The interaction of CH3Cl, CH2Cl2, CHCl3, and CCl4 with ozone on the surface of ice under stratospheric conditions

Vysokikh, T. A.; Mukhamedzyanova, D. F.; Yagodovskaya, T. V.; Savilov, S. V.; Лунин, В. В.

doi:10.1134/s0036024407110209

Cited by 6 publications

(8 citation statements)

References 15 publications

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“…focused on the interaction of ozone with CH 4-x Cl x molecules adsorbed on a thin ice film over the temperature range of 77-292 K, and showed that these molecules cannot dissociate at the surface on ice, and therefore do not release chlorine, at least below 210 K. 23 Despite these series of experimental studies, several questions remained open concerning the atomistic details of the interaction processes between chloromethane molecules and water at the ice surface, especially in the temperature range relevant for the upper troposphere -lower stratosphere (UTLS) region. Indeed, neither the orientation of the adsorbed molecules nor their exact location (i.e., above or within the surface layers of ice) are known in this temperature range.…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, it was also shown by means of metastable impact electron spectroscopy that CHCl 3 molecules are adsorbed at the ice surface with their H atom oriented toward the substrate below 120 K, and for all chlorinated methane derivatives (CH 4– x Cl x ) that their interaction with water occurs through the oxygen atom . Finally, Vysokikh et al focused on the interaction of ozone with CH 4– x Cl x molecules adsorbed on a thin ice film over the temperature range of 77–292 K, and showed that these molecules cannot dissociate at the surface of ice, and therefore do not release chlorine, at least below 210 K …”

Section: Introductionmentioning

confidence: 99%

“…20 Moreover, it was also shown by means of metastable impact electron spectroscopy that CHCl 3 molecules are adsorbed at the ice surface with their H atom oriented toward the substrate below 120 K, 21 and for all chlorinated methane derivatives (CH 4−x Cl x ) that their interaction with water occurs through the oxygen atom. 22 Finally, Vysokikh et al focused on the interaction of ozone with CH 4−x Cl x molecules adsorbed on a thin ice film over the temperature range of 77−292 K, and showed that these molecules cannot dissociate at the surface of ice, and therefore do not release chlorine, at least below 210 K. 23 Despite these series of experimental studies, several questions remained open concerning the atomistic details of the interaction processes between chloromethane molecules and water at the ice surface, especially in the temperature range relevant for the upper troposphere−lower stratosphere (UTLS) region. Indeed, neither the orientation of the adsorbed molecules nor their exact location (i.e., above or within the surface layers of ice) is known in this temperature range.…”

Section: Introductionmentioning

confidence: 99%

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Adsorption of Chlorinated Methane Derivatives at the Ice Surface: A Grand Canonical Monte Carlo Simulation Study

2017

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The adsorption behavior of three chlorinated methane derivative molecules, namely CH 3 Cl, CHCl 3 , and CCl 4 is investigated at the (0001) surface of I h ice at the tropospheric temperature of 200 K by means of grand canonical Monte Carlo simulations. This study completes our earlier investigations concerning the adsorption of CH 4 , CH 2 Cl 2 , and fluorinated methane derivatives. Our results show that neither CHCl 3 nor CCl 4 exhibits any adsorption. This complete lack of adsorption is attributed to the interplay of the very strong cohesion acting between the adsorbate molecules, and their relatively weak interaction with the ice phase. By contrast, CH 3 Cl does exhibit noticeable adsorption on ice, and the adsorbed molecules prefer to turn towards the ice surface by their H atoms, forming weak, C-H …. O type hydrogen bonds with surface waters. The lateral (i.e., adsorbate-adsorbate) contribution to the total interaction energy of the adsorbed molecules is always considerably larger (in magnitude) than in the case of the corresponding fluorinated analogs, making also the total adsorption energy lower for the chlorinated molecules than for their fluorinated counterpart. As a consequence of this strong attraction between the chlorinated adsorbate molecules, their condensation occurs at lower chemical potential (and, hence, pressure) values than that of the fluorinated analogs, which prevents the formation or completion of the adsorption layer of the chlorinated molecules.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Adsorption of Chlorinated Methane Derivatives at the Ice Surface: A Grand Canonical Monte Carlo Simulation Study

2017

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“…Vysokikh et al. studied the interaction of partially chlorinated methane derivatives, adsorbed on a thin ice film, with ozone in a broad temperature range between 77 K and 292 K. They excluded the possibility of the occurrence of a direct chemical reaction, at least at temperatures below 210 K, showing that these compounds do not dissociate at the ice surface, and hence do not release chlorine in this temperature range [23]. The adsorption of CHCl 3 at the surface of both crystalline and amorphous ice was studied by means of both x-ray photoelectron spectroscopy (PES) [24] and TPD [25] experiments.…”

Section: Introductionmentioning

confidence: 99%

Dependence of the adsorption of halogenated methane derivatives at the ice surface on their chemical structure

Sumi

Picaud

Jedlovszky

2017

Journal of Molecular Liquids

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The adsorption of all the fluorinated and chlorinated methane derivatives as well as methane itself at the surface of I h ice is studied at the tropospheric temperature of 200 K by grand canonical Monte Carlo simulations. The general behaviour of the obtained isotherms is in good accordance with existing experimental data, giving us confidence in the models used. The shape of the adsorption isotherms is discussed in terms of the interplay of adhesive and cohesive interactions. It is found that in cases when the former of the two interactions is clearly the stronger one, multilayer adsorption occurs; when the latter interaction is the dominant one, no considerable adsorption is observed, while in cases when the two interactions are of roughly the same strength, the formation of a saturated monolayer occurs. The isotherms exhibit the Langmuir shape, at least up to the pressures where multilayer adsorption starts to occur, given that the cohesion acting between the adsorbate molecules is only moderately strong. Too strong cohesion, on the other hand, leads to the deviation of the isotherm from the Langmuir shape. While the strength of cohesion depends on the properties of the adsorbate molecules, that of adhesion is determined by hydrogen bond formation between the adsorbed molecules and surface waters. Our results show that while CH 3 F and CH 3 Cl form several weak, C-H donated hydrogen bonds with the surface molecules of the ice phase, the adsorbates containing more than one halogen atom form only one, though strong, O-H donated hydrogen bond with them.

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“…Considering both of the aforementioned experimentally observed features, i.e., nondissociative adsorption of halogenocarbon compounds on ice at temperatures typical of the lower stratosphere/upper troposphere regions, 11 and differences in the interactions between ice and different halomethanes, 12 and also the lack of theoretical investigations on these systems, here we perform a detailed investigation of the adsorption behavior of two different halogenocarbon molecules, namely, methylene fluoride (CH 2 F 2 ) and methylene chloride (CH 2 Cl 2 ) at the surface of I h ice under tropospheric conditions by performing GCMC simulations. The two molecules considered differ only in the type of the halogen atoms (i.e., F vs Cl).…”

Section: Introductionmentioning

confidence: 99%

Adsorption of Methylene Fluoride and Methylene Chloride at the Surface of Ice under Tropospheric Conditions: A Grand Canonical Monte Carlo Simulation Study

Sumi¹,

Picaud

Jedlovszky

2015

J. Phys. Chem. C

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Abstract:The adsorption of two halogenated methane derivatives, namely methylene fluoride and methylene chloride at the surface of I h ice is studied by grand canonical Monte Carlo simulations under tropospheric conditions. The adsorption isotherms of the two molecules, differing only in the halogen atom type, are found to be markedly different from each other.Thus, while methylene fluoride exhibits multilayer adsorption, and its adsorption isotherm belongs to class II according to the IUPAC convention, methylene chloride does not show considerable adsorption at the ice surface, as its condensation well precedes the saturation of even the first adsorbed molecular layer. Interestingly, both the surface orientation and the binding energy of the two types of adsorbed molecules are rather similar to each other; first layer molecules form one single hydrogen bond with the dangling OH groups of the ice surface. The strong differences in the adsorption behavior of methylene fluoride and methylene chloride are traced back to the different cohesion in the liquid phase, and hence to the strongly different boiling point of the two molecules.4

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The interaction of CH3Cl, CH2Cl2, CHCl3, and CCl4 with ozone on the surface of ice under stratospheric conditions

Cited by 6 publications

References 15 publications

Adsorption of Chlorinated Methane Derivatives at the Ice Surface: A Grand Canonical Monte Carlo Simulation Study

Adsorption of Chlorinated Methane Derivatives at the Ice Surface: A Grand Canonical Monte Carlo Simulation Study

Dependence of the adsorption of halogenated methane derivatives at the ice surface on their chemical structure

Adsorption of Methylene Fluoride and Methylene Chloride at the Surface of Ice under Tropospheric Conditions: A Grand Canonical Monte Carlo Simulation Study

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