Analytical Sciences

Chemiluminescence from an Oxidation Reaction of Rhodamine B with Cerium(IV) in a Reversed Micellar Medium of Cetyltrimethylammonium Chloride in 1-Hexanol–Cyclohexane/Water

Tamer H. A. HASANIN, Yusuke TSUNEMINE, Satoshi TSUKAHARA, Yasuaki OKAMOTO, and Terufumi FUJIWARA

Department of Chemistry, Graduate School of Science, Hiroshima University, Kagamiyama, Higashi-Hiroshima 739-8526, Japan

The chemiluminescence (CL) emission, observed when rhodamine B (RB) in 1-hexanol–cyclohexane was mixed with cerium(IV) sulfate in sulfuric acid dispersed in a reversed micellar medium of cetyltrimethylammonium chloride (CTAC) in 1-hexanol–cyclohexane/water, was investigated using a flow-injection system. The CL emission from the oxidation reaction of RB with Ce(IV) was found to be stronger in the CTAC reversed micellar solution compared with an aqueous solution. Bearing on the enhancement effect of the CTAC reverse micelles on the RB-Ce(IV) CL, several studies including stopped-flow, fluorescence and electron spin resonance (ESR) spectrometries were performed. Rapid spectral changes of an intermediate in the RB-Ce(IV) reaction in the aqueous and reversed micellar solutions were successfully observed using a stopped-flow method. The effect of the experimental variables, i.e., oxidant concentration, sulfuric acid concentration, the mole fraction of 1-hexanol, water-to-surfactant molar concentration ratio, flow rate, upon the CL intensity was evaluated. Under the experimental conditions optimized for a flow-injection determination of RB based on the new reversed micellar-mediated CL reaction with Ce(IV), a detection limit of 0.08 μmol dm⁻³ RB was achieved, and a linear calibration graph was obtained with a dynamic range from 0.5 to 20 μmol dm⁻³. The relative standard deviation (n = 6) obtained at an RB concentration of 3 μmol dm⁻³ was 3%.

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