腐殖质吸附Zn~（2+）的电化学效应研究
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摘要
腐殖质是土壤与环境中广泛存在的一类重要的天然有机物质,它在提升土壤肥力、防治水土流失、固定与分解有毒物质、控制农田面源污染发生等方面都有重要应用。
近年来,国内外对于腐殖质与金属离子的相互作用已有大量的研究,然而这些研究大都直接应用经典热力学和动力学的有关理论,使得腐殖质胶体与这些离子相互作用的机理至今仍存在争议,平衡常数的理论计算至今无法实现。其根本原因是人们忽略了腐殖质胶体颗粒的表面电场对离子吸附速率与平衡吸附量的影响。
在胶体化学领域,胶体分散系的稳定与聚沉是重要的研究内容,它常用DLVO理论来描述。在研究胶体颗粒的生长动力学过程及凝聚体的分形结构时,逐渐形成了两种具有代表性的不可逆凝聚生长模型：一种是扩散控制簇团凝聚,另一种是反应控制簇团凝聚。光散射技术为实验室测定胶体凝聚过程的动态变化和凝聚体结构特征提供了有利的手段。
本课题将基于目前的研究成果,采用可变电荷“腐殖质胶体”样品作为研究对象,一方面,在不同浓度背景电解质溶液中,进行Zn2+／Ca2+交换的实验研究,测定不同电场体系中Zn2+的吸附速率和平衡吸附量,以及对比不发生专性吸附的Mg2+与Ca2+交换的交换吸附实验,从而揭示表面电场对Zn2+的吸附速率和平衡吸附量的影响。另一方面,由于Zn2+在腐殖质表面产生专性吸附和静电吸附后,腐殖质的表面电场将大大减弱,在这种情况下腐殖质颗粒之间将在分子力作用下发生快速的分形聚合过程并形成分形聚合体,本课题采用动态静态光散射相结合的方式,来研究Zn2+吸附对腐殖质凝聚动力学和凝聚体结构的影响。本课题初步研究表明：
(1)根据描述土壤离子扩散或吸附的严格的速率方程,腐殖酸对于Zn2+的吸附表现了一级动力学的特征。
(2)本文通过研究在腐殖质颗粒表面发生专性吸附的Zn2+和非专性吸附的Mg2+,证明表面电场对颗粒表面离子的吸附速率及平衡吸附量有显著的影响。
(3)通过Zn(NO3)2对腐殖质胶体凝聚动力学的研究,我们发现：①根据凝聚过程中光强的稳定与否,可以判断土壤胶体凝聚过程中碰撞的发生是由布朗运动支配还是由重力作用支配。②对不同浓度Zn(NO3)2溶液中胶体颗粒凝聚动力学过程的研究,发现：该体系下,凝聚体生长模型属于扩散控制簇团凝聚(DLCA)。③对不同浓度Zn(NO3)2溶液中胶体颗粒凝聚体结构特征的研究,发现：凝聚体具有较低的分形维数,从而对应有高的孔隙度和大的开放度。
Humus is an important kind of natural organic matter which is widespread in soil and environment. Humus plays an important role in improving soil fertility, controling erosion, fixing and decomposing toxic substance, and controling agricultural area source pollution,ect.
In recent years, a large number of studies on the interaction between metal ions and humus have been done. However, most of these studies always apply the relevant theory of classical thermodynamics and dynamics directly, making the mutual mechanism between humus and ions indistinct and the equilibrium constants uncalculated so far. The fundamental reason is that people have ignored the influence induced by the electric field of humus colloidal on adsorption rate and adsorption equilibrium.
In the field of colloidal chemistry, the stability and flocculation of colloidal dispersion system is an important research content, always using the DLVO theory to describe them. During the study of colloidal particles aggregation and the fractal structure, the two irreversible aggregation models were gradually formed:the one was diffusion limited cluster aggregation; the other was the reaction limited cluster aggregation. Light scattering techniques provide a favorable means for determining aggregation's dynamic change and structural features in laboratory.
This project bases on the current research results, taking variable charge "humus colloid" as the research material. On the one hand, researching on the Zn2+/Ca2+ ions exchanged in different concentrations of background electrolyte and comparing the result of Mg2+/Ca2+ ions exchange experiment; we concluded that the surface electric field had an influence on the coefficient rates of adsorption and equilibrium adsorption capacities. On the other hand, as the ligand adsorption and electrostatic adsorption of Zn2+ on the humus surface, the surface field of humus would be greatly weakened. In this case, humus particles will aggregate rapidly and form the fractal polymer by the molecular force. The project studied the influence of Zn2+ adsorption on the kinetics aggregation and the structure of aggregation using the dynamic light scattering and static light scattering. The preliminary results indicated that:
(1) According to the rigorous rate equation which is used to describe the ion diffusion /adsorption, the adsorption of Zn2+ to humus showed a first-order kinetics character.
(2) By compared the the specific adsorption of Zn2+ and the non-specific adsorption of Mg2+, we found the electric field force had a significant effect on adsorption rate and the equilibrium adsorption capacity.
(3) Studying on the aggregation kinetics of humus colloidal induced by Zn2+, we found that:①stability of the light intensity in an aggregation process is a basis for judging whether the collision is dominated by Brown force or gravity;②in different concentration of Zn(NO3)2 systems, humus colloidal aggregation exhibited a diffusion-limited cluster aggregation (DLCA) character;③in different concentrations of electrolyte, the structure of humus aggregates had the smaller fractal dimension, then had bigger porosity and open approach space.
近年来,国内外对于腐殖质与金属离子的相互作用已有大量的研究,然而这些研究大都直接应用经典热力学和动力学的有关理论,使得腐殖质胶体与这些离子相互作用的机理至今仍存在争议,平衡常数的理论计算至今无法实现。其根本原因是人们忽略了腐殖质胶体颗粒的表面电场对离子吸附速率与平衡吸附量的影响。
在胶体化学领域,胶体分散系的稳定与聚沉是重要的研究内容,它常用DLVO理论来描述。在研究胶体颗粒的生长动力学过程及凝聚体的分形结构时,逐渐形成了两种具有代表性的不可逆凝聚生长模型：一种是扩散控制簇团凝聚,另一种是反应控制簇团凝聚。光散射技术为实验室测定胶体凝聚过程的动态变化和凝聚体结构特征提供了有利的手段。
本课题将基于目前的研究成果,采用可变电荷“腐殖质胶体”样品作为研究对象,一方面,在不同浓度背景电解质溶液中,进行Zn2+／Ca2+交换的实验研究,测定不同电场体系中Zn2+的吸附速率和平衡吸附量,以及对比不发生专性吸附的Mg2+与Ca2+交换的交换吸附实验,从而揭示表面电场对Zn2+的吸附速率和平衡吸附量的影响。另一方面,由于Zn2+在腐殖质表面产生专性吸附和静电吸附后,腐殖质的表面电场将大大减弱,在这种情况下腐殖质颗粒之间将在分子力作用下发生快速的分形聚合过程并形成分形聚合体,本课题采用动态静态光散射相结合的方式,来研究Zn2+吸附对腐殖质凝聚动力学和凝聚体结构的影响。本课题初步研究表明：
(1)根据描述土壤离子扩散或吸附的严格的速率方程,腐殖酸对于Zn2+的吸附表现了一级动力学的特征。
(2)本文通过研究在腐殖质颗粒表面发生专性吸附的Zn2+和非专性吸附的Mg2+,证明表面电场对颗粒表面离子的吸附速率及平衡吸附量有显著的影响。
(3)通过Zn(NO3)2对腐殖质胶体凝聚动力学的研究,我们发现：①根据凝聚过程中光强的稳定与否,可以判断土壤胶体凝聚过程中碰撞的发生是由布朗运动支配还是由重力作用支配。②对不同浓度Zn(NO3)2溶液中胶体颗粒凝聚动力学过程的研究,发现：该体系下,凝聚体生长模型属于扩散控制簇团凝聚(DLCA)。③对不同浓度Zn(NO3)2溶液中胶体颗粒凝聚体结构特征的研究,发现：凝聚体具有较低的分形维数,从而对应有高的孔隙度和大的开放度。
Humus is an important kind of natural organic matter which is widespread in soil and environment. Humus plays an important role in improving soil fertility, controling erosion, fixing and decomposing toxic substance, and controling agricultural area source pollution,ect.
In recent years, a large number of studies on the interaction between metal ions and humus have been done. However, most of these studies always apply the relevant theory of classical thermodynamics and dynamics directly, making the mutual mechanism between humus and ions indistinct and the equilibrium constants uncalculated so far. The fundamental reason is that people have ignored the influence induced by the electric field of humus colloidal on adsorption rate and adsorption equilibrium.
In the field of colloidal chemistry, the stability and flocculation of colloidal dispersion system is an important research content, always using the DLVO theory to describe them. During the study of colloidal particles aggregation and the fractal structure, the two irreversible aggregation models were gradually formed:the one was diffusion limited cluster aggregation; the other was the reaction limited cluster aggregation. Light scattering techniques provide a favorable means for determining aggregation's dynamic change and structural features in laboratory.
This project bases on the current research results, taking variable charge "humus colloid" as the research material. On the one hand, researching on the Zn2+/Ca2+ ions exchanged in different concentrations of background electrolyte and comparing the result of Mg2+/Ca2+ ions exchange experiment; we concluded that the surface electric field had an influence on the coefficient rates of adsorption and equilibrium adsorption capacities. On the other hand, as the ligand adsorption and electrostatic adsorption of Zn2+ on the humus surface, the surface field of humus would be greatly weakened. In this case, humus particles will aggregate rapidly and form the fractal polymer by the molecular force. The project studied the influence of Zn2+ adsorption on the kinetics aggregation and the structure of aggregation using the dynamic light scattering and static light scattering. The preliminary results indicated that:
(1) According to the rigorous rate equation which is used to describe the ion diffusion /adsorption, the adsorption of Zn2+ to humus showed a first-order kinetics character.
(2) By compared the the specific adsorption of Zn2+ and the non-specific adsorption of Mg2+, we found the electric field force had a significant effect on adsorption rate and the equilibrium adsorption capacity.
(3) Studying on the aggregation kinetics of humus colloidal induced by Zn2+, we found that:①stability of the light intensity in an aggregation process is a basis for judging whether the collision is dominated by Brown force or gravity;②in different concentration of Zn(NO3)2 systems, humus colloidal aggregation exhibited a diffusion-limited cluster aggregation (DLCA) character;③in different concentrations of electrolyte, the structure of humus aggregates had the smaller fractal dimension, then had bigger porosity and open approach space.
引文
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