Shape reactant

Derouane and his co-workers14,15 proposed that hilly environments offered by pore openings, cut channels, and/or cavities at the external surface of zeolites will preferentially adsorb and shape reactant molecules depending on their stereochemistry and their ability to optimize their van der Waals interaction with the framework, i.e. their capacity to nest . Adsorption will be favored for molecules (or intermediates) which can easily adapt their geometry. 

Fig. 23 The outcome of thermodynamically controlled imine condensations was suggested to be a function of the conformational preference of the diimine linker that predisposes the bowl-shaped reactants with a minimal amount of strain.134 Reprinted with permission from Ref.134 (For color version of this figure, the reader is referred to the web version of this book.)...

The factor 0.5 relates to identically shaped reactant and product potential energy curves. Thus, through perturbation of A /, ionization of amino acids D and E will slow down the forward electron transfer and accelerate the reverse electron transfer. Because of the large distance between Qa and (3b (== 18 A), we neglect the electrostatic interactions between D and E and Qa, but some effect can be expected. 

Qualitative examples abound. Perfect crystals of sodium carbonate, sulfate, or phosphate may be kept for years without efflorescing, although if scratched, they begin to do so immediately. Too strongly heated or burned lime or plaster of Paris takes up the first traces of water only with difficulty. Reactions of this type tend to be autocat-alytic. The initial rate is slow, due to the absence of the necessary linear interface, but the rate accelerates as more and more product is formed. See Refs. 147-153 for other examples. Ruckenstein [154] has discussed a kinetic model based on nucleation theory. There is certainly evidence that patches of product may be present, as in the oxidation of Mo(lOO) surfaces [155], and that surface defects are important [156]. There may be catalysis thus reaction VII-27 is catalyzed by water vapor [157]. A topotactic reaction is one where the product or products retain the external crystalline shape of the reactant crystal [158]. More often, however, there is a complicated morphology with pitting, cracking, and pore formation, as with calcium carbonate [159]. 

If reliable quantum mechanical calcnlations of reactant and transition state stnictures in vacnnm are feasible, treating electrostatic solvent effects on the basis of SRCF-PCM rising cavity shapes derived from methods... 

Catalyst particles are usually cylindrical in shape because it is convenient and economical to fonii tliem by extmsion—like spaghetti. Otlier shapes may be dictated by tlie need to minimize tlie resistance to transport of reactants and products in tlie pores tlius, tlie goal may be to have a high ratio of external (peripheral) surface area to particle volume and to minimize the average distance from tlie outside surface to tlie particle centre, witliout having particles tliat are so small tliat tlie pressure drop of reactants flowing tlirough tlie reactor will be excessive. 

Figure C2.12.10. Different manifestations of shape-selectivity in zeolite catalysis. Reactant selectivity (top), product selectivity (middle) and transition state selectivity (bottom).

Catalytic Properties. In zeoHtes, catalysis takes place preferentially within the intracrystaUine voids. Catalytic reactions are affected by aperture size and type of channel system, through which reactants and products must diffuse. Modification techniques include ion exchange, variation of Si/A1 ratio, hydrothermal dealumination or stabilization, which produces Lewis acidity, introduction of acidic groups such as bridging Si(OH)Al, which impart Briimsted acidity, and introducing dispersed metal phases such as noble metals. In addition, the zeoHte framework stmcture determines shape-selective effects. Several types have been demonstrated including reactant selectivity, product selectivity, and restricted transition-state selectivity (28). Nonshape-selective surface activity is observed on very small crystals, and it may be desirable to poison these sites selectively, eg, with bulky heterocycHc compounds unable to penetrate the channel apertures, or by surface sdation. 

Volumetric heat generation increases with temperature as a single or multiple S-shaped curves, whereas surface heat removal increases linearly. The shapes of these heat-generation curves and the slopes of the heat-removal lines depend on reaction kinetics, activation energies, reactant concentrations, flow rates, and the initial temperatures of reactants and coolants (70). The intersections of the heat-generation curves and heat-removal lines represent possible steady-state operations called stationary states (Fig. 15). Multiple stationary states are possible. Control is introduced to estabHsh the desired steady-state operation, produce products at targeted rates, and provide safe start-up and shutdown. Control methods can affect overall performance by their way of adjusting temperature and concentration variations and upsets, and by the closeness to which critical variables are operated near their limits. 

A catalyst manufactured using a shaped support assumes the same general size and shape of the support, and this is an important consideration in the process design, since these properties determine packing density and the pressure drop across the reactor. Depending on the nature of the main reaction and any side reactions, the contact time of the reactants and products with the catalyst must be optimized for maximum overall efficiency. Since this is frequendy accompHshed by altering dow rates, described in terms of space velocity, the size and shape of the catalyst must be selected carehiUy to allow operation within the capabiUties of the hardware. 

Design possibilities for electrolytic cells are numerous, and the design chosen for a particular electrochemical process depends on factors such as the need to separate anode and cathode reactants or products, the concentrations of feedstocks, desired subsequent chemical reactions of electrolysis products, transport of electroactive species to electrode surfaces, and electrode materials and shapes. Cells may be arranged in series and/or parallel circuits. Some cell design possibiUties for electrolytic cells are... 

A less obvious scheme that can lead to a bell-shaped curve has been recognized by Zemer and Bender. The substrate is a weak acid or base, but possesses only one ionizable group, and no other ionizable reactant is involved (other than water). The second inflection in the curve is ascribed to an ionizable group created in an intermediate. An example has been discovered in the hydrolysis of o-carboxy-phthalimide ... 

The important property of ZSM-5 and similar zeolites is the intercrystalline catalyst sites, which allow one type of reactant molecule to diffuse, while denying diffusion to others. This property, which is based on the shape and size of the reactant molecules as well as the pore sizes of the catalyst, is called shape selectivity. Chen and Garwood document investigations regarding the various aspects of ZSM-5 shape selectivity in relation to its intercrystalline and pore structure. 

The shape of a photometric titration curve will be dependent upon the optical properties of the reactant, titrant, and products of the reaction at the wavelength used. Some typical titration plots are given in Fig. 17.23. 

The absorption of reactants (or desorption of products) in trickle-bed operation is a process step identical to that occurring in a packed-bed absorption process unaccompanied by chemical reaction in the liquid phase. The information on mass-transfer rates in such systems that is available in standard texts (N2, S6) is applicable to calculations regarding trickle beds. This information will not be reviewed in this paper, but it should be noted that it has been obtained almost exclusively for the more efficient types of packing material usually employed in absorption columns, such as rings, saddles, and spirals, and that there is an apparent lack of similar information for the particles of the shapes normally used in gas-liquid-particle operations, such as spheres and cylinders. 

Tenets (i) and (ii). These are applicable only where the reactant undergoes no melting and no systematic change of composition (e.g. by the diffusive removal of a constituent) and any residual solid product phase offers no significant barrier to contact between reactants or the escape of volatile products [33,34]. When all these conditions are obeyed, the shape of the fraction decomposed (a) against time (f) curve for an isothermal reaction can, in principle, be related to the geometry of formation and advance of the reaction interface. The general solution of this problem involves intractable mathematical difficulties but simplifications have been made for many specific applications [1,28—31,35]. 

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