Role of counterion association in colloidal stability.
ABSTRACT A generalized model for colloidal stability has been validated against experimentally measured values of Fuchs stability ratio and critical coagulation concentration (ccc) for electrolytes with mono- or divalent cation, i.e., potassium chloride and magnesium chloride, respectively. Besides the classical DLVO theory, the generalized model accounts for the interplay between colloidal interactions and the association of cations with the particles surface charge groups. The model parameters are either obtained or estimated purely on the basis of independent information available in the literature. For the monovalent salt, the predictions agree well with literature experimental data, forecasting both the ccc values and stability ratios quantitatively. For the divalent salt the predictions for large values of the stability ratio tend to deviate from the experimental data produced in this work, but it is noted that the onset of stability, i.e., the ccc, and small stability ratios are correctly predicted. Moreover, a comparison of the above results with those neglecting the effect of counterion association with the particles surface charge groups indicates that the latter substantially overestimates stability ratios in the presence of high salt concentration in the case of the monovalent salt, and leads to unrealistic large values of the ccc for the divalent salt. Including the association of cations with the particles surface charge groups can explain the relatively low values of experimental ccc for divalent salts compared to the theoretical predictions by the classical DLVO theory neglecting ion association, which is apoint of interest in industrial coagulation processes.
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ABSTRACT: Colloidal stability and charging behavior of amidine latex particles in the presence of multivalent oligomers of acrylic acid was investigated by electrophoresis and light scattering. The data were interpreted quantitatively with the theory of Derjaguin, Landau, Verwey and Overbeek (DLVO) whereby the surface potentials were estimated from electrophoresis. Monomer leads to slow aggregation at low concentrations and to rapid aggregation at high concentrations, as characteristic for simple salts. The oligomers induce a charge reversal of the particles. Close to the isoelectric point (IEP) aggregation is rapid while the suspension becomes stable away from this point. At high oligomer concentrations, the aggregation becomes rapid again. The agreement between DLVO theory and experiment is good close to the IEP. At higher oligomer concentrations, the theory predicts larger stabilities than observed experimentally. While inter-particle forces seem to be well described by DLVO theory near the IEP, additional attractive non-DLVO forces are becoming relevant at higher concentrations.Zeitschrift für Physikalische Chemie 08/2012; 226(7):597-612. · 1.18 Impact Factor
- Colloids and Surfaces A Physicochemical and Engineering Aspects 09/2013; 436:325-332. · 2.35 Impact Factor
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ABSTRACT: Force profiles as well as aggregation and deposition rates are studied for asymmetrically charged particles and surfaces in aqueous electrolytes theoretically. Interactions are calculated within the Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory, whereby the electrostatic part is modeled at Poisson-Boltzmann (PB) level. Unequally charged surfaces are examined, from the symmetric system, where both surfaces are equally charged, to fully asymmetric systems where the surfaces are oppositely charged. Charged-neutral systems, where one surface is charged and the other is neutral, emerge as an essential scenario. In this case, the choice of boundary conditions used for solving the PB equation is crucial, whereby constant charge and constant potential boundary conditions lead to either fully repulsive or fully attractive forces. Consequently, charge regulation has a major influence on particle aggregation and deposition rates too. In the charge-neutral case, substantial shifts in the critical coagulation concentration (CCC) are observed when the regulation properties are changed. In the presence of multivalent ions, these systems behave similarly to the symmetrically charged ones. The CCC decreases with the square of the valence in weakly charged systems, while unrealistically high charge densities are needed to recover the classical Schulze-Hardy limit, which predicts a sixth power dependence on valence.The Journal of Physical Chemistry B 05/2014; · 3.38 Impact Factor