Ion selective electrode
An ion-selective electrode (ISE), also known as a specific ion electrode (SIE), is a transducer (or sensor) that converts the activity of a specific ion dissolved in a solution into an electrical potential, which can be measured by a voltmeter or pH meter. The voltage is theoretically dependent on the logarithm of the ionic activity, according to the Nernst equation. The sensing part of the electrode is usually made as an ion-specific membrane, along with a reference electrode. Ion-selective electrodes are used in analytical chemistry and biochemical/biophysical research, where measurements of ionic concentration in an aqueous solution are required, usually on a real time basis.
Types of ion-selective membrane
There are four main types of ion-selective membrane used in ion-selective electrodes (ISEs): glass, solid state, liquid based, and compound electrode.
Glass membranes are made from an ion-exchange type of glass (silicate or chalcogenide). This type of ISE has good selectivity, but only for several single-charged cations; mainly H+, Na+, and Ag+. Chalcogenide glass also has selectivity for double-charged metal ions, such as Pb2+, and Cd2+. The glass membrane has excellent chemical durability and can work in very aggressive media. A very common example of this type of electrode is the pH glass electrode.
Crystalline membranes are made from mono- or polycrystallites of a single substance. They have good selectivity, because only ions which can introduce themselves into the crystal structure can interfere with the electrode response. Selectivity of crystalline membranes can be for both cation and anion of the membrane-forming substance. An example is the fluoride selective electrode based on LaF3 crystals.
Ion-exchange resin membranes
Ion-exchange resins are based on special organic polymer membranes which contain a specific ion-exchange substance (resin). This is the most widespread type of ion-specific electrode. Usage of specific resins allows preparation of selective electrodes for tens of different ions, both single-atom or multi-atom. They are also the most widespread electrodes with anionic selectivity. However, such electrodes have low chemical and physical durability as well as "survival time". An example is the potassium selective electrode, based on valinomycin as an ion-exchange agent.
These are a development from "A Calcium Ion-selective Electrode Based on a Liquid Ion-exchanger in a Poly(Vinyl Chloride) Matrix. Analyst, 1970,Vol. 95, 910-918, by J.D.R. Thomas, with G.J. Moody and R.B. Oke" These (modified, based on original 1970 technology) electrodes are prepared from glass capillary tubing approximately 2 millimeters in diameter, a large batch at a time. Polyvinyl chloride is dissolved in a solvent and plasticizers (typically phthalates) added, in the standard fashion used when making something out of vinyl. In order to provide the ionic specificity, a specific ion channel or carrier is added to the solution; this allows the ion to pass through the vinyl, which prevents the passage of other ions and water.
One end of a piece of capillary tubing about an inch or two long is dipped into this solution and removed to let the vinyl solidify into a plug at that end of the tube. Using a syringe and needle, the tube is filled with salt solution from the other end, and may be stored in a bath of the salt solution for an indeterminate period. For convenience in use, the open end of the tubing is fitted through a tight o-ring into a somewhat larger diameter tubing containing the same salt solution, with a silver or platinum electrode wire inserted. New electrode tips can thus be changed very quickly by simply removing the older electrode and replacing it with a new one.
In use, the electrode wire is connected to one terminal of a galvanometer or pH meter, the other terminal of which is connected to a reference electrode, and both electrodes are immersed in the solution to be tested. The passage of the ion through the vinyl via the carrier or channel creates an electrical current, which registers on the galvanometer; by calibrating against standard solutions of varying concentration, the ionic concentration in the tested solution can be estimated from the galvanometer reading.
In practice there are several issues which affect this measurement, and different electrodes from the same batch will differ in their properties. Leakage between the vinyl and the wall of the capillary, thereby allowing passage of any ions, will cause the meter reading to show little or no change between the various calibration solutions, and requires that that electrode be discarded. Similarly, with use the ion-sensitive channels in the vinyl appear to gradually become blocked or otherwise inactivated, causing the electrode to lose sensitivity. The response of the electrode and galvanometer is temperature sensitive, and also 'drifts' over time, requiring recalibration frequently during a series of measurements, ideally at least one calibration sample before and after each test sample. On the other hand, after immersion in the solution there is a 'settling time' which can be five minutes or even longer, before the electrode and galvanometer equilibrate to a new reading; so that timing of the reading is critical in order to find the most accurate 'window' after the response has settled, but before it has drifted appreciably.
Enzyme electrodes definitely are not true ion-selective electrodes but usually are considered within the ion-specific electrode topic. Such an electrode has a "double reaction" mechanism - an enzyme reacts with a specific substance, and the product of this reaction (usually H+ or OH−) is detected by a true ion-selective electrode, such as a pH-selective electrodes. All these reactions occur inside a special membrane which covers the true ion-selective electrode, which is why enzyme electrodes sometimes are considered as ion-selective. An example is glucose selective electrodes.
The most serious problem limiting use of ion-selective electrodes is interference from other, undesired, ions. No ion-selective electrodes are completely ion-specific; all are sensitive to other ions having similar physical properties, to an extent which depends on the degree of similarity. Most of these interferences are weak enough to be ignored, but in some cases the electrode may actually be much more sensitive to the interfering ion than to the desired ion, requiring that the interfering ion be present only in relatively very low concentrations, or entirely absent. In practice, the relative sensitivities of each type of ion-specific electrode to various interfering ions is generally known and should be checked for each case; however the precise degree of interference depends on many factors, preventing precise correction of readings. Instead, the calculation of relative degree of interference from the concentration of interfering ions can only be used as a guide to determine whether the approximate extent of the interference will allow reliable measurements, or whether the experiment will need to be redesigned so as to reduce the effect of interfering ions. The nitrate electrode has various ionic interferences, i.e. perchlorate, iodide, chloride, and sulfate. These interferences vary markedly in the extent to which they interfere. Thus, perchlorate gives a response which is about 50,000x as great as an equal amount of nitrate, while 1000x as much sulfate produces about a 10% error in the reading. Chloride causes a 10% error when present at about 30x the nitrate level, but can be removed by the addition of silver sulfate. Alternatively, nitrate can be determined by using an ammonia gas sensing electrode. This technique allows the user to determine both ammonium and nitrate ions sequentially. The procedure makes use of the reducing ability of titanium chloride. Trivalent titanium reduces any nitrate ion, up to 20 ppm, to ammonium ion (i.e., reverse nitrification). At pH 12-13, any ammonium ion in the sample is converted to ammonia gas and is ultimately detected by the electrode.
- Diffusion limited enzyme
- Total Ionic Strength Adjustment Buffer - sometimes used to control the ionic strength of the solution (and thus the activity coefficient of the analyte ion)
- Nitrate Electrode Instruction Manual, ThermoFisher Scientific, Beverly, MA 01915
- # D.W. Rich, B. Grigg, and G.H. Snyder, (2006) "Determining ammonium and nitrate using a gas sensing ammonia electrode." Soil and Crop Science Society of Florida (Proceedings, Vol. 65):1-4
||This article includes a list of references, but its sources remain unclear because it has insufficient inline citations. (November 2008)|
- R.P. Buck and E. Lindner (1994). "Recommendations for nomenclature of ion-selective electrodes". Pure & App. Chem. 66 (12): 2527–2536. doi:10.1351/pac199466122527.
- A. J. Bard and L. Faulkner (2000). Electrochemical Methods: Fundamentals and Applications. New York: Wiley. ISBN 978-0-471-04372-0.
- Eric Bakker and Yu Qin (2006). "Electrochemical sensors". Anal. Chem. 78 (12): 3965–3984. doi:10.1021/ac060637m. PMC 2883720. PMID 16771535. (Review article)
- D.W. Rich, B. Grigg, and G.H. Snyder, (2006) "Determining ammonium and nitrate using a gas sensing ammonia electrode." Soil and Crop Science Society of Florida (Proceedings, Vol. 65):1-4
- SCIMEDIA: Ion-Selective Electrodes
- Ion-selective electrodes by Wojciech Wroblewski
- Guide to use of ion-selective electrodes, with both simple and very detailed versions, including theoretical formulae and tables
- Sensoric Applications
- H+ ion-selective electrode – freeware for pH calculation and titration data analysis and simulation