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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Kinetics and Mechanism of the IO + BrO Reaction
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Kinetics and Mechanism of the IO + BrO Reaction

机译：IO + BrO反应的动力学和机理

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摘要

The kinetics and mechanism of reaction 1 between IO and BrO radicals have been studied by the mass spectrometric discharge flow method at 298 K. The value of the overall rate constant K_1 = (8.5 ± 1.5) * 10~(-11) cm~3 molecule~(-1) s~(-1) has been determined from the simultaneous monitoring of BrO and IO. The branching ratios have been measured for the various channels of reaction 1 in different series of experiments. The branching ratio for the major channel, producing Br and OIO, has been found in the range 0.65-1.0. The upper limits of the branching ratios for the channels producing I + Br + O_2, I + OBrO, and IBr + O_2 are 0.3, 0.2 and 0.05, respectively, whereas an upper limit of 0.3 has been found for the sum of the branching ratios for the I-atom-producing channels. Rate coefficients for side reactions have been also redetermined under the conditions of the present study: BrO + BrO → products, I + O_3 → IO + O_2, NO + O_3 → NO_2 + O_2, Br + IO → I + BrO, BrO + I_2 → products, and BrO + IBr → products. The kinetic data obtained for the IO + BrO reaction allow one to derive an upper limit for the enthalpy of formation of OIO: ΔH °_(F,298) (OIO) ≤ 32.2 kcal mol~(-1). The atmospheric implications of the present data are briefly discussed.
机译：通过质谱放电流量法研究了IO与BrO自由基在298 K下反应1的动力学和机理。总速率常数K_1 =（8.5±1.5）* 10〜（-11）cm〜3分子〜（-1）s〜（-1）是通过同时监测BrO和IO来确定的。在不同系列的实验中已经测量了反应1的各个通道的支化率。发现产生Br和OIO的主要通道的分支比在0.65-1.0的范围内。产生I + Br + O_2，I + OBrO和IBr + O_2的通道的分支比上限分别为0.3、0.2和0.05，而分支比之和的上限为0.3。用于生成I原子的通道。在本研究条件下，还重新确定了副反应的速率系数：BrO + BrO→产物，I + O_3→IO + O_2，NO + O_3→NO_2 + O_2，Br + IO→I + BrO，BrO + I_2 →产品，BrO + IBr→产品。从IO + BrO反应获得的动力学数据可以得出OIO形成焓的上限：ΔH°_（F，298）（OIO）≤32.2 kcal mol〜（-1）。简要讨论了本数据对大气的影响。

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