Indirect determination of zinc by thiol complexation and iodine coulometric titration with photocell detection

摘要

We have extended the capabilities of iodine coulometry for the determination of ionic zinc through its complexation with cysteine and subsequent titration of the thiol. The titration endpoint times of cysteine with zinc are proportionally longer as compared to cysteine itself. A homebuilt constant-current coulometer is employed for this method development. The instrument is composed of a constant-current source connected to nonisolated platinum electrodes contained in a 150-mL beaker (the coulometric cell) that sits on a photocell mounted in a styrofoam lid on top of a magnetic stirrer. Photometric endpoint detection is facilitated by connecting the photocell detector to an operational amplifier circuit; its output, recorded on a multifunctional chemical analysis system, resembled a sigmoidal curve. The titration conditions are optimized in terms of pH, temperature, stirring rate, and cysteine-to-zinc concentration ratios. Calibration curves generated as time versus increasing zinc concentrations in the presence of a constant cysteine concentration are used to determine zinc content in dietary supplements. The limit of detection is 5.5 x 10(-5) M Zn and the limit of quantification is 6.2 x 10(-5) M Zn. Percent relative standard deviations are at 4%. The recoveries of zinc from liquid zinc, enhanced zinc lozenges, and zinc tablets generally range from 80 to 120%. Titration of ascorbic acid and then zinc in the same solution is successfully performed with recoveries greater than 95% for both analytes. A comparison of the coulometry Zn data to atomic absorption results is also made for most samples. (C) 2017 Elsevier B.V. All rights reserved.