Transient time dependence

While this bound is not a particularly strong one and convergence is generally faster in practice [goles90], it does clearly point out the important fact that transient times are linearly bounded by the lattice size n. Notice that this is not true of more general classes of matrices, even those of the preceding section that are both symmetric and integer-valued. Equation 5.140 shows that the transient time depends on both A and 26 — Al if both A and b are arbitrary (save, perhaps, for A s symmetry), there is of course no particular reason to expect t to be linearly... 

These equations can be solved numerically with a computer, without making any approximations. Naturally all the involved kinetic parameters need to be either known or estimated to give a complete solution capable of describing the transient (time dependent) kinetic behavior of the reaction. However, as with any numerical solution we should anticipate that stability problems may arise and, if we are only interested in steady state situations (i.e. time independent), the complete solution is not the route to pursue. 

While it is not clear how the constant frequency low field dielectric relaxation measurements mentioned above should be applied to reactions in liquids, save for a complete time-dependent theory of liquids, these effects are very significant. At short times (<10ps) the effective Onsager distance may be 20 nm, even in methanol or ethanol, but over the next two or three decades of time reduce to more nearly 2 nm. Such a change can reduce the rate of reaction much more rapidly than that which occurs by decay of the transient time dependence discussed in the previous sub-section. 

Pick s second law of diffusion deals with the diffiisional transport of matter under transient (time-dependent) conditions. Transient means that the concentration profile of the diffusing species varies as a function of time ... 

The kinetic observations combined with quantum yields have been used to determine rate constants for the various steps. Some data from both studies are given in Table 8.2. The results show some variation, especially with regard to and k f.. A transient time-dependent signal was not observed for CO dissociation, although CO dissociation has a high quantum yield.This could be explained by a larger for CO,... 

Once in a while, polymer systems will falsely appear to be thixotropic or rheopectic. Careful checking (including before and after molecular weight determinations) invariably shows that the phenomenon is not reversible and is due to degradation or crosslinking of the polymer when in the viscometer for long periods of time, particularly at elevated temperatures. Other transient time-dependent effects in polymers are due to elasticity, and will be considered later, but for chemically stable polymer melts or solutions, the steady-state viscous properties are time independent. We treat only such systems from here on. 

Thermal power plant components operated at high temperatures (>500°C) and pressures, such as superheater headers, steamline sections and Y-junctions, deserve great attention for both operation safety and plant availability concerns. In particular, during plant operation transients -startups, shutdowns or load transients - the above components may undergo high rates of temperature / pressure variations and, consequently, non-negligible time-dependent stresses which, in turn, may locally destabilize existing cracks and cause the release of acoustic emission. 

The transmission coefficient Cl (Qj,t), considering transient (broadband) sources, is time-dependent and therefore accounts for the possible pulse deformation in the refraction process. It also takes account of the quantity actually computed in the solid (displacement, velocity potential,...) and the possible mode-conversion into shear waves and is given by... 

It is important to recognize that the time-dependent behaviour of tire correlation fimction during the molecular transient time seen in figure A3.8.2 has an important origin [7, 8]. This behaviour is due to trajectories that recross the transition state and, hence, it can be proven [7] that the classical TST approximation to the rate constant is obtained from A3.8.2 in the t —> 0 limit ... 

The elastic and viscoelastic properties of materials are less familiar in chemistry than many other physical properties hence it is necessary to spend a fair amount of time describing the experiments and the observed response of the polymer. There are a large number of possible modes of deformation that might be considered We shall consider only elongation and shear. For each of these we consider the stress associated with a unit strain and the strain associated with a unit stress the former is called the modulus, the latter the compliance. Experiments can be time independent (equilibrium), time dependent (transient), or periodic (dynamic). Just to define and describe these basic combinations takes us into a fair amount of detail and affords some possibilities for confusion. Pay close attention to the definitions of terms and symbols. 

The analysis of steady-state and transient reactor behavior requires the calculation of reaction rates of neutrons with various materials. If the number density of neutrons at a point is n and their characteristic speed is v, a flux effective area of a nucleus as a cross section O, and a target atom number density N, a macroscopic cross section E = Na can be defined, and the reaction rate per unit volume is R = 0S. This relation may be appHed to the processes of neutron scattering, absorption, and fission in balance equations lea ding to predictions of or to the determination of flux distribution. The consumption of nuclear fuels is governed by time-dependent differential equations analogous to those of Bateman for radioactive decay chains. The rate of change in number of atoms N owing to absorption is as follows ... 

In a foam where the films ate iaterconnected the related time-dependent Marangoni effect is mote relevant. A similar restoring force to expansion results because of transient decreases ia surface concentration (iacteases ia surface tension) caused by the finite rate of surfactant adsorption at the surface. 

Time-Dependent Cascade Behavior. The period of time during which a cascade must be operated from start-up until the desired product material can be withdrawn is called the equiUbrium time of the cascade. The equiUbrium time of cascades utilizing processes having small values of a — 1 is a very important quantity. Often a cascade may prove to be quite impractical because of an excessively long equiUbrium time. An estimate of the equihbrium time of a cascade can be obtained from the ratio of the enriched inventory of desired component at steady state, JT, to the average net upward transport of desired component over the entire transient period from start-up to steady state, T . In equation form this definition can be written as... 

Classification Process simulation refers to the activity in which mathematical models of chemical processes and refineries are modeled with equations, usually on the computer. The usual distinction must be made between steady-state models and transient models, following the ideas presented in the introduction to this sec tion. In a chemical process, of course, the process is nearly always in a transient mode, at some level of precision, but when the time-dependent fluctuations are below some value, a steady-state model can be formulated. This subsection presents briefly the ideas behind steady-state process simulation (also called flowsheeting), which are embodied in commercial codes. The transient simulations are important for designing startup of plants and are especially useful for the operating of chemical plants. 

Many transient flows of liquids may be analyzed by using the full time-dependent equations of motion for incompressible flow. However, there are some phenomena that are controlled by the small compressibility of liquids. These phenomena are generally called hydraulic transients. 

This is an old, familiar analysis that applies to any continuous culture with a single growth-limiting nutrient that meets the assumptions of perfect mixing and constant volume. The fundamental mass balance equations are used with the Monod equation, which has no time dependency and should be apphed with caution to transient states where there may be a time lag as [L responds to changing S. At steady state, the rates of change become zero, and [L = D. Substituting ... 

In the direct insertion technique, the sample (liquid or powder) is inserted into the plasma in a graphite, tantalum, or tungsten probe. If the sample is a liquid, the probe is raised to a location just below the bottom of the plasma, until it is dry. Then the probe is moved upward into the plasma. Emission intensities must be measured with time resolution because the signal is transient and its time dependence is element dependent, due to selective volatilization of the sample. The intensity-time behavior depends on the sample, probe material, and the shape and location of the probe. The main limitations of this technique are a time-dependent background and sample heterogeneity-limited precision. Currently, no commercial instruments using direct sample insertion are available, although both manual and h ly automated systems have been described. ... 

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