Understanding the Initial Decomposition Pathways of the n-Alkane/Nitroalkane Binary Mixture

Authors

  • Yulei Guan,

    1. Department of Chemical Engineering, State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi'an, Shannxi 710049, China
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  • Ying Zhang,

    1. Department of Chemical Engineering, State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi'an, Shannxi 710049, China
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  • Chunhai Yi,

    1. Department of Chemical Engineering, State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi'an, Shannxi 710049, China
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  • Bolun Yang

    Corresponding author
    1. Department of Chemical Engineering, State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi'an, Shannxi 710049, China
    • Department of Chemical Engineering, State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi'an, Shannxi 710049, China, Tel.: 0086-029-82663189; Fax: 0086-029-82668789
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Abstract

Addition of nitroalkanes into n-alkanes can lower the activation barriers of free-radical production and accelerate the decomposition of n-alkanes at relatively low temperatures. Four initial decomposition mechanisms of the n-butane/nitroethane binary mixture were proposed for the promoting effect and considered theoretically at the B3LYP, BB1K, BMK, MPW1K, and M06-2X levels with MG3S basis set. Energetics above was compared to high-level CBS-QB3 and G4 calculations. Calculated results confirm the feasibility of the four initial decomposition pathways: (I) the C[BOND]NO2 bond rupture of nitroethane to produce ethyl and ·NO2, (II) HONO elimination from nitroethane followed by decomposition to ·OH and ·NO, (III) rearrangement of nitroethane to ethyl nitrite which further dissociates into CH3CH2O· and ·NO, and (IV) direct hydrogen-abstraction of nitroethane with n-butane.

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