Reaction mechanism of O₃ uptake on MgCl₂ · 6H₂O as a sea salt component

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Abstract

Using a coated-insert flow tube reactor coupled to mass spectrometer with molecular beam sampling, the uptake of O₃ on a salt film coating of MgCl₂·6H₂O was studied under variation in the reactant concentration ([O₃] = 2.5 ‧ 10¹³ – 1.6 ‧ 10¹⁴ cm⁻³), humidity ([RH] = 0–24%), and reactor temperatures of 254 and 295 K. The time-dependent character of the uptake coefficient g(t) = γr exp(−t/τ) was obtained, the γr and t parameters being dependent on [O₃]. Using the method of mathematical modeling, based on the shape of the dependence of the uptake coefficient on ozone concentration and its time history, the uptake mechanism was proposed and the elementary kinetic parameters were assessed, on the basis of which it is possible to extrapolate the temporal behavior of the uptake coefficient to tropospheric conditions at arbitrary ozone concentrations. Based on their obtained dependencies, at room temperature the uptake occurs according to the reaction mechanism of an adsorbed molecule on the surface of the substrate: the mechanism includes the stage of reversible adsorption, formation of an adsorbed complex followed by its unimolecular decomposition with the release of molecular chlorine into the gas phase. At low temperatures, the uptake proceeds through recombination via the Eley–Ridil’s reaction mechanism: it includes reversible adsorption, formation of a surface complex, its reaction with an ozone molecule from the gas phase followed by the release of an oxygen molecule into the gas phase. In this case, no chlorine is formed. No dependence of the uptake coefficient on relative humidity was found in the range of RH from 0 to 24% at T = 254 K.

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V. V. Zelenov

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Author for correspondence.
Email: v.zelenov48@gmail.com
Russian Federation, Moscow

E. V. Aparina

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: v.zelenov48@gmail.com
Russian Federation, Moscow

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2. Fig. 1. Change in the concentration of the O₃ reagent in the reactor upon introduction of a movable rod coated with MgCl₂ 6H₂O. O₃ capture conditions: [O₃] = 8 10¹³ cm⁻³, T = 295 K, pressure p = 5 Torr, ΔL = 30 cm, average helium flow velocity u = 45 cm s⁻¹. Light symbols – measured O₃ concentration upon periodic removal of the coated rod from the contact zone; dark symbols – O₃ concentration with the rod introduced into the reaction zone.

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3. Fig. 2. Time-dependent O₃ capture coefficient (symbols), calculated from the data in Fig. 1 using formula (1); the solid curve is an approximation using formula (2) with the parameters from Table 1.

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4. Fig. 3. Dependence of the parameter γᵣ of time-dependent O₃ capture on the MgCl₂ 6H₂O coating at T = 295 K on [O₃]: symbols are experimental data from Table 1, solid line is approximation by formula (3) with parameters γᵣ,ₘₐₓ and KL from Table 3.

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5. Fig. 4. Dependence of the parameter τ⁻¹ of time-dependent O₃ capture on a MgCl₂ 6H₂O coating at T = 295 K on [O₃]: symbols are experimental data from Table 1, the solid line is an approximation using formula (4) with parameters KL and kᵣ from Table 3.

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6. Fig. 5. Dependence of the parameter γᵣ of time-dependent O₃ capture on the MgCl₂ 6H₂O coating at T = 254 K on [O₃]: symbols are experimental data from Table 2, the solid line is an approximation using formula (6) with parameters γᵣ,ₘₐₓ and KL from Table 3.

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7. Fig. 6. Dependence of the parameter τ⁻¹ of time-dependent O₃ capture on a coating of MgCl₂ 6H₂O at T = 254 K on [O₃]: symbols are experimental data from Table 2, solid line is approximation by formula (7) with parameters KL and kᵣ from Table 3

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