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Dissociation experimental evidence

According to the Sachtler-Biloen mechanism, the Fischer-Tropsch reaction is initiated through CO adsorption followed by CO dissociation. Experimental evidence for the involvement of an oxygen-free intermediate exists it was observed that predeposited C is incorporated into the product during Fischer-Tropsch synthesis when CO was included in the feed gas (3). It is important to distinguish whether during the Fischer-Tropsch s)mthesis CO dissociation is strictly monomolecular or instead involves a reaction with Hads to produce an intermediate "HCO" formyl species that in a subsequent reaction decomposes to "CH" and Oads-Another question is how the rates of CO dissociation, chain growth, and termination depend on the catalyst surface structure. Thus, it is essential to know the relative values of the rate constants for these three elementary reactions. [Pg.136]

An alternative approach is to assume, in the light of the experimental evidence just mentioned, that the reactions of cations and neutral molecules have similar values of (or, equivalently, of log ( /l mol and to try to calculate the difference which would arise from the fact that the observed entropy of activation for a minority free base includes a contribution from the acidic dissociation of the conjugate acid in the medium in question (see (5) above). Consider the two following reaction schemes one (primed symbols) represents nitration via the free base, the other the normal nitration of a non-basic majority species (unprimed symbols) ... [Pg.157]

There is convincing experimental evidence for the following important statement. To a degree of approximation satisfactory for most analytical work, the mass absorption coefficient of an element is independent of chemical or physical state. This means, for example, that an atom of bromine has the same chance of absorbing an x-ray quantum incident upon it in bromine vapor, completely or partially dissociated in potassium bromide or sodium bromate in liquid or solid bromine. X-ray absorption is predominantly an atomic property. This simplicity is without parallel in absorptiometry. [Pg.15]

On smooth Au surfaces, the adsorbed oxygen, which is only possible in molecular form [5], is not selective to form PO [6]. Therefore partial oxidation is contributed by oxygen adsorbed on Ti02. However, there are no direct experimental evidence whether O2 is adsorbed dissociatively or non-dissociatively. It is generally accepted that O2 adsorbs on Ti02 in a molecular form [7] and is activated at the Au/Ti02 interface [1]. [Pg.333]

Weissenrieder J, Mikkelsen A, Andersen JN, Feibehnan PJ, Held G. 2004. Experimental evidence for a partially dissociated water bilayer on Ru 0001. Phys Rev Lett 93 196102. [Pg.506]

The experimental evidence, first based on spectroscopic studies of coadsorption and later by STM, indicated that there was a good case to be made for transient oxygen states being able to open up a non-activated route for the oxidation of ammonia at Cu(110) and Cu(lll) surfaces. The theory group at the Technische Universiteit Eindhoven considered5 the energies associated with various elementary steps in ammonia oxidation using density functional calculations with a Cu(8,3) cluster as a computational model of the Cu(lll) surface. At a Cu(lll) surface, the barrier for activation is + 344 k.I mol 1, which is insurmountable copper has a nearly full d-band, which makes it difficult for it to accept electrons or to carry out N-H activation. Four steps were considered as possible pathways for the initial activation (dissociation) of ammonia (Table 5.1). [Pg.98]

Concerning the mode of formation of ES, we prefer the concept that the substrate in a monolayer is chemisorbed to the active center of the enzyme protein, just as the experimental evidence pertaining to surface catalysis by inorganic catalysts indicates that in these reactions chemisorbed, not physically adsorbed, reactants are involved. Such a concept is supported by the demonstration of spectroscopically defined unstable intermediate compounds between enzyme and substrate in the decomposition by catalase of ethyl hydroperoxide,11 and in the interaction between peroxidase and hydrogen peroxide.18 Recently Chance18 determined by direct photoelectric measurements the dissociation con-... [Pg.66]

The next question which presents itself is whether we can explain why in some systems solvent co-catalysis occurs, whereas in others, apparently similar, it does not. Let it be said first that in fact there is very little experimental evidence on this point. From the thermochemical point of view one can say that alkyl halide co-catalysis is the more probable, the lower the heterolytic bond dissociation energy of the alkyl halide, the more stable the cation derived from the monomer, and the smaller the anion derived from the metal halide. It must, however, be remembered that the non-occurrence of alkyl halide co-catalysis may be due to a kinetic prohibition, i.e., an excessively high activation energy for a reaction which is thermodynamically possible. [Pg.126]

The results of the present work are summarized in Figure 10. As far as the initial part of the reaction is concerned, we have found that the associative mechanism is slightly more favored than the dissociative one. However, the small energy difference found between the two mechanisms and the possible effect of the solvent, which has not been included in the present study, precludes formulation of a definitive conclusion on the most effective reaction pathway. Most likely depending on the reaction conditions and the initial reactants the two mechanisms can be operative. In fact, experimental evidence in favor of both the dissociative [37, 38] and associative [41] mechanisms has been provided. [Pg.282]

Prior to 1970 our understanding of the bonding of diatomic molecules to surfaces, and in many cases the type of adsorption (i.e., molecular or dissociative) was almost entirely dependent on indirect experimental evidence. By this we mean that deductions were made on the basis of data obtained from monitoring the gas phase whether in the context of kinetic studies based on gas uptake or flash desorption, mass spectrometry, or isotopic exchange. The exception was the important information that had accrued from infrared studies of mainly adsorbed carbon monoxide, a molecule that lent itself very well to this approach owing to its comparatively large extinction coefficient. [Pg.65]

We note in Figure 4.24 that the geometrical effect discussed for N2 dissociation holds for all the adsorbates considered. This means that CO, NO, and 02 dissociation should also be much faster at steps than at the most close-packed surface [81-83]. As noted above this is in agreement with a growing body of experimental evidence [83-85]. [Pg.286]


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