Flux Vectors

In principle, Chen, given the flux relations there is no difficulty in constructing differencial equations to describe the behavior of a catalyst pellet in steady or unsteady states. In practice, however, this simple procedure is obstructed by the implicit nature of the flux relations, since an explicit solution of usefully compact form is obtainable only for binary mixtures- In steady states this impasse is avoided by using certain, relations between Che flux vectors which are associated with the stoichiometry of Che chemical reaction or reactions taking place in the pellet, and the major part of Chapter 11 is concerned with the derivation, application and limitations of these stoichiometric relations. Fortunately they permit practicable solution procedures to be constructed regardless of the number of substances in the reaction mixture, provided there are only one or two stoichiomeCrically independent chemical reactions. 

In unsteady states the situation is less satisfactory, since stoichiometric constraints need no longer be satisfied by the flux vectors. Consequently differential equations representing material balances can be constructed only for binary mixtures, where the flux relations can be solved explicitly for the flux vectors. This severely limits the scope of work on the dynamical equations and their principal field of applicacion--Che theory of stability of steady states. The formulation of unsteady material and enthalpy balances is discussed in Chapter 12, which also includes a brief digression on stability problems. 

These are the flux relations associated with the dusty gas model. As explained above, they would be expected to predict only the diffusive contributions to the flux vectors, so they should be compared with equations (2.25) obtained from simple momentum transfer arguments. Equations (3,16) are then seen to be just the obvious vector generalization of the scalar equations (2.25), so the dusty gas model provides justification for the simple procedure of adding momentum transfer rates. 

These can easily be condensed into a single set of n equations for the flux vectors N, From (5.2) and (5,3)... 

Ac Che limic of Knudsen screaming Che flux relacions (5.25) determine Che fluxes explicitly in terms of partial pressure gradients, but the general flux relacions (5.4) are implicic in Che fluxes and cheir solution does not have an algebraically simple explicit form for an arbitrary number of components. It is therefore important to identify the few cases in which reasonably compact explicit solutions can be obtained. For a binary mixture, simultaneous solution of the two flux equations (5.4) is straightforward, and the result is important because most experimental work on flow and diffusion in porous media has been confined to pure substances or binary mixtures. The flux vectors are found to be given by... 

This is an explicit solution of the Stefan-Maxwell equations for the diffusion fluxes. The species flux vectors are then given by... 

Che pore size distribution and Che pore geometry. Condition (iil). For isobaric diffusion in a binary mixture Che flux vectors of Che two species must satisfy Graham s relation... 

The existence of these aimple algebraic relations enormously simplifies the problem of solving the implicit flux equations, since (11.3) permit all the flux vectors to be expressed In terms of any one of them. From equations (11.1), clearly... 

At the opposite limit of bulk diffusion control and high permeability, all flux models are required to he consistent with the Stefan-Maxwell relations (8.3). Since only (n-1) of these are independent, they are insufficient to determine all the flux vectors, and they permit the problem to be formulated in closed form only when they can be supplemented by the stoichiometric relations (11.3). At this limit, therefore, attention must be restricted from the beginning to those simple pellet shapes for ich equations (11.3) have been justified. Furthermore, since the permeability tends to infininty, pressure gradients within the pellet tend to zero and... 

We have used the fact that the concentration gradient grad c, or equivalently the pressure gradient, tends to zero as the permedility tends to infinity. Nevertheless, these vanishingly small pressure gradients continue to exert a nonvanishing influence on the flux vectors, and the course of Che above calculation Indicates explicitly how this comes about. 

The enthalpy flux vector N per unit total cross section in the... 

Then in terms of h and the enthalpy flux vector the enthalpy... 

When developing the dusty gas model flux relations in Chapter 3, the thermal diffusion contributions to the flux vectors, defined by equations (3.2), were omitted. The effect of retaining these terms is to augment the final flux relations (5.4) by terms proportional to the temperature gradient. Specifically, equations (5.4) are replaced by the following generalization... 

Since in most situations the perturbation quantities (V and c() are not explicitly resolved, it is not possible to evaluate the turbulent flux term directly. Instead, it must be related to the distribution of averaged quantities - a process referred to as parameterization. A common assumption is to relate the turbulent flux vector to the gradient of the averaged tracer distribution, which is analogous with the molecular diffusion expression. Equation (35). 

Transient computations of methane, ethane, and propane gas-jet diffusion flames in Ig and Oy have been performed using the numerical code developed by Katta [30,46], with a detailed reaction mechanism [47,48] (33 species and 112 elementary steps) for these fuels and a simple radiation heat-loss model [49], for the high fuel-flow condition. The results for methane and ethane can be obtained from earlier studies [44,45]. For propane. Figure 8.1.5 shows the calculated flame structure in Ig and Og. The variables on the right half include, velocity vectors (v), isotherms (T), total heat-release rate ( j), and the local equivalence ratio (( locai) while on the left half the total molar flux vectors of atomic hydrogen (M ), oxygen mole fraction oxygen consumption rate... 

The flux vector accounts for mass transport by both convection (i.e., blood flow, interstitial fluid flow) and conduction (i.e., molecular diffusion), whereas S describes membrane transport between adjacent compartments and irreversible elimination processes. For the three-subcompartment organ model presented in Figure 2, with concentration both space- and time-dependent, the conservation equations are... 

It is sometimes useful to write the rate of heat added to the control volume in terms of a heat flux vector, q", as... 

The divergence of the flux vector is therefore the net rate of accumulation of the quantity which is transported in and out of the volume element dK This can be integrated over an arbitrary volume Cl limited by the surface I to give the divergence theorem of Gauss... 

An analysis of the right nullspace K provides the conceptual basis of flux balance analysis and has led to a plethora of highly successful applications in metabolic network analysis. In particular, all steady-state flux vectors v° = v(S°,p) can be written as a linear combination of columns Jfcx- of K, such that... 

Alternatively, we may assume that there exists some (but possibly limited) knowledge about the typical concentrations involved. For each metabolite, we can then specify an interval St < S1- <. S ) that defines a physiologically feasible range of the respective concentration. Furthermore, the steady-state flux vector v° is subject to the mass-balance constraint Nv° = 0, leaving only r — rank(N) independent reaction rates. Again, an interval v(. < v9 < v+ can be specified for all independent reaction rates, defining a physiologically admissible flux space. 

In contrast, SKM does not assume knowledge of thespecific functional form of the rate equations. Rather, the system is evaluated in terms of generalized parameters, specified by the elements of the matrices A and 0X. In this sense, the matrices A and 0 x are bona fide parameters of the system The pathway is described in terms ofan average metabolite concentration S°, and a steady-state flux vector v°, together defining the metabolic state of the pathway. Additionally, we assume that the substrate only affects reaction v2, the saturation matrix is thus fully specified by a single parameter Of 6 [0,1], Note that the number of parameters is identical to the number used within the explicit equation. The structure of the parameter matrices is... 

All feasible steady-state flux vectors v(S°) are described by two basis vectors k, ... 

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