Kinetics local

Kinetics, local transport effects, and global contacting patterns... 

Limit A corresponds to conditions in the reformer where kinetics allow methane to decompose into carbon instead of reacting with steam, even if thermodynamics predict no carbon formation. Carbon formation is then a question of kinetics, local process conditions and reformer design. With proper reformer design, industrial operation at H2O/CH4 = 1.0 -1.1 depending on pressure is possible (Rostrup-Nielsen, J.R. 1988c). 

Model food emulsion Crystallization kinetics Localized spectroscopy... 

In general, it seems more reasonable to suppose that in chemisorption specific sites are involved and that therefore definite potential barriers to lateral motion should be present. The adsorption should therefore obey the statistical thermodynamics of a localized state. On the other hand, the kinetics of adsorption and of catalytic processes will depend greatly on the frequency and nature of such surface jumps as do occur. A film can be fairly mobile in this kinetic sense and yet not be expected to show any significant deviation from the configurational entropy of a localized state. 

General first-order kinetics also play an important role for the so-called local eigenvalue analysis of more complicated reaction mechanisms, which are usually described by nonlinear systems of differential equations. Linearization leads to effective general first-order kinetics whose analysis reveals infomiation on the time scales of chemical reactions, species in steady states (quasi-stationarity), or partial equilibria (quasi-equilibrium) [M, and ]. 

As the kinetic energy involved in the system goes higher, the interaction of energetic particles is more and more localized near the nuclei. When the interaction distance is much smaller than interatomic distances in the system, the BCA is valid ... 

In one of the earliest DFT models, the Thomas-Fermi theory, the kinetic energy of an atom or a molecule is approximated using the above type of treatment on a local level. That is, for each volume element in r space, one... 

The key to this method is thus to act with each operator (exponential of the potential or kinetic tenn) in the representation (coordinate or momentum grid) in which it is local [M,... 

An alternative way of deriving the BET equation is to express the problem in statistical-mechanical rather than kinetic terms. Adsorption is explicitly assumed to be localized the surface is regarded as an array of identical adsorption sites, and each of these sites is assumed to form the base of a stack of sites extending out from the surface each stack is treated as a separate system, i.e. the occupancy of any site is independent of the occupancy of sites in neighbouring stacks—a condition which corresponds to the neglect of lateral interactions in the BET model. The further postulate that in any stack the site in the ith layer can be occupied only if all the underlying sites are already occupied, corresponds to the BET picture in which condensation of molecules to form the ith layer can only take place on to molecules which are present in the (i — l)th layer. 

One of the most significant sources of change in isotope ratios is caused by the small mass differences between isotopes and their effects on the physical properties of elements and compounds. For example, ordinary water (mostly Ej O) has a lower density, lower boiling point, and higher vapor pressure than does heavy water (mostly H2 0). Other major changes can occur through exchange processes. Such physical and kinetic differences lead to natural local fractionation of isotopes. Artificial fractionation (enrichment or depletion) of uranium isotopes is the basis for construction of atomic bombs, nuclear power reactors, and depleted uranium weapons. 

Compressible Vlow. The flow of easily compressible fluids, ie, gases, exhibits features not evident in the flow of substantially incompressible fluid, ie, Hquids. These differences arise because of the ease with which gas velocities can be brought to or beyond the speed of sound and the substantial reversible exchange possible between kinetic energy and internal energy. The Mach number, the ratio of the gas velocity to the local speed of sound, plays a central role in describing such flows. 

The defects generated in ion—soHd interactions influence the kinetic processes that occur both inside and outside the cascade volume. At times long after the cascade lifetime (t > 10 s), the remaining vacancy—interstitial pairs can contribute to atomic diffusion processes. This process, commonly called radiation enhanced diffusion (RED), can be described by rate equations and an analytical approach (27). Within the cascade itself, under conditions of high defect densities, local energy depositions exceed 1 eV/atom and local kinetic processes can be described on the basis of ahquid-like diffusion formalism (28,29). 

The following mechanisms in corrosion behavior have been affected by implantation and have been reviewed (119) (/) expansion of the passive range of potential, (2) enhancement of resistance to localized breakdown of passive film, (J) formation of amorphous surface alloy to eliminate grain boundaries and stabilize an amorphous passive film, (4) shift open circuit (corrosion) potential into passive range of potential, (5) reduce/eliminate attack at second-phase particles, and (6) inhibit cathodic kinetics. 

Traditional chemical kinetics uses notation that is most satisfactory in two cases all components are gases with or without an inert buffer gas, or all components are solutes in a Hquid solvent. In these cases, molar concentrations represented by brackets, are defined, which are either constant throughout the system or at least locally meaningful. The reaction quotient Z is defined as... 

The distribution of current (local rate of reaction) on an electrode surface is important in many appHcations. When surface overpotentials can also be neglected, the resulting current distribution is called primary. Primary current distributions depend on geometry only and are often highly nonuniform. If electrode kinetics is also considered, Laplace s equation stiU appHes but is subject to different boundary conditions. The resulting current distribution is called a secondary current distribution. Here, for linear kinetics the current distribution is characterized by the Wagner number, Wa, a dimensionless ratio of kinetic to ohmic resistance. 

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