Investigation of Interfacial and Bulk Dissociation of HBr, HCl, and HNO3 Using Density Functional Theory-Based Molecular Dynamics Simulations

Journal Article · Thu Dec 18 00:00:00 EST 2014 · Journal of Physical Chemistry C, 118(50):29412-29420

DOI:https://doi.org/10.1021/jp5062896· OSTI ID:1188910

Baer, Marcel; Tobias, Douglas J.; Mundy, Christopher J.

In this study we investigate the free energy barrier associated with the dissociation of strong acids, XH (HBr, HCl and HNO3) deprotonation, and subsequent formation of ionpairs, X–___H3O+ in the vicinity of the air-water interface. We will show that the free energy for acid dissociation for HCl and HNO3 show significant differences at the air-water than under bulk solvation conditions producing a picture where at the interface associated molecular species can be stable. For the strongest acid we consider, HBr the more traditional picture of acids is preserved in the vicinity of the air-water interface. Our results have implications for our understanding of acids, and their surface tensions at the air-water interface.

• Research Organization: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1188910
• Report Number(s): PNNL-SA-103497; KC0301020
• Journal Information: Journal of Physical Chemistry C, 118(50):29412-29420, Journal Name: Journal of Physical Chemistry C, 118(50):29412-29420
• Country of Publication: United States
• Language: English