Oxidation of HOSO˙ by Cl˙: a new source of SO2 in the atmosphere?. Issue 34 (19th August 2021)

• Record Type: Journal Article
• Authors: Kumar, Amit; Mallick, Subhasish; Kumar, Pradeep
• Is Part Of: Physical chemistry chemical physics. Volume 23:Issue 34(2021)
• Page Start: 18707
• Page End: 18711
• Publication Date: 2021-08-19
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d1cp01048d
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : In the present work, we have studied the formation of SO2 in the atmosphere from the oxidation of HOSO˙ by Cl˙ at the CCSD(T)/aug-cc-pV(+d)TZ//MP2/aug-cc-pV(+d)TZ level of theory. Abstract : In the present work, we have studied the formation of SO2 in the atmosphere from the oxidation of HOSO˙ by Cl˙ at the CCSD(T)/aug-cc-pV(+d)TZ//MP2/aug-cc-pV(+d)TZ level of theory. The present work reveals that the title reaction is a barrierless reaction that proceeds through a stable intermediate sulfurochloridous acid having a stabilization energy of ∼−56.5 kcal mol −1 . The rate constant values within the temperature range of 213–400 K indicate that the rate of HOSO˙ + Cl˙ = SO2 + HCl reaction does not change much with the change in temperature. Besides, the reaction was also found to be insensitive towards pressure change. Interestingly, the relative rate of HOSO˙ + Cl˙ reaction with respect to HOSO˙ + OH˙ reaction indicates that HOSO˙ + Cl˙ is always much slower than HOSO˙ + OH˙ reaction, within the temperature range of 213–400 K.