Metal/electrolyte interface

Impedance spectra of partially degraded coatings cannot only be used to estimate the porosity of the film but also to estimate the area of the metal electrode wetted by electrolyte. Since the interface metal-electrolyte is represented by the parallel combination of the charge-transfer resistance and the double-layer capacitance both of these can be used to estimate the fraction of the electrode surface W wetted by electrolyte... 

Fig. 6 presents the system of A1 corrosion in 0.5 M NaCl solution, its frequency impedance characteristic in the form of Nyquist plot and the equivalent electrical circuit. Individual parts of the electric circuit reflect the electrochemical and electrical characteristics of the corrosion systems. In this arrangement, the spectral characteristic of the impedance in the Nyquist plot has the shape of a semicircle, whose intersection with the real axis in the high-frequency range determines the electrolyte solution resistance Rs. Conversely, the intersection of the real axis in the low-frequency range corresponds to the sum of Rs + Rci/ where Ret indicates the charge transfer resistance of the boundary metal/electrolyte, and characterizes the rate of corrosion. On the other hand, Cdi component of the circuit represents capacity of the double layer at the interface metal/electrolyte. 

M. Garreau, Etude du mecanisme de la formation des ions metalliques a I interface metal-electrolyte au cours de la dissolution anodiqne des metaux, Met. Cor. Ind. 541 3 (1970). 

The equations of electrocapillarity become complicated in the case of the solid metal-electrolyte interface. The problem is that the work spent in a differential stretching of the interface is not equal to that in forming an infinitesimal amount of new surface, if the surface is under elastic strain. Couchman and co-workers [142, 143] and Mobliner and Beck [144] have, among others, discussed the thermodynamics of the situation, including some of the problems of terminology. 

Kolb D M 1996 Reconstruction phenomena at metal-electrolyte interfaces Prog. Surf. Sc/. 51 109... 

Kolb D M and Franke C 1982 Surface states at the metal-electrolyte interface Appl. Phys A 49 379-87... 

Gordon J G, Melroy O R and Toney M F 1995 Structure of metal-electrolyte interfaces copper on gold(111), water on silver(111) Electrochim. Acta 40 3-8... 

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 ... 

Polarization can be divided into activation polarization and concentration polarization , Activation polarization is an electrochemical reaction that is controlled by the reaction occurring on the metal-electrolyte interface. Figure 4-418 illustrates the concept of activation polarization where hydrogen is being reduced over a zinc surface. Hydrogen ions are adsorbed on the metal surface they pick up electrons from the metal and are reduced to atoms. The atoms combine to... 

The thermodynamic and electrode-kinetic principles of cathodic protection have been discussed at some length in Section 10.1. It has been shown that, if electrons are supplied to the metal/electrolyte solution interface, the rate of the cathodic reaction is increased whilst the rate of the anodic reaction is decreased. Thus, corrosion is reduced. Concomitantly, the electrode potential of the metal becomes more negative. Corrosion may be prevented entirely if the rate of electron supply is such that the potential of the metal is lowered to the value where it is found that anodic dissolution does not occur. This may not necessarily be the potential at which dissolution is thermodynamically impossible. 

Current enters through the metal-electrolyte interface of the anode, which is usually made from the same metal as is plated on the cathode. The anode dissolves replacing the metal lost at the cathode ... 

The model more generally accepted for metal/electrolyte interfaces envisages the electrical double layer as split into two parts the inner layer and the diffuse layer, which can be represented by two capacitances in series.1,3-7,10,15,32 Thus, the total differential capacitance C is equal to... 

Barker et al.m have developed a photoemission method to obtain impedance data10 was found. 

Figure 16 shows the effect of the potential of passivated electrode and the interfacial tension of film-free metal/electrolyte interface on the activation barrier for film breakdown. From Eq. (22), the minimum potential for film breakdown AE corresponding to A b = is given by... 

This potential depends on the interfacial tension am of a passivated metal/electrolyte interface shifting to the lower potential side with decreasing am. The lowest film breakdown potential AEj depends on the surface tension of the breakdown site at which the film-free metal surface comes into contact with the electrolyte. A decrease in the surface tension from am = 0.41 J m"2 to nonmetallic inclusions on the metal surface, will cause a shift of the lowest breakdown potential by about 0.3 V in the less noble direction. 

Figure 16. Activation barrier A for the formation of a breakthrough pore in a thin surface oxide film on metal as a function of electrode potential at two different surface tensions, om, of the metal/electrolyte interface.7The solid lines indicate the values of A b against Aand the dotted lines correspond to die critical potentials for the pore formation. ACd= 1 F m-2, a = 0.01 J m-2, h = 2 x 10-9 m, a, am = 0.41 J m 2 b, am 0.21 J m 2 (From N. Sato, J. Electmchem. Soc. 129, 255, 1982, Fig. 3. Reproduced by permission of The Electrochemical Society, Inc.)...

Although the term non-Faradaic process has been used for many decades to describe transient electrochemical processes where part of the current is lost in charging-discharging of metal-electrolyte interfaces, in all these cases the Faradaic efficiency, A, is less than 1 (100%). Furthermore such non-Faradaic processes disappear at steady state. Electrochemical promotion (NEMCA) must be very clearly distinguished from such transient non-Faradaic processes for two reasons ... 

Figure 1.5. Schematic representation of a metal electrode deposited on a 02 -conducting (left) and on a Na -conducting (right) solid electrolyte, showing the location of the metal-electrolyte double layer and of the effective double layer created at the metal/gas interface due to potential-controlled ion migration (backspillover).

The non-zero value of e Fw-e FR in Eq. (5.35) implies that there are net surface charges on the gas exposed electrode surfaces. These charges (q+,q.) have to be opposite and equal as the cell is overall electrically neutral and all other charges are located at the metal-solid electrolyte interfaces to maintain their electroneutrality. The charges q+ = -q. are quite small in relation to the charges, Q, stored at the metal-electrolyte interface but nevertheless the... 

In aqueous electrochemistry electrochemical (charge transfer) reactions take place over the entire metal/electrolyte interface. 

S. Trasatti, Structure ofthe metal/electrolyte solution interface New data for theory, Electrochim. Acta 36, 1659-1667 (1991). 

Does the concept of absolute electrode potential, defined in chapter 7, allow one to measure the absolute electrical potential difference, A(p, at a metal/electrolyte interface, one of the famous unresolved problems in electrochemistry ... 

Non-situ and ex situ studies can provide important information for understanding the properties of metal/electrolyte interfaces. The applicability of these methods for fundamental studies of electrochemistry seems to be firmly established. The main differences between common electrochemical and UHV experiments are the temperature gap (ca. 300 vs. 150 K) and the difference in electrolyte concentration (very high concentrations in UHV experiments). In this respect, experimental research on double-layer properties in frozen electrolytes can be treated as a link between in situ experiments. The measurements of the work functions... 

The general way in which a Galvani potential is established is similar in all cases, but special features are observed at the metal-electrolyte interface. The transition of charged species (electrons or ions) across the interface is possible only in connection with an electrode reaction in which other species may also be involved. Therefore, equilibrium for the particles crossing the interface [Eq. (2.5)] can also be written as an equilibrium for the overall reaction involving all other reaction components. In this case the chemical potentials of aU reaction components appear in Eq. (2.6) (for further details, see Chapter 3). 

The conductivity of solid salts and oxides was first investigated by M. Faraday in 1833. It was not yet known at that time that the nature of conduction in solid salts is different from that in metals. A number of fundamental studies were performed between 1914 and 1927 by Carl Tubandt in Germany and from 1923 onward by Abram Ioffe and co-workers in Russia. These studies demonstrated that a mechanism of ionic migration in the lattice over macroscopic distances is involved. It was shown that during current flow in such a solid electrolyte, electrochemical changes obeying Faraday s laws occur at the metal-electrolyte interface. 

The Gibbs equation for metal-electrolyte interfaces is of the form... 

Matranga, C. and G-Sionnest, P. (2000) Vibrational relaxation of cyanide at the metal/electrolyte interface./. Chem. Phys., 112, 7615-7621. 

Kolh DM. 1996. Reconstruction phenomena at metal-electrolyte interfaces. Prog Surf Sci 51 109-173. 

Guyot-Sionnest P, Tadjeddine A. 1990. Spectroscopic investigations of adsorbates at the metal electrolyte interface using sum frequency generation. Chem Phys Lett 172 341-345. 

---