Recent experimental and computational investigations have shown that trace amounts of surfactants, unavoidable in practice, can critically impair the drag reduction of superhydrophobic surfaces (SHSs), by inducing Marangoni stresses at the air–liquid interface. However, predictive models for realistic SHS geometries do not yet exist, which has limited the understanding and mitigation of these adverse surfactant effects. To address this issue, we derive a model for laminar, three-dimensional flow over SHS gratings as a function of geometry and soluble surfactant properties, which together encompass 10 dimensionless groups. We establish that the grating length
Insights into the behavior of nonanoic acid and its conjugate base at the air/water interface through a combined experimental and theoretical approach
The partitioning of medium-chain fatty acid surfactants such as nonanoic acid (NA) between the bulk phase and the air/water interface is of interest to a number of fields including marine and atmospheric chemistry. However, questions remain about the behavior of these molecules, the contributions of various relevant chemical equilibria, and the impact of pH, salt and bulk surfactant concentrations. In this study, the surface adsorption of nonanoic acid and its conjugate base is quantitatively investigated at various pH values, surfactant concentrations and the presence of salts. Surface concentrations of protonated and deprotonated species are dictated by surface-bulk equilibria which can be calculated from thermodynamic considerations. Notably we conclude that the surface dissociation constant of soluble surfactants cannot be directly obtained from these experimental measurements, however, we show that molecular dynamics (MD) simulation methods, such as free energy perturbation (FEP), can be used to calculate the surface acid dissociation constant relative to that in the bulk. These simulations show that nonanoic acid is less acidic at the surface compared to in the bulk solution with a p K a shift of 1.1 ± 0.6, yielding a predicted surface p K a of 5.9 ± 0.6. A thermodynamic cycle for nonanoic acid and its conjugate base between the air/water interface and the bulk phase can therefore be established. Furthermore, the effect of salts, namely NaCl, on the surface activity of protonated and deprotonated forms of nonanoic acid is also examined. Interestingly, salts cause both a decrease in the bulk p K a of nonanoic acid and a stabilization of both the protonated and deprotonated forms at the surface. Overall, these results suggest that the deprotonated medium-chain fatty acids under ocean conditions can also be present within the sea surface microlayer (SSML) present at the ocean/atmosphere interface due to the stabilization effect of the salts in the ocean. This allows the transfer of these species into sea spray aerosols (SSAs). More generally, we present a framework with which the behavior of partially soluble species at the air/water interface can be predicted from surface adsorption models and the surface p K a can be predicted from MD simulations.
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- Award ID(s):
- 1801971
- NSF-PAR ID:
- 10232145
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 11
- Issue:
- 39
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 10647 to 10656
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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g is the key geometric parameter and predict that the ratio between actual and surfactant-free slip increases withg 2. Guided by our model, we perform synergistic numerical simulations and microfluidic experiments, finding good agreement with the theory as we vary surfactant type and SHS geometry. Our model also enables the estimation, based on velocity measurements, of a priori unknown properties of surfactants inherently present in microfluidic systems. For SHSs, we show that surfactant effects can be predicted by a single parameter, representing the ratio between the grating length and the interface length scale beyond which the flow mobilizes the air–water interface. This mobilization length is more sensitive to the surfactant chemistry than to its concentration, such that even trace-level contaminants may significantly increase drag if they are highly surface active. These findings advance the fundamental understanding of realistic interfacial flows and provide practical strategies to maximize superhydrophobic drag reduction. -
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D0SC02354J
