skip to main content
Explore Scholarly Publications and Datasets in the NSF-PAR

Title: Dissolving salt is not equivalent to applying a pressure on water
Abstract

Salt water is ubiquitous, playing crucial roles in geological and physiological processes. Despite centuries of investigations, whether or not water’s structure is drastically changed by dissolved ions is still debated. Based on density functional theory, we employ machine learning based molecular dynamics to model sodium chloride, potassium chloride, and sodium bromide solutions at different concentrations. The resulting reciprocal-space structure factors agree quantitatively with neutron diffraction data. Here we provide clear evidence that the ions in salt water do not distort the structure of water in the same way as neat water responds to elevated pressure. Rather, the computed structural changes are restricted to the ionic first solvation shells intruding into the hydrogen bond network, beyond which the oxygen radial-distribution function does not undergo major change relative to neat water. Our findings suggest that the widely cited pressure-like effect on the solvent in Hofmeister series ionic solutions should be carefully revisited.
Authors:
; ; ; ;
Award ID(s):
2053195
Publication Date:
NSF-PAR ID:
10362677
Journal Name:
Nature Communications
Volume:
13
Issue:
1
ISSN:
2041-1723
Publisher:
Nature Publishing Group
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ( , Journal of the American Chemical Society)
    Carreira, Erick M. (Ed.)
    In highly concentrated salt solutions, the water hydrogen bond (H-bond) network is completely disrupted by the presence of ions. Water is forced to restructure as dictated by the water-ion and ion-ion interactions. Using ultrafast polarization-selective pump-probe spectroscopy (PSPP) of the OD stretch of dilute HOD, we demonstrate that the limited water-water H-bonding present in concentrated lithium chloride solutions (up to 4 waters per ion pair) is, on average, stronger than that occurring in bulk water. Furthermore, information on the orientational dynamics and the angular restriction of water H-bonded to both water oxygens and chloride anions were obtained through analysis of the frequency-dependent anisotropy decays. It was found that the water showed increasing restriction and slowing at frequencies correlated with strong H-bonding when the salt concentration was increased. The angular restriction of the water molecules and strengthening of water-water H-bonds are due to the formation of a water-ion network not present in bulk water and dilute salt solutions. Finally, the structural evolution of the ionic medium was observed through spectral diffusion of the OD stretch using 2D IR spectroscopy. Compared to pure water, there is significant slowing of the biexponential spectral diffusion dynamics. The slowest component of the spectral diffusion, 13more »ps, is virtually identical to the time for complete orientation randomization of HOD measured with the PSPP experiments. This result suggests that the slowest component of the spectral diffusion reflects rearrangement of water molecules in the water-ion network.« less
  2. ; ; ( , Journal of the American Chemical Society)
    Carreira, Erick M. (Ed.)
    In highly concentrated salt solutions, the water hydrogen bond (H-bond) network is completely disrupted by the presence of ions. Water is forced to restructure as dictated by the water-ion and ion-ion interactions. Using ultrafast polarization-selective pump-probe spectroscopy (PSPP) of the OD stretch of dilute HOD, we demonstrate that the limited water-water H-bonding present in concentrated lithium chloride solutions (up to 4 waters per ion pair) is, on average, stronger than that occurring in bulk water. Furthermore, information on the orientational dynamics and the angular restriction of water H-bonded to both water oxygens and chloride anions were obtained through analysis of the frequency-dependent anisotropy decays. It was found that the water showed increasing restriction and slowing at frequencies correlated with strong H-bonding when the salt concentration was increased. The angular restriction of the water molecules and strengthening of water-water H-bonds are due to the formation of a water-ion network not present in bulk water and dilute salt solutions. Finally, the structural evolution of the ionic medium was observed through spectral diffusion of the OD stretch using 2D IR spectroscopy. Compared to pure water, there is significant slowing of the biexponential spectral diffusion dynamics. The slowest component of the spectral diffusion, 13more »ps, is virtually identical to the time for complete orientation randomization of HOD measured with the PSPP experiments. This result suggests that the slowest component of the spectral diffusion reflects rearrangement of water molecules in the water-ion network.« less
  3. ; ; ; ; ; ; ; ; ; ; et al ( , Limnology and Oceanography Letters)
    Abstract

    Salinization and eutrophication are nearly ubiquitous in watersheds with human activity. Despite the known impacts of the freshwater salinization syndrome (FSS) to organisms, we demonstrate a pronounced knowledge gap on how FSS alters wetland biogeochemistry. Most experiments assessing FSS and biogeochemistry pertain to coastal saltwater intrusion. The few inland wetland studies mostly add salt as sodium chloride. Sodium chloride alone does not reflect the ionic composition of inland salinization, which derives from heterogeneous sources, producing spatially and temporally variable ionic mixtures. We develop mechanistic hypotheses for how elevated ionic strength and changing ionic composition alter urban wetland sediment biogeochemistry, with the prediction that FSS diminishes nutrient removal capacity via a suite of related direct and indirect processes. We propose that future efforts specifically investigate inland urban wetlands, a category of wetland heavily relied on for its biogeochemical processing ability that is likely to be among the most impacted by salinization.

  4. ; ; ; ; ( , Advanced Energy Materials)
    Abstract

    Efficient mass transport and selective salt rejection are highly desirable for solar or thermally driven seawater desalination, but its realization is challenging. Here a new liquid supply mechanism is proposed, i.e., ionic pumping effect, using a polyelectrolyte hydrogel foam (PHF), demonstrated with poly(sodium acrylate) [P(SA)] embedded in a microporous carbon foam (CF). The PHF simultaneously possesses high osmotic pressure for liquid transport and a strong salt‐rejection effect. The PHF is able to sustain high flux of ≈24 L per m2per hour (LMH), comparable to the evaporative flux under 15 suns, and a salt rejection ratio over 80%. Compared to the porous carbon foam without the polyelectrolyte hydrogel, i.e., with only the capillary pumping effect, the PHF yields a 42.4% higher evaporative flux, at ≈1.6 LMH with DI water and ≈1.3 LMH with simulated seawater under one‐sun condition due to the more efficient ionic liquid pumping. More importantly, thanks to the strong salt‐rejection effect, the PHF shows a continuous and stable solar‐driven desalination flux of ≈1.3 LMH under one‐sun over 72 h, which has not been achieved before. The successful demonstration of both efficient ionic pumping and strong salt rejection effects makes the PHF an attractive platform for sustainable solar‐drivenmore »desalination.

    « less
  5. ; ; ; ; ( , Minerals)
    We report experimental constraints on the melting curve of potassium chloride (KCl) between 3.2 and 9 GPa from in situ ionic conduction measurements using a multi-anvil apparatus. On the basis of concurrent measurements of KCl and sodium chloride (NaCl) at 1 bar using the differential thermal analysis (DTA) method and Pt sphere marker, we show that the peak rate of increase in ionic current with temperature upon heating coincides with latent heat ledge and fall of Pt sphere, thus establishing the criterion for melting detection from ionic conduction measurements. Applying this criterion to high pressures, we found that the melting point of KCl rose steeply with increasing pressure to exceed 2443 ± 100 K at 9 GPa. Fitting the results of this study together with existing data at pressures below 4 GPa and above 20 GPa, we obtained the Simon’s melting equation for KCl in the simple cubic B2 structure between 1.8 and 50 GPa: T m = 1323 ( P − 1.87 2.2 ( 1 ) + 1 ) 1 2.7 ( 1 ) , where T is in K and P is in GPa. Starting at 1 bar, the melting point of KCl increases at an average ratemore »of ~150 K/GPa to cross that of Pt near 9 GPa. The highly refractory nature of KCl makes it a sensitive pressure calibrant for the large-volume pressure at moderate pressures and a potential sample container for experiments at moderate pressures and very high temperatures.« less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email