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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(r_0)等于100是可以确保B-H方程近似条件C_B~0≈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_P~0= 4×10~(-4)mol·L~(-1))时,则不需要对最小初态浓度比值r_0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_P~0)≥10可以保证处于平衡状态时的C_B/C_B~0≥0.91.而另一个条件KC_B~0>0.1并不是确保B-H方程近似条件成立的充分条件.
The Benesi-Hildebrand (BH) equation is now widely used in a variety of non-bond systems, especially systems with 1: 1 and 1: 2 ratios. This equation can be used to determine the equilibrium constants of the system of action, It is found by computer simulations that in some cases, the BH equation will give erroneous action ratio information for the 1: 2-type system of action, and either the weak or the strong system of action may exhibit 1 : 1 B-H equation curve showed a linear, at the same time (or) 1: 2 BH equation curve showed a nonlinear case.In addition, this article also studied the system of two active substances initial concentration ratio of 1: 1 type effect equilibrium constant calculation and found that the minimum initial concentration ratio (r_0) is equal to 100 is to ensure that BH approximation conditions C_B ~ 0 ≈ C_B establishment of the safety threshold. When the role is weak, such as the role of When the equilibrium constant K is less than 25 L · mol -1 (C_P 0 = 4 × 10 -4 mol·L -1), it is not necessary to limit the minimum initial concentration ratio r_0. On the other hand, Which can satisfy the approximate condition of BH equation.The two boundary conditions proposed in the literature are also analyzed by computer simulation. 1 / (KC_P ~ 0) ≥10 can guarantee C_B / C_B ~ 0≥0.91 in equilibrium, while the other condition KC_B ~ 0> 0.1 is not sufficient condition to ensure the approximation of B-H equation.