Wu J Z, Bratko D, Blanch H W, Prausnitz J M
Department of Chemical Engineering, University of California, Berkeley, California 94720, USA.
Phys Rev E Stat Phys Plasmas Fluids Relat Interdiscip Topics. 2000 Oct;62(4 Pt B):5273-80. doi: 10.1103/physreve.62.5273.
Monte Carlo simulations and the hypernetted chain theory are used to study the interaction between spherical macroions of opposite charge immersed in a solution of monovalent or divalent simple electrolyte. These calculations represent the first step toward studying phase behavior and precipitation kinetics in solutions containing a mixture of macroions with positive and negative net charges. The potential of mean force between colloidal particles is determined as a function of colloid-colloid separation. In addition to having an opposite sign, the calculated potential of mean force is found to be stronger and longer-ranged than observed in the case of equally charged macroparticles. The difference is more pronounced in the presence of divalent counterions and is especially noticeable when we compare distinct Coulombic and hard-core collision contributions to the interaction between equally and oppositely charged colloids. The present observations suggest the dominance of attractive forces between globally neutral but electrostatically heterogeneous macroparticles. While our numerical results cannot be successfully analyzed by existing theories, they provide useful guidance and benchmark data for the development of advanced analytic descriptions.
蒙特卡罗模拟和超网链理论被用于研究浸没在单价或二价简单电解质溶液中的带相反电荷的球形大离子之间的相互作用。这些计算代表了研究含有净电荷为正和负的大离子混合物的溶液中的相行为和沉淀动力学的第一步。胶体颗粒之间的平均作用力势作为胶体 - 胶体间距的函数被确定。除了具有相反的符号外,计算出的平均作用力势比在等电荷大颗粒情况下观察到的更强且范围更长。在存在二价抗衡离子的情况下,这种差异更为明显,当我们比较等电荷和异电荷胶体之间相互作用中不同的库仑和硬核碰撞贡献时,这种差异尤其显著。目前的观察结果表明,在整体呈中性但静电性质不均匀的大颗粒之间,吸引力占主导地位。虽然我们的数值结果无法用现有理论成功分析,但它们为先进分析描述的发展提供了有用的指导和基准数据。