Langmuir-Hinshelwood-Hougen-Watson kinetics

Butt and Petersen (1988) extended the Langmuir—Hinshelwood—Hougen—Watson kinetics to involve the varying activity (as a result of catalyst deactivation with time) to describe... 

The results can be interpreted in terms of Langmuir-Hinshelwood-Hougen-Watson kinetics. Styrene adsorbs more strongly than octenes and, as a consequence, only after styrene has been converted does the formation of octanes proceed at a high rate. The... 

Exemplary results of modeling processes inside the catalytic layer are presented in Fig. 9. The solid lines show the dependency of the overall effectiveness factor on the relative distribution of the catalyst between the comers and the side regions. The two cases represent two levels of the first-order rate constants, with the faster reaction in case (b). As expected, the effectiveness factor of the first reaction drops as more catalyst is deposited in the comers. The effectiveness factor for the second reaction increases in case (a) but decreases in case (b). The latter behavior is caused by depletion of B deep inside the catalytic layer. What might be surprising is the rather modest dependency of the effectiveness factor on the washcoat distribution. The explanation is that internal diffusion is not important for slow reactions, while for fast reactions the available external surface area becomes the key quantity, and this depends only slightly on the washcoat distribution for thin layers. The dependence of the effectiveness factor on the distribution becomes more pronounced for consecutive reactions described by Langmuir-Hinshelwood-Hougen-Watson kinetics [26]. 

Skrzypek el al. mode (19H5) Skrzypek el al. (1985) developed this model based on the Langmuir-Hinshelwood-Hougen-Watson kinetic model to explain the non-monotonic behaviour observed by Calder-bank (1974). They suggested that the reaction rate behaviour can be related to the Langmuir-Hinshelwood kinetic model for bimolecular reactions, where the surface reaction between o-Xylene and oxygen chemisorbed on the active centers is the rate determining step. The rate of appearance of various components can be written as ... 

Reversible reaction with Langmuir-Hinshelwood-Hougen-Watson kinetics... 

The problem posed by Eq. (6.22), without the additional complication of the O dependence, is a classical problem in heterogeneous catalysis. The usual approach it to use Langmuir isotherms to describe reactant (and sometimes product) adsorption. This leads to the well known Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetics.3 The advantage of this approach is... 

Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetics, 21 Nernst, 95... 

In general, the use of Langmuir-Hinshelwood-Hougen-Watson (LHHW)-type of rate equation for representing the hydrogenation kinetics of industrial feedstocks is complicated, and there are too many coefficients that are difficult to determine. Therefore, simple power law models have been used by most researchers to fit kinetic data and to obtain kinetic parameters. 

Herzfeld and Langmuir-Hinshelwood-Hougen-Watson cycles, could be formulated and solved in terms of analytical rate expressions (19,53). These rate expressions, which were derived from mechanistic cycles, are phrased, however, in terms of the formation and destruction of molecular species without the need for computing the composition of reactive intermediates. Thus, these expressions are the relevant kinetics required for molecular models and are rooted to the mechanistic cycles only implicitly by the mechanistic rate constants. The molecular model, in turn, transforms a vector of reactant molecules into a vector of product molecules, either of which is susceptible to thermodynamic analysis. This thermodynamic analysis helps to organize these components into relevant boiling point or solubility product classes. Thus the sequence of mechanistic to molecular to global models is intact. 

In heterogeneous catalysis these models are generally referred to as the Langmuir-Hinshelwood-Hougen-Watson (LHHW) models. The term Michaelis-Menten kinetics is often used in homogeneous catalysis, enzyme reactions and reactions of microbial systems. 

For a reaction of such complexity as methanation (or FTS) an exact kinetic theory is actually out of the question. One has to introduce one or more approximations. The usual assumption made is that one reaction step is rate determining (r.d.s.) and other steps are in equilibrium or steady state. Adsorption equilibria are described by Langmuir formulas (Langmuir-Hinshelwood, Hougen-Watson... 

Recently a rigorous quantitative model was developed in order to describe promotional and, more generally, catalytic kinetics [130,147]. The model can be viewed as an extension of classical Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetics. 

There are currently two available different ways in which one might use the predicted kinetic information on elementary reaction steps 1) the conventional Langmuir-Hinshelwood-Hougen-Watson (LHHW) approach [3], in which an explicit rate expression might be derived based on the common, but rather arbitrary. 

The pre-exponentials and the apparent activation energies corresponding to the rate coefficients ki, k2 and ks had to be estimated from the experimental data sets from fovir batch reactor and ten CSTR experiments. The initial concentration of reactant A and the temperature were varied. The kinetic rate equations of the catalytic reactions can be described by using the following so-called Langmuir-Hinshelwood Hougen-Watson equations. 

The major problem in describing the FT reaction kinetics is the complexity of its reaction mechanism and the large number of species involved. As discussed above, the mechanistic proposals for the FTS used a variety of surface species and different elementary reaction steps, resulting in empirical power law expressions for the kinetics. However, the rate equations of Langmuir—Hinshelwood—Hougen—Watson (LHHW) have been applied based on a reaction mechanism for the hydrocarbon-forming reactions. In most cases, the rate-determining step was assumed to be the formation of the monomer. 

As pointed out by Levenspid (2000), the usual procedure to study the kinetics of surface-catalyzed reactions is to propose a mechanism based on the Langmuir-Hinshelwood-Hougen-Watson (LHHW) model, derive the corresponding equation, and then fit it to the data at hand. If the fit is good, researchers often claim that thqr have found the actual mechanism. This procedure is questionable, as shown by Topic 4.5.4. It would be better to state that our experimental results are formally described (within the range of the investigated reaction conditions) by the selected kinetic equation (probably out of several possible others). 

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