【摘要】 Benesi-Hildebrand（B-H）方程现被广泛地应用于各种非键作用体系,特别是作用比为1:1型和1:2型的体系.该方程可以用来确定作用体系的平衡常数以及作用比.通过计算机模拟,发现在某些情况下,对于1:2型的作用体系,B-H方程会给出错误的作用比信息.无论是弱的作用体系还是强的作用体系,都可能会出现1:1的B- H方程曲线呈现出线性,同时（或者）1:2的B-H方程曲线呈现出非线性的情况.此外,本文还研究了体系中两种作用物质的初态浓度比对于1:1型作用的平衡常数计算的影响,发现最小的初态浓度比（r₀）等于100是可以确保B-H方程近似条件C_B⁰≈C_B成立的安全阈值.当作用很弱的时候,比如说作用的平衡常数K小于25L·mol^-1(C_P⁰= 4×10^-4mol·L^-1)时,则不需要对最小初态浓度比值r₀进行限制,就可以满足B-H方程的近似条件.通过计算机模拟还分析了文献中提出的两个边界条件.研究表明1/（KC_P⁰）≥10可以保证处于平衡状态时的C_B/C_B⁰≥0.91.而另一个条件KC_B⁰>0.1并不是确保B-H方程近似条件成立的充分条件.更多还原

【Abstract】 Benesi-Hildebrand（B-H）method is a widely used approach for determining the stoichiometry and equilibrium constants of nonbonded interactions,particularly 1:1 and 1:2 interactions.Using computer simulation,it was shown that,under certain conditions,the approach could generate inappropriate stoichiometric conclusions for 1:2 interactions.This problem could occur in the cases of both weak and strong interactions,where the 1:1 B-H plots showed a linear feature and the 1:2 B-H plots showed a nonlinear feature.In addition,effect of the initial concentrations on the accurate evaluation of equilibrium constants of 1:1 interactions was investigated.It was found that the minimum safe concentration ratio r₀ between ligand and central species was 100.However,for weak nonbonding interactions,for example K<25L·mol^-1(C_P⁰=4×10^-4mol·L^-1),the ratio r₀ has no limitation.Two conditions proposed in literatures for the safe application of the B-H method were examined.It was found that the inequation,1/（KC_P⁰）≥10,was a condition to secure C_B/C_B⁰>91%.The other inequation,KC_B⁰>0.1,was not found to be the safe condition to validate the B-H method.更多还原