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Participation of hydrogen peroxide in halogen activation in the low stratosphere

机译：低平流层中过氧化氢参与卤素活化

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摘要

Measurements of hydrogen peroxide conversion into Caro's acid in sulphuric acid at T ≈ 298 K and H_2SO_4 content 78/95 wt% were performed to monitor the equilibriums: H_2O_2 + H_3O~+ ←→ H_3O_2~+ + H_2O and H_2O_2 + HSO_4~-←→ HSO_5~- + H_2O yielded K(298) = 8 × 10~(-4) and K(298) = 1.2 × 10~(-2), respectively. The physical solubility of H_2O_2 as well as that including H_3O_2~+ and HSO_5~- has been estimated. The calculation of the Henry's law coefficient (T = 298) of H_2O_2 shows the typical salting-out effect, while for the case of H_3O_(2(aq))+ and HSO5_((aq))- this coefficient exhibits a sharp rising with H_2SO_4 content, starting from almost 50 wt%. An increase in the oxidative power of H_2O_2, H_3O_(2(aq))+ and HSO_(5(aq))- is observed, as H_2SO_4 concentration increases. In addition, the kinetics of the liquid-phase reactions involving these reagents are analysed on the basis of a correlation between the rate constants and the thermodynamic data. Finally, the occurrence of sulphate aerosol reactions involving the components that affect halogen activation in the low stratosphere is discussed.
机译：在T≈298 K且H_2SO_4含量为78/95 wt％的条件下进行了过氧化氢在硫酸中转化为Caro酸的测量，以监测平衡：H_2O_2 + H_3O〜+←→H_3O_2〜+ + H_2O和H_2O_2 + HSO_4〜-← →HSO_5〜-+ H_2O分别得到K（298）= 8×10〜（-4）和K（298）= 1.2×10〜（-2）。估计了H_2O_2以及包括H_3O_2〜+和HSO_5〜-的物理溶解度。 H_2O_2的亨利定律系数（T = 298）的计算显示了典型的盐析效应，而对于H_3O_（2（aq））+和HSO5 _（（aq））而言，该系数呈现出急剧的上升趋势。 H_2SO_4含量从几乎50 wt％开始。随着H_2SO_4浓度的增加，观察到H_2O_2，H_3O_（2（aq））+和HSO_（5（aq））-的氧化能力增加。另外，基于速率常数和热力学数据之间的相关性，分析了涉及这些试剂的液相反应的动力学。最后，讨论了涉及影响低平流层中卤素活化的组分的硫酸盐气溶胶反应的发生。

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  • 来源
    《International journal of remote sensing》 |2010年第2期|531-542|共12页
  • 作者

    I. K. LARIN; A. N. YERMAKOV;

  • 作者单位

    Institute of Energy Problems of Chemical Physics, Leninskii pr. 38/2, Moscow, 119334 Russia;

    rnInstitute of Energy Problems of Chemical Physics, Leninskii pr. 38/2, Moscow, 119334 Russia;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);
  • 原文格式 PDF
  • 正文语种 eng
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