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Figure 8.19. On-demand 3-D control of PS nanocylinders in a lm of PS-block-Az LC polymer. Reprinted with permission from the American Chemical Society.

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As the activities of the components of a solution are related by the Gibbs-Duhem equation, the measured activity coefficient of the solvent can readily be used to calculate the activity coefficient of a dissolved electrolyte All methods based on osmotic phenomena lead directly to measurement of activities; these include methods measuring the decrease in vapour pressure above the solution, boiling point elevation, freezing point suppression and direct measurement of the osmotic pressure Of these methods, the most commonly used is the cryoscopic method; ebulioscopic and osmometric methods are technically more complicated and are used less frequently Tensiometric methods are also often used, involving measurement of the vapour pressure of the solvent above the pure solvent / and above the solution p0 The ratio of these two values, po/poy gives the activity of the solvent in the solution Various methods are used to measure vapour pressure.

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An obvious effect of LPL irradiation to align MPS in block copolymer lms is demonstrated for a soft PEO-based Az-containing LC block copolymer lm by Yu et al. (2006) and a polystyrene (PS)-based block copolymer of higher Tg by Morikawa et al. (2007; Fig. 8.18). The MPS nanocylinders of the light-inert blocks aligned orthogonal to the direction of the electric eld vector of the irradiated LPL. As a rigid segment polymer, adjustment of annealing temperature is an important factor for the successful alignment. The macroscopically aligned MPS structure evolves at an annealing temperature slightly above Tg of PS block and below the smectic to isotropic transition of the LC Az polymer block. It is of note

Special tensiometers can be used to measure vapour pressure directly in tensiometric measurements Dynamic methods involve passing an inert gas first through the pure solvent, then through a drying adsorbent, further through the solution and then through another adsorbent; the ratio of the amounts of solvent adsorbed on the two adsorbents equals the ratio of the two vapour pressures The isopiestic method involves placing two solutions of various electrolytes B and C in a single solvent in a special cell and bringing them into equilibrium through the gaseous phase At osmotic equilibrium, the two solutions have the same vapour pressure and the same solvent activity; the molalities of the two solutions are measured at equilibrium, raB and mc.

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0.2 m (b) (c) (d)

If, for each value of the molality of one of the two electrolytes, for example B, the concentration dependence of the osmotic coefficient <j)B is also known, then <pc can be calculated from the equation Methodically, there is no great difference between measuring the mean activity coefficient in a solution of one electrolyte and measuring this quantity in a mixture of electrolytes Binary mixtures have been studied most extensively If osmotic methods are used, then the coefficients ocx and.

Figure 8.20. Hierarchical structures involved in photogenerated SRG of a block copolymer. (a) Topographical image, (b) phase images at a trough, (c) boundary, and (d) crest regions.

au can be calculated and, from these values, the activity coefficients using the above relationships. If the Harned rule is not valid, then similar, more complicated relationships are used that also contain the coefficients jSj and j8n. If potentiometric methods are used, then the activity coefficients are obtained directly, i.e. values of yY and y n for the given total molality and relative abundances of the two electrolytes. References

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Conway, B. E., Ionic interactions and activity behaviour, CTE, 5, Chap. 2 (1982). Friedman, H. L., Ionic Solution Theory, Wiley-Interscience, New York, 1962.

that the MPS alignment can be altered successively on demand both in the inplane and out-of-plane directions (Morikawa et al., 2007). This tunable procedure is a marked feature attained in the photoprocess (Fig. 8.19).

Harned, H. S., and B. B. Owen, The Physical Chemistry of Electrolytic Solutions,

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