Department of Chemistry, Fudan University, Shanghai 200433, China.
J Phys Chem A. 2011 Nov 3;115(43):11971-8. doi: 10.1021/jp204698b. Epub 2011 Oct 7.
The stored and wasted explosives are usually in an acid or alkali environment, leading to the importance of exploring the acid and alkali effects on the decomposition mechanism of explosives. The acid and alkali effects on the decomposition of HMX molecule in gaseous state and in aqueous solution at 298 K are studied using quantum chemistry and molecular force field calculations. The results show that both H(+) and OH(-) make the decomposition in gaseous state energetically favorable. However, the effect of H(+) is much different from that of OH(-) in aqueous solution: OH(-) can accelerate the decomposition but H(+) cannot. The difference is mainly caused by the large aqueous solvation energy difference between H(+) and OH(-). The results confirm that the dissociation of HMX is energetically favored only in the base solutions, in good agreement with previous HMX base hydrolysis experimental observations. The different acid and alkali effects on the HMX decomposition are dominated by the large aqueous solvation energy difference between H(+) and OH(-).
储存和废弃的爆炸物通常处于酸或碱环境中，因此探索酸、碱对爆炸物分解机制的影响至关重要。采用量子化学和分子力场计算方法研究了在 298 K 下气态和水溶液中 HMX 分子在酸、碱环境中的分解情况。结果表明，无论是 H(+)还是 OH(-)，都使气态分解更具能量优势。然而，在水溶液中 H(+)和 OH(-)的影响却大不相同：OH(-)可以加速分解，而 H(+)却不能。这种差异主要是由于 H(+)和 OH(-)之间存在较大的水合溶剂化能差异。结果证实，HMX 的离解仅在碱性溶液中具有能量优势，这与之前关于 HMX 碱性水解的实验观察结果一致。HMX 分解的酸、碱影响不同主要是由于 H(+)和 OH(-)之间存在较大的水合溶剂化能差异。
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