Specific adsorption rate constants

Q is the loading capacity of CH by the polymeric resin and m is the amount of the polymeric resin added. K is the specific adsorption rate constant of CH and P is tfie surface cyclohezimide concentration which is in equilibrium to Q ... 

Figure 4. The specific adsorption rate constants of the free XAD-4 resins and immobilized XAD-4 resins in K-carrageenan. CH fermentation broth , immobilized resin A, free resin , immobilized resin (dp<0.15 min).

Mention was made in Section XVIII-2E of programmed desorption this technique gives specific information about both the adsorption and the desorption of specific molecular states, at least when applied to single-crystal surfaces. The kinetic theory involved is essentially that used in Section XVI-3A. It will be recalled that the adsorption rate was there taken to be simply the rate at which molecules from the gas phase would strike a site area times the fraction of unoccupied sites. If the adsorption is activated, the fraction of molecules hitting and sticking that can proceed to a chemisorbed state is given by exp(-E /RT). The adsorption rate constant of Eq. XVII-13 becomes... 

DRIFT spectroscopy was used to determine Av0h shifts, induced by adsorption of N2 and hexane for zeolite H-ZSM-5 (ZSM-a and ZSM-b, Si/Al=15.5 and 26), H-mordenite (Mor-a and Mor-b, Si/AI— 6.8 and 10) and H-Y (Y-a and Y-b, Si/Al=2.5 and 10.4) samples. Catalysts were activated in 02 flow at 773 K in situ in the DRIFTS cell and contacted than with N2 at pressures up to 9 bar at 298 K or with 6.1% hexane/He mixture at 553 K, i.e., under reaction conditions. Catalytic activities of the solids were measured in a flow-through microreactor and kapp was obtained as slope of -ln(l-X0) vs. W/F plots. The concentration of Bronsted acid sites was determined by measuring the NH4+ ion-exchange capacity of the zeolite. The site specific apparent rate constant, TOFBapp, was obtained as the ratio of kapp and the concentration of Bronsted acid sites. 

It is rare that a catalyst can be chosen for a reaction such that it is entirely specific or unique in its behaviour. More often than not products additional to the main desired product are generated concomitantly. The ratio of the specific chemical rate constant of a desired reaction to that for an undesired reaction is termed the kinetic selectivity factor (which we shall designate by 5) and is of central importance in catalysis. Its magnitude is determined by the relative rates at which adsorption, surface reaction and desorption occur in the overall process and, for consecutive reactions, whether or not the intermediate product forms a localised or mobile adsorbed complex with the surface. In the case of two parallel competing catalytic reactions a second factor, the thermodynamic factor, is also of importance. This latter factor depends exponentially on the difference in free energy changes associated with the adsorption-desorption equilibria of the two competing reactants. The thermodynamic factor also influences the course of a consecutive reaction where it is enhanced by the ability of the intermediate product to desorb rapidly and also the reluctance of the catalyst to re-adsorb the intermediate product after it has vacated the surface. 

C , = total concentration of active centers, in moles per gram of catalyst = specific reaction-rate constant for surface reaction Kqo = adsorption equilibrium constant for CO... 

Because of its simplicity and wide utility, the Langmuir isotherm has found wide applicability in a number of useful situations. Like many such classic approaches, it has its fundamental weaknesses, but its utility generally outweighs its shortcomings. The Langmuir isotherm model is based on the assumptions that adsorption is restricted to monolayer coverage, that adsorption is localized (i.e., that specific adsorption sites exist and interactions are between the site and a specific molecule), and that the heat of adsorption is independent of the amount of material adsorbed. The Langmuir approach is based on a molecular kinetic model of the adsorption-desorption process in which the rate of adsorption (rate constant /ca) is assumed to be proportional to the partial pressure of the adsorbate (p) and the number of unoccupied adsorption sites (N - n), where N is the total number of adsorption sites on the surface and n is the number of occupied sites, and the rate of desorption (rate constant d) is proportional to n. 

An important, limiting form of the general Eq. (151b) arises when the adsorption rate constant kg becomes very small in comparison with kg. This situation occurs if the energy barrier due to the specific interactions becomes high (< )j > 10 kT). In this case, Eq. (151b) reduces to... 

Rate constant specific dark adsorption) trends (Langmuir-Hinshelwood)... 

The activation energy, -B/R, is positive for the specific rate, but negative for the adsorption equilibrium constants, ka and kc, as expected since adsorption usually falls off with increasing temperature. 

No carrier is completely specific for a given trace metal metals of similar ionic radii and coordination geometry are also susceptible to being adsorbed at the same site. The binding of a competing metal to an uptake site will inhibit adsorption as a function of the respective concentrations and equilibrium constants (or kinetic rate constants, see below) of the metals. Indeed, this is one of the possible mechanisms by which toxic trace metals may enter cells using transport systems meant for nutrient metals. The reduced flux of a nutrient metal or the displacement of a nutrient metal from a metabolic site can often explain biological effects [92]. 

When the vanadium oxide catalyst is used, is much smaller than kx, while the specific rate constant of the reaction of m-tolunitrile in the absence of xylene is larger than that of xylene. This seems to be caused by a strong adsorption of xylene on the catalyst surface. 

The individual specific rate and adsorption equilibrium constants are defined in Table 1. In Equations (4) and (5) [Sitesjrefer to the available concentration of sites for adsorption on the Ti02 film, [O2] to the liquid phase oxygen concentration, [M] to the concentration of water, atomic or free radical species, reactor walls or other surfaces trapping atomic chlorine, and Rg to the superficial rate of electrons and holes generation. 

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