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Theoretical study of the competitive decomposition and isomerization of 1-hexyl radical

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Abstract

The ground-state potential energy surface of the 1-hexyl system, including the main decomposition and isomerization processes, has been calculated with the MPW1K, BB1K, MPWB1K, MPW1B95, BMK, M05-2X and CBS-QB3 methods. On the basis of these data, thermal rate coefficients of different reaction channels and branching ratios were then calculated using the master equation formulation at 250–2,500 K. The results clearly point out that the 1,5 H atom transfer reaction of 1-hexyl radical with exothermicity proceeds through the lowest reaction barrier, whereas the decomposition processes are thermodynamically unfavorable with large endothermicity. The temperature effect is important on the relative importance of different reactions in the 1-hexyl system. In the low-temperature range of 250–900 K, isomerization reactions, especially 1,5 H atom transfer reaction of 1-hexyl radical, are dominating and responsible for over 82.17% of all the reactions, due to their smaller reaction barriers than those of the decomposition reactions. Furthermore, an equilibrium process involving the isomeric forms of the hexyl radicals appearing at relative low temperature was validated theoretically. However, isomerization and decomposition processes are kinetically competitive and simultaneously important under normal pyrolysis conditions.

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Notes

  1. Reaction enthalpies Δr H°(298) were calculated as the sum of heat of formation of the products minus those of reactants. The standard enthalpies of formation are from NIST Standard Reference Database (http://webbook.nist.gov) and [44], while the standard enthalpies of formation of 2-hexyl and 3-hexyl radical were derived by assuming the bond dissociation energy of secondary and third C-H bond of n-hexane to be 98.09 kcal/mol.

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Acknowledgments

The authors gratefully acknowledge the financial support from National Natural Science Foundation of China under Grant No. 20590361 and the National Outstanding Young Scientists Foundation of China under Grant No. 20625620. This work is also supported by Synfuels China Co., Ltd.

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Authors and Affiliations

  1. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, 030001, Taiyuan, China

    Feng Wang, Dong Bo Cao, Gang Liu, Jie Ren & Yong Wang Li

  2. Graduate University of Chinese Academy of Sciences, 100039, Beijing, China

    Feng Wang & Gang Liu

Authors
  1. Feng Wang
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  2. Dong Bo Cao
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  3. Gang Liu
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  4. Jie Ren
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  5. Yong Wang Li
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Corresponding author

Correspondence to Yong Wang Li.

Electronic supplementary material

Below is the link to the electronic supplementary material. Supporting Information Available: optimized geometries at the MPWB1K/6-31 + G(d,p) level of theory and classical potential energy of all reactions as function of the intrinsic reaction coordinate at the MPWB1K/6-31 + G(d,p) level of theory. This material is available in Supporting Information.

Supplementary material 1 (DOC 136 kb)

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Wang, F., Cao, D.B., Liu, G. et al. Theoretical study of the competitive decomposition and isomerization of 1-hexyl radical. Theor Chem Acc 126, 87–98 (2010). https://doi.org/10.1007/s00214-009-0685-y

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