Automatic analytical methods for environmental monitoring and control



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Figure III.2.10. (a) SFA manifold for ammonia determination in different types of waters. (b) SFA manifold for chloride determination in waters.
In Figure III.2.10.b is presented a SFA system for chloride ion determination in waters. It uses a dialysis unit to remove interferences. The reagent is a mixture of Hg(SCN)2 and Fe(NO3)3, which in the presence of analyte, generates a red coloration due to the Fe(SCN)2+ complex as a result of the much more stable HgCl+ complex. The reaction is sensitive enough to determine chloride over the range of concentration 1 – 20 mg/L.
III.2.1.3. Flow Injection Analysis
Flow injection analysis (FIA) is a form of flow analysis that does not rely on air segmentation to prevent the interactions between successive samples. Instead, it employs a non-segmented flow under conditions such that sample spreading is minimized and successive samples can be introduced at short time intervals.

Although, non-segmented flow systems have existed for a long time, only in 1975 J. Ruzicka and E. Hansen and K.K. Stewart et al, independently demonstrated that flow injection systems can be used for rapid and precise automated analysis if the proper flow conditions are selected. This approach is known as flow-injection analysis; term coined by J. Ruzicka and E. Hansen.

Since FIA was born, it found many applications both in the laboratory and in process control and became known simply as FI as it was realized that FI is not only a tool for analysis, but also a generally applicable solution handling technique. Its ability to control and monitor kinetic aspects of automated assays has been recognized, and identified as “kinetic advantage”.

By now its scope is broadening into environmental research and into a tool of biotechnology and for the study of the chemistry of life. FI’s versatility, or self-adaptation, and perfect computer compatibility makes it an ideal interface between a computer and a (bio)chemical system.


Principles

Flow-injection analysis is based on the insertion/injection of a liquid sample into a moving non-segmented carrier stream of a suitable liquid. The injected sample forms a zone, which is transported by the carrier through a coil of tubing to a detector. The detector measures a physical parameter of the sample (absorbance, electrode potential, pH, etc.) that changes continuously as a function of time as the sample passes through the flow cell. This means that the concentration of the species being monitored is continuously changing with time. The carrier may contain a reagent that reacts with the analyte to yield a detectable product, or may consist of an inert solution and in this case the carrier serves as a means of transporting the sample to the detector. Thus, the FIA response curve is a result of two processes, both of kinetic nature, the physical process of dispersion of the sample zone within the carrier stream, and the chemical process of the formation of chemical species.



The diagram of the simplest flow injection system is presented in Figure III.2.11 and it consists of:

  • a pump (P) that is used to propel the carrier stream through a thin tube;

  • an injection device (Vi) that introduces into the carrier a well-defined volume of sample solution (S) in a very reproducible manner;

  • a coil of tubing also named reaction coil (RC) in which the sample zone disperses and reacts with the components of the carrier, forming species that are detected by a flow-through detector;

  • a
    recorder which registers the FIA typical signals. A typical recorder output has a form of a peak, its height (H) being related to the analyte concentration.

(
a)

(b)
Figure III.2.11. (a) Diagram of a FIA system. (b) Typical recorder output. P – pump; V – injection device; RC – reactor (reaction coil); D – detector; C – carrier; S – sample; R – reagent; W – waste; H – peak height; T – residence time; tb – peak width, time that sample zone passes through flow-cell.


The time span between the sample injection S and the peak maximum, which yields the analytical output, is the residence time T, during which the chemical reaction occurs. For a well-designed FIA system characterized by a rapid response, this means two samples analyzed per minute, (T + tb) must be smaller then 30 s. The injected sample volumes are usually between 1 and 200 L that requires a maximum 0.5 mL of reagent per analysis. This makes FIA to be an automated microchemical technique capable of having a sample throughput of 100 determinations per hour, with a minimum consumption of sample and reagents.

In addition to such higher sampling rate and very rapid availability of the analytical response, the most important aspect of the FIA method is the concept of controlled dispersion of the sample zone, an entirely new concept in analytical chemistry at that time, and which allows the design of a FIA system suited to automate a given analytical procedure.



In order to explain the FIA response shape, let us examine the Figure III.2.12. After the sample injection into the carrier stream, the formed zone does not flow down the tube as a compact plug. In a FIA system, the injected sample zone disperses according to the parabolic velocity profile characteristic for laminar flow. This parabolic concentration profile develops because the sample molecules near the walls are retarded by friction while the molecules in the center of the tube are free to move more rapidly. In fact, the solution at the walls of the tube does not move at all whereas the solution in the center of the tube moves at twice the average flow rate.



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