Heterogeneous reaction of dimethyl sulfide with a chlorine atom

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Abstract

By the method of resonant fluorescence (RF) of chlorine atoms, the reaction rate constant of a chlorine atom with dimethyl sulfide (DMS) was measured in the temperature range 308–366 K. It is shown that the reaction rate constant decreases during experiments at a higher temperature. At a temperature of 308 K, the rate constant of this reaction was measured at different ratios of the reaction time and the diffusion time of chlorine atoms to the reactor wall. The data of these experiments showed that with an increase in the diffusion time of the active centers to the surface of the reactor, compared with the contact time of the reagents, a decrease in the measured reaction rate constant is observed. This allowed us to assert that the reaction is heterogeneous and the interaction of the chlorine atom with the DMC occurs on the surface of the reactor.

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About the authors

I. K. Larin

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

Email: eltrofimova@yandex.ru
Russian Federation, Moscow

G. B. Pronchev

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

Email: eltrofimova@yandex.ru
Russian Federation, Moscow

E. M. Trofimova

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

Author for correspondence.
Email: eltrofimova@yandex.ru
Russian Federation, Moscow

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2. Fig. 1. Reactor diagram.

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3. Fig. 2. Graph of the dependence of ln(J₀/J) on the concentration of DMS. Reaction conditions: temperature – 308 K, reactor pressure – 0.95 Torr, [Cl] = 3.2 ‧ 10¹¹ molecules/cm³ and [DMS] = 5.1 ‧ 10¹¹ molecules/cm³. Helium served as a diluent.

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4. Fig. 3. Graph of the dependence of ln(J0/J) on the contact time of the reactants. Reaction conditions: temperature – 308 K, reactor pressure – 0.8 Torr; [Cl] = 4.8 ‧ 10¹¹ molecules/cm³ and [DMS] = 5.1 ‧ 10⁻¹¹ molecules/cm³. Helium served as a diluent.

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5. Fig. 4. Dependence of the reaction rate of chlorine atoms with dimethyl sulfide on temperature in the temperature range of 308–366 K. Helium served as a diluent.

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6. Fig. 5. Graph of the theoretical dependence of k/kobs on λ² for the case of a purely homogeneous reaction (lower curve), a purely heterogeneous reaction (upper curve) and for the cases when the ratio khet /(khet + khom) = 0.1, 0.2 and 0.5. Black circles are experimental data.

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