用线性自由能关系预测金属络合物的热力学性质

摘要

The Sverjensky-Molling linear free energy relationship was originally developed to correlate the Gibbs free energies of formation of an isostrutural family of solid phases to the thermodynamic properties of aqueous cations. In this report, we demonstrate that the similar relationship also exists between metal complexes and simple metal cations in aqueous solutions. We extend the Sverjensky-Molling relationship to predict the Gibbs free energies of formation or dissociation constants for a family of metal complexes with a given complexing ligand.The discrepancies between the predicted and experimental data are generally less than 1.5 kcal/mol (or one log unit for stability constants). The use of this linear free energy correlation can significantly enhance our ability to predict the speciation, mobility, and toxicity of heavy metals in natural environments.%Sverjensky与Molling提出的线性自由能关系是根据金属阳离子的热力学性质来预测等结构系列中固体相的标准生成自由能.本文研究结果证实,水溶液中金属络合物与简单金属阳离子之间也存在类似的相关关系,预测值与实验值的差异通常小于1.5 kcal/mol或小于一个log单位,这一线性自由能关系对于预测自然环境中重金属的水溶物种的配分、迁移和毒性具有非常重要的应用价值.