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Where's the Salt? Sensing the Ionic Environment of the Air-Organic-Water Interface Using an Azide Probe
Sean W Parsons1, Kenneth D Judd1, Dmitry B Eremin1
1Department of Chemistry, The University of Southern California, Los Angeles, CA 90089, USA.
Angewandte Chemie (International Ed. in English)
|December 8, 2025
Summary
Small inorganic ions are depleted at the air-organic-water interface, even at high salt concentrations. Direct cation coordination only appears under extreme water-in-salt conditions, challenging previous assumptions about interfacial ion behavior.
Area of Science:
- Physical Chemistry
- Environmental Chemistry
- Electrochemistry
Background:
- Ionic behavior at aqueous interfaces is crucial for understanding environmental chemistry, microdroplet reactions, and electrochemical systems.
- The distribution of ions (accumulation vs. depletion) at aqueous boundaries remains a subject of debate.
Purpose of the Study:
- To investigate the partitioning of small inorganic ions at the air-organic-water interface.
- To determine the conditions under which ions interact directly with the interface.
Main Methods:
- Utilized an uncharged, surface-anchored azide probe to detect interfacial ion presence.
- Examined ion behavior across a range of salt concentrations, including high concentrations (5 M) and water-in-salt conditions (>10 M ZnCl2).
Main Results:
- The air-organic-water interface showed depletion of small inorganic ions, even at 5 M salt concentrations, contrasting with bulk solution behavior.
- Direct cation coordination at the interface was only observed under extreme water-in-salt conditions (e.g., >10 M ZnCl2).
Conclusions:
- Findings extend the stratified salt model to the air-organic-water interface.
- Provides molecular-level insights into interfacial reactivity, ion partitioning, and "on-water" chemical transformations.

