硝化甘油缓慢分解机理的密度泛函理论研究

doi:10.6023/A25030081

摘要/Abstract

采用M06-2X/6-311＋G**方法系统地研究了硝化甘油的分解机理, 包括单分子热分解、无催化水解、酸性杂质(HNO₃)催化水解以及金属盐/碱杂质(Zn²^＋/Mg²^＋阳离子与OH^－/ $NO 3 －$ /Cl^－阴离子的组合)参与的分解反应. 此前的理论研究多集中于硝化甘油的单分子分解路径, 而且没有考虑杂质的影响. 本研究发现, 在酸性杂质存在的条件下, 酸催化水解的能垒为28.1 kcal/mol, 比单分子分解的O—NO₂均裂能垒降低了5.8 kcal/mol, 是更合理的室温下缓慢分解的机理; 而且水解反应不断释放出HNO₃, 使分解速度不断加快; 中强碱Mg(OH)₂和硝化甘油的反应能垒仅为21.3 kcal/mol, 反应速度较快; 虽然该反应是化学计量反应, 但碱作为少量杂质存在时, 也可能触发酸催化分解反应; 酸催化机理可能最接近硝化甘油常温下缓慢分解的真实机理.

关键词: 硝化甘油, 硝化甘油(NG), 分解机理, 密度泛函, 理论研究

M06-2X/6-311＋G** method has been used to systematically study the decomposition mechanism of nitroglycerin (NG), including unimolecular thermal decomposition, non-catalytic hydrolysis, HNO₃ catalyzed hydrolysis, and decomposition involving metal salt/base impurities (combinations of Zn²^＋/Mg²^＋ cations with OH^－/ $NO 3 －$ /Cl^－ anions). Consistent with previous reports, the homolytic cleavage of the O—NO₂ to generate •NO₂ free radicals was identified as the optimal initial pathway in unimolecular decomposition. In the presence of acidic impurities, several reaction modes were explored. The optimal pathway involves proton-activated heterolytic cleavage of the O—NO₂ bond in the nitrate ester group, releasing the nitronium ion (NO²^＋), which subsequently reacts with water to form nitric acid. The energy barrier for acid-catalyzed hydrolysis was calculated as 28.1 kcal/mol, 5.8 kcal/mol lower than the O—NO₂ homolysis barrier in unimolecular decomposition, making it a more plausible mechanism for the slow room-temperature decomposition. Notably, the continuous release of HNO₃ during hydrolysis creates an autocatalytic acceleration effect. For reactions of Zn(OH)₂ and moderately strong base Mg(OH)₂ with NG, the energy barriers were 25.3 and 21.3 kcal/mol, respectively. In this reaction mode, there is a cooperation effect of Lewis acid activation and the direct attack by anionic ligands on the nitrate ester, enabling relatively rapid decomposition. Although stoichiometric in nature, the generated nitric acid intermediates exhibit higher collision probabilities with NG molecules than with alkaline species for neutralization, potentially triggering acid-catalyzed decomposition. Once initiated, this acid-catalyzed process becomes self-accelerating. Zn²^＋ and Mg²^＋ nitrates/chlorides showed limited catalytic activity. We conclude that the acid-catalyzed mechanism most likely represents the true pathway for NG’s gradual decomposition at ambient temperatures. Previous theoretical studies have predominantly focused on the unimolecular decomposition pathways of nitroglycerin and neglected the influence of impurities, failing to adequately account for the observed slow decomposition at ambient temperatures. Our research provides valuable references on the study of nitroglycerin.

Key words: nitroglycerin, nitroglycerin (NG), decomposition mechanism, density functional theory (DFT), theoretical research

引用此文

成守飞, 李婧, 凌琳, 李玉学, 吕龙. 硝化甘油缓慢分解机理的密度泛函理论研究[J]. 化学学报, 2025, 83(8): 833-843.

Shoufei Cheng, Jing Li, Lin Ling, Yuxue Li, Long Lu. Density Functional Theory Research on Decomposition Mechanisms of Nitroglycerin[J]. Acta Chimica Sinica, 2025, 83(8): 833-843.

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图/表 11

图1. 硝化甘油单分子初始分解机理

Figure 1. Possible unimolecular decomposition mechanisms of nitroglycerin

图2. 硝化甘油的单分子机理(O—NO2键均裂和NO2催化机理. 绿色和红色数字是自旋密度. 键长单位: Å)

Figure 2. Unimolecular decomposition mechanism of nitroglycerin (O—NO2 bond homolysis and NO2 catalized mechanism. The green and red numbers are spin densities. The bond lengths are in angstroms)

图3. Mode-3: 硝化甘油的单分子分解机理(HONO消除. 键长单位: Å)

Figure 3. Mode-3: Unimolecular decomposition mechanism of nitroglycerin (HONO elimination. The bond lengths are in angstroms)

Pathway	Gas phase		In NG		In H₂O
Pathway	α	β	α	β	α	β
Path-Mode-1	32.8	33.9	35.9	35.5	35.0	33.9
Path-Mode-2	61.7	64.0	63.6	64.4	58.9	60.3
Path-Mode-2-2	65.3	66.1	62.9	64.4	61.0	62.0
Path-Mode-2-3	67.1	65.8	67.2	66.2	64.9	64.4
Path-Mode-3	44.9	45.1	47.0	47.8	45.7	46.1

表1. 硝化甘油单分子分解各反应路径的能垒[ΔG/(kcal•mol－1)]

Table 1. Energy barriers of nitroglycerine unimolecular decomposition [ΔG/(kcal•mol－1)]

图4. NG的水解反应模式

Figure 4. Hydrolysis reaction modes of NG

图5. 无催化/酸催化硝化甘油水解机理(键长单位: Å)

Figure 5. Catalysis free/acid-catalyzed nitroglycerin hydrolysis mechanisms (The bond lengths are in angstroms)

图6. 过渡态中硝酰阳离子和周围主要氧原子的轨道作用(蓝色和粉红色的斜体数字是NBO原子电荷. 键长单位: Å)

Figure 6. Orbital interaction of nitryl cation and surrounding oxygen atoms in transition state (The blue and pink italic numbers are NBO atomic charges. The bond lengths are in angstroms)

Pathway	SMD in NG		SMD in H₂O
Pathway	α	β	α	β
Path-H-Mode-1	51.9	54.2	56.5	52.5
Path-H-Mode-2	49.3	50.9	42.1	43.1
Path-H-Mode-3	54.5	51.5	47.1	44.4
Path-H-Mode-4	39.0	32.5	29.4	28.1

表2. 硝化甘油各水解反应路径的活化能[ΔG/(kcal•mol－1)]

Table 2. Energy barriers of hydrolysis reaction pathways of nitroglycerin [ΔG/(kcal•mol－1)]

图7. 金属络合物促进的硝化甘油水解机理

Figure 7. Mechanism of metal complex promoted nitroglycerine hydrolysis

图8. 金属络合物促进的硝化甘油水解机理(键长单位: Å)

Figure 8. Mechanism of metal complex promoted nitroglycerine hydrolysis (The bond lengths are in angstroms)

	M=Zn^2＋						M=Mg^2＋
	OH^－		$NO 3 −$		Cl^－		OH^－		$NO 3 −$		Cl^－
	α	β	α	β	α	β	α	β	α	β	α	β
M-Mode-1	47.2	44.1	45.0	44.5			45.9	42.1	43.5	38.6
M-Mode-2	28.7	26.3	54.1	48.3			29.2	30.1	52.6	46.1
M-Mode-3	26.2	25.3					21.3	22.0
M-Mode-4	27.0	27.5			36.4	39.9	27.3	26.7			43.3	47.7

	M=Zn^2＋						M=Mg^2＋
	OH^－		$NO 3 −$		Cl^－		OH^－		$NO 3 −$		Cl^－
	α	β	α	β	α	β	α	β	α	β	α	β
M-Mode-1	47.2	44.1	45.0	44.5			45.9	42.1	43.5	38.6
M-Mode-2	28.7	26.3	54.1	48.3			29.2	30.1	52.6	46.1
M-Mode-3	26.2	25.3					21.3	22.0
M-Mode-4	27.0	27.5			36.4	39.9	27.3	26.7			43.3	47.7

表3. 金属离子催化硝化甘油的路径比较

Table 3. Comparison of hydrolysis pathways of nitroglycerin

表3. 金属离子催化硝化甘油的路径比较

Table 3. Comparison of hydrolysis pathways of nitroglycerin

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