Selecting a reference electrode

We have seen in Section 5.2 that one can determine the relative electrode potential by measuring cell voltage. To form a series of relative electrode potentials, one has to select a reference electrode and standard conditions of components of an electrode/ electrolyte interphase. 

The proper selection of electrodes is discussed in Chapter 3. The primary concern is to select a reference electrode which provides a stable liquid junction potential in the sample. With limited sample volume, the combination electrode is often required, but an electrode pair with a sleeve junction reference is frequently used in a colloidal sample because of its low junction resistance and ease of cleaning (see Figure 6.3). 

Consider a three-electrode electrochemical cell comprising an electrolyte solution of metal ions with a bulk concentration c, an inert, ideally polarizable working electrode, a counter electrode and a reference electrode with a fixed potential Eref. The whole system is kept at a constant temperature T. For the sake of convenience, we select a reference electrode made of the bulk metal M whose ions are present in the solution. The only requirement that we have to meet for the purpose is the bulk metal M to have a stable and reversible equilibrium potential JE x(c). That being the case. Ere/ = Ej(c) and any external potential E which we apply to the working electrode polarizes it directly to the electrochemical overpotential t] = EJ/f) - E, which is a measurable quantity with a clear physical significance. Certainly we can use any other reference electrode with a fixed potential Ere/ and this is what we should do if the bulk metal M has no reversible potential in the particular experimental system or if this potential is not known. However, then the external potential E will polarize the working electrode to the overpotential rjre/ = Ere/ - E, which relates to rj according to //re/ = // + AEref where AEre/= Ere/- Eao(c). Namely the difference Ere/-EJ/S) is which we eliminate with the special choice of our reference electrode. 

The concentration of Ca + in a sample of sea water is determined using a Ca ion-selective electrode and a one-point standard addition. A 10.00-mL sample is transferred to a 100-mL volumetric flask and diluted to volume. A 50.00-mL aliquot of sample is placed in a beaker with the Ca ion-selective electrode and a reference electrode, and the potential is measured as -0.05290 V. A 1.00-mL aliquot of a 5.00 X 10 M standard solution of Ca + is added, and a potential of -0.04417 V is measured. What is the concentration of Ca + in the sample of sea water ... 

Potcntiomctric Titrations In Chapter 9 we noted that one method for determining the equivalence point of an acid-base titration is to follow the change in pH with a pH electrode. The potentiometric determination of equivalence points is feasible for acid-base, complexation, redox, and precipitation titrations, as well as for titrations in aqueous and nonaqueous solvents. Acid-base, complexation, and precipitation potentiometric titrations are usually monitored with an ion-selective electrode that is selective for the analyte, although an electrode that is selective for the titrant or a reaction product also can be used. A redox electrode, such as a Pt wire, and a reference electrode are used for potentiometric redox titrations. More details about potentiometric titrations are found in Chapter 9. 

Ion-selective electrodes are a relatively cheap approach to analysis of many ions in solution. The emf of the selective electrode is measured relative to a reference electrode. The electrode potential varies with the logarithm of the activity of the ion. The electrodes are calibrated using standards of the ion under investigation. Application is limited to those ions not subject to the same interference as ion chromatography (the preferred technique), e.g. fluoride, hydrogen chloride (see Table 10.3). 

There are two types of fluoride lon-selective electrodes available [27] Onon model 96-09-00, a combination fluoride electrode, and model 94-09-00, which requires a reference electrode The author prefers to use Onon model 94-09-00 because it has a longer operational life and is less expensive When an electrode fails, the reference electrode is usually less expensive to replace The Fisher Accumet pH meter, model 825 MP, automatically computes and corrects the electrode slope It gives a direct reading for pH, electrode potential, and concentra tion in parts per million The fluoride lon-specific electrode can be used for direct measurement [2S, 29] or for potenPometric titration with Th" or nitrate solutions, with the electrode as an end point indicator... 

The equipment required for direct potentiometric measurements includes an ion-selective electrode (ISE), a reference electrode, and a potential-measuring device (a pH/millivolt meter that can read 0.2mV or better) (Figure 5-1). Conventional voltmeters cannot be used because only very small currents are allowed to be drawn. The ion-selective electrode is an indicator electrode capable of selectively measuring the activity of a particular ionic species. Such electrodes exhibit a fast response and a wide linear range, are not affected by color or turbidity, are not... 

A parameter that is convenient for said purpose is the electrode potential E it must not be confused with the concept of a potential difference between the electrode and the electrolyte. By convention the term electrode potential E is used to denote the OCV of a galvanic cell that consists of the given electrode (the one that is studied) and a reference electrode selected arbitrarily. Thus, the potential of this electrode is compared with that of a reference electrode that is identical for all electrodes being studied. In accordance with this dehnition, the electrode potential of the reference electrode itself is (conventionally) regarded as zero. Any electrode system for which the equilibrium Galvani potential is established sufficiently rapidly and reproducibly can be used as a reference electrode. We shall write the electrode system to be used as the reference electrode, generally, as M /E ... 

For any type of nonaqueous electrolyte (nonaqueous solutions, melts, solid electrolytes) we can select suitable reference electrodes, measure the potentials of other electrodes, and set up tables of electrode potentials. The order of the reactions (electrodes) as a rule does not strongly differ between the different media. A strong reducing agent such as lithium will have a more negative potential than a weaker reducing agent such as copper, both in water and in other media. 

The ISFET is an electrochemical sensor based on a modification of the metal oxide semiconductor field effect transistor (MOSFET). The metal gate of the MOSFET is replaced by a reference electrode and the gate insulator is exposed to the analyte solution or is coated with an ion-selective membrane as illustrated in Fig. 

One barrel-tip contains the organic membrane phase and an internal reference electrode the other constitutes a second reference electrode. A four-barrel configuration with a 1-pm tip in which three barrels are liquid membrane electrodes for Na, Ca and and the fourth is a reference electrode has been reported Some representative applications of ion-selective electrodes for intracellular measurements are shown in Table 3. 

The electrolytes Na", and Cl are second only to glucose in being the most frequently run hospital tests. Many clinical chemistry analyzers now contain an ISE module for electrolyte analysis. Most commonly the module will consist of a Na -glass electrode, a valinomycin/PVC electrode, a Ag/AgCl pellet or a quaternary ammonium ion/PVC electrode and a reference electrode. A selective electrode for the bicarbonate ion continues to elude workers in the field. An indirect measurement of HCOf must be made. The sample is usually reacted with acid to evolve carbon dioxide gas which is measured with a traditional Severinghaus type CO2 electrode. Alternatively, the sample is treated with base to convert HCO to CO3 and a carbonate ion-selective electrode is used In this manner, the complete primary electrolyte profile is obtained electrochemically. 

Curve 1 in Fig. 5 gives an example of the oscillation of membrane current observed with the liquid membrane system as in Eq. (3) by applying a constant AFwi-w2 of —0.48 V and measuring the time course of the current through the LM, /wi-w2- The cell used was the same as that used for the measurement of the potential oscillation, except a tetraphenyl-arsonium ion selective electrode [26,27], TPhAsE, was employed as a reference electrode in LM of NB ... 

One may think that the idea of detecting ionic compounds such as heparin using polymeric ion-selective electrodes seems very difficult due to the high charge of polyionic molecules, which makes the slope of the electrode function negligibly small for an analytical application. Indeed, for heparin-selective electrodes the theoretical slope is less than lmV decade 1 and the potential practically does not depend on heparin concentration, which means that this ISE can be useful as a reference electrode [33], Nonetheless, Ma and Meyerhoff noticed that the potential of polymeric membrane... 

The dissolved oxygen content of a solution can be determined by measuring the diffusion current that results at a selected voltage. The Clark electrode was developed for this purpose and various modifications have subsequently been introduced. It consists basically of a platinum electrode separated from the sample by a membrane which is permeable to oxygen, e.g. Teflon or polyethylene. A reference electrode of silver/silver chloride in potassium chloride is used to complete the system (Figure 4.21). When a voltage that is sufficient to give the... 

These measure the potential difference between the transducing electrode and a reference electrode under conditions of zero current. Three types of potentiometric detectors are commonly employed ion-selective electrodes (ISE), gas-sensing electrodes and field effect transistors (FET). 

The equilibrium potential of an electrode (e.g., M/M ) is defined in Section 5.2 as the voltage of the cell, Pt H2(l atm) H+(a = 1) M M, where a is the activity. Three issues have to be resolved to measure this equilibrium electrode potential (1) the selection of a reference electrode (2) the coupling of the reference electrode with the electrode whose potential is being measured, in this case M/M + and (3) the experimental method for the voltage measurement. 

In potentiometric sensors, an electrical potential between the working electrode and a reference electrode is measured at zero current conditions in a solution containing ions that exchange with the surface. The first potentiometric MIP sensor was prepared in 1992 by Vinokurov (1992). The substrate-selective polyaniline electrode was electrosynthesized with polypyrrole, polyaniline, and aniline-p-aminophenol copolymers. The development of an MIP-based potentiometric sensor was reported in 1995 by Hutchins and Bachas (1995). This potentiometric sensor has high selectivity for nitrite with a low detection limit of (2 + l)x 10 M (Fig. 15.10). 

Ion-Selective Field Effect Transistors [22b,c,d] An ion-selective field effect transistor (ISFET) is a hybrid of an ion-selective electrode and a metal-oxide semiconductor field effect transistor (MOSFET), the metal gate of the MOSFET being replaced by or contacted with a thin film of a solid or liquid ion-sensitive material. The ISFET and a reference electrode are immersed in the solution containing ion i, to which the ISFET is sensitive, and electrically connected as in Fig. 5.37. A potential which varies with the activity of ion i, o(i), as in Eq. (5.38), is developed at the ion-sensitive film ... 

A potentiometric electrochemical cell consisting of a reference electrode, solid-state electrolyte(s), and an indicator electrode can provide information about the partial pressure of gas in the same way as the cells utilizing ion-selective electrodes and liquid electrolytes can. The general mechanism is as follows. A sample gas, which is part of a redox couple, permeates into the solid-state structure usually through the porous metal electrode and sets up a reversible potential difference at that interface according to the reaction... 

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