STRUCTURAL MICELLAR TRANSITION FOR DILUTE-SOLUTIONS OF LONG-CHAIN BINARY CATIONIC SURFACTANT SYSTEMS - A CONDUCTANCE INVESTIGATION

被引:154
作者
TREINER, C
MAKAYSSI, A
机构
[1] Laboratoire d'Electrochimie, Université Pierre et Marie Curie, UA CNRS, Paris 75005, 430, 4 Place Jussieu, Bat. F.
关键词
D O I
10.1021/la00039a012
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The critical micelle concentrations of mixed binary cationic surfactant systems have been determined in water by conductivity measurements. The following systems have been studied: trimethyltetradecylammonium chloride + benzyldimethyltetradecylammonium chloride (I); trimethyltetradecylammonium chloride + benzyldimethylhexadecylammonium chloride (II); hexadecylpyridinium chloride + benzyldimethylhexadecylammonium chloride (III); trimethyltetradecylammonium bromide + didodecyldimethylammonium bromide (IV). Some additional single surfactant solutions were also investigated. The concentration domain studied extended to 10-20 times the critical micelle concentration (cmc). It is shown that for surfactants with more than 16 methylene groups (including the contribution of the head-group hydrophobicity), two breaks in the conductivity versus concentration plots are clearly observed. The effects are larger with mixed micelles than with pure ones. The first break corresponds to the classical cmc (C1), with a close-to-ideal mixing behavior for systems I-III. The second break, which is observed for the mixed surfactants at concentrations about 3 times the first one, should be considered as a second CMC (C2). It is shown that the degree of counterion binding is a characteristic constant of the surfactant system investigated only above C2. These findings are interpreted by assuming structural micellar transitions for long chain surfactants without added salt. The specificity of system IV with respect to the three other binaries is also considered. For example with this surfactant pair, contrary to the micellization process, counterion binding in very dilute surfactant concentration seems to be favored by mixing the single and the double chain surfactant. The relation of these observations to the well-known lamellae structures induced by double-chain surfactants is discussed.
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页码:794 / 800
页数:7
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