1. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 1 Electrochemistry The study of the interchange of chemical and electrical energy.

2. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 2 Review of Terms oxidation-reduction (redox) reaction: involves a transfer of electrons from the reducing agent to the oxidizing agent. oxidation: loss of electrons reduction: gain of electrons

3. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 3 Half-Reactions The overall reaction is split into two half-reactions, one involving oxidation and one reduction. 8H + + MnO 4  + 5Fe 2+  Mn 2+ + 5Fe 3+ + 4H 2 O Reduction: 8H + + MnO 4  + 5e   Mn 2+ + 4H 2 O Oxidation: 5Fe 2+  5Fe 3+ + 5e 

4. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 4 Figure 17.1 Schematic of a Method to Separate the Oxidizing and Reducing Agents of a Redox Reaction

5. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 5 Galvanic Cell A device in which chemical energy is changed to electrical energy.

6. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 6 Figure 17.2 Galvanic Cells

7. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 7 Anode and Cathode OXIDATION occurs at the ANODE. REDUCTION occurs at the CATHODE.

8. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 8 Figure 17.3 An Electrochemical Process Involves Electron Transfer at the Interface Between the Electrode and the Solution

9. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 9 Figure 17.4 Digital Voltmeters

10. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 10 Figure 17.5 A Zn/H Galvanic Cell

11. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 11 Figure 17.6 A Zn/Cu Galvanic Cell

12. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 12 Figure 17.7 A Schematic of a Galvanic Cell

13. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 13 Figure 17.8 A Schematic of a Galvanic Cell

14. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 14 Cell Potential Cell Potential or Electromotive Force (emf): The “pull” or driving force on the electrons.

15. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 15 Standard Reduction Potentials The E  values corresponding to reduction half-reactions with all solutes at 1M and all gases at 1 atm. Cu 2+ + 2e   Cu E  = 0.34 V vs. SHE SO 4 2  + 4H + + 2e   H 2 SO 3 + H 2 O E  = 0.20 V vs. SHE

16. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 16 emf and Work

17. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 17 Free Energy and Cell Potential  G  =  nFE  n = number of moles of electrons F = Faraday = 96,485 coulombs per mole of electrons

18. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 18 Concentration Cell...a cell in which both compartments have the same components but at different concentrations.

19. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 19 Figure 17.10 A Concentration Cell Containing Iron Electrode and Different Concentrations of Fe2+ Ion in the Two Compartments

20. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 20 Figure 17.9 A Concentration Cell That Contains a Sliver Electrode and Aqueous Silver Nitrate in Both Compartments

21. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 21 The Nernst Equation We can calculate the potential of a cell in which some or all of the components are not in their standard states.

22. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 22 Calculation of Equilibrium Constants for Redox Reactions At equilibrium, E cell = 0 and Q = K.

23. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 23 Batteries A battery is a galvanic cell or, more commonly, a group of galvanic cells connected in series.

24. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 24 Figure 17.13 One of the Six Cells in Storage Battery a 12-V Lead Storage Battery

25. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 25 Figure 17.14 A Common Dry Cell Battery

26. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 26 Figure 17.15 A Mercury Battery

27. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 27 Fuel Cells...galvanic cells for which the reactants are continuously supplied. 2H 2 (g) + O 2 (g)  2H 2 O(l) anode: 2H 2 + 4OH   4H 2 O + 4e  cathode: 4e  + O 2 + 2H 2 O  4OH 

28. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 28 Figure 17.16 Schematic of the Hydrogen-Oxygen Fuel Cell

29. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 29 Corrosion Some metals, such as copper, gold, silver and platinum, are relatively difficult to oxidize. These are often called noble metals.

30. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 30 Figure 17.17 The Electrochemical Corrosion of Iron

31. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 31 Figure 17.18 Cathodic Protection

32. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 32 Electrolysis...forcing a current through a cell to produce a chemical change for which the cell potential is negative.

33. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 33 Figure 17.19 (a) A Standard Galvanic Cell (b) A Standard Electrolytic Cell

34. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 34 Figure 17.22 A Schematic Diagram of an Electrolytic Cell for Producing Aluminum by the Hall-Heroult Process

35. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 35 Figure 17.25 The Downs Cell for the Electrolysis of Molten Sodium Chloride

36. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 36 Figure 17.26 The Mercury Cell for Production of Chlorine and Sodium Hydroxide

37. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 37 Stoichiometry of Electrolysis 4 How much chemical change occurs with the flow of a given current for a specified time? current and time  quantity of charge  moles of electrons  moles of analyte  grams of analyte