ABSTRACT
The problem of the distinction between the so-called free charge and the thermodynamic (total) charge of electrodes was discussed in the light of the relevant IUPAC definitions calling attention to the strict relationships existing between charge and mass balances during the formation of a double layer at electrodes or/and particles. It is demonstrated that the origins of controversial views concerning partial charge transfer and electrosorption valency, notions widely used nowadays in the electrochemical literature, could be ascribed to confusion of the free and thermodynamic charges. Although there are, even if sporadic, evidences and theoretical considerations in the literature proving that electrosorption valency as usually defined is an extrathermodynamic and self-contradictory concept, it is widely used by many authors for the interpretation of electrosorption phenomena. One of the most important aims of the present work was to demonstrate that independent of the thermodynamic considerations, the concept of electrosorption valency cannot be reconciled with elementary laws of electrochemistry. On the basis of analysis of real processes occurring in the interfacial layer of electrodes it was urged to avoid the treatment of some double-layer phenomena in terms of electrosorption valency in order to eliminate far-reaching misinterpretations leading to serious contradictions.
ABSTRACT
Critical remarks have been formulated in connection with the surface stress measurements reported by Tian et al. It has been shown that due to the shortcomings of the experimental procedure some conclusions of the authors are hardly acceptable.
ABSTRACT
The specific adsorption of radiolabeled sulfate and phosphate ions from perchlorate supporting electrolyte onto nano-AlOOH and nano-Fe(2)O(3) powder has been investigated. The pH dependence of the adsorption of anions onto nanopowders was compared with that of the same ions onto gamma-Al(2)O(3) and hematite. It was demonstrated that the character of the pH dependence of the adsorption is very similar in the comparable cases. It was found, however, that in contrast to the behavior of gamma-Al(2)O(3), nano-AlOOH dissolves at a significant rate at low pH values (pH<2). Thus the study of the pH dependence of the anion adsorption encounters difficulties at these pH values. Disregarding this fact, it can be concluded that no special effects can be observed in the anion adsorption onto the nano-oxides studied.
ABSTRACT
The specific adsorption of radiolabeled sulfate ions from perchlorate supporting electrolyte onto TiO2 powder (anatase) has been investigated. The pH and concentration dependence of the adsorption was determined. Langmuir-like adsorption behavior similar to that on other oxides was found. From the pH dependence it follows that the protonation of the surface should precede the specific anion adsorption. The results obtained are compared with those reported for TiO2 bulk electrodes.
ABSTRACT
The specific adsorption of radiolabeled phosphate ions from perchlorate supporting electrolyte onto gamma-Al2O3 and hematite powder has been investigated. The pH dependence of the adsorption of phosphate species was compared with that of sulfate ions. It was demonstrated that in contrast to the behavior of sulfate ions the pH dependence of phosphate ions goes through a maximum. On the other hand, it was found that the reversible adsorption of phosphate ions is accompanied by the formation of strongly chemisorbed species. Results obtained from a study of the competitive adsorption of sulfate and phosphate ions at various pH values are reported and interpreted. An attempt is made to correlate the experimental findings with the models for anion adsorption reported in the literature.
ABSTRACT
The pH dependence of adsorption of (14)C-labeled benzoic and oxalic acids on gamma-Al(2)O(3) and hematite was studied in acid medium in the presence of 0.5 mol dm(-3) NaClO(4) supporting electrolyte. It was found that the adsorption of the organic species starts at pH values where the protonation of the oxide surface takes place. In the case of benzoic acid the extent of adsorption with decreasing pH goes through a sharp maximum at a pH value not far from the pK (4.2) of the acid, while in the case of oxalic acid only a small decrease can be observed at very low pH values (pH<1). In indirect radiotracer studies using (35)S-labeled sulfate ions it was shown that the competitive adsorption of formic, malonic, maleic, and oxalic acids with sulfate ions depends on pH and the effect of the organic acid on the anion adsorption becomes pronounced at pH values about and above the pK of the acid. On the basis of these observations and considerations concerning the dissociation of the organic acids studied it is assumed that the specific adsorption of the anionic form of the acids takes place. It is, however, emphasized that the negative charge of the anions, consequently the electrostatic forces, do not play significant role in the adsorption.
ABSTRACT
The specific adsorption of radiolabeled anions (sulfate, chloride) from perchlorate supporting electrolyte on gamma-Al(2)O(3) powder has been investigated. It was demonstrated that a measurable adsorption occurs only at pH values under pH 6. The adsorption capacity of a given amount of gamma-Al(2)O(3) powder tends to a limiting value with decreasing pH. A Langmuir-like adsorption isotherm describes the concentration dependence of the adsorption of sulfate species. It was found that the experimental results are very similar to those obtained in the case of hematite. Copyright 2000 Academic Press.
ABSTRACT
The specific adsorption of radiolabeled sulfate ions from perchlorate supporting electrolyte on hematite powder has been investigated. It was demonstrated that a measurable adsorption occurs only at pH values under 5. The adsorption capacity of a given amount of hematite powder tends to a limiting value with decreasing pH. A Langmuir-like adsorption isotherm describes the concentration dependence of the adsorption of sulfate species. It was found that the experimental results are in good agreement with the model suggested recently (Hug, S. J. J. Colloid Interface Sci. 188, 415 (1997)). Copyright 2000 Academic Press.
ABSTRACT
The specific adsorption of anions (HSO(4)(-), H(2)PO(4)(-), and Cl(-)) was studied at Fe(2)O(3), ZnO, and CuO surfaces by the radiotracer technique in strongly acidic medium (1 M HClO(4)). A significant specific adsorption of HSO(4)(-) and H(2)PO(4)(-) ions was found in all cases studied while no measurable adsorption of Cl(-) ions was observed. In the cases of ZnO and CuO, the specific adsorption takes place over the course of continuous dissolution of the oxide. Copyright 2000 Academic Press.
