Phenomenological mechanical theory equations

The first is the phenomenological mechanical theory. One form of the equation reads r6-9L... 

If it cannot be guaranteed that the adsorbate remains in local equilibrium during its time evolution, then a set of macroscopic variables is not sufficient and an approach based on nonequihbrium statistical mechanics involving time-dependent distribution functions must be invoked. The kinetic lattice gas model is an example of such a theory [56]. It is derived from a Markovian master equation, but is not totally microscopic in that it is based on a phenomenological Hamiltonian. We demonstrate this approach... 

Parallel with the phenomenological development, an alternative point of view has developed toward thermodynamics, a statistical-mechanical approach. Its philosophy is more axiomatic and deductive than phenomenological. The kinetic theory of gases naturally led to attempts to derive equations describing the behavior of matter in bulk from the laws of mechanics (first classic, then quanmm) applied to molecular particles. As the number of molecules is so great, a detailed treatment of the mechanical problem presents insurmountable mathematical difficulties, and statistical methods are used to derive average properties of the assembly of molecules and of the system as a whole. 

The plan of this chapter is the following. Section II gives a summary of the phenomenology of irreversible processes and set up the stage for the results of nonequilibrium statistical mechanics to follow. In Section III, it is explained that time asymmetry is compatible with microreversibility. In Section IV, the concept of Pollicott-Ruelle resonance is presented and shown to break the time-reversal symmetry in the statistical description of the time evolution of nonequilibrium relaxation toward the state of thermodynamic equilibrium. This concept is applied in Section V to the construction of the hydrodynamic modes of diffusion at the microscopic level of description in the phase space of Newton s equations. This framework allows us to derive ab initio entropy production as shown in Section VI. In Section VII, the concept of Pollicott-Ruelle resonance is also used to obtain the different transport coefficients, as well as the rates of various kinetic processes in the framework of the escape-rate theory. The time asymmetry in the dynamical randomness of nonequilibrium systems and the fluctuation theorem for the currents are presented in Section VIII. Conclusions and perspectives in biology are discussed in Section IX. 

This section summarizes results of the phenomenological theory of viscoelasticity as they apply to homogeneous polymer liquids. The theory of incompressible simple fluids (76, 77) is based on a very general set of ideas about the nature of mechanical response. According to this theory the flow-induced stress at any point in a substance at time t depends only on the deformations experienced by material in an arbitrarily small neighborhood of that point in all times prior to t. The relationship between stress at the current time and deformation history is the constitutive equation for the substance. 

The theory described so far is based on the Master Equation, which is a sort of intermediate level between the macroscopic, phenomenological equations and the microscopic equations of motion of all particles in the system. In particular, the transition from reversible equations to an irreversible description has been taken for granted. Attempts have been made to derive the properties of fluctuations in nonlinear systems directly from the microscopic equations, either from the classical Liouville equation 18 or the quantum-mechanical equation for the density matrix.19 We shall discuss the quantum-mechanical treatment, because the formalism used in that case is more familiar. 

The difference this derivation has in comparison to the previous derivation of the nonlinear Schrodinger equation is that the nonlinearity is more fundamentally due to the non-Abelian wavefunction rather than from material coefficients. In effect these material coefficients and phenomenology behave as they do because the variable index of refraction is associated with non-Abelian electrodynamics. Ultimately these two views will merge, for the mechanisms on how photons interact with atoms and molecules will give a more complete picture on how non-Abelian electrodynamics participates in these processes. However, at this stage we can see that we obtain nonlinear terms from a non-Abelian electrodynamics that is fundamentally nonlinear. This is in contrast to the phenomenological approach that imposes these nonlinearities onto a fundamentally linear theory of electrodynamics. 

States away from global equilibrium are called the thermodynamic branch (Figure 2.2). Systems not far from global equilibrium may be extrapolated around equilibrium state. For systems near equilibrium, linear phenomenological equations may represent the transport and rate processes. The linear nonequilibrium thermodynamics theory determines the dissipation function or the rate of entropy production to describe such systems in the vicinity of equilibrium. This theory is particularly useful to describe coupled phenomena, and quantify the level of coupling in physical, chemical, and biological systems without detailed process mechanisms. 

The formulation of linear nonequilibrium thermodynamics is based on the combination of the first and second laws of thermodynamics with the balance equations including the entropy balance. These equations allow additional effects and processes to be taken into account. The linear nonequilibrium thermodynamics approach is widely recognized as a useful phenomenological theory that describes the coupled transport without the need for the examination of the detailed coupling mechanisms of complex processes. 

Researchers have examined the creep and creep recovery of textile fibers extensively (13-21). For example, Hunt and Darlington (16, 17) studied the effects of temperature, humidity, and previous thermal history on the creep properties of Nylon 6,6. They were able to explain the shift in creep curves with changes in temperature and humidity. Lead-erman (19) studied the time dependence of creep at different temperatures and humidities. Shifts in creep curves due to changes in temperature and humidity were explained with simple equations and convenient shift factors. Morton and Hearle (21) also examined the dependence of fiber creep on temperature and humidity. Meredith (20) studied many mechanical properties, including creep of several generic fiber types. Phenomenological theory of linear viscoelasticity of semicrystalline polymers has been tested with creep measurements performed on textile fibers (18). From these works one can readily appreciate that creep behavior is affected by many factors on both practical and theoretical levels. 

Time constants are related to the relaxation times and can be found in equations based on mechanical models (phenomenological approaches), in constitutive equations (empirical or semiempirical) for viscoelastic fluids that are based on either molecular theories or continuum mechanics. Equations based on mechanical models are covered in later sections, particularly in the treatment of creep-compliance studies while the Bird-Leider relationship is an example of an empirical relationship for viscoelastic fluids. 

Cation, anion, and water transport in ion-exchange membranes have been described by several phenomenological solution-diffusion models and electrokinetic pore-flow theories. Phenomenological models based on irreversible thermodynamics have been applied to cation-exchange membranes, including DuPont s Nafion perfluorosulfonic acid membranes [147, 148]. These models view the membrane as a black box and membrane properties such as ionic fluxes, water transport, and electric potential are related to one another without specifying the membrane structure and molecular-level mechanism for ion and solvent permeation. For a four-component system (one mobile cation, one mobile anion, water, and membrane fixed-charge sites), there are three independent flux equations (for cations, anions, and solvent species) of the form... 

Kinetic theory interprets the phenomenological laws of transport in gases on the basis of a single mechanism, and expresses the values of kj, rj, and D in terms of the mean free path, the density, and the average velocity of the molecules. The equations are... 

In the present conribution, we develop a continuum-based model to describe experimentally observable interphases in thin adhesive films. The model is based on an extended contiuum theory, i.e. the mechanical behaviour in these interphases is captured by an additional field equation. The introduced scalar order parameter models the microscopical mechanical properties of the film phenomenologically. 

To be more definite, the mass action law is a postulate in the phenomenological theory of chemical reaction kinetics. In the golden age of the quantum, chemistry seemed to be reducible to (micro)physics The underlying physical laws for the mathematical theory of a large part of physics and the whole of chemistry are thus completely known, and the diflBculty is only that exact application of these laws leads to equations much too complicated to be soluble (Dirac, 1929). As was clearly shown by Golden (1969) the treatment of chemical reactions needs additional requirements, even at the level of quantum statistical mechanics. The broad-minded book of Primas (1983), in which the author deeply analyses why chemistry cannot be reduced to quantum mechanics is strongly recommended. 

Once we have determined the detail mechanisms of HC thermal cracking, it is important to link the atomistic, elemental reactions to the overall petroleum and natural gas generation. One of the common questions is how to compare the calculated activation energies with the measured ones. From atomic theory, an activation energy is the energy difference between the reactant and transition state of an elementary reaction. It is directly linked to the nature of the chemical bond in a molecular system. From a phenomenological approach, activation energy is derived from the classical Arrhenius equation ... 

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