Simultaneous determination of trace amounts of free cyanide and thiocyanate by a stopped-flow spectrophotometric method

Simultaneous determination of free cyanide and thiocyanate was investigated using a stopped-flow spectrophotometric method. 1,3-dimethylbarbituric acid/isonicotinic acid at pH 5.2 was used as the colour reagent for both cyanide and thiocyanate determinations. The absorption spectrum of the complex formed by cyanide and thiocyanate with the colour reagent has a maximum wavelength at 600 nm, giving a low detection limit of 0.5 μg l−1 for cyanide and 1.5 μg l−1 for thiocyanate. Two proposed processes — 1,3-dimethylbarbituric acid combined with formaldehyde masking cyanide and the ferric-thiocyanate methods — can simultaneously determine free and other simple forms of cyanide and thiocyanate existing at pH 5.2; comparison of results demonstrates that both approaches are in agreement. By taking into account the effect of temperature on colour development and by using the ratio of the regression slopes, one kind of standard solution (thiocyanate) can be used for both cyanide and thiocyanate calibration, thereby avoiding the need to use toxic cyanide standard solutions.