CH3SO3裂解反应的机理和热力学性质

doi:10.3866/PKU.WHXB201304021

Abstract

Abstract:

The mechanism and kinetics of unimolecular decomposition of CH₃SO₃ are studied at the G3XMP2//B3LYP/6-311+G(3df,2p) level of theory. Six possible dissociation channels and potential energy surface for the CH₃SO₃ decomposition are investigated. Rate constants over the temperature range of 200-3000 K are calculated using Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The results indicate that the product P1(CH₃+SO₃) is dominant between 200-3000 K. Products P2(CH₃O+SO₂) and P3(HCHO+HOSO) increase significantly at higher temperatures (>3000 K). Products P4(CHSO₂+H₂O), P5(CH₂SO₃+H) and P6(CHSO₃+H₂) show little formation in the temperature range (200-3000 K). The total rate constant can be expressed as k_total=1.40×10¹²T^0.15exp(7831.58/T). Thermodynamic properties including enthalpies of formation (D_fH^Θ_{298 K}, D_fH_{0 K}), entropies (S^Θ_{298 K}), and heat capacities (C_p, 298-2000 K) of all the minima and transition states are predicted from statistical mechanics, and found to be in good agreement with the available experimental values.

Key words: CH₃SO₃, Decomposition mechanism, Thermodynamic property, Rate constant

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CAO Jia, WANG Wen-Liang, GAO Lou-Jun, FU Feng. Mechanism and Thermodynamic Properties of CH₃SO₃ Decomposition[J]. Acta Phys. -Chim. Sin. 2013, 29(06), 1161-1167. doi: 10.3866/PKU.WHXB201304021

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Mechanism and Thermodynamic Properties of CH₃SO₃ Decomposition

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Mechanism and Thermodynamic Properties of CH₃SO₃ Decomposition