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distance r is large and thus K is very small Consequently, in the evolution of hydrogen at metals that adsorb hydrogen atoms very weakly, such as Hg, Pb, Tl, Cd, Zn, Ga and Ag, reaction (571) is the rate-controlling step At high overpotentials, Eq (5317) is valid for the dependence of the rate constant on the potential At lower overpotentials (at very small current densities) barrierless charge transfer occurs (see page 274), as indicated in Fig 539 Distinct adsorption of hydrogen can be observed with electrodes with a lower hydrogen overpotential, such as the platinum electrode This phenomenon can be studied by cyclic voltammetry, as shown in Fig 540 for a poly crystalline electrode The potential pulse begins at E = 00 V, where the electrode is covered with a layer of adsorbed hydrogen.

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LC copolymers were prepared, and their photochemical phase transition behavior was examined (Tsutsumi et al, 1998a; Sasaki et al, 1992; Ikeda et al, 1990b,c) One of the important factors of the photoresponsive LCs is their responses to optical stimuli In this respect, the response time of the photochemical phase transition has been explored by time-resolved measurements (Sasaki et al, 1992; Ikeda et al, 1991; Kurihara et al, 1990) Photochromic reactions are in general very fast, occurring on a timescale of picoseconds If an ultrafast laser with a pulse width on the picosecond scale is used as an excitation light source to induce phase transitions of LC systems containing photochromic molecules, photochemical reactions of the photochromic molecules can be completed in picoseconds, and the Tc of the system can be decreased below the irradiation temperature on this timescale.

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When the potential is shifted to a more positive value, the adsorbed hydrogen is oxidized in two anodic peaks in the potential range from 01 to 04 V At even more positive potentials, no electrode process occurs and only the current for electrode charging flows through the system This is especially noticeable at high polarization rates The potential range from 04 to 08 V is termed the double-layer region At potentials of E > 08 V, 'adsorbed oxygen' begins to form, ie a surface oxide or a layer of adsorbed OH radicals This process is characterized by a drawn-out wave Evolution of molecular oxygen starts at a potential of 18 V When the direction of polarization is reversed, the oxide layer is first gradually reduced This process has a certain activation energy and occurs at more negative potentials than the anodic process.

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This means that immediately after pulse irradiation, a nonequilibrium state is produced, which is thermodynamically an isotropic phase in its equilibrium state but shows an anisotropy because orientational relaxation of mesogens is not completed The response of the whole LC systems depends strongly on this orientational relaxation of the mesogens, which in fact is the rate-determining step, especially in highly viscous LC polymers that require a relatively long time (Ikeda, 2003) A new system has been developed in which every mesogen in the LC or LC polymer is photosensitive (Ikeda, 2001; Tsutsumi et al, 1998b; Tsutsumi et al, 1997; Ikeda and Tsutsumi, 1995) For example, the azobenzene moiety could play roles as both a mesogen and a photosensitive moiety (Fig 320) in azobenzene derivatives that form LC phases.

The reduction of oxonium ions, accompanied by adsorption, occurs at the same potentials as the opposite anodic process If this experiment is carried out on the individual crystal faces of a single-crystal electrode (see Fig 541),.

These azobenzene LCs show a stable LC phase only when the azobenzene moiety is in the trans form, but do not show an LC phase when all the azobenzene moieties are in the cis form Examination of these azobenzene LCs revealed that a nematic isotropic phase transition is induced in the azobenzene LC polymers within 200 ns over a wide temperature range under optimized conditions (Ikeda, 2001)..

Fig. 5.39 Tafel plot of hydrogen evolution at a mercury cathode in 0.15 M HC1, 3.2 M KI electrolyte at 25 C. (According to L. I. Krishtalik)

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