高等学校化学学报

高等学校化学学报 ›› 2009, Vol. 30 ›› Issue (4): 777.

• 研究论文 • 上一篇    下一篇

气固色谱中分子热运动能的作用

张大力1, 柯家骏2, 卢立柱2   

    1. 北京联合大学生物化学工程学院, 北京 100023;
    2. 中国科学院过程工程研究所, 北京 100080
  • 收稿日期:2008-06-02 出版日期:2009-04-10 发布日期:2009-04-10
  • 通讯作者: 张大力, E-mail:Dali@buu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号: 20276074)资助.

Action of Molecular Kinetic Energy on a Gas-solid Chromatography

ZHANG Da-Li1*, KE Jia-Jun2, LU Li-Zhu2   

    1. Biochemical Engineering College of Beijing Union University, Beijing 100023, China;
    2. Institute of Process Engineering, Chinese Academy of Science, Beijing 100080, China
  • Received:2008-06-02 Online:2009-04-10 Published:2009-04-10
  • Contact: ZHANG Da-Li, E-mail:Dali@buu.edu.cn

PDF (PC)

摘要：

用麦克斯韦(Maxwell)能量分布和能量均分原理推导溶质迁移速度方程, 研究了N2- GDX-101气固色谱体系中5种烷烃的迁移速度、迁移活化能和迁移中溶质分子热运动的作用. 得到的迁移活化能可以很好地解释溶质的迁移速度. 研究结果表明, 溶质分子的转动\, 振动能量显著地影响迁移活化能. 用统计热力学的估算验证的计算结果表明, 迁移活化能明显小于脱附焓. 溶质迁移时可能远未达到解吸脱附的状态. 流动相驱动的溶质迁移可能主要为吸附状态下的滑移.

关键词: 分子热运动, 迁移活化能, 麦克斯韦能量分布, 能量均分原理, 气固色谱, 滑移机理

Abstract:

The migration velocity, the migratory activation energy and the action of molecular motion on migration were researched for five alkanes in the gas-solid chromatography of N2/GDX-101 system. Maxwell distribution of energy which originally shows the molecule fraction of molecular translation energy exceeding E, was used for expressing the time fraction of the translation energy exceeding E. The kinetic energy of rotation and vibration was expressed by the times of kT/2 in the light of the principle of equiparation of energy, to modify the ideal equation. The migratory activation energy(E) which is calculated with the rate equation, could well explain the migration velocity. The kinetic energy of rotation and vibration observably influences E. These properties were also authenticated with the estimate of statistical thermodynamics. The calculation showed that E was obviously smaller than the desorption enthalpy(ΔHDesorption). The solute migration might not reach the state of desorption. The solute driven by mobile phase should mainly slip under the state of adsorption.

Key words: Molecular ehermoclynamic movement, Migratory activation energy, Maxwell distribution of energy, Principle of equiparation of energy, Gas-solid chromatography, Slip mechanism

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