Chem1112 – Spring 2025
Chapter 17
Electrochemistry
Why Electrochemistry?
- Understand and prevent corrosion
- Understand and mimic photosynthesis
- Design smaller, lighter and longer-lasting batteries for laptops, cell phones, etc.
- Develop new waste treatments
- Etc.
Outline
- Balancing Redox Reactions
- Galvanic (Voltaic) Cells
- Standard Reduction Potentials
- Spontaneity of Redox Reactions
- Batteries
- Electrolysis
- Corrosion
Electrochemical Reactions
Electron transfer reactions.
Oxidation:
Reduction:
H+ oxidizes Zn: H+ is the oxidizing agent.
Zn reduces H+: Zn is the reducing agent.
Activity Series
Oxidants and Reductants
Assigning Oxidation Numbers
1. Elements in their elemental form have an oxidation number of 0.
2. The oxidation number of a monatomic ion is the same as its charge.
3. Nonmetals tend to have negative oxidation numbers, although some are positive in certain compounds or ions.
- Oxygen has an oxidation number of −2, except in the peroxide ion, which has an oxidation number of −1.
- Hydrogen is −1 when bonded to a metal, and +1 when bonded to a nonmetal.
Assigning Oxidation Numbers
4. Nonmetals tend to have negative oxidation numbers, although some are positive in certain compounds or ions.
– Fluorine is ALWAYS −1.
– Other halogens, −1 when bonded to metals and other less electronegative atoms. Can have positive oxidation
number when bonded to more electronegative atoms.
5. The sum of the oxidation numbers in a neutral compound is 0.
6. The sum of the oxidation numbers in a polyatomic ion is the charge on the ion.
17.1: Determine the oxidation number of each element in the following compounds.
(a) Ag2Cr2O7 (b) KMnO4 (c) CaMnO4
Balancing Red-Ox Reactions
The half-reaction method
17.2: Balance the following redox equation
Au3+ (aq) + Cu (s) Au (s) + Cu2+ (aq)
Balancing Red-Ox Reactions
The half-reaction method
17.3: Balance the following redox equation (in acidic solution)
H2O2 (aq) + MnO4- (aq) O2 (g) + Mn2O3 (s)
Balancing Red-Ox Reactions
The half-reaction method
17.4: Balance the following redox equation (in basic solution)
H2O2 (aq) + MnO4- (aq) O2 (g) + MnO2 (s)
One last example
Balance the following redox equation (in acidic solution)
NO3- (aq) + Cu (s) Cu2+ (aq) + NO (g)
Electrochemistry
Voltaic Cells
Electrochemistry
Voltaic Cells
Voltaic (Galvanic) Cells
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
Electromotive Force (emf)
Potential difference between the anode and cathode
Also called cell potential, Ecell.
Units of E: Volt
Joule
1 Volt = 1
Coulomb
Standard Hydrogen Electrode (SHE)
E˚H+(aq, 1M)/H2(g, 1 atm) = 0.000V (by definition)
2 H+(aq, 1M) + 2e− ⎯→ H2(g, 1 atm)
Standard Hydrogen Electrode (SHE)
E˚H+(aq, 1M)/H2(g, 1 atm) = 0.000V (by definition)
2 H+(aq, 1M) + 2e− ⎯→ H2(g, 1 atm)
Standard Cell Potentials
E˚cell = E˚red (cathode) – E˚red (anode)
Cell potential: potential energy per unit of charge intensive property.
Oxidation: H2(g) 2H+(aq) + 2e– Oxidation: H2(g) 2H+(aq) + 2e– Oxidation: Zn(s) Zn2+(aq) + 2e–
E˚red (anode) = 0.000 V E˚red (anode) = 0.000 V E˚red (anode) = –0.76 V
Reduction: Cu2+(aq) + 2e– Cu(S) Reduction: Ag+(aq) + e– Ag(s) Reduction: 2H+(aq) + 2e– H2(g)
E˚red (cathode) = +0.337 V E˚red (cathode) = +0.800 V E˚red (cathode) = 0.00 V
Standard Cell Potentials
E˚cell = E˚red (cathode) – E˚red (anode)
E˚red (anode) = -0.76V E˚red (cathode) = +0.34 V
17.5: Balance the reaction and calculate the standard cell potential.
Al (s) + I2 (s) Al3+ (aq) + I- (aq)
17.6: Balance the reaction and calculate the standard cell potential.
Show how to build a voltaic cell with using this redox reaction.
Fe2+ (aq) + O2 (g) Fe3+ (aq) + H2O (l)
17.7: Based on the data presented below, which is the strongest
reducing agent and the strongest oxidizing agent?
E°(V)
Al3+(aq)/Al(s) -1.66
AgBr(s)/Ag(s) +0.07
Sn4+(aq)/Sn2+(aq) +0.14
Fe3+(aq)/Fe2+(aq) +0.77
E˚ and ∆G˚
The Nernst Equation
∆G˚, E˚ and K
∆G˚
∆G˚= -nFE˚
∆G˚= -RT ln K
E˚
K
E˚= RT ln K
nF
17.8: Calculate the potential for the following galvanic cell:
Ni (s) | Ni2+ (aq, 1.2 M) || H+ (aq, pH = 6.0) | H2 (g, 1.0 atm) | Pt (s)
Concentration cells
17.9: The standard reduction potential for the reduction of AgBr (s) is +0.095 V. The standard reduction potential for the
reduction of Ag+ (aq) is +0.799 V.
(a) Calculate the standard potential for the cell:
Ag (s) | AgBr (s) | Br- (aq) || Ag+ (aq) | Ag (s)
(b) Determine the Ksp for AgBr.
(c) A silver electrode coated with AgBr (s) is immersed in a sample solution with an unknown concentration of Br -(aq). When
this half-cell is connected to a standard Ag+/Ag electrode, the measured potential is +0.50 V, with the Ag+/Ag electrode
acting as the cathode. What is the concentration Br- in the sample?
The standard reduction potential for the reduction of AgBr (s) is +0.095 V. The standard
reduction potential for the reduction of Ag+ (aq) is +0.799 V.
(b) Determine the Ksp for AgBr.
The standard reduction potential for the reduction of AgBr (s) is +0.095 V. The standard reduction potential for the reduction
of Ag+ (aq) is +0.799 V.
(c) A silver electrode coated with AgBr (s) is immersed in a sample solution with an unknown concentration of Br - (aq). When
this half-cell is connected to a standard Ag+/Ag electrode, the measured potential is +0.50 V, with the Ag+/Ag electrode
acting as the cathode. What is the concentration Br- in the sample?
17.10: The reaction for the formation of Zn(OH) 42-(aq),
-
2+
Zn (aq) + 4OH (aq) = Zn(OH)2-
4 (aq)
has an equilibrium constant Kf = 5.0 x 1014 at 25˚C. The standard reduction potential for the Zn2+/Zn couple is -0.76 V.
Calculate the standard reduction potential for the following half-reaction:
- -
Zn(OH)2-
4 (aq) + 2e ® Zn(s) + 4OH (aq)
Batteries & Fuel Cells
Batteries: Dry Cells
▪ No fluid component
▪ Zinc container (anode)
▪ Graphite cathode
▪ 1.5 V
Anode: Zn(s) → Zn2+ (aq) + 2e–
Cathode: 2 NH4+(aq) + 2MnO2(s) + 2e– → Mn2O3(s) + 2NH3(aq) + H2O(l)
Overall: Zn(s) + 2NH4+(aq) + 2MnO2(s) → Zn2+(aq)+ Mn2O3(s) + 2NH3(aq) + H2O(l)
Alkaline Batteries
▪ Basic medium
Anode: Zn(s) + 2OH–(aq) → Zn(OH)2(s) + 2e–
Cathode: 2MnO2(s) + 2H2O(l) + 2e– → 2MnO(OH)(s) + 2OH–(aq)
Overall: Zn(s) + 2H2O(l) + 2MnO2(s) → Zn(OH)2(s)+ 2MnO(OH)(s)
Lead Storage Batteries
▪ 6 cells
▪ 2 V per cell
▪ 12 V total
▪ Rechargeable
Anode: Pb(s) + 2SO42-(aq) → PbSO4(s) + 2e–
Cathode: PbO2(s) + 4H+(aq) + SO42-(aq) + 2e– → PbSO4(s) + 2H2O(l)
Overall: Pb(s) + PbO2(s) + 4H+(aq) + 2SO42-(aq) → 2PbSO4(s) + 2H2O(l)
Lithium Ion Batteries
▪ Cell potential: 3.4 V
▪ Rechargeable (many times)
Anode: Li(s) → Li+ + e–
Cathode: Li+(aq) + CoO2(s) + e– → LiCoO2(s)
Overall: Li+(s) + CoO2(s) → LiCoO2(s)
Fuel cells Chemical energy is directly converted into electricity
Oxidation-Reduction reactions
Oxidation: loss of electrons
H2 (g) 2 H+ (aq) + 2e-
Reduction: gain of electrons
1 O2 (g) + 2 H+ (aq) + 2e- H2O (l)
2
Overall reaction: H2 (g) + 12 O2 (g) H2O (l)
Fuel Cell
Electrical conductor
H H H+
H H O O
Hydrogen from tank H+ Oxygen from air
H
H+ O
H
H+
H
O
H
Proton Exchange
Membrane
Exhaust
