单核Zn(Ⅱ)水合和水解形态的量子化学计算  

STUDIES OF MONONUCLEAR ZINC SPECIES OF HYDRATION AND HYDROLYSIS BY QUANTUM CHEMICAL CALCULATIONS

作　　者：朱孟强[1] 潘纲[1] 

机构地区：[1]中国科学院生态环境研究中心,环境水质学国家重点实验室,北京100085

出　　处：《环境化学》2005年第5期497-501,共5页Environmental Chemistry

基　　金：国家自然科学基金项目(20073060);中国科学院优秀"百人计划"资助

摘　　要：利用量子化学计算气相中锌离子各种水合和水解形态的几何结构、电荷分布以及水合和水解反应的Gibbs自由能变和焓变.结果表明,除了水合锌离子外,锌离子各种水解络合物的配位数均小于6;对于深度水解产物Zn(OH)3-和Zn(OH)42-,内层无水分子的键合.水合作用和水解作用互相抑制,水合作用阻碍了水解产物进一步水解(Zn(OH)2除外),水解作用使得水合变得困难.内层键合水分子数的增加降低了水合形态中Zn上的电荷,使得水解形态Zn上的电荷升高.Optimal geometries, charge distributions, changes of Gibbs free energy, entropies and enthalpies of hydration and hydrolysis reactions for mononuclear species of Zn^2＋ including hydrated and hydrolysis complexes were investigated in the gas phase using quantum chemical calculations. The coordination number of hydrolysis complexes of zinc was less than 6 except hydrated ion. For the high degree of hydrolysis products, Zn（OH）3^- and Zn （OH）4^2-, there were no water molecules in the inner-sphere. Hydration and hydrolysis processes restrained each other. Hydration made hydrolysis products （except Zn（OH） 2 ） difficult to hydrolyze further, while hydrolysis process cumbered hydration reaction. The increase of the inner-sphere water molecules decreased the charge of Zinc for hydrated ions while increased the charge of zinc for hydrolysis complexes. The results are important to understand aquatic environmental behaviors of zinc.

关 键 词：水合 水解 锌离子 量子化学计算 量子化学计算 Zn(Ⅱ) 水合作用 水解形态 单核 电荷分布 水解产物 水解作用 锌离子 

分 类 号：O614.241[理学—无机化学]