Electrical double layer interactions between dissimilar oxide surfaces with charge regulation and Stern-Grahame layers

Models of surfaces with intrinsic ionisable amphoteric surface sites governed by the dissociation of acid-base potential determining ion species together with the capacity for the adsorption of anion and cations of the supporting electrolyte are required to describe both the results of electrokinetic and titration measurements of inorganic oxides. The Gouy-Chapman-Stern-Grahame (CGSG) model is one such model that has been widely used in the literature. The electrical double layer interaction between two dissimilar CGSG surfaces has been studied by Usui recently [S. Usui, J. Colloid Interface Sci. 280 (2004) 113] where erroneous discontinuities in the slope of the pressure-separation relation were observed. We revisit this calculation and provide a simple general methodology to analyse the electrical double layer interaction between dissimilar ionisable surfaces with ion adsorption.     

Electrical double-layer interaction between oppositely charged dissimilar oxide surfaces with charge regulation and Stern-Grahame layers

The force of double-layer interaction between dissimilar flat oxide surfaces charged oppositely at infinite separation and with Stern-Grahame layers was calculated as a function of the surface separation under the conditions of charge regulation. The interaction force showed a monotonic attraction with respect to the surface separation, lying between constant surface potential and constant surface charge conditions. The variations of surface potentials and surface charge densities of respective double layers were also presented as functions of the surface separation. When the negative diffuse-layer potential at infinite separation changed its sign to positive as a result of specific adsorption of cations on the negatively changed surface, the double-layer interaction force showed a repulsive force barrier followed by an attraction at some particular separation.     

Interaction of silver halides with gelatin of like charge

Summary Interactions of gelatin with silver bromide and silver iodide sols of like charges have been studied as a function of gelatin concentration, pH, and addition of neutral electrolytes. Silver halide solsin statu nascendi and aged sols were used in the experiments. Solsin statu nascendi showed a scattering intensity maximum indicating coagulation, while aged sols did not. At higher pH values, the maximum appeared, if sufficient amounts of electrolyte and gelatin were present. It is suggested that gelatin reduces the effective surface charge density of the colloidal particles. Such silver halide sols of reduced charge are then coagulated by smaller amounts of electrolytes than the same sols in the absence of gelatin. For very large concentrations of gelatin, close to the gel point, coagulation occurred wheter sols were aged orin statu nascendi.

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Zusammenfassung Es wurde die Wechselwirkung zwischen Gelatine und AgBr- bzw. AgJ-Solen gleichen Ladungszeichens in Abhängigkeit von der Gelatinekonzentration, dem pH-Wert und der Konzentration an neutralen Elektrolyten untersucht. Zu den Untersuchungen wurden Solein statu nascendi und gealterte Sole verwendet. Bei Solenin statu nascendi trat ein Maximum in der Streuintensität auf, das Koagulationsvorgänge anzeigt; bei gealterten Solen wurde ein derartiges Maximum erst bei höherenPh-Werten beobachtet, wenn ausreichende Mengen an Elektrolyt und Gelatine vorhanden waren. Bei sehr hohen Gelatine-Konzentrationen (im Bereich um den Gelpunkt) tritt die Koagulation sowohl in gealterten wiein statu nascendi-Solen ein.Es wird angenommen, daß die Gelatine die wirksame Oberflächenladungsdichte der kolloidalen Partikel ver-ringert. Derartige Silberhalogenidesole mit verringerter Oberflächenladung werden dann durch geringere Mengen von Elektrolyt ausgefällt als dieselbe Sole bei Abwesenheit von Gelatine.

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With 8 figures

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Supported by the Federal Water Pollution Control Administration Grant WP-00815 and by the U. S. Army Research Office (Durham), Grant No. DA-ARO (D)-31-124-G 656.

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Presented at the 153. ACS National Meeting, Miami Beach, Florida, April 1967.

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Part of the M. S. Thesis byR. Nemeth     

Interaction between electrical double layers of soil colloids and Fe/Al oxides in suspensions

Phyllosilicates with net negative surface charge and Fe/Al oxides with net positive surface charge coexist in variable-charge soils, and the interaction between these oppositely charged particles affects the stability of mixed colloids, aggregation, and even the surface chemical properties of variable-charge soils. The interaction of the diffuse layers of electrical double layers between the negatively charged soil colloidal particles and the positively charged particles of goethite or gamma-Al(2)O(3) was investigated in this article through the comparison of zeta potentials between single-soil colloidal systems and binary systems containing soil colloids and Fe/Al oxides. The results showed that the presence of goethite and gamma-Al(2)O(3) increased the zeta potential of the binary system containing soil colloids and Fe/Al oxides, which clearly suggests the overlapping of the diffuse layers in soil colloids and Fe/Al oxides. The overlapping of the diffuse layers leads to a decrease in the effective negative charge density on soil colloid and thus causes a shift of pH-zeta potential curves toward the more positive-value side. The interaction of the electrical double layers is also related to the charge characteristics on the Fe/Al oxides: the higher the positive charge density on Fe/Al oxides, the stronger the interaction of the electrical double layers between the soil colloid particles and the Fe/Al oxides.     

Electrostatic double layer forces in the case of extreme charge regulation

We analyze the interaction forces between charged surfaces across aqueous solutions under the conditions of extreme charge regulation. Under such conditions, interactions may be weaker than those given by the constant potential (CP) boundary conditions. Thermodynamically, even vanishing electrostatic interactions are conceivable. Within the constant regulation approximation, the known results can be extended to this sub-CP regime by adopting regulation parameters outside of the common range. A mean-field lattice model of an adsorbed layer shows that such conditions are most likely found near critical points within the adsorbed layer.     

Effect of the surface charge discretization on electric double layers: a Monte Carlo simulation study

The structure of the electric double layer in contact with discrete and continuously charged planar surfaces is studied within the framework of the primitive model through Monte Carlo simulations. Three different discretization models are considered together with the case of uniform distribution. The effect of discreteness is analyzed in terms of charge density profiles. For point surface groups, a complete equivalence with the situation of uniformly distributed charge is found if profiles are exclusively analyzed as a function of the distance to the charged surface. However, some differences are observed moving parallel to the surface. Significant discrepancies with approaches that do not account for discreteness are reported if charge sites of finite size placed on the surface are considered.     

Electrostatic interactions between double layers: influence of surface roughness, regulation, and chemical heterogeneities

Electrostatic interactions between two surfaces as measured by atomic force microscopy (AFM) are usually analyzed in terms of DLVO theory. The discrepancies often observed between the experimental and theoretical behavior are usually ascribed to the occurrence of chemical regulation processes and/or to the presence of surface chemical or morphological heterogeneities (roughness). In this paper, a two-gradient mean-field lattice analysis is elaborated to quantifying double layer interactions between nonplanar surfaces. It allows for the implementation of the aforementioned sources of deviation from DLVO predictions. Two types of ion-surface interaction ensure the adjustment of charges and potentials upon double layer overlap, i.e., specific ionic adsorption at the surfaces and/or the presence of charge-determining ions for the surfaces considered. Upon double layer overlap, charges and potentials are adjusted via reequilibrium of the different ion adsorption processes. Roughness is modeled by grafting asperities on supporting planar surfaces, with their respective positions, shapes, and chemical properties being assigned at will. Local potential and charge distributions are derived by numerically solving the nonlinear Poisson-Boltzmann equation under the boundary conditions imposed by the surface profiles and regulation mechanism chosen. Finite size of the ions is taken into account. A number of characteristic situations are briefly discussed. It is shown how the surface irregularities are reflected in the Gibbs energy of interaction.     

Generalized model for time periodic electroosmotic flows with overlapping electrical double layers

In this article, an analytical model is devised for analyzing time periodic electroosmotic flows through nanochannels within the continuum regime, without presuming the validity of the Boltzmann distribution of ionic charges. The charge density distributions are obtained from the conservation considerations of the individual ionic species and other thermochemical constraints and are subsequently utilized to derive the potential distribution within the electrical double layer (EDL). This, coupled with the Navier-Stokes equation, yields a closed-form expression of the time-dependent velocity field that is valid under overlapped EDL conditions. This expression is first validated in asymptotic limits of thin EDLs, for which closed form expressions have been benchmarked in the literature. Further analyses are carried out to bring out the influences of the frequency of the electrical field on the electroosmotic flow features in the presence of overlapped EDLs.     

Formation of dielectric layers and charge regulation in protein adsorption at biomimetic interfaces

Protein charge is an important parameter in the understanding of protein interactions and function. Proteins are subject to dynamic charge regulation, that is, the influence of the local environment (such as charged interfaces and biopolymers) on protein charge. Charge regulation is governed by differences in the dielectric and electrostatic environment between adsorbed protein and the free protein in bulk solution. In this work protein charge regulation is addressed experimentally by employing electrochemistry at interfaces between two immiscible electrolyte solutions (ITIES) as well as theoretically by developing a new protein adsorption model at ITIES. Electrochemistry at ITIES is shown to be particularly well suited to study protein charge regulation as the adsorbed protein experiences a different dielectric environment compared to the bulk phase and the external control of the water/oil potential difference allows systematic studies on how potential induced ion gradients affect protein charge. The theoretical model incorporates all the features of the experimental system and specifically takes into account protein charge regulation at ITIES as well as the impact of the formation of dielectric layers on the experimentally observed impedance. The model parameters include the protein charge-pH profile, bulk pH, and the overall potential difference. It is shown that the formation of a dielectric layer and the associated charge regulation are the main factors dictating the observed experimental behavior. Finally, the theoretical model is used to interpret literature results, and the consistency between the model and the relatively large data set suggests that the model may be used more generally for understanding and predicting protein adsorption.     

Interaction between polyelectrolyte gels and surfactants of opposite charge

Investigations dealing with fundamental aspects of the interaction between covalently cross-linked polyelectrolyte gels and oppositely charged surfactants are reviewed. For reference, a brief summary of results from recent studies of associative phase separation in linear polyelectrolyte/surfactant mixtures is also included. It is found that great progress has been made in several sub-areas since the first reports appeared in the early 1990's. The frequently observed surfactant-induced volume transition has been studied in detail. Its relation to associative phase separation in solutions and the important role of polyion-mediated micelle–micelle attractions have been clarified. Phase separation in gels, in particular core/shell structures, has been studied in great detail. The importance of network mediated elastic forces between two phases coexisting in the same gel has been demonstrated and some of their consequences have been clarified. Hydrophobic interactions between polyion and micelle have been found to have strong effects on both binding and swelling isotherms. The effect of salt, which has been found to sometimes disfavor, sometimes promote surfactant binding, is quite well understood. The microstructure of gels in the collapsed state has been studied in great detail and is often found to be highly ordered, resembling liquid crystalline phases common to surfactant/water systems. The kinetics of surfactant binding and the associated volume change has been investigated to some extent. Progress has been made for gels displaying phase separation during the volume transition.     

Effects of image charges, interfacial charge discreteness, and surface roughness on the zeta potential of spherical electric double layers

We investigate the effects of image charges, interfacial charge discreteness, and surface roughness on spherical electric double layer structures in electrolyte solutions with divalent counterions in the setting of the primitive model. By using Monte Carlo simulations and the image charge method, the zeta potential profile and the integrated charge distribution function are computed for varying surface charge strengths and salt concentrations. Systematic comparisons were carried out between three distinct models for interfacial charges: (1) SURF1 with uniform surface charges, (2) SURF2 with discrete point charges on the interface, and (3) SURF3 with discrete interfacial charges and finite excluded volume. By comparing the integrated charge distribution function and the zeta potential profile, we argue that the potential at the distance of one ion diameter from the macroion surface is a suitable location to define the zeta potential. In SURF2 model, we find that image charge effects strongly enhance charge inversion for monovalent interfacial charges, and strongly suppress charge inversion for multivalent interfacial charges. For SURF3, the image charge effect becomes much smaller. Finally, with image charges in action, we find that excluded volumes (in SURF3) suppress charge inversion for monovalent interfacial charges and enhance charge inversion for multivalent interfacial charges. Overall, our results demonstrate that all these aspects, i.e., image charges, interfacial charge discreteness, their excluding volumes, have significant impacts on zeta potentials of electric double layers.     

Image charges and dispersion forces in electric double layers: the dependence of wall-wall interactions on salt concentration and surface charge density

The interaction pressure between two planar charged walls is calculated for a range of conditions. The diffuse electric double layers between the two wall surfaces are treated with ion-wall dispersion forces and ionic image charge interactions taken into account. Both these interactions are due to dielectric discontinuities at the surfaces. Ion-ion and ion-image charge correlations are explicitly included. The ion-wall dispersion interactions can give rise to appreciable ion specific effects, which are particularly strong when the counterions to the surfaces are highly polarizable. The mechanisms of these effects are investigated, and their influence on the net interaction pressure between the walls is studied for a range of surface charge densities, strengths of the anion-wall dispersion interaction and bulk electrolyte concentrations. When the strength of the anion-wall dipersion interaction is increased, the pressure generally becomes less repulsive (or more attractive) for positive surfaces. The opposite happens in general for negative surfaces but to a much lesser extent. The effects are largest for large surface charge densities and high electrolyte concentrations. The image charge interactions give rise to a considerable depletion attraction between the walls for low surface charge densities.     

Modeling of co-adsorption of cations and anions localized in different layers of the dense part of electrical double layer under the conditions of linear charge dependence of the adsorption energy

Effects of interference of the adsorption of cations and anions located in different layers of the electrical double layer dense part (under the conditions of linear dependence of their adsorption energy on the electrode charge) analyzed in the context of a system comprising two Frumkin mixed isotherms. The model was shown to suit for the explaining of the retraction of weakly adsorbed cations into the dense layer in the case of practical independence of the total surface excess of the cations on their localizing plane in the electrical double layer. The effect of co-adsorption of cations and anions in such systems on the total differential capacitance of electrode is analyzed.     

A rapidly convergent series for computation of the interaction between two similar plane-parallel double layers

A rapidly convergent series for computation of the interaction between two similar plane-parallel double layers is derived by expanding the interaction energy in power series of omega(0)(omega(0)相似文献   

阿替洛尔与紫色素的荷移反应研究

采用光度法研究了电子给予体阿替洛尔与电子接受体紫色素之间的荷移反应,据此建立了荷移光度法测定阿替洛尔含量的方法。实验表明,阿替洛尔与紫色素在乙醇介质中,室温条件下即可形成稳定的1∶1型荷移络合物,该络合物的最大吸收波长为542nm,表观摩尔吸光系数为6.17×103L.mo-l1.cm-1。阿替洛尔的质量浓度在0~35 mg.L-1范围内符合比尔定律,相关系数为0.9993。当阿替洛尔的质量浓度为20 mg.L-1时,测定结果的相对标准偏差(n=6)为0.78%。采用本法测定片剂中阿替洛尔的含量,平均回收率在98.9%~101.6%之间。     

Interaction Mechanisms between guaiacols and lignin: the conjugated double bond makes the difference

Lignin is considered to be responsible for a selective sorption of phenolic compounds on wood. In order to investigate the mechanisms involved, two similar guaiacol compounds--only differing by the nature of the para side chain--were adsorbed on oak wood extracted lignin. Vapor sorption-desorption isotherms indicated that about 3.5 wt % of 4-vinylguaiacol is adsorbed near saturation whereas it is only 0.8% for 4-ethylguaiacol. For both compounds, the isotherms displayed a hysteresis though significantly greater for 4-vinylguaiacol. Analyses of the hydroxyl stretching region of FTIR spectra of the lignin/4-ethylguaiacol and lignin/4-vinylguaiacol complexes indicated that physisorption via hydrogen bonds occurs for both sorbates with lignin phenolic hydroxyl groups but which would be more condensed for the former than for the latter. According to NMR spectra, these phenolic hydroxyl groups correspond to non-etherified guaiacyl subunits. In contrast with other para substituents, the conjugated vinyl bond favors not only physisorption but also chemisorption as witnessed by the fact that upon desorption in the vapor phase, even after pumping under dynamic vacuum for several days, about 1 wt % of 4-vinylguaiacol remains adsorbed onto lignin.     

Interaction of long chain alkylammonium cations with reduced charge montmorillonite

Reduced charge montmorillonites (RCM) were prepared using lithium thermal treatment. The sorption of octylammonium (OA), dodecylammonium (DDA) and hexadecylammonium ions (HDA) on differently charged samples were studied. The amounts of DDA and HDA sorbed on each RCM exceed the cation exchange capacity (CEC) but that of OA exceeds only the CEC of samples with the lowest CEC. The sorption is affected not only by the layer charge but also by the formation of collapsed interlayer spaces in the lowest charged montmorillonites. X-ray measurements confirmed the decrease of the layer charge after lithium thermal treatment and the layer charge heterogeneity in RCMs.     

Interaction of triplet excitons with charge carriers in crystalline anthracene

The influence of a magnetic field on photo-enhanced hole and electron injected space charge limited currents in anthracene has shown the current enhancement is predominantly due to triplet-trapped charge carrier interactions. The observed current enhancement is too large to be produced by the production of one detrapped carrier for each annihilated triplet exciton. It is suggested that on detrapping the free carriers are in a quartet state, in which they gain energy from the applied field and then detrap further carriers themselves by scattering processes.