Harkot Joanna, Jańczuk Bronisław
Department of Interfacial Phenomena of Chemistry, Faculty of Chemistry, Maria Curie-Skłodowska University, Maria Curie-Skłodowska Sq. 3, 20-031 Lublin, Poland.
J Colloid Interface Sci. 2009 Feb 15;330(2):467-73. doi: 10.1016/j.jcis.2008.10.078. Epub 2008 Nov 6.
Density measurements were carried out for aqueous solutions of two cationic surfactants: dodecylethyldimethylammonium bromide (C(12)(EDMAB)) and benzyldimethyldodecylammonium bromide (BDDAB). On the basis of the obtained results of the measurements the CMC and partial molar volumes of the surfactants studied were also determined. The obtained CMC values were also analyzed with those accounted on the basis of the surface tension data from the previous paper [J. Harkot, B. Jańczuk, J. Colloid Interface Sci. (2008), submitted for publication]. The values of CMC determined from the surface tension and density measurements for C(12)(EDMAB) are equal to 9.9x10(-3) and 1.5x10(-2) M and for BDDAB to 5.25x10(-3) and 5.3x10(-3) M, respectively. These obtained values are very similar. However, in the literature it is difficult to find the CMC values for C(12)(EDMAB) and BDDAB determined by these two methods used by us-especially from the density measurements for BDDAB and surface tension measurements for C(12)(EDMAB). In the case of the apparent molar volumes of C(12)(EDMAB) there is a good agreement between the values obtained by us and those found in the literature. The CMC values for C(12)(EDMAB) and BDDAB were also determined on the basis of their surface tension and free energy of electrostatic interactions between the polar heads of these surfactants and compared with those obtained from the surface tension and density measurements. It was found that the theoretically obtained CMC values were close to those determined from the density and surface tension data for the C(12)(EDMAB) and that the ratios of the CMC values of the surfactants to their concentration at which the water surface tension decreased by about 20 mN/m proved that the presence of the aryl group in the BDDAB head instead of the methyl group caused that its micellization process was more inhibited in relation to its adsorption at air-water interface than that of C(12)(EDMAB).
十二烷基乙基二甲基溴化铵(C(12)(EDMAB))和苄基二甲基十二烷基溴化铵(BDDAB)。根据测量所得结果,还测定了所研究表面活性剂的临界胶束浓度(CMC)和偏摩尔体积。所获得的CMC值还与根据前文[J. Harkot, B. Jańczuk, J. Colloid Interface Sci. (2008), 待发表]表面张力数据计算得出的值进行了分析比较。由表面张力和密度测量确定的C(12)(EDMAB)的CMC值分别为9.9×10⁻³和1.5×10⁻² M,BDDAB的CMC值分别为5.25×10⁻³和5.3×10⁻³ M。这些所得值非常相似。然而,在文献中很难找到通过我们所使用的这两种方法确定的C(12)(EDMAB)和BDDAB的CMC值——尤其是BDDAB的密度测量值和C(12)(EDMAB)的表面张力测量值。就C(12)(EDMAB)的表观摩尔体积而言,我们所获得的值与文献中发现的值有很好的一致性。还根据这些表面活性剂极性头之间的表面张力和静电相互作用自由能确定了C(12)(EDMAB)和BDDAB的CMC值,并与从表面张力和密度测量获得的值进行了比较。结果发现,理论上获得的CMC值与根据C(12)(EDMAB)的密度和表面张力数据确定的值相近,并且表面活性剂的CMC值与其浓度(此时水的表面张力降低约20 mN/m)的比值证明,BDDAB头部的芳基而非甲基的存在导致其胶束化过程相对于其在空气 - 水界面的吸附受到更大抑制,相比C(12)(EDMAB)而言。