Kinetics surface composition

The physical chemist is very interested in kinetics—in the mechanisms of chemical reactions, the rates of adsorption, dissolution or evaporation, and generally, in time as a variable. As may be imagined, there is a wide spectrum of rate phenomena and in the sophistication achieved in dealing wifli them. In some cases changes in area or in amounts of phases are involved, as in rates of evaporation, condensation, dissolution, precipitation, flocculation, and adsorption and desorption. In other cases surface composition is changing as with reaction in monolayers. The field of catalysis is focused largely on the study of surface reaction mechanisms. Thus, throughout this book, the kinetic aspects of interfacial phenomena are discussed in concert with the associated thermodynamic properties. 

AES Auger electron spectroscopy After the ejection of an electron by absorption of a photon, an atom stays behind as an unstable Ion, which relaxes by filling the hole with an electron from a higher shell. The energy released by this transition Is taken up by another electron, the Auger electron, which leaves the sample with an element-specific kinetic energy. Surface composition, depth profiles... 

Surface composition. The principle of surface segregation in ideal systems is easy to understand and to derive thermodynamically the equilibrium relations (surface concentration Xg as a function of the bulk concentration Xb at various temperatures) is also very easy (4,8). Even easier is a kinetic description which can also comprise some of the effects of the non-ideality (9). We consider an equilibrium between the surface(s) and the bulk(b) in the exchange like ... 

Stamenkovic V, Schmidt TJ, Markovic NM, Ross PN Jr. 2002. Surface composition effects in electrocatalysis Kinetics of oxygen reaction on well defined PtsNi and PtsCo alloy surfaces. J Phys Chem B 106 11970-11979. 

Fig. 33 a Surface composition of oxidized Hf(Sio.5Aso.5)As. b Logarithmic kinetics of Hf(Sio.5As0.5)As oxidation for three different samples. Reprinted with permission from [113]. Copyright Wiley... 

The methodology of surface electrochemistry is at present sufficiently broad to perform molecular-level research as required by the standards of modern surface science (1). While ultra-high vacuum electron, atom, and ion spectroscopies connect electrochemistry and the state-of-the-art gas-phase surface science most directly (1-11), their application is appropriate for systems which can be transferred from solution to the vacuum environment without desorption or rearrangement. That this usually occurs has been verified by several groups (see ref. 11 for the recent discussion of this issue). However, for the characterization of weakly interacting interfacial species, the vacuum methods may not be able to provide information directly relevant to the surface composition of electrodes in contact with the electrolyte phase. In such a case, in situ methods are preferred. Such techniques are also unique for the nonelectro-chemical characterization of interfacial kinetics and for the measurements of surface concentrations of reagents involved in... 

The tools used for the experiments described below have been described in several books and review articles (1-3). Surface structure is determined by low energy electron diffraction (LEED), surface composition by Auger electron spectroscopy (AES), and reaction kinetics and mechanism by temperature programmed reaction spectroscopy (TPRS). Standard ultra-high vacuum technology is used to maintain the surface in a well-defined state. As this article is a consolidation of previously published work, details of the experiments are not discussed here. 

The combined use of the modem tools of surface science should allow one to understand many fundamental questions in catalysis, at least for metals. These tools afford the experimentalist with an abundance of information on surface structure, surface composition, surface electronic structure, reaction mechanism, and reaction rate parameters for elementary steps. In combination they yield direct information on the effects of surface structure and composition on heterogeneous reactivity or, more accurately, surface reactivity. Consequently, the origin of well-known effects in catalysis such as structure sensitivity, selective poisoning, ligand and ensemble effects in alloy catalysis, catalytic promotion, chemical specificity, volcano effects, to name just a few, should be subject to study via surface science. In addition, mechanistic and kinetic studies can yield information helpful in unraveling results obtained in flow reactors under greatly different operating conditions. 

The application of heterogeneous catalysis plays a key role in technological processes. Engineering of the catalytic activities requires the study of the complex chemistry between absorbate and the catalyst at the surface. Static SIMS has been used to determine the surface composition and properties of solid catalysts before and after the catalytic actions by several groups.138-140 In addition, the dissociation kinetics of NO on Rh (111) surfaces have been studied by temperature programmed static SIMS.139... 

Applicability of Surface Compositional Analysis Techniques for the Study of the Kinetics of Hydride Formation... 

In the SIMS a primary noble gas atom or ion (e.g. Ar°, Ar+, Xe°, Xe+) beam is bombarded on the sample in ultra-high vacuum, penetrating to a depth of 30-100 A. The kinetic energy of the particle is assumed to dissipate via a collision cascade process, which causes the emission of electrons, neutral species and secondary ions, the yields of which vary with polymer surface composition and obviates the possibility of quantitative SIMS informa-... 

There are also two factors that have already been noted in the numerical analysis of the kinetic model of CO oxidation (1) fluctuations in the surface composition of the gas phase and temperature can lead to the fact that the "actual multiplicity of steady states will degenerate into an unique steady state with high parametric sensitivity [170] and (2) due to the limitations on the observation time (which in real experiments always exists) we can observe a "false hysteresis in the case when the steady state is unique. Apparently, "false hysteresis will take place in the region in which the relaxation processes are slow. 

The special construction of the spectrometer permits not only a safe specimen transfer without chemical changes, but also a well-defined specimen pre-treatment by sputtering previous to the electrochemical preparation. This is very important in the case of alloys because active dissolution or etching and transpassive corrosion or electropolishing may change the surface by preferential dissolution of one component. The altered surface composition may have an effect on the kinetics of passivation and on the composition of the passive layer, formed subsequently as has been... 

In concluding this part, three main points emerge from the summary of these results. First, the difficulty in achieving the preparation of these solids in a reproducible way can be solved only if a precision in the experimental parameters similar to that employed for physical or analytical chemistry measurements is used. This is a clear demonstration of the second point, which states that the textural parameters of the materials (porosity, specific surface area and surface composition) are under kinetic control. Temperature, solvent, catalyst, water/precursor ratio and concentration of reagents are the main parameters which, beside the nature of the organic subunit R, control the texture of the final material. The third point is the difficulty in rationalizing the effect of these parameters due to the numerous mechanisms involved in the sol-gel process and their interconnections. However, it must be kept in mind that all these parameters are also powerful tools that can be very useful for the development of further applications, because they allow one to tune the texture of the materials. 

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