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next begins, which is of great importance in crystal growth. In addition to steps, the crystal plane also contains individual metal atoms {ad-atoms, Fig. 5.24a) and ad-atom clusters (Fig. 5.24b). A. Kossel and I. Stranski have stated that the individual atoms in the crystal plane have different energies depending on their degree of contact with the other atoms of the crystal. The atoms inside the crystal have the lowest energy, as would be expected, followed by the atoms incorporated in the crystal plane and then by atoms in steps and in kinks and by ad-atoms. In addition, in the great majority of cases metal crystals contain irregularities in the crystal lattice, termed dislocations. The role of screw dislocations will be considered in Section 5.8. In this type of dislocation, the individual atomic planes in the crystal are mutually translocated by a small angle, so that a wedge-shaped step arises from the crystal surface (Fig. 5.25). A single-crystal electrode without dislocations can be made by the method described by E. Budevski et al. A silver single crystal is fused in a glass tube with a capillary opening. This electrode is used as the cathode in the electrolysis of AgNO3 by direct current with a small superimposed a.c. component. The front face then grows as a perfect, dislocation-free face, filling the cross-section of the capillary, usually approximately 0.2 mm in diameter. Fundamental studies of the electrolyte solution/solid electrode interface



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The Alcatel-Lucent SR/ESS series products can be accessed in three ways: in-band ports such as on MDAs, a console port, and a CPM Ethernet management port. The console port is a DB-9 serial port on the SF/CPM card for a modular chassis or on the chassis itself for the SR-1 or ESS-1. The location of these ports is shown in Figure 2.14.





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can only be made by using well-defined single crystal electrodes. This additionally requires not only electrochemical methods of characterization, but also other methods supplying detailed structural information (LEED, STM, etc., see Section 5.5.6). Solid metal electrodes are usually polished mechanically and are sometimes etched with nitric acid or aqua regia. Purification of platinum group metal electrodes is effectively achieved also by means of high-frequency plasma treatment. However, electrochemical preparation of the electrode immediately prior to the measurement is generally most effective. The simplest procedure is to polarize the electrode with a series of cyclic voltammetric pulses in the potential range from the formation of the oxide layer (or from the evolution of molecular oxygen) to the potential of hydrogen evolution (Fig. 5.18F). The most important electrode material is platinum. Its widespread electrochemical use follows from its relatively high chemical inertness and electrocatalytic properties. The available potential window of platinum (the potential region where there is comparatively small faradaic current flow) is the interval from about 0 to +1.6 V versus SHE in acidic aqueous electrolytes; the negligible hydrogen overpotential of platinum makes it ideally suitable for the preparation of a standard hydrogen electrode (see Section 3.2.1). Platinum electrode is in aqueous electrolytes quickly covered, according to the polarization voltage, either with adsorbed hydrogen or surface oxide; only in a narrow potential interval (from 0.4 to 0.8 V versus SHE, the so-called 'double layer region') the Pt surface might be considered almost free from adsorbed or chemisorbed species. In practice, however, anions or organic impurities are always adsorbed even in this potential region. The Pt surface particularly interacts with double bonds in organic molecules. Chemisorption of electroactive olefinic molecules has also been employed for the preparation of chemically modified electrodes (see below).

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Platinum electrodes are made usually from polycrystalline metal; the crystal planes at the surface include both the (111) and (100) faces in approximately equal proportions The electrochemical properties of Pt(lll) and Pt(100) faces are not identical (Generally, the physical properties of individual metal crystal faces, such as work function, catalytic activity, etc, are different) Cyclic voltammetry studies of single-crystal platinum electrodes in acidic aqueous electrolytes showed that the two characteristic peaks of hydrogen adsorption/desorption on platinum (see Fig 540) correspond in fact to reactions at two different crystal faces: the peak at lower potential to Pt(lOO) and the other one to Pt(lll) The opposite case to Pt single crystal are electrodes whose surface area has been increased by covering with platinum black.

Figure 2.14 This figure shows the CPM serial console port and the CPM out-of-band Ethernet management port.

This so-called platinized platinum electrode (see page 173) shows up to 1000 x higher physical surface area than the geometric surface area (the ratio of these two quantities is called roughness factor, see page 246) An increase in the physical surface area (roughness factor) of the electrode results in decreasing the relative coverage with surface-active impurities The roughness factor of a single- crystal electrode is theoretically equal to one, but this value can hardly be achieved in view of microscopic imperfections of the real crystal face (see Fig 524) A bright polycrystalline platinum electrode shows a roughness factor 13-3 depending on the level of polishing The second most widely used noble metal for preparation of electrodes is gold Similar to Pt, the gold electrode, contacted with aqueous electrolyte, is covered in a broad range of anodic potentials with an oxide film.

SR-1

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