Salt concentration and particle density dependence of electrophoretic mobilities of spherical colloids in aqueous suspension.
ABSTRACT Using laser Doppler velocimetry in the superheterodyne mode, we conducted a systematic study of the electrophoretic mobility of dispersions of small silica spheres (a=18 nm) suspended in water at different salinities and particle concentrations. The concentration of NaCl was varied from 40 microM up to 16 mM, while the particle concentrations were varied between 4.2x10(18) and 2.1x10(20) m-3. We find a decrease of mobility with increasing salt concentrations and an increase with increased particle number densities. The latter observation is not backed by the standard cell model of electrophoresis with Shilov-Zharkikh boundary conditions. Rather, if the experimental data are interpreted within that model, an unexpected change of the zeta potential at constant added salt concentration results. Interestingly, all experimental data collapse onto a single master curve, if plotted versus the ratio C* of particle counterions to added salt ions. We obtain a logarithmic increase of mobility for C*<1 and a plateau for C*>1. This may indicate a change of the Stern layer structure not yet included in the theoretical model.
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ABSTRACT: In this work we report on the simultaneous measurement of the hydrodynamic coefficient and the electric charge of single Bacillus subtilis spores. The latter has great importance in protein binding to spores and in the adhesion of spores onto surfaces. The charge and the hydrodynamic coefficient were measured by an accurate procedure based on the analysis of the motion of single spores confined by an optical trap. The technique has been validated using charged spherical polystyrene beads. The excellent agreement of our results with the expected values demonstrates the quality of our procedure. We measured the charge of spores of B. subtilis purified from a wild type strain and from two isogenic mutants characterized by an altered spore surface. Our technique is able to discriminate the three spore types used, by their charge and by their hydrodynamic coefficient which is related to the hydrophobic properties of the spore surface.Colloids and surfaces B: Biointerfaces 02/2014; 116C:568-575. · 4.28 Impact Factor
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ABSTRACT: In this work we describe the fundamentals of the phenomenon of dielectric dispersion in aqueous colloidal suspensions, as well as the most recent advances on the subject. We begin by establishing the admitted definitions of the permittivity of a heterogeneous system consisting of a certain volume of a material dispersed in the form of identical spheres (the particles) in a liquid medium (an electrolyte solution). Attention is also paid to the relationship between the electric permittivity of the suspension and the strength and frequency dependence of the dipole moment induced by the external field.A thorough historical revision is provided, describing the key contributions, both experimental and theoretical, to the development of this field of electrokinetics and interface physics. In fact, elucidation of the mechanisms responsible for the values of the permittivity of disperse systems over a wide enough frequency range is a rich exercise in electromagnetism, fluid mechanics and electrochemistry of interfaces.Three mechanisms are typically responsible for the dielectric dispersion of the suspension. The gamma dispersion is a manifestation of the frequency dependence of the permittivity of the aqueous electrolyte solution where the particles are suspended. It is mainly determined by the polar nature of the water molecules and its characteristic frequency is in the GHz range. The delta dispersion (typically in the MHz range) is determined by the Maxwell–Wagner–O'Konski relaxation mechanism: it occurs because of the different permittivities and conductivities of the particle and the surrounding medium. Finally, the alpha- or Low Frequency Dielectric Dispersion (LFDD) is a phenomenon characterized by a huge increase of the permittivity at very low frequencies (kHz range). Its relationship with the phenomenon of concentration polarization is carefully discussed, as it is an essential feature of the electric permittivity of suspensions.The mathematical treatment of the problem is rather complex, and analytical solutions are only available in a limited number of cases. Attention is hence also devoted to describing and comparing the numerical approaches that can be used. Experimental determination of the (particularly low frequency) dielectric dispersion is complicated mainly because of the phenomenon of the polarization of the electrode–solution interface. In this contribution we describe the solutions reported to this problem, both in the frequency and in the time domains.An interesting aspect of dielectric dispersion determinations, not shared by other techniques, is their applicability to concentrated suspensions. The modifications of the theory of the permittivity of suspensions, required to account for the hydrodynamic and electrical interactions are also described, stressing the fact that suspensions often considered as dilute are actually far from being so.The review is finished with a description of the most recent advances, namely the consideration of suspensions of soft particles and extensions of the standard electrokinetic model in order to reach a better agreement between theory and experiments. The conclusion of the work refers to the expected developments, particularly in the field of experimental determinations (mainly in the high frequency side of the dispersion), and of descriptions of the solid/liquid interface with corresponding extensions of the standard electrokinetic model.Current Opinion in Colloid & Interface Science - CURR OPIN COLLOID INTERFACE S. 01/2010; 15(3):145-159.
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ABSTRACT: An integral equations theory is derived and applied to a modified colloidal primitive model (MCPM), for finite concentration colloidal dispersions. In MCPM the charge on the colloidal particle is assumed to be smeared on its surface. We find important quantitative and qualitative differences of the ζ-potential, induced charge, and the colloid-colloid electric effective force, calculated in the MCPM, with those obtained from the colloidal primitive model (CPM), where the colloidal charge is assumed to be in the center of the particle, in spite of the fact that, due to Gauss's law, both models have the same particle distribution function. In particular, for the same parameters, while the ζ-potential is positive in MCPM, is negative in the CPM, implying opposite electrophoretic mobilities, μ. An inverse μ has been theoretically predicted in the past, for infinite dilution colloidal dispersions. The MCPM could be a better model for some colloidal particles.In both models, the CPM and the MCPM, it is found a very longrange colloid-colloid correlation, in accordance with previous Monte Carlo simulations. The electrostatic, as well as entropic, like-charged colloid-colloid forces are oscillatory, implying a long-range attraction.The Journal of Physical Chemistry B 08/2013; · 3.61 Impact Factor