化学学报 ›› 1996, Vol. 54 ›› Issue (9): 900-905. 上一篇    下一篇

研究论文

反相高效液相色谱中溶质保留过程的热力学研究Ⅲ: 熵变及其分量,吸附及解吸附熵变

张瑞燕;白泉;耿信笃   

  1. 西北大学现代分离科学研究所
  • 发布日期:1996-09-15

Studies on thermodynamics in solution retention of reversed-phase high performance liquid chromatographyⅢ: Entropy change and its fractions, adsorption and desorption changes

ZHANG RUIYAN;BAI QUAN;GENG XINDU   

  • Published:1996-09-15

从理论上推导出了用柱相比和不用柱相比时溶质在反相高效液相色谱保留过程中的总熵变△S~(~P~a~)的两个表达式, 后者亦为计量置换保留模型中线性参数与该过程热力学函数间的定量表达式。△S~(~P~a~)也能够被分成两个独立的分量,吸附熵变△S~(~Ⅰ~,~a~)和解吸附熵变△S~(~Z~,~D~)。依据液相色谱中溶质计量置换保留模型中容量因子与流动相中置换剂活度a~D间的定量关系, 对在不同a~D条件下熔质的总熵变、吸附及解吸附熵变进行了估算, 并用实验测定的总熵变△S~(~P~a~,~e~)与估算总熵变△S~(~P~a~,~c~)进行了比较, 获得了结果的一致性。本文对传统的"吸附伴随着熵减小, 相反, 解吸伴随着熵增大"的定性规律予以定量的说明。

关键词: 吸附, 保留, 溶质, 解吸, 热力学研究, 反相高效液相色谱, 熵变

Two expressions of calculating entropy changes △S~(~P~a~) solute either with, or without column phase ratio in reversed-phase liquid chromatography were theoretically derived. The latter is also an equation to express the quantitative relationship between some linear parameters in stoichiometric displacement model for retention (SDM-R) and the thermodynamic functions in the same process. The △S~(~P~a~), liking Gibbs free energy and enthalpy changes, can also be divided into two independent fractions, adsorption entropy change, △S~(~Ⅰ~,~a~) and desorption entropy △S~(~Z~,~D~). Based on the quantitative relationship between the solute retention and the activity of displacing agent in mobile phase described by te SDM-R, the △S~(~P~a~), △S~(~Ⅰ~,~a~) and △S~(~Z~,~D~) under various a~D can be evaluated, respectively. The experimental and the evaluated results of entropy were obtained with a good agreement. The traditionally qualitative rule that adsorption of component is companied with the decrease in entropy, on a contrary, desorption is that with the increase in it can be quantitatively elucidated with the studies.

Key words: ADSORPTION, RETENTION, SOLUTE, DESORPTION, RP-HPLC

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