyze pure liquids and concentrated samples based on temperature difference absorption spectra (TDAS) without the need for dilution. This method was performed by simultaneously scanning the spectra of the reference and the sample, which are both obtained from the same analyte for detection but are at different temperatures. Compared to conventional absorption spectra with a blank reference, the red-shifted peak wavelengths of TDAS enable the detection of many far UV absorptive compounds in the near-ultraviolet region (λ > 190 nm). More importantly, organic compounds with similar structures can be easily distinguished. In addition, TDAS can also be used for the quantitative detection of concentrated analytes. The proposed SRA-TDAS method is a rapid and effective method; this approach does not require dilution and utilizes a self-reference, implying the wide potential applicability in security checks, and the real-time monitoring of concentrated compounds in chemical production lines.

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