ReaxFF-Based Molecular Dynamics Study of the Mechanism of the Reaction of N(2)O(4) with H(2)O

基于ReaxFF的分子动力学方法研究N₂O₄与H₂O反应的机理

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Abstract

During long-term storage of the liquid propellant N(2)O(4), it absorbs H(2)O to form the N(2)O(4)(H(2)O)(n) system, and this in turn generates HNO(3), HNO(2), and other substances in the storage tank because of corrosion, which seriously affects the performance of weaponry. In this work, we carried out computational simulations of N(2)O(4) with different masses of water based on ReaxFF, analyzed the reaction intermediates and products, and investigated the mechanism of the reaction of N(2)O(4) with H(2)O and of N(2)O(4)(H(2)O)(n). The results show that the reaction product ω(HNO(3)+HNO(2)) undergoes a rapid growth in the early stage of the reaction and then tends toward dynamic equilibrium; the potential energy of the system decreases with the increase of ω(H(2)O), the reaction rate increases, and the rate of decomposition of HNO(2) to form HNO(3) increases. When ω(H(2)O) is 0.2 or 1.0%, the intermediate products are N(2)O(4)H(2)O or N(2)O(4)(H(2)O)(2), respectively, and the reaction proceeds along two paths; when ω(H(2)O) ≥ 2.0%, N(2)O(4)(H(2)O)(3) appears as the intermediate product, HNO(3) and HNO(2) are directly produced in one step, and a stable current loop can be formed within the whole system.

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