Diffusivities intrinsic

Self-diffusivity tracer diffusivity intrinsic diffusivity Thickness... 

All these factors are functions of the concentration of the chemical species, temperature and pressure of the system. At constant diffu-sionai resistance, the increase in the rate of chemical reaction decreases the effectiveness factor while al a constant intrinsic rate of reaction, the increase of the diffusional resistances decreases the effectiveness factor. Elnashaie et al. (1989a) showed that the effect of the diffusional resistances and the intrinsic rate of reactions are not sufficient to explain the behaviour of the effectiveness factor for reversible reactions and that the effect of the equilibrium constant should be introduced. They found that the effectiveness factor increases with the increase of the equilibrium constants and hence the behaviour of the effectiveness factor should be explained by the interaction of the effective diffusivities, intrinsic rates of reaction as well as the equilibrium constants. The equations of the dusty gas model for the steam reforming of methane in the porous catalyst pellet, are solved accurately using the global orthogonal collocation technique given in Appendix B. Kinetics and other physico-chemical parameters for the steam reforming case are summarized in Appendix A. 

Lorenz [100] combined diffusion, intrinsic adsorption, and surface association as separate contributions and developed the first model, which attributes a slow (dynamic) adsorption step to the 2D association of adsorbed species at an electrochemical interface. 

The propagation rate constant kp and the termination rate constant are calculated as functions of free volume, following a model developed by Anseth and Bowman." In that model, the two constants are calculated by summing different resistances for diffusion, intrinsic reaction, and reaction— diffusion (for termination). 

Figure 6.17.14 Calculated influence of modified residence time on the concentration of menthol in the absence of pore diffusion (intrinsic kinetics) and for two industrially relevant particle sizes (175°C,...

When one chooses next a more diffuse intrinsic profile such as an exponential profile with a decay length equal to the bulk correlation length K becomes simply ... 

At first glance, the contents of Chap. 9 read like a catchall for unrelated topics. In it we examine the intrinsic viscosity of polymer solutions, the diffusion coefficient, the sedimentation coefficient, sedimentation equilibrium, and gel permeation chromatography. While all of these techniques can be related in one way or another to the molecular weight of the polymer, the more fundamental unifying principle which connects these topics is their common dependence on the spatial extension of the molecules. The radius of gyration is the parameter of interest in this context, and the intrinsic viscosity in particular can be interpreted to give a value for this important quantity. The experimental techniques discussed in Chap. 9 have been used extensively in the study of biopolymers. 

This chapter contains one of the more diverse assortments of topics of any chapter in the volume. In it we discuss the viscosity of polymer solutions, especially the intrinsic viscosity the diffusion and sedimentation behavior of polymers, including the equilibrium between the two and the analysis of polymers by gel permeation chromatography (GPC). At first glance these seem to be rather unrelated topics, but features they all share are a dependence on the spatial extension of the molecules in solution and applicability to molecular weight determination. 

This concludes our discussion of the viscosity of polymer solutions per se, although various aspects of the viscous resistance to particle motion continue to appear in the remainder of the chapter. We began this chapter by discussing the intrinsic viscosity and the friction factor for rigid spheres. Now that we have developed the intrinsic viscosity well beyond that first introduction, we shall do the same (more or less) for the friction factor. We turn to this in the next section, considering the relationship between the friction factor and diffusion. 

A = 4.05 X lO " cm/(s-kPa)(4.1 X 10 cm/(s-atm)) and = 1.3 x 10 cm/s (4)//= 1 mPa-s(=cP), NaCl diffusivity in water = 1.6 x 10 cm /s, and solution density = 1 g/cm . Figure 4 shows typical results of this type of simulation of salt water permeation through an RO membrane. Increasing the Reynolds number in Figure 4a decreases the effect of concentration polarization. The effect of feed flow rate on NaCl rejection is shown in Figure 4b. Because the intrinsic rejection, R = 1 — Cp / defined in terms of the wall concentration, theoretically R should be independent of the Reynolds... 

When a relatively slow catalytic reaction takes place in a stirred solution, the reactants are suppHed to the catalyst from the immediately neighboring solution so readily that virtually no concentration gradients exist. The intrinsic chemical kinetics determines the rate of the reaction. However, when the intrinsic rate of the reaction is very high and/or the transport of the reactant slow, as in a viscous polymer solution, the concentration gradients become significant, and the transport of reactants to the catalyst cannot keep the catalyst suppHed sufficientiy for the rate of the reaction to be that corresponding to the intrinsic chemical kinetics. Assume that the transport of the reactant in solution is described by Fick s law of diffusion with a diffusion coefficient D, and the intrinsic chemical kinetics is of the foUowing form... 

In the former case, the rate is independent of the diffusion coefficient and is determined by the intrinsic chemical kinetics in the latter case, the rate is independent of the rate constant k and depends on the diffusion coefficient the reaction is then diffusion controlled. This is a different kind of mass transport influence than that characteristic of a reactant from a gas to ahquid phase. 

Figure 10 shows that Tj is a unique function of the Thiele modulus. When the modulus ( ) is small (- SdSl), the effectiveness factor is unity, which means that there is no effect of mass transport on the rate of the catalytic reaction. When ( ) is greater than about 1, the effectiveness factor is less than unity and the reaction rate is influenced by mass transport in the pores. When the modulus is large (- 10), the effectiveness factor is inversely proportional to the modulus, and the reaction rate (eq. 19) is proportional to k ( ), which, from the definition of ( ), implies that the rate and the observed reaction rate constant are proportional to (1 /R)(f9This result shows that both the rate constant, ie, a measure of the intrinsic activity of the catalyst, and the effective diffusion coefficient, ie, a measure of the resistance to transport of the reactant offered by the pore stmcture, influence the rate. It is not appropriate to say that the reaction is diffusion controlled it depends on both the diffusion and the chemical kinetics. In contrast, as shown by equation 3, a reaction in solution can be diffusion controlled, depending on D but not on k. 

Figure 5.4 The intrinsic conduction electron concentration as a function of temperature and band gap energy together with the values of the ionic diffusion coefficient which would provide an equal contribution to the conduction...

As we saw in Chapter 10, the stress required to make a crystalline material deform plastically is that needed to make the dislocations in it move. Their movement is resisted by (a) the intrinsic lattice resistance and (b) the obstructing effect of obstacles (e.g. dissolved solute atoms, precipitates formed with undissolved solute atoms, or other dislocations). Diffusion of atoms can unlock dislocations from obstacles in their path, and the movement of these unlocked dislocations under the applied stress is what leads to dislocation creep. 

The heart of the energy-dispersive spectrometer is a diode made from a silicon crystal with lithium atoms diffiised, or drifted, from one end into the matrix. The lithium atoms are used to compensate the relatively low concentration of grown-in impurity atoms by neutralizing them. In the diffusion process, the central core of the silicon will become intrinsic, but the end away from the lithium will remain p-type and the lithium end will be n-type. The result is a p-i-n diode. (Both lithium-... 

Many inorganic solids lend themselves to study by PL, to probe their intrinsic properties and to look at impurities and defects. Such materials include alkali-halides, semiconductors, crystalline ceramics, and glasses. In opaque materials PL is particularly surface sensitive, being restricted by the optical penetration depth and carrier diffusion length to a region of 0.05 to several pm beneath the surface. 

The diffusion stage, characterized by H(t), will be discussed in detail with respect to the instantaneous wetting condition. However, in the presence of a time dependent wetting function (p(t), Eq. 2.1, we see from Eig. 2 that diffusion will have progressed to different extents in different areas of the interface. If the intrinsic diffusion function, H(t) as given by Eq. 1.1 does not change its nature with time due to the other stages, then the net diffusion, H"(t) can be expressed as the convolution product... 

Some rubber base adhesives need vulcanization to produce adequate ultimate strength. The adhesion is mainly due to chemical interactions at the interface. Other rubber base adhesives (contact adhesives) do not necessarily need vulcanization but rather adequate formulation to produce adhesive joints, mainly with porous substrates. In this case, the mechanism of diffusion dominates their adhesion properties. Consequently, the properties of the elastomeric adhesives depend on both the variety of intrinsic properties in natural and synthetic elastomers, and the modifying additives which may be incorporated into the adhesive formulation (tackifiers, reinforcing resins, fillers, plasticizers, curing agents, etc.). 

The model is intrinsically irreversible. It is assumed that both dissociation of the dimer and reaction between a pair of adjacent species of different type are instantaneous. The ZGB model basically retains the adsorption-desorption selectivity rules of the Langmuir-Hinshelwood mechanism, it has no energy parameters, and the only independent parameter is Fa. Obviously, these crude assumptions imply that, for example, diffusion of adsorbed species is neglected, desorption of the reactants is not considered, lateral interactions are ignored, adsorbate-induced reconstructions of the surface are not considered, etc. Efforts to overcome these shortcomings will be briefly discussed below. 

In all of these tests, flame acceleration was minimal or absent. Acceleration, when it occurred, was entirely due to intrinsic flame instability, for example, hydrodynamic instability (Istratov and Librovich 1969) or instability due to selective diffusion (Markstein 1964). To investigate whether the flame would accelerate when allowed to propagate over greater distances, tests were carried out in an open-sided test apparatus 45 m long (Harris and Wickens 1989). Flame acceleration was found to be no greater than in the balloon experiments (Table 4.1a). 

Most radicals are transient species. They (e.%. 1-10) decay by self-reaction with rates at or close to the diffusion-controlled limit (Section 1.4). This situation also pertains in conventional radical polymerization. Certain radicals, however, have thermodynamic stability, kinetic stability (persistence) or both that is conferred by appropriate substitution. Some well-known examples of stable radicals are diphenylpicrylhydrazyl (DPPH), nitroxides such as 2,2,6,6-tetramethylpiperidin-A -oxyl (TEMPO), triphenylniethyl radical (13) and galvinoxyl (14). Some examples of carbon-centered radicals which are persistent but which do not have intrinsic thermodynamic stability are shown in Section 1.4.3.2. These radicals (DPPH, TEMPO, 13, 14) are comparatively stable in isolation as solids or in solution and either do not react or react very slowly with compounds usually thought of as substrates for radical reactions. They may, nonetheless, react with less stable radicals at close to diffusion controlled rates. In polymer synthesis these species find use as inhibitors (to stabilize monomers against polymerization or to quench radical reactions - Section 5,3.1) and as reversible termination agents (in living radical polymerization - Section 9.3). 

The production of heat by friction, the passage of heat from one body to another at a lower temperature by conduction or radiation, and the diffusion of material substances, are intrinsically irreversible processes. A process (Carnot s cyclic process) will be described in the next chapter by means of which heat generated by friction may be withdrawn and reconverted into work. 

Copper is intrinsically a better metal than aluminum for the metallization of IC s. Latest developments in MOCVD show that it can be readily deposited without major changes in existing processing equipment. Diffusion problems are minimized and it appears that present barrier materials, such as titanium nitride or titanium-tungsten alloys, should provide adequate diffusion barriers for the copper-silicon couple, certainly up to the highest temperatures presently used in IC s processing (see Ch. 6). The development of CVD copper for semiconductor metallization is on a considerable scale at this time.Clt ]... 

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