Kinetics of the Simplest Criegee Intermediate CH2OO Reaction with tert-Butylamine. 2023

Yang Chen, and Haotian Jiang, and Siyue Liu, and Jiayu Shi, and Yuqi Jin, and Xueming Yang, and Wenrui Dong
Key Laboratory of Chemical Lasers, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.

The kinetics of the simplest Criegee intermediate (CH2OO) reaction with tert-butylamine ((CH3)3CNH2) was studied under pseudo-first-order conditions with the OH laser-induced fluorescence (LIF) method at the temperature range of 283-318 K and the pressure range of 5-75 Torr. Our pressure-dependent measurement showed that at 5 Torr─the lowest pressure measured in the current experiment─this reaction was under the high-pressure limit condition. At 298 K, the reaction rate coefficient was measured to be (4.95 ± 0.64) × 10-12 cm3 molecule-1 s-1. The title reaction was observed to be negative temperature-dependent; the activation energy of (-2.82 ± 0.37) kcal mol-1 and the pre-exponential factor of (4.21 ± 0.55) × 10-14 cm3 molecule-1 s-1 were derived from the Arrhenius equation. The rate coefficient of the title reaction is slightly larger than (4.3 ± 0.5) × 10-12 cm3 molecule-1 s-1 of the CH2OO reaction with methylamine; the electron inductive effect and the steric hindrance effect might play a role in contributing to such difference.

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