Free-radical reactions in glow and explosion of carbon monoxideoxygen mixtures
Free-radical reactions in glow and explosion of carbon monoxideoxygen mixtures
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DOI：
10.1016/0010-2180(86)90116-1
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发表时间：
1986
影响因子：
4.4
通讯作者：
G. V. Elbe;B. Lewis
中科院分区：
文献类型：
--
作者：
G. V. Elbe;B. Lewis
对已发表的自由基反应速率系数的汇编进行检查，得出以下反应，这些反应与CO和O 2以及少量氢气或水蒸气的混合物中的链支化有关：I′ OH+ CO→ CO2 + H，II H+ O2 → OH+ O，III O+ H2 → OH+ H，III′ O+ H2O → 2 OH，XI′ HO2 + CO→ CO2 + OH，VI H+ O2 + M→ HO2 + M，XX O+ CO+ M→ CO2 + M，XXI O+ O2 + M→ O3 + M，完整的机理包括HO 2自由基向管壁的扩散和在管壁的吸附反应。这一机制适用于Buckler和Norrish的数据的支链爆炸的CO-O 2混合物含有H2在1毫米汞柱的顺序。理论和实验之间发现了实质性的一致性。此外，该机制被应用到实验的债券，灰色，和格里菲斯与H2含量为0.01-0.05毫米汞柱。根据Langmuir吸附等温线，详细描述了HO 2的吸附和表面反应，解释了辉光现象，并描述了慢反应区、辉光区和爆炸区，与实验数据雅阁。证实了CO与O2的反应需要H2、H2O、CH 4等含氢化合物的存在，并且除非在非常高的温度下，否则“干燥”均相反应是不可能的。
Examination of published compilations of rate coefficients of free-radical reactions yields the following reactions that are associated with chain branching in mixtures of CO and O 2 and small quantities of hydrogen or water vapor: I′ OH+ CO→ CO 2+ H, II H+ O 2→ OH+ O, III O+ H 2→ OH+ H, III′ O+ H 2 O→ 2 OH, XI′ HO 2+ CO→ CO 2+ OH, VI H+ O 2+ M→ HO 2+ M, XX O+ CO+ M→ CO 2∗+ M, XXI O+ O 2+ M→ O 3+ M, The complete mechanism includes diffusion of HO 2 radicals to the vessel wall and their adsorption and reaction at the surface. This mechanism is applied to the data of Buckler and Norrish on the branched-chain explosion of CO O 2 mixtures containing H 2 in the order of 1 mm Hg. Substantial agreement is found between theory and experiment. Further, the mechanism is applied to experiments of Bond, Gray, and Griffiths with an H 2 content of 0.01–0.05 mm Hg. By specifying details of the adsorption and surface reaction of HO 2 on the basis of Langmuir's adsorption isotherm the phenomenon of glow is explained and the regions of slow reaction, glow, and explosion are described in accord with the experimental data. It is confirmed that the reaction between CO and O 2 requires the presence of a hydrogenous compound such as H 2, H 2 O, CH 4, etc., and that “dry” homogenous reaction is not possible except at very high temperatures.