Adsorption/desorption ratio

Fig. 230 Adsorption of nitrogen at 77 K on a silica powder a) adsorption isotherms b) /-plot. Broken line, uncompacted powder continuous line, power compacted at 2-00 x 10 N m (130 ton in ). (—>—) adsorption (—<-) desorption. / is the ratio of the amount adsorbed on the powder to the amount adsorbed on the compact at the same relative...

The quantitative solution of the problem, i.e. simultaneous determination of both the sequence of surface chemical steps and the ratios of the rate constants of adsorption-desorption processes to the rate constants of surface reactions from experimental kinetic data, is extraordinarily difficult. The attempt made by Smith and Prater 82) in a study of cyclohexane-cyclohexene-benzene interconversion, using elegant mathematic procedures based on the previous theoretical treatment 28), has met with only partial success. Nevertheless, their work is an example of how a sophisticated approach to the quantitative solution of a coupled heterogeneous catalytic system should be employed if the system is studied as a whole. 

In general, the flow rate F(t) consists of the following additive components the controlled flow rate Fd of the entering gas, the flow rate Fi which is due to parasitic leaks and/or diffusion, and the flow rate Fw resulting from possible adsorption-desorption processes on the system walls (in Section I, references are given to papers dealing with the elimination or control of the wall effects in the flash filament technique). In each of these flow rate components a particular ratio of the investigated adsorbate and of the inert gas exists and all these components contribute to the over-all mean values Fh(t) and F (t). 

Figure 5. Top Adsorption isotherms of C02 for 1-en at the indicated temperatures. Bottom Adsorption-desorption cycling of C02 for 1-en showing reversible uptake from (a) simulated air (0.39 mbar C02 and 21% 02 balanced with N2) and from (b) simulated flue gas (0.15 bar C02 balanced with N2). (c) time-dependent C02 adsorption for porous materials (A = 1-en, B = mmen-Mg2(dobpdc), C = 1, D = Mg-MOF-74, E = Zeolite 13X, F = MOF-5). (d) C02 adsorption ratio of 1-en in flue gas (after 6 min exposure to 100% RH at 21 °C) to 1-en in flue gas (Adapted from [192]).

It is interesting to note that, although the intrinsic rate of desorption is slower than that of adsorption, both rates were found to be sufficiently fast under our experimental conditions so that the adsorption-desorption process on the Pt surface can be assumed to rapidly equilibrate at all times that is, even a ten-fold increase in both the adsorption and desorption rate constants (while keeping their ratio constant) did not significantly change the predicted step responses. With the assumption of chemisorption equilibrium, Equations (1) and (4) can be combined into the form (35)... 

Following mono-layer uptake, further increase in pressure results in multi-layer adsorption of N2. For this part of the isotherm, condensation-evaporation equilibrium is assumed to take place, instead of adsorption-desorption equilibrium for each individual layer other than the first layer. This dynamic equiUbria for the first and higher layers and some simplifying assumptions form the basis for the B ET treatment of the multi-layer adsorption isotherm. A lengthy derivation leads to the BET relation between adsorbed volume of N2 and relative pressure. Here relative pressure is defined as the ratio of the equilibrium pressure to the... 

To describe the NH3 + NO/NO2 reaction system over a wide range of temperatures and NO2 NOxfeed ratios in addition to ammonia adsorption-desorption, ammonia oxidation and standard SCR reaction with the associated kinetics already discussed in Section 2.3.2, the following reactions and kinetics have been considered by Chatterjee and co-workers [79] ... 

Figure 4. N2 adsorption-desorption isotherms (a) and pore size distributions (b) for samples prepared using the same CTAB/Si02 ratio (0.45) and different H20/Si02 ratios as indicated.

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. 

The next step in the reaction kinetics analysis is to choose for each family of reactions (i.e., adsorption/desorption, oligomerization//-) -scission, isomerization, and hydride transfer) whether to parameterize the kinetic model in terms of either the forward or the reverse rate constant (kj,for or khrey) since the ratio of the forward and the reverse rate constants must equal the known value of Kit q ... 

Many authors have proposed reactors with similar basic principles. The best known are those of Garanin et al. [44], Livbjerg and Villadsen [45] and new versions of Berty reactor [34]. Variants of internal recycling reactors have also been proposed by Bennett et al. [43] who tried to decrease the ratio of reactor volume to catalyst volume. In this arrangement the amount of reactant adsorbed increases compared to that in the gas space as a result the dynamics of the adsorption - desorption processes can be detected through the gas phase measurements. 

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