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Niessen described the electric double layer at ITIES using a simplifying assumption that consists of only two diffuse electric layers, each in one of the phases (see Fig 41C) The overall potential difference between the two phases, A^^, is thus given by the relationship A:0 = 0 2 (o)-0 2 (w) (4518) where the potential differences in the diffuse layers, 02(o) and 02(w), are defined such that the potential in the bulk of the phase is subtracted from the potential at the interface The terms <j)2{o) and $2(w) are given by Eq (4314), where the appropriate permittivity, e(w) or e(o), is substituted for each phase, along with the electrolyte concentrations c(w) and c(o) As the surface charges a(w) and a(o) are equal except for the sign (cf Eq 411), Eqs (4518) and (43.

248 HPMC [Zheng, 2004] Neutral [Alonso, 2001] 5.5 1.7 Elastin carboxylate-modi ed [Strzegowski, 1994] N.A. 2.8 acrylic/glycolic acids [Liu, 2001] n.a. 2.0 B16b 6.370.7

14) can be used to calculate the dependence of $2(o) and 02(w) on A ^ The electrical double layer has, of course, a similar structure when a single electrolyte is present in the distribution equilibrium in the system It is interesting that the experimentally measured zero-charge potential is practically identical with the value of A 0 = 0, calculated using the TATB assumption (3264) This fact helps to justify the use of this assumption The electrical double layer at the solid electrolyte-electrolyte solution interface has been studied primarily in colloid suspensions, especially for silver halides The potential difference between the solid and liquid phases can be changed by changing the concentration of the 'potential-determining ions', ie either the silver or halide ions In solid oxide suspensions, hydrogen ions act as potential-determining ions.

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TAB L E 7 .1 . Indices of LCST Shifts with Integration Level of Azobenzene Side Groups and Upon Photo-isomerisation

The zero-charge potential of this system can be found from the dependence of the electrophoretic mobility (see Section 454) on the concentration of potential-determining ions, ie it corresponds to zero electrophoretic mobility With this type of interface the structure of the electrical double layer depends to a marked degree on the preparation and thus also on the final structure of the solid phase Two cases are most often observed: (a) Ions are adsorbed from solution on the surface of the solid phase and counter ions form a diffuse layer..

(b) The electrical double layer has a structure similar to ITIES, but the diffuse layer in the solid becomes a simple Helmholtz layer because of the high concentration of ions. It should, however, be noted that the electrical double layer at the metal-fused electrolyte interface does not have this character, in spite of the ion concentration being high. In this system, the space charge includes several ion layers at the interface. 4.5.3 Electrokinetic phenomena The adsorption of ions at insulator surfaces or ionization of surface groups can lead to the formation of an electrical double layer with the diffuse layer present in solution. The ions contained in the diffuse layer are mobile while the layer of adsorbed ions is immobile. The presence of this mobile space charge is the source of the electrokinetic phenomena.^ Electrokinetic phenomena are typical for insulator systems or for a poorly conductive electrolyte containing a suspension or an emulsion, but they can also occur at metal-electrolyte solution interfaces. Consider a solid surface in contact with a dilute electrolyte solution. The plane where motion of the liquid can commence is parallel to the outer Helmholtz plane but shifted in the direction into the bulk of the solution. The electric potential in this plane with respect to the solution is termed the

effects of photoisomerization into the cis state, thermal relaxation back to the trans state, and possibly cis reconversion upon light absorption The steady-state composition is unique to each system, as it depends on the quantum yields for the two processes (Ftrans and Fcis) and the thermal relaxation rate constant The composition also depends on irradiation intensity, wavelength, temperature, and the matrix (gas phase, solution, liquid crystal, sol gel, monolayer, polymer matrix, etc) Azos are photochromic (their color changes on illumination), since the effective absorption spectrum (a combination of the trans and cis spectra) changes with light intensity Thus absorption spectroscopy can be conveniently used to measure the cis fraction in the steady state (Rau et al, 1990; Fischer, 1967), and the subsequent thermal relaxation to an all-trans state (Beltrame et al, 1993; Hair et al, 1990; Eisenbach, 1980a; Gabor and Fischer, 1971).

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Nuclear magnetic resonance (NMR) spectroscopy can also be used (Magennis et al, 2005) Under moderate irradiation, the composition of the photostationary state is predominantly cis for azobenzenes, mixed for aminoazobenzenes, and predominantly trans for pseudo-stilbenes In the dark, the cis fraction is below most detection limits, and the sample can be considered to be in an all-trans state Isomerization is induced by irradiating with a wavelength within the azo s absorption spectrum, preferably close to lmax Modern experiments typically use laser excitation with polarization control, delivering on the order of 1 100 mW cm 2 of power to the sample Various lasers cover the spectral range of interest, from the UV (Ar+ line at 350 nm) through blue (Ar+ at 488 nm), green (Ar+ at 514 nm, YAG at 532 nm, HeNe at 545 nm), and into the red (HeNe at 633 nm, GaAs at 675 nm).