Mechanisms for the heterogeneous hydrolysis of hydrogen chloride, chlorine nitrate and dinitrogen pentoxide on water‐rich atmospheric particle surfaces

Koch, Thomas; Banham, Sally F.; Sodeau, John R.; Horn, Andrew B.; McCoustra, Martin R. S.; Chesters, M.A.

doi:10.1029/96jd00299

Cited by 59 publications

(136 citation statements)

References 42 publications

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“…The spectrum of Fig. 10 corresponds to the deposition conditions of case (b) displayed in Table 4 and reveals the formation of a crystalline ionic hydrate of HCl with ice in agreement with the literature (Koch et al, 1997;Uras-Aytemiz et al, 2001) and with theoretical studies (Kroes et al, 1992;Gertner et al, 1996;Svanberg et al, 2000). We point out that this spectrum has been measured at a time in the film evaporation history that corresponds to the time interval given by points B and D of the interferogram displayed in Fig.…”

Section: Resultssupporting

confidence: 48%

“…Ritzhaupt et al (1990) have identified a stretching vibration of H 3 O + at 1079 cm −1 whereas H 2 O bending and H 3 O + bond deformation modes contribute to the absorption at 1696 cm −1 in their FTIR absorption spectra. Koch et al (1997) attribute a 1250 cm −1 band to the H 3 O + stretching mode and a 1780 cm −1 vibration to the H 2 O and H 3 O + deformation mode. We therefore follow these assignments in this work and identify the broad absorption band centered at approximately 1100 cm −1 in Figs.…”

Section: Resultsmentioning

confidence: 99%

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The rate of water vapor evaporation from ice substrates in the presence of HCl and HBr: implications for the lifetime of atmospheric ice particles

2003

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Abstract.Using a multidiagnostic approach the rate R ev [molec cm −3 s −1 ] or flux J ev [molec cm −2 s −1 ] of evaporation of H 2 O and its corresponding rate constant for condensation, k cond [s −1 ], on a 1 µm thick ice film have been studied in the temperature range 190 to 240 K as well as in the presence of small amounts of HCl and HBr that left the vapor pressure of H 2 O on ice unchanged. The resulting Arrhenius expressions for pure ice are J ev = 1.6 · 10 28±1 · expHCl mole fraction in the range 3.2 · 10 −5 − 6.4 · 10 −3 :, and a HBr mole fraction smaller than 6.4 · 10 −3 : J ev = 7.4 · 10 25±1 · expThe small negative activation energy for H 2 O condensation on ice points to a precursor mechanism. The corresponding enthalpy of sublimation is H subl = E ev − E cond = 11.9 ± 2.7 kcal mol −1 , H subl = 11.2 ± 2.8 kcal mol −1 , and H subl = 11.7 ± 2.8 kcal mol −1 whose values are identical within experimental uncertainty to the accepted literature value of 12.3 kcal mol −1 . Interferometric data at 633 nm and FTIR absorption spectra in transmission support the kinetic results. The data are consistent with a significant lifetime enhancement for HCl-and HBr-contaminated ice particles by a factor of 3-6 and 10-20, respectively, for submonolayer coverages of HX once the fraction of the ice not contaminated by HX has evaporated.

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Section: Resultssupporting

confidence: 48%

Section: Resultsmentioning

confidence: 99%

The rate of water vapor evaporation from ice substrates in the presence of HCl and HBr: implications for the lifetime of atmospheric ice particles

2003

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Section: Rtmentioning

confidence: 93%

The rate of water vapor evaporation from ice substrates in the presence of HCl and HBr: Implications for the lifetime of atmospheric ice particles

Delval¹,

Flückiger²,

Rossi³

2003

Preprint

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Abstract. Using a multidiagnostic approach the rate Rev or flux Jevof evaporation of H2O and its condensation, kcond, on a 1mm thick ice film have been studied in the temperature range 190 to 240 K as well as in the presence of small amounts of HCl and HBr that left the vapor pressure of H2O on ice unchanged. The resulting Arrhenius expressions with RT in kcal mol-1 for pure ice are Jev=1.6×1028+/−1·exp({−10.3+\\−1.2}/{RT}) [molec cm−2 s−1], kcond=1.7×10−2+\\-1×exp({+1.6+\\−1.5}/{RT}) [s−1], in the presence of an HCl mole fraction in the range 3.2×10−5-6.4×10−3: Jev=6.4×1026+/−1×exp({−9.7+/−1.2}/{RT}) [molec cm−2 s−1], kcond=2.8×10−2+/-1×exp({+1.5+/−1.6}/{RT}) [s−1], and an HBr mole fraction smaller than 6.4×10−3:Jev=7.4×1025+/−1×exp({−9.1+/−1.2}/{RT}) [molec cm−2 s−1], kcond=7.1×10−5+\\−1×exp({+2.6+/−1.5}/{RT}) [s−1]}. The small negative activation energy for H2O condensation on ice points to a precursor mechanism. The corresponding enthalpy of sublimation is DHsubl=Eev-Econd=11.9+/−2.7 kcal mol−1, DHsubl=11.2+/−2.8 kcal mol−1, and DHsubl=11.7+/−2.8 kcal mol−1 whose values are identical within experimental uncertainty to the accepted literature value of 12.3 kcal mol−1. Interferometric data at 633 nm and FTIR absorption spectra in transmission support the kinetic results. The data are consistent with a significant lifetime enhancement for HCl- and HBr-contaminated ice particles by a factor of 3–6 and 10–20, respectively, for submonolayer coverages of HX.

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“…Furthermore, our cluster models confirm the experimental observations that at stratospherically relevant temperatures, the final reaction products contain the ionized form of nitric acid H 3 O + NO 3 -. 6,[13][14][15][16][17][18][19][20][21][22] Finally, in light of our calculations, the implications for stratospheric chemistry are discussed.…”

Section: Introductionmentioning

confidence: 97%

Exploration of the Mechanism of the Activation of ClONO₂by HCl in Small Water Clusters Using Electronic Structure Methods

2000

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High-level electronic structure calculations were used to study the mechanism of the reaction of ClONO 2 with HCl in neutral water clusters containing one to five solvating water molecules. For the reaction between molecular HCl and ClONO 2 , the barrier decreases from 42 kcal mol -1 (uncatalyzed) to essentially zero when catalyzed by only two water molecules, where the reaction products involve Cl 2 and HONO 2 . The calculations thus predict that the gas-phase reaction may be important in the stratospheric reactivation of ClONO 2 . The reaction between ClONO 2 and solvated H 3 O + Cl -, as on the polar stratospheric cloud (PSC) surface, was investigated with clusters involving up to seven water molecules. The ice-catalyzed reaction involves an ionic mechanism whereby charge transfer to ClONO 2 from the attacking nucleophile leads to significant ionization along the Cl-ONO 2 bond. The effect of the size of the first solvation shell of Cl -is addressed by our calculations. In a cluster containing three waters and a five-water cluster structurally related to hexagonal ice, ClONO 2 reacts spontaneously with HCl to yield Cl 2 /HONO 2 in the three-water reaction and Cl 2 /H 3 O + -NO 3 -in the five-water-catalyzed reaction. The calculations thus predict that the reaction of ClONO 2 with HCl on PSC ice aerosols can proceed spontaneously via an ionic pathway.

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Mechanisms for the heterogeneous hydrolysis of hydrogen chloride, chlorine nitrate and dinitrogen pentoxide on water‐rich atmospheric particle surfaces

Cited by 59 publications

References 42 publications

The rate of water vapor evaporation from ice substrates in the presence of HCl and HBr: implications for the lifetime of atmospheric ice particles

The rate of water vapor evaporation from ice substrates in the presence of HCl and HBr: implications for the lifetime of atmospheric ice particles

The rate of water vapor evaporation from ice substrates in the presence of HCl and HBr: Implications for the lifetime of atmospheric ice particles

Exploration of the Mechanism of the Activation of ClONO₂by HCl in Small Water Clusters Using Electronic Structure Methods

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Mechanisms for the heterogeneous hydrolysis of hydrogen chloride, chlorine nitrate and dinitrogen pentoxide on water‐rich atmospheric particle surfaces

Cited by 59 publications

References 42 publications

The rate of water vapor evaporation from ice substrates in the presence of HCl and HBr: implications for the lifetime of atmospheric ice particles

The rate of water vapor evaporation from ice substrates in the presence of HCl and HBr: implications for the lifetime of atmospheric ice particles

The rate of water vapor evaporation from ice substrates in the presence of HCl and HBr: Implications for the lifetime of atmospheric ice particles

Exploration of the Mechanism of the Activation of ClONO2by HCl in Small Water Clusters Using Electronic Structure Methods

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Exploration of the Mechanism of the Activation of ClONO₂by HCl in Small Water Clusters Using Electronic Structure Methods