In typical aqueous systems, including naturally occurring
sweet
and salt water and tap water, multiple ion species are co-solvated.
At the water–air interface, these ions are known to affect
the chemical reactivity, aerosol formation, climate, and water odor.
Yet, the composition of ions at the water interface has remained enigmatic.
Here, using surface-specific heterodyne-detected sum-frequency generation
spectroscopy, we quantify the relative surface activity of two co-solvated
ions in solution. We find that more hydrophobic ions are speciated
to the interface due to the hydrophilic ions. Quantitative analysis
shows that the interfacial hydrophobic ion population increases with
decreasing interfacial hydrophilic ion population at the interface.
Simulations show that the solvation energy difference between the
ions and the intrinsic surface propensity of ions determine the extent
of an ion’s speciation by other ions. This mechanism provides
a unified view of the speciation of monatomic and polyatomic ions
at electrolyte solution interfaces.