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首页> 外文期刊>The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical >Thermodynamic Study on Phase Transition in Adsorbed Films of Fluoroalkanol at the Hexane/Water Interface. 5. Miscibility in the Adsorbed Film of an Alkanol and Fluoroalkanol Mixture
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Thermodynamic Study on Phase Transition in Adsorbed Films of Fluoroalkanol at the Hexane/Water Interface. 5. Miscibility in the Adsorbed Film of an Alkanol and Fluoroalkanol Mixture

机译：己烷/水界面处氟烷醇吸附膜相变的热力学研究。 5.烷醇和氟代链烷醇混合物在吸附膜中的混溶性

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摘要

The miscibility of 1-icosanol (C_(20)OH) and 1,1,2,2-tetrahydroheptadecafluorodecanol (FC_(10)OH) in the adsorbed film at the hexane/water interface was investigated by evaluating the composition of FC_(10)OH in the adsorbed film X_2~H from the interfacial tension data and drawing the phase diagram of adsorption (PDA). We found that the PDA changes its shape from the positive azeotrope in the expanded state, where the C_(20)OH and FC_(10)OH molecules are miscible at all proportions, to the heteroazeotrope in the condensed state, where they are completely immiscible with each other, as the interfacial tension γ decreases. To examine the deviation from the ideal mixing in the adsorbed film quantitatively, the activity coefficient of component i, f_i~H, and the excess Gibbs energy, g~(H,E), in the expanded state were estimated from the PDA. It was found that the f_i~H value is larger than unity in a whole X_2~H range, and therefore, the corresponding g~(H,E) value is positive at all compositions and increases with decreasing γ. This result shows that the C_(20)OH and FC_(10)OH molecules mix nonideally in the adsorbed film and the mutual interaction between the different kinds of alcohol molecules is very weak compared with that between the same kinds. Furthermore, w estimated the excess area in the adsorbed film A~(H,E) from the dependence of g~(H,E) on γ. The A~(H,E) value was positive, and therefore, the mixing of C_(20)OH and FC_(10)OH molecules in the adsorbed film causes an increase in area A. By comparison of this result with the corresponding volume increase associated with the mixed micelle formation of hydrocarbon and fluorocarbon surfactants, it was suggested that the difference in the geometrical structure between adsorbed films and micelle affects appreciably the molecular packing in them and eventually the molecular interaction between hydrocarbon and fluorocarbon molecules.
机译：通过评估FC_（10）的组成，研究了1-二十烷醇（C_（20）OH）和1,1,2,2-四氢十七氟癸醇（FC_（10）OH）在己烷/水界面的吸附膜中的混溶性根据界面张力数据，得出吸附膜X_2〜H中的）OH（PDA）。我们发现，PDA的形状从处于扩张状态的正共沸物（其中C_（20）OH和FC_（10）OH分子可按所有比例互溶）改变为处于浓缩状态的杂相，其中它们完全不互溶彼此之间，随着界面张力γ减小。为了定量地检验偏离吸附膜中理想混合的偏差，从PDA估算了组分i的活度系数f_i〜H和膨胀状态下的过量吉布斯能量g〜（H，E）。发现在整个X_2〜H范围内，f_i〜H值大于1，因此，对应的g〜（H，E）值在所有组成下均为正，并随着γ的减小而增加。该结果表明C_（20）OH和FC_（10）OH分子在吸附膜中非理想地混合，并且与相同种类的醇分子相比，不同种类的醇分子之间的相互作用非常弱。此外，w根据g〜（H，E）对γ的依赖性来估计吸附膜A〜（H，E）中的剩余面积。 A〜（H，E）值为正，因此，吸附膜中C_（20）OH和FC_（10）OH分子的混合导致面积A增大。通过将该结果与相应的体积进行比较与碳氢化合物和碳氟化合物表面活性剂的混合胶束形成有关的碳纳米管的增加，表明吸附膜和胶束之间的几何结构差异显着影响了它们之间的分子堆积，最终影响了碳氢化合物和碳氟化合物分子之间的分子相互作用。

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