2012
DOI: 10.1007/s11237-012-9265-7
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DFT analysis of the mechanism for the gas-phase chlorination of methane in the HOCL–H2O system

Abstract: The DFT method was used to study gas-phase chlorination reactions CH 4 + HOCl (1) and CH 4 + HOCl + H 2 O (2). These reactions entail singlet-triplet (s®t) preactivation of HOCl and terminate in a reverse t®s transition. At 298 K, the barrier DG t ¹ for reaction (2) is higher than for reaction (1) by 1.5 kcal/mol, while the singlet transition state TS s -2 lies higher than TS t -2 by DG ¹ = 21.4 kcal/mol. The reactions of alkanes (RH) with chlorine in the gas phase and in acid media such as Cl 2 -CH 3 CO 2 H-H… Show more

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Cited by 4 publications
(2 citation statements)
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“…It is remarkable that the 1 3 A″ triplet state of HOCl plays a crucial role in gas-phase chlorination of methane. Litvinenko and Rudakov recently showed 157 that the reaction CH 4 + HOCl + H 2 O → CH 3 Cl + 2H 2 O entails the singlet−triplet preactivation of HOCl. They also showed that the involving of the 1 3 A″ dissociative state into the chlorination of methane by HOCl−H 2 O system makes it possible to reduce the TS energy barrier by 21.4 kcal/mol compared with the singlet transition state reaction pathway.…”
Section: Some Examples Of Phosphorescence From Triatomic Speciesmentioning
confidence: 99%
“…It is remarkable that the 1 3 A″ triplet state of HOCl plays a crucial role in gas-phase chlorination of methane. Litvinenko and Rudakov recently showed 157 that the reaction CH 4 + HOCl + H 2 O → CH 3 Cl + 2H 2 O entails the singlet−triplet preactivation of HOCl. They also showed that the involving of the 1 3 A″ dissociative state into the chlorination of methane by HOCl−H 2 O system makes it possible to reduce the TS energy barrier by 21.4 kcal/mol compared with the singlet transition state reaction pathway.…”
Section: Some Examples Of Phosphorescence From Triatomic Speciesmentioning
confidence: 99%
“…Litvinenko and Rudakov [84] studied the activation of methane in the gaseous phase with HOCl with and without a spectator water molecule. They found out that these reactions require a preactivation of HOCl, which occurs by a spin transition between the singlet and triplet state.…”
Section: Density Functional Theory (Dft)mentioning
confidence: 99%