Characteristic time scale

A parameter indicating whether viscoelastic effects are important is the Deborah number, which is the ratio of the characteristic relaxation time of the fluid to the characteristic time scale of the flow. For small Deborah numbers, the relaxation is fast compared to the characteristic time of the flow, and the fluid behavior is purely viscous. For veiy large Deborah numbers, the behavior closely resembles that of an elastic solid. 

Here the lattice positions i and j should be adjacent and the -function assures that one of the two lattice positions is occupied and the other one is free, r/j is a characteristic time scale for a diffusion jump. The time-dependence of the average si) is calculated by approximating the higher moments (siSj) [49]. In practice the analysis is rather involved, so we do not give further details here. An important result, for example, is the correction to the Wilson-Frenkel rate (33) at high temperatures ... 

The fact that there are no characteristic length scales immediately implies a similar lack of any characteristic time scales for the fluctuations. Consider the effect of a single perturbation of a random site of a system in the critical state. The perturbation will spread to the neighbors of the site, to the next nearest neighbors, and so on, until, after a time r and a total of / sand slides, the effects will die out. The distribution of the life-times of the avalanches, D t), obeys the power law... 

A particular fluid flow problem must have an associated characteristic length L and characteristic velocity V. These values may be more or less arbitrarily specified, with the only constraint being that they represent some typical scales. For example, if the problem involves a flow past a sphere, L could be the diameter of the sphere and V could be the velocity of the fluid at infinity. The characteristic length and characteristic velocity also fix a characteristic time scale T = L/V. 

In order to exemplify the potential of micro-channel reactors for thermal control, consider the oxidation of citraconic anhydride, which, for a specific catalyst material, has a pseudo-homogeneous reaction rate of 1.62 s at a temperature of 300 °C, corresponding to a reaction time-scale of 0.61 s. In a micro channel of 300 pm diameter filled with a mixture composed of N2/02/anhydride (79.9 20 0.1), the characteristic time-scale for heat exchange is 1.4 lO" s. In spite of an adiabatic temperature rise of 60 K related to such a reaction, the temperature increases by less than 0.5 K in the micro channel. Examples such as this show that micro reactors allow one to define temperature conditions very precisely due to fast removal and, in the case of endothermic reactions, addition of heat. On the one hand, this results in an increase in process safety, as discussed above. On the other hand, it allows a better definition of reaction conditions than with macroscopic equipment, thus allowing for a higher selectivity in chemical processes. 

In Table 1.4, the characteristic time-scales for selected operations are listed. The rate constants for surface and volume reactions are denoted by and respectively. Furthermore, the Sherwood number Sh, a dimensionless mass-transfer coefficient and the analogue of the Nusselt number, appears in one of the expressions for the reaction time-scale. The last column highlights the dependence of z p on the channel diameter d. Apparently, the scale dependence of different operations varies from dy f to (d ). Owing to these different dependences, some op-... 

Table 1.4 Characteristic time-scale and length scale-dependence for selected operations [114],...

In order to examine the nature of the friction coefficient it is useful to consider the various time, space, and mass scales that are important for the dynamics of a B particle. Two important parameters that determine the nature of the Brownian motion are rm = (m/M) /2, that depends on the ratio of the bath and B particle masses, and rp = p/(3M/4ttct3), the ratio of the fluid mass density to the mass density of the B particle. The characteristic time scale for B particle momentum decay is xB = Af/ , from which the characteristic length lB = (kBT/M)i lxB can be defined. In derivations of Langevin descriptions, variations of length scales large compared to microscopic length but small compared to iB are considered. The simplest Markovian behavior is obtained when both rm << 1 and rp 1, while non-Markovian descriptions of the dynamics are needed when rm << 1 and rp > 1 [47]. The other important times in the problem are xv = ct2/v, the time it takes momentum to diffuse over the B particle radius ct, and Tp = cr/Df, the time it takes the B particle to diffuse over its radius. 

Table 8-1. Characteristic time scales of different events in macromolecular systems...

To our knowledge, the first paper devoted to obtaining characteristic time scales of different observables governed by the Fokker-Planck equation in systems having steady states was written by Nadler and Schulten [30]. Their approach is based on the generalized moment expansion of observables and, thus, called the generalized moment approximation (GMA). 

A number of other spectroscopies provide information that is related to molecular structure, such as coordination symmetry, electronic splitting, and/or the nature and number of chemical functional groups in the species. This information can be used to develop models for the molecular structure of the system under study, and ultimately to determine the forces acting on the atoms in a molecule for any arbitrary displacement of the nuclei. According to the energy of the particles used for excitation (photons, electrons, neutrons, etc.), different parts of a molecule will interact, and different structural information will be obtained. Depending on the relaxation process, each method has a characteristic time scale over which the structural information is averaged. Especially for NMR, the relaxation rate may often be slower than the rate constant of a reaction under study. 

To more fully appreciate the equilibrium models, like SCRF theories, and their usefulness and limitations for dynamics calculations we must consider three relevant times, the solvent relaxation time, the characteristic time for solute nuclear motion in the absence of coupling to the solvent, and the characteristic time scale of electronic motion. We treat each of these in turn. 

In hindsight, the primary factor in determining which approach is most applicable to a particular reacting flow is the characteristic time scales of the chemical reactions relative to the turbulence time scales. In the early applications of the CRE approach, the chemical time scales were larger than the turbulence time scales. In this case, one can safely ignore the details of the flow. Likewise, in early applications of the FM approach to combustion, all chemical time scales were assumed to be much smaller than the turbulence time scales. In this case, the details of the chemical kinetics are of no importance, and one is free to concentrate on how the heat released by the reactions interacts with the turbulent flow. More recently, the shortcomings of each of these approaches have become apparent when applied to systems wherein some of the chemical time scales overlap with the turbulence time scales. In this case, an accurate description of both the turbulent flow and the chemistry is required to predict product yields and selectivities accurately. 

Note that Tu(k, t) and Eu k, t) can be used to derive a characteristic time scale for spectral transfer at a given wavenumber Tst(/c, t) defined by... 

By definition, the dissipation range is dominated by viscous dissipation of Kolmogorov-scale vortices. The characteristic time scale rst in (2.74) can thus be taken as proportional to the Kolmogorov time scale rn, and taken out of the integral. This leads to the final form for (2.70),... 

Note that as Re/, goes to infinity with Sc constant, both the turbulent energy spectrum and the scalar energy spectrum will be dominated by the energy-containing and inertial/inertial-convective sub-ranges. Thus, in this limit, the characteristic time scale for scalar variance dissipation defined by (3.55) becomes... 

For a passive scalar, the turbulent flow will be unaffected by the presence of the scalar. This implies that for wavenumbers above the scalar dissipation range, the characteristic time scale for scalar spectral transport should be equal to that for velocity spectral transport tst defined by (2.67), p. 42. Thus, by equating the scalar and velocity spectral transport time scales, we have23 t)... 

Equation (3.82) illustrates the importance of the scalar spectral energy transfer rate in determining the scalar dissipation rate in high-Reynolds-number turbulent flows. Indeed, near spectral equilibrium, 7 (/cd, 0 (like Tu(kDi, 0) will vary on time scales of the order of the eddy turnover time re, while the characteristic time scale of (3.82) is xn <[Pg.99]

Note that in (3.163) the characteristic time scale for scalar-covariance dissipation is... 

As described in Fox (1995), the wavenumber bands are chosen to be as large as possible, subject to die condition that the characteristic time scales decrease as the band numbers increase. This condition is needed to ensure that scalar energy does not pile up at intermediate wavenumber bands. The rate-controlling step in equilibrium spectral decay is then die scalar spectral energy transfer rate (T ) from die lowest wavenumber band. 

Figure 5.1. Closures for the chemical source term can be understood in terms of their relationship to the joint composition PDF. The simplest methods attempt to represent the joint PDF by its (lower-order) moments. At the next level, the joint PDF is expressed in terms of the product of the conditional joint PDF and the mixture-fraction PDF. The conditional joint PDF can then be approximated by invoking the fast-chemistry or flamelet limits, by modeling the conditional means of the compositions, or by assuming a functional form for the PDF. Similarly, it is also possible to assume a functional form for the joint composition PDF. The best method to employ depends strongly on the functional form of the chemical source term and its characteristic time scales.

For elementary chemical reactions, it is sometimes possible to assume that all chemical species reach their chemical-equilibrium values much faster than the characteristic time scales of the flow. Thus, in this section, we discuss how the description of a turbulent reacting flow can be greatly simplified in the equilibrium-chemistry limit by reformulating the problem in terms of the mixture-fraction vector. 

The final term in (A.41) (Daa) is modeled by the product of the inverse of a characteristic time scale for the scalar dissipation range and eau- The characteristic time scale is taken to be proportional to ,2)i)/ u so that the final term has the form Cd 2D/(2)D. The proportionality constant Cd is thus defined by... 

In all studies involving methods based on absorption or scattering of light, X rays, or neutrons, the characteristic time scales on which radiation interacts with the substance are many orders of magnitude shorter than those of atomic motions. Therefore, it is not the motions themselves but the disordering which arises due to molecular dynamics that should be investigated. 

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