Electrode selectively blocking

As for the permeability measurements, most techniques based on the analysis of transient behavior of a mixed conducting material [iii, iv, vii, viii] make it possible to determine the ambipolar diffusion coefficients (- ambipolar conductivity). The transient methods analyze the kinetics of weight relaxation (gravimetry), composition (e.g. coulometric -> titration), or electrical response (e.g. conductivity -> relaxation or potential step techniques) after a definite change in the - chemical potential of a component or/and an -> electrical potential difference between electrodes. In selected cases, the use of blocking electrodes is possible, with the limitations similar to steady-state methods. See also - relaxation techniques. 

Figure 6. Bipolar precipitates consisting of an inner anion-selective layer and an outer cation-selective layer.19 When the electrode is polarized to the more noble side, protons and chloride ions are kept from permeating through the film, so that anodic dissolution of the substrate metal is blocked. (Reproduced from N. Sato, Corrosion, 45 354, 1989, Fig. 24 with permission of NACE International.)...

Figure 4.20.A shows a more recent cell reported by Cobben et al. It consists of three Perspex blocks, of which two (A) are identical and the third (B) different. Part A is a Perspex block (1) furnished with two pairs of resilient hooks (3) for electrical contact. With the aid of a spring, the hooks press at the surface of the sensor contact pads (4), the back side of which rests on the Perspex siuface, so the sensor gate is positioned in the centre of the block, which is marked by an engraved cross as in the above-described wall-jet cell. Part B is a prismatic Perspex block (2) (85 x 24 x 10 mm ) into which a Z-shaped flow channel of 0.5 mm diameter is drilled. Each of the wedges of the Z reaches the outside of the block. The Z-shaped flow-cell thus built has a zero dead volume. As a result, the solution volume held between the two CHEMFETs is very small (3 pL). The cell is sealed by gently pushing block A to B with a lever. The inherent plasticity of the PVC membrane ensures water-tight closure of the cell. The closeness between the two electrodes enables differential measurements with no interference from the liquid junction potential. The differential signal provided by a potassium-selective and a sodium-selective CHEMFET exhibits a Nemstian behaviour and is selective towards potassium in the presence of a (fixed) excess concentration of sodium. The combined use of a highly lead-selective CHEMFET and a potassium-selective CHEMFET in this type of cell also provides excellent results.

Manipulation of the mass transfer resistances is another possibility. Let us assume that the analyte is an electrically neutral species, but the major interferant is charged. By placing an ion-exchange membrane with immobile charge of opposite polarity to that of the interferant in front of the electrode, the access of the charged interferant becomes blocked by the electrostatic repulsion. These selectivity design strategies can be summarized in a statement that applies also to other life situations. In amperometric sensors, the information is obtained from the current path of least resistance. 

To this table we can also add nonconducting blocking layers that selectively hinder access of certain species, for example, interferants to the electroactive part of the electrode. 

We will consider these cells, primarily the oxygen cells, under open circuit conditions and under load (or even short-circuit condition). In the transient and in the steady state it is not necessary to treat them all in detail, since (as outlined below) cells with one selectively blocking electrode and those with two of the same kind show far-reaching similarities (compare cell 3 with cell 4 and cell 5 with cell 6). The same is true if we compare cells with electrodes that are selectively blocking for electrons with cells that are specifically blocking for ions (compare cell 3 with cell 5 and cell 4 with cell 6) it is easy to show that the relations are symmetrical as regards the indices e" and O2" (see below and Appendix l).21011... 

Eq. (62) can take account of the dielectric response of a boundary (electrode, grain boundary) but would not be sufficient to describe bulk polarization phenomena (appearing at longer times or lower frequencies) induced by strongly selectively blocking electrodes or grain boundaries (see below). The latter effect will be touched upon in the next section. 

Electrochemical Polarization—The Effect of Selectively Blocking Electrodes... 

Now we wish to consider the electrochemical polarization with the help of selectively blocking electrodes (connected with the neutral phase at x=L, while x=0 is the position of the reversible electrode contact) on a more fundamental level3 15 210 225 231 and refer, to be specific, to a galvanostatic experiment on cells 3 and 4. We start with the steady state. 

The membrane conductivity was measured in HCl(aq) solutions of different concentrations and in 2 M HC1 + 0.2 M CuCl solution to model the catholyte and anolyte solutions in the electrolyser. All membranes were equilibrated in the same solutions for 20 hours before starting the measurements. Detailed characterisation data for a number of commercial anion exchange membranes are published elsewhere (Gong, 2009). The AHA membrane, which demonstrated the highest conductivity in HC1 (12.61 mS/cm) compared to other membranes with similar IEC and water uptake, was selected to prepare a membrane electrode assembly (MEA) and carry out electrolysis tests with this MEA. The ACM membrane with lower conductivity values was also chosen for the electrolysis tests due to its proton blocking properties and high Cl- selectivity. 

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