Cell, amalgam reactions

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 ... 

Chloiine is pioduced at the anode in each of the three types of electrolytic cells. The cathodic reaction in diaphragm and membrane cells is the electrolysis of water to generate as indicated, whereas the cathodic reaction in mercury cells is the discharge of sodium ion, Na, to form dilute sodium amalgam. 

The catholyte from diaphragm cells typically analyzes as 9—12% NaOH and 14—16% NaCl. This ceUHquor is concentrated to 50% NaOH in a series of steps primarily involving three or four evaporators. Membrane cells, on the other hand, produce 30—35% NaOH which is evaporated in a single stage to produce 50% NaOH. Seventy percent caustic containing very Httie salt is made directiy in mercury cell production by reaction of the sodium amalgam from the electrolytic cells with water in denuders. 

Overvoltages for various types of chlor—alkali cells are given in Table 8. A typical example of the overvoltage effect is in the operation of a mercury cell where Hg is used as the cathode material. The overpotential of the H2 evolution reaction on Hg is high hence it is possible to form sodium amalgam without H2 generation, thereby eliminating the need for a separator in the cell. 

In the case of the alkaline manganese dioxide cell, only high quaUty synthetic manganese dioxide, typically an EMD (224), is used and graphite is the cathode. The anode is an amalgamated 2inc. Potassium hydroxide serves as the electrolyte and the reaction can be summari2ed as follows ... 

Manufacture is either by reaction of molten sodium with methyl alcohol or by the reaction of methyl alcohol with sodium amalgam obtained from the electrolysis of brine in a Castner mercury cell (78). Both these methods produce a solution of sodium methylate in methanol and the product is offered in two forms a 30% solution in methanol, and a soHd, which is a dry, free-flowing white powder obtained by evaporating the methanol. The direct production of dry sodium methylate has been carried out by the introduction of methanol vapors to molten sodium in a heavy duty agitating reactor. The sohd is supphed in polyethylene bags contained in airtight dmms filled in a nitrogen atmosphere. 

Another important primary battery is the mercury cell. It usually comes in very small sizes and is used in hearing aids, watches, cameras, and some calculators. The anode of this cell is a zinc-mercury amalgam the reacting species is zinc. The cathode is a plate made up of mercury(II) oxide, HgO. The electrolyte is a paste containing HgO and sodium or potassium hydroxide. The electrode reactions are... 

The decrease in free energy (—AG) which provides the driving force in a cell may ensue either from a chemical reaction or from a physical change. In particular, one often studies cells in which the driving force is a change in concentration (almost always a dilution process). These cells are called concentration cells. The alteration in concentration can take place either in the electrolyte or in the electrodes. As examples of alterations in concentration in electrodes, mention may be made of amalgams or alloy electrodes with different concentrations of the solute metal and in gas electrodes with different pressures of the gas. 

N 0 chemical change takes place, and the reaction comprises the transfer of zinc from an amalgam of one concentration to that of another concentration. The emf of such a cell, which necessarily possesses T° = 0, is ... 

Potentiometric EDTA titrations are best carried out with a mercury pool electrode (Figure 5.6) or a gold amalgam electrode. When this electrode dips into a solution containing the analyte together with a small amount of added Hg-EDTA complex, three interdependent reactions occur. For example, at pH = 8 the half cell reaction (a) which determines the electrode potential is related to the solution equilibrium by (b) and (c). 

The Kolbe reaction is earned out in an undivided cell with closely spaced platinum electrodes. Early examples used a concentrated, up to 50 %, aqueous solution of an alkali metal salt of the carboxylic acid and the solution became strongly alkaline due to hydrogen evolution at the cathode. Ingenious cells were devised with a renewing mercury cathode, which allowed removal of alkali metal amalgam. These experimental conditions have been replaced by the use of a solution of the carboxylic acid in methanol partially neutralised by sodium methoxide or trieth-... 

Contemporary mercury cells are based on the original designs of Castner and Kellner. Mercury is used as the cathode. Sodium produced forms an amalgam, which passes to a water chamber. Here graphite is used to catalyze the dissociation of sodium from the mercury. The sodium reacts with water to produce sodium hydroxide according to the reaction 2Na(s) + 2H —> 2NaOH. + H. .. 

All species are aqueous unless otherwise indicated. The reference state for amalgams is an infinitely dilute solution of the element in Hg. The temperature coefficient, dE°/dT, allows us to calculate the standard potential, E°(T), at temperature T E°(T) — Ec + (dE°/dT)AT. where A T is T — 298.15 K. Note the units mVIK for dE°ldT. Once you know E° for a net cell reaction at temperature T, you can find the equilibrium constant, K, for the reaction from the formula K — lOnFE°,RTln w, where n is the number of electrons in each half-reaction, F is the Faraday constant, and R is the gas constant. 

These processes differ by the reaction which occur at the cathodes. At a solid cathode which is generally made of iron, hydrogen ions are discharged and simultaneously alkali hydroxide is formed in the electrolyte. At the mercury cathode metallic sodium or potassium is deposited which forms amalgam. This intermediary product is subsequently decomposed by water in a separate compartment whereby hydroxide and hydrogen are obtained while the liberated (denuded) mercury is returned into the electrolytic cell. 

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