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The Periodic Table and Kinetics?

机译:元素周期表和动力学?

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摘要

Mendeleev in his first publication ordered the chemical elements following an apparent periodicity of properties such as atomic volume and valence. The reactivity of the elements was only studied systematically many years later. To illustrate the systematic variation of kinetics across the periodic table we compare water residence times for monoatomic ions in aqueous solution. A tremendous variation of τ_(H_2O) by over 20 orders of magnitude is found, ranging from ~10 ps to about 200 years. Apart from some small +2 and +3 cations, all main group elements have very short residence times <10 ns. Transition metal cations of the d-block have water residence times that depend on the electronic configuration. τ_(H_2O) of lanthanide ions are surprisingly short with values of 10 ns and shorter. This is due to an equilibrium between 8 and 9 coordinated ions leading to a low energy of the transition state for the water exchange reaction.
机译:门捷列夫在他的第一本出版物中以明显的周期性周期性(例如原子体积和化合价)对化学元素进行了排序。多年以后才系统地研究了元素的反应性。为了说明整个周期表动力学的系统变化,我们比较了水溶液中单原子离子的水停留时间。发现τ_(H_2O)的巨大变化超过20个数量级,范围从〜10 ps到大约200年。除了一些小的+2和+3阳离子外,所有主族元素的停留时间都非常短,小于10 ns。 d-嵌段的过渡金属阳离子的水停留时间取决于电子结构。镧系离子的τ_(H_2O)令人惊讶地短,值为10 ns或更短。这是由于8到9个配位离子之间的平衡导致水交换反应的过渡态能量低。

著录项

  • 来源
    《Chimia》 |2019年第3期|179-184|共6页
  • 作者

    Lothar Helm; Andre E. Merbach;

  • 作者单位

    Institute of Chemical Sciences and Engineering ISIC, EPFL, Station 6, CH-1015 Lausanne;

    Institute of Chemical Sciences and Engineering ISIC, EPFL, Station 6, CH-1015 Lausanne;

  • 收录信息 美国《科学引文索引》(SCI);
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

    Ions in solution; Periodic Table; Water exchange;

    机译:溶液中的离子;元素周期表水交换;

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