物理化学学报2007，Vol.23Issue(9)：1353-1359,7.
Benesi-Hildebrand方程的正确性与可靠性
Validity and Reliability of Benesi-Hildebrand Method
摘要
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＜ 25 L·mol-1 (C0P=4×10-4 mol· 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/(KC0P) ≥ 10, was a condition to secure CB/C0B＞91%. The other inequation, KC0B＞0.1, was not found to be the safe condition to validate the B-H method.关键词
Benesi-Hildebrand方程/分子间相互作用/平衡常数/作用比Key words
Benesi-Hildebrand method/ Molecular interaction/ Equilibrium constant/ Stoichiometry evaluation分类
化学化工引用本文复制引用
王睿,尉志武..Benesi-Hildebrand方程的正确性与可靠性[J].物理化学学报,2007,23(9):1353-1359,7.基金项目
国家自然科学基金(20633080,20675046)资助项目 （20633080,20675046）
