Electrodes polarization measurement

Bamartt S (1961) Magnitude of IR-drop correctitHis in electrode polarization measurements made with a Luggin-Haber capillary. J Electrochem Soc 108 102-104... 

The trends of behavior described above are found in solutions containing an excess of foreign electrolyte, which by definition is not involved in the electrode reaction. Without this excess of foreign electrolyte, additional effects arise that are most distinct in binary solutions. An appreciable diffusion potential q) arises in the diffusion layer because of the gradient of overall electrolyte concentration that is present there. Moreover, the conductivity of the solution will decrease and an additional ohmic potential drop will arise when an electrolyte ion is the reactant and the overall concentration decreases. Both of these potential differences are associated with the diffusion layer in the solution, and strictly speaking, are not a part of electrode polarization. But in polarization measurements, the potential of the electrode usually is defined relative to a point in the solution which, although not far from the electrode, is outside the diffusion layer. Hence, in addition to the true polarization AE, the overall potential drop across the diffusion layer, 9 = 9 + 9ohm is included in the measured value of polarization, AE. ... 

Figure 15.2 shows polarization curves for hydrogen evolution at electrodes of different metals in acidic electrolyte solutions. The results of polarization measurements are highly sensitive to the experimental conditions, in particular to the degree of solution and electrode surface purification for this reason, marked differences exist among the data reported by different workers. The curves shown still provide the correct picture of the common features. 

FIGURE 32.2 Scheme of a four-electrode system for polarization measurements at an ITIES comprising a potentiostat (POT), two reference electrodes connected to the cell by means of Luggin capillaries (REl, RE2), and two counter electrodes (CEl, CE2). The planar ITIES is formed at the edge of a round hole in a glass barrier between the spaces for the aqueous (water) and the organic (org) phases. 

During measurement, the conductivity cell is filled with an electrolyte solution this cell is usually made of glass with sealed platinum electrodes. Various shapes are used, depending on the purpose that it is to serve. Figure 2.9 depicts examples of suitable cell arrangements. The electrodes are covered with platinum black, to avoid electrode polarization. The electrodes are placed close to one another in poorly conductive solutions and further apart in more conductive solutions. 

Various carbon-based catalysts for the electrochemical oxygen reduction have been tested in the air gas-diffusion electrodes [7]. The polarization curves of the air electrodes were measured when operating against an inert electrode in 2 N NaCl-solution. The potential of the air electrodes was measured versus saturated calomel electrode (SCE). 

Kleinfeld, M. Wiemhofer, H.-D. 1988. Chemical diffusion coefficients and stabihty of CuInS2 and CuInSe2 from polarization measurements with point electrodes. Solid State Ionics. 28-30 1111-1115. 

The electrocatalytic activity of MIEC cathodes also depends strongly on the properties of the electrolyte, as shown by Liu and Wu [109], The electrode polarization resistances, RE, or area specific resistance (ASR) measured by the electrochemical... 

Variations of resistance with frequency can also be caused by electrode polarization. A conductance cell can be represented in a simplified way as resistance and capacitance in series, the latter being the double layer capacitance at the electrodes. Only if this capacitance is sufficiently large will the measured resistance be independent of frequency. To accomplish this, electrodes are often covered with platinum black 2>. This is generally unsuitable in nonaqueous solvent studies because of possible catalysis of chemical reactions and because of adsorption problems encountered with dilute solutions required for useful data. The equivalent circuit for a conductance cell is also complicated by impedances due to faradaic processes and the geometric capacity of the cell 2>3( . 

Consequently, by measuring the polarization curves for the transfer reaction of anodic holes both at a photoexdted n-type electrode and at a dark p-type electrode of the same semiconductor, we obtain the relationship between the Fermi level of the electrode (polarization potential E) and the quasi-Fermi level of interfadal holes in the photoexcited n-type dectrode as a function of... 

Figure 71. Tafel polarization measurement at different temperatures performed on MCMB and LiNiCo02 electrodes in 1.0 M LiPFe/EC/DEC/DMC/EMC (1 1 1 3). (Reproduced with permission from ref 515 (Figure 8). Copyright 2003 Elsevier.)...

A perfect prototype of an ideally cation-permselective interface is a cathode upon which the cations of a dissolved salt are reduced. Experimental polarization curves measured on metal electrodes fit the theory very closely. Since in dimensional units the limiting current is proportional to the bulk concentration, the polarization measurements on electrodes may serve for determining the former. This is the essence of the electrochemical analytical method named polarography. (For the theory of polarographical methods see [28]—[30].)... 

Electromagnetic measurements of high conductivity soil-fluid mixtures at low frequencies are difficult to obtain due to electrode polarization. Caution must be used when interpreting data in the literature, as electrode effects may be viewed as being material behaviour. In addition, difficulties with data interpretation arise at kHz and MHz frequencies for clay-fluid mixtures due to the possible manifestation of both double layer polarization and interfacial polarization phenomena. 

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