Potentiometry 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. 

The potential of the indicator electrode in a potentiometric electrochemical cell is proportional to the concentration of analyte. Two classes of indicator electrodes are used in potentiometry metallic electrodes, which are the subject of this section, and ion-selective electrodes, which are covered in the next section. 

If metallic electrodes were the only useful class of indicator electrodes, potentiometry would be of limited applicability. The discovery, in 1906, that a thin glass membrane develops a potential, called a membrane potential, when opposite sides of the membrane are in contact with solutions of different pH led to the eventual development of a whole new class of indicator electrodes called ion-selective electrodes (ISEs). following the discovery of the glass pH electrode, ion-selective electrodes have been developed for a wide range of ions. Membrane electrodes also have been developed that respond to the concentration of molecular analytes by using a chemical reaction to generate an ion that can be monitored with an ion-selective electrode. The development of new membrane electrodes continues to be an active area of research. 

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 . 

Potentiometry, which measures the open-circuit equilibrium potential of an indicator electrode, for which the substance being examined is potential determining... 

Potentiometry is suitabie for the analysis of substances for which electrochemical equilibrium is established at a suitable indicator electrode at zero current. According to the Nemst equation (3.31), the potential of such an electrode depends on the activities of the potential-determining substances (i.e., this method determines activities rather than concentrations). 

An important condition for potentiometry is high selectivity the electrode s potential shonld respond only to the snbstance being examined, not to other components in the solntion. This condition greatly restricts the possibilities of the version of potentiometry described here when metal electrodes are nsed as the indicator electrodes. The solntion shonld be free of ions of more electropositive metals and of the components of other redox systems (in particnlar, dissolved air). Only corrosion-resistant materials can be nsed as electrodes. It is not possible at all with this method to determine alkali or alkaline-earth metal ions in aqneons solntions. 

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. 

The indicator electrode is of paraihount importance in analytical potentiometry. This electrode should interact with the species of interest so that the potential of the... 

One of the most fruitful uses of potentiometry in analytical chemistry is its application to titrimetry. Prior to this application, most titrations were carried out using colour-change indicators to signal the titration endpoint. A potentiometric titration (or indirect potentiometry) involves measurement of the potential of a suitable indicator electrode as a function of titrant volume. The information provided by a potentiometric titration is not the same as that obtained from a direct potentiometric measurement. As pointed out by Dick [473], there are advantages to potentiometric titration over direct potentiometry, despite the fact that the two techniques very often use the same type of electrodes. Potentiometric titrations provide data that are more reliable than data from titrations that use chemical indicators, but potentiometric titrations are more time-consuming. 

The so-called indicator electrodes must be considered as microelectrodes, which means that the active surface area is very small compared with the volume of the analyte solution as a consequence, the electrode processes cannot perceptibly alter the analyte concentration during analysis in either non-faradaic potentiometry or faradaic voltammetry. 

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. 

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. 

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

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. 

The characteristics of redox reactions in non-aqueous solutions were discussed in Chapter 4. Potentiometry is a powerful tool for studying redox reactions, although polarography and voltammetry are more popular. The indicator electrode is a platinum wire or other inert electrode. We can accurately determine the standard potential of a redox couple by measuring the electrode potential in the solution containing both the reduced and the oxidized forms of known concentrations. Poten-tiometric redox titrations are also useful to elucidate redox reaction mechanisms and to obtain standard redox potentials. In some solvents, the measurable potential range is much wider than in aqueous solutions and various redox reactions that are impossible in aqueous solutions are possible. 

Ion solvation has been studied extensively by potentiometry [28, 31]. Among the potentiometric indicator electrodes used as sensors for ion solvation are metal and metal amalgam electrodes for the relevant metal ions, pH glass electrodes and pH-ISFETs for H+ (see Fig. 6.8), univalent cation-sensitive glass electrodes for alkali metal ions, a CuS solid-membrane electrode for Cu2+, an LaF3-based fluoride electrode for l , and some other ISEs. So far, method (2) has been employed most often. The advantage of potentiometry is that the number and the variety of target ions increase by the use of ISEs. 

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. 

As indicated at the beginning of this chapter, the methodology of chrono-potentiometry is straightforward. Some care is necessary to ensure that the electrode configuration and placement are such as to cause the electrolysis to be limited by semiinfinite linear diifusion. Chapter 5 indicates a number of indicator-electrode designs that are appropriate for such performance. As in... 

The goal of this volume is to provide (1) an introduction to the basic principles of electrochemistry (Chapter 1), potentiometry (Chapter 2), voltammetry (Chapter 3), and electrochemical titrations (Chapter 4) (2) a practical, up-to-date summary of indicator electrodes (Chapter 5), electrochemical cells and instrumentation (Chapter 6), and solvents and electrolytes (Chapter 7) and (3) illustrative examples of molecular characterization (via electrochemical measurements) of hydronium ion, Br0nsted acids, and H2 (Chapter 8) dioxygen species (02, OJ/HOO-, HOOH) and H20/H0 (Chapter 9) metals, metal compounds, and metal complexes (Chapter 10) nonmetals (Chapter 11) carbon compounds (Chapter 12) and organometallic compounds and metallopor-phyrins (Chapter 13). The later chapters contain specific characterizations of representative molecules within a class, which we hope will reduce the barriers of unfamiliarity and encourage the reader to make use of electrochemistry for related chemical systems. 

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

Indicator electrode — In -> potentiometry the electrode for which the -> potential is recorded, in -> amperometry the electrode for which the -> current is recorded. 

Ascorbic acid and Na ascorbate can be determined in an automated constant current coulometric system. Under optimal conditions, an excellent precision of 0.3% was achieved, with 95% probability . Ca ascorbate can be determined by potentiometry (using Ag as indicator electrode) and constant current coulometric methods. Automatic coulom-etry possesses the advantage of speed and, with its satisfactory precision, is well suited to routine pharmaceutical analysis . 

Potentiometry is a method of electroanalytical measurement in which the equilibrium voltage of the cell consisting of an indicator electrode and a proper reference electrode is measured using a high-impedance voltmeter, i.e., effective at zero current. The potential of the indicator electrode is a function of particular species present in solutions and their concentration. By judicious choice of electrode material, the selectivity of the response to one of the species can be increased, and thus, interferences from other ions can be minimized. The method allows the determination of concentrations with detection limits of the order of 0.1 pmol per liter, although in some cases, as little as lOpmol differences in concentration can be measured. 

Direct potentiometric measurements are used to complete chemical analyses of species for which an indicator electrode is available. The technique is simple, requiring only a comparison of the voltage developed by the measuring cell in the test solution with its voltage when immersed in a standard solution of the analyte. If the electrode response is specific for the analyte and independent of the matrix, no preliminary steps are required. In addition, although discontinuous measurements are mainly carried out, direct potentiometry is readily adapted to continuous and automatic monitoring. 

Although electrochemistry has the stigma of being difficult to use, and therefore is often overlooked as an analysis option, potentiometric measurements are probably the most common technique encountered. Many analytical chemists make potentiometric measurements daily, whenever they use a pH meter. Potentiometry is based on the measurement of the potential between two electrodes immersed in a test solution. As the electrical potential of the cell is measured with no current flow between the electrodes, potentiometry is an equilibrium technique. The first electrode, the indicator electrode, is chosen to respond to the activity of a specific species in the test solution. The second electrode is a reference of known and fixed potential. The design of the indicator electrode is fundamental to potentiometric measurements, and should interact selectively with the analyte of interest so that other sample constituents do not interfere with the measurement. Many different strategies have been developed to make indicator electrodes that respond selectively to a number of species including organic ions. 

An example of an electrochemical cell for potentiometry is shown schematically in Fig. 1. The cell consists of an external reference electrode and an indicator electrode immersed in a test solution of analyte with some activity, (aOsampie- The indicator electrode is constructed of a reference electrode contained within a membrane and an internal reference electrolyte of fixed activity, (aOmtemai- The potential (F ceii) is measured by a pH/mV meter, and is equal to the sum of the potential between the internal (Fref.int) and external ( ref,ext) reference electrodes, the membrane potential (i memb), plus the liquid junction potential (Ey) that exists at the junction between the external reference electrode and the sample solution. 

Potentiometric Titration Potentiometry may be used to follow a titration and to determine its end point. The principles have already been discussed in connection with acid-base or complex formation titrations where pH or pMe is used as a variable. Any potentiometric electrode may serve as an indicator electrode, which indicates either a reactant or a reaction product. Usually the measured potential will vary during the course of the reaction and the end point will be characterized by a jump in the curve of voltage versus amount of reactant added. 

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