Simplified solute model

Solubility behavior of compounds in supercritical fluids is interpreted using a simplified solution model. Solid-fluid and liquid-fluid phase equilibria data are presented and discussions of the phase behavior are provided. Phase transitions and transport properties are briefly discussed. 

Miyauchi and Vermeulen (M7, M8) have presented a mathematical analysis of the effect upon equipment performance of axial mixing in two-phase continuous flow operations, such as absorption and extraction. Their solutions are based, in one case, upon a simplified diffusion model that assumes a mean axial dispersion coefficient and a mean flow velocity for... 

Eq. (122) represents a set of algebraic constraints for the vector of species concentrations expressing the fact that the fast reactions are in equilibrium. The introduction of constraints reduces the number of degrees of freedom of the problem, which now exclusively lie in the subspace of slow reactions. In such a way the fast degrees of freedom have been eliminated, and the problem is now much better suited for numerical solution methods. It has been shown that, depending on the specific problem to be solved, the use of simplified kinetic models allows one to reduce the computational time by two to three orders of magnitude [161],... 

Simplified mathematical models These models typically begin with the basic conservation equations of the first principle models but make simplifying assumptions (typically related to similarity theory) to reduce the problem to the solution of (simultaneous) ordinary differential equations. In the verification process, such models must also address the relevant physical phenomenon as well as be validated for the application being considered. Such models are typically easily solved on a computer with typically less user interaction than required for the solution of PDEs. Simplified mathematical models may also be used as screening tools to identify the most important release scenarios however, other modeling approaches should be considered only if they address and have been validated for the important aspects of the scenario under consideration. 

For steady-state design scenarios, the required vent rate, once determined, provides the capacity information needed to properly size the relief device and associated piping. For situations that are transient (e.g., two-phase venting of a runaway reactor), the required vent rate would require the simultaneous solution of the applicable material and energy balances on the equipment together with the in-vessel hydrodynamic model. Special cases yielding simplified solutions are given below. For clarity, nonreactive systems and reactive systems are presented separately. 

Most theoretical studies of outer-sphere (nonbond-breaking) electron transfer reactions at the metal-solution interface involve major simplifying assumptions regarding the molecular and electronic structure of the solvents and the metal. Although the importance of molecular structure and the dynamics of the solvent has been recognized, most of the theoretical work in this area has been based on a highly simplified continuum model. ... 

On a lattice, so-called crankshaft moves are trivial implementations of concerted rotations [77]. They have been generalized to the off-lattice case [78] for a simplified protein model. For concerted rotation algorithms that allow conformational changes in the entire stretch, a discrete space of solutions arises when the number of constraints is exactly matched to the available degrees of freedom. The much-cited work by Go and Scheraga [79] formulates the loop-closure problem as a set of algebraic equations for six unknowns reducible... 

Maestro, M. and Luisi, P. L. (1990). A simplified thermodynamic model for protein uptake by reverse micelles. In Surfactants in Solution, ed. K. L. Mittal. Plenum, vol. 9. 

The use of isotopic models in the literature—practical limits of usage As mentioned above, simplified solutions are employed in ion exchange for the estimation of diffusion coefficients. For example, the equations of Vermeulen and Patterson, derived from isotopic exchange systems, have been successfully used, even in processes that are not isotopic. Inglezakis and Grigoropoulou (2001) conducted an extended review of the literature on the use of isotopic models for ion-exchange systems. 

These partial derivatives provide a lot of information (ref. 10). They show how parameter perturbations (e.g., uncertainties in parameter values) affect the solution. Identifying the unimportant parameters the analysis may help to simplify the model. Sensitivities are also needed by efficient parameter estimation procedures of the Gauss - Newton type. Since the solution y(t,p) is rarely available in analytic form, calculation of the coefficients Sj(t,p) is not easy. The simplest method is to perturb the parameter pj, solve the differential equation with the modified parameter set and estimate the partial derivatives by divided differences. This "brute force" approach is not only time consuming (i.e., one has to solve np+1 sets of ny differential equations), but may be rather unreliable due to the roundoff errors. A much better approach is solving the sensitivity equations... 

Fig. 2. Simplified schematic model of ionic distribution at the electrode—solution interface with (a) and without (b) specific anion adsorption and the corresponding potential distributions at the interface (c) and (d).

The Debye-Huckel theory was developed to extend the capacitor model and is based on a simplified solution of the Poisson equation. It assumes that the double layer is really a diffuse cloud in which the potential is not a discontinuous function. Again, the interest is in deriving an expression for the electrical potential function. This model states that there is an exponential relationship between the charge and the potential. The distribution of the potential is ... 

In the old days , one had to simplify the models and the modeling or design equations greatly in order to make them simple enough for an analytical solution. This was done at the expense of rigor, accuracy, and reliability of the results . 

From the theoretical point of view, the analysis of the faradaic electrochemical behavior of these systems is simpler than that corresponding to solution soluble species since the mass transport is not present, a fact which greatly simplifies the modellization of these processes (note that, in general, for a redox species in solution, a two- or three-variable problem (coordinates and time) needs to be considered, whereas at the electrode surface only time variable is needed). Thus, it is possible to deduce the electrochemical response of these molecules in a more direct way. 

This chapter gave an overview of how to simplify complex processes sufficiently to allow the use of analytical models for their analysis and optimization. These models are based on mass, momentum, energy and kinetic balance equations, with simplified constitutive models. At one point, as the complexity and the depth of these models increases by introducing more realistic geometries and conditions, the problems will no longer have an analytical solution, and in many cases become non-linear. This requires the use of numerical techniques which will be covered in the third part of this book, and for the student of polymer processing, perhaps in a more advanced course. 

Chemical kinetics plays a major role in modeling the ideal chemical batch reactor hence, a basic introduction to chemical kinetics is given in the chapter. Simplified kinetic models are often adopted to obtain analytical solutions for the time evolution of concentrations of reactants and products, while more complex kinetics can be considered if numerical solutions are allowed for. 

In Fig. 4.5, temperature profiles are reported in subcritical, critical, and supercritical conditions. Supercritical solutions of the simplified mathematical model proposed by Semenov are, however, purely theoretical since the assumption of negligible reactant conversion becomes very unrealistic. As an example, in the worst case where

theory predicts an infinitely increasing temperature in the reactor. 

Approaches based on parameter estimation assume that the faults lead to detectable changes of physical system parameters. Therefore, FD can be pursued by comparing the estimates of the system parameters with the nominal values obtained in healthy conditions. The operative procedure, originally established in [23], requires an accurate model of the process (including a reliable nominal estimate of the model parameters) and the determination of the relationship between model parameters and physical parameters. Then, an online estimation of the process parameters is performed on the basis of available measures. This approach, of course, might reveal ineffective when the parameter estimation technique requires solution to a nonlinear optimization problem. In such cases, reduced-order or simplified mathematical models may be used, at the expense of accuracy and robustness. Moreover, fault isolation could be difficult to achieve, since model parameters cannot always be converted back into corresponding physical parameters, and thus the influence of each physical parameters on the residuals could not be easily determined. 

Basically, the impedance behavior of a porous electrode cannot be described by using only one RC circuit, corresponding to a single time constant RC. In fact, a porous electrode can be described as a succession of series/parallel RC components, when starting from the outer interface in contact with the bulk electrolyte solution, toward the inner distribution of pore channels and pore surfaces [4], This series of RC components leads to different time constant RC that can be seen as the electrical response of the double layer charging in the depth of the electrode. Armed with this evidence, De Levie [27] proposed in 1963 a (simplified) schematic model of a porous electrode (Figure 1.24a) and its related equivalent circuit deduced from the model (Figure 1.24b). 

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