The mole fraction of chloride ion of dodecyltrimethylammonium bromide (DTAB) and dodecyltrimethylammonium chloride (DTAC) mixture in the adsorbed film XHC was estimated not only by the thermodynamic analysis of the surface tension data but also by analyzing the Br K-edge jump of the XAFS spectrum under the total reflection condition (TRXAFS method). The phase diagrams of adsorption (PDA) at several surface tensions from the two methods were in good agreement. On the basis of the PDA obtained, it was clearly shown that the criterion of an ideal mixing for the DTAB-DTAC system is not given by the linear relation between the total molality of surfactant mixture m and XHC, m = m0B + (m0C - m0B)XHC, but by the one between m2 and XHC, m2 = (m0B)2 + [(m0C)2 - (m0B)2]XHC.
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