## Abstract

The mechanisms for reactions of H, HO, and Cl with HOClO_{3}, important elementary processes in the early stages of the ammonium perchlorate (AP) combustion reaction, have been investigated at the CCSD(T)/6-311+G(3df,2p)/ /PW91PW91/6-311+G(3df) level of theory. The rate constants for the low-energy channels have been calculated by statistical theory. For the reaction of H and HOClO_{3}, the main channels are the production of H_{2} + ClO_{4} (k_{1a}) and HO + HOClO_{2} (k_{1b}); k_{1a} and k_{1b} can be represented as 1.07 × 10 ^{-17} T ^{1.97} exp(-7484/T ) and 6.08 × 10 ^{-17}T ^{1.96} exp(-7729/T ) cm^{3} molecule ^{-1} s^{-1}, respectively. For the HO + HOClO_{3} reaction, the main pathway is the H_{2}O + ClO_{4} (k _{2a}) production process, with the predicted rate constant k _{2a} = 1.24 × 10 ^{-8} T ^{-2.99} exp(1664/T ) for 300-500 K and k_{2a} = 1.27 × 10^{-19} T ^{2.12} exp(-1474/T) for 500-3000 K. For the Cl + HOClO_{3} reaction, the formation of HOCl + ClO_{3} (k_{3a}) andHCl + ClO_{4} (k_{3b}) is dominant, with k_{3a} = 1.33 × 10^{-12} T ^{0.67} exp(-9658/T ) and k_{3b} = 1.75 × 10^{16} T ^{1.63} exp(-11156/T ) cm^{3} molecules^{-1} in the range of 300-3000 K. In addition, the heats of formation of ClO_{3} and HOClO_{3} have been predicted based on several isodesmic and/or isogyric reactions with Δ_{f}H _{0}^{o} (ClO_{3}) = 47.0 ± 1.0 and Δ_{f}H_{0}^{o} (HOClO_{3}) = 5.5 ± 1.5 kcal/mol, respectively. These data may be used for kinetic simulation of the AP decomposition and combustion reaction.

Original language | English |
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Pages (from-to) | 253-261 |

Number of pages | 9 |

Journal | International Journal of Chemical Kinetics |

Volume | 42 |

Issue number | 4 |

DOIs | |

State | Published - 1 Apr 2010 |

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