All ion selective electrodes are similar in operation and use. They differ only in the process by which the ion to be measured moves across the membrane and by which other ions are kept away. Therefore electrode interferences must be discussed in terms of membrane materials.

Glass electrodes and solid-matrix/liquid-ion exchange electrodes both function by an exchange of mobile ions within the membrane, and ion exchange processes are not specific. Reactions occur among many ions with similar chemical properties, such as alkali metals, alkaline earths, or transition elements. Thus, a number of ions can produce a potential when an ion selective electrode is immersed in a solution. Even the pH glass electrode responds to sodium ions at a high pH (low hydrogen ion activity). Fortunately, an empirical relationship can predict electrode interferences, and a list of selectivity ratios for the interfering ions is available from the manufacturers' specifications or other chemical publications.

Solid-state matrix electrodes are made of crystalline materials. Interferences resulting from ions moving into the solid membrane are not expected. Interference usually occurs from a chemical reaction with the membrane. An interference with the silver-halide membranes (for chloride, bromide, iodide, and cyanide activity measurements) involves a reaction with an ion in the sample solution, such as sulfide, to form a more insoluble silver salt.

A true interference produces an electrode response that can be interpreted as a measure of the ion of interest. For example, the hydroxyl ion, OH—, causes a response with the fluoride electrode at fluoride levels below 10 ppm. Also, the hydrogen ion, H+, creates a positive interference with the sodium ion electrode. Often an ion is regarded as interfering if it reduces ion activity through chemical reaction. This reaction (complexation, precipitation, oxidation-reduction and hydrolysis) results in ion activity that differs from the ion concentration by an amount greater than that caused by ionic interactions. However, the electrode still measures true ion activity in the solution.

An example of solution interference illustrates this point. A silver ion in the presence of ammonia forms a stable silver-ammonia complex that is not measured by the silver electrode. Only the free, uncombined silver ion is measured. Environmental engineers can obtain the total silver ion from calculations involving the formation constant of the silver-ammonia complex and the fact that the total silver equals the free silver plus the combined silver. Alternately, they can draw a calibration curve relating the total silver (from analysis or sample preparation) to the measured activity. The ammonia is not an electrode interference.

Most confusion stems from the fact that analytical measurements are in terms of concentration without regard to the actual form of the material in solution, and electrode measurements often disagree with the laboratory analyst's results. However, the electrode reflects what is actually taking place in the solution at the time of measurement. This information can be more important in process applications than the classic information. With suggested techniques, environmental engineers can reconcile the two measurements.

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