Adsorption of water on the NaCl(001) surface. II. An infrared study at ambient temperatures

Foster, Michelle; Ewing, George E.

doi:10.1063/1.481256

Cited by 133 publications

(195 citation statements)

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“…Note that 79.1% RH above a 14 nm particle surface is equivalent, after accounting for the Kelvin effect (eq 4), to 67.3% RH (20.0 mbar at 297K) above a bulk NaCl crystalline surface, which has roughly 3 ML of adsorbed surface water. 1 It can be concluded that the thickness of the water film on predeliquesced NaCl particle is quantitatively consistent with measurements done on bulk NaCl after properly accounting for the Kelvin effect.…”

Section: Discussionsupporting

confidence: 76%

“…This is consistent with ordered thin films of water on NaCl surfaces under ambient conditions. 1 For water interacting with structures that Figure 7. MD simulation snapshots of varying SDS coverage (Θ SDS ) on SDS/NaCl slabs on (a) crystalline NaCl core and (b) aqueous NaCl solution core.…”

Section: Resultsmentioning

confidence: 99%

“…Appropriate FHH (A ) 0.96, B ) 1) and BET (c ) 1.5) constants are used for water adsorption on the NaCl(001) surface. 1,8,58,59 The bulk density of water (997.1 kg m -3 ) is converted to the molecular units (33 molecules nm -3 ) for F w molec .…”

Section: Discussionmentioning

confidence: 99%

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Hygroscopic Growth and Deliquescence of NaCl Nanoparticles Mixed with Surfactant SDS

et al. 2010

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Several complementary experimental and theoretical methodologies were used to explore water uptake on sodium chloride (NaCl) particles containing varying amounts of sodium dodecyl sulfate (SDS) to elucidate the interaction of water with well-defined, environmentally relevant surfaces. Experiments probed the hygroscopic growth of mixed SDS/NaCl nanoparticles that were generated by electrospraying aqueous 2 g/L solutions containing SDS and NaCl with relative NaCl/SDS weight fractions of 0, 5, 11, 23, or 50 wt/wt %. Particles with mobility-equivalent diameters of 14.0(±0.2) nm were size selected and their hygroscopic growth was monitored by a tandem nano-differential mobility analyzer as a function of relative humidity (RH). Nanoparticles generated from 0 and 5 wt/wt % solutions deliquesced abruptly at 79.1(±1.0)% RH. Both of these nanoparticle compositions had 3.1(±0.5) monolayers of adsorbed surface water prior to deliquescing and showed good agreement with the Brunauer−Emmett−Teller and the Frenkel−Halsey−Hill isotherms. Above the deliquescence point, the growth curves could be qualitatively described by Köhler theory after appropriately accounting for the effect of the particle shape on mobility. The SDS/NaCl nanoparticles with larger SDS fractions displayed gradual deliquescence at a RH that was significantly lower than 79.1%. All compositions of SDS/NaCl nanoparticles had monotonically suppressed mobility growth factors (GFm) with increasing fractions of SDS in the electrosprayed solutions. The Zdanovskii−Stokes−Robinson model was used to estimate the actual fractions of SDS and NaCl in the nanoparticles; it suggested the nanoparticles were enhanced in SDS relative to their electrospray solution concentrations. X-ray photoelectron spectroscopy (XPS), FTIR, and AFM were consistent with SDS forming first a monolayer and then a crystalline phase around the NaCl core. Molecular dynamics simulations of water vapor interacting with SDS/NaCl slabs showed that SDS kinetically hinders the initial water uptake. Large binding energies of sodium methyl sulfate (SMS)−(NaCl)4, H2O−(NaCl)4, and SMS−H2O−(NaCl)4 calculated at the MP2/cc-pVDZ level suggested that placing H2O in between NaCl and surfactant headgroup is energetically favorable. These results provide a comprehensive description of SDS/NaCl nanoparticles and their properties. Disciplines Chemistry CommentsReprinted (adapted) ReceiVed: October 8, 2009; ReVised Manuscript ReceiVed: January 5, 2010 Several complementary experimental and theoretical methodologies were used to explore water uptake on sodium chloride (NaCl) particles containing varying amounts of sodium dodecyl sulfate (SDS) to elucidate the interaction of water with well-defined, environmentally relevant surfaces. Experiments probed the hygroscopic growth of mixed SDS/NaCl nanoparticles that were generated by electrospraying aqueous 2 g/L solutions containing SDS and NaCl with relative NaCl/SDS weight fractions of 0, 5, 11, 23, or 50 wt/wt %. Particles with mobility-equivalent diameters of ...

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Section: Discussionsupporting

confidence: 76%

Section: Resultsmentioning

confidence: 99%

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Hygroscopic Growth and Deliquescence of NaCl Nanoparticles Mixed with Surfactant SDS

et al. 2010

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“…In the range of 50-75% RH, below the DRH of NaNO 3 , NO 2 continues to be generated but at a smaller rate. While the salt is solid under these conditions, it holds significant amounts of surface-adsorbed water [101][102][103][104] which increases ion mobility at the interface and provides some liquid-like character to the surface. These results for NaNO 3 suggest that R NO 2 from KNO 3 would be higher if photolysis experiments were conducted 5% above the DRH rather than 7% below, and hence the data in Fig.…”

Section: Resultsmentioning

confidence: 99%

The effect of cations on NO₂ production from the photolysis of aqueous thin water films of nitrate salts

Richards-Henderson

Anderson

Anastasio

et al. 2015

Phys. Chem. Chem. Phys.

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The photochemistry of nitrate ions in bulk aqueous solution is well known, yet recent evidence suggests that the photolysis of nitrate may be more efficient at the air-water interface. Whether and how this surface enhancement is altered by the presence of different cations is not known. In the present studies, thin aqueous films of nitrate salts with different cations were deposited on the walls of a Teflon chamber and irradiated with 311 nm light at 298 K. The films were generated by nebulizing aqueous 0.5 M solutions of the nitrate salts and the generation of gas-phase NO 2 was monitored with time. The nitrate salts fall into three groups based on their observed rate of NO 2 formation (R NO 2 ): (1) RbNO 3 and KNO 3 , which readily produce NO 2 (R NO 2 4 3 ppb min À1 ), (2) Ca(NO 3 ) 2 , which produces NO 2 more slowly (R NO 2 o 1 ppb min À1 ), and (3) Mg(NO 3 ) 2 and NaNO 3 , which lie between the other two groups. Neither differences in the UV-visible spectra of the nitrate salt solutions nor the results of bulk-phase photolysis studies could explain the differences in the rates of NO 2 production between these three groups. These experimental results, combined with some insights from previous molecular dynamic simulations and vibrational sum frequency generation studies, show that cations may impact the concentration of nitrate ions in the interface region, thereby directly impacting the effective quantum yields for nitrate ions.

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“…[42][43][44][45][46] Findings generally indicate that, as humidity increases from 0% RH, water first adsorbs onto surface defect sites or in the form of small 2D islands with partial coverage up to ∼40% RH. 44 Between ∼40-50% RH, coverage increases rapidly to the point where it exhibits hydrogen bonding properties resembling that of bulk water.…”

Section: Discussionmentioning

confidence: 99%

Effect of Relative Humidity on Corrosion of Steel under Sea Salt Aerosol Proxies

Schindelholz

Risteen

Kelly

2014

J. Electrochem. Soc.

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This paper is the first of two that examine the relationship between relative humidity, the hygroscopic behavior of sea salt aerosol proxies, and the atmospheric corrosion of mild steel contaminated with them. Here, the association between the deliquescence phase transitions (solid-aqueous) of a single salt, NaCl, and the corrosion response of steel contaminated with this salt is examined. Specific focus is given to mechanisms that allow corrosion below the deliquescence relative humidity of NaCl (76% RH). Mild steel loaded with aqueous NaCl drops or crystals (9 μg · cm −2 ) was subjected to isohumidity exposures for up to 300 days. The resulting damage was quantified by optical profilometry. The corrosion chemistry that developed was identified using EDS and Raman spectroscopy. The wetting and drying of simulated corrosion chemistries were characterized by impedance measurements across an interdigitated electrode sensor. Taken together, these results show that corrosion can initiate by adsorbed water on NaCl crystals at as low as 33% RH. At 53% RH and above, attack proceeded at rates comparable to that observed above the deliquescence RH due to the development of hygroscopic corrosion chemistry. The governing role of the hygroscopic properties of this chemistry on attack rate and morphology is discussed.

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Adsorption of water on the NaCl(001) surface. II. An infrared study at ambient temperatures

Cited by 133 publications

References 50 publications

Hygroscopic Growth and Deliquescence of NaCl Nanoparticles Mixed with Surfactant SDS

Hygroscopic Growth and Deliquescence of NaCl Nanoparticles Mixed with Surfactant SDS

The effect of cations on NO₂ production from the photolysis of aqueous thin water films of nitrate salts

Effect of Relative Humidity on Corrosion of Steel under Sea Salt Aerosol Proxies

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Adsorption of water on the NaCl(001) surface. II. An infrared study at ambient temperatures

Cited by 133 publications

References 50 publications

Hygroscopic Growth and Deliquescence of NaCl Nanoparticles Mixed with Surfactant SDS

Hygroscopic Growth and Deliquescence of NaCl Nanoparticles Mixed with Surfactant SDS

The effect of cations on NO2 production from the photolysis of aqueous thin water films of nitrate salts

Effect of Relative Humidity on Corrosion of Steel under Sea Salt Aerosol Proxies

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Product

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The effect of cations on NO₂ production from the photolysis of aqueous thin water films of nitrate salts