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Ion-selective electrodes have demonstrated unique features for the measurement of a variety of ionic and gaseous species. While the advantages of these electrodes are widely known and appreciated, it is usually not until one is actually using these sensors that the problems and pitfalls become apparent and may result in serious errors and considerable aggravation. The causes of these problems are almost as varied as the sensors and the samples, but several common sources can be identified: interferences and/or fouling of the electrode, sample matrix effects, reference electrode instability, and improper calibration of the measurement system. These pitfalls are discussed in some detail with suggestions for overcoming or minimizing the problems and their associated errors. These sensors can be a useful and convenient means for the determination and monitoring of selected species, but only if the potential pitfalls are recognized and eliminated. More than any other modern analytical technique, ion-selective electrodes require a sound knowledge of solution chemistry in order to achieve the maximum effectiveness of these sensors.