Activation energy adsorbed formate

This reaction is catalyzed by iron, and extensive research, including surface science experiments, has led to an understanding of many of the details (72). The adsorption of H2 on iron is fast, and the adsorption of N2 is slow and characterized by a substantial activation energy. N2 and H2 are both dis so datively adsorbed. Adsorption of N2 leads to reconstmction of the iron surface and formation of stmctures called iron nitrides that have depths of several atomic layers with compositions of approximately Fe N. There is a bulk compound Fe N, but it is thermodynamically unstable when the surface stmcture is stable. Adsorbed species such as the intermediates NH and NH2 have been identified spectroscopically. 

When gaseous or liquid molecules adhere to thesurface of the adsorbent by means of a chemical reaction and the formation of chemical bonds, the phenomenon is called chemical adsorption or chemisorption. Heat releases of 10 to 100 kcal/g-mol are typical for chemisorption, which are much higher than the heat release for physisorption. With chemical adsorption, regeneration is often either difficult or impossible. Chemisorption usually occurs only at temperatures greater than 200 C when the activation energy is available to make or break chemical bonds. 

The kinetic expression was derived by Akers and White (10) who assumed that the rate-controlling factor in methane formation was the reaction between the adsorbed reactants to form adsorbed products. However, the observed temperature-dependence of the rate was small, which indicates a low activation energy, and diffusion was probably rate-controlling for the catalyst used. 

We did not extensively discuss the consequences of lateral interactions of surface species adsorbed in adsorption overlayers. They lead to changes in the effective activation energies mainly because of consequences to the interaction energies in coadsorbed pretransition states. At lower temperatures, it can also lead to surface overlayer pattern formation due to phase separation. Such effects cannot be captured by mean-field statistical methods such as the microkinetics approaches but require treatment by dynamic Monte Carlo techniques as discussed in [25]. 

For the reduction of NO with propene, the catalyst potential dependence of the apparent activation energies does not show a step change and is much less pronounced than it is for the CO+O2 and NO+CO systems. There is persuasive evidence [20] that the step change is associated with a surface phase transition - the formation or disruption of islands of CO. It is reasonable to assume that this phenomenon cannot occur in the NO+propene case, since there is no reason to expect that large amounts of chemisorbed CO can be present under any conditions. That there should be a difference in this respect between CO+O2/CO+NO on the one hand, and NO+propene on the other hand, is therefore understandable however, the chemical complexity of the adsorbed layer in the NO+-propene precludes any detailed analysis of the Ea(VwR> effect. 

The linear dependence of the pitting potential on ionic radius is likely a reflection of the similarly linear relationship between the latter and the free energy of formation of aluminum halides.108 It is reasonable to assume that the energy of adsorption of a halide on the oxide is also related to the latter. Hence, one could postulate that the potential at which active dissolution takes place is the potential at which the energy of adsorption overcomes the energy of coulombic repulsion so that the anions get adsorbed. 

For some metals the transfer of metallic ions involves a reaction intermediate of an adsorbed metallic ion complex which is coordinated with anionic ligands hence, the overall reaction occurs in a series of two elementaiy steps rather than one. Such a multistep transfer of ions can result, in the course of metallic ion transfer, from the reduction of the activation energy for ion transfer due to the formation of adsorbed intermediates. We examine a transfer reaction of divalent metallic ions via an adsorbed complex ion according to the steps in Eqn. 9-13 ... 

Chemisorption. Chemisorption involves heats of adsorption which are large as compared to the heat of van der Waal s adsorption. The term chemisorption implies formation of semi-chemical bonds of the adsorbed gas with the solid surface. Chemisorption may be a process involving measurable activation energy—that is, a measurable rate of adsorption and a measurable temperature coefficient of rate of adsorption. As in the case of hydrogen adsorption on metals, chemisorption may have no measurable rate of adsorption, the adsorption being essentially instantaneous. 

Che and Naccache (199) have studied the kinetics of 02 formed on slightly reduced anatase using EPR. They found that the adsorption could be explained on the basis of different formation rates for 02 adsorbed at different sites, with zero- and first-order kinetics for the oxygen and Ti3+ concentrations, respectively. Using the same approach, Hauser (200) has extended this work and proposed different models to explain the kinetics based on the formation of 02, O2-, and 02 ions for which activation energies around 1 kcal/mol were obtained. Nikisha et al. (201) have studied the oxygen adsorption kinetics using EPR, conductivity, and volumetric measurements. 

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