Thermodynamics defect

The parameter c0 measuring the concentration in the first layer adjacent to the core, i.e., in the first layer of the assumed bulk structure, is a convenient parameter for the mathematical description but not a 

In the simplest case the perfect structure changes at the boundary in an abrupt way, and the standard chemical potential of the carriers can 

The different structure is energetically reflected by a non-zero interfacial tension y. The terms y (a interfacial area) and add 

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Electron microscopy and defect thermodynamics a new understanding of oxidation catalysis... 

Earlier work in the literature on the defect thermodynamics of oxides containing CS planes is based on conventional TEM studies of CS planes on static oxide systems. However, much of the earlier work contains the implicit assumption that all point defects due to the oxide anion loss are eliminated to produce CS planes. Several workers have made important contributions to understanding defect thermodynamics in oxides containing a finite number of... 

Two reasons are responsible, for the greater complexity of chemical reactions 1) atomic particles change their chemical identity during reaction and 2) rate laws are nonlinear in most cases. Can the kinetic concepts of fluids be used for the kinetics of chemical processes in solids Instead of dealing with the kinetic gas theory, we have to deal with point, defect thermodynamics and point defect motion. Transport theory has to be introduced in an analogous way as in fluid systems, but adapted to the restrictions of the crystalline state. The same is true for (homogeneous) chemical reactions in the solid state. Processes across interfaces are of great... 

Chemical solid state processes are dependent upon the mobility of the individual atomic structure elements. In a solid which is in thermal equilibrium, this mobility is normally attained by the exchange of atoms (ions) with vacant lattice sites (i.e., vacancies). Vacancies are point defects which exist in well defined concentrations in thermal equilibrium, as do other kinds of point defects such as interstitial atoms. We refer to them as irregular structure elements. Kinetic parameters such as rate constants and transport coefficients are thus directly related to the number and kind of irregular structure elements (point defects) or, in more general terms, to atomic disorder. A quantitative kinetic theory therefore requires a quantitative understanding of the behavior of point defects as a function of the (local) thermodynamic parameters of the system (such as T, P, and composition, i.e., the fraction of chemical components). This understanding is provided by statistical thermodynamics and has been cast in a useful form for application to solid state chemical kinetics as the so-called point defect thermodynamics. 

After the formulation of defect thermodynamics, it is necessary to understand the nature of rate constants and transport coefficients in order to make practical use of irreversible thermodynamics in solid state kinetics. Even the individual jump of a vacancy is a complicated many-body problem involving, in principle, the lattice dynamics of the whole crystal and the coupling with the motion of all other atomic structure elements. Predictions can be made by simulations, but the relevant methods (e.g., molecular dynamics, MD, calculations) can still be applied only in very simple situations. What are the limits of linear transport theory and under what conditions do the (local) rate constants and transport coefficients cease to be functions of state When do they begin to depend not only on local thermodynamic parameters, but on driving forces (potential gradients) as well Various relaxation processes give the answer to these questions and are treated in depth later. 

In 1937, dost presented in his book on diffusion and chemical reactions in solids [W. lost (1937)] the first overview and quantitative discussion of solid state reaction kinetics based on the Frenkel-Wagner-Sehottky point defect thermodynamics and linear transport theory. Although metallic systems were included in the discussion, the main body of this monograph was concerned with ionic crystals. There was good reason for this preferential elaboration on kinetic concepts with ionic crystals. Firstly, one can exert, forces on the structure elements of ionic crystals by the application of an electrical field. Secondly, a current of 1 mA over a duration of 1 s (= 1 mC, easy to measure, at that time) corresponds to only 1(K8 moles of transported matter in the form of ions. Seen in retrospect, it is amazing how fast the understanding of diffusion and of chemical reactions in the solid state took place after the fundamental and appropriate concepts were established at about 1930, especially in metallurgy, ceramics, and related areas. 

Since the state of a crystal in equilibrium is uniquely defined, the kind and number of its SE s are fully determined. It is therefore the aim of crystal thermodynamics, and particularly of point defect thermodynamics, to calculate the kind and number of all SE s as a function of the chosen independent thermodynamic variables. Several questions arise. Since SE s are not equivalent to the chemical components of a crystalline system, is it expedient to introduce virtual chemical potentials, and how are they related to the component potentials If immobile SE s exist (e.g., the oxygen ions in dense packed oxides), can their virtual chemical potentials be defined only on the basis of local equilibration of the other mobile SE s Since mobile SE s can move in a crystal, what are the internal forces that act upon them to make them drift if thermodynamic potential differences are applied externally Can one use the gradients of the virtual chemical potentials of the SE s for this purpose ... 

It has long been known that defect thermodynamics provides correct answers if the (local) equilibrium conditions between SE and chemical components of the crystal are correctly formulated, that is, if in addition to the conservation of chemical species the balances of sites and charges are properly taken into account. The correct use of these balances, however, is equivalent to the introduction of so-called building elements ( Bauelemente ) [W. Schottky (1958)]. These are properly defined in the next section and are the main content of it. It will be shown that these building units possess real thermodynamic potentials since they can be added to or removed from the crystal without violating structural and electroneutrality constraints, that is, without violating the site or charge balance of the crystal [see, for example, M. Martin et al. (1988)]. 

In this section, we will outline point defect thermodynamics and quantify the considerations of the introduction. 

Some Practical Aspects of Point Defect Thermodynamics... 

Defect thermodynamics is more complicated when applied to binary (or multi-component) compound crystals. For binary systems, there is one more independent thermodynamic variable to control. In the case of extended binary solid solutions, one would normally choose a composition variable for this purpose. For compounds with very narrow ranges of homogeneity (i.e., point defect concentrations), however, the composition is obviously not a convenient variable. The more natural choice is the chemical potential of one of the two components of the compound crystal. In practice one will often use the vapor pressure ( activity) of this component. 

It can be seen from Eqn. (2.65) and equivalent relations that phenomenological point defect thermodynamics does not give us absolute values of defect concentrations. Rather, within the limits of the approximations (e.g., ideally dilute solutions of irregular SE s in the solvent crystal), we obtain relative changes in defect concentrations as a function of changes in the intensive thermodynamic variables (P, T, pk). Yet we also know that the crystal is stoichiometric (i.e., S = 0) at the inflection... 

We have discussed point defects in elements (A) and in nearly stoichiometric compounds having narrow ranges of homogeneity. Let us extend this discussion to the point defect thermodynamics of alloys and nonmetallic solid solutions. This topic is of particular interest in view of the kinetics of transport processes in those solid solutions which predominate in metallurgy and ceramics. Diffusion processes are governed by the concentrations and mobilities of point defects and, although in inhomogeneous crystals the components may not be in equilibrium, point defects are normally very close to local equilibrium. 

In the case of nonideal solid solutions, the vacancies (or other point defects) by necessity interact differently with components A and B in their immediate surroundings. Therefore, the alloy composition near a vacancy differs from the bulk composition Nb. This is analogous to the problem of energies and concentrations of gas atoms dissolved in alloys under a given gas vapor pressure [H. Schmalzried, A. Navrotsky (1975)]. Let us briefly indicate the approach to its solution and transfer it to the formulations in defect thermodynamics. 

The basis of defect thermodynamics is the concept of regular and irregular SE s and the constraints which crystallography and electroneutrality (in the case of ionic crystals) impose on the derivation of the thermodynamic functions. Thermodynamic potential functions are of particular interest, since one derives the driving forces for the chemical processes in the solid state from them. 

Defect thermodynamics, as outlined in this chapter, is to a large extent thermodynamics of dilute solutions. In this situation, the theoretical calculation of individual defect energies and defect entropies can be helpful. Numerical methods for their calculation are available, see [A. R. Allnatt, A. B. Lidiard (1993)]. If point defects interact, idealized models are necessary in order to find the relations between defect concentrations and thermodynamic variables, in particular the component potentials. We have briefly discussed the ideal pair (cluster) approach and its phenomenological extension by a series expansion formalism, which corresponds to the virial coefficient expansion for gases. 

We have to evaluate the diffusion coefficient or any other transport coefficient with the help of point defect thermodynamics. This can easily be done for reaction products in which one type of point defect disorder predominates. Since we have shown in Chapter 2 that the concentration of ideally diluted point defects depends on the chemical potential of component k as d lncdefec, = n-dp, we obtain quite generally... 

Defect thermodynamics provide the guidelines for the solution of this practical problem. In Chapter 2, the basic ideas on how to influence point defect concentrations by doping with (heterovalent) additions were presented. Due to the electroneutrality condition and the laws of mass action, we can control the point defect... 

These assumptions, however, oversimplify the problem. The parent (A,B)0 phase between the surface and the reaction front coexists with the precipitated (A, B)304 particles. These particles are thus located within the oxygen potential gradient. They vary in composition as a function of ( ) since they coexist with (A,B)0 (AT0<1 see Fig. 9-3). In the Af region, the point defect thermodynamics therefore become very complex [F. Schneider, H. Schmalzried (1990)]. Furthermore, Dv is not constant since it is the chemical diffusion coefficient and as such it contains the thermodynamic factor /v = (0/iV/01ncv). In most cases, one cannot quantify these considerations because the point defect thermodynamics are not available. A parabolic rate law for the internal oxidation processes of oxide solid solutions is expected, however, if the boundary conditions at the surface (reaction front ( F) become time-independent. This expectation is often verified by experimental observations [K. Ostyn, et al. (1984) H. Schmalzried, M. Backhaus-Ricoult (1993)]. 

Nv( f) can be determined by the application of point defect thermodynamics at F, where the equilibrium defect concentrations are found from the following reaction... 

SrTi03 may serve as a well-investigated material for such a bulk conductivity sensor. Its defect thermodynamics and also the relevant kinetic parameters have been discussed in detail in Part I.2 In particular at low temperatures and at small sample thicknesses L, the kinetics of oxygen incorporation becomes surface reaction controlled, and ks the decisive kinetic parameter. 

In common cases, the grain-boundary thickness is close to a few nanometers the overall volume fraction of the boundaries is very small. The opposite situation is observed in nano crystalline solids, with profound effects on defect - thermodynamics and transport. 

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