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In view of this equation the effect of the ionic atmosphere on the potential of the central ion is equivalent to the effect of a charge of the same magnitude (that is zke) distributed over the surface of a sphere with a radius of a + L D around the central ion. In very dilute solutions, LD a; in more concentrated solutions, the Debye length L D is comparable to or even smaller than a. The radius of the ionic atmosphere calculated from the centre of the central ion is then L D + a. Work w2 can now be calculated and, from this value, the total electric work Wel, found in an analogous way to that previously used for the case of the limiting law, yielding Ve2 Y Nz2 ln W*i= - A (! + K ) 3 V t

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the absorbance of the p p* transition band at 360 nm decreases and the absorbance of the n p* transition band at 450 nm increases gradually. The relative absorbance A(t) is de ned as A/Aorigin, where Aorigin and A are the absorbance at 360 nm before the light irradiation and after the irradiation for different time periods. The gure shows the relative absorbance of the solutions and suspensions as a function of the UV light irradiation time and the tting curves of the rstorder exponential decay function. The suspensions have an initial polymer concentration of 0.5 mg/mL and different water contents. When the water content is in the range 23.1% 33.3% (vol%), the trans-to-cis photoisomerization kinetics is similar for the systems. As CWC is 26.8% (vol%) obtained from light-scattering measurement, the observation indicates that the isomerization rate does not change signi cantly just above CWC. When the water content further increases to 40% 50% (vol%), the photoisomerization rate starts to decrease obviously. When the water content is even higher (80%, vol%), the isomerization rate decreases drastically, but it is still faster than that of the spheres obtained from the quenching and dialysis procedure. The trans-to-cis isomerization degree at the photostationary state indicates a similar tendency (Fig. 5.6). The isomerization degree at the photostationary state is estimated from (Victor and Torkelson, 1987) 5:1 isomerization degree 1:05 1 As =Aorigin where As is the 360 nm absorbance measured at the photostationary state. When the water content increases in range from 25% to 37.5% (vol%), the isomerization degree is 80% (vol%) and almost keeps constant with the water content increase.

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0.85 0.80 Isomerization degree 0.75 0.70 0.65 0.60 0.55 0.50 20 30 40 50 60 Water content (v%) 70 80

(L3.28)

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Figure 5.6. The relationship between the isomerization degree at the photostationary state and the water content. The suspension was prepared from a THF solution with the initial polymer concentration of 0.5 mg/mL. Source: From Li et al., 2006a.

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(The expression in square brackets follows from the integral a3 J [q2/(l + Ka)] dq after introducing the limits 0 and zke.) The expression for the activity coefficient is calculated from the differential dWjdnk (neglecting the dependence of V on nk) by substitution into Eq. (1.3.21). Rearrangement yields

When the water content further increases, the isomerization degree starts to decrease. When the water content increases from 37.5% to 80% (vol%), the isomerization degree decreases from 80% to ca. 55%. For the spheres in the water suspension, obtained by quenching with an excessive amount of water and dialysis, the isomerization degree decreases to even 33%. The preceding results obtained from the UV-vis spectroscopic measurements indicate that in the water addition process, the aggregates undergo a collapse process after the water content is above 40% (vol%). In the water addition process, the water-adding rate shows a critical in uence on the colloid formation. The slow addition rate is necessary to obtain uniform colloids. In a broad water-dropping rate, the sizes of the colloids obtained at the nal stage are almost the same. However, when the water-dropping rate is extremely slow, the colloid size will abruptly increase as the dropping rate further decreases and even the aggregates will precipitate from the suspension.

/2P2N () \

17

The numerical value of this constant is B = 1.5903 x 10 10 (D7r 1/2 = 502.90(DTym m1/2 mol"1/2 dm3/2 mol" m nm"1

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