Phenomenological Theories

Sipe J E, Moss D J and van Driel H M 1987 Phenomenological theory of optical second- and third-harmonic generation from cubic centrosymmetric crystals Phys. Rev. B 35 1129-41... 

In this section, the general inelastic theory of Section 5.2 will be specialized to a simple phenomenological theory of plasticity. The inelastic strain rate tensor e may be identified with the plastic strain rate tensor e . In order to include isotropic and kinematic hardening, the set of internal state variables, denoted collectively by k in the previous theory, is reduced to the set (k, a) where k is a scalar representing isotropic hardening and a is a symmetric second-order tensor representing kinematic hardening. The elastic limit condition in stress space (5.25), now called a yield condition, becomes... 

The simplified failure envelopes are not derived from physical theories of failure in which the actual physical processes that cause failure on a microscopic level are integrated to obtain a failure theory. We, instead, deal with phenomenological theories in which we ignore the actual failure mechanisms and concentrate on the gross macroscopic events of failure. Phenomenological theories are based on curve-fitting, so they are failure criteria and not theories of any kind (the term theory implies a formal derivation process). 

D. Blankschtein, G. Thurston, G. Benedek. Phenomenological theory of equilibrium thermodynamic properties and phase separation of micellar solutions. J Chem Phys 25 7268-7288, 1986. 

The first step in studying phenomenological theories (Ginzburg-Landau theories and membrane theories) has usually been to minimize the free energy functional of the model. Fluctuations are then included at a later stage, e.g., using Monte Carlo simulations. The latter will be discussed in Sec. V and Chapter 14. 

A. E. Yaroshchuk, S. S. Durkhin. Phenomenological theory of reverse osmosis in macroscopically homogeneous membranes and its specification for the capillary charged model. J Memb Sci 79 133, 1993. 

Classical surface and colloid chemistry generally treats systems experimentally in a statistical fashion, with phenomenological theories that are applicable only to building simplified microstructural models. In recent years scientists have learned not only to observe individual atoms or molecules but also to manipulate them with subangstrom precision. The characterization of surfaces and interfaces on nanoscopic and mesoscopic length scales is important both for a basic understanding of colloidal phenomena and for the creation and mastery of a multitude of industrial applications. 

The present theory can be placed in some sort of perspective by dividing the nonequilibrium field into thermodynamics and statistical mechanics. As will become clearer later, the division between the two is fuzzy, but for the present purposes nonequilibrium thermodynamics will be considered that phenomenological theory that takes the existence of the transport coefficients and laws as axiomatic. Nonequilibrium statistical mechanics will be taken to be that field that deals with molecular-level (i.e., phase space) quantities such as probabilities and time correlation functions. The probability, fluctuations, and evolution of macrostates belong to the overlap of the two fields. 

If the approach does not go beyond the ordinary entropy, or if it applies an optimized result to a constrained state, then one can immediately conclude that a quantitative theory for the nonequilibrium state is unlikely to emerge. Regrettably, for phenomenological theories of the type just discussed, the answer to both questions is usually negative. The contribution of Prigogine, in particular, will be critically assessed from these twin perspectives (see Section HE). 

The elastic free energy given by the elementary and the more advanced theories are symmetric functions of the three extension ratios Xx, Xy, and Xz. One may also express the dependence of the elastic free energy on strain in terms of three other variables, which are in turn functions of Xx, Xy, and Xz. In phenomenological theories of continuum mechanics, where only the observed behavior of the material is of concern rather than the associated molecular deformation mechanisms, these three functions are chosen as... 

N, W. Tschoegl, The Phenomenological Theory of Linear Viscoelastic Behavior, Springer-Verlag, New York, 1989. 

This idea is elegant for its simplicity and also for its usefulness. While often in phenomenological theories of materials, control of parameters with molecular structure would provide useful properties, but the parameters are not related in any obvious way to controllable molecular structural features. Meyer s idea, however, is just the opposite. Chemists have the ability to control enantiomeric purity and thus can easily create an LC phase lacking reflection symmetry. In the case of the SmC, the macroscopic polar symmetry of this fluid phase can lead to a macroscopic electric dipole, and such a dipole was indeed detected by Meyer and his collaborators in a SmC material, as reported in 1975.2... 

As soon as the concentration of the solute becomes finite, the coulombic forces between the ions begin to play a role and we obtain both the well-known relaxation effect and an electrophoretic effect in the expression for the conductivity. In Section V, we first briefly recall the semi-phenomenological theory of Debye-Onsager-Falkenhagen, and we then show how a combination of the ideas developed in the previous sections, namely the treatment of long-range forces as given in Section III and the Brownian model of Section IV, allows us to study various microscopic... 

Clearly enough, for a knowledge of this force we would require a complete calculation of the motion of the fluid particles, i.e. the solution of the (N + l)-body problem involving the N fluid particles and the B-particle. This point of view will be adopted in Section IV-C but, in the phenomenological theory, stochastic assumptions are made about this force. 

In this section, we shall first give a brief review of the phenomenological theory of these effects.5 -6 26 We shall then show how the methods we have discussed in the previous sections may be extended to derive a microscopic theory of the relaxation effect the microscopic theory of electrophoresis will be considered in the next section. 

We want to analyze here the effect of these long-range Coulomb forces in the large friction limit (396) we shall thus consider the Brownian-dynamic approximation, which, as we shall see presently, gives exactly the same result as the classical semi-phenomenological theory developed in Section V-A. 

As summarized above, there are many transport models and flow mechanisms describing reverse osmosis. Each requires some specific assumptions regarding membrane structure. In general, membranes could be continuous or discontinuous and porous or non-porous and homogeneous or non-homogeneous. One must be reasonably sure about the membrane structure before he analyzes a particular set of experimental data based on one of the above theories. Since this is difficult, in many cases, it would be desirable to develop a model-independent phenomenological theory which can interpret the experimental data. 

In the following discussion, a purely phenomenological theory will be presented for the tranport of salt and total volume. 

An exact mathematical relationship is obtained between the salt rejection and total volume flux in reverse osmosis based on a purely phenomenological theory assuming constant salt permeability. This approach does not require a specific membrane model ... 

The electron theory of catalysis and other, mainly phenomenological, theories of catalysis are not as a rule mutually exclusive. They deal with different aspects of catalysis and thus differ from one another mainly in their approach to the problem. The electron theory is interested in the elementary (electronic) mechanism of the phenomenon and approaches the problems of catalysis from this point of view. 

The existing phenomenological theories of catalysis bear approximately the same relation to the electron theory as the theory of the chemical bond, which was prevalent in the last century and which made use of valence signs (and dealt only with these signs), bears to the modern quantum-mechanical theory of the chemical bond which has given the old valence signs physical content, thereby disclosing the physical nature of the chemical forces. 

Theoretical studies are primarily concentrated on the treatment of flame blow-off phenomenon and the prediction of flame spreading rates. Dunskii [12] is apparently the first to put forward the phenomenological theory of flame stabilization. The theory is based on the characteristic residence and combustion times in adjoining elementary volumes of fresh mixture and combustion products in the recirculation zone. It was shown in [13] that the criteria of [1, 2, 5] reduce to Dunskii s criterion. Longwell et al. [14] suggested the theory of bluff-body stabilized flames assuming that the recirculation zone in the wake of the baffle is so intensely mixed that it becomes homogeneous. The combustion is described by a second-order rate equation for the reaction of fuel and air. 

As mentioned in section 12.1, Dunskii [12] was the first who put forward the phenomenological theory of flame stabilization. The theory is based on the characteristic residence time, L, and combustion time, tc, in adjoining elementary volumes of fresh mixture and combustion products in the recirculation zone behind the bluff body. Dunskii s condition for flame blow-off is U/tc = Mi, where Mi is the Mikhelson number close to unity (for example, for cone flame holder the measurements give Mi = 0.45 [36]). Residence time L is taken proportional to the flame holder size, H, and inversely proportional to the approach flow velocity, U, i.e., L = H/U. Combustion time is estimated as tc = at/Si, where... 

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