Chemistry concept on FIA

Lecture #7

Chemistry on FIA

Play important role in FIA

Converting the analyte into a detectable species compatible with the used detector
Initially colorimetric reactions dominated the chemistry of FIA, however other reactions has also been applied to FIA One of the most important points to keep in mind in adapting a manual method to FIA is that manual methods are generally equilibrium based while FIA methods are non-equilibrium based.

Available method

Searching internet based database: http://www.fia.unf.edu/ Searching FIA reference books

Searching for a conventional

analytical method which can be adapted to FIA/SIA

Single stream FIA

A stream containing reagent is pumped through the system. A volume of sample is injected into the stream and dispersion causes mixing of the reagent with the sample zone leading to chemical reaction between analyte and reagent as the zone passes through the reactor and detector.

Single stage chem. reaction in two stream FIA

The sample is injected into a reagentless carrier, and the reagent stream is merged with it downstream. This provides a uniform mixing of the reagent with sample over the length of the sample zone, and often provides better sensitivity and performance compared to the single-steam approach. For this reason, the two-stream manifold is often preferred over the single-stream manifold for simple chemistries.

Two stage chem. reaction in two stream FIA

The sample is injected into the first stream containing reagent 1. The analyte reacts with the reagent, generating an intermediate. On merging with stream two downstream, the intermediate reacts with reagent 2, forming the product that is measured by the detector.

Analysing cyanide based on the Knig reaction

The first stream contains the reagent, chloramine-T. On injecting the sample into this stream, the cyanide reacts with the chloramine-T to form cyanogen chloride. The second stream contains a mixture of sodium isonicotinate (INA) and 3-methyl-1-phenyl2-pyrazollin-5-one (PZ). On merging with this stream, the cyanogen chloride reacts with the PZ to form a highly colored purple product.

Three stream FIA

Three stream manifolds are generally used for two stage or three stage chemistries. When used for two stage chemistries, the sample is injected into a reagentless carrier, and merges downstream with the first reagent. Further downstream, it merges with the second reagent.

Multi-determinations in FIA
whether the sample is injected once or many times (simultaneously or sequentially); and the number of detectors used (a single multi-channel detector or several detectors arranged in series or in parallel).

Two examples of FIA assemblies for multi-determinations, (a) Schematic diagram of an FIA manifold for multi-determinations on the basis of a reverse FIA procedure with sequential injection of reagents. R1 , R2 and R3 are different reagents inserted into the sample solution, S. (b) Schematic diagram of an FIA manifold with simultaneous double injection of sample and an asymmetric merging configuration. Each injected sample aliquot is submitted to a different chemical reaction; R (reagents) and C (carrier) can be different. Both sample plugs arrive separately to the detector flow-cell due to the asymmetric configuration. D, detector; Rc, recorder; Iv, injection valve; P, propulsion unit

Spliting the sample into two boluses with different ways (and lengths) to detector. The chemical treatments are different for both sample parts. S, sample; C, carrier; R, reagent; Iv, injection valve

Configurations with a Single Detector

Multi-determinations by changing the composition of the carrier-reagent. P2 is the pump for changing the rotating speed to produce a mixture (C1 and C2) of variable pH. S, sample; R, derivatizing reagent; Iv, injection valve

FIA Configurations using Several Detectors

(a) Schematic diagram of an F1A manifold with several detectors in serial configuration; (b) schematic diagram of FIA manifolds for simultaneous determinations with several detectors in parallel configuration. P, pump; S, sample; C, carrier; R, reagent; Iv, injection valve; Rc, recorder; D, detector; W, waste

Reversed FIA

Reverse FIA manifold (on top) compared with the normal FIA mode. No differences are observed in manifolds. Differences are in how the method is operated. P, pump; R, reagent; S, sample; C, carrier; D, detector; W, waste; Iv, njection valve

Monitoring Industrial Processes

Continuous monitoring without injecting samples (no FIA). The system is alternately working with the sample and with the standard solutions. The calibration can be periodically repeated. Types of signal are depicted in the bottom part of the figure. Stn, standard solution; Br, branch stream; R, reagents; W, waste; D, detector;P, pump; Sk, selecting key