Hydrogen Abstraction Reaction Mechanisms and Rate Constants for Isoflurane with a Cl Atom at 200～2000 K:A Theoretical Investigation

The kinetics and mechanisms of H abstraction reaction between isoflurane and a CI atom have been investigated using DFT and G3（MP2） methods of theory. The geometrical structures of all species were optimized by the wB97XD/6-311＋＋G＊＊ method. Intrinsic reaction coordinate （IRC） analysis has been carried out for the reaction channels. Thermochemistry data have been obtained by utilizing the high accurate model chemistry method G3（MP2） combined with the standard statistical thermodynamic calculations. Gibbs free energies were used for reaction channels analysis. Two channels were obtained, which correspond to P（1） and P（2）. The rate constants for the two channels over a wide temperature range of 200-2000 K were also obtained. The results show that the barriers of P（1） and P（2） reaction channels are 50.36 and 50.34 kJ/mol, respectively, predicting that it exists two competitive channels. The calculated rate constant is in good agreement with the experiment value. Additionally, the results also show that the rate constants also increase from 1.85x10^-16 to 2.16x 10^12 cm3.moleculel.s-1 from 200 to 2000 K

切槽炮孔偏心装药爆源近区裂纹动态力学特征实验研究

为研究切槽炮孔偏心不耦合装药爆源近区裂纹动态力学特征,采用数字激光动态焦散线实验系统,对比分析3种切槽形状(三角形、圆形和矩形)对爆源近区裂纹扩展速度v和动态应力强度因子K_Ι~d和K_(ΙΙ)~d,以及能量释放率G的影响规律。实验结果表明:偏心爆炸荷载下,3种切槽尖端均产生非对称性裂纹,主、次裂纹分别位于装药耦合、不耦合侧;切槽形状对裂纹起裂影响较大,对裂纹扩展影响较小;起裂阶段,各主裂纹相比,三角形尖端主裂纹K_Ι~d,v,G最大,K_(ΙΙ)~d最小,有利于张开型裂纹起裂,而矩形尖端主裂纹K_Ι~d,v,G最小,K_(ΙΙ)~d最大,有利于压剪型裂纹起裂;扩展阶段,各主裂纹主要为张开型,K_(ΙΙ)~d趋于0,K_Ι~d,v,G整体变化一致。各次裂纹相比,矩形尖端次裂纹K_Ι~d,K_(ΙΙ)~d,v,G均最大,消耗较多爆炸能量,不利于主裂纹起裂和扩展。实验结果对于工程实践具有理论参考意义。