Oxidation of thiocyanate by hydrogen peroxide - a reaction kinetic study by capillary electrophoresis.

The oxidation reaction kinetics of thiocyanate by excess hydrogen peroxide has been studied by using capillary electrophoresis. The paper illustrates for the first time the use of capillary electrophoresis in studying reaction kinetics and provides a non-laborious way to determine the rate law and the rate constant for the above reaction in the pH range 6-8. Standard solutions of thiocyanate were mixed with buffer solutions of different pHs (6-8) and the reactions were initiated by adding appropriate volumes of hydrogen peroxide in capillary electrophoresis vials. Each reaction mixture was sampled at regular time intervals using an automatic injection programme to follow the progress of the reaction and identify the reaction products. The peak areas, representing the products, were integrated and their concentrations were quantified using calibration plots. The concentration profiles obtained from a series of experiments at a particular pH were then used to determine the rate law and the rate constant for the reaction. Furthermore, the rate of decomposition of hypothiocyanite formed during the reaction is determined for the first time. The rate law is zero order with respect to hypothiocyanite and first order with respect to hydrogen peroxide. The results indicate that the rate law for the oxidation reaction is zero order with respect to thiocyanate and first order with respect to hydrogen peroxide. The rate constant for the reaction at 25 degrees C and at zero ionic strength is 3.6(+/-0.2)x10((-4)) min(-1).