Double layer surface states

Ardizzone, S., Bianchi, C.L., and Galassi, C., Chromium doped Y-AI2O3 powders. Features of the electrical double layer and state of the surface species, J. Organometall. Chem., 490, 48, 2000. 

In the preceding derivation, the repulsion between overlapping double layers has been described by an increase in the osmotic pressure between the two planes. A closely related but more general concept of the disjoining pressure was introduced by Deijaguin [30]. This is defined as the difference between the thermodynamic equilibrium state pressure applied to surfaces separated by a film and the pressure in the bulk phase with which the film is equilibrated (see section VI-5). 

The basic assumption is that the Langmuir equation applies to each layer, with the added postulate that for the first layer the heat of adsorption Q may have some special value, whereas for all succeeding layers, it is equal to Qu, the heat of condensation of the liquid adsorbate. A furfter assumption is that evaporation and condensation can occur only from or on exposed surfaces. As illustrated in Fig. XVII-9, the picture is one of portions of uncovered surface 5o, of surface covered by a single layer 5, by a double-layer 52. and so on.f The condition for equilibrium is taken to be that the amount of each type of surface reaches a steady-state value with respect to the next-deeper one. Thus for 5o... 

For many practically relevant material/environment combinations, thennodynamic stability is not provided, since E > E. Hence, a key consideration is how fast the corrosion reaction proceeds. As for other electrochemical reactions, a variety of factors can influence the rate detennining step. In the most straightforward case the reaction is activation energy controlled i.e. the ion transfer tlrrough the surface Helmholtz double layer involving migration and the adjustment of the hydration sphere to electron uptake or donation is rate detennining. The transition state is... 

A number of theories have been put forth to explain the mechanism of polytype formation (30—36), such as the generation of steps by screw dislocations on single-crystal surfaces that could account for the large number of polytypes formed (30,35,36). The growth of crystals via the vapor phase is beheved to occur by surface nucleation and ledge movement by face specific reactions (37). The soHd-state transformation from one polytype to another is beheved to occur by a layer-displacement mechanism (38) caused by nucleation and expansion of stacking faults in close-packed double layers of Si and C. 

F r d ic Current. The double layer is a leaky capacitor because Faradaic current flows around it. This leaky nature can be represented by a voltage-dependent resistance placed in parallel and called the charge-transfer resistance. Basically, the electrochemical reaction at the electrode surface consists of four thermodynamically defined states, two each on either side of a transition state. These are (11) (/) oxidized species beyond the diffuse double layer and n electrons in the electrode and (2) oxidized species within the outer Helmholtz plane and n electrons in the electrode, on one side of the transition state and (J) reduced species within the outer Helmholtz plane and (4) reduced species beyond the diffuse double layer, on the other. 

Anodically polished and then cathodically reduced Cd + Pb alloys have been studied by impedance in aqueous electrolyte solutions (NaF, KF, NaC104, NaN02, NaN03).827 For an alloy with 2% Pb at cNap 0.03 M, Emfo = -0.88 V (SCE) and depends on cNaF, which has been explained by weak specific adsorption of F" anions. Surface activity increases in the sequence F" < CIO4 < N02. The Parsons-Zobel plot at E is linear, with /pz = 1.33 and CT° = 0.31 F m"2. Since the electrical double-layer parameters are closer to those for pc-Pb than for pc-Cd, it has been concluded that Pb is the surface-active component in Cd + Pb alloys827 (Pb has a lower interfacial tension in the liquid state). 

The value obtained by Hamm et alm directly by the immersion method is strikingly different and much more positive than others reported. It is in the right direction with respect to a polycrystalline surface, even though it is an extrapolated value that does not correspond to an existing surface state. In other words, the pzc corresponds to the state of a bare surface in the double-layer region, whereas in reality at that potential the actual surface is oxidized. Thus, such a pzc realizes to some extent the concept of ideal reference state, as in the case of ions in infinitely dilute solution. 

Models and theories have been developed by scientists that allow a good description of the double layers at each side of the surface either at equilibrium, under steady-state conditions, or under transition conditions. Only the surface has remained out of reach of the science developed, which cannot provide a quantitative model that describes the surface and surface variations during electrochemical reactions. For this reason electrochemistry, in the form of heterogeneous catalysis or heterogeneous catalysis has remained an empirical part of physical chemistry. However, advances in experimental methods during the past decade, which allow the observation... 

Figure 5.18. Schematic representation of the density of states N(E) in the conduction band and of the definitions of work function d>, chemical potential of electrons p, electrochemical potential of electrons or Fermi level p, surface potential x> Galvani (or inner) potential

The presence of this backspillover formed effective double layer is important not only for interpreting the effect of electrochemical promotion, but also for understanding the similarity of solid state electrochemistry depicted in Fig. 7.3 with the case of emersed electrodes in aqueous electrochemistry (Fig. 7.2) and with the gedanken experiment of Trasatti (Fig. 7.1) where one may consider that H2O spillovers on the metal surface. This conceptual similarity also becomes apparent from the experimental results. 

Figure 11.7 confirms that electrochemically induced and controlled O2 backspillover from the support to the metal film surface is the promoting mechanism both in the case of YSZ (Fig. 11.7a) and in Ti02 (Fig. 11.7b). These figures show the Ols spectrum of the Pt film deposited on YSZ and on TiC>2, first under open-circuit conditions (Fig. 11.7aC, 11.7bA) and then under positive current and potential application (Fig. 11.7aB, 11.7bB). Figures 11.7aC and 11.7bC show the difference spectra. In both cases, XPS clearly shows the presence of the O2 double layer, even under open-circuit conditions (Figs. 11.7aA, 11.7bA) and also clearly confirms the electrochemically controlled backspillover of O2 from the YSZ orTi02 support onto the catalyst surface. Note that the binding energy of the backspillover O species is in both cases near 529 eV, which confirms its strongly anionic (probably O2 ) state.31,32...

Consider an atom approaching the surface in Fig. 6.23. If the upper level of the atom originally contained an electron, then upon adsorption it will transfer part of this electron density to the metal and become positively charged. This is the case with alkali atoms. The atom forms a dipole with the positive end towards the outside, which counteracts the double layer that constitutes the surface contribution to the work function of the metal (Fig. 6.13). Thus alkali atoms reduce the work function of a metal surface simply because they all have a high-lying s electron state that tends to donate charge to the metal surface. 

Studies of theadsorption of surface-active electrolytes at the oil,water interface provide a convenient method for testing electrical double-layer theory and for determining the state of water and ions in the neighborhood of an interface. The change in the surface amount of the large ions modifies the surface charge density. For instance, a surface ionic area of 100 per ion corresponds to 16 pC per square centimeter. " " ... 

Among MC lattice models of the double layer, it is also worth mentioning the work of Nazmutdinov et al. (1988), who used a lattice model involving two mono-layers of water molecules on the surface of an electrode, forming a hexagonal close-packed array. The interaction of each water molecule in contact with the metal surface (assumed to be Hg) was taken from quantum-mechanical calculations. Information was obtained concerning the relative numbers of molecules with different numbers of hydrogen bonds, and it was concluded that the hypothesis of an icelike state of water in a monolayer on Hg is rather unlikely. 

The fact of a transfer of an electron from an absorbed particle to adsorbent [25] is widely considered as a criterion to differentiate between various forms of adsorption. Yet, as it has been already mentioned in previous section, there is a neutral form of chemisorption, i.e. weak binding formed without changing the surface charge state which only affects the dipole component of the work function. On the other hand, in several cases the physical adsorption can result in electron transitions in solids. Indeed, apart from formation of a double layer, changing the work function of adsorbent [26] the formation of surface dipoles accompanying physical adsorption can bring free charge carriers to substan-... 

These measurements have verified that the work function of an electrode, emersed with the double layer intact, depends only on the electrode potential and not on the electrode material or the state of the electrode (oxidized or covered with submonolayer amounts of a metal) [20]. Work function measurements on emersed electrodes do not serve the same purpose as in surface science investigations of the solid vacuum interface. At the electrochemical interface, any change of the work function by adsorption is compensated by a rearrangement of the electrochemical double layer in order to keep the applied potential i.e. overall work function, constant. Work function measurements, however, could well be used as a probe for the quality of the emersion process. Provided the accuracy of the measurement is good enough, a combination of electrochemical and UPS measurements may lead to a determination of the components of equation (4). 

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