MACROSCOPIC CONSERVATION EQUATIONS

Macroscopic mass, energy, and momentum balances provide the simplest starting point for reactor modeling. These equations give little spatial detail, but provide a first approximation to the performance of chemical reactors. This section builds on Chapter 22 of Bird, Stewart, and Llghtfoot (2002). A table of notation is given at the end of the current chapter. 

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In this section the statistical theorems or mathematical tools needed to understand the Boltzmann equation in itself, and the mathematical operations performed developing the macroscopic conservation equations starting out from the microscopic Boltzmann equation, are presented. 

However, the various macroscopic conservation equations used to describe such systems are incomplete. Most obviously, the various coefficients in the conservation equations are at this level phenomenological. Also, these equations give no information on statistical fluctuations which may be of importance. 

The usage of the term micro/macro is justified by the two-level description of the fluid that lies at its core a microscopic approach permits evaluation of the stress tensor to be used in closing the macroscopic conservation equations. The macro part can be thought of as corresponding to the Eulerian description of the fluid, while the micro part has Lagrangian character. 

In this section the statistical theorems or mathematical tools needed to understand the Boltzmann equation in itself, and the mathematical operations performed developing the macroscopic conservation equations starting out from the microscopic Boltzmann equation, are presented. Introductory it is stressed that a heuristic theory, which resembles the work of Boltzmann [10] and the standard kinetic theory literature, is adopted in this section and the subsequent sections deriving the Boltzmann equation. Irrespective, the notation and concepts presented in Sect. 2.2 are often referred, or even redefined in a less formal wrapping, thus the underlying elements of classical mechanics are prescience of outmost importance understanding the true principles of kinetic theory. 

Analogous to the equation of change of mean molecular properties for dilute gas that was examined in Sect. 2.6, similar macroscopic conservation equations may be derived for dense gas from the Enskog equation. Multiplying the Enskog s equation (2.663) with the summation invariant property, //, and integrating over c, the result... 

On the continuum level of gas flow, the Navier-Stokes equation forms the basic mathematical model, in which dependent variables are macroscopic properties such as the velocity, density, pressure, and temperature in spatial and time spaces instead of nf in the multi-dimensional phase space formed by the combination of physical space and velocity space in the microscopic model. As long as there are a sufficient number of gas molecules within the smallest significant volume of a flow, the macroscopic properties are equivalent to the average values of the appropriate molecular quantities at any location in a flow, and the Navier-Stokes equation is valid. However, when gradients of the macroscopic properties become so steep that their scale length is of the same order as the mean free path of gas molecules,, the Navier-Stokes model fails because conservation equations do not form a closed set in such situations. 

Macroscopic and Microscopic Balances Three postulates, regarded as laws of physics, are fundamental in fluid mechanics. These are conservation of mass, conservation of momentum, and conservation of energy. In addition, two other postulates, conservation of moment of momentum (angular momentum) and the entropy inequality (second law of thermodynamics) have occasional use. The conservation principles may be applied either to material systems or to control volumes in space. Most often, control volumes are used. The control volumes may be either of finite or differential size, resulting in either algebraic or differential conservation equations, respectively. These are often called macroscopic and microscopic balance equations. 

The differential forms of the conservation equations derived in the appendixes for reacting mixtures of ideal gases are summarized in Section 1.1. From the macroscopic viewpoint (Appendix C), the governing equations (excluding the equation of state and the caloric equation of state) are not restricted to ideal gases. Most of the topics considered in this book involve the solutions of these equations for special flows. The forms that the equations assume for (steady-state and unsteady) one-dimensional flows in orthogonal, curvilinear coordinate systems are derived in Section 1.2, where specializations accurate for a number of combustion problems are developed. Simplified forms of the conservation equations applicable to steady-state problems in three dimensions are discussed in Section 1.3. The specialized equations given in this chapter describe the flow for most of the combustion processes that have been analyzed satisfactorily. 

Computational fluid dynamics involves the analysis of fluid flow and related phenomena such as heat and/or mass transfer, mixing, and chemical reaction using numerical solution methods. Usually the domain of interest is divided into a large number of control volumes (or computational cells or elements) which have a relatively small size in comparison with the macroscopic volume of the domain of interest. For each control volume a discrete representation of the relevant conservation equations is made after which an iterative solution procedure is invoked to obtain the solution of the nonlinear equations. Due to the advent of high-speed digital computers and the availability of powerful numerical algorithms the CFD approach has become feasible. CFD can be seen as a hybrid branch of mechanics and mathematics. CFD is based on the conservation laws for mass, momentum, and (thermal) energy, which can be expressed as follows ... 

The available continuum models for dispersed multi-phase flows thus follow one of two asymptotic approaches. The dilute phase approach is formulated based on the continuum mechanical principles in terms of the local conservation equations for each of the phases. A macroscopic model is then obtained by averaging the local equations based on an appropriate averaging procedure. In the dense phase approach, on the other hand, a kinetic theory description is adopted for the dispersed particulate phase (granular material), whereas an averaged continuum model formulation is adopted for the interstitial phase. 

One consequence of the continuum approximation is the necessity to hypothesize two independent mechanisms for heat or momentum transfer one associated with the transport of heat or momentum by means of the continuum or macroscopic velocity field u, and the other described as a molecular mechanism for heat or momentum transfer that will appear as a surface contribution to the macroscopic momentum and energy conservation equations. This split into two independent transport mechanisms is a direct consequence of the coarse resolution that is inherent in the continuum description of the fluid system. If we revert to a microscopic or molecular point of view for a moment, it is clear that there is only a single class of mechanisms available for transport of any quantity, namely, those mechanisms associated with the motions and forces of interaction between the molecules (and particles in the case of suspensions). When we adopt the continuum or macroscopic point of view, however, we effectively spht the molecular motion of the material into two parts a molecular average velocity u = (w) and local fluctuations relative to this average. Because we define u as an instantaneous spatial average, it is evident that the local net volume flux of fluid across any surface in the fluid will be u n, where n is the unit normal to the surface. In particular, the local fluctuations in molecular velocity relative to the average value (w) yield no net flux of mass across any macroscopic surface in the fluid. However, these local random motions will generally lead to a net flux of heat or momentum across the same surface. 

The flow behavior of fluids is governed by the basic laws for conservation of mass, energy, and momentum coupled with appropriate expressions for the irreversible rate processes (e.g., friction loss) as a function of fluid properties, flow conditions, geometry, etc. These conservation laws can be expressed in terms of microscopic or point values of the variables, or in terms of macroscopic or integrated average values of these quantities. In principle, the macroscopic balances can be derived by integration of the microscopic balances. However, unless the local microscopic details of the flow field are required, it is often easier and more convenient to start with the macroscopic balance equations. 

The macroscopic conservation of mass, or continuity, equation for any system is... 

To derive the macroscopic transport equations, the conservation Relation [10] and [11] must be converted to differential equations. The main assumption needed is that the mean density and the mean velocity vary slowly in space and in time. Starting from Eq. [10] and [11], the macro dynamic equations describing the large-scale behavior of the lattice gas are obtained by multiple-scale perturbation expansion technique (Frisch et al., 1987). We shall not derive this formalism here. In the continuous limit, Eq. [10] leads to the macro dynamical conservation of mass or Euler equation... 

The second-order expansion of Eq. [11] leads to a macroscopic momentum conservation equation that differs from Navier-Stokes equations only in irrelevant terms of higher order provided that the mean velocity u is small. Thus lattice-gases may be used as models for fluids. 

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