Diffusion, facilitated, limits

The effects of substituents on the carbon acidity of 5H-dibenzo[a,d]cyclohepta-triene (suberene) have been studied, and deprotonation has been shown to approach the diffusion controlled limit in acetonitrile solution in the presence of primary amines. However, secondary and tertiary amines facilitate photoreduction of the substrate. 

The different types of diffusion (facilitated versus simple diffusion) can be distinguished because facilitated systems have only a fixed number of sites through which transport occurs, but simple diffusion occurs across the entire surface of the cell. Thus, facilitated transport has a rate which is limited by the number of sites. Researchers attempting to increase the rate by increasing the concentration of transported molecule find that facilitated systems reach a maximum rate than cannot... 

Claus et al. concluded that an ionic liquid is able to modify the active sites facilitating limited reactant diffusion to the active sites which may affect the selectivity comparable to egg-shell-type catalysts. Thus, modification of supported metal catalysts by ILs results in a novel class of solid catalysts on the frontier between homogeneous and heterogeneous catalysis [57]. 

Two distinguishing features of gastrointestinal active and facilitated transport processes are that they are capacity-limited and inhibitable. Passive transcellular solute flux is proportional to mucosal solute concentration (C), where the proportionality constant is the ratio of the product of membrane diffusion coefficient (Dm) and distribution coefficient (Kd) to the length of the transcellular pathway (Lm). 

Slurry Reactors. Slurry reactors are commonly used in situations where it is necessary to contact a liquid reactant or a solution containing the reactant with a solid catalyst. To facilitate mass transfer and effective catalyst utilization, the catalyst is usually suspended in powdered or in granular form. This type of reactor has been used where one of the reactants is normally a gas at the reaction conditions and the second reactant is a liquid, e.g., in the hydrogenation of various oils. The reactant gas is bubbled through the liquid, dissolves, and then diffuses to the catalyst surface. Obviously mass transfer limitations can be quite significant in those instances where three phases (the solid catalyst, and the liquid and gaseous reactants) are present and necessary to proceed rapidly from reactants to products. 

In terms of shape and size, catalysts are typically presented as extrudates (cylindrical, tri-lobes or four-lobes), in sizes of diameters from 0.8 mm to about 1.7 mm and lengths from 3 mm to about 7 mm. The effect of size and shape on operation concerns the pressure drop control, the fluid flow through the bed, the interparticle and intraparticle flow, the diffusion of the fluids from the external surface to the internal surface. The three and four lobes extrudates facilitates diffusion, but they are usually more fragile than the cylindrical extrudates increasing the risk of pressure drop build up. For operation of a trickle bed reactor with heavy feedstocks, for which the diffusion limitations are important, lobed extrudates are preferred. Meanwhile, for vapor phase reactors large cylindrical extrudates are used. 

Acidic micro- and mesoporous materials, and in particular USY type zeolites, are widely used in petroleum refinery and petrochemical industry. Dealumination treatment of Y type zeolites referred to as ultrastabilisation is carried out to tune acidity, porosity and stability of these materials [1]. Dealumination by high temperature treatment in presence of steam creates a secondary mesoporous network inside individual zeolite crystals. In view of catalytic applications, it is essential to characterize those mesopores and to distinguish mesopores connected to the external surface of the zeolite crystal from mesopores present as cavities accessible via micropores only [2]. Externally accessible mesopores increase catalytic effectiveness by lifting diffusion limitation and facilitating desorption of reaction products [3], The aim of this paper is to characterize those mesopores by means of catalytic test reaction and liquid phase breakthrough experiments. 

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