When we first inject a sample into an FIA’s carrier stream it has the rectangular flow profile of width w as shown below in (a). As the sample moves through the mixing zone and reaction zone, the width of its flow profile increases as the sample disperses into the carrier stream. Dispersion results from two processes: convection due to the flow of the carrier stream and diffusion due to the concentration gradient between the sample and the carrier stream. Convection occurs by laminar flow. The linear velocity of the sample at the tube’s walls is zero, but the sample at the center of the tube moves with a linear velocity twice that of the carrier stream. The result is the parabolic flow profile shown in (b). Convection is the primary means of dispersion in the first 100 ms following the sample’s injection.
The second contribution to the sample’s dispersion is diffusion due to the concentration gradient between the sample and the carrier stream. As shown in the illustration below, diffusion occurs parallel (axially) and perpendicular (radially) to the direction in which the carrier stream is moving. Only radial diffusion is important in flow injection analysis. Radial diffusion decreases the sample’s linear velocity at the center of the tubing, while the sample at the edge of the tubing experiences an increase in its linear velocity. Diffusion helps to maintain the integrity of the sample’s flow profile, as shown in (c) above, preventing samples in the carrier stream from dispersing into one another. Both convection and diffusion make significant contributions to dispersion from approximately 3–20 s after the sample’s injection. This is the normal time scale for a flow injection analysis. After approximately 25 s, diffusion is the only significant contributor to dispersion, resulting in a flow profile similar to that shown in (d) above.
