Interfacial Water Structure of Binary Liquid Mixtures Reflects Nonideal Behavior
Xiaoqing Yu, Takakazu Seki, Chun-Chieh Yu, Kai Zhong, Shumei Sun, Masanari Okuno, Ellen H. G. Backus, Johannes Hunger, Mischa Bonn, Yuki Nagata
Abstract
The evaporation of molecules from water-organic solute binary mixtures is key for both atmospheric and industrial processes such as aerosol formation and distillation. Deviations from ideal evaporation energetics can be assigned to intermolecular interactions in solution, yet evaporation occurs from the interface, and the poorly understood interfacial, rather than the bulk, structure of binary mixtures affects evaporation kinetics. Here we determine the interfacial structure of nonideal binary mixtures of water with methanol, ethanol, and formic acid, by combining surface-specific vibrational spectroscopy with molecular dynamics simulations. We find that the free, dangling OH groups at the interfaces of these differently behaving nonideal mixtures are essentially indistinguishable. In contrast, the ordering of hydrogen-bonded interfacial water molecules differs substantially at these three interfaces. Specifically, the interfacial water molecules become more disordered (ordered) in mixtures with methanol and ethanol (formic acid), showing higher (lower) vapor pressure than that predicted by Raoult's law.