Simultaneous spectrophotometric determination of cyanide and thiocyanate after separation on a melamine-formaldehyde resin

A simple indirect spectrophotometric method for the determination of cyanide, based on the oxidation of the cyanide with chlorine (Cl2) is described. The residual chlorine is determined by the color reaction with o-tolidine (3,3′-dimethylbenzidine). The maximum absorbance for Cl2 is at 437 nm. A linear calibration graph (0–4.0×10−5 M CN−) is obtained under optimal reaction conditions at room temperature and pH 11–12. The stoichiometric mole ratio of chlorine to cyanide is 1:1. The effective molar absorptivity for cyanide is 5.87×104 l mol−1 cm−1 at pH 1.6. The limit of quantification (LOQ) is 3.6×10−7 M or 9.4 ppb. Effects of pH, excess reagent, sensitivity, reaction time and tolerance limits of interferent ions are reported. The method was applied to the determination of cyanide in a real sample. The basic interferent usually accompanying CN−, i.e. thiocyanate, is separated from cyanide by sorption on a melamine-formaldehyde resin at pH 9 while cyanide is not retained. Thiocyanate is eluted with 0.4 M NaOH from the column and determined spectrophotometrically using the acidic FeCl3 reagent. The initial column effluent containing cyanide was analyzed by both the developed chlorine-o-tolidine method and the conventional barbituric acid-pyridine (Spectroquant 14800) procedure, and the results were statistically compared. The developed method is relatively inexpensive and less laborious than the standard (Spectroquant) procedure, and insensitive to the common interferent, cyanate (CNO−).