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Electrochemistry

Electrochemistry

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Electrochemistry
Chemical reactions at an electrode, galvanic and electrolytic cells
A Chem1 Reference Text
Stephen K. Lower \u2022 Simon Fraser University1
Table of contents
1: Chemistry and electricity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Electroneutrality. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Potential differences at interfaces. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2: Electrochemical cells. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

Transport of charge within the cell. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 Cell description conventions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 Electrodes and electrode reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 Standard half-cell potentials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 Reference electrodes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

3: Prediction and significance of cell potentials. . . . . . . . . . . . . . . . . . . . . . . . . 12
Cell potentials and the electromotive series. . . . . . . . . . . . . . . . . . . . . . . . . . 13
Cell potentials and free energy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4: The Nernst equation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

Concentration cells. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 Thermodynamics of galvanic cells. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 Analytical applications of the Nernst equation. . . . . . . . . . . . . . . . . . . . . . . 23 Membrane potentials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

5: Batteries and fuel cells. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

The ideal and the real. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 Primary and secondary batteries. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29 Timeline of battery development. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30 The fuel cell. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

6: Electrochemical Corrosion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
7: Electrolytic cells. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35

Electrolysis in aqueous solutions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36 Faraday's laws of electrolysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37 Industrial electrolytic processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38

1. To contact the author, please use the Web form athttp://www.chem1.com/VT_mail.html
This document covers Electrochemistry at a level appropriate for \ufb01rst-year college chemistry.

It was last modi\ufb01ed on 23 September 2004 .
It can be downloaded fromhttp://www.chem1.com/acad/pdf/elchem.pdf
A Web-based version is available athttp://www.chem1.com/acad/webtext/elchem/.

The Chem1 Virtual Textbook is a collection of reference textbook chapters and tutorial units providing in-depth coverage of topics in college-level General Chemistry.

For a more information on the Virtual Textbook contents, see
http://www.chem1.com/acad/webtext/virtualtextbook.html
Page 3
1 \u2022 Chemistry and electricity
Th e conn ection between chemistry and electricity is a very old one, going back to ALESSAN-
DRO VOLTA'S discovery, in 1793, tha t electricity could be pr odu ced by placing two dissimilar
metals on opposite sides of a moistened pa per. In 1800, Nicholson and Ca rlisle, using Volta's
pr imitive battery as a sour ce, showed tha t an electric cur rent could decompose wa ter int o

oxygen and hydr ogen. Th is wa s sur ely one of the most significant experiment s in the history of chemistry, for it implied tha t the atoms of hydr ogen and oxygen were associated with pos- itive and negative electric cha rges, wh ich mu st be the sour ce of the bonding forces between them. By 1812, the Swedish chemist BERZELIUS could pr opose tha t all atoms are electrified, hydr ogen and the metals being positive, the nonm etals negative. In electrolysis, the applied voltage wa s thought to overpower the attraction between these opposite cha rges, pu lling the electrified atoms apa rt in the form of io n s (na med by Berzelius from the Gr eek for \u201ctravel- ers\u201d). It would be almost exactly a hu ndred years later before the sha red electron pa ir theory of G.N. LEWIS could offer a significant improvement over this view of chemical bonding.

Meanwhile the use of electricity as a means of bringing about chemical cha nge cont inu ed to play a cent ral role in the developm ent of chemistry. HUMPHREY DAVEY pr epa red the first ele- ment al sodium by electrolysis of a sodium hydr oxide melt. It wa s left to Da vey's former

assistant , MICH AEL FARADAY, to show tha t there is a direct relation between the amoun t of electric cha rge pa ssed thr ough the solut ion and the qua nt ity of electrolysis pr odu cts. JAME S CLERK MAXWE LL imm ediately saw this as evidence for the \u201cmolecule of electricity\u201d, but the world would not be recept ive to the concept of the electron un til the end of the cent ur y.

1.1 Electroneutrality

Na tur e seems to strongly discour age any pr ocess tha t would lead to an excess of positive or negative cha rge in ma tter. Su ppose, for example, tha t we imm erse a piece of zinc metal in pu re wa ter. A sma ll nu mber of zinc atoms go int o solut ion as Zn ions, leaving their electrons behind in the metal:

Zn(s)\u2192 Zn2+ + 2e\u2013
As this pr ocess goes on, the electrons wh ich rema in in the zinc cause a negative cha rge to

build up within the metal wh ich ma kes it increasingly difficult for additiona l positive ions to leave the metallic ph ase. A similar buildu p of positive cha rge in the liquid ph ase adds to this inh ibition. Very soon, therefore, the pr ocess comes to a ha lt, resulting in a solut ion in wh ich the concent ration of Zn2+ is still too low (aroun d 10\u201310M ) to be detected by ordina ry chemi- cal means.

Fig. 1: Oxidation of metallic zinc in contact with water

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