Infrared chemiluminescence and energy partitioning from reactions of fluorine atoms with hydrides of carbon, silicon, oxygen, sulfur, nitrogen, and phosphorus
Infrared chemiluminescence and energy partitioning from reactions of fluorine atoms with hydrides of carbon, silicon, oxygen, sulfur, nitrogen, and phosphorus
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DOI：
10.1063/1.1679506
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发表时间：
1973-03
影响因子：
4.4
通讯作者：
W. Duewer;D. Setser
中科院分区：
文献类型：
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作者：
W. Duewer;D. Setser
用与前文相同的方法研究了氟原子与Ph_3、SiH_4、H_2O、H_2O、H_2S、NH_3、N_2H_4以及三种附加碳化合物(CH_3)_2O、(CH_3)_2S和(CH_3)_3N反应的HF-†红外化学发光。除了N2H4反应外，很大一部分能量≳45%被释放为HF†产物的振动能，经常发现布居反转。HF†与NH_3、(CH_3)_3N、N_2H_4和Ph_3之间的强相互作用可能导致了这些反应的有效振动弛豫，但加合物的再解离可能主要产生HF†(v=0)，振动分布的改变可能不严重。这些结果可以用来建立一些不确定键能的上限：D(SiH_3-H)≤87千卡分子−1，D(PH2-H)≤78千卡分子−1，D(NH_2-H)≤110千卡分子−1和D(N_2H_3-H)≤85千卡分子−1。
The HF† infrared chemiluminescence from the reactions of fluorine atoms with PH3, SiH4, H2O, H2O2, H2S, NH3, N2H4, and three additional carbon compounds, (CH3)2O, (CH3)2S, and (CH3)3N, was studied in the same way as described in the preceding paper. With the exceptions of the N2H4 reaction, a large fraction of the energy, ≳ 45%, was released as vibrational energy of the HF† product, and population inversions were frequently found. The strong chemical interaction between HF† and NH3, (CH3)3N, N2H4, and PH3 may have led to efficient vibrational relaxation for these reactions; however, the redissociation of the adducts may give mainly HF† (v = 0), and modification of the vibrational distribution may not be severe. The results can be used to establish upper limits to some uncertain bond energies: D(SiH3–H)≤ 87 kcal mole−1; D(PH2–H)≤ 78 kcal mole−1, D(NH2–H)≤ 110 kcal mole−1 and D(N2H3–H)≤ 85 kcal mole−1. Since these F atom reactions tend to populate vibrational levels up to the maximum allowed by the thermoch...