Details of the fabrication and resulting microstructure of the glass membrane of the pH electrode are maintained as trade secrets by the manufacturers. However, certain aspects of design are published. Glass is a solid electrolyte, for which alkali-metal ions can carry current. The pH-sensitive glass membrane is generally spherical to simplify the manufacture of a uniform membrane. These membranes are up to 0.4 millimeters in thickness, thicker than original designs, so as to render the probes durable. The glass has silicate chemical functionality on its surface, which provides binding sites for alkali-metal ions and hydrogen ions from the solutions. This provides an ion-exchange capacity in the range of 10 to 10 mol/cm. Selectivity for hydrogen ions (H) arises from a balance of ionic charge, volume requirements versus other ions, and the coordination number of other ions. Electrode manufacturers have developed compositions that suitably balance these factors, most notably lithium glass.
The silver chloride electrode is most commonly used as a reference electrode in pH meters, although some designs use the saturated calomel electrode. The silver chloride electrode is simple to manufacture and provides high reproducibility. The reference electrode usually consists of a platinum wire that has contact with a silver/silver chloride mixture, which is immersed in a potassium chloride solution. There is a ceramic plug, which serves as a contact to the test solution, providing low resistance while preventing mixing of the two solutions.
With these electrode designs, the voltmeter is detecting potential differences of ±1400 millivolts. The electrodes are further designed to rapidly equilibrate with test solutions to facilitate ease of use. The equilibration times are typically less than one second, although equilibration times increase as the electrodes age.