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This chapter will be concerned with the kinetics of charge transfer across an electrically charged interface and the transport and chemical processes accompanying this phenomenon. Processes at membranes that often have analogous features will be considered in 6. The interface that is most often studied is that between an electronically conductive phase (mostly a metal electrode) and an electrolyte, and thus these systems will be dealt with first. A system consisting of two electrodes in an electrolyte medium is called an electrolytic cell. It should be realized here that there is no basic difference between the concepts of a 'galvanic cell' and an 'electrolytic cell'. In common usage, the term 'galvanic cell' is understood to refer to a system in the absence of current flow (it can be at equilibrium, as mentioned in the previous chapter, or only in a steady state, as will be demonstrated in Section 5.8.4 on mixed potentials) or to a system that yields electric work to its surroundings; an 'electrolytic cell' is then a system receiving energy from its surroundings to carry out the required chemical conversions. In fact, however, a given system sometimes can have both functions depending on the electrical potential difference between the electrodes. If an electrode reaction at a given electrode results in the transfer of a positive electric charge from the electrolyte to the electrode material or a negative charge from the electrode material to the electrolyte, then the corresponding current is defined as cathodic (/c) and the process is termed a

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As generally LbL procedure is rather tedious and time consuming (even using robotic technique available nowadays), from the practical viewpoint it would be attractive only in case of rather thin lms Figure 27 displays low molecular azobenzene derivatives, some of them commercially available, which were used to study photoinduced orientation Both negatively and positively charged dyes have been employed Relatively high dichroic ratio up to 23 due to geometry of the molecule (high aspect ratio of Direct Red 80) has been achieved (Advincula et al, 2003) To manufacture these lms with PDADMAC of ca 100-nm thickness, 100 layers were necessary Less effective photoorientation of spin-coated and LbL lms with other polyelectrolyte (PAH, PEI) was attributed to speci c formation of J-aggregates in LbL lms In the LbL lms produced from chitosan and Sunset Yellow (dos Santos et al, 2002), spontaneous birefringence of 0.

246 cathodic reaction or reduction In the opposite case, the current is termed anodic (/a) and the process is an anodic reaction or oxidation The terms cathode and anode have already been defined in Section 111 For example, in a Daniel cell (see Section 314), the cathode is the copper electrode when the cell carries out work; if the applied voltage is greater than the equilibrium value, current flows in the opposite direction and the cathode becomes the zinc electrode at which zinc ions are reduced According to the IUPAC convention, anodic current is considered to be positive and cathodic current to be negative Generally, an electrode that is macroscopically characterized by a smooth surface actually contains many steps and other microscopic irregularities The real (physical) electrode surface Ar is thus mostly larger than the geometric (macroscopic) surface Ag.

04 for the lm of 300-nm thickness was observed; however, the value was not affected by the light This fact underlines the importance of selection of dye and polyelectrolyte Some indications of the in uence of ionic azobenzene derivative structure (Fig 27) and polyelectrolyte can be deduced from a number of azobenzene derivative studied (Ziegler et al, 2002) All studied LbL lms (24 layers) exhibited only out-of-plane orientation Only for anionic-derivative Z1 (indicated in Fig 27) and only with PDADMAC, dichroic ratio of 2 was observed In the layers of Z1, but with PEI as polyelectrolyte, photoorientation and photoisomerization are totally restricted by strong aggregation The high value of dichroism of PDADMAC/Z1 layers should be caused by the hexamethylene spacer of Z1, which results in higher mobility necessary for the orientation process.

The current density is usually defined as the current divided by the geometric surface area The ratio of the real and geometric surface areas is termed the roughness factor, / R = AT/Ag The physical and geometric surface areas are identical at mercury and other liquid electrodes The flow of electric current through the electrolytic cell is connected with chemical, electrochemical and physical processes which, as a whole, are termed the electrode process The main electrochemical step in the electrode process is the actual exchange of charged species between the electrode and the electrolyte, which will be termed the electrode reaction (charge transfer reaction) Substances participating directly in the charge transfer reaction are termed electroactive These substances can be either soluble or insoluble in the electrolyte or electrode material Common basic types of electrode reactions are as follows: 1.

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