Reactor replacement is proposed as means of realizing different sample
residence times in flow-injection analysis. As an application, an imp
roved spectrophotometric determination of cobalt and nickel is propose
d. The method exploits differences in reaction rates between cobalt an
d nickel citrate complexes and 4-(2-pyridylazo)resorcinol (PAR). The i
nfluence of pH, reagent concentrations, temperature, ionic strength, f
low-rates and masking agent addition were investigated. Selectivity wa
s enhanced by adding EDTA plus pyrophosphate and exploiting kinetic di
scrimination. The system is very stable and allows the determination o
f cobalt and nickel up to 5.00 mg l-1 with a sampling frequency of 40
h-1. For tool steel samples characterized by low nickel/cobalt concent
ration ratios, the system can be simplified, allowing kinetic masking
of nickel and single cobalt determination. The reagent consumption is
65.3 mug of PAR per determination, and precise results (R.S.D. < 1%) i
n agreement with inductively coupled plasma atomic emission spectromet
ry are obtained at a sampling frequency of 100 h-1.