pH electrode technology hasn't changed much in the past 50 to 60 years, yet pH electrode manufacturing remains an art. The special glass body of the electrode is blown to its configuration by glass blowers. This is neither a terribly advanced nor "high tech" process but a very critical and important step in the electrode manufacturing. In fact, the thickness of the glass determines its resistance and affects its output.
pH electrodes are constructed from a special composition glass which senses the hydrogen ion concentration. This glass is typically composed of alkali metal ions. The alkali metal ions of the glass and the hydrogen ions in solution undergo an ion exchange reaction, generating a potential difference. In a combination pH electrode, the most widely used variety, there are actually two electrodes in one body. One portion is called the measuring electrode, the other the reference electrode. The potential generated at the junction site of the measuring portion is due to the free hydrogen ions present in solution.
The potential of the reference portion is produced by the internal element in contact with the reference fill solution. This potential is always constant. In summary, the measuring electrode delivers a varying voltage and the reference electrode delivers a constant voltage to the meter. The voltage signal produced by the pH electrode is a very small, high impedance signal. The input impedance requires that it be interfaced only with equipment with high impedance circuits. The input impedance required is greater than 1013 ohms. This is the reason pH electrodes do not interface directly with all equipment.
pH electrodes are available in a variety of styles for both laboratory and industrial applications. All are composed of glass and are therefore subject to breakage. Electrodes are designed to measure mostly aqueous media. They are not designed to be used in solvents, such as CCI4, which does not have any free hydrogen ions.
The pH electrode, due to the nature of its construction, needs to be kept moist at all times. In order to operate properly, glass needs to be hydrated. Hydration is required for the ion exchange process to occur. If an electrode should become dry, it is best to place it in some tap water for a half hour to condition the glass.
pH electrodes are like batteries; they run down with time and use. As an electrode ages, its glass changes resistance. This resistance change alters the electrode potential. For this reason, electrodes need to be calibrated on a regular basis. Calibration in pH buffer solution corrects for this change. Calibration of any pH equipment should always begin with buffer 7.0 as this is the "zero point." The pH scale has an equivalent mV scale. The mV scale ranges from +420 to -420 mV. At a pH of 7.0 the mV value is 0. Each pH change corresponds to a change of ±60 mV. As pH values become more acidic the mV values become greater. For example, a pH of 4.0 corresponds to a value of 180 mV. As pH values become more basic the mV values become more negative; pH=9 corresponds to -120 mV. Dual calibration using buffers 4.0 or 10.0 provides greater system accuracy.
pH electrodes have junctions which allow the internal fill solution of the measuring electrode to leak out into the solution being measured. This junction can become clogged by particulates in the solution and can also facilitate poisoning by metal ions present in the solution. If a clogged junction is suspected it is best to soak the electrode in some warm tap water to dissolve the material and clear the junction. pH electrodes should always be stored in a moistened condition. When not in use it is best to store the electrode in either buffer 4.0 or buffer 7.0. Never store an electrode in distilled or deionized water as this will cause migration of the fill solution from the electrode. pH electrodes have a finite lifespan due to their inherent properties. How long a pH electrode will last will depend on how it is cared for and the solutions it is used to measure. Typically, a gel-filled combination pH electrode will last six months to 1 year depending on the care and application. Even if an electrode is not used it still ages. On the shelf, the electrode should last approximately a year if kept in a moistened condition. Electrode demise can usually be characterized by a sluggish response, erratic readings or a reading which will not change. When this occurs an electrode can no longer be calibrated. pH electrodes are fragile and have a limited lifespan. How long an electrode will last is determined by how well the probe is maintained and the pH application. The harsher the system, the shorter the lifespan. For this reason it is always a good idea to have a back-up electrode on hand to avoid any system down time. Calibration is also an important part of electrode maintenance. This assures not only that the electrode is behaving properly but that the system is operating correctly.