Potentiometric electrode system

Other potentiometric electrode systems are ion-selective electrodes such as fluoride, calcium, magnesium, sodium, potassium and chloride, selective gas electrodes based on membranes such as 02, C02, CO, NO, N02 and S02, and enzyme electrodes. These electrodes fall beyond the scope of this book and are not discussed further. 

Because any potentiometric electrode system ultimately must have a redox couple (or an ion-exchange process in the case of membrane electrodes) for a meaningful response, the most common form of potentiometric electrode systems involves oxidation-reduction processes. Hence, to monitor the activity of ferric ion [iron(III)], an excess of ferrous iron [iron(II)] is added such that the concentration of this species remains constant to give a direct Nemstian response for the activity of iron(III). For such redox couples the most common electrode system has been the platinum electrode. This tradition has come about primarily because of the historic belief that the platinum electrode is totally inert and involves only the pure metal as a surface. However, during the past decade it has become evident that platinum electrodes are not as inert as long believed and that their potentiometric response is frequently dependent on the history of the surface and the extent of its activation. The evidence is convincing that platinum electrodes, and in all probability all metal electrodes, are covered with an oxide film that changes its characteristics with time. Nonetheless, the platinum electrode continues to enjoy wide popularity as an inert indicator of redox reactions and of the activities of the ions involved in such reactions. 

A number of the most common potentiometric electrode systems and their applications are summarized in Table 2.2. Additional information is available in the biennial reviews of Analytical Chemistry within the section on potentiometric measurements. 

Figure 2.3 Differential potentiometric electrode system for titrations. After each addition of titrant and reading, the solution in the dropper is exchanged with the bulk solution.

A number of the most common potentiometric electrode systems and their applications are summarized in Table I. One of the most important and extensively used indicator electrode systems is the glass-membrane electrode that is used to monitor hydronium-ion activity. Although developed in 1909, it did not become popular until reliable electrometer amplifiers were developed in the 1930s (modern pH meters use high-input-impedance digital voltmeters). Figure 1 gives a schematic representation of this electrode and indicates that the primary electrode system is a silver/silver-chloride (or mercury/mercurous-chloride) electrode in contact with a known and fixed concentration of hydrochloric acid (usually about 0.1 M). When... 

Potentiometric titration using a bright platinum-saturated calomel electrode system this can be used when the reaction involves two different oxidation states of a given metal. 

To measure the e.m.f. the electrode system must be connected to a potentiometer or to an electronic voltmeter if the indicator electrode is a membrane electrode (e.g. a glass electrode), then a simple potentiometer is unsuitable and either a pH meter or a selective-ion meter must be employed the meter readings may give directly the varying pH (or pM) values as titration proceeds, or the meter may be used in the millivoltmeter mode, so that e.m.f. values are recorded. Used as a millivoltmeter, such meters can be used with almost any electrode assembly to record the results of many different types of potentiometric titrations, and in many cases the instruments have provision for connection to a recorder so that a continuous record of the titration results can be obtained, i.e. a titration curve is produced. 

Instead of immobilizing the antibody onto the transducer, it is possible to use a bare (amperometric or potentiometric) electrode for probing enzyme immunoassay reactions (42). In this case, the content of the immunoassay reaction vessel is injected to an appropriate flow system containing an electrochemical detector, or the electrode can be inserted into the reaction vessel. Remarkably low (femtomolar) detection limits have been reported in connection with the use of the alkaline phosphatase label (43,44). This enzyme catalyzes the hydrolysis of phosphate esters to liberate easily oxidizable phenolic products. 

Chloride can be determined in AOS by potentiometric titration of a sample with silver nitrate after acidification with nitric acid. A silver/glass electrode system is used. 

Dissolve about 350 mg of miconazole nitrate, accurately weighed, in 50 mL of glacial acetic acid, and titrate with 0.1 N perchloric acid VS, determining the endpoint potentiometrically using a glass calomel-electrode system. Perform a blank determination, and make any necessary correction. Each milliliter of 0.1 N perchloric acid is equivalent to 47.92 mg of Ci8H14C14N2OHN03. 

FIGURE 10.1 A schematic diagram for a typical electrode system for potentiometric pH measurements. A potential is established on the pH sensitive membrane-solution interface of a pH electrode that responds to the activity or concentration of hydrogen ions in the solution. The reference electrode has a very stable half-cell potential. The cell potential, which is proportional to the pH in the test solution, is measured using a high input impedance voltmeter between the pH electrode and the reference electrode. 

Electrode Systems. Direct Potentiometric Measurements. Potentiometric Titrations. Null -point Potentiometry. Applications of Potentiometry. 

Bromocriptine mesilate may be assayed in glacial acetic acid/acetic anhydride 1 7 by titration with 0.1 N perchloric acid. The endpoint may be determined potentiometrically using a glass/calomel electrode system. 

Valproic acid can be potentiometrically titrated with standardized 0.1 N tetra-n-butylammonium hydroxide in chlorobenzene using a modified glass-calomel electrode system, in which 1.0 M aqueous tetra-n-butylammonium chloride has been substituted for potassium chloride, and employing acetone as the sample solvent. 

The sensitivity of instruments using low resistance circuits is determined primarily by the sensitivity of the galvanometer (Figure 4.5). Electrode systems that have a high resistance, e.g. glass electrodes, require a high impedance voltmeter, which converts the potential generated into current which can be amplified and measured. Such instruments are commonly known as pH meters but may be used for many potentiometric measurements other than pH. 

Fig. 3.7 Potentiometric titration curve of a mixture of acids in MIBK [21]. Titrated with 0.2 M Bu4NOH using a glass electrode-Pt electrode system.

Electrodes classified in the second group of electrode systems are those in which the metal electrode is coated with a layer of a sparingly soluble salt of the electroactive species and the metal ion of the metal electrode, such that the potentiometric response is indicative of the concentration of the inactive anion species. Thus the silver/silver-chloride electrode system, which is representative of this class of electrodes, gives a potential response that is directly related to the logarithm of the chloride ion activity (see also Chapter 1, section 1.5), even though it is not the electroactive species ... 

This is true because the chloride ion concentration, through the solubility product, controls the activity of the silver ion, which is measured directly by the potentiometric silver-electrode system. 

Ion-selective electrodes belong to the group of potentiometric methods. Many electrode systems, partly well known, partly in development and under investigation, show a Nemstian relationship between the measured electrode potential and the activity of a species in solution. Important conditions to be fulfilled for the development of ion-selective electrodes are the affinity of a membrane surface for a typical ion or molecule and a minimum ion conductivity over the membrane. If possible, but not necessarily, these conditions should be fulfilled at room temperature. 

The GECE sensors were used for lead determination in real water samples suspected to be contaminated with lead obtained from water suppliers. The same samples were previously measured by three other methods a potentiometric FIA system with a lead ion-selective-electrode as detector (Pb-ISE) graphite furnace atomic absorption spectrophotometry (AAS) inductively coupled plasma spectroscopy (ICP). The results obtained for lead determination are presented in Table 7.1. The accumulation times are given for each measured sample in the case of DPASV. Calibration plots were used to determine the lead concentration. GEC electrode results were compared with each of the above methods by using paired -Test. The results obtained show that the differences between the results of GECE compared to other methods were not significant. The improvement of the reproducibility of the methods is one of the most important issues in the future research of these materials. 

Direct potentiometric measurement an Agl membrane electrode with a double junction reference electrode system must be used to quantify CN-. 

The indicator electrodes for potentiometric measurements traditionally have been categorized into three separate classes. First-class electrodes consist of a metal immersed in a solution that contains the metal ion. These electrode systems provide a direct response to the ion or species to be measured ... 

For many systems the gold electrode is as satisfactory as the platinum electrode. Both rhodium and palladium as well as carbon have been used for specialized systems as inert potentiometric electrodes. 

Figure 4.8 Cell system for coulometric titration by a platinum generator electrode and an isolated auxiliary electrode system includes provision for potentiometric endpoint detection.

Because the generator electrodes must have a significant voltage applied across them to produce a constant current, the placement of the indicator electrodes (especially if a potentiometric detection system is to be used) is critical to avoid induced responses from the generator electrodes. Their placement should be adjusted such that both the indicator electrode and the reference electrode occupy positions on an equal potential contour. When dual-polarized amperometric electrodes are used, similar care is desirable in their placement to avoid interference from the electrolysis electrodes. These two considerations have prompted the use of visual or spectrophotometric endpoint detection in some applications of coulometric titrations. 

Reference to Table 4.1 indicates that olefins can be determined by the electrochemical generation in situ of halogens. Bromine is effective for both olefins and sulfur compounds and is the basis for an automatic coulometric titrator for continuous analysis of petroleum streams.17 The basic principle of this instrument is a potentiometric sensing system that monitors bromine concentration in a continuously introduced sample stream. The bromine in the solution reacts with the sample components and causes a decrease in the concentration of bromine. When this decrease is sensed by the potentiometric detection electrodes, the electrolysis current producing bromine adjusts itself to maintain the bromine concentration. Because the sample is introduced at a constant rate, the electrolysis current becomes directly proportional to the concentration of the sample component. Thus, the instrument records the electrolysis current as concentration of sample component and provides a continuous monitor for olefins or sulfur in petroleum streams. 

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