Surface charge direct ionization

For typical aqueous colloidal dispersions, the particles may carry some charges most likely due to the preferential (or differential) dissolution of particle surface ions, direct ionization of particle surface groups, substitution of particle surface ions, specific adsorption of ions, and particle surface charges originating from specific crystal structures. 

The measurement of the surface potential asa function of pH for an oxide provides valuable information for the determination of the parameters which describe the surface reactions. Ionizable surface site theories of the formation of surface charge and potential at an oxide surface in contact with a liquid electrolyte involve many more parameters than can be directly experimentally determined. Additional assumptions are required to evaluate these parameters, which explains why there is often no agreement in the literature about their value. A mathematical treatment of the amphoteric surface site model is given which exhibits the characteristic quantities which can be experimentally measured. It is shown that the measurement of both the surface potential i/>o and the surface charge 00 are required to completely determine these characteristic quantities. This approach is applied to Si02 and AI2O3, two surfaces for which both charge and potential measurements are available. 

The intrinsic constants are thermod3mamic constants written for reactions occurring at a hypothetical isolated site on the surface. Actual activities on the surface cannot be directly determined but Q or apparent stability quotients can be calculated based on measurable bulk concentrations. The intrinsic constants and apparent stability quotients are related by considering the electrostatic correction for an ion in solution near the surface compared to an isolated ion on the surface. In an idealized planar model, is the mean potential at the plane of surface charge created by the ionization of the surface functional groups and the formation of surface complexes and is the mean potential at the plane of adsorbed counter ions at a distance 3 from the surface (17). The electrostatic interaction energies at the surface and at a distance 3 are expressed as exponentials. Therefore ... 

The fused-silica surface also provides another mechanism, electro-osmosis, which drives solutes through the tube under the influence of an electric field. The principle of electro-osmotic flow (EOF) is illustrated in Fig. 1. The inner wall of the capillary contains silanol groups on the surface that become ionized as the pH is raised above about 3.0. This creates an electrical double layer in the presence of an applied electric field so that the positively charged species of the buffer which are surrounded by a hydrated layer carry solvent toward the cathode (negatively charged electrode). This results in a net movement of solvent toward the cathode that will carry solutes in the same direction as if the solvent were pumped through the capillary. This electrically driven solvent pumping mechanism results in a flat flow profile in contrast to... 

Provided that there is no additional surface charge, fj, is a pure bulk term which is independent of any electrostatic potential. The term is the contribution of surface dipoles [1, 2] (Fig. 2.1). Such a dipole can be caused by an unsymmetrical distribution of charges at the surface because there is a certain probability for the electrons to be located outside the surface. In the case of compound semiconductors, dipoles based on the surface structure caused by a particular ionic charge distribution occur. These effects depend on the crystal plane and on the reconstruction of the surface atoms [3, 4]. These dipole effects also influence the electron affinity and ionization energy. In the case of metals, the work function is a directly measurable quantity, and for semiconductors it is calculable from ionization measurements. However, the relative contributions of fi and ex are not accessible experimentally and data given in the literature are based on theoretical calculations (see e.g. ref. [1]). 

An interface may acquire an electrical charge by one or more of several mechanisms, the most common of which include (1) preferential (or differential) solution of surface ions, (2) direct ionization of surface groups, (3) substi-... 

FIGURE 5.1. The principle sources of surface charge in solids include (a) differential ion solubility phenomena, (h) direct ionization of surface groups, (c) isomorphous substitution of ions from solution, and (d) speciflc-ion adsorption from the solution phase (e) anisotropic crystal lattice structures. 

Materials containing surface groups that can be directly ionized, but in which one of the ions is permanently bound to the surface, illustrate a second important mechanism for the development of surface charge. This group of materials includes many metal oxides as well as many polymer latexes (Fig. 5.1b). Some metal oxides are amphoteric in that they can develop either negative or positive surfaces, depending on the pH of the solution. Such surfaces will obviously exhibit a characteristic point of zero charge such as that found for the silver... 

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