Reacting electrodes

Reacting Electrodes with Soluble and Insoluble Reaction Products (Reactants)... 

In addition to metals, other substances that are solids and have at least some electronic conductivity can be used as reacting electrodes. During reaction, such a solid is converted to the solid phase of another substance (this is called a solid-state reaction), or soluble reaction products are formed. Reactions involving nomnetaUic solids occur primarily in batteries, where various oxides (MnOj, PbOj, NiOOH, Ag20, and others) and insoluble salts (PbS04, AgCl, and others) are widely used as electrode materials. These compounds are converted in an electrochemical reaction to the metal or to compounds of the metal in a different oxidation state. 

Zinc is also used in making alloys, the most important of which is brass (the alloy with copper), and as a reacting electrode in dry cells and wet cells. 

Also, Faraday s law can obviously have nothing to say concerning which ions in an electrolyte will take part in an electrochemical reaction. In fact, the current can be carried through an electrolyte by ions which do not enter into the electrochemical reactions by which the current enters and leaves the electrolyte. For instance, in the electrolysis of a sodium chloride solution with inert, ie., non-reacting, electrodes, the current is carried, except for an almost negligible amount, by the sodium ions, Na+, and the chloride ions, Cl". However, for low current densities, the electrochemical reactions at the anode and cathode are... 

The zinc-zinc ion, the hydrogen, and the silver-silver chloride electrodes are typical of three common types of aqueous half-cell. A fourth type is the so-called redox half-cell, which involves, for example, both ferrous and ferric ions in solution. A non-reacting electrode, usually of platinum, facilitates the following half-cell process ... 

Reacting electrodes, e.g. the electrolysis of CUSO4 solution between Cu electrodes. Cu and S04 are the current-carrying ions. Cu is deposited on the cathode and Cu passes from the anode into... 

By analogy, ammonium salts should behave as acids in liquid ammonia, since they produce the cation NH4 (the solvo-cation ), and soluble inorganic amides (for example KNHj, ionic) should act as bases. This idea is borne out by experiment ammonium salts in liquid ammonia react with certain metals and hydrogen is given off. The neutralisation of an ionic amide solution by a solution of an ammonium salt in liquid ammonia can be carried out and followed by an indicator or by the change in the potential of an electrode, just like the reaction of sodium hydroxide with hydrochloric acid in water. The only notable difference is that the salt formed in liquid ammonia is usually insoluble and therefore precipitates. 

Graphite reacts with alkali metals, for example potassium, to form compounds which are non-stoichiometric but which all have limiting compositions (for example K C) in these, the alkaU metal atoms are intercalated between the layers of carbon atoms. In the preparation of fluorine by electrolysis of a molten fluoride with graphite electrodes the solid compound (CF) polycarbon fluoride is formed, with fluorine on each carbon atom, causing puckering of the rings. 

Bromine has a lower electron affinity and electrode potential than chlorine but is still a very reactive element. It combines violently with alkali metals and reacts spontaneously with phosphorus, arsenic and antimony. When heated it reacts with many other elements, including gold, but it does not attack platinum, and silver forms a protective film of silver bromide. Because of the strong oxidising properties, bromine, like fluorine and chlorine, tends to form compounds with the electropositive element in a high oxidation state. 

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 ... 

Membrane Potentials Ion-selective electrodes, such as the glass pH electrode, function by using a membrane that reacts selectively with a single ion. figure 11.10 shows a generic diagram for a potentiometric electrochemical cell equipped with an ion-selective electrode. The shorthand notation for this cell is... 

An electrode that responds to the concentration of a substrate by reacting the substrate with an immobilized enzyme, producing an ion that can be monitored with an ion-selective electrode. 

Coulometric methods of analysis are based on an exhaustive electrolysis of the analyte. By exhaustive we mean that the analyte is quantitatively oxidized or reduced at the working electrode or reacts quantitatively with a reagent generated at the working electrode. There are two forms of coulometry controlled-potential coulometry, in which a constant potential is applied to the electrochemical cell, and controlled-current coulometry, in which a constant current is passed through the electrochemical cell. 

Since the current due to the oxidation of H3O+ does not contribute to the oxidation of Fe +, the current efficiency of the analysis is less than 100%. To maintain a 100% current efficiency the products of any competing oxidation reactions must react both rapidly and quantitatively with the remaining Fe +. This may be accomplished, for example, by adding an excess of Ce + to the analytical solution (Figure 11.24b). When the potential of the working electrode shifts to a more positive potential, the first species to be oxidized is Ce +. 

The Ce + produced at the working electrode rapidly mixes with the solution, where it reacts with any available Fe +. 

In 1976 the first section of a new smelting process that requited 30% less electric power than the best Hah-HAroult cehs came on stream. In this process, alumina, carbon, and chlorine reacted to produce aluminum chloride and carbon dioxide. The aluminum chloride was electrolyzed in bipolar electrode cehs to produce aluminum and chlorine and the chlorine was recycled to make more aluminum chloride. After six years of operation, the plant... 

If the cations in solution are condensable as a soHd, such as copper, they can plate out on the cathode of the cell. As the same time, perhaps some hydrogen is also produced at the cathode. The SO can react with a copper anode material by taking it into solution to replace the lost copper ions. Thus the anode is a consumable electrode in the process. 

Cyanide compounds are classified as either simple or complex. It is usually necessary to decompose complex cyanides by an acid reflux. The cyanide is then distilled into sodium hydroxide to remove compounds that would interfere in analysis. Extreme care should be taken during the distillation as toxic hydrogen cyanide is generated. The cyanide in the alkaline distillate can then be measured potentiometricaHy with an ion-selective electrode. Alternatively, the cyanide can be determined colorimetricaHy. It is converted to cyanogen chloride by reaction with chloramine-T at pH <8. The CNCl then reacts with a pyridine barbituric acid reagent to form a red-blue dye. 

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