Surface potential adsorption

Fig. XI-13. Adsorption isotherms for SNBS (sodium p-3-nonylbenzene sulfonate) (pH 4.1) and DPC (dodecyl pyridinium chloride) (pH 8.0) on mtile at approximately the same surface potential and NaCl concentration of O.OlAf showing the four regimes of surfactant adsorption behavior, from Ref. 175. [Reprinted with permission from Luuk K. Koopal, Ellen M. Lee, and Marcel R. Bohmer, J. Colloid Interface Science, 170, 85-97 (1995). Copyright Academic Press.]...

A quantitative treatment for the depletive adsorption of iogenic species on semiconductors is that known as the boundary layer theory [84,184], in which it is assumed that, as a result of adsorption, a charged layer is formed. Doublelayer theory is applied, and it turns out that the change in surface potential due to adsorption of such a species is proportional to the square of the amount adsorbed. The important point is that very little adsorption, e.g., a 0 of about 0.003, can produce a volt or more potential change. See Ref. 185 for a review. 

Electrostatic Interaction. Similarly charged particles repel one another. The charges on a particle surface may be due to hydrolysis of surface groups or adsorption of ions from solution. The surface charge density can be converted to an effective surface potential, /, when the potential is <30 mV, using the foUowing equation, where -Np represents the Faraday constant and Ai the gas law constant. 

An important feature of such films is their low ionic conductivity that restricts cation transport through the film substance. Electronic semiconduction, however, permits other electrode processes (oxidation of H2O to O2) to take place at the surface without further significant film growth. At elevated anodic potentials adsorption and entry of anions, particularly chloride ions, may lead to instability and breakdown of these protective films (Sections 1.5 and 1.6). 

Thus the potential difference at the interface between a metal and electrolyte solution is due to both the charges at the interface (electrostatic potential difference) and the surface dipole layers the latter is referred to as the surface or adsorption potential difference. On the basis of the above considerations it might appear that adsorption at a metal surface with an excess charge is solely due to electrostatic interaction with charged species in the solution, i.e. if the metal surface has an excess negative charge the cations... 

Another important feature of polymer adsorption is the influence exerted on it by the surface roughness. Ball et al. [22] proposed that if the surface potential is not attractive enough to bind the polymer when flat, then corrugation can aid binding as follows. For a sinusoidal corrugation, one might anticipate that some... 

The Kinetics of the Stereospecific Polymerization of a-Olefins G. Natta and I. Pasquon Surface Potentials and Adsorption Process on Metals... 

In contrast to the ionizing electrode method, the dynamic condenser method is based on a well-understood theory and fulfills the condition of thermodynamic equilibrium. Its practical precision is limited by noise, stray capacitances, and variation of surface potential of the air-electrode surface, i.e., the vibrating plate. At present, the precision of the dynamic condenser method may be limited severely by the nature of the surfaces of the electrode and investigated system. In common use are adsorption-... 

Adsorption of a dipolar substance at the w/a and w/o interfaces changes surface tension and modifies the surface potential of water (Fig. 11). As seen in Fig. 11, the change in compensation voltage due to adsorption is the surface potential difference, usually called the surface potential or better the adsorption potential and often indicated unnecessarily by AV. ... 

The popular applications of the adsorption potential measurements are those dealing with the surface potential changes at the water/air and water/hydrocarbon interface when a monolayer film is formed by an adsorbed substance. " " " Phospholipid monolayers, for instance, formed at such interfaces have been extensively used to study the surface properties of the monolayers. These are expected to represent, to some extent, the surface properties of bilayers and biological as well as various artificial membranes. An interest in a number of applications of ordered thin organic films (e.g., Langmuir and Blodgett layers) dominated research on the insoluble monolayer during the past decade. 

Recently, changes in the surface potential of some organic solvents, specifically ethylene glycol, y-butyrolactonej and dimethylo-sulfoxide upon adsorption of dipolar organic substances (e.g., chloroform and octanol) have been measured systematically for the first time. 

The measurement of change in the surface potentials of aqueous solutions of electrolytes caused hy adsorption of ionophore (e.g., crown ether) monolayers seems to he a convenient and promising method to ascertain selectivity and the effective dipole moments of the ionophore-ion complexes created at the water surface. 

Pritchard, J. and Tompkins, F.C. (1960) Surface-potential measurements. Adsorption of hydrogen by Group IB metals. Transactions of the Faraday, Society, 56, 540-550. 

The work function of charged particles found for a particular conductor depends not only on its bulk properties (its chemical nature), which govern parameter but also on the state of its surface layer, which influences the parameter (a) xhis has the particular effect that for different single-crystal faces of any given metal, the electron work functions have different values. This experimental fact is one of the pieces of evidence for the existence of surface potentials. The work function also depends on the adsorption of foreign species, since this influences the value of... 

Two types of EDL are distinguished superficial and interfacial. Superficial EDLs are located wholly within the surface layer of a single phase (e.g., an EDL caused by a nonuniform distribution of electrons in the metal, an EDL caused by orientation of the bipolar solvent molecules in the electrolyte solution, an EDL caused by specific adsorption of ions). Tfie potential drops developing in tfiese cases (the potential inside the phase relative to a point just outside) is called the surface potential of the given phase k. Interfacial EDLs have their two parts in dilferent phases the inner layer with the charge density in the metal (because of an excess or deficit of electrons in the surface layer), and the outer layer of counterions with the charge density = -Qs m in the solution (an excess of cations or anions) the potential drop caused by this double layer is called the interfacial potential... 

Hence, the question arose whether the lifting of reconstruction is due to surface charging (as a result of the electrode potential), adsorption of electrolyte ions (or molecules), or both. Although various experimental and theoretical investigations have been carried out, the driving force for the lifting of reconstruction is not yet clear. 

In this picture, the kinetic barriers hindering the exchange between the two adlayers are related to the presence of metastable, but rather strongly bound, adsorbed species (Hupd and OHad), which cannot be removed easily, and which block the surface for adsorption of the respective other species. The nonequilibrium situation is also reflected in the shape of the corresponding peaks A and A, where the anodic one (A) is less sharp and extends over a larger potential range. 

The concept of adsorption potential comes from work with high-purity, synthetic microporous carbon, which relies solely on van der Waals dispersive and electrostatic forces to provide the energy for adsorption. The polymeric microporous adsorbents that operate solely through van der Waals dispersive and electrostatic forces often cannot provide the surface potential energy needed to trap compounds that are gases under ambient conditions, and for very volatile compounds the trapping efficiency can be low for similar reasons. 

Every liquid interface is usually electrified by ion separation, dipole orientation, or both (Section II). It is convenient to distinguish two groups of immiscible liquid-liquid interfaces water-polar solvent, such as nitrobenzene and 1,2-dichloroethane, and water-nonpolar solvent, e.g., octane or decane interfaces. For the second group it is impossible to investigate the interphase electrochemical equilibria and the Galvani potentials, whereas it is normal practice for the first group (Section III). On the other hand, these systems are very important as parts of the voltaic cells. They make it possible to measure the surface potential differences and the adsorption potentials (Section IV). 

Replacement of gas by the nonpolar, e.g., hydrocarbon phase (or oil phase) is used to modify the interactions between molecules in a spread film of investigated long-chain substances [6,15,17,18]. The nonpolar solvent-water interface possesses the advantage over that between gas and water, that the cohesion (i.e., interactions between adsorbed molecules due to dipole and van der Waals forces) is negligible. Thus, at the oil-water interfaces behavior of adsorbates is much closer to ideal, but quantitative interpretation may be uncertain, in particular for the higher chains which are predominantly dissolved in the oil phase to an unknown activity. Adsorption of dipolar substances at the w/a and w/o interfaces changes surface tension and modifies the surface potential of water [15] ... 

As seen in this sketch, the change of compensation voltage A.E, due to adsorption is the surface potential difference, usually called shortly surface potential, or better the adsorption potential... 

Studies of the adsorption of surface active electrolytes at the oil-water interface provide a convenient method for testing electrical double layer theory and for determining the state of water and ions in the neighborhood of an interface. The change in the surface amount of the large ions modifies the surface charge density. For instance, the surface ionic area of 100 per ion corresponds to 16, /rC/cm. The measurement of the concentration dependence of the changes of surface potential were also applied to find the critical concentration of formation of the micellar solution [18]. 

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