Electrochemical systems, thermodynamics electrolytes

Regarding the electrode/electrolyte interface, it is important to distinguish between two types of electrochemical systems thermodynamically closed (and in equilibrium) and open systems. While the former can be understood by knowing the equilibrium atomic structure of the interface and the electrochemical potentials of all components, open systems require more information, since the electrochemical potentials within the interface are not necessarily constant. Variations could be caused by electrocatalytic reactions locally changing the concentration of the various species. In this chapter, we will focus on the former situation, i.e., interfaces in equilibrium with a bulk electrode and a multicomponent bulk electrolyte, which are both influenced by temperature and pressures/activities, and constrained by a finite voltage between electrode and electrolyte. 

Aimed at master s degree or PhD students as well as researchers and specialist engineers, this work focuses on electrochemical systems using electrolytes in solid phases (ionic crystals, ceramics, different types of glass and polymers). The fundamental concepts of electrochemistry are laid out (the thermodynamics of point defects and amorphous phases, transport mechanisms, mixed conduction, and gas electrode reactions) alongside the specific research methods used. Several applications are also described. 

The EMF values of galvanic cells and the electrode potentials are usually determined isothermally, when all parts of the cell, particularly the two electrode-electrolyte interfaces, are at the same temperature. The EMF values will change when this temperature is varied. According to the well-known thermodynamic Gibbs-Helmholtz equation, which for electrochemical systems can be written as... 

In this chapter, we will give a general description of electrochemical interfaces representing thermodynamically closed systems constrained by the presence of a hnite voltage between electrode and electrolyte, which will then be taken as the basis for extending the ab initio atomistic thermodynamics approach [Kaxiras et ah, 1987 Scheffler and Dabrowski, 1988 Qian et al., 1988 Reuter and Scheffler, 2002] to electrochemical systems. This will enable us to qualitatively and quantitatively investigate and predict the structures and stabilities of full electrochemical systems or single electrode/electrolyte interfaces as a function of temperature, activi-ties/pressures, and external electrode potential. 

Before we will discuss the electrochemical system, it is important to define the properties and characteristics of each component, especially the electrolyte. In the following, we assume macroscopic amounts of an electrolyte containing various ionic and nonionic components, which might be solvated. In the case that this bulk electrolyte is in thermodynamic equilibrium, each of the species present is characterized by its electrochemical potential, which is defined as the free energy change with respect to the particle number of species i ... 

Now having specified the bulk electrode, the bulk electrolyte, and the interface between them, our aim in this section is to quantify the atomistic structure of the interface and derive an expression that allows us to evaluate its stabUity. Based on (5.5), we wUl extend the ab initio atomistic thermodynamics approach to electrochemical systems. 

Although the extended ab initio atomistic thermodynamics approach provides an exact expression for the interfacial stability, the formalism requires self-consistent modeling of the entire electrochemical system, or electrode/electrolyte interface, exceeding presently available computational capabilities. Therefore, certain assumptions had to be made that reduce the effort to the calculation of the electrode surface only. Even with this simplified approach, which has been applied to the two examples discussed in this chapter, the qualitative behavior can be reproduced. 

The theory for cyclic voltammetry was developed by Nicholson and Shain [80]. The mid-peak potential of the anodic and cathodic peak potentials obtained under our experimental conditions defines an electrolyte-dependent formal electrode potential for the [Fe(CN)g] /[Fe(CN)g]" couple E°, whose meaning is close to the genuine thermodynamic, electrolyte-independent, electrode potential E° [79, 80]. For electrochemically reversible systems, the value of7i° (= ( pc- - pa)/2) remains constant upon varying the potential scan rate, while the peak potential separation provides information on the number of electrons involved in the electrochemical process (Epa - pc) = 59/n mV at 298 K [79, 80]. Another interesting relationship is provided by the variation of peak current on the potential scan rate for diffusion-controlled processes, tp becomes proportional to the square root of the potential scan rate, while in the case of reactants confined to the electrode surface, ip is proportional to V [79]. 

The thermodynamic description of a system consisting of a 3D Me-S bulk alloy phase (instead of an ideally polarizable substrate S) in contact with the electrolyte phase is based on an interphase concept similar to that in Section 8.2 [3.54, 3.322, 3.323). The necessary changes in the thermodynamic formalism are given in Section 8.6. The electrochemical system considered is schematically shown in Fig. 8.5. 

Electrodeposited Me alloys are of great practical importance because of their unconventional electric, magnetic, mechanical and protective properties. The problem of electroplating of alloys is related to the processes of codeposition of metals from multicomponent electrolyte systems. Thermodynamic and kinetic aspects of electrochemical codeposition of metals and the processes of alloy phase formation have been discussed in details by Brenner [6.134], Gorbunova and Polukarov [6.135] and Despic [6.136]. 

Another well-established heterogeneous interface is that between the electrode surface and the electrolyte in electrochemistry, where there are regimes of various degrees of order, characterized by differing mass transport phenomena and involving different kinetic and thermodynamic requirements. Adsorption and surface phenomena are important and in general it has been recognized for some time that vibration of an electrochemical system can produce a variety of effects. 

To this point, we have examined only systems at equilibrium, and we have learned that the potential differences in equilibrium electrochemical systems can be treated exactly by thermodynamics. However, many real cells are never at equilibrium, because they feature different electrolytes around the two electrodes. There is somewhere an interface between the two solutions, and at that point, mass transport processes work to mix the solutes. Unless the solutions are the same initially, the liquid junction will not be at equilibrium, because net flows of mass occur continuously across it. 

A closed system solid electrolyte electrochemical cell has been designed to investigate the thermodynamic properties of metal oxides. This technique gave a rapid cell response and highly stable potentials through the elimination of mixed potentials. The... 

It is well recognized that the addition of a large excess of an inert electrolyte has an effect on the kinetics and thermodynamics of electrochemical systems and in some cases it would be highly desirable to determine the influence of the electrolyte nature and concentration, and of the solvent, on the behaviour of such systems. The unique properties of microelectrodes allow electrochemical studies to be carried out in non-conventional media, such as very resistive solvents or in the absence of electrolyte (4). 

Electrochemical reaction kinetics is essential in determining the rate of corrosion of a metal M exposed to a corrosive medium (electrolyte). On the other hand, thermodynamics predicts the possibility of corrosion, but it does not provide information on how slow or fast corrosion occurs. The kinetics of a reaction on a electrode surface depends on the electrode potential. Thus, a reaction rate strongly depends on the rate of electron flow to or from a metal-electrolyte interface. If the electrochemical system (electrode and electrolyte) is at equilibrium, then the net rate of reaction is zero. In comparison, reaction rates are governed by chemical kinetics, while corrosion rates are primarily governed by electrochemical kinetics. 

Equilibrium electrochemistry allows us to calculate the standard values of open circuit potential (OCP) of a fuel cell and the decomposition potential (DP = -OCP) of an electrolytic cell if thermodynamic properties required for such calculations are available. The equilibrium electrochemical calculations should be done first before any other calculations or even experimental measurements to see any thermodynamic constrains of the electrochemical system. As an example. Figure 4.3 shows results of such calculations for three fuel cell reactions over a wide tanperature range from ambient up to 900°C. 

Nevertheless, carbonaceous materials are most often used as anodes in Uthium-ion batteries. Unfortunately the electrochemical and thermodynamical stability of these systems depends on the composition of the electrolyte. Because of the layered stracture and high surface area, irreversible parasitical reactions proceed on the surface along with reversible intercalation of lithium ions, including electrolyte decomposition and co-intercalations, for example, of solvent molecules. 

The overall pattern of behaviour of titanium in aqueous environments is perhaps best understood by consideration of the electrochemical characteristics of the metal/oxide and oxide-electrolyte system. The thermodynamic stability of oxides is dependent upon the electrical potential between the metal and the solution and the pH (see Section 1.4). The Ti/HjO system has been considered by Pourbaix". The thermodynamic stability of an... 

Before considering the principles of this method, it is useful to distinguish between anodic protection and cathodic protection (when the latter is produced by an external e.m.f.). Both these techniques, which may be used to reduce the corrosion of metals in contact with electrolytes, depend upon the electrochemical mechanisms that result from changing the potential of a metal. The appropriate potential-pH diagram for the Fe-H20 system (Section 1.4) indicates the magnitude and direction of the changes in the potential of iron immersed in water (pH about 7) necessary to make it either passive or immune in the former case the stability of the metal depends on the formation of a protective film of metal oxide (passivation), whereas in the latter the metal itself is thermodynamically stable and egress of metal ions from the lattice into the solution is thus prevented. 

Chapters 7 to 9 apply the thermodynamic relationships to mixtures, to phase equilibria, and to chemical equilibrium. In Chapter 7, both nonelectrolyte and electrolyte solutions are described, including the properties of ideal mixtures. The Debye-Hiickel theory is developed and applied to the electrolyte solutions. Thermal properties and osmotic pressure are also described. In Chapter 8, the principles of phase equilibria of pure substances and of mixtures are presented. The phase rule, Clapeyron equation, and phase diagrams are used extensively in the description of representative systems. Chapter 9 uses thermodynamics to describe chemical equilibrium. The equilibrium constant and its relationship to pressure, temperature, and activity is developed, as are the basic equations that apply to electrochemical cells. Examples are given that demonstrate the use of thermodynamics in predicting equilibrium conditions and cell voltages. 

Bard AJ, Wrighton MS (1977) Thermodynamic potential forthe anodic dissolution of n-type semiconductors - A crucial factor controlling durability and efficiency in photoelectrochem-ical cells and an important criterion in the selection of new electrode/electrolyte systems. J Electrochem Soc 124 1706-1710... 

As a rule, because of the high temperatures, electrochemical reactions in melts are fast and involve little polarization. For such reactions the exchange current densities are as high as 10 to KFmA/cm. Therefore, reactivities in melts (and also in high-temperature systems with solid electrolytes) are usually determined not by kinetic but by thermodynamic features of the system. 

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