Ab initio Calculation and Kinetic Investigation of Monacid-catalyzed Decomposition of Sulfurous Acid

doi:10.7503/cjcu20170162

Abstract

Abstract:

The mechanism of decomposition of sulfurous acid to sulfur dioxide and water catalyzed by formic acid, acetic acid, propionic acid and nitric acid, respectively, was investigated by ab initio calculations at the CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ level of theory herein. The computational results showed that all the four acids presented catalytic effect for the decomposition of sulfurous acid. The reduction extent of the energy barrier was in the order propionic acid > acetic acid > formic acid > nitric acid. Furthermore, the energy barrier of propionic acid-catalyzed reaction decreased dramatically from 99.84 kJ/mol of naked reaction to 27.24 kJ/mol. The rate constants of the catalyzed reactions in the temperature range of 200-320 K had been calculated. In addition, the effective rate constants were also calculated in combination with the atmospheric concentrations of these acids. The results indicated that the acetic acid had the most effective catalytic effect in the atmospheric environment, and the lifetime of sulfurous acid was only 0.02 s with the appearance of acetic acid.

Key words: Sulfurous acid, Monacid, Catalysis, Ab initio calculation, Rate constant

CLC Number:

O641

TrendMD:

FANG Sheng, LIU Jingjing, DUAN Xuemei, TAO Fuming, LIU Jingyao. Ab initio Calculation and Kinetic Investigation of Monacid-catalyzed Decomposition of Sulfurous Acid[J]. Chem. J. Chinese Universities, 2017, 38(8): 1390.

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