The Surface Activity of the Hydrated Proton Is Substantially Higher than That of the Hydroxide Ion

• Published in: Angewandte Chemie International Edition 2019-10, Vol.58 (44), p.15636-15639
• Main Authors: Das, Sudipta, Bonn, Mischa, Backus, Ellen H. G.
• Format: Article
• Language: English
• Subjects: Communication; Communications; hydronium ions; hydroxide ions; Ionization; Perturbation; Protons; Spectroscopy; sum-frequency generation; Surface activity; water interface
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201908420

The behavior of hydroxide and hydrated protons, the auto‐ionization products of water, at surfaces is important for a wide range of applications and disciplines. However, it is unknown at which bulk concentration these ions start to become surface active at the water–air interface. Here, we report changes in the D2O–air interface in the presence of excess D+hyd/OD−hyd determined using surface‐sensitive vibrational sum‐frequency generation (SFG) spectroscopy. The onset of the perturbation of the D2O surface occurs at a bulk concentration as low as 2.7±0.2 mm D+hyd. In contrast, a concentration of several hundred mm OD−hyd is required to change the D2O surface. The hydrated proton is thus orders of magnitude more surface‐active than hydroxide at the water–air interface. At the border: The relative surface propensity of hydrated proton and hydroxide at the D2O–air interface in the presence of excess D3O+/OD− was determined by probing the stretching vibration of interfacial water with sum‐frequency generation spectroscopy. The hydrated proton is found to be orders of magnitude more surface active than the hydroxide ion.