超和正的相互转换的动力学,由偏磁复合离子催化
Mitsuru Matsumoto1, James H Espenson
1Department of Chemistry, Iowa State University of Science and Technology, Ames, Iowa 50011, USA.
Journal of the American Chemical Society
|August 11, 2005
概括
准和正 (p-/o-H2) 的核自旋同质化是由磁性金属复合体催化. 速率常数与磁矩相关,支持维格纳的观点.
科学领域:
- 物理化学 物理化学
- 化学动力学 化学动力学
- 核磁共振光谱学 核磁共振光谱学
背景情况:
- 准/正 (p-/o-H2) 核自旋异构化是一个基本的化学过程.
- 超磁性复合离子是这种同质化反应的已知催化剂.
- 了解催化剂特性对于控制反应速率至关重要.
研究的目的:
- 测量p-/o-H2核自旋异构化的速率常数.
- 为了研究催化剂特性 (磁矩,大小) 和反应速率之间的关系.
- 评估维格纳理论对这种催化过程的适用性.
主要方法:
- 质子核磁共振 (1H NMR) 光谱法用于速率常数测量.
- 实验是在恒温 (298.2 K) 的化溶剂中进行的.
- 分析了动力数据,以确定二次速率常数和有效碰撞半径.
主要成果:
- 速率常数与催化剂度成正比.
- 二阶速率常数显示3D过渡金属和化物复合体的磁矩的平方与正比.
- 连接体大小对3D过渡金属复合物的速率常数产生影响,尽管比理论预测的要小.
结论:
- 速率常数和磁矩之间的相关性与维格纳理论一致.
- 催化剂大小对反应速率的影响不如预期那么大.
- 实际碰撞半径在各系列的化金属复合体内相对不变.
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