Kinetic dispersive model

The observed nonexponential character of the decays observed in films containing >70 wt% PVC (or in the PMMA films) was ascribed to the existence of a distribution of unimolecular combination rates, apparently caused by the dependence of the rate constants on the properties of different local environments in the polymer films. This effect was quantified according to a kinetic dispersive model, which predicts... 

Most biochemical reactors operate with dilute reactants so that they are nearly isothermal. This means that the packed-bed model of Section 9.1 is equivalent to piston flow. The axial dispersion model of Section 9.3 can be applied, but the correction to piston flow is usually small and requires a numerical solution if Michaehs-Menten kinetics are assumed. 

Numerical solutions to equation 11.2.9 have been obtained for reaction orders other than unity. Figure 11.11 summarizes the results obtained by Levenspiel and Bischoff (18) for second-order kinetics. Like the chart for first-order kinetics, it is most appropriate for use when the dimensionless dispersion group is small. Fan and Bailie (19) have solved the equations for quarter-order, half-order, second-order, and third-order kinetics. Others have used perturbation methods to arrive at analogous results for the dispersion model (e.g. 20,21). 

The dispersion model has the advantage in that all correlations for flow in real reactors invariably use that model. On the other hand the tanks-in-series model is simple, can be used with any kinetics, and it can be extended without too much difficulty to any arrangement of compartments, with or without recycle. 

The ideal model and the equilibrium-dispersive model are the two important subclasses of the equilibrium model. The ideal model completely ignores the contribution of kinetics and mobile phase processes to the band broadening. It assumes that thermodynamics is the only factor that influences the evolution of the peak shape. We obtain the mass balance equation of the ideal model if we write > =0 in Equation 10.8, i.e., we assume that the number of theoretical plates is infinity. The ideal model has the advantage of supplying the thermodynamical limit of minimum band broadening under overloaded conditions. 

In the lumped kinetic model, various kinetic equations may describe the relationship between the mobile phase and stationary phase concentrations. The transport-dispersive model, for instance, is a linear film driving force model in which a first-order kinetics is assumed in the following form ... 

To quantify this treatment of migration as influenced by kinetics, a model has been developed in which instantaneous or local equilibrium is not assumed. The model is called the Argonne Dispersion Code (ARDISC) ( ). In the model, adsorption and desorption are treated independently and the rates for adsorption and desorption are taken into account. The model treats one dimensional flow and assumes a constant velocity of solution through a uniform homogeneous media. 

First we introduce the reader to the principles of such problems and their solution in Sections 5.1.2 and 5.1.2. As an educational tool we use the classical axial dispersion model for finding the steady state of one-dimensional tubular reactors. The model is formulated for the isothermal case with linear kinetics. This case lends itself to an otherwise rare analytical solution that is given in the book. From this example our students can understand many characteristics of such systems. 

Mass transport in laminar flow is dominated by diffusion and by the laminar velocity profile. This combined effect is known as dispersion and the underlying model for the theoretical derivation of a kinetic study had to be derived from the dispersion model, which Taylor [91] and Aris [92] developed. Taylor concluded that in laminar flow the speed of an inert tracer impulse initially given to a channel will have the same speed as the steady laminar carrier gas flow originally prevailing in this channel. 

Cameron, D. R., and Klute, A. (1977). Convective-dispersive solute transport with a combined equilibrium and kinetic adsorption model. Water Res. 13, 183-188. 

The comparison of kinetic sorption models presented here was made possible by the use of the mixing-cell dynamic technique, which eliminates the masking effects of hydraulic dispersion. 

Both the tank in series (TIS) and the dispersion plug flow (DPF) models require tracer tests for their accurate determination. However, the TIS model is relatively simple mathematically and thus can be used with any kinetics. Also, it can be extended to any configuration of compartments with or without recycle. The DPF axial dispersion model is complex and therefore gives significantly different results for different choices of boundary conditions. 

Wilson and Liu showed that both location and travel time probabilities can be calculated directly, using a backward-in-time version of traditional continuum advection-dispersion modeling. In addition, they claimed that by choosing the boundary conditions properly, the method can be readily generalized to include linear adsorption with kinetic effects and 1st order decay. An extension of their study for a 2D heterogeneous aquifer was reported in Liu and Wilson [39]. The results for travel time probability are in very close agreement with the simulation results from traditional forward-in-time methods. 

Vaia et al. [12] have observed that the kinetics of intercalation even under quiescent conditions (absence of external shear) are quite rapid. Using in-situ XRD (which monitors the angular shift and integrated intensity of the silicate reflections, Fig. 9) they studied the intercalation kinetics of model polymers (mono-disperse polystyrene) in organically modified fluorohectorite. 

In this report, a kinetic model based on the solid film linear driving force assumption is used. Unlike the equilibrium-dispersive model, which lumps all transfer and kinetic effects into an effective dispersion term, the kinetic model is effective when the column efficiency is low and the effects of column kinetics are significant. 

A few reactor models have recently been proposed (30-31) for prediction of integral trickle-bed reactor performance when the gaseous reactant is limiting. Common features or assumptions include i) gas-to-liquid and liquid-to-solid external mass transfer resistances are present, ii) internal particle diffusion resistance is present, iii) catalyst particles are completely externally and internally wetted, iv) gas solubility can be described by Henry s law, v) isothermal operation, vi) the axial-dispersion model can be used to describe deviations from plug-flow, and vii) the intrinsic reaction kinetics exhibit first-order behavior. A few others have used similar assumptions except were developed for nonlinear kinetics (27—28). Only in a couple of instances (7,13, 29) was incomplete external catalyst wetting accounted for. 

To couple the intrinsic coke burning kinetics described in Section II.B with gas and solid flow models, the simplest approach is provided by the one-dimensional solid dispersion model based on following assumptions ... 

This chapter discusses four methods of gas phase ceramic powder synthesis by flames, fiunaces, lasers, and plasmas. In each case, the reaction thermodynamics and kinetics are similar, but the reactor design is different. To account for the particle size distribution produced in a gas phase synthesis reactor, the population balance must account for nudeation, atomistic growth (also called vapor condensation) and particle—particle segregation. These gas phase reactors are real life examples of idealized plug flow reactors that are modeled by the dispersion model for plve flow. To obtain narrow size distribution ceramic powders by gas phase synthesis, dispersion must be minimized because it leads to a broadening of the particle size distribution. Finally the gas must be quickly quenched or cooled to freeze the ceramic particles, which are often liquid at the reaction temperature, and thus prevent further aggregation. 

Roberts, M.S. Rowland, M. A dispersion model of hepatic ehmination 3. Application to metabolite formation and ehmination kinetics. J. Pharmacokinet. Biopharm. 1986, 14, 289-307. 

This part demonstrates how deterministic models of impedance response can be developed from physical and kinetic descriptions. When possible, correspondence is drawn between hypothesized models and electrical circuit analogues. The treatment includes electrode kinetics, mass transfer, solid-state systems, time-constant dispersion, models accounting for two- and three-dimensional interfaces, generalized transfer functions, and a more specific example of a transfer-function tech-nique.in which the rotation speed of a disk electrode is modulated. 

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