Ion Selective Electrodes: Measurement Considerations
This article is designed to apply, in general, to all specific ion electrodes. Typically, the ISE (Ion Selective Electrode) that is purchased will come with its own instruction manual that pertains to that particular type of electrode. It is best to read all instructions thoroughly before using the electrode. When the ISE is received, it is advised that you open up the package immediately and check all the parts of the electrode. Most ISE's have a pre-treatment procedure that should be followed prior to operation.
Before beginning your measurements the following are a few basic facts that will aid in designing your analysis procedure.
Agitation 
                
                When carrying out selective ion measurements, it is important 
                to have good agitation. This allows a fresh supply of ions to 
                be exposed to the sensing portion of the ISE. It is best to select 
                a speed that keeps a constant, smooth motion. A turbulent rate 
                should be avoided. 
Sample 
                pH 
                Most ISE's require a specific pH range for optimum performance 
                of the electrode. Some ISE's require a precise adjustment. Consult 
                OMEGA's pH Engineering staff for details on purchasing a pH adjustment 
                reagent formulated for your particular electrode. 
Response 
                Time 
                ISE's require a much longer time for the readings to stabilize. 
                At least fifteen minutes should be allowed for equilibrium to 
                be established when measuring your standard solutions. 
Establishing 
                a Calibration Curve 
                It is recommended to use three standard solutions when establishing 
                a calibration curve. To choose the concentrations of the standard 
                solutions it is helpful to know the approximate values of your 
                unknown solutions. For example, if your unknown solutions are 
                in the 100 ppm range, the choice of standards may include a 10 
                ppm, a 100 ppm, and a 1000 ppm solution. 
Rinsing 
                
                It is necessary to rinse the ISE between measurements to insure 
                accurate readings. Use a steady stream of deionized or distilled 
                water. Take care not to rub the electrode with a cloth to dry 
                the probe. It is usually best to "shake off" any excess water. 
                Take care not to hit the probe against anything while shaking 
                the electrode. 
Conditioning 
                
                The ISE needs to remain moist at all times even when not in use. 
                Consult the operator's manual that accompanies your electrode 
                for details on cleaning, conditioning and storing the ISE. Common 
                Questions and Answers About Ion-Selective Electrodes 
What 
                is an Ion-Selective Electrode? 
                An Ion Selective Electrode measures the potential of a specific 
                ion in solution. (The pH electrode is an ISE for the Hydrogen 
                ion.) This potential is measured against a stable reference electrode 
                of constant potential. The potential difference between the two 
                electrodes will depend upon the activity of the specific ion in 
                solution. This activity is related to the concentration of that 
                specific ion, therefore allowing the end-user to make an analytical 
                measurement of that specific ion. Several ISE's have been developed 
                for a variety of different ions. 
What 
                Type of Equipment is Needed for an ISE Measurement?
                A pH meter that also measures millivolts can be used to interface 
                with an ISE. Most ISE's are combination electrodes that have the 
                reference electrode built into the body of the ISE, however, some 
                ISE's require a separate reference electrode. If this is the case, 
                the pH/mV meter must have a pin-connector to connect the reference 
                electrode. 
How 
                Does the mV Reading Correspond to the Concentration? 
                Standard solutions of known concentrations must be accurately 
                prepared. These solutions are then measured with the pH/mV meter. 
                The mV reading of each solution is noted and a graph of concentration 
                vs. mV reading must be plotted. Now the unknown solution can be 
                measured. The mV value of the unknown solution is then located 
                on the graph and the corresponding solution concentration is determined. 
                Please see the graph shown above as an example. 
What 
                is Ionic Activity?
                Ionic activity is a thermodynamic measurement that represents 
                the energy available due to free and reactive ions in solution. 
                The activity coefficient is the ratio between the free ions and 
                the total ionic concentration in the solution.
 Why 
                is pH Adjustment Necessary?
                I n many cases pH control is necessary for accurate, repeatable 
                measurements. Certain ions exhibit different activity when different 
                concentrations of hydrogen ions are present in solution. This 
                occurrence will not only alter the potential due to the specific 
                ion that is measured, it may also allow other ions in solution 
                to become active that otherwise were not. This increased activity 
                from the other ions will interfere with the ability to evaluate 
                the ion of interest.  
|  | 
| 
 |   | |
|  | ||