Electrochemical analysis potentiometry

Principles and Characteristics A substantial percentage of chemical analyses are based on electrochemistry, although this is less evident for polymer/additive analysis. In its application to analytical chemistry, electrochemistry involves the measurement of some electrical property in relation to the concentration of a particular chemical species. The electrical properties that are most commonly measured are potential or voltage, current, resistance or conductance charge or capacity, or combinations of these. Often, a material conversion is involved and therefore so are separation processes, which take place when electrons participate on the surface of electrodes, such as in polarography. Electrochemical analysis also comprises currentless methods, such as potentiometry, including the use of ion-selective electrodes. 

Electrochemical analysis is composed of a vast range of techniques such as potentiometry, polarography, amperometry and coulometry. Selection of the technique best suited to the purpose and of the appropriate working conditions ensure a high degree of sensitivity and selectivity. 

Other Methods. Turbidimetry, light scattering and refractive index measurements are spectrophotometric methods used to obtain surfactant cmcs. Viscosity, diffusion coefficient measurements, flow injection analysis and electrochemical methods (potentiometry and polarography and even... 

The results of the linearization of the polarization curves using Equation 4.5.2 for current densities corresponding to the range of concentrations in which Henry s law is fulfilled [16] are presented in Table 4.5.1. One can see that the value of n (number of electrons involved in the electrode process) is below two. Based on the conventional electrochemical analysis this indicates that vanadium is partially dissolved following a one-electron reaction. This however contradicts our data obtained previously by coulometry, oxidimetry, and potentiometry [16]. 

In potentiometry, the potential of an electrochemical cell under static conditions is used to determine an analyte s concentration. As seen in the preceding section, potentiometry is an important and frequently used quantitative method of analysis. Dynamic electrochemical methods, such as coulometry, voltammetry, and amper-ometry, in which current passes through the electrochemical cell, also are important analytical techniques. In this section we consider coulometric methods of analysis. Voltammetry and amperometry are covered in Section 1 ID. 

Electrical methods of analysis (apart from electrogravimetry referred to above) involve the measurement of current, voltage or resistance in relation to the concentration of a certain species in solution. Techniques which can be included under this general heading are (i) voltammetry (measurement of current at a micro-electrode at a specified voltage) (ii) coulometry (measurement of current and time needed to complete an electrochemical reaction or to generate sufficient material to react completely with a specified reagent) (iii) potentiometry (measurement of the potential of an electrode in equilibrium with an ion to be determined) (iv) conductimetry (measurement of the electrical conductivity of a solution). 

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). 

J. Thompson, 1893) and the development of chemical thermodynamics (G. N. Lewis, 1923). Building on this foundation, the utilization of electrochemical phenomena for thermodynamic characterization and analysis of molecules and ions (electroanalytical chemistry) began at the beginning of this century [po-tentiometry (1920) and polarography (1930)]. Relationships that describe the techniques of potentiometry and polarography derive directly from solution thermodynamics. In the case of polarography, there is a further dependence on the diffusion of ionic species in solution. The latter is the basis of conductivity measurements, another area that traces its origin to the nineteenth century. These quantitative relationships make it possible to apply electrochemistry to... 

Twenty years ago the main applications of electrochemistry were trace-metal analysis (polarography and anodic stripping voltammetry) and selective-ion assay (pH, pNa, pK via potentiometry). A secondary focus was the use of voltammetry to characterize transition-metal coordination complexes (metal-ligand stoichiometry, stability constants, and oxidation-reduction thermodynamics). With the commercial development of (1) low-cost, reliable poten-tiostats (2) pure, inert glassy-carbon electrodes and (3) ultrapure, dry aptotic solvents, molecular characterization via electrochemical methodologies has become accessible to nonspecialists (analogous to carbon-13 NMR and GC/MS). 

Electrochemical methods, namely polarography and potentiometry, can also be used for quantitative analysis of surfactants of all types. Several types of polarographic methods are available to measure the concentration of surfactants in solution via the effects they cause on a dropping mercury electrode at the surface of which they adsorb. Although... 

Electrochemistry involves the study of the relationship between electrical signals and chemical systems that are incorporated into an electrochemical cell. It plays a very important role in many areas of chemistry, including analysis, thermodynamic studies, synthesis, kinetic measurements, energy conversion, and biological electron transport [1]. Electroanalytical techniques such as conductivity, potentiometry, voltammetry, amperometric detection, co-ulometry, measurements of impedance, and chronopotentiometry have been developed for chemical analysis [2], Nowadays, most of the electroanalytical methods are computerized, not only in their instrumental and experimental aspects, but also in the use of powerful methods for data analysis. Chemo-metrics has become a routine method for data analysis in many fields of analytical chemistry that include electroanalytical chemistry [3,4]. 

Potentiometry—the measurement of electric potentials in electrochemical cells—is probably one of the oldest methods of chemical analysis still in wide use. The early, essentially qualitative, work of Luigi Galvani (1737-1798) and Count Alessandro Volta (1745-1827) had its first fruit in the work of J. Willard Gibbs (1839-1903) and Walther Nernst (1864-1941), who laid the foundations for the treatment of electrochemical equilibria and electrode potentials. The early analytical applications of potentiometry were essentially to detect the endpoints of titrations. More extensive use of direct potentiometric methods came after Haber developed the glass electrode for pH measurements in 1909. In recent years, several new classes of ion-selective sensors have been introduced, beginning with glass electrodes more or less selectively responsive to other univalent cations (Na, NH ", etc.). Now, solid-state crystalline electrodes for ions such as F , Ag", and sulfide, and liquid ion-exchange membrane electrodes responsive to many simple and complex ions—Ca , BF4", CIO "—provide the chemist with electrochemical probes responsive to a wide variety of ionic species. 

In practice, electrochemistry not only provides a means of elemental and molecular analysis, but also can be used to acquire information about equilibria, kinetics, and reaction mechanisms from research using polarography, amperometry, conductometric analysis, and potentiometry. The analytical calculation is usually based on the determination of current or voltage or on the resistance developed in a cell under conditions such that these are dependent on the concentration of the species under study. Electrochemical measurements are easy to automate because they are electrical signals. The equipment is often far less expensive than spectroscopy instrumentation. Electrochemical techniques are also commonly used as detectors for LC, as discussed in Chapter 13. 

While all analysts are familiar with the principles of potentiometry and polarography and, indeed, most analytical laboratories will contain a pH meter and a polarograph, electrochemical methods are, in general, not very important in modern analysis. In... 

Sensitive and selective detection techniques are of crucial importance for capillary electrophoresis, microfluidic chips, and other microfluidic analysis systems. Electrochemical detector has attracted considerable interest in these fields owing to its high sensitivity, inherent miniaturization of both the detection and control instrumentation, low cost and power demands, and high compatibility with microfabrication technology. The commonly used electrochemical detection approaches can be classified into three general modes COTiductimetry, potentiometry, and amperometry. 

This article provides some general remarks on detection requirements for FIA and related techniques and outlines the basic features of the most commonly used detection principles, including optical methods (namely, ultraviolet (UV)-visible spectrophotometry, spectrofluorimetry, chemiluminescence (CL), infrared (IR) spectroscopy, and atomic absorption/emission spectrometry) and electrochemical techniques such as potentiometry, amperometry, voltammetry, and stripping analysis methods. Very few flowing stream applications involve other detection techniques. In this respect, measurement of physical properties such as the refractive index, surface tension, and optical rotation, as well as the a-, //-, or y-emission of radionuclides, should be underlined. Piezoelectric quartz crystal detectors, thermal lens spectroscopy, photoacoustic spectroscopy, surface-enhanced Raman spectroscopy, and conductometric detection have also been coupled to flow systems, with notable advantages in terms of automation, precision, and sampling rate in comparison with the manual counterparts. 

Potentiometry is the most common method of electrochemical detection used in flow injection analysis. This methodology creates more favorable conditions for potentiometric measurements when compared to batch procedures. In FIA measurements, it is easier to avoid incidental contamination or that resulting from leakage of the solution from the reference electrode. Moreover, deactivation of the sensing surface of the indicator electrode due to adsorption, precipitation, or corrosion is minimized greatly as a consequence of the short contact time with the sample... 

To overcome the problem of detection in CE, many workers have used inductively coupled plasma-mass spectrometry (ICP-MS) as the method of detection. Electrochemical detection in CE includes conductivity, amperometry, and potentiometry detection. The detection limit of amperometric detectors has been reported to be up to 10 M. A special design of the conductivity ceU has been described by many workers. The pulsed-amperometric and cyclic voltametry waveforms, as well as multi step wave forms, have been used as detection systems for various pollutants. Potentiometric detection in CE was first introduced in 1991 and was further developed by various workers. 8-Hydroxyquinoline-5-sulfonic acid and lumogallion exhibit fluorescent properties and, hence, have been used for metal ion detection in CE by fluorescence detectors. Overall, fluorescence detectors have not yet received wide acceptance in CE for metal ions analysis, although their gains in sensitivity and selectivity over photometric detectors are significant. Moreover, these detectors are also commercially available. Some other devices, such as chemiluminescence, atomic emission spectrometry (AES), refractive index, radioactivity, and X-ray diffraction, have also been used as detectors in CE for metal ions analysis, but their use is stiU limited. 

Three broad classifications of electrochemical methods are used in this chapter. Po-tentiometric methods include zero-current potentiometry and methods in which current of controlled magnitude is apphed to the working electrode, such as in potentiometric stripping analysis (PSA). Amperometric methods consider all techniques in which current is measured these include constant-potential amper-ometry and amperometric measurements made in response to a variety of applied potential waveforms in voltammetric methods. Impedimetric methods comprise a final classification in these methods, faradaic currents are generally absent, and impedance, conductance, or capacitance is the measured property. 

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