skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


  • NSF Public Access
  • Search Results
  • Insights into the behavior of nonanoic acid and its conjugate base at the air/water interface through a combined experimental and theoretical approach
Title: 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.  more » « less
Award ID(s):
1801971
PAR ID:
10232145
Author(s) / Creator(s):
; ; ; ; ; ; ;
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
More Like this
  1. ; ; ; ; (, Chemical Science)
    null (Ed.)
    Surface-sensitive vibrational spectroscopy is a common tool for measuring molecular organization and intermolecular interactions at interfaces. Peak intensity ratios are typically used to extract molecular information from one-dimensional spectra but vibrational coupling between surfactant molecules can manifest as signal depletion in one-dimensional spectra. Through a combination of experiment and theory, we demonstrate the emergence of vibrational exciton delocalization in infrared reflection–absorption spectra of soluble and insoluble surfactants at the air/water interface. Vibrational coupling causes a significant decrease in peak intensities corresponding to C–F vibrational modes of perfluorooctanoic acid molecules. Vibrational excitons also form between arachidic acid surfactants within a compressed monolayer, manifesting as signal reduction of C–H stretching modes. Ionic composition of the aqueous phase impacts surfactant intermolecular distance, thereby modulating vibrational coupling strength between surfactants. Our results serve as a cautionary tale against employing alkyl and fluoroalkyl vibrational peak intensities as proxies for concentration, although such analysis is ubiquitous in interface science. 
    more » « less
  2. ; ; ; ; ; (, Proceedings of the National Academy of Sciences)
    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 lengthgis the key geometric parameter and predict that the ratio between actual and surfactant-free slip increases withg2. 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. 
    more » « less
  3. ; ; ; ; (, Atmosphere)
    Field measurements have shown that sub-micrometer sea spray aerosol (SSA) is significantly enriched in organic material, of which a large fraction has been attributed to soluble saccharides. Existing mechanistic models of SSA production struggle to replicate the observed enhancement of soluble organic material. Here, we assess the role for divalent cation mediated co-adsorption of charged surfactants and saccharides in the enrichment of soluble organic material in SSA. Using measurements of particle supersaturated hygroscopicity, we calculate organic volume fractions for molecular mimics of SSA generated from a Marine Aerosol Reference Tank. Large enhancements in SSA organic volume fractions (Xorg > 0.2) were observed for 50 nm dry diameter (dp) particles in experiments where cooperative ionic interactions were favorable (e.g., palmitic acid, Mg2+, and glucuronic acid) at seawater total organic carbon concentrations (<1.15 mM C) and ocean pH. Significantly smaller SSA organic volume fractions (Xorg < 1.5 × 10−3) were derived from direct measurements of soluble saccharide concentrations in collected SSA with dry diameters <250 nm, suggesting that organic enrichment is strongly size dependent. The results presented here indicate that divalent cation mediated co-adsorption of soluble organics to insoluble surfactants at the ocean surface may contribute to the enrichment of soluble saccharides in SSA. The extent to which this mechanism explains the observed enhancement of saccharides in nascent SSA depends strongly on the concentration, speciation, and charge of surfactants and saccharides in the sea surface microlayer. 
    more » « less
  4. ; ; ; (, Journal of Membrane Science Letters)
    Pore wetting is a major constraint to the performance of membrane distillation (MD) for hypersaline brine treatment. Despite the existence of surfactants with diverse properties, an explicit relationship between the properties of surfactants and their capabilities of inducing pore wetting has yet to be established. In this study, we perform a comparative analysis of the wetting behaviors of various surfactants with different charges and molecular weights in MD desalination. The induction time of surfactants to initiate pore wetting was correlated to the apparent contact angle and surface tension of the feedwater. Our results show that different surfactants resulting in similar feedwater surface tensions can lead to drastically different wetting potential, suggesting that both charge of the head group and molecular weight of surfactants have a significant influence on membrane pore wetting. Further, we demonstrate that parameters that have been commonly used to indicate wetting potential, including apparent contact angle and solution surface tension, are not reliable in predicting the wetting behavior of MD membranes, which is intricately linked with surfactant properties such as charge and molecular size. We envision that our results not only improve our fundamental understanding of surfactant-induced wetting but also provide valuable insights that necessitate thorough consideration of surfactant properties in evaluating wetting potential and membrane wetting resistance for MD desalination. 
    more » « less
  5. ; ; ; ; ; (, Journal of Fluid Mechanics)
    The effects of surfactants on a mechanically generated plunging breaker are studied experimentally in a laboratory wave tank. Waves are generated using a dispersively focused wave packet with a characteristic wavelength of$$\lambda _0 = 1.18$$m. Experiments are performed with two sets of surfactant solutions. In the first set, increasing amounts of the soluble surfactant Triton X-100 are mixed into the tank water, while in the second set filtered tap water is left undisturbed in the tank for wait times ranging from 15 min to 21 h. Increasing Triton X-100 concentrations and longer wait times lead to surfactant-induced changes in the dynamic properties of the free surface in the tank. It is found that low surface concentrations of surfactants can dramatically change the wave breaking process by changing the shape of the jet and breaking up the entrained air cavity at the time of jet impact. Direct numerical simulations (DNS) of plunging breakers with constant surface tension are used to show that there is significant compression of the free surface near the plunging jet tip and dilatation elsewhere. To explore the effect of this compression/dilatation, the surface tension isotherm is measured in all experimental cases. The effects of surfactants on the plunging jet are shown to be primarily controlled by the surface tension gradient ($$\Delta \mathcal {E}$$) while the ambient surface tension of the undisturbed wave tank ($$\sigma _0$$) plays a secondary role. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email