Colloid Polym Sci (2010) 288:13131320 DOI 10.

1007/s00396-010-2263-1

ORIGINAL CONTRIBUTION

Miscibility of calcium chloride and sodium dodecyl sulfate in the adsorbed film and aggregates
Hidemi Iyota & Takako Tomimitsu & Makoto Aratono

Received: 15 April 2010 / Revised: 21 June 2010 / Accepted: 3 July 2010 / Published online: 25 July 2010 # Springer-Verlag 2010

Abstract The adsorption, micelle formation, and coagelparticle formation of sodium dodecyl sulfate in the presence of calcium chloride were studied from the viewpoint of mixed adsorption and aggregate formation of inorganic salt and surfactant. Judging from the phase diagrams of adsorption and aggregate formation, negative azeotropy takes place in the mixed adsorption and aggregate formation of calcium chloride and sodium dodecyl sulfate due to electrostatic attraction between calcium and dodecyl sulfate ions. The miscibility of calcium chloride and sodium dodecyl sulfate in the oriented states increases in the order, particle > adsorbed film > micelle. The difference in the miscibility was ascribed to the difference in geometry between the adsorbed film and micelle and to the interaction between bilayer surfaces in the particle. The particle-micelle equilibrium was thermodynamically considered by using the equilibrium composition of aggregates. Keywords Mixture of calcium chloride and sodium dodecyl sulfate . Miscibility . Adsorption and aggregate formation . Azeotropy . Particle-micelle equilibrium . Surface tension . Thermodynamic treatment of surfactant mixture

Introduction Adsorption and micelle formation of ionic surfactants in the presence of inorganic salts have been studied by many researchers [19]. Theoretical considerations of the surface tension vs. surfactant concentration and critical micelle concentration (CMC) vs. counterion concentration curves were made by modeling the electric double layers around adsorbed films and micelles [3, 6, 10, 11]. For ionic surfactant solutions with multivalent counterions, adsorption and micelle formation are highly affected by the valence of counterions and formation of micelles with mixed counterions or preferential binding of multivalent counterions to micellar surfaces is observed [8, 12, 13]. Furthermore, precipitation takes place due to strong electrostatic interaction between the multivalent counterion and surfactant ion [2, 14, 15]. Turbid solutions of the precipitates become transparent due to micelle formation by increasing the surfactant concentration [15, 16]. Precipitation boundaries have been determined for anionic surfactants in the presence of multivalent cations and described by the solubility product of precipitates [1518]. However, the miscibility of multi-univalent salt and surfactant and their interaction in micelles and coagel particles are required to understand the physico-chemical states of the aggregates [1921]. Particle-micelle equilibrium should also be thermodynamically considered to clarify the dissolution of precipitates in micellar solutions. In the previous studies [1921], we have investigated the adsorption, micelle formation, and salting out of ionic surfactants in the presence of inorganic salts from the viewpoint of mixed adsorption and aggregate formation of salt and surfactant. For the mixtures of salt and ionic surfactant with a common counterion, the miscibility of salt and surfactant in the adsorbed film and micelle is

H. Iyota (*) : T. Tomimitsu Department of Life and Environmental Science, Kagoshima Prefectural College, Shimo-Ishiki, Kagoshima 890-0005, Japan e-mail: iyota@k-kentan.ac.jp M. Aratono Department of Chemistry, Faculty of Science, Kyushu University, Fukuoka 812-858, Japan

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attributable to the repulsive interaction between inorganic coion and surfactant ion in the oriented states [19, 21]. The repulsion is enhanced by increasing the valence of coions [20]. Such repulsions and miscibility were not elucidated from the experimental results of Corrin and Harkins (the Corrin-Harkins plot) for the depression of CMC by added salts and the theoretical equations of Shinoda applied for the CMC depression neglecting the effect of coions compared with that of counterions [1, 3, 6]. The aim of the study is to investigate how the valence of counterions affects the miscibility of salt and ionic surfactant in adsorbed films and aggregates. Adsorption and aggregate formation of an ionic surfactant in the presence of bivalent counterions are studied by applying the thermodynamic treatment of surfactant mixture to the mixture of bi-univalent salt and anionic surfactant. Calcium chloride CaCl2 and sodium dodecyl sulfate (SDS) were selected because a sodium chloride-SDS mixture was studied previously [21] and the CMC of calcium dodecyl sulfate is much smaller than that of SDS [2224].

b Sample solutions at constant X2 were prepared by dilution from the stock solution. The stock solutions at the b X2 below 0.993 were kept at higher temperatures above 298.15 K during the sample preparation because they became turbid at 298.15 K. The prepared solutions were allowed to stand in a water thermostat at 298.15 K before measurement. Surface tension measurements The surface tension of aqueous solutions of a CaCl2-SDS b b mixture was measured as a function of the m and X2 at 298.15 K by the drop volume technique previously described [25]. In the drop volume technique, a glass tip at which a solution drop is formed was weakly coated with dimethyl polysiloxane (Siliconize L-25, Fuji Systems Co., Ltd., Japan) to give reproducible values of surface tension for anionic surfactants [26]. Temperature was kept at 298.15 K within 0.01 K by immersing the measuring cell in a water thermostat. The densities of water and aqueous CaCl2 solutions were used for the calculation of surface tension because the concentration of SDS is very low [27]. The errors inherent in the measurement were less than 0.05 mN m1 [25]. Solubility determination

Experimental Materials Sodium dodecyl sulfate is the same sample as that used in the previous study [21]. Its purity was checked by no minimum in the surface tension vs. concentration curve around the CMC. The purified SDS was kept under a dried atmosphere and reduced pressure in a desiccator to prevent its hydrolysis. Calcium chloride (JIS special grade reagent, Wako Pure Chemical Industries) was dried at 200 C for 12 h under reduced pressure and stored under a dried atmosphere in a desiccator. Water, deionized and distilled, was further purified by distilling it twice from dilute alkaline solution of potassium permanganate. An aqueous calcium chloride solution (5 or 10 mmol kg1) was added into a flask in which a certain b quantity of SDS was put, to give the mole fraction X2 of SDS in the CaCl2-SDS mixture. A known amount of water was then added into the flask to give a stock solution of the b b total molality m of the mixture at the X2 . Taking into b b account of the dissociation into ions, m and X2 are defined by b m 3m1 2m2 and b X2 2m2 =b ; m 2 1

The aqueous solutions of a CaCl2-SDS mixture became b b b turbid above a certain m depending on X2 . The lowest m at which the solution becomes turbid was determined from a b b break in the surface tension vs. m curve at constant X2 . b The solutions at concentrations far above the lowest m became turbid within 20 min. after preparation during their standing in the water thermostat at 298.15 K. However, the b solutions at concentrations around the lowest m were allowed to stand for 12 h in the thermostat before measurement so that equilibrium is reached, because the surface tension attained to a stationary value after the aging of 12 h.

Results and discussion Surface tension and aggregate formation b It is noticed from Fig. 1a and b that the mixture of the X2 around 0.7 (curve 7) is the most surface active of all the b mixtures. The vs. m curves of single SDS (curve 16) and b the mixtures of the X2 above 0.993 (curves 14 and 15) b break at the critical micelle concentration C of mixture. The b2 below 0.993 become turbid above a certain solutions at X b b m at which the vs. m curve breaks. For the mixture of b X2 0:945 (curve 10) in Fig. 1b and c, the surface tension

where m1 and m2 are the molalities of CaCl2 and SDS, respectively.

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Fig. 1 Surface tension vs. total molality curves at constant compob sition: X2 =1, 0; 2, 0.1000; 3, 0.1682; 4, 0.2986; 5, 0.4201; 6, 0.5501; 7, 0.6581; 8, 0.7801; 9, 0.9002; 10, 0.9450; 11, 0.9705; 12, 0.9850; 13, 0.9919; 14, 0.9975; 15, 9990; 16, 1; closed symbols turbid

solutions. In Fig. 1b and c, the arrow with a filled head indicates the onset of micelle formation and the one with an open head the disappearance of particles in the region of particle-micelle coexistence

b of turbid solutions decreases with increasing m and slightly b decreases above the m denoted by the arrow with a filled b head. The turbid solution becomes transparent at the m denoted by the arrow with an open head. The of b transparent solutions increases with increasing m, in sharp contrast to the decrease of the of turbid solutions with b increasing m. Figure 1c shows the of turbid and b b transparent solutions as a function of m at the X2 between b 0.945 and 0.992. There are three breaks on those vs. m curves. The first break shows the onset of coagel particle b b formation and the m at the break is denoted by C P, the critical concentration of particle formation. The second break shows the appearance of micelles in the solution of coagel particles and the third one the disappearance of coagel particles in the

micellar solution. The coexistence of particles and micelles between the second and third breaks is thermodynamically considered later. b b The C and C P values taken from the breaks in the vs. b b m curves in Fig. 1 are plotted as a function of X2 in Fig. 2. It is noticed that micelle formation takes place only in the b b highly limited range of X2 and C P has the minimum value b b b b b at around X2 0:67. The C vs. X2 and C P vs. X2 curves b meet at X2 0:993, and particles and micelles coexist in b b eq b eq equilibrium at the X2 , X2 . It is noteworthy that the X2 of a NaCl-SDS mixture is 0.00042 [21] and extremely smaller than 0.993 of a CaCl2-SDS mixture because the electrostatic attraction between Ca2+ and DS ions stronger than that between Na+ and DS ions enhances the particle

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Fig. 2 Critical aggregate concentration vs. composition curves: blank b b b b circles C vs. X2 , filled circles C P vs. X2 curve

b formation. Figure 3 shows the surface tension C at the C P b P , read from the breaks in the vs. m curve, b and at the C b b as a function of X2 . As X2 decreases C decreases, in sharp b b contrast, P increases. The C vs. X2 and P vs. X2 curves are related to the difference in composition between the adsorbed film and aggregates as shown later. Miscibility in the adsorbed film b b The m values at a given taken from the vs. m curves in b b b Fig. 1 are plotted against X2 in Fig. 4a. The m vs. X2 curve b2 0:67 both for 50 mNm-1 has the minimum at around X bH and for 60 mNm1. The mole fraction X2 of SDS in the adsorbed film defined by bH X2 H H = H 2 H H Na DS Cl Na Ca H DS was numerically evaluated by applying b b m b b bH b X2 X2 X1 X2 =b @ m=@ X2 T ;p;g 4 3

adsorption observed for the anionic and cationic surfactant mixture [26]. It is worth noting that even the inorganic saltsurfactant mixture shows a negative azeotropy in adsorption due to strong electrostatic attraction between Ca2+ and DS ions in the adsorbed film. We therefore conclude that negative azeotropy takes place in the mixed adsorption of bH CaCl2 and SDS at the water/air interface. The X2 of the H azeotrope, 0.669, indicates that the ratio of Ca2 to H is DS almost 1: 2 and the adsorption of Ca2+ and DS ions is much larger than that of Na+ and Cl ions. The miscibility of SDS with NaCl and CaCl2 can be compared with each other at 50 mN m1 in Fig. 4b. The phase diagram of the NaCl-SDS mixture is greatly different from that of the bH CaCl2-SDS mixture. The X2 of the NaCl-SDS mixture is larger than unity due to the electrostatic repulsion between Cl and DS ions in the adsorbed film although the surface charges due to adsorbed DS ions are partly shielded by the Na+ ions adsorbed at around the ionic head groups of DS bH ions. In sharp contrast to the NaCl-SDS mixture, the X2 of the CaCl2-SDS mixture is smaller than unity because of the strong electrostatic attraction between Ca2+ and DS ions in the adsorbed film. Miscibility in the aggregates bM The mole fraction of SDS in the micelle X2 and that in the b P are defined by coagel particle X2
A A A A A bA X2 NNa NDS =NCa2 NCl NNa A NDS ; A M; P;

where NjA is the excess number of j ions in one aggregate defined with respect to the dividing surface around the aggregate so as to make the excess number of water

b b to the m vs. X2 curves [28]. Here H 2 , H , H , and Cl Na Ca H DS are the surface densities of calcium ion Ca2+, chloride ion Cl, sodium ion Na+, and dodecyl sulfate ion DS, respectively, and aqueous solutions of the CaCl2-SDS b mixture were assumed to be ideal because of small m. bH bH b The X2 values are shown in the form of the m vs. X2 curve b b together with the m vs. X2 curve to give the phase diagram bH b b b of adsorption, Fig. 4a [28]. The m vs. X2 and m vs. X2 curves touch each other at the minimum and the diagram is similar to that for the negative azeotropy in mixed

Fig. 3 Surface tension vs. composition curves at critical aggregate b b concentration: blank circle C vs. X2 , filled circle P vs. X2 curve

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bA molecules zero [21, 29]. Numerical values of X2 were evaluated by applying bM b b b b b b X2 X2 X1 X2 =C@ C=@ X2 T;p and b bP b b b b b X2 X2 X1 X2 =C P @ C P =@ X2 T ;p 7 6

b X2 . When the mole fraction in the surrounding solution b eq goes up to the X2 , micelles appear in the turbid solution. b Further increase in m causes the disappearance of particles and the transformation of the turbid solution to transparent b M;eq micellar one in which the composition of micelles is X2 . Comparison of the miscibility between the adsorbed film and aggregate The miscibility in the adsorbed film and aggregate can be compared with each other by use of the phase diagram for adsorbed film-aggregate equilibrium. We have b b H;C b M b b b X2 X2 X1 X2 =RT H;C @g C =@ X2 T;p for the adsorbed film-micelle equilibrium and b b H;P b P b b b X2 X2 X1 X2 =RT H;P @g P =@ X2 T ;p 9 8

b b b b to the C vs. X2 and C P vs. X2 curves in Fig. 2, respectively b bM [21, 29]. They are shown in the form of the C vs. X2 b P vs. X P curves together with the C vs. X2 and C P vs. b b b b and C 2 b X2 curves to draw the phase diagram of aggregate bM formation, Fig. 5 [21, 28, 29]. It is noticed that the X2 b P are smaller than the X2 , that is, CaCl2 is richer in the b and X2 aggregates than in the bulk solution due to electrostatic attraction between Ca2+ and DS ions in the aggregates. The bM bP b eq difference between X2 and X2 at the X2 (the difference M;eq P;eq b b between X2 and X2 designated in Fig. 5) is attributable to the difference in size between the micelle and particle and to the interaction between bilayer surfaces bH in a particle, which is shown in relation to the X2 in the next section. Judging from the diagram, a homogeneous negative azeotrope is formed in the mixed aggregate bP formation of SDS with CaCl2 [30, 31] and the X2 of the azeotrope is 0.669, the same value as that of the corresponding azeotrope of adsorption. We can now explain the change of a solution from turbid to transparent due to micelle formation by using the phase b diagram (Fig. 5). At a given X2 (e.g., 0.945) a little smaller b eq , increasing m of a turbid solution causes an b than X2 increase in the mole fraction of SDS in the solution bP surrounding coagel particles because X2 is smaller than

b H;C for the adsorbed film-particle equilibrium [21, 28]. Here X2 H;P b b b bH and X2 are the X2 at the C and C P , respectively and b H;C and H;P are the corresponding total surface density b b H of constituent ions calculated by applying a thermob dynamic equation to the vs. m curves in Fig. 1. Figure 6 b H;C b H;P shows the phase diagram representing the X2 and X2 M P b b together with the X2 and X2 in the form of the surface b b tension vs. composition curves at the C and C P . It is bM b H;C and X P < X H;P . The former b b noticed that X2 > X2 2 2 inequality stems from the fact that the ionic head groups of DS ions are less densely packed in the micelle than in the adsorbed film due to the difference in geometry between the adsorbed film and micelle, and then the DS ions in the micelle attract Ca2+ ions less than those in the adsorbed film.

Fig. 4 a Total molality vs. composition curves at constant surface tension: =1 50; 2 60 mN m1; b total molality vs. composition curves at b bH b b 50 mN m-1: 1 CaCl2-SDS, 2 NaCl-SDS mixture; blank circle m vs. X2 , broken lines m vs. X2 curve

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b of particle formation; for a turbid solution at a given X2 , an b increase in m brings about increases in the amount of particles and the mole fraction of SDS in the solution bP b surrounding the particles because X2 is smaller than X2 , and then the of turbid solution decreases. The increase in b of micellar solutions with increasing m can be similarly b bM explained by the use of the C vs. X2 and C vs. X2 curves (a phase diagram of micelle formation). Equilibrium between the aggregates Let us consider the particle-micelle equilibrium in the range b b M;eq < X2 b b eq of X2 , X2 X2 . Mass balance relations are given by b b b b m C eq mM mP for the mixture and b b eq b b M;eq mP X P;eq ; bb b b2 mX2 C eq X2 mM X2 11 10

Fig. 5 Critical aggregate concentration vs. composition curves: b b b bM bP broken lines C vs. X2 , dash-dot lines C P vs. X2 ; blank circle C P b b b vs. X2 , filled circle C vs. X2 curve

The latter inequality shows that the miscibility of CaCl2 and SDS in the bilayers in a coagel particle is larger than the corresponding one in the adsorbed film at water/air interface. The curvature effect on miscibility is negligible for the bilayers in a coagel particle because coagel particles are bP much larger than micelles [32, 33]. The X2 smaller than the b H;P can therefore be ascribed to the interaction between X2 surfaces of the adjacent bilayers in a coagel particle because the interaction causes an increase in the counterion concentration in the layer between the bilayers by overlapping of two electric double layers [34]. Actually, for a foam black film stabilized with SDS, the interaction between surfaces in the film enhances the adsorption of Na+ ions at the film surfaces compared with that at the bulk surface [35]. The corresponding diagram for a NaCl-SDS mixture is also drawn in the figure for comparison [21]. The composition of adsorbed films and aggregates sits in the same order for the two mixtures, although the surface tension at the particle-micelle coexistence is much lower for the NaCl-SDS mixture than for the CaCl2-SDS mixture b because of the extremely higher m of the NaCl-SDS b eq mixture at the X2 . b The decrease in of turbid solutions with increasing m in Fig. 1b and c can be explained by comparing the P vs. bP b X2 curve in Fig. 6 with the P vs. X2 curve in Fig. 3. The P b2 and P vs. X P curves together form a phase diagram b vs. X 2

b b b for SDS, where mM and mP are the m ascribed to the micelle b b M;eq b P;eq and particle, respectively and X2 , X2 , and C eq are the M bP b at the X eq (see Fig. 5). As m increases above b b b X2 , X2 , and C 2 b b the C P at a given X2 , an infinitesimal amount of micelles b b appears in a turbid solution at a certain m, mI , indicated by the arrow with a filled head in Fig. 1c. Further b increase in m makes particles disappear in the particleb b micelle coexisting solution at a m, mII , shown by the arrow b with an open head in Fig. 1c. Eliminating the mP in

Fig. 6 Surface tension vs. composition curves at critical aggregate bM b H;C bP concentration: 1 C vs. X2 , 2 C vs. X2 , 3 P vs. X2 , 4 P b H;P curve; blank circle C of single SDS; straight line CaCl2vs. X2 SDS, broken line NaCl-SDS mixture

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b b b Fig. 7 a Total molality vs. composition curves: 1 mI vs. X2 , 2 mII vs. b b b b b X2 , 3 C vs. X2 , 4 C P vs. X2 curve; b Surface tension vs. composition b b b b b b curves; 1 vs. X2 at mI , 2 vs. X2 at mII , 3 C vs. X2 , 4 P vs. X2

curve. M, P, and M+P regions of micelle and particle and the micelle particle coexisting region, respectively

b Eqs. 10 and 11 and solving the resulting equation for m at M b m 0 give b b eq b P;eq b b P;eq b mI C eq X2 X2 =X2 X2 : 12

b Similarly eliminating the mM in Eqs. 10 and 11 and solving P b b b b for m at m 0, we have the relation between mII and X2 : b b eq b M;eq b b M;eq b mII C eq X2 X2 =X2 X2 : 13

Equations 12 and 13 are respectively equivalent to Eqs. A.5 and A.7 in the previous study [36] and to Eqs. 5 and 6 in [31] for vesicle-micelle equilibrium. b eq For the CaCl2-SDS mixture, we obtain X2 0:993 and b b M;eq 0:866 and C eq =13.45 mmol kg1 from Fig. 2 and X2 b P;eq 0:682 from Fig. 5. Table 1 shows those values X2 together with the corresponding ones of the NaCl-SDS b P;eq mixture for comparison [10]. X2 is smaller than unity for P;eq b the two mixtures. The X2 of the CaCl2-SDS mixtures is due to the interaction of Ca2+ ions with DS ions in the aggregates larger than the corresponding one of Na+ ions. b P;eq smaller than unity is For the NaCl-SDS mixture, X2 ascribed to non-electrostatic interaction between Na+ ion and the head group of SDS in the particles after the P P apparent neutralization (NNa NDS ) at very large NaCl
Table 1 The total molality and the mole fraction of SDS in the b eq aggregates at the X2 Mixture NaCl-SDS CaCl2-SDS

b b concentration [21]. Figure 7a shows the mI and mII values b read from the second and third breaks on the vs. m curves b b b b b in Fig. 1c as a function of X2 . The mI vs. X2 and mII vs. X2 b eq , X eq , X M;eq , and b b curves obtained by substituting the C 2 2 b P;eq X2 values into Eqs. 12 and 13 are also shown in Fig. 7a. b b It is noticed that the experimental values of mI and mII are well fitted by the theoretical curves of Eqs. 12 and 13, respectively. Therefore, we conclude that the micelles and b coagel particles coexist in equilibrium in the range of m b b between mI and mII . b b Figure 7b shows the surface tension at the mI and mII b against X2 . The surface tension of the particle-micelle b coexisting solutions is almost constant irrespective of X2 . This finding substantiates the above conclusion and is consistent with the Gibbs phase rule from which the degrees of freedom for the particle-micelle coexisting solutions of the binary mixture (a four-phase fourcomponent system) is two, taking into consideration that micelle formation can be regarded as an appearance of macroscopic phase. The small difference between the b b surface tension at mI and mII is due to the finite aggregation number of micelles.

Conclusions Application of the thermodynamic treatment of surfactant mixture to the mixture of CaCl2 and SDS is useful in clarifying their miscibility and interaction in the adsorbed film and aggregates. The critical mole fraction of SDS to form particles in a solution is much larger for the CaCl2-

b eq X2
0.00042 0.993

b C eq (mmol kg1)
1465 13.45

b M; X2 eq
0.999 0.866

b P;eq X2
0.731 0.682

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Colloid Polym Sci (2010) 288:13131320 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. Satake I, Tahara T, Matuura R (1969) Bull Chem Soc Jpn 42:319 Oko MU, Venable RL (1971) J Colloid Interface Sci 35:53 Ozeki S, Tsunoda M, Ikeda S (1978) J Colloid Interface Sci 64:28 Kalinin VV, Radka CJ (1996) Colloids Surf 114:337 Warszyski P, Barzyk W, Lunkenheimer K, Fruhner H (1998) J Phys Chem B 102:10948 Corkill JM, Goodman JF (1962) Trans Faraday Soc 58:206 Koshinuma M (1983) Bull Chem Soc Jpn 56:2341 Peacock JM, Matijevi E (1980) J Colloid Interface Sci 77:548 Chou SL, Bae JH (1983) J Colloid Interface Sci 96:192 Baviere M, Bazin B, Aude R (1983) J Colloid Interface Sci 92:580 Kallay N, Pastuovi P, Matijevi E (1985) J Colloid Interface Sci 106:452 Stellner KL, Scamehorn JF (1989) Langmuir 5:70 Yamanaka M, Matsuki H, Ikeda N, Aratono M, Motomura K (1994) Langmuir 10:2950 Iyota H, Tomimitsu T, Aratono M (2006) J Colloid Interface Sci 302:330 Iyota H, Krastev R (2009) Colloid Polym Sci 287:425 Miyamoto S (1960) Bull Chem Soc Jpn 33:375 Sasaki J, Tajima K, Sasaki K (1972) Bull Chem Soc Jpn 45:348 Hat M, Shinoda K (1973) Bull Chem Soc Jpn 46:3889 Motomura K, Iwanaga S, Hayami Y, Uryu S, Matuura R (1981) J Colloid Interface Sci 80:32 Matsuki H, Aratono M, Kaneshina S, Motomura K (1997) J Colloid Interface Sci 191:120 Isono T (1984) J Chem Eng Data 29:45 Motomura K, Aratono M (1993) In: Ogino K, Abe M (eds) Mixed Surfactant Systems. Marcel Dekker, New York, pp 99144 Motomura K, Yamanaka M, Aratono M (1984) Colloid Polym Sci 262:948 Rowlinson JS, Swinton FL (1982) Liquids and liquid mixtures, 3rd edn. Butterworths, London, Chapter 6 Villeneuve M, Kaneshina S, Imae T, Aratono M (1999) Langmuir 15:2029 Clint JH (1992) Surfactant aggregation. Blackie, New York, pp 186188 Laughlin RG (1994) The aqueous phase behavior of surfactants. Academic Press, New York, pp 190193 Israelachvili JN (1992) Intermolecular and surface forces, 2nd edn. Academic Press, New York, Chapter 12 de Feijter JA, Vrij A (1978) J Colloid Interface Sci 64:269 Aratono M, Onimaru N, Yoshikai Y, Shigehisa M, Koga I, Wongwaihikhit K, Ohta A, Takiue T, Lhoussaine B, Strey R, Takata Y, Villeneuve M, Matsubara H (2007) J Phys Chem B 111:107

SDS mixture than for the NaCl-SDS mixture due to the electrostatic attraction between Ca2+ and DS ions in the aggregates larger than that between Na+ and DS ions. Negative azeotropy in mixed adsorption and aggregate formation was observed for the CaCl2-SDS mixture due to the strong electrostatic attraction between Ca2+ and DS ions in the adsorbed film and aggregates. The composition of the azeotrope is almost 1:2 of the ratio CaCl2/SDS. The miscibility of CaCl2 and SDS in the oriented states increases in the order, particle > adsorbed film > micelle. The difference in miscibility between the adsorbed film and micelle is ascribable to the difference in geometry between the adsorbed film and micelle because the ionic head groups of DS ions are less densely packed in the micelle than in the adsorbed film. The miscibility in the coagel particle larger than that in the adsorbed film is attributable to the interaction between adjacent bilayer surfaces in the particle which causes an increase in Ca2+ ion concentration in the layer between the bilayer surfaces. The particle-micelle equilibrium can be quantitatively described by using the equilibrium composition of the aggregates. The surface tension of the solutions in which micelles and particles coexist in equilibrium was almost constant irrespective of the total molality and bulk composition, which is in conformity with the Gibbs phase rule.

References
1. 2. 3. 4. Corrin ML, Harkins WM (1947) J Am Chem Soc 69:683 Lange H Kolloid-Z (1951) 121:66 Shinoda K (1955) Bull Chem Soc Jpn 28:340 Matuura R, Kimizuka H, Matsubara A, Matsunobu K, Matsuda T (1962) Bull Chem Soc Jpn 35:552 5. Satake I, Iwamatsu I, Hosokawa S, Matuura R (1963) Bull Chem Soc Jpn 36:204 6. Shinoda K (1963) In: Shinoda K, Tamamushi B, Nakagawa T, Isemura T (eds) Colloidal surfactants. Academic Press, New York, pp 3762

31. 32. 33. 34. 35. 36.