Improved Voltammetric Procedure for Chloride Determination in Highly Acidic Media.

Cyclic voltammetry (CV) can be applied as a reliable method for the determination of chloride ions in a range from several to a couple hundred (about 200) ppm. Since the standard potential of chloride ion/gaseous chlorine is 1.36 V vs. normal hydrogen electrode (NHE), the efficient oxidation of Cl ion occurs at very positive electrode potentials, usually higher than +1.7 V vs. NHE. It is possible to observe this phenomenon only at noble-metal or inert carbon electrodes. Many other solutes, usually organic compounds, are often oxidized at this potential. This is the reason why the determination of Cl content directly from an increase in the oxidation current is not reliable and could lead to overestimated values. However, gaseous chlorine, generated at a positive potential dissolve in the analyzed solution, could be reduced in the reverse scan of a cyclic voltammetric curve. Optimization of the experimental procedure using statistical tools enables the development of an improved method for the direct quantification of chloride ions in acid copper electroplating baths. Under the proposed experimental conditions, the calibration curve (Cl voltammetric reduction current vs. chloride ions concentration) is represented by the linear model for the concentration of chlorides ranging from 10 to 200 mg/dm. The developed method for analyzing chloride ions in an acid sulfate electroplating copper bath has many unique properties. It is fast; the time of a single analysis is less than 20 min. In automatic mode, it can be repeated up to 50 times a day. The method does not require processing of the sample of the analyzed bath before measurement. As a result, no additional chemical reagents are used, and the test sample can be returned to the plating bath.