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Energetic reversibility is achieved when the same amount of electrical work is supplied from the cell reaction proceeding in one direction as is gained from the reaction proceeding to the same degree in the opposite direction Reversible operation of the cell requires that no other process occurs in the cell than that connected with the current flow An electrochemical process that need not be always connected with the passage of current is the dissolution of a metal in an acid (eg zinc in sulphuric acid in the Volta cell) or the dissolution of a gas in an electrolyte solution (eg in a cell consisting of hydrogen and chlorine electrodes, hydrogen and chlorine are dissolved.

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Figure 6.12. A possible design of light-responsive schizophrenic micelle based on azobenzene-containing diblock copolymers.

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159 and hydrogen chloride can be formed in solution even without current flow; this reaction, however, is strongly inhibited kinetically). Another process that can occur in the absence of current passage is diffusion. In a concentration cell (see Section 3.2.1), the concentrations of the two solutions can be equalized, even in the absence of current passage, through diffusion alone. However, this part will consider cells for which both of the criteria of thermodynamic reversibility are satisfied. The irreversible processes described must not occur even on open circuit. In a reversible cell, a definite equilibrium must be established and this may be defined in terms of the intensive variables in a similar way to the description of phase and chemical equilibria of electroneutral components. Further, the passage of a finite amount of charge corresponds to a certain degree of energetic irreversibility, as the electrical work is converted into Joule heat because of the internal resistance of the cell and also in the external circuit; in addition, electrode processes involve a certain overpotential (see 5). Thus, the cell can work reversibly only on passage of negligible current, i.e. when the difference between the balancing external voltage and the EMF of the cell approaches zero. It should be noted that the reversibility of the galvanic cell has so far been considered from a purely thermodynamic point of view. 'Reversible electrode processes' are sometimes considered in electrochemistry in a rather different sense, as will be described in 5. A galvanic cell is usually depicted in terms of chemical symbols. The phase boundary is designated by a vertical line. For aqueous solutions, the dissolved substances and their concentrations are indicated, and for non-aqueous solutions, also the solvent. For example, the cell Hg, Zn(12%) | ZnSO4(sat.), Hg2SO4(sat.) | Hg (3.1.37)

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described pH-responsive schizophrenic BCP micelle composed of blocks of weak polyacid and polybase, which switches between two structures upon pH change (Butun et al, 2001) Later, BCP micelles with temperature change induced switching were demonstrated with the use of two polymers having respectively an LCST and a upper critical solution temperature (UCST) (Arotcarena et al, 2002) Conceptually, it would be possible to design a diblock copolymer, while both blocks bearing an azobenzene moiety with a very different substitution pattern (azobenzene-1 and azobenzene-2) Azobenzene-1 should have a large dipole moment for the more stable trans isomer and a low dipole moment for the cis isomer, while azobenzene-2 must have exactly the opposite change in dipole moment In a blockselective solvent, BCP micelles can be formed.

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consists of a zinc amalgam electrode and a mercury electrode; the common electrolyte is a saturated solution of zinc and mercury sulphates. As has already been mentioned, the EMF (the electromotive force) of a cell is given by the potential difference between leads of identical metallic material. In view of this, a galvanic cell is represented schematically as having identical metallic phases at either end. The phases in the scheme are always numbered from the left to the right, but the cell can be depicted graphically in two ways. For example, there are two possibilities for the Daniell cell: 1 2 3 4 1' 2+ 2+ Zn | Zn | Cu | Cu | Zn 1 2 3 4 1' Cu | Cu24" | Zn2+ | Zn | Cu

In a highly polar solvent, micelles would be formed with the azobenzene-2-containing block forming the core of micelle and the azobenzene-1-containing block forming the shell In a low polar solvent, the situation should be reversed In all cases, upon alternating UV and visible light irradiation for the trans cis and cis trans isomerization, micelles should reverse their structure as depicted in Fig 612, as a result of the switching polarity of the two azobenzene moieties By incorporating the two azobenzene moieties in a double hydrophilic BCP, it would be possible to obtain such light-responsive polymer micelles in aqueous solution.

The choice between (a) and (b) is not specified, but does determine the sign of the EMF of the cell. This quantity is always defined so that the electrical

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