Detailed Kinetic Model for the Thermal Decomposition of Hydrazine Nitrate in Nitric Acid Solution Based on Quantum Chemistry Calculations Combined with the Polarizable Continuum Model
Detailed Kinetic Model for the Thermal Decomposition of Hydrazine Nitrate in Nitric Acid Solution Based on Quantum Chemistry Calculations Combined with the Polarizable Continuum Model
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基于量子化学计算结合极化连续体模型的硝酸肼在硝酸溶液中热分解的详细动力学模型
DOI：
10.1021/acs.jpca.2c00629
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Miyake Atsumi
中科院分区：
文献类型：
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作者：
Izato Yu-ichiro;Shiota Kento;Miyake Atsumi
在CBS-QB 3//ω B 97 X-D/SMD水平上，采用极化连续模型结合量子化学计算方法研究了硝酸肼在硝酸溶液中的分解机理.这些计算提供了一个详细的动力学模型，将速率系数和热力学数据。速率系数使用传统的过渡态理论确定，而扩散限制反应基于Einstein-Stokes方程建模。所得到的模型包括108个反应的动力学和58个物种的热力学数据。通过将分解过程中化学物质变化的模拟与在100 °C等温条件下获得的实验数据进行比较，验证了该模型。该模型准确地再现了N2 H4、HN 3和NH3的浓度变化，并解释了反应机理。热分解过程有两条平行的路径：N_2H_4 + HNO_3 → H_2O + HONO + N_2H_2和N_2H_4 + HONO → HN_3 + 2H_2O。在这些反应之后，一部分HN 3通过多步过程分解产生NH3。敏感性分析表明，分解速率受溶液pH值的影响很大。
The decomposition mechanism of hydrazine nitrate in nitric acid solutions was investigated using quantum chemistry calculations combined with the polarizable continuum model at the CBS-QB3//ωB97X-D/SMD level of theory. These calculations provided a detailed kinetic model incorporating rate coefficients and thermodynamic data. Rate coefficients were determined using traditional transition state theory, while diffusion-limited reactions were modeled based on the Einstein–Stokes equations. The resulting model comprised the kinetics for 108 reactions and thermodynamic data for 58 species. This model was validated by comparing simulations of the variations in chemical species during the decomposition process to experimental data acquired under isothermal conditions at 100 °C. The model was found to accurately reproduce the concentration changes of N2H4, HN3, and NH3and also explained the reaction mechanism. The thermal decomposition was found to proceed via two parallel paths: N2H4+ HNO3→ H2O + HONO + N2H2and N2H4+ HONO → HN3+ 2H2O. Following these reactions, a portion of the HN3decomposes to produce NH3through a multistep process. A sensitivity analysis showed that the rate of decomposition is greatly affected by the pH of the solution.