Kinetic adsorption coefficient

The proposed mechanism of the effect of water can be supported by two other findings (i) the calculations of Maatman et al. [410] revealed that the active sites could be identified with surface silanol groups [Sect. 4.1.2.(a)] and(ii) independent studies of other authors [424—426] showed that silica gel could actually adsorb two layers of water the first layer is strongly chemisorbed whereas the second is less strongly adsorbed and retains much of the character of free water. The standard enthalpy and entropy changes on adsorption determined from kinetic adsorption coefficients, Kr and Kr, for the first and second layer, respectively [411], are consistent with this observation. 

Note. tb is the breakthrough time at the outlet concentration cx = 10-5 mg/dm3 Wc is the kinetic adsorption capacity / e is effective overall adsorption rate coefficient m0 is the weight of bed, and ph is the bulk density of carbon bed. 

The selection of adsorbents is critical for determining the overall separation performance of the above-described PSA processes for hydrogen purification. The separation of the impurities from hydrogen by the adsorbents used in these processes is generally based on their thermodynamic selectivities of adsorption over H2. Thus, the multicomponent adsorption equilibrium capacities and selectivities, the multi-component isosteric heats of adsorption, and the multicomponent equilibrium-controlled desorption characteristics of the feed gas impurities under the conditions of operation of the ad(de)sorption steps of the PSA processes are the key properties for the selection of the adsorbents. The adsorbents are generally chosen to have fast kinetics of adsorption. Nonetheless, the impact of improved mass transfer coefficients for adsorption cannot be ignored, especially for rapid PSA (RPSA) cycles. 

Table 5 shows examples of LDF mass transfer coefficients for adsorption of several binary gas mixtures on BPL activated carbon particles (6-16 mesh) at 23-30°C. The data show that the mass transfer coefficients are relatively large for these systems. There is a scarcity of multicomponent adsorption equilibria, kinetics, and heat data in the published literature. This often restricts extensive testing of theoretical models for prediction of multicomponent behavior. 

Kinetic coefficients. The kinetic adsorption and desorption coefficients can be estimated [82, 219, 412] if the form of the potential (Z) of interaction between a particle (a surfactant molecule) and the solution surface is known here Z is the coordinate measured from the surface into the bulk of liquid. If the function (Z) has the form of a potential barrier with a potential well, then the saddle-point method [261] implies... 

The kinetic rate coefficients and adsorption equilibrium constants are given by Xu and Froment (1989a,b) as follows ... 

De Deken et al. (1982) gave the following values for the kinetic rate coefficients and adsorption equilibrium constant ... 

The aim of this section is to consider the dynamic adsorption layer structure of ionic surfactant on the surface of rising bubbles. Results obtained in the previous section cannot be transferred directly to this case. The theory describing dynamic adsorption layers of ionic surfactant in general should take into accoimt the effect of electrostatic retardation of the adsorption kinetics of surfactant ions (Chapter 7). The structure of the dynamic adsorption layer of nonionic surfactants was analysed in the precedings section in the case when the adsorption process is kinetic controlled. In this case, it was assumed that the kinetic coefficients of adsorption and desorption do not depend on the surface coverage. On the other hand, the electrostatic barrier strongly depends on F , and therefore, the results of Section 9.1. cannot be used for the present case.. 

The values for the exudation rate F, interaction coefficient (A), buffer power of exudate in soil b and the decomposition rate constant for the exudate k were adopted from Kirk (1999). The value of the forward rate constant was estimated from Scheckel and Sparks (2001), who evaluated kinetic adsorption data of Ni to different minerals where ranged from 2.5 x 10 to 9.78 X 10 s For the simulation, an average value of 5.00 x 10 was used. This value also coincides with the values that Kirk and Staunton (1989) suggested for the kinetic adsorption of Q to soil, where the values ranged from lO" to 10 2 s f This same value was assumed for the rate constant for the two-stage sorption model, a2- The fraction of type 1 sites (F ) was assumed to be 0.3. Table 7 summarizes all input parameter values. 

M l designates the molar mass of the gas and Pj its partial pressure. Only a fraction 5k of the molecules that collide with the surface can transfer their kinetic energy to the atoms of the solid and, by this process, remain adsorbed. We call 5k the sticking coefficient. The adsorption rate is thus equal to... 

The kinetics of adsorption and the amount of polar (alcohols) and nonpolar molecules, Keggin type compounds, was extensively studied through IR spectroscopy and thermogravimetric analysis [16,31,32,34,35]. Misono and coworkers [31] established that the rate of alcohol adsorption depends on the size of the probe molecule, and that the amount of adsorbed molecules in H3PW12O40 is an integral multiple of the number of protons. The observation of the diffusion coefficients and adsorption of polar molecules into the bulk structure of the HPAs proved unequivocally the pseudo-liquid phase behavior of those compounds. 

Coupling constant Hydrodynamic coefficients Equilibrium adsorption constant Hydrodynamic resistance coefficient Long-time expansion coefficient Boltzmann constant Adsorption kinetic constants Dimensionless adsorption constant Bulk-transfer rate constants (reduced flux)... 

Certainly, most reactor models are semi-empirical. Starting from strong physical and chemical bases, model equations are obtained and, typically, an ordinary differential equations (ODE) or partial differential equations (PDE) set has to be solved. In an equation set, parameters usually need to be fitted (for example reaction-kinetics rate coefficients, catalyst adsorption coefficients, heat-transfer coefficients, etc.), and they are calculated using experimental data. Semi-empirical models have three important advantages (Seborg et al., 1989) ... 

If the fraction of sites occupied is 0, and the fraction of bare sites is 0q (so that 00 + 1 = 0 then the rate of condensation on unit area of surface is OikOo where p is the pressure and k is a constant given by the kinetic theory of gases (k = jL/(MRT) ) a, is the condensation coefficient, i.e. the fraction of incident molecules which actually condense on a surface. The evaporation of an adsorbed molecule from the surface is essentially an activated process in which the energy of activation may be equated to the isosteric heat of adsorption 4,. The rate of evaporation from unit area of surface is therefore equal to... 

Adsorption Kinetics. In zeoHte adsorption processes the adsorbates migrate into the zeoHte crystals. First, transport must occur between crystals contained in a compact or peUet, and second, diffusion must occur within the crystals. Diffusion coefficients are measured by various methods, including the measurement of adsorption rates and the deterniination of jump times as derived from nmr results. Factors affecting kinetics and diffusion include channel geometry and dimensions molecular size, shape, and polarity zeoHte cation distribution and charge temperature adsorbate concentration impurity molecules and crystal-surface defects. 

If the UCKRON expression is simplified to the form recommended for reactions controlled by adsorption of reactant, and if the original true coefficients are used, it results in about a 40% error. If the coefficients are selected by a least squares approach the approximation improves significantly, and the numerical values lose their theoretical significance. In conclusion, formalities of classical kinetics are useful to retain the basic character of kinetics, but the best fitting coefficients have no theoretical significance. 

For adsorbates out of local equilibrium, an analytic approach to the kinetic lattice gas model is a powerful theoretical tool by which, in addition to numerical results, explicit formulas can be obtained to elucidate the underlying physics. This allows one to extract simplified pictures of and approximations to complicated processes, as shown above with precursor-mediated adsorption as an example. This task of theory is increasingly overlooked with the trend to using cheaper computer power for numerical simulations. Unfortunately, many of the simulations of adsorbate kinetics are based on unnecessarily oversimplified assumptions (for example, constant sticking coefficients, constant prefactors etc.) which rarely are spelled out because the physics has been introduced in terms of a set of computational instructions rather than formulating the theory rigorously, e.g., based on a master equation. 

The values of the rate constants and adsorption coefficients obtained by the study of isolated reactions agreed well with those obtained by the study of parallel reactions (Table V). The three values of the adsorption coefficient of each acid were obtained independently. In addition to one value from the study of isolated reactions, two additional values were determined by the study of the parallel system one from the kinetics of the consumption of the given acid by reaction (Vila) or (Vllb), and one from the kinetics of reaction (Vile). 

We have further attempted to suggest a procedure which would make use of the advantages of the method of competitive reactions, i.e. its simplicity and little time demand, and at the same time would yield separately the absolute values of rate constants and adsorption coefficients also for reactions with a more complicated kinetics. Using the values of relative reactivities S from the method of competitive reactions, the adsorption coefficients, for example, of the alcohols (Kb) in the reesterification reaction described by Eq. (26) can be evaluated from the relation... 

From the results of this kinetic study and from the values of the adsorption coefficients listed in Table IX, it can be judged that both reactions of crotonaldehyde as well as the reaction of butyraldehyde proceed on identical sites of the catalytic surface. The hydrogenation of crotyl alcohol and its isomerization, which follow different kinetics, most likely proceed on other sites of the surface. From the form of the integral experimental dependences in Fig. 9 it may be assumed, for similar reasons as in the hy-drodemethylation of xylenes (p. 31) or in the hydrogenation of phenol, that the adsorption or desorption of the reaction components are most likely faster processes than surface reactions. 

It is noteworthy that even a separate treatment of the initial data on branched reactions (1) and (2) (hydrogenation of crotonaldehyde to butyr-aldehyde and to crotyl alcohol) results in practically the same values of the adsorption coefficient of crotonaldehyde (17 and 19 atm-1)- This indicates that the adsorbed form of crotonaldehyde is the same in both reactions. From the kinetic viewpoint it means that the ratio of the initial rates of both branched reactions of crotonaldehyde is constant, as follows from Eq. (31) simplified for the initial rate, and that the selectivity of the formation of butyraldehyde and crotyl alcohol is therefore independent of the initial partial pressure of crotonaldehyde. This may be the consequence of a very similar chemical nature of both reaction branches. 

Unraveling catalytic mechanisms in terms of elementary reactions and determining the kinetic parameters of such steps is at the heart of understanding catalytic reactions at the molecular level. As explained in Chapters 1 and 2, catalysis is a cyclic event that consists of elementary reaction steps. Hence, to determine the kinetics of a catalytic reaction mechanism, we need the kinetic parameters of these individual reaction steps. Unfortunately, these are rarely available. Here we discuss how sticking coefficients, activation energies and pre-exponential factors can be determined for elementary steps as adsorption, desorption, dissociation and recombination. 

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