A new iodometric method for quantifying aqueous solutions of iodide-oxidizing and iodine-reducing substances, as well as plain iodine/iodide solutions, is presented. It is based on the redox potential of said solutions after reaction with iodide (or iodine) of known initial concentration. Calibration of the system and calculations of unknown concentrations was performed on the basis of developed algorithms and simple GWBASIC-programs. The method is distinguished by a short analysis time (2-3 min) and a simple instrumentation consisting of pH/mV meter, platinum and reference electrodes. In general the feasible concentration range encompasses 0.1 to 10(-6) mol/L, although it goes down to 10(-8) mol/L (0.001 mg Cl-2/L) for oxidants like active chlorine compounds. The calculated imprecision and inaccuracy of the method were found to be 0.4-0.9 and 0.3-0.8, respectively, resulting in a total error of 0.5-1.2. Based on the experiments, average imprecisions of 1.0-1.5 at c(Ox)> 10(-5) M, 1.5-3 at 10(-5) to 10(-7) M, and 4-7 at < 10(-7) M were found. Redox-iodometry is a simple, precise, and time-saving substitute for the more laborious and expensive iodometric titration method, which, like other well-established colorimetric procedures, is clearly outbalanced at low concentrations; this underlines the practical importance of redox-iodometry.
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