At the Forefront of Electrode Technology Hanna is the largest family-owned manufacturer of scientific analytical instrumentation, and a major European producer of electrodes. Hanna has helped propel the field of sensor technology with it’s innovative methodology. The Hanna line of pH electrodes is produced in state of the art manufacturing facilities, and is available with glass or thermal plastic bodies. In 1981, Hanna developed its own formulation for sensing glass with the help of the Experimental Institute for Glass in Murano Italy. From that point forward, the company has continued to offer these premium pH sensing glass electrodes that cannot be imitated. While other companies have reduced their offerings, Hanna has continued to expand their electrode line to support a multitude of specific applications. An extensive variety of cleaning and maintenance solutions are also available to keep electrodes at peak performance. pH Electrode Manufacturing Other electrode producers use the continuous fusion technique in crucibles with induction furnaces. In this practice, the glass is exposed to the fusion temperature for hours, where it is difficult to retain the quality of the product due to the evaporation of some of its components. Hanna uses glass blowing technology typical of the Murano masters, with sensitive glass sticks fused in controlled batches. Only this technique, which exposes the sensitive glass to the high fusion temperature for a matter of seconds, can guarantee the consistency and quality of the pH half-cell. pH Theory and Measurement The most common pH measurement system utilizes glass pH electrodes. The system consists of a pH sensor (whose voltage varies proportionately to the hydrogen ion activity of the solution), a reference electrode (which provides a stable and constant reference voltage), a conductive measurement solution, and a special meter to measure and display the pH. The pH sensor incorporates a thin membrane of hydrogen-sensitive glass blown on the end of an inert glass tube. This tube is filled with a buffered electrolyte and an Ag/AgCl wire. This system is called a pH half-cell. A complementary system produces a constant voltage; it also contains a Ag/AgCl wire and an electrolyte (often a KCl solution saturated with AgCl). A small “filter", often a porous ceramic component, connects this tube to the external sample. This system is called a reference half-cell. The meter measures the voltage difference between the pH half-cell and the reference half cell in DC millivolts. The measurement is read by the meter and displayed in either mV or pH units. The mV response by a pH electrode follows the Nernst Equation: Eobs = Ec + ln(10)(RT / nF)(log[a H +]) Eobs = Observed potential Ec = Reference potential including other stable and fixed potentials aH + = The hydrogen ion activity T = Temperature in Kelvin (C° + 273.15) n = Valence of the ion measured (1) F = Faraday’s constant (9.6485 x 104) R = Gas constant (8.31432J / KMol) From this equation one can see that if the temperature (T) changes, the term ln(10)RT / nF known as the slope factor, will change also. The table below illustrates the change in slope factor for changes in temperature. Temperature (°C) Slope Factor (mV/pH) 05 55.18 10 56.18 15 57.18 20 58.17 25 59.16 30 60.15 35 61.14 How Temperature Affects Solution pH Samples change pH as a function of temperature due to changes in ion dissociation; as temperature increases, ion activity also increases. An example of this is pH buffers, whose well-characterized values are published on the buffer bottles. With very pure water, a change of ~1.3 pH is observed between 0 and 100°C. This example shows that even a neutral solution can have a large temperature coefficient. All samples have a temperature coefficient that is variable for actual samples. Changes in pH due to the sample temperature coefficient are not compensated for. There is, however, an exception to this; because buffers are well-characterized, they are compensated for during calibration on intelligent pH meters. The buffers will display a 25°C value during calibration but will change after the calibration to read their actual pH at the temperature of measurement. pH Electrodes Designed and Manufactured by Hanna 2 pH 2.124 | www.hannainst.com electrodes
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