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首页> 外文期刊>Environmental Science & Technology >Multiphase Chemistry of Glyoxal: Revised Kinetics of the Alkyl Radical Reaction with Molecular Oxygen and the Reaction of Glyoxal with OH, NO_3, and SO_4~- in Aqueous Solution
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Multiphase Chemistry of Glyoxal: Revised Kinetics of the Alkyl Radical Reaction with Molecular Oxygen and the Reaction of Glyoxal with OH, NO_3, and SO_4~- in Aqueous Solution

机译：乙二醛的多相化学：分子氧与烷基自由基反应的动力学以及水溶液中乙二醛与OH，NO_3和SO_4〜-的反应

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摘要

The rate constant for the reaction of the hydrated glyoxyi radical (CH(OH)_(2-) C(OH)_2 with O_2 has been determined as k_(298) = (1.2 ± 0.3) × 10~9 L mol~(-1) s~(-1) at pH 4.8. This experimental value is considerably higher than a widely used estimated value of about k = 1 × 10~6 L mol~(-1)s~(-1). As the aqueous phase conversion of glyoxal is of wide interest for aqSOA formation, we suggest that the newly determined rate constant should be applied in multiphase models. The formation of the dimerization product tartaric acid has as well been studied. This product is found, however in significant yields only when the oxygen content of the solution is reduced. The formation of dimers from the recombination of alleyl radicals in the atmospheric aqueous phase should hence be treated with great care. Finally, the reactions of the free radicals OH, NO_3, and SO_4~- with glyoxal have been investigated and rate constants of k_(298 k) (OH) = (9.2 ± 0.5) × 10~8 L mol~(-1) s~(-1), k_(298) (SO_4~-) = (2.4 ± 0.2) × 10~7 L mol~(-1) s~(-1) and k_(298 k) (NO_3) = (4.5 ± 0.3) × 10~6 L mol~(-1) s~(-1) were obtained.
机译：水合乙二醛自由基（CH（OH）_（2-）C（OH）_2与O_2反应的速率常数已确定为k_（298）=（1.2±0.3）×10〜9 L mol〜（ -1）s〜（-1）在pH 4.8时，该实验值大大高于广泛使用的估计值k = 1×10〜6 L mol〜（-1）s〜（-1）。乙二醛的水相转化对于aqSOA的形成具有广泛的意义，我们建议在多相模型中应用新确定的速率常数，还研究了酒石酸二聚产物的形成，但发现该产物具有重要意义。仅当溶液中的氧含量降低时才会产生，因此应谨慎处理由大气水相中的烯丙基自由基重组形成的二聚体，最后，自由基OH，NO_3和SO_4〜 -用乙二醛进行了研究，速率常数k_（298 k）（OH）=（9.2±0.5）×10〜8 L mol〜（-1）s〜（-1），k_（298）（SO_4〜- ）=（2.4±0.2）×10〜7 L mol〜（-1）和k_（298 k）（NO_3）=（4.5±0.3）×10〜6 L mol〜（-1）得到s〜（-1）。

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  • 来源
    《Environmental Science & Technology》 |2015年第1期|343-350|共8页
  • 作者

    T. Schaefer; D. van Pinxteren; H. Herrmann;

  • 作者单位

    Leibniz-Institute for Tropospheric Research (TROPOS), Atmospheric Chemistry Department, Permoserstrasse 15, 04318 Leipzig, Germany;

    Leibniz-Institute for Tropospheric Research (TROPOS), Atmospheric Chemistry Department, Permoserstrasse 15, 04318 Leipzig, Germany;

    Leibniz-Institute for Tropospheric Research (TROPOS), Atmospheric Chemistry Department, Permoserstrasse 15, 04318 Leipzig, Germany;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
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