反相液相色谱中计量置换线性参数logI的热力学特征

依据液相色谱中溶质计量置换保留模型及线性参数 log I(与 1mol溶质对固定相的亲和势大小有关的常数 ) ,通过作图得知非极性和极性小分子溶质及生物大分子的 log I与绝对温度的倒数 1/T,以及小分子溶质的log I与其在正辛醇 -水中分配系数的对数 log Po/ w呈线性关系 ,从两方面进一步证明了 log I具有热力学平衡常数的性质。基于小分子溶质、生物大分子的 log I和分配系数大小的差别 ,对两者在反相液相色谱中的保留对柱长的依赖关系给予了定量的说明

Thermodynamic Characteristics of Stoichiometric Displacement Linear Parameter log I in Reversed Phase Liquid Chromatography

Based on the physical meaning of each term in the linear parameter log I (a constant correlating the affinity of solute to stationary phase) of stoichiometric displacement model for retention(SDM R) of solute, the thermodynamic characteristics of log I of solute in reversed phase liquid chromatography (RPLC) were investigated theoretically. This point was tested by experimental data with two linear relationships: (1) plot of log I vs 1/T (T is absolute temperature) with apolar, polar small solutes and proteins; (2) plot of log I s log P o/w (partition coefficient of solute between n octanol and water) with apolar and polar small solutes. From the comparison of the magnitude of partition coefficient between small solute and proteins, a phenomenon that the resolution of small solutes depends on column length but that of proteins almost to be independent of column length is quantitatively explained.