Chemistry at the Surfaces of Ice and Sulfuric Acid:  Toward an Understanding of Adsorption at Molecular Solids

Roberts, Jeffrey T.

doi:10.1021/ar950205q

Cited by 28 publications

(28 citation statements)

References 47 publications

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“…They tend to adopt a flat orientation relative to the water surface, consistent with π-bonding of the PAH to the dangling OH at the air-water interface. Several experimental studies [25][26][27] indicate that annealed ice surfaces are less polar than water surfaces, i.e. there are fewer dangling OH at the ice surface.…”

Section: Spectra Of Phenanthrene On Water and Icementioning

confidence: 99%

Heterogeneous ozonation kinetics of phenanthrene at the air–ice interface

Kahan

Donaldson

2008

Environ. Res. Lett.

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Phenanthrene ozonation kinetics were measured on ice at −30 and −10 • C, and on a water surface at 22 • C using glancing angle laser-induced fluorescence. A Langmuir-Hinshelwood type kinetic mechanism was observed on ice. The maximum ozonation rates were a factor of ten higher on ice than on water. No temperature dependence to the kinetics was observed between −30 and −10 • C, suggesting that the differences in the rates on ice and water are due to different physical properties at the two surfaces. Fluorescence spectra of phenanthrene show significant self-association on ice that is not observed on water, adding further evidence for the hypothesis that the quasi-liquid layer at the air-ice interface presents a very different environment to liquid water.

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Section: Spectra Of Phenanthrene On Water and Icementioning

confidence: 99%

Heterogeneous ozonation kinetics of phenanthrene at the air–ice interface

Kahan

Donaldson

2008

Environ. Res. Lett.

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“…In this region, the ice surface is in a dynamic equilibrium with temperature dependent H 2 O adsorption and desorption rates of several hundred (at 200 K) to several thousand monolayers per second (at 220 K) [ Haynes et al , 1992]. Rapid water exchange may facilitate solvation of adsorbates and allow an adsorbed molecule to pass into the quasi‐liquid layer [ Roberts , 1998]. Doeppenschmidt and Butt [2000] demonstrated recently that in the 238–270 K region the thickness of the liquid‐like layer on ice increases strongly with temperature.…”

Section: Discussionmentioning

confidence: 99%

Interaction of HOBr and HCl on ice surfaces in the temperature range 205–227 K

2002

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[1] The uptake of HOBr on ice surfaces as well as the interaction of HOBr with HCldoped ice surfaces has been studied in a wall-coated tubular flow reactor coupled to a quadrupole mass spectrometer. The uptake coefficient for HOBr on ice (g HOBr ) was measured between 205 and 227 K and was independent of HOBr concentration over the range (2-22) Â 10 11 mol cm À3. A negative temperature dependence of g was observed with g = 0.003 ± 0.001 at 227 K increasing to g = 0.040 ± 0.007 at 205 K. The reaction of HOBr + HCl on ice was studied over a temperature range of 205-227 K using an HCl concentration of (4.0-8.0) Â 10 11 mol cm À3 and an HOBr concentration of (2-22) Â 10 11 mol cm À3 . On exposing HOBr to the HCl-doped ice surface, BrCl was observed as a reaction product. Under conditions with the HCl concentration in excess of the HOBr concentration, the rate of the surface reaction was found to be diffusion controlled at all temperatures, with an approximate lower limit of the uptake coefficient for HOBr + HCl on ice of g ! 0.1. Under conditions with the HOBr concentration in excess of the HCl concentration, a change in uptake behavior of HOBr on HCl-doped ice was noted. Experimental evidence suggests that the reaction follows an Eley-Rideal-type mechanism. The atmospheric implications of these results on the chemistry of the upper troposphere are discussed.

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“…Thus, to match the Lindemann criterium, we must have δ = 0.276Å. Returning to equation (9) we see that this is the case when δ/δ 0 = 3.03. The latter occurs when ǫ/γ = 0.91 and ǫ/γ = 0.89 for Θ = 0.8 and Θ = 1, respectively.…”

Section: Single-site Approachmentioning

confidence: 95%

“…The exceptional importance of the problem has initiated extensive theoretical [2][3][4][5] and experimental [7][8][9][10][11] investigations in this field. One of the most important points is the mechanism for chlorine accumulation through the HCl ionization upon adsorption on ice.…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, recent experiments [7][8][9] give a convincing evidence that adsorbateinduced effects should be considered in order to make a link between all the aspects concerning the HCl-ice interface. In particular, we have already demonstrated that in the quite general case (when the cohesion energy of a crystal is comparable to the adsorbate-substrate or adsorbate-adsorbate interactions), the adsorbate-substrate coupling may lead to a distortion [13] or restructuring [14] of the substrate lattice.…”

Section: Introductionmentioning

confidence: 99%

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ADSORBATE-INDUCED DISTORTION OF SOLID SURFACES. APPLICATION TO HCl ON ICE AT STRATOSPHERIC CONDITIONS

Vakarin¹,

Holovko²,

Badiali³

2001

Condens. Matter Phys.

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It is shown that the adsorption of HCl molecules at the surface of ice increases, if the HCl binding energy increases with the distortion amplitude of the oxygen sites of ice. At the same time, the adsorption stimulates an increase of the Lindemann parameter for the ice lattice, driving its melting at temperatures (T = 190 K) relevant to the polar stratosphere. Similar effects take place when the lateral interaction between HCl molecules becomes more attractive due to the coupling through the ice lattice.

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Chemistry at the Surfaces of Ice and Sulfuric Acid: Toward an Understanding of Adsorption at Molecular Solids

Abstract: The surfaces we study are those of ultrathin ice and sulfuric acid films deposited on a single-crystal metal † Phone:

Cited by 28 publications

References 47 publications

Heterogeneous ozonation kinetics of phenanthrene at the air–ice interface

Heterogeneous ozonation kinetics of phenanthrene at the air–ice interface

Interaction of HOBr and HCl on ice surfaces in the temperature range 205–227 K

ADSORBATE-INDUCED DISTORTION OF SOLID SURFACES. APPLICATION TO HCl ON ICE AT STRATOSPHERIC CONDITIONS

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