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Mechanism diffusion theory

Combustion models which consider the thickness of the reaction zone usually accentuate cither heat conduction mechanisms (thermal theory) or the diffusion mechanisms (diffusion theory) and the models are of necessity of limited value. Simpler models in which the reaction zone or flame front is considered to be an infinitesimally thin discontinuity in the flow, while not simulating exactly the observed conditions, allow the model to be of more general utility and many combustion phenomena become easier to understand because of this simplification. It is the latter approach which is discussed first in this paper—i.e., the combustion process is regarded as a wave phenomenon. [Pg.70]

The mechanisms of adhesion are explained by four main theories mechanical theory, adsorption theory, diffusion theory, and electrostatic theory. [Pg.822]

The molecular weight (M) dependence of the steady (stationary) primary nucleation rate (I) of polymers has been an important unresolved problem. The purpose of this section is to present a power law of molecular weight of I of PE, I oc M-H, where H is a constant which depends on materials and phases [20,33,34]. It will be shown that the self-diffusion process of chain molecules controls the Mn dependence of I, while the critical nucleation process does not. It will be concluded that a topological process, such as chain sliding diffusion and entanglement, assumes the most important role in nucleation mechanisms of polymers, as was predicted in the chain sliding diffusion theory of Hikosaka [14,15]. [Pg.155]

If these conditions are not satisfied, some process will be involved to prevent accumulation of the intermediates at the interface. Two possibilities are at hand, viz. transport by diffusion into the solution or adsorption at the electrode surface. In the literature, one can find general theories for such mechanisms and theories focussed to a specific electrode reaction, e.g. the hydrogen evolution reaction [125], the reduction of oxygen [126] and the anodic dissolution of metals like iron and nickel [94]. In this work, we will confine ourselves to outline the principles of the subject, treating only the example of two consecutive charge transfer processes O + n e = Z and Z 4- n2e — R. [Pg.300]

The so-called diffusion theories of flame propagation, as exemplified by the work of Tanford and Pease 38), emphasize the transport of mass, in that concentration of an active radical is assumed to be the rate-controlling property. Its use seems to be fairly limited in that only a few specific reactions have been successfully studied with this theory. What is more interesting, however, is that this theory forms the counterpart to the thermal theory. These two extreme views bracket the actual case, and their study allows a consideration of each of two of the basic flame mechanisms, unencumbered by the other. Actual deflagration depends on both the transport of heat and the transport of mass, and a successful theory should contain both phenomena. [Pg.77]

There are two arenas for describing diffusion in materials, macroscopic and microscopic. Theories of macroscopic diffusion provide a framework to understand particle fluxes and concentration profiles in terms of phenomenological coefficients and driving forces. Microscopic diffusion theories provide a framework to understand the physical basis of the phenomenological coefficients in terms of atomic mechanisms and particle jump frequencies. [Pg.22]

The pure compound rate constants were measured with 20-28 mesh catalyst particles and reflect intrinsic rates (—i.e., rates free from diffusion effects). Estimated pore diffusion thresholds are shown for 1/8-inch and 1/16-inch catalyst sizes. These curves show the approximate reaction rate constants above which pore diffusion effects may be observed for these two catalyst sizes. These thresholds were calculated using pore diffusion theory for first-order reactions (18). Effective diffusivities were estimated using the Wilke-Chang correlation (19) and applying a tortuosity of 4.0. The pure compound data were obtained by G. E. Langlois and co-workers in our laboratories. Product yields and suggested reaction mechanisms for hydrocracking many of these compounds have been published elsewhere (20-25). [Pg.129]

The electron transport mechanism in mesoporous Ti02 film is modeled mainly by using diffusion theory, except in the report by Augustinski et al.,45) who proposed the explanation that the initial film charging by dye-sensitization, in terms of the self-doping, causes an insulator-metal (Mott) transition in a donor band of Ti02, accompanied by a sharp rise in conductivity of the nanoparticles. [Pg.174]

J.H. Petropoulos, Mechanisms and Theories for Sorption and Diffusion of Gases in Polymers, in Polymeric Gas Separation Membranes, D.R. Paul and Y.P. Yampol skii (eds), CRC Press, Boca Raton, FL, pp. 17-82 (1994). [Pg.85]

The theory and the mathematical foundations of KMC date back approximately for 40 years and saw widespread application since then.90-94 Apart from the elucidation of complex reaction mechanisms diffusion and relaxation processes have been modelled with it. In the field of NMR spectroscopy, it has been used, for example, for the evaluation of DOSY spectra95-98 and relaxation models.99 100... [Pg.183]

Agutter PS, Malone PC, Wheatley DN. Intracellular transport 39. mechanisms a critique of diffusion theory. J. Theor. Biol. 1995 176 261-272. [Pg.2092]

While an understanding of the molecular processes at the fuel cell electrodes requires a quantum mechanical description, the flows through the inlet channels, the gas diffusion layer and across the electrolyte can be described by classical physical theories such as fluid mechanics and diffusion theory. The equivalent of Newton s equations for continuous media is an Eulerian transport equation of the form... [Pg.149]

A related matter concerns the physical mechanism by which radicals (primary or oligomeric) are acquired by the reaction loci. One possibility, first proposed by Garden (1968) and subsequently developed by Fitch and Tsai (1971), is that capture occurs by a collision mechanism. In this case, the rate of capture is proportional to, inter alia, the surface area of the particle. Thus, if the size of the reaction locus in a compartmentalized free-radical polymerization varies, then a should be proportional to r, where r is the radius of the locus. A second possibility (Fitch, I973) is that capture occurs by a diffusion mechanism. In this case, the rate of capture is approximatdy proportional to r rather than to r. A fairly extensive literature now exists concerning this matter (see, e.g., Ugelstad and Hansen, 1976, 1978. 1979a, b). The consensus of present opinion seems to favor the diffusion theory rather than the collision theory. The nature of the capture mechanism is not. however, relevant to the theory discussed in this chapter. It is merely necessary to note that both mechanisms predict that the rate of capture will depend on the size of the reaction locus constancy of a therefore implies that the size of the locus does not change much as a consequence of polymerization. [Pg.154]

In his monograph. Clarke (32) makes extensive use of graph theory to study the stability of complex reaction mechanisms. Graph theory is also used to describe kinetics of chemical reactions complicated by diffusion of reagents into solid catalysts (33). [Pg.28]

Thermodynamics of this situation at equilibrium Metallurgy of defects on metal surfaces Crystallography of surface Quantum mechanics of transfer of electrons through barrier at interface Pick s second law diffusion theory of time dependence of concentration... [Pg.69]

Note that nowhere in the spatiotemporal postulate is the term transition state used. This term is not used because the transition state, for reasons just mentioned, is considered peripheral to time and distance. Perhaps the love affair that physical organic chemists are having with transition structure is overly passionate. Diffusion theory, not quantum mechanics, may be the key to future progress. [Pg.211]

Another attempt to combine the diffusion theory with transfer mechanisms was made by Fainerman et al. (1987). He derived approximate solutions by averaging the rate of the two different processes in the following way... [Pg.114]

A full exposition of diffusion theory and diffusion mechanisms is beyond the scope of this chapter but the reader is referred to McDougall and Harrison (1999). Many observations show that argon diffusion rates in natural and laboratory experiments follow an Arrhenius relationship. There are however, important departures where fast track diffusion dominates in nature (Kramar et al. 2001 Reddy et al. 2001b) and laboratory analysis of hydrous minerals (Gaber et al. 1988 Lee 1993 Lo et al. 2000). Even in natural cases which might earlier have been identified as volume diffusion effects, careful compositional control shows that phase mixing can mimic argon loss profiles (e g., Onstott and Peacock 1987 Wartho 1995). In such cases the data can not easily be inverted to produce thermal histories. [Pg.795]


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See also in sourсe #XX -- [ Pg.76 ]




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