Electrochemical corrosion reference electrodes

Returning now to stress corrosion cracking, it is evident that it is premature to expect calculation of the ECP in the coolant circuit. Of a SCWNPP, but it is possible to perform experiments under electrochemical control using the electrochemical techniques (reference electrodes, etc.) discussed above. However, none of the work reported to date has employed a reference electrode to moni-... 

Since metals have very high conductivities, metal corrosion is usually electrochemical in nature. The tenn electrochemical is meant to imply the presence of an electrode process, i.e. a reaction in which free electrons participate. For metals, electrochemical corrosion can occur by loss of metal atoms tluough anodic dissolution, one of the fiindamental corrosion reactions. As an example, consider a piece of zinc, hereafter referred to as an electrode, inunersed in water. Zinc tends to dissolve in water, setting up a concentration of Zn ions very near the electrode... 

This handbook deals only with systems involving metallic materials and electrolytes. Both partners to the reaction are conductors. In corrosion reactions a partial electrochemical step occurs that is influenced by electrical variables. These include the electric current I flowing through the metal/electrolyte phase boundary, and the potential difference A( = 0, - arising at the interface. and represent the electric potentials of the partners to the reaction immediately at the interface. The potential difference A0 is not directly measurable. Therefore, instead the voltage U of the cell Me /metal/electrolyte/reference electrode/Me is measured as the conventional electrode potential of the metal. The connection to the voltmeter is made of the same conductor metal Me. The potential difference - 0 is negligibly small then since A0g = 0b - 0ei ... 

Reference Electrode an equilibrium (reversible) electrochemical half-cell of reproducible potential against which an unknown electrode potential can be measured. Examples of those commonly used in corrosion are the Pt, H /H (the hydrogen electrode), Hg/Hg Clj/Cl" (the calomel electrode), Cu/CuS04/Cu, Ag/AgCl/Cl", all with fixed activities of the dissolved ions. 

In many STM studies little effort has been made to control the atmosphere within the electrochemical cell. Yet oxygen is known to exert a major role in the chemistry and corrosion of many transition metals. For example, several STM studies have used the copper/copper ion reference electrode, yet the electrode is known to be polarized from its reversible condition by oxygen, leading to significant dissolution [154]. These effects become particularly significant in the smdy of metal deposition and dissolu-... 

Monitoring of the electrochemical potential of steel reinforcement in concrete is a well established technique for assessing the severity of corrosion and for controlling cathodic protection systems. A reference electrode is the electrochemical device used for measuring these potentials. The reference electrode is either placed on the concrete surface during the measurements or permanently embedded in the concrete in close proximity to the steel. The latter technique enables remote long-term monitoring. 

Ideally, a reference electrode should have a stable potential with respect to time. However, time stability requirements depend on the objective of the electrochemical measurement. For example, for long-term monitoring of the corrosion potential a time stable reference electrode is a must. Otherwise, it will be almost impossible to distinguish between drift in reference electrode potential and drift in corrosion state. 

The electrochemically active part of the electrode consists of a molybdenum wire or rod that has been oxidised in molten potassium nitrate and soldered to an insulated copper wire [26]. Joints are normally sealed with epoxy or silicone compounds. M0/M0O3 was suggested as a possible reference electrode in highly corrosive alkaline systems as early as 1967 [27], For concrete application, two-year stability is reported [25]. The potential of M0/M0O3 in concrete is approximately -450 mV vs SCE [26]. Field performance documentation is scarce. 

The three goals of the thermodynamic section are (1) to relate the thermodynamics of corrosion-related electrochemistry to concepts with which the reader may be familiar, (2) to describe the need for and characteristics of reference electrodes, and (3) to describe the origin, use, and limitations of electrochemical phase diagrams (a.k.a., F-pH or Pourbaix diagrams). 

Analysis methods for electrochemical noise data can be separated into three categories, (1) deterministic, (2) statistical, and (3) spectral. Deterministic methods involve the use of mixed potential theory to explain the oscillations that occur. For example, if the ZRA current increases suddenly while the potential difference between the two current electrodes and the potential electrode increases, localized corrosion has likely initiated on one of the current electrodes. A common pitfall in such a measurement is that if a nominally identical reference electrode is used, it could pit as well, leading to no change in potential versus the coupled electrodes. Due to the need for careful interpretation, deterministic methods are not widely used. 

It is common in corrosion laboratories and in field corrosion monitoring probes to immerse two vertical rods parallel to one another in an electrolyte. In the lab, one of the rods consists of a high-density graphite counterelectrode while the other is a working electrode. A reference electrode may be placed in between the two rods. In the field, polarization resistance or electrochemical noise measurements are often made between two nominally identical rods that both consist of the material of interest. The primary current distribution is nonuniform with respect to circumferential position about each electrode when the distance between the two rods is small in comparison to the radius of the rod, Fig. 10a (16). Again, the value of Ra varies from where the rods face each other to where they... 

Polarization experiments on a corrosion system are carried out by using a potentiostat. The experimental arrangement of the cell consists of a working electrode, reference electrode and a counter-electrode. The counter-electrode is used to apply a potential on the working electrode both in the anodic and the cathodic direction, and measure the resulting currents. The electrochemical cell is depicted in Figure 1.26. 

Electrochemical noise measurements may be performed in the potentiostatic mode (current noise is measured), the galvanostatic mode (potential noise is measured), or in the ZRA mode (zero resistance ammeter mode, whereby both current and potential noise are measured under open-circuit conditions). In the ZRA mode, two nominally identical metal samples (electrodes) are used and the ZRA effectively shorts them together while permitting the current flow between them to be measured. At the same time, the potential of the coupled electrodes is measured versus a low-noise reference electrode (or in some cases a third identical electrode). The ZRA mode is commonly used for corrosion monitoring. 

The conditions under which IGA occurs in Alloy 600 in high-temperature caustic solutions (20-25% NaOH, 290-320 °C) have been somewhat better defined, from an electrochemical viewpoint, in the work of Cayla et al. [38]. These workers employed an external Hg/HgO reference electrode that was calibrated to the reversible hydrogen electrode (RHE) scale at the pH and temperature of interest. However, even in this ease, it is not clear to whieh hydrogen partial pressure this scale refers (presumably/hj = 1), which again emphasizes the need for the nuclear corrosion community to settle on a single potential scale that is understood by everyone involved in this type of work. Nevertheless, Cayla et al. [38] found that IGA occurs in a limited range of potential close to (within 100 mV of) the reversible hydrogen potential. 

In another study [35], the electrochemical emission spectroscopy (electrochemical noise) was implemented at temperatures up to 390 °C. It is well known that the electrochemical systems demonstrate apparently random fluctuations in current and potential around their open-circuit values, and these current and potential noise signals contain valuable electrochemical kinetics information. The value of this technique lies in its simplicity and, therefore, it can be considered for high-temperature implementation. The approach requires no reference electrode but instead employs two identical electrodes of the metal or alloy under study. Also, in the same study electrochemical noise sensors have been shown in Ref. 35 to measure electrochemical kinetics and corrosion rates in subcritical and supercritical hydrothermal systems. Moreover, the instrument shown in Fig. 5 has been tested in flowing aqueous solutions at temperatures ranging from 150 to 390 °C and pressure of 25 M Pa. It turns out that the rate of the electrochemical reaction, in principle, can be estimated in hydrothermal systems by simultaneously measuring the coupled electrochemical noise potential and current. Although the electrochemical noise analysis has yet to be rendered quantitative, in the sense that a determination relationship between the experimentally measured noise and the rate of the electrochemical reaction has not been finally established, the results obtained thus far [35] demonstrate that this method is an effective tool for... 

HS Isaacs, B Vyas. Scanning reference electrode technique in Localized Corrosion. In F Mansfeld, U Bertocci, eds., Electrochemical Corrosion Testing. ASTM STP 727 3, 1981. 

If two or more electrochemical half-cell reactions can occur simultaneously at a metal surface, the metal acts as a mixed electrode and exhibits a potential relative to a reference electrode that is a function of the interaction of the several electrochemical reactions. If the metal can be considered inert, the interaction will be between species in the solution that can be oxidized by other species, which, in turn, will be reduced. For example, ferrous ions can be oxidized to ferric ions by dissolved oxygen and the oxygen reduced to water, the two processes occurring at different positions on the inert metal surface with electron transfer through the metal. If the metal is reactive, oxidation (corrosion) to convert metal to ions or reduction of ions in solution to the neutral metal introduces additional electrochemical reactions that contribute to the mixed electrode. 

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