Spontaneous potentials and electrochemical cells

Selective leach techniques have become popular in mineral exploration for the treatment of geochemical soil samples. Their popularity stems from the fact that they are considered to extract selectively a particular hydromorphically-transported component of metals in the sample and, as such, show better anomaly-to-background contrasts than do conventional strong acid digestions which dissolve most of the chemical matrix of the soil. 

During the weathering process, elements can disperse from source mineralisation by a variety of chemical processes. For reasons discussed below, electrochemical processes are increasingly thought to be the primary transport mechanism in environments of thick, young, exotic (i.e., transported) overburden. They are also likely to operate in other environments but their dominance as a transport mechanism is less certain. This chapter presents the principles behind electrochemical masj transport and discusses the role of natural geoelectrochemical processes in the formation of selective leach and conventional geochemical soil anomalies. 

This chapter is published with permission of the Senior Manager, Sedimentary Geoscience Section, Ontario Geological Survey. 

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Spontaneous potentials and electrochemical cells Post overburden deposition... 

The iron half-reaction has the more negative electrode potential and therefore repels electrons and undergoes oxidation. The lead half-reaction has the more positive electrode potential and therefore attracts electrons and undergoes reduction. Therefore, the reaction is spontaneons as written. (The reaction pairs the reduction of Pb with the reverse of a half-reaction below it in Table 18.1—such pairings are always spontaneous.) The corresponding electrochemical cell is shown in Figure 18.10 . 

C19-0123. A cell is set up using two zinc wires and two solutions, one containing 0.250 M ZnCl2 solution and the other containing 1.25 M Zn (N03)2 solution, (a) What electrochemical reaction occurs at each electrode (b) Draw a molecular picture showing spontaneous electron transfer processes at the two zinc electrodes, (c) Compute the potential of this cell. 

In this section, you learned about electrolytic cells, which convert electrical energy into chemical energy. You compared the spontaneous reactions in galvanic cells, which have positive cell potentials, with the non-spontaneous reactions in electrolytic cells, which have negative cell potentials. You then considered cells that act as both galvanic cells and electrolytic cells in some common rechargeable batteries. These batteries are an important application of electrochemistry. In the next two sections, you will learn about many more electrochemical applications. 

The electrochemical cell with zinc and copper electrodes had an overall potential difference that was positive (+1.10 volts), so the spontaneous chemical reactions produced an electric current. Such a cell is called a voltaic cell. In contrast, electrolytic cells use an externally generated electrical current to produce a chemical reaction that would not otherwise take place. 

A positive standard cell potential tells you that the cathode is at a higher potential than the anode, and the reaction is therefore spontaneous. What do you do with a cell that has a negative " gii Electrochemical cells that rely on such nonspontaneous reactions cire called electrolytic cells. The redox reactions in electroljdic cells rely on a process called electrolysis. These reactions require that a current be passed through the solution, forcing it to split into components that then fuel the redox reaction. Such cells are created by applying a current source, such as a battery, to electrodes placed in a solution of molten salt, or salt heated until it melts. This splits the ions that make up the salt. 

Is an acidified aqueous permanganate solution a more powerful oxidizing agent than an acidified aqueous dichromate solution under standard conditions Design an electrochemical cell that could be used to answer the question. Write the chemical equation for the spontaneous reaction between the two reagents and determine the standard cell potential. 

Intercalation reactions of the dichalcogenides with alkali metals are redox reactions in which the host lattice is reduced by electron transfer from the alkali metal. Lithium and sodium intercalation reactions, for example, have been studied using cells of the type Li/LiC104-dioxolane/MX2 andNa/Nal-propylene carbonate/MX2. The reactions proceed spontaneously to form the intercalation compound if the cell is short circuited alternatively, a reverse potential can be apphed to control the composition of the final product. Apart from their application in synthesis, such electrochemical cells can be used to obtain detailed thermodynamic information and to establish phase relations by measuring the dependence of the equilibrium cell voltage on composition (see Figure 4). 

Fig. 4.6.1. Schematic diagram showing the direction of the emf, electrochemical potential gradient, electrostatic potential gradient, and electric field during spontaneous operation of a cell operating in conformity with Conventions 1 and 2, described below.

Virtually all discussion in mineral exploration regarding SP cells and associated electrochemical phenomena assumes the presence of an electronic conductor. There has been little discussion of voltaic cells that involve no electronic conduction, but these cells undoubtedly exist. The nervous systems and muscles of organisms use the transfer of purely ionic current with no electronic conduction. Spontaneous potentials in the absence of electronic conductors have long been recognised in the petroleum industry and result from salinity and redox differences between strata. The presence of spontaneous potentials has also been noted in relatively thick overburden overlying mineralisation in the absence of an overburden conductor of electrons (Burr, 1982). Since electrons cannot move freely in an electrolyte solution, many of these cases must involve electrochemical cells of sorts in which current is transferred exclusively in the form of ions. 

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