Charge distribution at the gas-water interface the surface potential of water

Borazio, Antonio; Farrell, John R.; McTigue, Peter T.

doi:10.1016/0022-0728(85)85055-5

Cited by 25 publications

(11 citation statements)

References 10 publications

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“…Although the surface potential of bulk water is not accurately known and has not been directly measured,19 many estimates4,15,19,130 and quantum chemical ab initio theoretical results18 indicate that this potential is relatively small. Thus, any differences in the surface of these nanodrops from that in bulk solution should contribute negligibly to any uncertainties in these absolute reduction enthalpy measurements.…”

Section: Resultsmentioning

confidence: 99%

Directly Relating Reduction Energies of Gaseous Eu(H₂O)_n³⁺, n = 55−140, to Aqueous Solution: The Absolute SHE Potential and Real Proton Solvation Energy

et al. 2009

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In solution, half-cell potentials are measured relative to other half-cells resulting in a ladder of thermodynamic values that is anchored to the standard hydrogen electrode (SHE), which is assigned an arbitrary value of exactly 0 V. A new method for measuring the absolute SHE potential is introduced in which reduction energies of Eu(H 2 O) n 3+ , from n = 55 to 140, are extrapolated as a function of the geometric dependence of the cluster reduction energy to infinite size. These measurements make it possible to directly relate absolute reduction energies of these gaseous nanodrops containing Eu 3+ to the absolute reduction enthalpy of this ion in bulk solution. From this value, an absolute SHE potential of +4.11 V and a real proton solvation energy of −269.0 kcal/mol are obtained. The infrared photodissociation spectrum of Eu(H 2 O) 119-124 3+ indicates that the structure of the surface of the nanodrops is similar to that at the bulk air-water interface and that the hydrogen bonding of interior water molecules is similar to that in aqueous solution. These results suggest that the environment of Eu 3+ in these nanodrops and the surface potential of the nandrops are comparable to those of the condensed phase. This method for obtaining absolute potentials of redox couples has the advantage that no explicit solvation model is required, which eliminates uncertainties associated with these models, making this method potentially more accurate than previous methods.

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Section: Resultsmentioning

confidence: 99%

Directly Relating Reduction Energies of Gaseous Eu(H₂O)_n³⁺, n = 55−140, to Aqueous Solution: The Absolute SHE Potential and Real Proton Solvation Energy

et al. 2009

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“…The results obtained from various measurements of the interface electrostatic potential, which would give the absolute orientation of water, are not in agreement. − On the theoretical side most calculations indicate that the oxygen is up, i.e. the dipole moment is down. − , From the SH phase measurements the preferred orientation of the water molecule was inferred to be the one where the dipole moment is down, in agreement with most calculations .…”

Section: Orientation Of Water At the Air/neat Water Interfacementioning

confidence: 89%

“…The results obtained from various measurements of the interface electrostatic potential, which would give the absolute orientation of water, are not in agreement. [43][44][45][46][47][48] On the theoretical side most calculations indicate that the oxygen is up, i.e. the dipole moment is down.…”

Section: Orientation Of Water At the Air/neat Water Interfacementioning

confidence: 99%

Liquid Interfaces Probed by Second-Harmonic and Sum-Frequency Spectroscopy

1996

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“…(Until now there has been no agreement on the surface potential of the water-air interface. The published values range from 25 mV (Borazio et al, 1985) to 100 mV positive (Parfenyuk and Krestov, 1992) to several hundred millivolts negative (Davis and Rideal, 1961;Colacicco, 1988) toward air.) Although this represents an approximation, it is obvious that ⌿ 0 should be at the right order of magnitude.…”

Section: How High Is the Dipole Potential Of Monolayers And Bilayers?mentioning

confidence: 99%

The Adsorption of Phloretin to Lipid Monolayers and Bilayers Cannot Be Explained by Langmuir Adsorption Isotherms Alone

Cseh

Benz

1998

Biophysical Journal

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Phloretin and its analogs adsorb to the surfaces of lipid monolayers and bilayers and decrease the dipole potential. This reduces the conductance for anions and increases that for cations on artificial and biological membranes. The relationship between the change in the dipole potential and the aqueous concentration of phloretin has been explained previously by a Langmuir adsorption isotherm and a weak and therefore negligible contribution of the dipole-dipole interactions in the lipid surface. We demonstrate here that the Langmuir adsorption isotherm alone is not able to properly describe the effects of dipole molecule binding to lipid surfaces--we found significant deviations between experimental data and the fit with the Langmuir adsorption isotherm. We present here an alternative theoretical treatment that takes into account the strong interaction between membrane (monolayer) dipole field and the dipole moment of the adsorbed molecule. This treatment provides a much better fit of the experimental results derived from the measurements of surface potentials of lipid monolayers in the presence of phloretin. Similarly, the theory provides a much better fit of the phloretin-induced changes in the dipole potential of lipid bilayers, as assessed by the transport kinetics of the lipophilic ion dipicrylamine.

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Charge distribution at the gas-water interface the surface potential of water

Cited by 25 publications

References 10 publications

Directly Relating Reduction Energies of Gaseous Eu(H₂O)_n³⁺, n = 55−140, to Aqueous Solution: The Absolute SHE Potential and Real Proton Solvation Energy

Directly Relating Reduction Energies of Gaseous Eu(H₂O)_n³⁺, n = 55−140, to Aqueous Solution: The Absolute SHE Potential and Real Proton Solvation Energy

Liquid Interfaces Probed by Second-Harmonic and Sum-Frequency Spectroscopy

The Adsorption of Phloretin to Lipid Monolayers and Bilayers Cannot Be Explained by Langmuir Adsorption Isotherms Alone

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Charge distribution at the gas-water interface the surface potential of water

Cited by 25 publications

References 10 publications

Directly Relating Reduction Energies of Gaseous Eu(H2O)n3+, n = 55−140, to Aqueous Solution: The Absolute SHE Potential and Real Proton Solvation Energy

Directly Relating Reduction Energies of Gaseous Eu(H2O)n3+, n = 55−140, to Aqueous Solution: The Absolute SHE Potential and Real Proton Solvation Energy

Liquid Interfaces Probed by Second-Harmonic and Sum-Frequency Spectroscopy

The Adsorption of Phloretin to Lipid Monolayers and Bilayers Cannot Be Explained by Langmuir Adsorption Isotherms Alone

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Product

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Directly Relating Reduction Energies of Gaseous Eu(H₂O)_n³⁺, n = 55−140, to Aqueous Solution: The Absolute SHE Potential and Real Proton Solvation Energy

Directly Relating Reduction Energies of Gaseous Eu(H₂O)_n³⁺, n = 55−140, to Aqueous Solution: The Absolute SHE Potential and Real Proton Solvation Energy