Electrochemical zinc

The "classical" Leclanche cell uses zinc sheet formed into a cylindrical can serving simultaneously as the anode and as the cell container (AB1C1). The cathode is a mixture of Mn02 and graphite wrapped into a piece of separator and contacted by a central carbon rod. The can dissolves slowly when the cell is not in use and faster when the cell delivers electrical energy. The reaction following the primary electrochemical zinc dissolution [Eq. (19)] leads, in the case of an ammonium chloride electrolyte, to a zinc diammine cation ... 

As for the above-mentioned reactions, the reaction rate can be accelerated if a low additional reduction current is applied after the electrochemical zinc activation. 

Nevertheless, this electrochemical zinc activation procedure, which looks like the chemical activation developed by Rieke, does not appear to be very convenient for the electrochemical synthesis of organozinc compounds in one step (equation 24) without preparation of the active zinc in a preliminary step4,13. 

Tin films were deposited onto the fine grained underlayer of electrochemical zinc from solution 1 containing tin sulphate and sodium citrate (0.1 and 0.3 mol/1) and solutions 2 and 3 analogous to the first one but containing zinc sulphate (0.1 and... 

Electrochemical zinc-rich paints) automotive/transport 3 N... 

The reaction following the primary electrochemical zinc dissolution (Equation 8.18) leads, in the case of an ammonium chloride electrolyte, to a zinc diammine cation ... 

Since metals have very high conductivities, metal corrosion is usually electrochemical in nature. The tenn electrochemical is meant to imply the presence of an electrode process, i.e. a reaction in which free electrons participate. For metals, electrochemical corrosion can occur by loss of metal atoms tluough anodic dissolution, one of the fiindamental corrosion reactions. As an example, consider a piece of zinc, hereafter referred to as an electrode, inunersed in water. Zinc tends to dissolve in water, setting up a concentration of Zn ions very near the electrode... 

When the reaction between zinc and copper(II) sulphate was carried out in the form of an electrochemical cell (p. 94), a potential difference between the copper and zinc electrodes was noted. This potential resulted from the differing tendencies of the two metals to form ions. An equilibrium is established when any metal is placed in a solution of its ions. 

Despite its electrode potential (p. 98), very pure zinc has little or no reaction with dilute acids. If impurities are present, local electrochemical cells are set up (cf the rusting of iron. p. 398) and the zinc reacts readily evolving hydrogen. Amalgamation of zinc with mercury reduces the reactivity by giving uniformity to the surface. Very pure zinc reacts readily with dilute acids if previously coated with copper by adding copper(II) sulphate ... 

Production. Indium is recovered from fumes, dusts, slags, residues, and alloys from zinc or lead—zinc smelting. The source material itself, a reduction bullion, flue dust, or electrolytic slime intermediate, is leached with sulfuric or hydrochloric acid, the solutions are concentrated, if necessary, and cmde indium is recovered as 99+% metal. This impure indium is then refined to 99.99%, 99.999%, 99.9999%, or higher grades by a variety of classical chemical and electrochemical processes. 

The standard electrode potential for zinc reduction (—0.763 V) is much more cathodic than the potential for hydrogen evolution, and the two reactions proceed simultaneously, thereby reducing the electrochemical yield of zinc. Current efficiencies slightly above 90% are achieved in modem plants by careful purification of the electrolyte to bring the concentration of the most harmful impurities, eg, germanium, arsenic, and antimony, down to ca 0.01 mg/L. Addition of organic surfactants (qv) like glue, improves the quaUty of the deposit and the current efficiency. 

The electrochemical process, commercialized in the late 1980s, is the newest available technology and utilizes only caustic and sulfur dioxide as raw materials (359). Anhydrous or solution product can be manufactured by all processes however, the formate and zinc processes typically produce dry product, the amalgam and electrochemical processes typically produce solution product. 

Economic Aspects. U.S. capacity for production of merchant sodium dithionite (soHds basis) was estimated at 93,000 metric tons in 1994. There are three North American producers of sodium dithionite. Hoechst Celanese is the largest producer (68,000 tons capacity) with two formate production locations and one zinc process location. Olin (25,000 t capacity) produces solution product only at two locations using both the amalgam and electrochemical processes. In 1994, Vulcan started a small solution plant in Wisconsin using the Olin electrochemical process. In addition, it is estimated that 13,000 t/yr is produced at U.S. pulp mills using the Borol process from sulfur dioxide and sodium borohydride. Growth is estimated at 2—3%/yr. The... 

Fig. 1. Schematic representation of a battery system also known as an electrochemical transducer where the anode, also known as electron state 1, may be comprised of lithium, magnesium, zinc, cadmium, lead, or hydrogen, and the cathode, or electron state 11, depending on the composition of the anode, may be lead dioxide, manganese dioxide, nickel oxide, iron disulfide, oxygen, silver oxide, or iodine.

M. Klein and A. Charkey, Zinc—Ocygen Battery Development, Electrochemical Society, Atianta, Ga., Oct. 1977. 

Reference 38 is a good guide to the selection of plate thickness test methods. Test methods may vary with the purity and electrochemical activity of the deposit. Metals deposited from commercial plating solutions are seldom pure. For example, zinc deposits from the three commonly used baths, ie, cyanide, chloride, and zincate, vary significantly in purity and activity (39). Standard ASTM test methods for determining plate thickness are... 

Coupling reactions and related fluoroalkylations with polytTuoioalkyl halides are induced by vanous reagents, among them metals such as copper and zinc, or by an electrochemical cell. More recently, examples of carbon-carbon bond forma tion by coupling of unsaturated fluorides have been reported Both acyclic and cyclic fluoroolefins of the type (Rp)2C=CFRp undergo reducUve dimerization on treatment with phosphines [42] (equation 33) The reaction shown in equation 33 IS also accompbshed electrocheimcally but less cleanly [43]... 

Reductive dunenzation to form fluorinated benzopinacols proceeds m the partly fluormated case either with zinc or by photolysis but is not observed with perfluorobenzophenone [651 (equation 53). Trifluoroacetophenone is reduced electrochemically in dimethylformamide to a stable radical anion, which, m the presence ot lithium ion, rapidly dunerizes to pinacol in higher yield than that available by photoreduction [66] (equation 54)... 

An electrochemical reaction is said to be polarized or retarded when it is limited by various physical and chemical factors. In other words, the reduction in potential difference in volts due to net current flow between the two electrodes of the corrosion cell is termed polarization. Thus, the corrosion cell is in a state of nonequilibrium due to this polarization. Figure 4-415 is a schematic illustration of a Daniel cell. The potential difference (emf) between zinc and copper electrodes is about one volt. Upon allowing current to flow through the external resistance, the potential difference falls below one volt. As the current is increased, the voltage continues to drop and upon completely short circuiting (R = 0, therefore maximum flow of current) the potential difference falls toward about zero. This phenomenon can be plotted as a polarization diagram shown in Figure 4-416. 

Polarization can be divided into activation polarization and concentration polarization , Activation polarization is an electrochemical reaction that is controlled by the reaction occurring on the metal-electrolyte interface. Figure 4-418 illustrates the concept of activation polarization where hydrogen is being reduced over a zinc surface. Hydrogen ions are adsorbed on the metal surface they pick up electrons from the metal and are reduced to atoms. The atoms combine to... 

During the operation of the cell (or during the direct interaction of zinc metal and cupric ions in a beaker) the zinc is oxidised to Zn and corrodes, and the Daniell cell has been widely used to illustrate the electrochemical mechanism of corrosion. This analogy between the Daniell cell and a corrosion cell is perhaps unfortunate, since it tends to create the impression that corrosion occurs only when two dissimilar metals are placed in contact and that the electrodes are always physically separable. Furthermore, although reduction of Cu (aq.) does occur in certain corrosion reactions it is of less importance than reduction of HjO ions or dissolved oxygen. 

For these reasons a somewhat different approach will be adopted here, and an attempt will be made to show how a corrosion reaction may be represented by a well-defined reversible electrochemical cell, although again there are a number of difficulties. Consider the corrosion of metallic zinc in a reducing acid... 

In certain alloys and under certain environmental conditions selective removal of one metal (the most electrochemically active) can occur resulting in either localised attack, with the consequent possibility of perforation (plug type), or in a more uniform attack (layer type) that results in a weakening of the strength of the component. Although the selective removal of metals such as Al, Fe, Co, Ni and Cr from their alloys is known, the most prevalent form of de-alloying is the selective removal of zinc from the brasses —a phenomenon that is known as dezincification. 

There is considerable metallographic and electrochemical evidence in support of each theory and it is of interest to note that two of the most authoritative works on corrosion appear to support opposite views — Uhlig favours the selective dissolution of zinc theory, whereas Fontana and Greene favour the dissolution-precipitation theory. 

Lucey concludes from his electrochemical studies that dezincification involves anodic dissolution of both copper and zinc followed by the cathodic deposition of copper, and on this basis he has explained why arsenic is capable of inhibiting dezincification of a-brass but not of a 3-brass. 

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