1. Electrochemistry
the study of the interchange of chemical and electrical energy

2. Electrochemistry Terminology #1
Oxidation – the loss of electrons, increase in oxidation number
Na(s)  Na+ + e-
Reduction – the gain of electrons, decrease of oxidation number
Cl2 + 2e-  2Cl-

3. Electrochemistry Terminology #2
An old memory device for oxidation and reduction goes like this…
LEO says GER
Lose Electrons = Oxidation
Gain Electrons = Reduction

4. Electrochemistry Terminology #3
Oxidizing agent
The substance that is reduced is the oxidizing agent
Reducing agent
The substance that is oxidized is the reducing agent

5. Electrochemistry Terminology #4
Voltaic or Galvanic cell
is a battery but not a dry cell; generates useful electrical energy
Electrolytic cell
Requires useful electrical energy to drive a thermodynamically unfavorable reaction.

6. Electrochemistry Terminology #5
Anode
The electrode where oxidation occurs
Cathode
The electrode where reduction occurs
Memory device:
Reduction
at the
Cathode

7. Table of Reduction Potentials
Measured against the Standard Hydrogen Electrode

8. Measuring Standard Electrode Potential
Potentials are measured against a hydrogen ion reduction reaction, which is arbitrarily assigned a potential of zero volts.

9. Galvanic (Electrochemical) Cells
Spontaneous redox processes have:
A positive
cell potential, E0
A negative free energy change, (-G)

10. Zn - Cu Galvanic Cell From a table of reduction potentials:
Zn2+ + 2e-  Zn E = -0.76V
Cu2+ + 2e-  Cu E = +0.34V

11. Zn - Cu Galvanic Cell Zn  Zn2+ + 2e- E = +0.76V
Cu2+ + 2e-  Cu E = +0.34V
Zn  Zn2+ + 2e E = +0.76V
Zn + Cu2+  Zn2+ + Cu E0 = V

12. Line Notation Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s) | || |
An abbreviated representation of an electrochemical cell
Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)
Anode
material
Anode
solution
Cathode
solution
Cathode
material | || |

13. Calculate cell potential
Eocell = EoCathode – Eo Anode

14. Calculating G0 for a Cell
G0 = -nFE0
n = moles of electrons in balanced redox equation
F = Faraday constant = 96,485 coulombs/mol e-
Zn + Cu2+  Zn2+ + Cu E0 = V

15. The Nernst Equation R = 8.31 J/(molK) T = Temperature in K
Standard potentials assume a concentration of 1 M. The Nernst equation allows us to calculate potential when the two cells are not 1.0 M.
R = 8.31 J/(molK)
T = Temperature in K
n = moles of electrons in balanced redox equation
F = Faraday constant = 96,485 coulombs/mol e-

16. Nernst Equation Simplified
At 25 C (298 K) the Nernst Equation is simplified this way:

17. Equilibrium Constants and Cell Potential
At equilibrium, forward and reverse reactions occur at equal rates, therefore:
The battery is “dead”
The cell potential, E, is zero volts
Modifying the Nernst Equation (at 25 C):

18. Calculating an Equilibrium Constant from a Cell Potential
Zn + Cu2+  Zn2+ + Cu E0 = V

19. Both sides have the same components but at different concentrations.
???
Concentration Cell
Both sides have the same components but at different concentrations.
Step 1: Determine which side undergoes oxidation, and which side undergoes reduction.

20. Both sides have the same components but at different concentrations.
???
Concentration Cell
Both sides have the same components but at different concentrations.
Anode
Cathode
The 1.0 M Zn2+ must decrease in concentration, and the 0.10 M Zn2+ must increase in concentration
Zn2+ (1.0M) + 2e-  Zn (reduction)
Zn  Zn2+ (0.10M) + 2e- (oxidation)
Zn2+ (1.0M)  Zn2+ (0.10M)

21. Both sides have the same components but at different concentrations.
Concentration Cell
???
Concentration Cell
Both sides have the same components but at different concentrations.
Anode
Cathode
Step 2: Calculate cell potential using the Nernst
Equation (assuming 25 C).
Zn2+ (1.0M)  Zn2+ (0.10M)

22. Nernst Calculations
Zn2+ (1.0M)  Zn2+ (0.10M)

23. Electrolytic Processes
Electrolytic processes are NOT spontaneous. They have:
A negative
cell potential, (-E0)
A positive free energy change, (+G)

24. Electrolysis of Water In acidic solution Anode rxn: Cathode rxn:
-1.23 V
Cathode rxn:
-0.83 V
-2.06 V

25. Electroplating of Silver
Anode reaction:
Ag  Ag+ + e-
Cathode reaction:
Ag+ + e-  Ag
Electroplating requirements:
1. Solution of the plating metal
2. Anode made of the plating metal
3. Cathode with the object to be plated
4. Source of current

26. Solving an Electroplating Problem
Q: How many seconds will it take to plate out 5.0 grams of silver from a solution of AgNO3 using a 20.0 Ampere current?
Ag+ + e-  Ag
5.0 g
1 mol Ag
1 mol e- C
1 s
1 mol e-
20.0 C g
1 mol Ag
= 2.2 x 102 s