Shapes of flow injection signals: effect of refractive index on spectrophotometric signals obtained for on-line formation of bromine from bromate, bromide and hydrogen ion in a single-channel manifold using large-volume time-based injections

The shapes of the spectrophotometric signals obtained with a single-channel manifold for large-volume (4 ml) time-based injections for the six possible combinations of the reagents bromate, bromide and nitric acid in the injectate and carrier stream, by which bromine can be formed on-line, have been determined. The injectate and carrier stream were 5.25 × 10–4M in bromate, 0.030 M in bromide and 1 M in nitric acid when these reagents were present. The signals consisted of two separate peaks caused by formation of bromine at the front and rear boundaries of the injected bolus. When both injectate and carrier stream were 1 M in nitric acid (i.e., for the reagent combination H+BrO3–-H+Br–) the two peaks were of equal height, and the signal was virtually the same whichever solution was used as the injectate. In reagent combinations where only one solution contained nitric acid the peaks were different in size, the smaller peak being that produced by the boundary in which the acidic solution was flowing behind the other solution. This difference in size between the front and rear peaks was shown to be caused by refractive index effects. When the refractive indices of the two solutions were matched either by increasing the potassium bromide concentration or by making the non-acidic solution 7% in sodium nitrate, the peaks became equal in size. When the potassium bromide concentration was increased there was an appreciable increase in peak size (about 4-fold): the changes in the amount of bromine formed must be due to kinetic or equilibrium effects. This increase in size did not occur when sodium nitrate was used to balance the refractive indices.