Oxidation of Metals in Aqueous Solutions

This is an example of a displacement reaction. Zinc displaces, or replaces, copper in the dissolved salt by being oxidized from Zn to Zn . Copper is displaced from the salt (and removed from solution) by being reduced from Cu to Cu. Chloride (CF), which is neither oxidized nor reduced, is a spectator ion in this reaction. 

What would happen, then, if we placed copper metal into a solution containing zinc chloride (ZnCy Would Cu(s) be oxidized to Cu (a ) by Zn (ag) the way Zn(5) is oxidized to 7 aq) by Cu (a ) The answer is no. In fact, no reaction would occur if we were to immerse copper metal into an aqueous. solution of ZnCl2. 

No reaction occurs between Cu(i) and 7.x (aq), whereas a reaction does occur between Zn(5) and C aq) because zinc is more easily oxidized than copper. 

Metals listed at the top of the activity series are called the active metals. These include the alkali and alkaline earth metals. These metals are so reactive that they are not found in nature in their elemental forms. Metals at the bottom of the series, such as copper, silver, platinum, and gold, are called the noble metals because they have veiy little tendency to react These are the metals most often used for jewelry and coins. 

Some metals such as copper are so unreactive that they are found In nature In the uncombined state. 

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Chemical plants are designed and constructed with a variety of metals, alloys, and nonmetallic materials such as plastics. The nature and mechanism of degradation of these materials differ. Corrosion of metals and alloys in aqueous media occurs by electrochemical mechanisms, whereas the degradation of a plastic is by the penetration of chemicals into its matrix. Nevertheless, the term corrosion is used liberally to describe the oxidation of metals in aqueous solutions or gas phases and the deterioration of plastics by chemical attack. 

After tq is passed, the second step starts by scanning the potential from Ed to a potential when all the deposited metals are re-oxidized (the reverse of reaction 25). The oxidation current recorded as a function of potential is the anodic stripping voltammogram (ASV). A typical ASY of three metals (Cd, Pb, and Cu) deposited on a mercury film electrode is shown in Fig. 18b.12b. The sensitivity of ASY can be improved by increasing the deposition time and by using the pulse technique to record the oxidation current. ASV in Fig. 18b. 12b was obtained by using the square wave voltammetry. In most cases a simple linear or step ramp is sufficient to measure sub-ppm level of metals in aqueous solution. The peak current of a linear scan ASV performed on a thin mercury film electrode is given by... 

The Wacker oxidation was discovered by Smidt and co-workers at Consortium fiir Electrochemie (a subsidiary of Wacker Chemie and Farbwerken Bayer). It is actually a combination of known reactions and thus not a catalytic reaction in the strictest sense (Scheme 1). The first and most basic reaction, the oxidation of ethene in aqueous solution was first discovered by Phillips in 9AP The precipitation of palladium metal from a palladium(II) chloride solution was used as a test for olefins. However, it was the discovery by Smidt and co-workers that the Pd(0) formed could be regenerated by cupric chloride that made the reaction a commercial success. The final step, the oxidation of CuCl to CuCl2 is one of the fastest reactions in inorganic chemistry, The three reactions add up to the simple air oxidation of ethene to ethanal. At one point over two billion pounds a year of ethanal was produced by the Wacker process. Presently, the Monsanto acetic acid process has largely replaced the Wacker procednre.t" ... 

The anodic oxidation of water to oxygen is an impoitant process in electrolysis as well as the cathodic reduction of oxygen for the corrosion of metals in aqueous solutions or a moist atmosphere. The net reaction... 

Lower oxidation states are rather sparsely represented for Zr and Hf. Even for Ti they are readily oxidized to +4 but they are undoubtedly well defined and, whatever arguments may be advanced against applying the description to Sc, there is no doubt that Ti is a transition metal . In aqueous solution Ti can be prepared by reduction of Ti, either with Zn and dilute acid or electrolytically, and it exists in dilute acids as the violet, octahedral [Ti(H20)6] + ion (p. 970). Although this is subject to a certain amount of hydrolysis, normal salts such as halides and sulfates can be separated. Zr and are known mainly as the trihalides or their derivatives and have no aqueous chemistry since they reduce water. Table 21.2 (p. 960) gives the oxidation states and stereochemistries found in the complexes of Ti, Zr and Hf along with illustrative examples. (See also pp. 1281-2.)... 

Half reactions involving the oxidation of a metal in aqueous solutions... 

Another common type of reaction in aqueous solution involves a transfer of electrons between two species. Such a reaction is called an oxidation-reduction or redox reaction. Many familiar reactions fit into this category, including the reaction of metals with acid. 

The differential capacitance method cannot be used for reactive metals, such as transition metals in aqueous solutions, on which the formation of a surface oxide occurs over a wide potential re ion. An immersion method was thus developed by Jakuszewski et al. 3 With this technique the current transient during the first contact of a freshly prepared electrode surface with the electrolyte is measured for various immersion potentials. The electrode surface must be absolutely clean and discharged prior to immersion.182-18 A modification of this method has been described by Sokolowski et al. The values of obtained by this method have been found to be in reasonable agreement with those obtained by other methods, although for reactive metals this may not be a sufficient condition for reliability. 

Wilson, Abel Lewis (1974), in a detailed chemical study of erosion in aqueous solution, found that in the first 24 hours of the cement s life the ions eluted were Zn, Mg, HPO " and H2PO4. Far more Mg ions were eluted than Zn ions, despite zinc being the major metal constituent of the zinc phosphate cement. These workers deduced that magnesium is far less firmly bound to phosphate than is zinc and that, consequently, its presence in the oxide is a source of weakness. These results were later confirmed by Anzai et al. (1977). 

Lamy, C., Electrocatalytic oxidation of organic compounds on noble metals in aqueous solutions, Electrochim. Acta, 29, 1581 (1984). 

The first interest in the electroreduction of N02 or NO catalyzed by metal complexes is to model the activity of nitrite reductase enzymes.327 There is also an extensive growth in studies related to the development of metal complex-based electrochemical sensors for NO determination in biological and environmental samples 328 329 Nitrate disproportionates to nitric oxide and nitrate in aqueous solution. 

Russian scientists (Avrorin et al., 1981, 1985) have reported that reactions of complex mixtures of radon, xenon, metal fluorides, bromine pentafluoride, and fluorine yield a higher fluoride of radon which hydrolyzes to form RnO. However, efforts to confirm these findings have been unsuccessful. In similar experiments which have been carried out at Argonne National Laboratory (Stein, 1984), it has been found that radon in the hydrolysate is merely trapped in undissolved solids centrifugation removes the radon from the liquid phase completely. This is in marked contrast to the behavior of a solution of XeO, which can be filtered or centrifuged without loss of the xenon compound. Hence there is no reliable evidence at present for the existence of a higher oxidation state of radon or for radon compounds or ions in aqueous solutions. Earlier reports of the preparation of oxidized radon species in aqueous solutions (Haseltine and Moser, 1967 Haseltine, 1967) have also been shown to be erroneous (Flohr and Appelman, 1968 Gusev and Kirin, 1971). 

Ketones are resistant to oxidation by dioxygen in aqueous solutions at T= 300-350 K. Transition metal ions and complexes catalyze their oxidation under mild conditions. The detailed kinetic study of butanone-2 oxidation catalyzed by ferric, cupric, and manganese complexes proved the important role of ketone enolization and one-electron transfer reactions with metal ions in the catalytic oxidation of ketones [190-194],... 

TABLE 5- Tbe flat band potential , the iso-electric point pHi, the potential of the conduction band edge aiep) at pH q> for metal oxide semiconductor electrodes in aqueous solutions t, = band gap of metal oxides pH= solution pH at which the flat band potential is measured. [From Morrison, 1980.]... 

Even in an excess of ligands capable of stabilizing low oxidation state transition metal ions in aqueous systems, one may often observe the reduction of the central ion of a catalyst complex to the metallic state. In many cases this leads to a loss of catalytic activity, however, in certain systems an active and selective catalyst mixture is formed. Such is the case when a solution of RhCU in water methanol = 1 1 is refluxed in the presence of three equivalents of TPPTS. Evaporation to dryness gives a brown solid which is an active catalyst for the hydrogenation of a wide range of olefins in aqueous solution or in two-phase reaction systems. This solid contains a mixture of Rh(I)-phosphine complexes, TPPTS oxide and colloidal rhodium. Patin and co-workers developed a preparative scale method for biphasic hydrogenation of olefins [61], some of the substrates and products are shown on Scheme 3.3. The reaction is strongly influenced by steric effects. 

The electrochemical treatment of contaminated groundwater technology uses direct electrical current applied between two immersed electrodes to produce oxidation-reduction reactions in aqueous solutions. Positively charged metal ions are attracted to the negatively charged electrode (the cathode), where they are reduced. 

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