Heterogeneous activation energies

Thus there are compelling reasons for regarding the initiation step (la) as a low activation energy heterogeneous process at low temperatures. In any case from estimates of ki (homogeneous) for acetaldehyde and propionaldehyde made by Baldwin et al. [21, 22] a value for ja for 40 kcal. mole" was calculated. Although this may represent an upper limit (see also Sect. 4.4), it is obvious that the rate of (la) in the gas phase below 200 °C is far too low to allow the oxidation to get started. 

Formation of such droplets must then be an activated process whose rate is proportional to exp [—AF /(A 7 ]. We can estimate this rate using equation (4.2.6) for the interfacial energy y, and the result is that the rate of homogeneous nucleation we should expect for polymer systems is vanishingly small. In practice nucleation is usually aided by the presence of other interfaces, for example impurity particles such as dust or the container walls may well be able to nucleate critical droplets with much lower activation energies (heterogeneous nucleation) or indeed with no activation energy at all. We will return to this subject in section 5.3 when we discuss the effects of surfaces on phase separation. 

In practice the kinetics are usually more complex than might be expected on this basis, siace the activation energy generally varies with surface coverage as a result of energetic heterogeneity and/or sorbate-sorbate iateraction. As a result, the adsorption rate is commonly given by the Elovich equation (15) ... 

It is apparent, from the above short survey, that kinetic studies have been restricted to the decomposition of a relatively few coordination compounds and some are largely qualitative or semi-quantitative in character. Estimations of thermal stabilities, or sometimes the relative stabilities within sequences of related salts, are often made for consideration within a wider context of the structures and/or properties of coordination compounds. However, it cannot be expected that the uncritical acceptance of such parameters as the decomposition temperature, the activation energy, and/or the reaction enthalpy will necessarily give information of fundamental significance. There is always uncertainty in the reliability of kinetic information obtained from non-isothermal measurements. Concepts derived from studies of homogeneous reactions of coordination compounds have often been transferred, sometimes without examination of possible implications, to the interpretation of heterogeneous behaviour. Important characteristic features of heterogeneous rate processes, such as the influence of defects and other types of imperfection, have not been accorded sufficient attention. 

Catalysts participate in reactions but are not themselves used up they provide a reaction pathway with a lower activation energy. Catalysts are classified as either homogeneous or heterogeneous. 

Computational chemistry has reached a level in which adsorption, dissociation and formation of new bonds can be described with reasonable accuracy. Consequently trends in reactivity patterns can be very well predicted nowadays. Such theoretical studies have had a strong impact in the field of heterogeneous catalysis, particularly because many experimental data are available for comparison from surface science studies (e.g. heats of adsorption, adsorption geometries, vibrational frequencies, activation energies of elementary reaction steps) to validate theoretical predictions. 

As an example the experimental results on heterogeneous recombination of CH3 radicals on glass at different temperatures are plotted on Fig. 4.1. The experimental conditions in this case are chosen in such a way that inequality (4.3) is satisfied (A < 1 cm, y is about 1(H, r = 3 cm). Thus, formula (4.1) holds in this experiment. This conclusion is supported by the fact that for all experimental series the results obtained at different temperatures of the reaction vessel walls are satisfactorily approximated by the same straight line. This means that methyl radicals on glass substrate undergo recombination governed by the first-order kinetics, and the activation energy is close to zero. 

For an oxidized surface, the value of y is 10" - 1.7-10 and it decreases with increasing the experimental temperature. In this case the activation energy of a change in yis 2.1 kcal/mole. From these data it can be inferred that the heterogeneous de-excitation of singlet oxygen proceeds in terms of the physical adsorption mechanism similar to that described for glass. 

It is well known that Rh(I) complexes can catalyze the carbonylation of methanol. A heterogenized catalyst was prepared by ion exchange of zeolite X or Y with Rh cations.126 The same catalytic cycle takes place in zeolites and in solution because the activation energy is nearly the same. The specific activity in zeolites, however, is less by an order of magnitude, suggesting that the Rh sites in the zeolite are not uniformly accessible. The oxidation of camphene was performed over zeolites exchanged with different metals (Mn, Co, Cu, Ni, and Zn).127 Cu-loaded zeolites have attracted considerable attention because of their unique properties applied in catalytic redox reactions.128-130 Four different Cu sites with defined coordinations have been found.131 It was found that the zeolitic media affects strongly the catalytic activity of the Cd2+ ion sites in Cd zeolites used to catalyze the hydration of acetylene.132... 

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