Monitoring colorless electroactive chemicals in complex background based on electrochemical difference absorption...

Conventional UV/Vis absorption spectroscopy is an economical and user-friendly technique for online monitoring, however, by which some electroactive chemicals are hardly determined in the presence of fluctuating background due to the formation of colored chemicals. Here, we propose an electrochemical difference absorption spectroscopy (EDAS) to accurately quantify colorless chemicals based on visible color change via electrolysis with strong variation in the background. EDAS is realized by twin spectroelectrochemical flow cells system, replacing the two cuvette cells of a dual beam spectrophotometer. Each cell consists of a three-electrode system, quartz windows and a thin flow channel. Flowing of analyte from one cell (reference cell) to the other (sample cell) can eliminate the influence of colored interferents even while their concentrations are changing. When different potentials are applied on the sample and reference cells respectively, electrolysis occurs and colored products flowing through quartz windows can absorb the incident light, resulting in difference absorption spectra induced from potential difference. We find that steady-state difference absorbance (ΔA) at characteristic wavelength is linearly changed with sample concentrations. EDAS is firstly verified by Fe(CN)₆^4- at different potentials and flow rates, in good agreements with a simplified theory that describes linear relationship between ΔA and analyte concentration. Then EDAS is used to determine Cu(I) in Cu(I)-Cu(II) mixed solutions and tetramethylbenzidine in its partially oxidized solutions to illustrate the powerful ability to detect colorless chemicals with varied background, implying its promising potential applications in the chemical industry.