Anodes adsorption

Xanthate compounds are widely used as collectors in flotation. Their function is to render the mineral surface hydrophobic and thus facilitate bubble attachment. The adsorption of xanthates onto sulfide minerals occurs via an electrochemical mechanism involving the reduction of oxygen and the anodic adsorption of xanthate. 

The original C.P.D. determinations of Oatley (44) were made with Ha and Oa on a Pt anode. The gases were ionized, and the work function of the anode increased by 1.2 v. with Oa and decreased by 1.15 v. with Ha. Similarly, Weissler and Wilson (46) obtained C.P.D. values of —1.2 v. and up to —1.4 V. for the adsorption of Oa on W and Ag films which were evaporated on to the inside of a cylindrical Ta anode. Adsorption was promoted by means of a glow discharge. Less reliable positive S.P. values were obtained for the adsorption of Ha and Na. The results were not always reproducible, and it is possible that the anode was a source of contamination. 

The mechanism of anodic hydrogen oxidation is much simpler than that of oxygen reduction. Reaction pathways would be the reverse of the Volmer-Heyrovsky or the Volmer-Tafel mechanism, that is, with anodic adsorption... 

Aboul-Kasim, E., 2000. Anodic adsorptive voltammetric determination of vitamin Bi (thiamine). Journal of Pharmaceutical and Biomedical Analysis. 22 1047-1054. 

All these effects combined make mercury electrodes especially attractive for stripping analysis of trace metals by anodic, adsorptive and cathodic stripping procedures. 

Gonzalez P, Cortinez VA, Fontan CA (2002) Determination of nickel by anodic adsorptive stripping voltammetry with a cation exchanger-modified carbon paste electrode. Talanta 58 679-690... 

Stripping Voltammetry One of the most important quantitative voltammetric techniques is stripping voltammetry, which is composed of three related techniques anodic, cathodic, and adsorptive stripping voltammetry. Since anodic strip-... 

In adsorptive stripping voltammetry the deposition step occurs without electrolysis. Instead, the analyte adsorbs to the electrode s surface. During deposition the electrode is maintained at a potential that enhances adsorption. For example, adsorption of a neutral molecule on a Hg drop is enhanced if the electrode is held at -0.4 V versus the SCE, a potential at which the surface charge of mercury is approximately zero. When deposition is complete the potential is scanned in an anodic or cathodic direction depending on whether we wish to oxidize or reduce the analyte. Examples of compounds that have been analyzed by absorptive stripping voltammetry also are listed in Table 11.11. 

XPS was used to determine the surface composition of the anodized aluminum substrate during exposure to warm, moist environments. The information obtained was used to construct surface behavior diagrams that showed that hydration of the surface involved three steps [38]. Step one, which was reversible, consisted of adsorption of water onto the AIPO4 monolayer. The second step, which was rate-controlling, involves dissolution of the phosphate followed by rapid hydration... 

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). 

There are in fact many possible further steps that could be included in the basic mechanisms described above, for example, involving adsorption processes for H O and OH , and interactions among the adsorbed species. The most widely studied is the reaction of iron, but broadly similar steps are encountered in the anodic oxidation of many metals. These several mechanisms still include the same basic steps as described above... 

With regard to the anodic dissolution under film-free conditions in which the metal does not exhibit passivity, and neglecting the accompanying cathodic process, it is now generally accepted that the mechanism of active dissolution for many metals results from hydroxyl ion adsorption " , and the sequence of steps for iron are as follows ... 

The dissolution of passive films is, in the main, controlled by a chemical activation step in contrast to film-free conditions at. Many protective anodic films are oxides and hydroxides whose dissolution depends upon the hydrogen ion concentration, and the rate follows a Freundlich adsorption equation ... 

As indicated when discussing anodic behaviour the mechanism of film formation is complex, involving adsorption of OH ions to form a prepassive layer followed by either dissolution or film formation as alternative processes. 

In modern practice, inhibitors are rarely used in the form of single compounds — particularly in near-neutral solutions. It is much more usual for formulations made up from two, three or more inhibitors to be employed. Three factors are responsible for this approach. Firstly, because individual inhibitors are effective with only a limited number of metals the protection of multi-metal systems requires the presence of more than one inhibitor. (Toxicity and pollution considerations frequently prevent the use of chromates as universal inhibitors.) Secondly, because of the separate advantages possessed by inhibitors of the anodic and cathodic types it is sometimes of benefit to use a formulation composed of examples from each type. This procedure often results in improved protection above that given by either type alone and makes it possible to use lower inhibitor concentrations. The third factor relates to the use of halide ions to improve the action of organic inhibitors in acid solutions. The halides are not, strictly speaking, acting as inhibitors in this sense, and their function is to assist in the adsorption of the inhibitor on to the metal surface. The second and third of these methods are often referred to as synergised treatments. 

The effects of adsorbed inhibitors on the individual electrode reactions of corrosion may be determined from the effects on the anodic and cathodic polarisation curves of the corroding metaP . A displacement of the polarisation curve without a change in the Tafel slope in the presence of the inhibitor indicates that the adsorbed inhibitor acts by blocking active sites so that reaction cannot occur, rather than by affecting the mechanism of the reaction. An increase in the Tafel slope of the polarisation curve due to the inhibitor indicates that the inhibitor acts by affecting the mechanism of the reaction. However, the determination of the Tafel slope will often require the metal to be polarised under conditions of current density and potential which are far removed from those of normal corrosion. This may result in differences in the adsorption and mechanistic effects of inhibitors at polarised metals compared to naturally corroding metals . Thus the interpretation of the effects of inhibitors at the corrosion potential from applied current-potential polarisation curves, as usually measured, may not be conclusive. This difficulty can be overcome in part by the use of rapid polarisation methods . A better procedure is the determination of true polarisation curves near the corrosion potential by simultaneous measurements of applied current, corrosion rate (equivalent to the true anodic current) and potential. However, this method is rather laborious and has been little used. 

Blocking of reaction sites The interaction of adsorbed inhibitors with surface metal atoms may prevent these metal atoms from participating in either the anodic or cathodic reactions of corrosion. This simple blocking effect decreases the number of surface metal atoms at which these reactions can occur, and hence the rates of these reactions, in proportion to the extent of adsorption. The mechanisms of the reactions are not affected and the Tafel slopes of the polarisation curves remain unchanged. Behaviour of this type has been observed for iron in sulphuric acid solutions containing 2,6-dimethyl quinoline, /3-naphthoquinoline , or aliphatic sulphides . 

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