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Surface accumulation and acid-base equilibrium of phenol at the liquid-vapor interface.

ABSTRACT: We have investigated the surfactant properties of phenol in aqueous solution as a function of pH and bulk concentration using liquid-jet photoelectron spectroscopy (LJ-PES) and surface tension measurements. The emphasis of this work is on the determination of the Gibbs free energy of adsorption and surface excess of phenol and its conjugate base phenolate at the bulk pK_a (9.99), which can be determined for each species using photoelectron spectroscopy. These values are compared to those obtained in measurements well below and well above the pK_a, where pure phenol or phenolate, respectively, are the dominant species, and where the Gibbs free energy of adsorption determined from surface tension and LJ-PES data are in excellent agreement. At the bulk pK_a the surface-sensitive LJ-PES measurements show a deviation of the expected phenol/phenolate ratio in favor of phenol, i.e., an apparent upward shift of the at the surface. In addition, the Gibbs free energies of adsorption determined by LJ-PES at the bulk pK_a for phenol and phenolate deviate from those observed for the pure solutions. We discuss these observations in view of the different surface propensity of phenol and phenolate as well as potential cooperative interactions between them in the near-surface region.

SUBMITTER: Richter C

PROVIDER: S-EPMC11348876 | biostudies-literature | 2024 Aug

REPOSITORIES: biostudies-literature

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Surface accumulation and acid-base equilibrium of phenol at the liquid-vapor interface.

Richter Clemens C Dupuy Rémi R Trinter Florian F Buttersack Tillmann T Cablitz Louisa L Gholami Shirin S Stemer Dominik D Nicolas Christophe C Seidel Robert R Winter Bernd B Bluhm Hendrik H

Physical chemistry chemical physics : PCCP 20241107 43

We have investigated the surfactant properties of phenol in aqueous solution as a function of pH and bulk concentration using liquid-jet photoelectron spectroscopy (LJ-PES) and surface tension measurements. The emphasis of this work is on the determination of the Gibbs free energy of adsorption and surface excess of phenol and its conjugate base phenolate at the bulk p<i>K</i><sub>a</sub> (9.99), which can be determined for each species using photoelectron spectroscopy. These values are compared ...[more]

PMID: 39189878

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Project description:ConspectusPhotoelectron spectroscopy (PES) is a powerful tool for the investigation of liquid-vapor interfaces, with applications in many fields from environmental chemistry to fundamental physics. Among the aspects that have been addressed with PES is the question of how molecules and ions arrange and distribute themselves within the interface, that is, the first few nanometers into solution. This information is of crucial importance, for instance, for atmospheric chemistry, to determine which species are exposed in what concentration to the gas-phase environment. Other topics of interest include the surface propensity of surfactants, their tendency for orientation and self-assembly, as well as ion double layers beneath the liquid-vapor interface. The chemical specificity and surface sensitivity of PES make it in principle well suited for this endeavor. Ideally, one would want to access complete atomic-density distributions along the surface normal, which, however, is difficult to achieve experimentally for reasons to be outlined in this Account. A major complication is the lack of accurate information on electron transport and scattering properties, especially in the kinetic-energy regime below 100 eV, a pre-requisite to retrieving the depth information contained in photoelectron signals.In this Account, we discuss the measurement of the photoelectron angular distributions (PADs) as a way to obtain depth information. Photoelectrons scatter with a certain probability when moving through the bulk liquid before being expelled into a vacuum. Elastic scattering changes the electron direction without a change in the electron kinetic energy, in contrast to inelastic scattering. Random elastic-scattering events usually lead to a reduction of the measured anisotropy as compared to the initial, that is, nascent PAD. This effect that would be considered parasitic when attempting to retrieve information on photoionization dynamics from nascent liquid-phase PADs can be turned into a powerful tool to access information on elastic scattering, and hence probing depth, by measuring core-level PADs. Core-level PADs are relatively unaffected by effects other than elastic scattering, such as orbital character changes due to solvation. By comparing a molecule's gas-phase angular anisotropy, assumed to represent the nascent PAD, with its liquid-phase anisotropy, one can estimate the magnitude of elastic versus inelastic scattering experienced by photoelectrons on their way to the surface from the site at which they were generated. Scattering events increase with increasing depth into solution, and thus it is possible to correlate the observed reduction in angular anisotropy with the depth below the surface along the surface normal.We will showcase this approach for a few examples. In particular, our recent works on surfactant molecules demonstrated that one can indeed probe atomic distances within these molecules with a high sensitivity of ∼1 Å resolution along the surface normal. We were also able to show that the anisotropy reduction scales linearly with the distance along the surface normal within certain limits. The limits and prospects of this technique are discussed at the end, with a focus on possible future applications, including depth profiling at solid-vapor interfaces.

Dataset Information

Surface accumulation and acid-base equilibrium of phenol at the liquid-vapor interface.

Publications

Surface accumulation and acid-base equilibrium of phenol at the liquid-vapor interface.

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