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依据液相色谱中溶质计量置换保留模型,从理论上分别推导出了在反相高效液相色谱(RPLC)中同系物端基和重复结构单元对Z(1mol)溶剂化溶质被固定相吸附时,在其接触表面释放出溶剂的摩尔总数)与绝对温度倒数间的线性关系式。也从分子结构参数推导出了同系物端基对总焓变的贡献△Hi和同系物非端基(或链长)对总焓变的贡献△HsNc的表达式。从而建立了等焓点的坐标方程,阐明了等焓点的纵坐标相等是溶质在等焓点处的焓变为零,等焓点的横坐标是当流动相中有机溶剂的浓度为10%时同系物端基的保留焓变。它们的物理意义为在此点溶质的焓变相等。其各溶质自由能变的差别完全取决于熵变,并以实验数据对该坐标方程进行了验证,两者符合较好。还用分值△Hi和△HsNe对总焓变面△H进行了估算,其估算值与实验值符合程度尚可,其相对偏差小于±8%。
According to the retention model of solute mass displacement in liquid chromatography, we theoretically deduced that when solvated solute of Z (1mol) was adsorbed on the stationary phase in the reversed phase high performance liquid chromatography (RPLC) , The total number of moles of solvent released at its contact surface) and the reciprocal of absolute temperature. From the molecular structure parameters, the contribution △ HsNc of the contribution of end groups to the total enthalpy and the contribution of non-terminal homologues (or chain lengths) to the total enthalpy change were deduced. Thus, the equation of isochoric enthalpy is established. It is clarified that if the vertical coordinate of isenthalpic point is equal, the enthalpy of solute at isenthalpic point becomes zero, and the abscissa of isenthalpic point is when the concentration of organic solvent in mobile phase is 10% The retention enthalpy change of the homologue end groups. Their physical meaning is that the enthalpy of the solute is equal at this point. The difference of solute free energy changes depends entirely on entropy change, and verified by the experimental data of the coordinate equation, both in good agreement. The total enthalpy change ΔH was also estimated with the scores ΔHi and ΔHsNe. The estimated values agree well with the experimental values, and the relative deviation is less than ± 8%.