Potentiostatic

Figure C2.8.3. A tliree-electrode electrochemical set-up used for the measurement of polarization curves. A potentiostat is used to control the potential between the working electrode and a standard reference electrode. The current is measured and adjusted between an inert counter-electrode (typically Pt) and the working electrode.

Schematic diagram of a manual potentiostat C = counter electrode ...

Schematic diagram of a manuai potentiostat SW = siide-wire resistor A = auxiiiary eiectrode R = reference eiectrode W = working eiectrode ...

Time, Cost, and Equipment Controlled-potential coulometry is a relatively time-consuming analysis, with a typical analysis requiring 30-60 min. Coulometric titrations, on the other hand, require only a few minutes and are easily adapted for automated analysis. Commercial instrumentation for both controlled-potential and controlled-current coulometry is available and is relatively inexpensive. Low-cost potentiostats and constant-current sources are available for less than 1000. 

The solution to reference electrode instabiUty is the introduction of a third or auxiUary electrode. This particular electrode is intended to carry whatever current is required to keep the potential difference between the working and reference electrodes at a specified value, and virtually all potentiostats (instmments designed specifically for electrochemistry) have this three-electrode configuration. Its use is illustrated in Figure 3. 

Anodic Protection This electrochemical method relies on an external potential control system (potentiostat) to maintain the metal or alloy in a noncorroding (passive) condition. Practical applications include acid coolers in sulfuric acid plants and storage tanks for sulfuric acid. 

FIG. 28-8 The potentiostat apparatus and circuitry associated with controlled potential measurements of polarization curves. 

Rapid-Scan Corrosion Behavior Diagram (CBD) Basically, all the same equipment used in the conductance of an ASTM G5 slow-scan polarization study is used for rapid-scan CBDs (that is, a standard test cell, potentiostat, voltmeters, log converters, X-Y recorders, and electronic potential scanning devices). The differences... 

Separated Anode/Cathode Realizing, as noted in the preceding, that locahzed corrosion is usually active to the surrounding metal surface, a stress specimen with a limited area exposed to the test solution (the anode) is elec trically connec ted to an unstressed specimen (the cathode). A potentiostat, used as a zero-resistance ammeter, is placed between the specimens for monitoring the galvanic current. It is possible to approximately correlate the galvanic current 7g and potential to crack initiation and propagation, and, eventually, catastrophic fail-... 

Polarization probe.s. Polarization methods other than LPR are also of use in process control and corrosion analysis, but only a few systems are offered commercially. These systems use such polarization techniques as galvanodynamic or potentiodynamic, potentiostatic or galvanostatic, potentiostaircase or galvanostaircase, or cyclic polarization methods. Some systems involving these techniques are, in fact, used regularly in processing plants. These methods are used in situ or... 

In such conditions, it is recommended that the T-R be equipped with an electrical control circuit, which primarily keeps the potential constant, and, in exceptional circumstances, also the protection current. These pieces of equipment are potentiostats (for controlling potential) and galvanostats (for controlling current) [8]. 

Fig. 8-6 Principle of a potentiostatic transformer-rectifier (Vq = amplification factor, S = power factor).

With increasing distance from the crossing or the proximity of the tramway rails, the stray currents absorbed in the pipeline emerge again. The current exit occurs mainly at crossings with other tramway tracks. In addition to potentiostatic control, a basic current adjustment is necessary. 

In Fig. 15-9 two potentiostatically controlled protection rectifiers and an additional diode are included to drain peak currents. At pipeline crossings with an external rail network (e.g., in regions outside the urban area), the forced stray current drainage should be installed as close as possible to the rails that display negative potentials for the longest operation time. The currents absorbed from the positive rails continue to flow also in the region outside the rail crossings. Here the use of potentiostatically controlled rectifiers is recommended these should be connected not only to the rails but also to impressed current anodes. 

Fig. 15-8 Synchronous current, voltage and potential recording with stray current interference from dc railways (a) Without protective measures, (b) direct stray current drainage to the rails, (c) rectified stray current drainage to the rails, (d) forced stray current drainage with uncontrolled protection rectifier, (e) forced stray current drainage with galvanostatically controlled protection rectifier (constant current), (f) forced stray current drainage with potentiostatically controlled protection rectifier (constant potential), (g) forced stray current drainage with potentiostatically controlled protection rectifier and superimposed constant current.

Protection current devices with potential control are described in Section 8.6 (see Figs. 8.5 and 8.6) information on potentiostatic internal protection is given in Section 21.4.2.1. In these installations the reference electrode is sited in the most unfavorable location in the protected object. If the protection criterion according to Eq. (2-39) is reached there, it can be assumed that the remainder of the surface of the object to be protected is cathodically protected. 

Since usually the reference electrode is not equipped with a capillary probe (see Fig. 2-3), there is an error in the potential measurement given by Eq. (2-34) in this connection see the data in Section 3.3.1 on IR-free potential measurement. The switching method described there can also be applied in a modified form to potential-controlled protection current devices. Interrupter potentiostats are used that periodically switch off the protection current for short intervals [5]. The switch-off phase is for a few tens of microseconds and the switch-on phase lasts several hundred microseconds. 

Figure 20-13 shows current and potential time curves for a stainless steel 500-liter tank with cathodic protection by impressed current and interrupter potentiostat. 

Fig. 20-13 Current and potential-time curves for a 500-liter stainless steel water tank. Impressed current protection with an interrupter potentiostat X (20 C) = 2250 IJ.S cm-i c (CF) = 0.02 mol L" 60 C.

Reference electrodes at the test points may only be needed part of the time, depending on the mode of operation of the protective systems (e.g., for monitoring or for permanent control of potential-controlled protection current equipment). Potentiostatic control is always preferred to galvanostatic systems where operational parameters are changing. 

The determination and evaluation of potentiodynamic curves can only be used as a preliminary assessment of corrosion behavior. The protection current requirement and the limiting value for the potential control can only be determined from so-called chronopotentiostatic experiments as in DIN 50918. in systems that react with spontaneous activation after the protection current is switched off or there is a change in the operating conditions, quick-acting protection current devices must be used. Figure 8-6 shows the circuit diagram for such a potentiostat. 

Anodic protection today allows safe and efficient protection of air coolers and banks of tubes in sulfuric acid plants. In 1966 the air cooler in a sulfuric acid plant in Germany was anodically protected. Since then more than 10,000 m of cooling surfaces in air- and water-cooled sulfuric acid plants worldwide have been protected. The dc output supply of the potentiostats amounts to >25 kW, corresponding to an energy requirement of 2.5 W per m of protected surface. As an example. Fig. 21-9 shows two parallel-connected sulfuric acid smooth tube exchangers in a production plant in Spain. 

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