Control potential

Stripping voltammetry involves the pre-concentration of the analyte species at the electrode surface prior to the voltannnetric scan. The pre-concentration step is carried out under fixed potential control for a predetennined time, where the species of interest is accumulated at the surface of the working electrode at a rate dependent on the applied potential. The detemiination step leads to a current peak, the height and area of which is proportional to the concentration of the accumulated species and hence to the concentration in the bulk solution. The stripping step can involve a variety of potential wavefomis, from linear-potential scan to differential pulse or square-wave scan. Different types of stripping voltaimnetries exist, all of which coimnonly use mercury electrodes (dropping mercury electrodes (DMEs) or mercury film electrodes) [7, 17]. 

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. 

Potential/control transformers must be provided with current limiting fuses at both ends. 

Greater deviations which are occasionally observed between two reference electrodes in a medium are mostly due to stray electric fields or colloid chemical dielectric polarization effects of solid constituents of the medium (e.g., sand [3]) (see Section 3.3.1). Major changes in composition (e.g., in soils) do not lead to noticeable differences of diffusion potentials with reference electrodes in concentrated salt solutions. On the other hand, with simple metal electrodes which are sometimes used as probes for potential controlled rectifiers, certain changes are to be expected through the medium. In these cases the concern is not with reference electrodes, in principle, but metals that have a rest potential which is as constant as possible in the medium concerned. This is usually more constant the more active the metal is, which is the case, for example, for zinc but not stainless steel. 

CU-CUSO4 electrodes with saturated CUSO4 solution are recommended for potential measurements in soil. Their potential constancy is about 5 mV. Larger errors can be traced to chemical changes in the CUSO4 solution. These electrodes have been developed for long-life applications in potential-controlled rectifiers and built-... 

The adjustment of a protection station or of a complete protection system where there is stray current interference is made much easier by potential control. Potential control can be indispensable for electrochemical protection if the protection potential range is very small (see Sections 2.4 and 21.4). This saves anode material and reduces running costs. 

Figure 8-5 shows the main circuit diagram of a potential control rectifier provided with magnetic amplifiers (transducers). The chosen potential is set at the nominal value with a potentiometer. The actual potential is compared with this value, which corresponds to the voltage between a reference electrode and the protected object. 

Potential control rectifiers can also be constructed using thyristors. However, these produce strong high-frequency harmonic waves that can be transmitted to... 

Fig. 8-5 Circuit diagram illustrating the principle of a potential-controlled transformer-rectifier.

Current-controlling rectifiers are constructed in general on the same circuit principles as potential-controlling rectifiers only with them, the protection current is converted to a voltage via a constant shunt in the control circuit and fed in as the actual value. With devices with two-point control, the ammeter has limiting value contacts that control the motor-driven controlled transformer. 

No potential control Failure of rectifier control Test the instmment installation, ac interference... 

Hlh potential controlled corrosion protection rectifier tramway... 

The protection current equipment must be installed on the deck, so great lengths of cable with a corresponding cross-section are required. Only potential-controlling protection current equipment, as in the case of ships, should be employed since the necessary current densities are continually changing due to the changing heavy seas (Figs. 16-2 and 16-3). 

Different microstructural regions in a material which has an almost uniform composition can also lead to the formation of corrosion cells (e.g., in the vicinity of welds). Basically, corrosion cells can be successfully overcome by cathodic protection. However, in practice, care has to be taken to avoid electrical shielding by large current-consuming cathode surfaces by keeping the area as small as possible. In general, with mixed installations of different metals, it must be remembered that the protection potentials and the protection range depend on the materials (Section 2.4). This can restrict the use of cathodic protection or make special potential control necessary. 

Another possibility is to decentralize the dc supply. Here the ac supply for the individual protection rectifiers comes from a potential-controlled central supply that is situated in the engine control room. The protection rectifiers can then be situated amidships with relatively short dc cables to the anodes. The dimension of the dc cable should maintain a voltage drop below 2 V. 

Measuring electrodes for impressed current protection are robust reference electrodes (see Section 3.2 and Table 3-1) which are permanently exposed to seawater and remain unpolarized when a small control current is taken. The otherwise usual silver-silver chloride and calomel reference electrodes are used only for checking (see Section 16.7). All reference electrodes with electrolytes and diaphragms are unsuitable as long-term electrodes for potential-controlled rectifiers. Only metal-medium electrodes which have a sufficiently constant potential can be considered as measuring electrodes. The silver-silver chloride electrode has a potential that depends on the chloride content of the water [see Eq. (2-29)]. This potential deviation can usually be tolerated [3]. The most reliable electrodes are those of pure zinc [3]. They have a constant rest potential, are slightly polarizable and in case of film formation can be regenerated by an anodic current pulse. They last at least 5 years. 

The impressed current protection method is used mainly for the internal protection of large objects and particularly where high initial current densities have to be achieved (e.g., in activated charcoal filter tanks and in uncoated steel tanks). There are basically two types of equipment those with potential control, and those with current control. 

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. 

By using only a single reference electrode in the object to be protected, the potential can be determined only in the vicinity of this electrode and not in more remote areas. Section 3.3.1 together with Eq. (3-27) provides further explanation of this. To improve the current and potential distribution, the number and location of the anodes must suit the geometry of the object to be protected. Occasionally, additional reference electrodes are required for potential control [2]. The optimum nominal potential for potential control can be found by this method by considering remote IR errors. 

Cathodic protection of enamelled tanks with Mg anodes has long been the state of the art, with potential-controlled equipment being used with increasing frequency in recent years. A high-resistance coating with limited defects according to Ref. 4 enables uniform current distribution to be maintained over the whole tank. 

As an example. Fig. 20-7 shows potential and protection currents of two parallel-connected 750-liter tanks as a function of service life. The protection equipment consists of a potential-controlled protection current rectifier, a 0.4-m long impressed current anode built into the manhole cover, and an Ag-AgCl electrode built into the same manhole [10,11]. A second reference electrode serves to control the tank potential this is attached separately to the opposite wall of the tank. During the whole of the control period, cathodic protection is ensured on the basis of the potential measurement. The sharp decrease in protection current in the first few months is due to the formation of calcareous deposits. 

Figure 20-9 shows the negative effect of uninsulated heating elements on corrosion protection. In a 250-liter tank, an electric tube heating element with a 0.05-m surface area was screwed into the upper third without electrical separation, and in the lower third a tinned copper tube heat exchanger with a 0.61 -m surface area was built in. The Cu heat exchanger was short-circuited for measurements, as required. For cathodic protection, a potential-controlled protection system with impressed current anodes was installed between the two heating elements. The measurements were carried out with two different samples of water with different conductivities. 

A tank with a fixed cover of plain carbon steel for storing 60°C warm, softened boiler feed water that had a tar-pitch epoxy resin coating showed pits up to 2.5 mm deep after 10 years of service without cathodic protection. Two separate protection systems were built into the tank because the water level varied as a result of service conditions. A ring anode attached to plastic supports was installed near the bottom of the tank and was connected to a potential-controlled protection rectifier. The side walls were protected by three vertical anodes with fixed adjustable protection current equipment. 

Potential control with zinc reference electrodes presented a problem because deposits of corrosion products are formed on zinc in hot water. This caused changes in the potential of the electrode which could not be tolerated. Other reference electrodes (e.g., calomel and Ag-AgCl reference electrodes) were not yet available for this application. Since then, Ag-AgCl electrodes have been developed which successfully operate at temperatures up to 100°C. The solution in the previous case was the imposition of a fixed current level after reaching stationary operating conditions [27]. 

The bottom ring anode was 45 m long. The vertical wall anodes were fixed 1.8 m above the bottom and had lengths of 30 and 57 m for the inner and outer walls respectively. High-grade zinc reference electrodes which have a stable rest potential in drinking water acted as potential control. The supporting bolts for the anodes and reference electrodes were plastic. 

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 impressed current method with metal oxide-coated niobium anodes is usually employed for internal protection (see Section 7.2.3). In smaller tanks, galvanic anodes of zinc can also be used. Potential control should be provided to avoid unacceptably negative potentials. Pure zinc electrodes serve as monitoring and control electrodes in exposed areas which have to be anodically cleaned in the course of operation. Ag-AgCl electrodes are used to check these reference electrodes. 

Six iron anodes are required for corrosion protection of each condenser, each weighing 13 kg. Every outflow chamber contains 14 titanium rod anodes, with a platinum coating 5 /tm thick and weighing 0.73 g. The mass loss rate for the anodes is 10 kg A a for Fe (see Table 7-1) and 10 mg A a for Pt (see Table 7-3). A protection current density of 0.1 A m is assumed for the coated condenser surfaces and 1 A m for the copper alloy tubes. This corresponds to a protection current of 27 A. An automatic potential-control transformer-rectifier with a capacity of 125 A/10 V is installed for each main condenser. Potential control and monitoring are provided by fixed zinc reference electrodes. Figure 21-2 shows the anode arrangement in the inlet chamber [9]. 

Cathodic protection of water power turbines is characterized by wide variations in protection current requirements. This is due to the operating conditions (flow velocity, water level) and in the case of the Werra River, the salt content. For this reason potential-controlled rectifiers must be used. This is also necessary to avoid overprotection and thereby damage to the coating (see Sections 5.2.1.4 and 5.2.1.5 as well as Refs. 4 and 5). Safety measures must be addressed for the reasons stated in Section 20.1.5. Notices were fixed to the turbine and the external access to the box headers which warned of the danger of explosion from hydrogen and included the regulations for the avoidance of accidents (see Ref. 4). 

In addition, the reactions occurring at the impressed current cathode should be heeded. As an example. Fig. 21-7 shows the electrochemical behavior of a stainless steel in flowing 98% H2SO4 at various temperatures. The passivating current density and the protection current requirement increase with increased temperature, while the passive range narrows. Preliminary assessments for a potential-controlled installation can be deduced from such curves. 

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. 

In contrast to many other surface analytical techniques, like e. g. scanning electron microscopy, AFM does not require vacuum. Therefore, it can be operated under ambient conditions which enables direct observation of processes at solid-gas and solid-liquid interfaces. The latter can be accomplished by means of a liquid cell which is schematically shown in Fig. 5.6. The cell is formed by the sample at the bottom, a glass cover - holding the cantilever - at the top, and a silicone o-ring seal between. Studies with such a liquid cell can also be performed under potential control which opens up valuable opportunities for electrochemistry [5.11, 5.12]. Moreover, imaging under liquids opens up the possibility to protect sensitive surfaces by in-situ preparation and imaging under an inert fluid [5.13]. 

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