【摘要】 本文从简化Ouano扩散方程出发,选用非均匀圆柱形孔模型和合适的D_s（M）、D_m（M）关系,模拟Ouano、Smit和Tung的数据,得到较好的结果,应用Gram-Charlier级数形式的解析解讨论了V_e（Q）关系,解释了Haller和Yau的实验并评价了后者的KGPC公式,从理论上指出如若单分散标样的V_e符合Benoit普适标定,那么由于峰加宽效应引起的σ_B²、α_3B、α_4B和G（v-y）也是可以普适标定的,解释了Tung关于σ_B²不依赖于试样化学组成的发现,讨论了σ_B²、α_3B、α_4B（K_e）对粒子大小、孔径分布、流速和装柱效率的依赖性,应用物料平衡方程的理论解释了Limpert关于细粒子凝胶柱效在某一流速下出现极大值的实验,并指出不应理解为对于高分子试样在该流速下也会有最好的分离,提出了根据色谱柱总柱效估计（?）_n（t）/（?）_n（∞）或（?）_w（t）/（?）_n（∞）的近似公式。更多还原

【Abstract】 The simplified Ouano’s diffusion equation has been solved with a nonuniform cylindrical pore model for the gel and an appropriate choice of D. (M) = KDM-γ(?), in which γ, depends on the pore structure. Experimental GPC data in the literature have been successfully simulated on a computer with y. and the pore uniformity parameter (?) as two adjustable parameters. The experiments of Haller and of Yau on the flow rate dependence of the elution peak can be explained from our analytical solution of the diffusion equation in Gram-Charliers’ series form. Yau’s formula for KGPC can be shown to be not a theoretically strict one. It is pointed out that if V. of monodisperse standard amples obey Benoit’s universal calibration, σn2, α3B, α4B and peak spreading function G(v-y) should also obey universal calibration. This explains Tung’s experimental discovery that σB2 is dependent on elution volumes only and independent on chemical constitution of the polymer. Computer simulation has been carried out for the variation of peak spreading function for 160 cases of gel and column operation conditions (4 bead sizes × 2 types of pore distribution × 4 flow rates ×5 packing efficiencies). Lamport’s experiment concerning the existence of a maximum column efficiency in fine beads of gel at certain flow rate can be explained by our material balance equation, and it is pointed out that the best resolution for polymer sample would not necessarily occur at this flow rate. Approximate relations for calculating Mn(t)/Mn(∞) and Mw(t)/Mw(∞) from the total column efficiency are also formulated.更多还原