Improvements in the N,N-diethyl-p-phenylenediamine method for the determination of free and combined residual chlorine through the use of FIA

In the determination of free and combined chlorine, the reaction of permanganate standards with N,N-diethyl-p-phenylenediamine (DPD) exhibits nonlinearity presumably because both the colored semiquinoid product and the colorless quinoid product are both formed. The titrimetric DPD method titrates both of the products while the colorimetric method monitors only the colored semiquinoid products. This results in a nonlinear response for the colorimetric method above 1.0 mg/l. as Cl(2). Under FIA conditions, the nonlinearity of the DPD colorimetric method is eliminated in the 0.1-5.0 mg/l. (as Cl(2)) range and the linear range is expanded to 0.1-8.0 mg/l. as Cl(2). Also, relative standard deviations are improved by 0.5-11% relative to the colorimetric method and 1.5-4.0% relative to the titrimetric method. The FIA method was developed further to sequentially determine both free and combined chlorine, since chloramine was found to have a negligible interference in the free chlorine determination.