Double layer adsorption

Figure 6.17. Effective double layer adsorption equilibrium isotherms for kj=l and various values of the parameter Ajll.

Molecules in adsorbed layers have also a definite orientation. If a complete layer is formed over a surface, with those groups possessing the greatest attraction for the surface turned inward, we have virtually a new surface with properties determined by the nature of the groups which are directed outwards. There seems to be no very good reason why this, in certain cases, should not adsorb a second layer of molecules. Indeed, the assumption that this double-layer adsorption occurs has occasionally been found helpful. But there is a large difference between this extension of the single-layer theory and the atmospheric. theory. 

For minor species, in the presence of supporting electrol3rte and with neglect of double-layer adsorption of these minor species, the concentration gradient is related to the Faradaic current density by... 

The properties of the surface layers have a strong effect on the deposition process. The driving force of the electrochemical reaction is the potential difference over the electrochemical double layer. Adsorption of species can change this potential. For example, the additives used in electrodeposition adsorb in the Helmholtz layer. They can change the local potential difference, block active deposition sites, and so on. The thickness of the diffusion layer affects the mass-transfer rate to the electrode. The diffusion layer becomes thinner with increasing flow rate. When the diffusion layer is thicker than the electrode surface profile, local mass-transfer rates are not equal along the electrode surface. This means that under mass-transfer control, metal deposition on electrode surface peaks is faster than in the valleys and a rough deposit will result. 

Electric double-layer adsorption of R-SO3 and R-SO4 on mineral surface ... 

An electrode capacitor may be considered as a membrane material made from either a dielectric or a semiconductor which can adsorb cations and anions on its active sites. The membrane potential is believed to derive from the two interfaces that hold charges on the surface through double layer adsorptions. The glass electrode potential follows the capacitance law. 

The adsorption can be carried on to formation of a double layer adsorption. 1.0 mMol of the PFPE-surfac-... 

The authors aim was to produce a text which critically reviews the available literature on solution adsorption phenomena and offers an interpretation of the surface-related interactions of activated carbons that is consistent for the adsorption of a wide variety of solutes ranging from strong electrolytes to organic non-electrolytes. The seven chapters cover the activation of carbon, surface oxygen functional groups and neutralization of base by acidic surface oxides, spectroscopic methods for molecular structure determinations on surfaces, nature of the electrical double layer, adsorption of electrolytes, and adsorption of weak and non-electrolytes from aqueous solution. 

The electrochemical resistances ESR (equivalent series resistance) and EDR (equivalent diffusion resistance) evaluated using electrochemical impedance spectroscopy (EIS) measurements clearly demonstrate that according to the nature of the anion, the mechanism of ion adsorption can be described by pure double-layer adsorption at the specific surface, or by the insertion of desolvated ions into the... 

Here, the only surface adsorption is taken to be that of the charge balancing the double-layer charge, and the electrochemical potential change is equated to a change in o- Integration then gives... 

A logical division is made for the adsorption of nonelectrolytes according to whether they are in dilute or concentrated solution. In dilute solutions, the treatment is very similar to that for gas adsorption, whereas in concentrated binary mixtures the role of the solvent becomes more explicit. An important class of adsorbed materials, self-assembling monolayers, are briefly reviewed along with an overview of the essential features of polymer adsorption. The adsorption of electrolytes is treated briefly, mainly in terms of the exchange of components in an electrical double layer. 

Stem layer adsorption was involved in the discussion of the effect of ions on f potentials (Section V-6), electrocapillary behavior (Section V-7), and electrode potentials (Section V-8) and enters into the effect of electrolytes on charged monolayers (Section XV-6). More speciflcally, this type of behavior occurs in the adsorption of electrolytes by ionic crystals. A large amount of wotk of this type has been done, partly because of the importance of such effects on the purity of precipitates of analytical interest and partly because of the role of such adsorption in coagulation and other colloid chemical processes. Early studies include those by Weiser [157], by Paneth, Hahn, and Fajans [158], and by Kolthoff and co-workers [159], A recent calorimetric study of proton adsorption by Lyklema and co-workers [160] supports a new thermodynamic analysis of double-layer formation. A recent example of this is found in a study... 

Stahlberg has presented models for ion-exchange chromatography combining the Gouy-Chapman theory for the electrical double layer (see Section V-2) with the Langmuir isotherm (. XI-4) [193] and with a specific adsorption model [194]. 

For example, van den Tempel [35] reports the results shown in Fig. XIV-9 on the effect of electrolyte concentration on flocculation rates of an O/W emulsion. Note that d ln)ldt (equal to k in the simple theory) increases rapidly with ionic strength, presumably due to the decrease in double-layer half-thickness and perhaps also due to some Stem layer adsorption of positive ions. The preexponential factor in Eq. XIV-7, ko = (8kr/3 ), should have the value of about 10 " cm, but at low electrolyte concentration, the values in the figure are smaller by tenfold or a hundredfold. This reduction may be qualitatively ascribed to charged repulsion. 

The basic assumption is that the Langmuir equation applies to each layer, with the added postulate that for the first layer the heat of adsorption Q may have some special value, whereas for all succeeding layers, it is equal to Qu, the heat of condensation of the liquid adsorbate. A furfter assumption is that evaporation and condensation can occur only from or on exposed surfaces. As illustrated in Fig. XVII-9, the picture is one of portions of uncovered surface 5o, of surface covered by a single layer 5, by a double-layer 52. and so on.f The condition for equilibrium is taken to be that the amount of each type of surface reaches a steady-state value with respect to the next-deeper one. Thus for 5o... 

Tanahashi, I., Yoshida, A. and Nishino, A., Characterization of activated carbon fiber cloths for electric double layer capacitors by adsorption method. Carbon, 1991, 29(7), 1033 1037. 

In some cases, e.g., the Hg/NaF q interface, Q is charge dependent but concentration independent. Then it is said that there is no specific ionic adsorption. In order to interpret the charge dependence of Q a standard explanation consists in assuming that Q is related to the existence of a solvent monolayer in contact with the wall [16]. From a theoretical point of view this monolayer is postulated as a subsystem coupled with the metal and the solution via electrostatic and non-electrostatic interactions. The specific shape of Q versus a results from the competition between these interactions and the interactions between solvent molecules in the mono-layer. This description of the electrical double layer has been revisited by... 

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