ε １ ε ２ Q 1 Q 2 Q ｓ 電気的中性の条件： Q 1 + Q ｓ + Q 2 =0 z 1 z 0 z 2 断面積 S の Gauss Box1 および Gauss Box2 内の電荷 Q 1,Q 2 とし, 界面に特異吸着した分子の電荷を Q s とする。

Gauss Box1: At z 1 : Between z 1 and z 0 : and between z 0 and z 2, no charge. At z 0 : At z 2 : Gauss Box2:

Algorithm 0) ε 1 、 ε 2 、 z 1, and z 2 are given. 1) At a given Q s (This is the big issue. It should be determined from the independent experiments such as interfacial tension measurements.) 2) Give Q 1 and Q 2 subject to Q 1 + Q s + Q 2 =0 3) calculate φ(z) 4) Detetmine Δφ 5) Check Δφis in agreement with exp. results Calculation example

Fig. 1. Schematic representation of potential profile across the RTMS|W interface with and without specific adsorption.  RTMS W was defined on the basis of  RTMS and  potential was defined on the basis of  w.  RTMS Mesi  water

Fig. 2. Structure of tetrahexylammonium1,4- bis(2-ethylhexyl) sulfosuccinate.

Fig. 3. Electrochemical cell for cyclic voltammogrammetry at the RTMS|W interfaces. Polarized RMTS|W interface Porous glass Water(25 ℃ ） a Micropipette

Fig. 4. Electrochemical cell for potentiometry at the RTMS|W interfaces.

Table 1. Physicochemical properties of water-saturated RTMSs.

図 RTMS の含水量と導電 率の関係

Fig. 5. SAXS spectra for. dry RTMSs(red) and water-saturated RTMSs(Blue) n=8 n=7 n=6 n=

Fig. 6. Cyclic voltammograms at the RTMS|W interfaces. Scan rate: 20 mV s -1. W ref. contains 1 mM NaBEHSS, 10mM KCl. Ag/AgClW ref. N nnnn BEHSS - (RTMS) 100 mM LiCl (W) Ag/AgCl

Fig. 7. Cyclic voltammograms at the N 5555 BEHSS|W interface. W contains x mM LiCl. Wref contains 100 mM NaCl, 1 mM N 5555 Cl.

Fig. 8. Plots of E of cell 1 against the time. W ref. contains 1 mM N 7777 Cl and 9 mM KCl. W contains x mM N 7777 Cl and 10-x mM KCl.

Fig. 9. Plots of E against the concentration of common ion in the W phase. Ionic Strength was 10 mM for n=6,7, 100 mM for n=5. W2 contains 10 mM N 5555 Cl for n=5, 1 mM N nnnn Cl for n=6,7. n=5 7 6

Fig. 10. Plots of E of cell 1 against the time. W ref. contains 1 mM N 6666 Cl. a ) W contains x mM N 6666 Cl and 1-x mM KCl. b) W contains x mM NaBEHSS and 1-x mM KCl. a) b)

Fig. 11. Plots of E of cell 1 against the time. W ref. contains 1 mM N 6666 Cl and 9 mM KCl. a ) W contains x mM N 6666 Cl and 10-x mM KCl. b) W contains x mM NaBEHSS and 10-x mM KCl. a) b)

Fig. 12. Plots of E against the concentration of common ion in the W phase. ●, ○ represents results with 1 mM ionic strength. ▲, △ represents results with 10 mM ionid strength.

Fig. 13. Size distribution of o/w type RTMS emulsion of N 7777 BEHSS.

Fig. 14. Dependence of  of O/W type N nnnn BEHSS emulsions on the concentration of the common ions in water. NaCl was added to the water phase to maintain ionic strength to 100 mM. n= 7 n=6 n=5 n= 8 n=7 n=6 n=5

Fig. 15. Plots of  potential of the O/W type N 6666 BEHSS emultion against the concentration of co-ions in the W phase. ○ (1 st ）, □ (2 nd ): W with ionic strength 1 mM. ▲, △ (1 st ), ☆ (2 nd ): W with ionic strength 10 mM. *: W with ionic strength 50 mM. ◎ : W with ionic strength 100 mM

Table 2. Change in slope of  potential against the concentration of common ion.

Fig. 16. Influence of  potential on light scattering intensity and average diameter of O/W type RTMS(N 5555 DOSS) emulsion dispersed into aquaous phase. ● : emulsion was kept at 25 ℃ for 100 minutes, ● : emulsion was kept at 25 ℃ for 2 days..

Fig. 17. plots of  potential against the phase boundary potential at the N 6666 BEHSS|W interface. We assumed smolchowski’s formula. W contains x mM co-ion and 1-x or 10-x mM KCl. Phase boundary potential across the N 6666 BEHSS|W interface was determined from the standard ion transfer potential at the 1,2-DCE|W interface.

Fig. 18. Dependence of electrophoretic mobility on  potential. We have used the formula for liquid suspension. The value for parameter was set to the real value. Viscosity of the water: mPa s, viscosity of the N 6666 BEHSS: 500 mPa s, diameter of the liquid particle: 1  m.

Fig. 19. electrophoretic mobility was plotted against the  potential. Viscosity of RTMS was set to be 100 times smaller than the real value. Diameter of the O/W emulsion was set to be 1000 times smaller than the real value.

Fig. 20. Blue points represent  potential from the Oshima’s formula for liquid particle. And it was obtained with following parameters. Viscosity of the particle was 100 times smaller than the real value. Diameter of the liquid particle was 1000 times smaller than the real value. Blue solid line represents the potential at the 2 nm from the RTMS|Winterface, and 3 nm from the interface.