Potentiometry reference electrodes

Define potentiometry, reference electrode, ground, and indicator electrode. 

Finding the End Point Potentiometrically Another method for locating the end point of a redox titration is to use an appropriate electrode to monitor the change in electrochemical potential as titrant is added to a solution of analyte. The end point can then be found from a visual inspection of the titration curve. The simplest experimental design (Figure 9.38) consists of a Pt indicator electrode whose potential is governed by the analyte s or titrant s redox half-reaction, and a reference electrode that has a fixed potential. A further discussion of potentiometry is found in Chapter 11. 

Potentiometric measurements are made using a potentiometer to determine the difference in potential between a working or, indicator, electrode and a counter electrode (see Figure 11.2). Since no significant current flows in potentiometry, the role of the counter electrode is reduced to that of supplying a reference potential thus, the counter electrode is usually called the reference electrode. In this section we introduce the conventions used in describing potentiometric electrochemical cells and the relationship between the measured potential and concentration. 

This procedure of using a single measurement of electrode potential to determine the concentration of an ionic species in solution is referred to as direct potentiometry. The electrode whose potential is dependent upon the concentration of the ion to be determined is termed the indicator electrode, and when, as in the case above, the ion to be determined is directly involved in the electrode reaction, we are said to be dealing with an electrode of the first kind . 

In the present chapter consideration is given to various types of indicator and reference electrodes, to the procedures and instrumentation for measuring cell e.m.f., to some selected examples of determinations carried out by direct potentiometry, and to some typical examples of potentiometric titrations. 

Potentiometric methods are based on the measurement of the potential of an electrochemical cell consisting of two electrodes immersed in a solution. Since the cell potential is measured under the condition of zero cmrent, usually with a pH/mV meter, potentiometry is an equilibrium method. One electrode, the indicator electrode, is chosen to respond to a particular species in solution whose activity or concentration is to be measured. The other electrode is a reference electrode whose half-cell potential is invariant. 

As in normal potentiometry one uses and indicator electrode versus a reference electrode, the electrodes should, especially in pH measurements, be those recommended by the supplier of the pH meter in order to obtain a direct reading of the pH value displayed. In redox or other potential measurements any suitable reference electrode of known potential can be applied. However, a reference electrode is only suitable if a junction potential is excluded, e.g., an Ag-AgCl electrode in a solution of fixed Ag+ concentration or a calomel electrode in a saturated KC1 solution as a junction in many instances a direct contact of Cl" with the solution under test (possibly causing precipitation therein) is not allowed, so that an extra or so-called double junction with KN03 solution is required. Sometimes micro-electrodes or other adaptations of the surface are required. 

Covington, A. K., and M. J. F. Rebello, Reference electrodes and liquid junction effect in ion-selective electrode potentiometry, lon-Sel. Electrode Revs., 5, 93 (1983)... 

Sodium valproate has been determined in pharmaceuticals using a valproate selective electrode [13,14]. The electroactive material was a valproate-methyl-tris (tetra-decyl)ammonium ion-pair complex in decanol. Silver-silver chloride electrode was used as the reference electrode. The electrode life span was >1 month. Determination of 90-1500 pg/mL in aqueous solution by direct potentiometry gave an average recovery of 100.0% and a response time of 1 min. 

The electrochemical detection of pH can be carried out by voltammetry (amper-ometry) or potentiometry. Voltammetry is the measurement of the current potential relationship in an electrochemical cell. In voltammetry, the potential is applied to the electrochemical cell to force electrochemical reactions at the electrode-electrolyte interface. In potentiometry, the potential is measured between a pH electrode and a reference electrode of an electrochemical cell in response to the activity of an electrolyte in a solution under the condition of zero current. Since no current passes through the cell while the potential is measured, potentiometry is an equilibrium method. 

A schematic diagram of a typical pH electrode system is shown in Fig. 10.1. The cell potential, i.e. the electromotive force, is measured between a pH electrode and a reference electrode in a test solution. The pH electrode responds to the activity or concentration of hydrogen ions in the solution. The reference electrode has a very stable half-cell potential. The most commonly used reference electrodes for potentiometry are the silver/silver chloride electrodes (Ag/AgCl) and the saturated calomel electrodes (SCE). 

In potentiometry, the variation of the potential of a Pt electrode relative to a calomel reference electrode represents the time-dependent bromine concentration. Available [Br2] is about 2 x 10-5-10-4 m pseudo-first-order conditions ([Ol] [Br2]) have to be used. Rate constants up to 104 5 m- 1 s 1 can thus be obtained (Atkinson and Bell, 1963 Dubois et ai, 1968). 

Potentiometric measurements with ISEs can be approached by direct potentiometry, standard addition and titrations. The determination of an ionic species by direct potentiometry is rapid and simple since it only requires pretreatment and electrode calibration. Here, the ion-selective and reference electrodes are placed in the sample solution and the change in the cell potential is plotted against the activity of the target ion. This method requires that the matrix of the calibration solutions and sample solutions be well matched so that the only changing parameter allowed is the activity of the target ion. 

As mentioned previously, electroanalytical techniques that measure or monitor electrode potential utilize the galvanic cell concept and come under the general heading of potentiometry. Examples include pH electrodes, ion-selective electrodes, and potentiometric titrations, each of which will be described in this section. In these techniques, a pair of electrodes are immersed, the potential (voltage) of one of the electrodes is measured relative to the other, and the concentration of an analyte in the solution into which the electrodes are dipped is determined. One of the immersed electrodes is called the indicator electrode and the other is called the reference electrode. Often, these two electrodes are housed together in one probe. Such a probe is called a combination electrode. 

Potentiometry is the measurement of electrode potential in chemical analysis procedures for the purpose of obtaining qualitative and quantitative information about an analyte. The reference electrode is a half-cell that is designed such that its potential is a constant, making it useful as a reference point for potential measurements. Ground is the ultimate reference point in electronic measurements. 

In this present book, we will look at the analytical use of two fundamentally different types of electrochemical technique, namely potentiometry and amper-ometry. The distinctions between the two are outlined in some detail in Chapter 2. For now, we will anticipate and say that a potentiometric technique determines the potential of electrochemical cells - usually at zero current. The potential of the electrode of interest responds (with respect to a standard reference electrode) to changes in the concentration of the species under study. The most common potentiometric methods used by the analyst employ voltmeters, potentiometers or pH meters. Such measurements are generally relatively cheap to perform, but can be slow and tedious unless automated. 

Potentiometry is a method of obtaining chemical information by measuring the potential of an indicator electrode under zero current flow. It is based on the Nernst equation, which expresses the electrode potential as a function of the activity (or activities) of the chemical species in solution. The information obtained varies with indicator electrode, from the activity (concentration) of a chemical species to the redox potential in the solution. The potential of the indicator electrode is measured against a reference electrode using a high inptit-impedance mV/pH me-... 

In potentiometry, we measure the emf of a cell consisting of an indicator electrode and a reference electrode. For emf measurements, we generally use a pH/ mV meter of high input impedance. The potential of the reference electrode must be stable and reproducible. If there is a liquid junction between the indicator electrode and the reference electrode, we should take the liquid junction potential into account. 

When three-electrode devices are used, reference electrodes similar to those in potentiometry (Section 6.1.2) are applicable, because no appreciable current flows through them. The reference electrodes used in non-aqueous solutions can be classified into two groups [1, 2, 5, 10]. Reference electrodes of the first group are prepared by using the solvent under study and those of the second group are... 

Acetonitrile interacts with the d10 metal ions Cu1 and Ag1 to form solvated species of marked stability. This stability has been used in potentiometry where the Ag, 0.01 M AgN03 couple in acetonitrile has been recommended as a reversible reference electrode.154... 

Direct Potentiometry and Ion-Selective Electrodes. The reference electrode, Ag-AgCl, illustrated in Figure 2 may be taken as... 

In potentiometry, a two-electrode setup is used and is given schematically in Fig. 1.3. This setup consists of a working and a reference electrode, and it is the aim of this method to measure equilibrium conditions at the surface of the working electrode. Under equilibrium, the Nernst equation is valid ... 

Equation 2.16 shows that potentiometry is a valuable method for the determination of equilibrium constants, ffowever, it should be borne in mind that the system should be in equilibrium. Some other conditions, which are described below, also need to be fulhlled for use of potentiometry in any application. The basic measurement system must include an indicator electrode that is capable of monitoring the activity of the species of interest, and a reference electrode that gives a constant, known half-cell potential to which the measured indicator electrode potential can be referred. The voltage resulting from the combination of these two electrodes must be measured in a manner that minimises the amount of current drawn by the measuring system. This condition includes that the impedance of the measuring device should be much higher than that of the electrode. 

Potentiometry has found extensive application over the past half-century as a means to evaluate various thermodynamic parameters. Although this is not the major application of the technique today, it still provides one of the most convenient and reliable approaches to the evaluation of thermodynamic quantities. In particular, the activity coefficients of electroactive species can be evaluated directly through the use of the Nemst equation (for species that give a reversible electrochemical response). Thus, if an electrochemical system is used without a junction potential and with a reference electrode that has a well-established potential, then potentiometric measurement of the constituent species at a known concentration provides a direct measure of its activity. This provides a direct means for evaluation of the activity coefficient (assuming that the standard potential is known accurately for the constituent half-reaction). If the standard half-reaction potential is not available, it must be evaluated under conditions where the activity coefficient can be determined by the Debye-Hiickel equation. 

When voltammetry measurements are made in nonaqueous solvents, the problems of an adequate reference electrode are compounded. Until the 1960s the most common reference electrode was the mercury pool, because of its convenience rather than because of its reliability. With the advent of sophisticated electronic voltammetric instrumentation, more reliable reference electrodes have been possible, especially if a three-electrode system is used. Thus, variation of the potential of the counter electrode is not a problem if a second non-current-canying reference electrode is used to monitor the potential of the sensing electrode. If three-eleetrode instrumentation is used, any of the conventional reference electrodes common to potentiometry may be used satisfactorily. Our own preference is a silver chloride electrode connected to the sample solution by an appropriate noninterfering salt bridge. The one problem with this system is that it introduces a junction potential between the two solvent systems that may be quite large. However, such a reference system is reproducible and should ensure that two groups of workers can obtain the same results. 

Measurements can be done using the technique of redox potentiometry. In experiments of this type, mitochondria are incubated anaerobically in the presence of a reference electrode [for example, a hydrogen electrode (Chap. 10)] and a platinum electrode and with secondary redox mediators. These mediators form redox pairs with Ea values intermediate between the reference electrode and the electron-transport-chain component of interest they permit rapid equilibration of electrons between the electrode and the electron-transport-chain component. The experimental system is allowed to reach equilibrium at a particular E value. This value can then be changed by addition of a reducing agent (such as reduced ascorbate or NADH), and the relationship between E and the levels of oxidized and reduced electron-transport-chain components is measured. The 0 values can then be calculated using the Nernst equation (Chap. 10) ... 

Bipotentiometry — Whereas in - potentiometry the - potential of one -> indicator electrode is measured versus the constant potential of a -> reference electrode, in... 

Refs. [i] Kahlert H (2002) Potentiometry. In Scholz F (ed) Electroana-lytical methods. Springer, Berlin, p 229 [ii] Petrii OA, TsirlinaGA (2002) Electrode potentials. In Bard AJ, Stratman M, Gileadi E, Urbakh M (eds) Thermodynamics and electrified interfaces. Encyclopedia of electrochemistry, vol.l. Wiley-VCH, Weinheim, p 10 [iii] KahlertH (2002) Reference electrodes. In Scholz F (ed) Electroanalytical methods. Springer, Berlin, pp 261-277... 

Open-circuit potential (OCP) — This is the - potential of the - working electrode relative to the - reference electrode when no potential or - current is being applied to the - cell [i]. In case of a reversible electrode system (- reversibility) the OCP is also referred to as the - equilibrium potential. Otherwise it is called the - rest potential, or the - corrosion potential, depending on the studied system. The OCP is measured using high-input - impedance voltmeters, or potentiometers, as in - potentiometry. OCP s of - electrodes of the first, the second, and the third kind, of - redox electrodes and of - ion-selective membrane electrodes are defined by the - Nernst equation. The - corrosion po-... 

---