Emersion

As a furtlier example for tire meaning of ex situ investigations of emersed electrodes witli surface analytical teclmiques, results obtained for tire double layer on poly crystalline silver in alkaline solutions are presented in figure C2.10.3. This system is of scientific interest, since tliin silver oxide overlayers (tliickness up to about 5 nm) are fonned for sufficiently anodic potentials, which implies tliat tire adsorjDtion of anions, cations and water can be studied on tire clean metal as well as on an oxide covered surface [55, 56]. For tire latter situation, a changed... 

Figure C2.10.3. Ex situ investigation of the electrochemical double layer on Ag after hydrophobic emersion from 1 M NaClO + 0.1 M NaOH. (a) Peak deconvolution of the XPS 01s signals after emersion at +0.2 V A surface...

Figure C2.10.4. XPS Cl 2p signals of an iron specimen emersed from 1 M HCIO (a) after passivation at 1 V (SHE) (b) after 2 minutes pitting corrosion at 1.5 V (SHE). Contributions of CIOj at 208 eV and CE at 198 eV are visible in different amounts.

Kolb D M, Rath D L, Wille R and Flansen W N 1983 An ESCA study on the electrochemical double layer of emersed electrodes Ber. Bunsenges. Phys. Chem. 87 1108-11 131... 

Refraction Index. Refraction index is deterrnined with a petrographic microscope by submersing a sample in emersion oils of known refractive index. 

A third experimental configuration was proposed by Kolb and Hansen40 emersed electrodes. If an electrode is emersed from a solution while the control of the potential is maintained, the solvent layer dragged off with the metal (Fig. 3) would reproduce UHV conditions, but with potential control and at room temperature, as in the actual electrode situation. This appears to be the most convenient configuration for measuring 0. However, there are doubts that the solvent layer retains the properties of a bulk phase. It has in fact been demonstrated41 that a contact potential difference exists between an electrode in the emersed state and the same electrode regularly immersed in solution. 

Figure 3. Sketch of an emersed electrode. M is the metal, S is the solvent (electrolyte solution), (a) < is the work to extract an electron from M through S. (b) The emersed electrode drags a liquid layer with it, through which the measurement of is apparently the same as in (a). The question mark is meant to cast doubts on that.

A value close to 4.8 V has been obtained in four different laboratories using quite different approaches (solid metal/solution Ay, 44 emersed electrodes,40,47 work function changes48), and is apparently supported by indirect estimates of electronic energy levels. The consistency of results around 4.8 V suggests that the value of 4.44 V is probably due to the value of 0 not reflecting the actual state of an Hg jet or pool. According to some authors,44 the actual value of 0 for Hg in the stream should be 4.8 V in that the metal surface would be oxidized. 

On the other hand, potential measurements at the free surface of purified water have shown50 that the value for a flowing surface differs by about 0.3 V from that for a quiescent surface, as a result of adsorption of surface-active residual impurities in the solution (probably also coming from the gas phase). Since emersed electrodes drag off the surface layer of the solution as they come out of the liquid phase, the liquid layer attached to emersed solid surfaces might also be contaminated. 

It is intriguing that upon emersion the value of A0 changes up to about 0.3 V compared with the immersed state.41 This has been attributed42,51 to the different structure of the liquid interfacial layer in the two conditions. In particular, the air/solvent interface is missing at an emersed electrode because of the thinness of the solvent layer, across which the molecular orientation is probably dominated by the interaction with the metal surface. 

The situation believed to exist at an emersed electrode is sketched in Fig. 4. It is seen that while A in the immersed state is given by Eq. (20) rewritten as... 

Figure 4. Sketch to illustrate the situation believed to exist at a metal surface upon adsorption of water from the gas phase (or at the surface of an emersed electrode). In particular, the layer thickness is so small that the orientation of solvent molecules at the external surface is strongly affected by the orientation at the internal surface.

Emersed electrode, 12 Energy scales and electrode potentials, 7 Energy transitions via polaronic and bipolaronic levels, 362 Engineering models, for fluorine generation cells, 539 Esin and Markov plots, 259-260 Experimental data comparison thereof, 149 on potential of zero charge, 56... 

Murphy and Waynewright, and change of upthrust on emersed metal, as a method of measuring, 34 Nikitas, at the air-solution interface, 30 in non-aqueous solutions, 71 for a nonpolarizable electrode, 4... 

The deviations of type (a) are similar to these observed with emersed... 

Z. Samec, B.W. Johnson, and K. Doblhofer, The absolute electrode potential of metal electrodes emersed from liquid electrolytes, Surf. Sci. 264, 440-448 (1992). 

Figure 7.2. Schematic of a normal (a) and an emersed (b) electrode in aqueous electrochemistry showing the conceptual similarity of case (b) with Fig. 7.1b (adapted from Trasatti16). Reprinted with permission from Elsevier Science.

It is worth noting in Figures 7. lb and 7.2b that the zero energy level choice (point C) is not only, by definition, a point in vacuum close to the surface of the solution (Fig. 7.1a, 7.2a), but also, as clearly shown by Trasatti,16 a point in vacuum close to the surface of the emersed (liquid or adsorption covered) electrode. 

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. 

In summary, the creation via ion spillover of an effective electrochemical double layer on the gas exposed electrode surfaces in solid electrolyte cells, which is similar to the double layer of emersed electrodes in aqueous electrochemistry, and the concomitant experimentally confirmed equation... 

D.L. Rath, and D.M. Kolb, Continuous work function monitoring for electrode emersion, Surf. Sci. 109, 641-647 (1981). 

It is also worth noting that the one-to-one correspondence between change in (ohmic drop-free) catalyst potential and work function in solid-state electrochemistry,7,8 may also be applicable to the work function of liquid-free gas-exposed electrode surfaces in aqueous electrochemistry.8 Such surfaces, created when gases are consumed or produced on an electrode surface, may also play a role in the observed NEMCA behaviour. The one-to-one correspondence between eAUwR and AO is strongly reminiscent of the similar one-to-one relationship established with emersed electrodes previously polarized in aqueous solutions,9,10 as already discussed in Chapter 7. 

The contact angle between electrode and electrolyte solution can be determined using a solid and partially emersed electrode and observing the meniscus rise [68Mor, 69Mor, 71Mor]. (Data obtained with these methods are labelled CA). 

In studies designed to examine dermal absorption of trichloroethylene, emersion of the hand (Sato and Nakajima 1978) or thumb (Stewart and Dodd 1964) for 30 minutes was reported to be pairrful. The pain was described as excruciating in one study (Sato and Nakajima 1978), and in another study it was described as mild by one subject and moderately severe by two subjects (Stewart and Dodd 1964). Occupational exposure to trichloroethylene that involved both dermal and inhalation exposure has been reported to result in dizziness, headache, insomnia, lethargy, forgetfulness, and loss of feeling in the hands and feet (Bauer and Rabens 1974 Kohlmuller and Kochen 1994). 

Lewera A, Inukai J, Zhou WP, Cao D, Duong HT, Alonso-Vante N, Wieckowski A (2007) Chalcogenide oxygen reduction reaction catalysis X-ray photoelectron spectroscopy with Ru, Ru/Se and Ru/S samples emersed from aqueous media. Electrochim Acta 52 5759-5765... 

A relatively new arrangement for the study of the interfacial region is achieved by so-called emersed electrodes. This experimental technique developed by Hansen et al. consists of fully or partially removing the electrode from the solution at a constant electrical potential. This ex situ experiment (Fig. 9), usually called an emersion process, makes possible an analysis of an electrode in an ambient atmosphere or an ultrahigh vacuum (UHV). Research using modem surface analysis such as electron spectroscopy for chemical analysis (ESCA), electroreflectance, as well as surface resistance, electrical current, and in particular Volta potential measurements, have shown that the essential features (e.g., the charge on... 

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