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Potential of Far-Ultraviolet Absorption Spectroscopy as a Highly Sensitive Quantitative and Qualitative Analysis Method for Aqueous Solutions, Part I: Determination of Hydrogen Chloride in Aqueous Solutions

Volume 58, Number 8 (Aug. 2004) Page 910-916

Higashi, Noboru; Ozaki, Yukihiro

This paper reports the usefulness of far-ultraviolet (FUV) absorption spectroscopy in highly sensitive quantitative and qualitative analysis of aqueous solutions. We propose a totally new idea for the utilization of FUV spectroscopy in pure water and aqueous solution analyses. We use an absorption band near 170 nm due to an n → σ* transition of water. The intensity of the foot of this band, which can be observed in the 190-210 nm region by use of an ordinary ultraviolet-visible (UV-Vis) spectrometer, is very sensitive to changes in hydration and hydrogen bonds of water. To demonstrate the potential of FUV spectroscopy in analytical chemistry, we undertook three kinds of experiments. The first one is concerned with the discrimination of eight kinds of commercial natural mineral water. The eight kinds of mineral water can be discriminated straightforwardly from the spectral patterns in the 190-250 nm region without any spectral pretreatment or spectral analysis such as multivariate analysis. The second experiment is the determination of hydrogen chloride (HCl) in aqueous solutions. FUV spectra of aqueous solutions of HCl over a concentration of 0-20 ppm were measured. A calibration model for predicting the concentration of HCl in the aqueous solutions was developed based on the absorbance at 193 nm. This method does not require any spectral pretreatment or multivariate analysis. The correlation coefficient and standard error of prediction of the calibration model developed are 0.9987 and 0.18 ppm, respectively. The detection limit of the proposal method for the determination of HCl in aqueous solutions was estimated to be 0.5 ppm (13.7 μM). The determination of HCl was also tried for natural mineral water to which HCl solutions with the concentrations of 2, 4, 6, 8, 12, 16, and 20 ppm were artificially added. The third study was the determination of ammonia (NH3) and hydrogen peroxide (H2O2) in aqueous solutions containing both NH3 and H2O2. It has been found that the present method is also useful for the determination of the two-component system.