Equilibrium problem

Ladder diagrams are a useful tool for evaluating chemical reactivity, usually providing a reasonable approximation of a chemical system s composition at equilibrium. When we need a more exact quantitative description of the equilibrium condition, a ladder diagram may not be sufficient. In this case we can find an algebraic solution. Perhaps you recall solving equilibrium problems in your earlier coursework in chemistry. In this section we will learn how to set up and solve equilibrium problems. We will start with a simple problem and work toward more complex ones. 

Besides equilibrium constant equations, two other types of equations are used in the systematic approach to solving equilibrium problems. The first of these is a mass balance equation, which is simply a statement of the conservation of matter. In a solution of a monoprotic weak acid, for example, the combined concentrations of the conjugate weak acid, HA, and the conjugate weak base, A , must equal the weak acid s initial concentration, Cha- ... 

The solubility of a precipitate can be improved by adding a ligand capable of forming a soluble complex with one of the precipitate s ions. For example, the solubility of Agl increases in the presence of NH3 due to the formation of the soluble Ag(NH3)2°" complex. As a final illustration of the systematic approach to solving equilibrium problems, let us find the solubility of Agl in 0.10 M NH3. 

You should be able to describe a system at equilibrium both qualitatively and quantitatively. Rigorous solutions to equilibrium problems can be developed by combining equilibrium constant expressions with appropriate mass balance and charge balance equations. Using this systematic approach, you can solve some quite complicated equilibrium problems. When a less rigorous an-... 

A quantitative solution to an equilibrium problem may give an answer that does not agree with the value measured experimentally. This result occurs when the equilibrium constant based on concentrations is matrix-dependent. The true, thermodynamic equilibrium constant is based on the activities, a, of the reactants and products. A species activity is related to its molar concentration by an activity coefficient, where a = Yi[ ] Activity coefficients often can be calculated, making possible a more rigorous treatment of equilibria. 

At the equivalence point, the moles of Fe + initially present and the moles of Ce + added are equal. Because the equilibrium constant for reaction 9.16 is large, the concentrations of Fe and Ce + are exceedingly small and difficult to calculate without resorting to a complex equilibrium problem. Consequently, we cannot calculate the potential at the equivalence point, E q, using just the Nernst equation for the analyte s half-reaction or the titrant s half-reaction. We can, however, calculate... 

Substituting here the corresponding geometrical and constitutive relations of Sections 1.1.3 and 1.1.4, we obtain H = H(17, w). The set of admissible displacements K is defined by the boundary conditions at F and nonpenetration conditions at the crack F, stated in Section 1.1.7. The variational form of the equilibrium problem is the following ... 

In this chapter we analyse a wide class of equilibrium problems with cracks. It is well known that the classical approach to the crack problem is characterized by the equality type boundary conditions considered at the crack faces, in particular, the crack faces are considered to be stress-free (Cherepanov, 1979, 1983 Kachanov, 1974 Morozov, 1984). This means that displacements found as solutions of these boundary value problems do not satisfy nonpenetration conditions. There are practical examples showing that interpenetration of crack faces may occur in these cases. An essential feature of our consideration is that restrictions of Signorini type are considered at the crack faces which do not allow the opposite crack faces to penetrate each other. The restrictions can be written as inequalities for the displacement vector. As a result a complete set of boundary conditions at crack faces is written as a system of equations and inequalities. The presence of inequality type boundary conditions implies the boundary problems to be nonlinear, which requires the investigation of corresponding boundary value problems. In the chapter, plates and shells with cracks are considered. Properties of solutions are established existence of solutions, regularity up to the crack faces, convergence of solutions as parameters of a system are varying and so on. We analyse different constitutive laws elastic, viscoelastic. 

The equilibrium problem for the plate contacting with the punch z = x, y)... 

The equilibrium problem for the plate can be formulated as variational, namely, it corresponds to the minimum of the functional H over the set of admissible displacements. To minimize the functional H over the set we can consider the variational inequality... 

The crack shape is defined by the function -ip. This function is assumed to be fixed. It is noteworthy that the problems of choice of the so-called extreme crack shapes were considered in (Khludnev, 1994 Khludnev, Sokolowski, 1997). We also address this problem in Sections 2.4 and 4.9. The solution regularity for biharmonic variational inequalities was analysed in (Frehse, 1973 Caffarelli et ah, 1979 Schild, 1984). The last paper also contains the results on the solution smoothness in the case of thin obstacles. As for general solution properties for the equilibrium problem of the plates having cracks, one may refer to (Morozov, 1984). Referring to this book, the boundary conditions imposed on crack faces have the equality type. In this case there is no interaction between the crack faces. 

L flc) be some given functions of the external forces. The equilibrium problem for a plate with a crack is formulated as the following variational inequality ... 

Here inequalities (2.185), (2.186) are assumed to be satisfied almost everywhere in the Lebesgue sense on F, and in We assume that < 0 on F, so that the set Kg is nonempty. The equilibrium problem for a shallow shell with a solution satisfying the nonpenetration conditions (2.185), (2.186) can be formulated as follows ... 

We shall investigate the regularity of the solution in a neighbourhood of the crack tip = (1,0). Suppose, first, that (W, w) is a solution of the equilibrium problem (2.188). We assume that a neighbourhood W of the graph exists such that for any function (p G C W) there is an c > 0, for which... 

We consider an equilibrium problem for a shell with a crack. The faces of the crack are assumed to satisfy a nonpenetration condition, which is an inequality imposed on the horizontal shell displacements. The properties of the solution are analysed - in particular, the smoothness of the stress field in the vicinity of the crack. The character of the contact between the crack faces is described in terms of a suitable nonnegative measure. The stability of the solution is investigated for small perturbations to the crack geometry. The results presented were obtained in (Khludnev, 1996b). 

In so doing, the boundary value of on F is assumed to provide nonemptiness of the set K. The equilibrium problem for the plate contacting with the punch and having the crack can be formulated as a variational one ... 

In this case the equilibrium problem (2.265) takes the form... 

An existence theorem to the equilibrium problem of the plate is proved. A complete system of equations and inequalities fulfilled at the crack faces is found. The solvability of the optimal control problem with a cost functional characterizing an opening of the crack is established. The solution is shown to belong to the space C °° near crack points provided the crack opening is equal to zero. The results of this section are published in (Khludnev, 1996c). 

We shall consider an equilibrium problem with a constitutive law corresponding to a creep, in particular, the strain and integrated stress tensor components (IT ), ay(lT ) will depend on = (lT, w ), where (lT, w ) are connected with (IT, w) by (3.1). In this case, the equilibrium equations will be nonlocal with respect to t. 

The structure of the section is as follows. In Section 3.1.2 we prove a solvability of the equilibrium problem. This problem is formulated as a variational inequality holding in Q. The equations (3.3), (3.4) are fulfilled in the sense of distributions. On the other hand, if the solution is smooth and satisfies (3.3), (3.4) and all the boundary conditions then the above variational inequality holds. 

In this subsection we prove an existence theorem of the equilibrium problem for the plate. The problem is formulated as a variational inequality which together with (3.2), (3.5) contains full information about other boundary conditions holding on x (0, T). An exact form of these conditions is found in the next subsection. 

Consider an approximate description of the nonpenetration condition between the crack faces which can be obtained by putting c = 0 in (3.45). Similar to the case c > 0, we can analyse the equilibrium problem of the plates and prove the solution existence of the optimal control problem of the plates with the same cost functional. We aim at the convergence proof of solutions of the optimal control problem as —> 0. In this subsection we assume that T, is a segment of a straight line parallel to the axis x. 

The equilibrium problem for a plate is formulated as some variational inequality. In this case equations (3.92)-(3.94) hold, generally speaking, only in the distribution sense. Alongside (3.95), other boundary conditions hold on the boundary F the form of these conditions is clarified in Section 3.3.3. To derive them, we require the existence of a smooth solution to the variational inequality in question. On the other hand, if we assume that a solution to (3.92)-(3.94) is sufficiently smooth, then the variational inequality is a consequence of equations (3.92)-(3.94) and the initial and boundary conditions. All these questions are discussed in Section 3.3.3. In Section 3.3.2 we prove an existence theorem for a solution to the variational equation and in Section 3.3.4 we establish some enhanced regularity properties for the solution near F. ... 

We can now give an exact statement of the equilibrium problem for a plate. Suppose that / G L Q ). An element (0, x) G 17 is said to be a solution to the equilibrium problem for a thermoelastic plate with a crack if it satisfies the variational inequality... 

It is noteworthy that the original equilibrium problem for a plate with a crack can be stated twofold. On the one hand, it may be formulated as variational inequality (3.98). In this case all the above-derived boundary conditions are formal consequences of such a statement under the supposition of sufficient smoothness of a solution. On the other hand, the problem may be formulated as equations (3.92)-(3.94) given initial and boundary conditions (3.95)-(3.97) and (3.118)-(3.122). Furthermore, if we assume that a solution is sufficiently smooth then from (3.92)-(3.97) and (3.118)-(3.122) we can derive variational inequality (3.98). 

In this section we derive a nonpenetration condition between crack faces for inclined cracks in plates and discuss the equilibrium problem. As it turns out, the nonpenetration condition for inclined cracks is of nonlocal character. This means that by writing the condition at a fixed point we have to take into account the displacement values both at the point and at the other point chosen at the opposite crack face. As a corollary of this fact, the equilibrium equations hold only in a domain located outside the crack surface projection on the mid-surface of the plate. This section follows the papers (Khludnev, 1997b Kovtunenko et ah, 1998). 

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