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SUMMARY
A galvanic cell is composed of two half-cells, each containing an electrode in contact with an electrolyte reactant. A spontaneous redox reaction is thus divided into separate oxidation and reduction half-reactions, with the electron transfer occurring through an external electrical circuit. Reduction occurs at the cathode; oxidation occurs at the anode. In a galvanic cell, the cathode is positively charged and the anode is negatively charged. The half-cells must be connected electrolytically by a salt bridge to complete the electrical circuit, which permits electrical neutrality to be maintained by allowing cations to move toward the cathode and anions toward the anode. The potential (expressed in volts) produced by a cell is equal to the standard cell potential when all ion concentrations are 1.00 M and the partial pressures of any gases involved equal 1.00 atm and the temperature is 25.0 C. The standard cell potential is the difference between the standard reduction potentials of the half-cells. In the spontaneous reaction, the half-cell with the higher standard reduction potential undergoes reduction and forces the other to undergo oxidation. The standard reduction potentials of isolated half-cells can't be measured, but values are assigned by choosing the hydrogen electrode as a reference electrode; its standard reduction potential is assigned a value of exactly 0 V. Species more easily reduced than H1 have positive standard reduction potentials; those less easily reduced have negative standard reduction potentials. Standard reduction potentials can be used to predict the cell reaction. They can also be used to predict spontaneous redox reactions not occurring in galvanic cells and to predict whether or not a given reaction is spontaneous. Often, they can be used to determine the products of electrolysis reactions. Standard reduction potentials are used to calculate . Since reduction potentials under nonstandard conditions are often numerically close to standard reduction potentials, we can usually use standard reduction potentials to make predictions about reactions with nonstandard conditions. The predictions above about spontaneous reactions, cell reactions, electrolysis products, and reactions outside of galvanic cells are usually valid under nonstandard conditions also.

Galvanic Cells.

Thermodynamics and Cell Potentials.

from .They all involve the faraday, per mole of electrons (1

The values of G and K for a reaction can be calculated c , a constant equal to the number of coulombs (C) of charge

= 96,500 C/mol e - ). The Nernst equation relates the cell potential to the

standard cell potential and the reaction quotient. It allows the cell potential to be calculated for ion concentrations other than 1.00 M. The important equations are summarized as

In an electrolytic cell, a flow of electricity causes an otherwise nonspontaneous reaction to occur. A negatively charged cathode causes reduction of one reactant and a positively charged anode causes oxidation of another. Ion movement instead of electron transport occurs in the electrolyte. The electrode reactions are determined by which species is most easily reduced and which is most easily oxidized, but in aqueous solutions complex surface effects at the electrodes can alter the natural order. In the electrolysis of water, an electrolyte must be present to maintain electrical neutrality at the electrodes.

Electrolysis.

The product of current (amperes) and time (seconds) gives coulombs. This relationship and the half-reactions that occur at the anode or cathode permit us to relate the amount of chemical change to measurements of current and time.

Quantitative Aspects of Electrochemical Reactions. Practical Galvanic Cells.

The lead storage battery and the nickelcadmium (nicad) battery are secondary cells and are rechargeable. The state of charge of the lead storage battery can be tested with a hydrometer, which measures the density of the sulfuric acid electrolyte. The zincmanganese dioxide cell (the Leclanch cell or common dry cell) and the common alkaline battery (which uses essentially the same reactions as the less expensive dry cell) are primary cells and are not rechargeable. The rechargeable nickelmetal hydride (NiMH) battery uses hydrogen contained in a metal alloy as its anode reactant and has a higher energy density than the nicad battery. Primary

lithiummanganese dioxide cells and rechargeable lithium ion cells produce a large cell potential and have a very high energy density. Lithium ion cells store and release energy by transferring lithium ions between electrodes where the Li+ ions are intercalated between layers of atoms in the electrode materials. Fuel cells, which have high thermodynamic efficiencies, are able to provide continuous power because they consume fuel that can be fed continuously. Electroplating, the production of aluminum, the refining of copper, and the electrolysis of molten and aqueous sodium chloride are examples of practical applications of electrolysis.

Applications of Electrolysis.

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