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本文系统地分析了氢和卤素的反应动力学规律,认为在热自燃的条件下氢—溴和氢—碘系统的反应速度分别和[H_2][I_2]、[H_2][Br_2]~(1/2)成比例。氢—氟系统的动力学规律在文献中尚没有明确报导。文内着重地分析了氢和氟的反应中链的引发、发展和终止,从此得出总的反应速度和成比例。由链终止的规律出发,认为氢—氯系统在热自燃条件下,反应速度和浓度的关系应和氢—氟系统相仿佛。这反应速度和浓度的关系得到了氢和氯的热自燃实验数据的验证。从富兰克—卡缅涅茨基的热自燃稳定理论出发,结合混气的导热率和浓度的关系导出了氢和卤素系统的最小热自燃压力的计算方程式。藉此作出了“压力—组成”和“压力—温度”曲线。所得计算值和实验数据有很好的符合。计算氢和卤素系统的热自燃条件参数后,得出含70%左右的卤素时混气具有最小的热自燃压力,这并非是偶然的事实,而是和该系统的动力学规律与氢具有很高的导热率有关。同时得出了氢和卤素的热自燃规律:以氢和氟最易发生热自燃,氢和氯次之,氢和溴再次之,而氢和碘根本就不易发生热自燃。
This paper systematically analyzes the reaction kinetics of hydrogen and halogen. It is concluded that the reaction rate of hydrogen - bromine and hydrogen - iodine system is proportional to [H_2] [I_2], [H_2] [Br_2] ~ (1 / 2) is proportional. The kinetics of the hydrogen-fluorine system has not been clearly reported in the literature. This paper focuses on the initiation, development and termination of the mid-chain reaction of hydrogen and fluorine, from which the overall reaction rate and proportionate are derived. Starting from the chain of termination of the law that the hydrogen-chlorine system in the case of thermal autoignition, the reaction rate and concentration of the relationship should be similar to the hydrogen-fluorine system. The relationship between the reaction rate and the concentration was verified by experimental data of thermal spontaneous combustion of hydrogen and chlorine. Based on the theory of thermal autoignition stability of Frank-Kamenetzky, the equations for calculating the minimum thermal spontaneous combustion pressure of hydrogen and halogen systems are derived based on the relationship between the thermal conductivity and the concentration of the mixed gas. This gives a “pressure - composition” and “pressure - temperature” curve. The calculated value is in good agreement with the experimental data. It is not a coincidence that it is not by chance fact that the gas with a halogen content of about 70% has the lowest thermal spontaneous combustion pressure when the thermal self-ignition parameters of hydrogen and halogen systems are calculated. High thermal conductivity. At the same time, the laws of spontaneous combustion of hydrogen and halogen are obtained: the most spontaneous combustion of hydrogen and fluorine occurs, followed by hydrogen and chlorine, hydrogen and bromine again, while hydrogen and iodine are not easy to spontaneous combustion.