实时在线拉曼光谱气相均相反应动力学研究中的逆命题

提出一种全新的气相均相反应动力学的研究方法. 利用实时在线拉曼光谱的点测量特点，将所测得的气相浓度和温度值通过逆命题运算对气相均相反应过程直接去卷积，确定过程的物理和化学系数. 实时在线测量得到的沿垂直射流反应器中轴线上的组分分子振动拉曼光谱被用来确定气相组分的浓度分布.同时氮气的纯转动拉曼光谱被用来确定气相温度分布.通过该方法，得到了稳定状态下TMGa-N₂二元系中组分浓度扩散系数和气相均相化学反应速度常数，所得到的结果与其他文献值相一致.

Inverse problem in gas phase homogeneous chemical reaction kinetics study using in situ Raman spectroscopy-parameter identification

A new scheme was proposed for investigating homogeneous gas phase chemical reaction kinetics.Direct mathematical deconvolution through inverse problem scheme was achieved by taking the advantage of the spatial resolved nature of Raman spectroscopy.Three-dimentional, spatially resolved gas phase species concentration profiles along the centerline of a cylindrical inverted vertical impinging flow reactor were obtained by in situ measuring the ratio of the vibrational Raman intensity of reactant to that of N₂.Gas phase temperature profile along the centerline was obtained simultaneously through N₂ Raman rotational spectra.Binary diffusion coefficient and homogeneous gas phase chemical reaction rate constant were then estimated through the output least square method.The stability of the inverse problem was achieved by using the Tikhonov regularization method.TMGa-N₂ binary diffusion coefficient and homogeneous decomposition reaction rate constant of TMGa in N₂ were identified.The identified TMGa-N₂ binary mass diffusion coefficient and TMGa thermal decomposition rate constant are 0.08 cm²•s^-1 and 3.4×10¹⁵ exp(60.1/RT) respectively, which match literature values very well.