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167 0.2224 V vs. SHE. Sometimes electrode potentials are referred to other reference electrodes, such as the saturated calomel electrode (SCE), etc. So far, a cell containing a single electrolyte solution has been considered (a galvanic cell without transport). When the two electrodes of the cell are immersed into different electrolyte solutions in the same solvent, separated by a liquid junction (see Section 2.5.3), this system is termed a galvanic cell with transport. The relationship for the EMF of this type of a cell is based on a balance of the Galvani potential differences. This approach yields a result similar to that obtained in the calculation of the EMF of a cell without transport, plus the liquid junction potential value A0 L . Thus Eq. (3.1.66) assumes the form cell = rhs - .hs + A0 L (3.1.67)

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The orientation of lamellar and cylindrical microdomains in azo LCBCs has been triggered with a shearing ow yielding highly oriented samples (e.g., Osuji et al., 1999; Osuji et al., 2000). During oscillatory shearing of PS-based azo LCBCs at LC temperature or in an isotropic phase, the LC phase has a distinct effect on the orientation of microphase-separated nanodomains. Upon transformation from the LC phase to the isotropic phase, the LC orientation is lost, whereas the orientation of nanocylinders is sustained. Interestingly, the uniaxial planar orientation of the mesogens is recovered completely on cooling from an isotropic melt. This spontaneous reorientation of the LC phase takes place after repeating the heating and cooling cycles above and below the LC isotropic phase transition temperature,

However, in contrast to the EMF of a galvanic cell, the resultant expressions contain the activities of the individual ions, which must be calculated by using the extrathermodynamic approach described in Section 1.3. Concentration cells are a useful example demonstrating the difference between galvanic cells with and without transfer. These cells consist of chemically identical electrodes, each in a solution with a different activity of potential-determining ions, and are discussed on page 171. It is very often necessary to characterize the redox properties of a given system with unknown activity coefficients in a state far from standard conditions. For this purpose, formal {conditional) potentials are introduced, defined in terms of concentrations. Definitions are not given unambiguously in the literature; the following would seem most suitable. The formal (conditional) potential is the potential assumed by an electrode immersed in a solution with unit concentrations of all the species appearing in the Nernst equation; its value depends on the overall composition of the solution. If the solution also contains additional species that do not appear in the Nernst equation (indifferent electrolyte, buffer components, etc.), their concentrations must be precisely specified in the formal potential data. The formal potential, denoted as EOf, is best characterized by an expression in parentheses, giving both the half-cell reaction and the composition of the medium, for example '(Zn 2+ 4- 2e = Zn, 10"3M H2SO4). Coming back to equations for Galvani potential differences, (3.1.11) to (3.1.26), we find that equation (3.1.67) can be written in the form cci = A^220 - Agj'0 + A0 L (3.1.68)

showing that the oriented nanocylinders act as an anchoring substrate for the LC mesogens (Tokita et al., 2007; Tokita et al., 2006). Undoubtedly, other approaches for controlling microphase separation in lms of amorphous BCs, such as solvent evaporation, lm thickness, modi ed substrates, mixture with homopolymers, and roll casting, can also be used with azo LCBC.

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where A 20 is the Galvani potential difference between the right-hand side electrode and the solution S2 in which it is immersed and A '0 is the analogous quantity for the left-hand side electrode. When the left-hand side electrode is the standard electrode and A0 L is kept constant (see page 114), then Ecell can be identified with a formal electrode potential given by the

Holographic gratings have potential applications in information technology, which can be recorded on both amorphous and LC polymers through photoisomerization or photochemical phase transition of azo chromophores (e.g., Rochon et al., 1995; Kim et al., 1995). Diffraction ef ciency (DE) is one of the most important parameters of holographic gratings. In amorphous materials, surface relief grating (SRG) contributes mainly to DE. Azo BCs are good candidates to control DE by SRG enhancement upon microphase separation (Yu et al., 2009, 2005b). As shown in Fig. 12.18, after a preirradiation treatment, both SRGs and refractive index gratings (RIGs) were recorded in PEO-based azo LCBC lms upon irradiation of an interference pattern obtained with two coherent laser beams, in which selective

168 approximate relationship + constant (3.1.69)