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Differences in the extent of protonation of functional groups lying on either side of water-hydrophobe interfaces are deemed essential to enzymatic catalysis, molecular recognition, bioenergetic transduction, and atmospheric aerosol-gas exchanges. The sign and range of such differences, however, remain conjectural. Herein we report experiments showing that gaseous carboxylic acids RCOOH(g) begin to deprotonate on the surface of water significantly more acidic than that supporting the dissociation of dissolved acids RCOOH(aq). Thermodynamic analysis indicates that> 6 H2O molecules must participate in the deprotonation of RCOOH(g) on water, but quantum mechanical calculations on a model air-water interface predict that such event is hindered by a significant kinetic barrier unless OH ions are present therein. Thus, by detecting RCOO we demonstrate the presence of OH on the aerial side of on pH > 2 water exposed to RCOOH(g). Furthermore, because in similar experiments the base (Me)3N(g) is protonated only on pH < 4 water, we infer that the outer surface of water is Brønsted neutral at pH ~3 (rather than at pH 7 as bulk water), a value that matches the isoelectric point of bubbles and oil droplets in independent electrophoretic experiments. The OH densities sensed by RCOOH(g) on the aerial surface of water, however, are considerably smaller than those at the (>1 nm) deeper shear planes probed in electrophoresis, thereby implying the existence of OHgradients in the interfacial region. This fact could account for the weak OH signals detected by surface-specific spectroscopies. [ABSTRACT FROM AUTHOR]

Proton transfer (PT) through and across aqueous interfaces is a fundamental process in chemistry and biology. Notwithstanding its importance, it is not generally realized that interfacial PT is quite different from conventional PT in bulk water. Here we show that, in contrast with the behavior of strong nitric acid in aqueous solution, gas-phase HN03 does not dissociate upon collision with the surface of water unless a few ions (>1 per106 H2O) are present. By applying online electrospray ionization mass spectrometry to monitor in situ the surface of aqueous jets exposed to HN03(g, beams we found that N03∼ production increases dramatically on >30-µΜ inert electrolyte solutions. We also performed quantum mechanical calculations confirming that the sizable barrier hindering HN03 dissociation on the surface of small water clusters is drastically lowered in the presence of anions. Anions electrostatically assist in drawing the proton away from N03∼ lingering outside the cluster, whose incorporation is hampered by the energetic cost of opening a cavity therein. Present results provide both direct experimental evidence and mechanistic insights on the counterintuitive slowness of PT at water-hydrophobe boundaries and its remarkable sensitivity to electrostatic effects. [ABSTRACT FROM AUTHOR]

Differences in the extent of protonation of functional groups lying on either side of water-hydrophobe interfaces are deemed essential to enzymatic catalysis, molecular recognition, bioenergetic transduction, and atmospheric aerosol-gas exchanges. The sign and range of such differences, however, remain conjectural. Herein we report experiments showing that gaseous carboxylic acids RCOOH(g) begin to deprotonate on the surface of water significantly more acidic than that supporting the dissociation of dissolved acids RCOOH(aq). Thermodynamic analysis indicates that > 6 H(2)O molecules must participate in the deprotonation of RCOOH(g) on water, but quantum mechanical calculations on a model air-water interface predict that such event is hindered by a significant kinetic barrier unless OH(-) ions are present therein. Thus, by detecting RCOO(-) we demonstrate the presence of OH(-) on the aerial side of on pH > 2 water exposed to RCOOH(g). Furthermore, because in similar experiments the base (Me)(3)N(g) is protonated only on pH < 4 water, we infer that the outer surface of water is Brønsted neutral at pH ∼3 (rather than at pH 7 as bulk water), a value that matches the isoelectric point of bubbles and oil droplets in independent electrophoretic experiments. The OH(-) densities sensed by RCOOH(g) on the aerial surface of water, however, are considerably smaller than those at the (>1 nm) deeper shear planes probed in electrophoresis, thereby implying the existence of OH(-) gradients in the interfacial region. This fact could account for the weak OH(-) signals detected by surface-specific spectroscopies.