The Reaction between Sodium Hydroxide and Atomic Hydrogen in Atmospheric and Flame Chemistry.
The Reaction between Sodium Hydroxide and Atomic Hydrogen in Atmospheric and Flame Chemistry.
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大气和火焰化学中氢氧化钠与原子氢的反应。
DOI：
10.1021/acs.jpca.7b07808
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
J. Plane
中科院分区：
文献类型：
--
作者：
J. C. G. Martín;C. Seaton;M. P. D. Miranda;J. Plane
我们报告的第一个直接动力学研究的气相反应NaOH + H → Na + H2O，这是核心的钠在高层大气和火焰中的化学。在快流管中研究了反应，其中通过多光子电离和飞行时间质谱观察到NaOH，产生k（NaOH + H，230-298 K）=（3.8 ± 0.8）× 10-11 cm 3分子-1 s-1（2σ置信水平），显示在所示温度范围内没有显著的温度依赖性，并且基本上与先前对氢气中速率常数的估计一致。丰富的火焰。我们表明，使用理论轨迹计算，出乎意料的缓慢，但T-独立，NaOH + H的速率系数的解释是严格的限制，H可以使NaOH产生H2O的攻击角。该反应也是解释Na催化的火焰抑制的核心，已经提出通过顺序Na + OH（+ M）→ NaOH然后NaOH + H → Na + H2O发生，从而有效地将H和OH重组为H2O。RRKM计算的Na和OH的复合产率k（Na + OH + N2，300-2400 K）= 2.7 × 10-29（300/T）1.2 cm-6分子-2秒-1，与先前在653 K的闪光光解测量和在1800-2200 K范围内的Na种子火焰研究一致。这些结果为钠的阻燃机理提供了有力的证据。
We report the first direct kinetic study of the gas-phase reaction NaOH + H → Na + H2O, which is central to the chemistry of sodium in the upper atmosphere and in flames. The reaction was studied in a fast flow tube, where NaOH was observed by multiphoton ionization and time-of-flight mass spectrometry, yielding k(NaOH + H, 230-298 K) = (3.8 ± 0.8) × 10-11 cm3 molecule -1 s-1 (at 2σ confidence level), showing no significant temperature dependence over the indicated temperature range and essentially in agreement with previous estimates of the rate constant in hydrogen-rich flames. We show, using theoretical trajectory calculations, that the unexpectedly slow, yet T-independent, rate coefficient for NaOH + H is explained by severe constraints in the angle of attack that H can make on NaOH to produce H2O. This reaction is also central to explaining Na-catalyzed flame inhibition, which has been proposed to occur via the sequence Na + OH (+ M) → NaOH followed by NaOH + H → Na + H2O, thereby effectively recombinating H and OH to H2O. RRKM calculations for the recombination of Na and OH yield k(Na + OH + N2, 300-2400 K) = 2.7 × 10-29 (300/T)1.2 cm6 molecule-2 s-1, in agreement with a previous flash photolysis measurement at 653 K and Na-seeded flame studies in the 1800-2200 K range. These results therefore provide strong evidence to support the mechanism of flame inhibition by Na.
影响因子：
5.2
作者：
D. Janches;L. Dyrud;S. Broadley;J. Plane
通讯作者：
D. Janches;L. Dyrud;S. Broadley;J. Plane
DOI：
10.1016/j.jastp.2011.10.019
发表时间：
2012
影响因子：
1.9
作者：
Plane J
通讯作者：
Plane J