Open circuit electrode metal corrosion

Another example of a galvanic cell reaction is provided by open circuit corrosion of the metal deposit. Freshly deposited (and particularly finely-divided) metals are more active than their bulk, compact counter parts. Corrosion of the mixed electrode deposit may ensue if the cathode surface is left under open circuit conditions metal dissolution is balanced via reduction of species such as dissolved oxygen, protons or higher oxidation states of transition metal ions. Illustrative (simplified) examples of such oxidising agents include the following ... 

The simplest procedure in studying galvanic corrosion is a measurement of the open-circuit potential difference between the metals in a couple in the environment under consideration. This will at least indicate the probable direction of any galvanic effect although no information is provided on the rate. A better procedure is to make similar open-circuit potential measurements between the individual metals and some appropriate reference electrode, which will yield the same information and will also permit obser-... 

Measurements of open-circuit potentials relative to some reference electrode have been assumed on occasion to provide a means of rating metals as to their relative resistance to corrosion on the basis that the more negative the measured potential, the higher will be the rate of corrosion, but this assumption is obviously invalid, since it disregards polarisation of the anodic and cathodic areas. 

Fig. 19.16 Schematic E — I diagrams of local cell action on stainless steel in CUSO4 + H2SO4 solution showing the effect of metallic copper on corrosion rate. C and A are the open-circuit potentials of the local cathodic and anodic areas and / is the corrosion current. The electrode potentials of a platinised-platinum electrode and metallic copper immersed in the same solution as the stainless steel are indicated by arrows, (a) represents the corrosion of stainless steel in CUSO4 -I- H2 SO4, (b) the rate when copper is introduced into the acid, but is not in contact with the steel, and (c) the rate when copper is in contact with the stainless steel...

A prepassivated platinum electrode and an electrode of the metal of interest have been used to follow the development of a biofilm to determine its effects on the corrosion behavior of structural materials. The time dependence of the open circuit potential of several stainless steels... 

If one of the partial electrode reactions is the dissolution of the electrode (i.e. metal, semiconductor, etc.), the open circuit potential is a corrosion potential and the system undergoes corrosion at a rate given by the corrosion current density (/corr), which is a measure of the corrosion rate of the system. The magnitude of corr of corroding systems... 

Corrosion — Corrosion current density — Figure. Polarization curves of a metal/metal ion electrode and the H2/H+ electrode including the anodic and cathodic partial current curves, the Nernst equilibrium electrode potentials E(Me/Mez+) and (H2/H+), their exchange current densities / o,M> o,redox and related overpotentials Me) and 77(H), the rest potential r, the polarization n and the corrosion current density ic at open circuit conditions (E = Er) [i]... 

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. 

In the case of codeposition of Co and Mo on Au and Fe electrodes, very strong synergistic effects of coplating of these two elements were found (168), with Tafel slopes of around 60 mV in the low current-density range being observed. With Ni and Mo coplating on Ni or Fe, slopes of 23-28 mV are observed (75). The Co plus Mo electrodeposits remain cathodically protected during the Hj evolution but on open circuit evolve H2 rapidly-from active Mo centers, as in decomposition of Raney nickels. However, this may be due as much to desorption of codeposited H as to evolution of H2 by corrosion of the base metal. Mo. 

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... 

Among the electrochemical techniques available for the study of corrosion of metals, potential monitoring is the most simple and inexpensive of all. Its nondestructive character is also an advantage. The measurements are made using only a reference electrode and a high impedance voltmeter (Fig. 9). The readings correspond to the open circuit... 

Open circuit potential As defined by the McGraw-Hill Dictionary of Scientific and Technical Terms, open circuit potential (OCP) is the steady-state or equilibrium potential of an electrode in absence of external current flow to or from the electrode. OCP measures the corrosion potential of a corroding metal with regard to a reference electrode. For instance, increased susceptibility of stainless steels to pitting and crevice corrosion in seawater has been attributed to increase in OCP, which could partly be due to biofllm formation. Monitoring of OCP spectra can be used to rank the corrosion vulnerability of metals in comparison with each other. 

For instance, in an opencurrent density is not strictly zero at any point in the electrolyte. Even if the overall current is zero, the electrol e and the electrodes are not necessarily equipotential and therefore the ohmic drop terms may not necessarily be zero in open-circuit conditions. 

Examples of metals that are passive under Definition 1, on the other hand, include chromium, nickel, molybdenum, titanium, zirconium, the stainless steels, 70%Ni-30% Cu alloys (Monel), and several other metals and alloys. Also included are metals that become passive in passivator solutions, such as iron in dissolved chromates. Metals and alloys in this category show a marked tendency to polarize anodicaUy. Pronounced anodic polarization reduces observed reaction rates, so that metals passive under Definition 1 usually conform as well to Definition 2 based on low corrosion rates. The corrosion potentials of metals passive by Definition 1 approach the open-circuit cathode potentials (e.g., the oxygen electrode) hence, as components of galvanic cells, they exhibit potentials near those of the noble metals. 

Under open-circuit conditions (i.e., when the metal surface is not connected to an external potentiostat), the net current ia - ic will be zero, and the electrode potential E will adjust according to the corrosion potential, con- In this case, the corrosion current density (i.e., the current density associated with the loss of metal) is 4 = ic = icon-... 

The establishment of active-passive cells is facilitated by pH changes induced by the anodic and cathodic partial reactions. To understand this behavior, we recall first that passivation of metals is favored by a high pH (Chapter 6). The Evans diagram of Figure 7.17 shows the anodic partial current of a passivating metal exposed to an aerated electrolyte. Curve (b), which exhibits a lower passivation current than curve (a), corresponds to a solution of a higher pH. Oxygen is assumed to be reduced at the same rate on both metals. Clearly, at open circuit the electrode (a) is in the active state, while the electrode (b) is in the passive state. Electrical contact between the two therefore leads to the establishment of a corrosion cell in which metal (b) is the cathode. 

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