高等学校化学学报 ›› 2012, Vol. 33 ›› Issue (07): 1444-1449.doi: 10.3969/j.issn.0251-0790.2012.07.014

• 分析化学 • 上一篇    下一篇

通过红外光谱结合化学计量学方法研究奥克托今的合成机理

张淑利1, 熊贤锋2, 尉涛2, 王友兵2, 王伯周2, 葛忠学2, 翟高红1, 李华1   

  1. 1. 西北大学化学与材料科学学院, 西安 710069;
    2. 西安近代化学研究所, 西安 710065
  • 收稿日期:2011-07-19 出版日期:2012-07-10 发布日期:2012-07-10
  • 通讯作者: 李 华, 男, 博士, 教授, 博士生导师, 主要从事化学计量学与过程分析化学研究. E-mail: huali@nwu.edu.cn E-mail:huali@nwu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号: 21175106)资助.

Synthetic Reaction Mechanism of Octogen by Chemometrics and Infrared Spectroscopy

ZHANG Shu-Li1, XIONG Xian-Feng2, YU Tao2, WANG You-Bing2, WANG Bo-Zhou2, GE Zhong-Xue2, ZHAI Gao-Hong1, LI Hua1   

  1. 1. Chemical and Material Science, Northwest University, Xi’an 710069, China;
    2. Xi’an Modern Chemistry Research Institute, Xi’an 710065, China
  • Received:2011-07-19 Online:2012-07-10 Published:2012-07-10

摘要: 通过红外(IR)光谱在线监测醋酐法合成奥克托今(HMX)的反应过程, 采用渐进因子分析(EFA)结合多元曲线分辨-交替最小二乘法(MCR-ALS)以及直观推导式演进特征投影法(HELP)等化学计量学方法对反应过程的光谱数据矩阵进行解析, 获得了各组分浓度变化曲线和对应的IR光谱; 并采用密度泛函理论(DFT)的B3LYP方法, 在6-31G*基组水平上得到该化合物的全优化结构, 在振动分析的基础上求得体系的振动频率和IR光谱. 通过对比发现, MCR-ALS和HELP法可得出相互验证的一致结论; 将通过量子化学计算的中间体的IR光谱特征吸收峰与2种方法进行比较, 结果吻合, 从而推导出合理的反应机理. 实验结果表明, 化学计量学方法结合在线红外光谱是研究反应机理的有效手段, 对反应路线的选择具有指导意义.

关键词: 红外光谱, 多元曲线分辨-交替最小二乘法, 直观推导式演进特征投影法, 量子化学, 反应机理, 奥克托今

Abstract: Online IR spectrum was used for monitoring the reaction process of synthesizing octogen(HMX). The concentration profiles and IR spectra of reactants, intermediates and product were determined by analyzing the spectral data using multivariate curve resolution-alternating least squares(MCR-ALS) and heuristic evolving latent projection(HELP), and the reasonable mechanism was deduced. The stable geometry of intermediates was optimized at B3LYP/6-31G* theoretical level. Its vibrational frequencies and IR spectra were obtained on the basis of vibrational analysis. The results showed that the variation of intermediates could be obtained quickly with the aid of chemometric resolution and provided significant guidance to the choice of reaction.

Key words: IR spectrum, Multivariate curve resolution-alternating least squares(MCR-ALS), Heuristic evolving latent projection(HELP), Quantum chemistry, Reaction mechanism, Octogen

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