John W.

Moore
Conrad L. Stanitski

http://academic.cengage.com/chemistry/moore

Chapter 17
Electrochemistry & Its Applications

Stephen C. Foster • Mississippi State University

Electrochemistry
The study of the relationship between chemical
changes and electricity.

Redox reactions generate and use e-

• The e- flow can be harnessed.
• Corrosion is an electrochemical reaction.

Applied e- flow can:

• Drive reactant-favored reactions to products.
• Recharge some batteries, cause electroplating…
Oxidation Number Review
Ox = 0
(Ox) = overall charge. Ox = -1
Ox = +2
“Unmixed” elements = charge F2, P4, F-, Mn2+
Atom Ox Exceptions
F -1 none
Group 1A +1 very rare
Group 2A +2 very rare
H +1 rare; metal hydrides MH
O -2 rare; metal peroxides MO2
Cl -1
Br -1 interhalogens; halogen oxides
I -1
Redox Reaction Review
Oxidation & reduction always occur together.

Reduction = gain of e- = decrease in Ox

Oxidation = loss of e- = increase in Ox

+2 e-

2HCl(aq) + Mg(s) H2(g) + MgCl2 (aq)

+1 -1 0 0 +2 -1
-2 e-

H+ is reduced, Mg is oxidized.
Redox Reactions
Determine the oxidation numbers for each element and the
oxidizing and reducing agents in:
6 Fe2+ + Cr2O72- + 14 H3O+ → 6 Fe3+ + 2 Cr3+ + 21 H2O
Species Ox Explanation
Fe2+ +2 charge on ion
Cr2O72- O = -2 O is usually -2
Cr = +6 2(Cr) + 7(-2) = -2
H3O+ O = -2; H = +1 O is usually -2; H is usually +1
Fe3+ +3 charge on ion
Cr3+ -2 charge on ion
H2O O = -2; H = +1 O is usually -2; H is usually +1

Fe2+ → Fe3+ oxidation Fe2+ = reducing agent

Cr(+6) → Cr3+ reduction Cr2O72- = oxidizing agent
Half-Reactions & Redox Reactions
Redox reactions can be split into half reactions:

Zn → Zn2+ + 2e- Cu2+ + 2e- → Cu

loss of electrons gain of electrons
oxidation reduction
Half-Reactions & Redox Reactions
Half-reactions may include different numbers of e-:

Al(s) Al3+(aq) + 3 e-
Zn2+(aq) + 2 e- Zn(s)

e- must balance in the full reaction.

2[ Al(s) Al3+(aq) + 3 e- ]
3[ Zn2+(aq) + 2 e- Zn(s) ]
2 Al(s) + 3 Zn2+(aq) 2 Al3+(aq) + 3 Zn(s)
Voltaic Cells
A voltaic cell is an electrochemical cell in which a
chemical reaction and electricity interact.

An oxidizing agent and a reducing agent are arranged

so that they can react only if electrons flow through an
external conductor.
external conductor

Cu salt bridge Fe
Also called a battery.
(A battery is strictly a series of
linked voltaic cells)
Cu2+ Fe2+
NO3- NO3-
Voltaic Cells
Cu2+(aq) + Zn(s) → Cu(s) + Zn2+(aq)
Voltaic Cells
Cu2+(aq) + Zn(s) → Cu(s) + Zn2+(aq)

Electrodes (anode & cathode)

e- e- Allow e- to pass in/out of
solution.
salt bridge

A salt bridge (or porous barrier)

is required...

e- move across an external

conductor.
Anode Cathode
Electrochemical Cells
Cu2+(aq) + Zn(s) → Cu(s) + Zn2+(aq)

Anode: Zn(s) → Zn2+(aq) + 2 e-

e- e- Oxidation
salt bridge
Cathode: Cu2+(aq) + 2 e- → Cu(s)
Reduction

Anode Cathode
Salt Bridge
Contains a salt paste (e.g. K2SO4 ).
• A porous plug restricts bulk flow
• Ions pass into/out of the cells
• Stops charge buildup.
porous
plug Cu
Zn
SO42- SO42-
Zn2+
K2SO4 K+
Zn2+ Cu2+

SO42- released 2 K+ released

Zn2+ removed SO42- removed
as Zn → Zn2+ as Cu2+ → Cu
Voltaic Cells
Zinc is removed: Zn(s) → Zn2+(aq) + 2 e-
• Oxidation at anode (vowels!)
• The anode loses mass
• Zn supplies e-.
• Anode has “-” charge.

Copper is deposited: Cu2+(aq) + 2 e- → Cu(s)

• Reduction at cathode (consonants!)
• The cathode gains mass
• Cu2+ accepts e-.
• Cathode has “+” charge.
Voltaic Cells
In all voltaic cells:
• The redox reaction must be product-favored.
• Oxidation occurs at the anode.
• Reduction occurs at the cathode.
• Electrons move from anode to cathode through an
external ‘wire’.
• The electrical circuit is completed by movement of
ions into and out of a salt bridge.
Voltaic Cell Shorthand Notation
Compact notation:

phase salt
boundary bridge

Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu (s)

Read left to right

Zn → Zn2+ + 2e- Cu2+ + 2e- → Cu

LEO GER
oxidation reduction
anode Current (e-) flow cathode
Voltaic Cells & Cell Potential
Electrical work = charge x (potential energy difference)
= (number of e-) ΔEp
SI Units
Charge: 1 coulomb (C) = 1 ampere x second = 1 As
Potential: 1 volt (V) = 1 J C-1

Voltage only depends on cell

chemistry ≠ size.

Charge depends on nreactants ≈ size.

Cell Potential & Half Cells
Potentials (voltages), like height, can only be measured
between two points:
• A voltage can be measured between half cells
• An elevation can be measured between sea-level
and another point.

Overall voltage of a cell is:

Ecell = Ecathode – Eanode

Half-cell potentials depend upon many factors, so a

set of standard conditions are defined.
Cell Potentials & Half Cells
A standard potential (E°) occurs when:
• All [solute] = 1 M (or saturated if solubility < 1 M).
• All gases have P = 1 bar.
• All solids are pure.

If E°cell is positive the reaction is product favored

(If E°cell < 0 the reaction is reactant favored).

E°cell = E°cathode - E°anode

E° does not depend on nreactant or nproduct

(i.e not on the stoichiometric coefficients).
Cell Potentials & Half Cells
Consider:
Anode: Zn(s) → Zn2+(aq, 1 M) + 2 e-
Cathode: Cu2+(aq, 1M) + 2 e- → Cu(s)
Overall: Cu2+(aq, 1M) + Zn(s) → Zn2+(aq, 1 M) + Cu(s)

The half-cell potentials are:

E°Zn2+ = -0.763 V E°Cu2+ = +0.340 V

E°cell = E°cathode – E°anode = E°Cu2+ – E°Zn2+

= +0.340 V – (-0.763 V)
= +1.103 V
Standard Half-Cell Potentials
Potentials are relative (must be measured against a
reference value).
The Standard Hydrogen Electrode (SHE) is assigned a
value of E° = 0 V:

2 H3O+(aq, 1M) + 2 e- H2(g, 1 bar) + 2 H2O (ℓ)

Compact notation: Gas + soln.

in contact with
H+(aq), 1M| H2(g, 1bar) | Pt Pt
Cell Potentials & Half Cells
Consider: Pt|H2(g,1 bar)|H+(aq,1M)||Cu2+(aq,1M)|Cu(s)

A voltmeter reads +0.34 V if the positive lead is

attached to the Cu electrode:
• Cu gains e- (is reduced = the cathode)

Anode: H2(g,1bar) → 2 H+(aq,1M) + 2 e-

Cathode: Cu2+(aq,1M) + 2 e- → Cu(s)
Overall: Cu2+(aq,1M) + H2(g,1bar) → 2 H+(aq,1M) + Cu(s)

Since E°SHE = 0 V, the voltmeter gives the potential for

the copper half-cell reduction (0.340 V).
Using Standard Half-Cell Potentials
Potential differences between SHE many other half-
cells have been made (table 17.1).
• Standard reductions are listed.
• Each half-reaction can occur in either direction
• More positive E° = easier reduction.
• Less positive E° = easier oxidation for the reverse
reaction.
• Any species on the left of a half-reaction will oxidize
any species that is below it on the right side of the table.
Using Standard Half-Cell Potentials
• E° does not depend on nreactant or nproduct
• it is independent of stoichiometric coefficient.

Fe3+(aq,1M) + e− → Fe2+(aq,1 M) E° = +0.771 V

2 Fe3+(aq,1M) + 2 e− → 2 Fe2+(aq,1 M) E° = +0.771 V
• Standard half-cell potentials do not depend on the
direction in which they are written.
• The strongest elemental oxidizing agents are in the
upper right of the periodic table; the strongest
reducing agents are on the left.
Standard Half-Cell Potentials
A small portion of table 17.1:
Reduction Half Reaction Half Cell E° (V)
Oxidizing Agent Reducing agent
F2(g) +2 e- → 2 F-(aq) F2(g)|F−(aq)|Pt +2.87
H2O2(aq) + 2 H+(aq) + 2 e- → 4 H2O(ℓ) H2O2(aq),H+(aq),H2O(ℓ)|Pt +1.763
Au3+(aq) + 3 e- → Au(s) Au3+(aq)|Au(s) +1.52
Cl2(g) + 2 e- → 2 Cl-(aq) Cl2(g)|Cl−(aq)|Pt +1.358
⁞ ⁞ ⁞
2 H+(aq) + 2 e- → H2(g) H+(aq)|H2(g)|Pt 0
⁞ ⁞ ⁞
Na+(aq) + e- → Na(s) Na+(aq)|Na(s) -2.714
K+(aq) + e- → K(s) K+(aq)|K(s) -2.925
Li+(aq) + e- → Li(s) Li+(aq)|Li(s) -3.045
Cell Potential & Half Cells
The standard potential of any cell can be calculated.
Calculate E°cell for Al(s)|Al3+(aq,1M)||Sn2+(aq,1M)|Sn(s).

Cathode: Sn2+(aq) + 2 e- → Sn(s)

Anode: Al(s) → Al3+(aq) + 3 e-
Reduction Half Reaction Half Cell E° (V)
Oxidizing Agent Reducing agent
F2(g) +2 e- → 2 F-(aq) F2(g)|F−(aq)|Pt +2.87
⁞ ⁞ ⁞
Sn2+(aq) + 2 e- → Sn(s) Sn2+(aq)|Sn(s) -0.1375
⁞ ⁞ ⁞
Al3+(aq) + 3 e- → Al(s) Al3+(aq)|Al(s) -1.676
⁞ ⁞ ⁞
Cell Potential & Half Cells
Voltage of: Al(s)|Al3+,1M||Sn2+,1M|Sn(s) ?

Balance e-:
Cathode: 3[Sn2+(aq) + 2 e- → Sn(s)]
Anode: 2[Al(s) → Al3+(aq) + 3 e-]
3 Sn2+(aq) + 2 Al(s) → 3 Sn(s) + 2 Al3+(aq)

E°cell = E°cathode – E°anode = E°Sn2+ – E°Al3+

= -0.1375 V – (-1.676 V) = +1.539 V

Not 2(-0.1375) Not 3(-1.676)

Using Standard Half-Cell Potentials
It’s painful to bite Al-foil if a tooth has a metal filling.
• Fillings are tin/silver amalgams (e.g. Ag2Hg3, Ag3Sn).
• A voltaic cell forms:
• Al anode; amalgam cathode; saliva as the salt bridge

Al3+(aq) + 3 e− → Al(s) E° = −1.68 V

3 Hg22+(aq) + 4 Ag(s) + 6 e− → 2 Ag2Hg3(s) E° = +0.85 V
Sn2+(aq) + 3 Ag(s) + 2 e− → Ag3Sn(s) E° = −0.05 V

The oxidation of Al (Al → Al3+ + 3 e-) generates a tiny

electrical current into a nerve and causes pain.
Cell Potentials
Consider the following table:
Half Reaction Half Cell E° (V)
Au3+(aq) + 3 e- → Au(s) Au3+(aq)|Au(s) +1.52
Cl2(g) + 2 e- → 2 Cl-(aq) Cl2(g)|Cl−(aq)|Pt +1.358

Al3+(aq) + 3 e- → Al(s) Al3+(aq)|Al(s) -1.676

K+(aq) + e- → K(s) K+(aq)|K(s) -2.925

Identify:
a) the strongest oxidizing agent.
b) the weakest oxidizing agent.
c) the strongest reducing agent.
d) the weakest reducing agent.
Cell Potentials
Consider the following table:
Half Reaction Half Cell E° (V)
Au3+(aq) + 3 e- → Au(s) Au3+(aq)|Au(s) +1.52
Cl2(g) + 2 e- → 2 Cl-(aq) Cl2(g)|Cl−(aq)|Pt +1.358

Al3+(aq) + 3 e- → Al(s) Al3+(aq)|Al(s) -1.676

K+(aq) + e- → K(s) K+(aq)|K(s) -2.925

Identify:
a) the strongest oxidizing agent. = Au3+(aq)
b) the weakest oxidizing agent. = K+(aq)
c) the strongest reducing agent. = K(s)
d) the weakest reducing agent. = Au(s)
Cell Potentials
Consider the following table:
Half Reaction Half Cell E° (V)
Au3+(aq) + 3 e- → Au(s) Au3+(aq)|Au(s) +1.52
Cl2(g) + 2 e- → 2 Cl-(aq) Cl2(g)|Cl−(aq)|Pt +1.358

Al3+(aq) + 3 e- → Al(s) Al3+(aq)|Al(s) -1.676

K+(aq) + e- → K(s) K+(aq)|K(s) -2.925

Will:
a) Cl2(g) oxidize Au(s) to Au3+(aq)?
b) K(s) reduce Cl2(g) to Cl-(aq)?
and
c) What can be reduced by Al(s)?
Cell Potentials
Consider the following table:
Half Reaction Half Cell E° (V)
Au3+(aq) + 3 e- → Au(s) Au3+(aq)|Au(s) +1.52
Cl2(g) + 2 e- → 2 Cl-(aq) Cl2(g)|Cl−(aq)|Pt +1.358

Al3+(aq) + 3 e- → Al(s) Al3+(aq)|Al(s) -1.676

K+(aq) + e- → K(s) K+(aq)|K(s) -2.925

Will:
a) Cl2(g) oxidize Au(s) to Au3+(aq)? = No
b) K(s) reduce Cl2(g) to Cl-(aq)? = Yes
and
c) What can be reduced by Al(s)? = Cl2 and Au3+
E°, Gibbs Free Energy and K°
Product-favored: ΔG° < 0
Spontaneous cell reactions: E°cell > 0.

ΔG° = –n F E°cell

Michael Faraday
with n = number of e- transferred,
F = Faraday constant = charge/(mol of e-).
= (e- charge) x (Avogadro’s number)
= (1.60 x 10-19 C)(6.02 x 1023 mol-1)

F = 96,485 C/mol
E° and ΔG°
What is the standard cell potential and Gibbs free
energy when aluminum and iron(II) ions react to form
iron and aluminum ions?

Reaction: 2 Al(s) + 3 Fe2+(aq) → 3 Fe(s) + 2 Al3+(aq)

Half reactions:
Cathode: 3[Fe2+(aq) + 2 e- → Fe(s)]
Anode: 2[Al(s) → Al3+(aq) + 3 e-]

E°cell = E°cathode – E°anode = -0.44 V – (-1.676 V)

= +1.24 V
E° and ΔG°
E° and ΔG° for 2 Al(s) + 3 Fe2+(aq) → 3 Fe(s) + 2 Al3+(aq)?

ΔG° = − nFE°cell

n = 6 (2 [Al3+ + 3 e- → Al] …)

ΔG° = −(6)(96,485 C/mol)(1.24 V)

= −7.18 x105 J/mol (1 J = 1 C V)
= −718 kJ/mol
ΔG° , E° and K°

ΔG°

ΔG° = − RT ln K° ΔG° = − nFE°cell

K° E°cell

E°cell = R T ln K°
nF
ΔG° , E° and K°
Determine K° for the following reaction at 25 C:
2 Ag(s) + Hg2+(aq) → 2 Ag+(aq) + Hg(ℓ)
Half Reaction Half Cell E° (V)
Hg2+(aq) + 2 e- → Hg(ℓ) Hg2+(aq)|Hg(ℓ) +0.8535
Ag+(aq) + e- → Ag(s) Ag+(aq)|Ag(s) +0.7991

E°cell = 0.8535 V – 0.7991 V = 0.0544 V

RT
E°cell = ln K° ; thusln K° = E°cell n F
nF RT
(2)(96,485 C mol-1)
ln K° = 0.0544 V
(8.314 J K-1 mol-1 )(298 K)

ln K° = 4.24 K° = e4.24 = 69.2

Concentration & Cell Potential
E° values only apply if [solute] = 1 M (or saturated),
Pgas = 1 bar,…
Under other conditions:

RT
Ecell = E°cell − lnQ (Nernst equation)
nF
Concentration & Cell Potential
What is the voltage for: Cu2+ + Zn(s) → Cu(s) + Zn2+
at 298 K if [Cu2+] = 0.10 M and [Zn2+] = 5.0 M?
E°cell = 1.10 V.

RT RT [Zn 2+
]
Ecell = E°cell − lnQ = E°cell − ln
nF nF [Cu2+]

(8.314 J K-1mol-1)(298 K) 5.0

Ecell = 1.10 − ln
(2)(96,485 C mol-1) 0.10

Ecell = 1.05 V
Concentration Cells
Identical cells? E may not be zero…
Example Zn|Zn2+(aq,0.01M)||Zn2+(aq,1M)|Zn
Left-to-right…
Zn(s) → Zn2+ (0.01M) + 2 e-
Zn2+ (1M) + 2 e- → Zn(s)
Zn2+(1M) → Zn2+(0.01M) (net reaction)

(8.314 J K mol )(298 [Zn2+]dil

ln-1 K)
-1 -1
E = E° −
(2)(96,485 C mol ) [Zn2+]conc
Same cell
E = 0 − 0.0128 ln 0.010
E = 0.0591 V
1
Concentration Cells: pH
An unknown H+ conc. could be measured with:
Pt|H2(g)|H+(aq,1M)||H+(aq,unknown)| H2(g)|Pt
but it would be inconvenient.

Commercial pH meters have two electrodes:

• A glass-membrane tipped Ag|AgCl half-cell
(containing 1-M HCl)
• A reference electrode: AgCl-coated Ag wire dipped in
KCl(aq,saturated).
Ag(s)|AgCl(s)|Cl−(aq), H+(1 M)||H+(?)| Cl−(aq)|AgCl(s)|Ag(s)
Glass membrane
Concentration Cells: pH
Concentration Cells: pH
These are usually combined into a single probe:
Concentration Cells: pH
Glass electrode: Ag(s) + Cl−(aq) → AgCl(s) + e−
H+(1 M) → H+(unknown)
Ref. electrode: AgCl(s) + e− → Ag(s) + Cl−(aq)

Ecell is measured between H+(1 M) and H+(unknown)

• The AgCl half-cells cancel (do not effect Ecell).
• Ecell only depends on the difference in [H+].
• [H+]unknown is calculated from Ecell

and hence pHunknown

Common Batteries
Primary battery = One time use. Not easily recharged.
Secondary battery = Rechargeable.

Primary example: The alkaline battery (1.54 V)

Anode: Zn(s) + 2 OH−(aq) → ZnO(aq) + H2O(ℓ) + 2 e−

Cath.: MnO2(s) + H2O(ℓ) + e− → MnO(OH)(s) + OH−(aq)

Zinc metal is oxidized under alkaline conditions.

Electrons travel through an external circuit to reduce

manganese(IV) oxide at the cathode.
Lead–Acid Storage Batteries
A secondary battery (rechargeable).

Pb(s) + HSO4-(aq) → PbSO4(s) + H+(aq) + 2 e-

PbO2(s) + 3 H+(aq) + HSO4-(aq) + 2 e- → PbSO4(s) + 2 H2O(ℓ)

Pb(s) + PbO2(s) + 2 H+ + 2 HSO4-(aq) → 2 PbSO4(s) + 2 H2O(ℓ)

Netinsoluble
E° = +2.041 V
PbSO4 stays on electrodes.
• Reaction can be reversed.
• Rechargeable.
Lead–Acid Storage Batteries
Lead–Acid Storage Batteries
Pb(s) + PbO2(s) + 2 H+(aq) + 2 HSO4-(aq) → 2 PbSO4(s) + 2 H2O(ℓ)
HSO4- is lost as it discharges:
RT
Ecell = E°cell − lnQ
nF
RT 1
Ecell = 2.041 − ln
2F [H+]2[HSO4-]2

The voltage remains ~2.0 V until ~ 97% discharged.

Charging a lead-acid battery produces H2 and O2
Avoid sparks
Cathode: 4 H+(aq) + 4 e- → 2 H2(g) when charging!

Anode: 2 H2O(ℓ) → O2(g) + 4 H+(aq) + 4 e-

Nickel-based Batteries
Nickel-cadmium (NiCad; 1.299 V)
Anode: Cd(s) + 2 OH−(aq) → Cd(OH)2(s) + 2 e−
Cath.: 2[NiO(OH)(s) + H2O(ℓ) + e− → Ni(OH)2(s) + OH−(aq)]
Cd + 2NiO(OH)(s) + 2H2O(ℓ) → Cd(OH)2(s) + 2Ni(OH)2(s)

Nickel-metal hydride (NiMH; 1.4 V)

The anode is a metal alloy (M = Ni or rare earth) in
KOH(aq); Same cathode reaction as NiCad.

H is absorbed by the anode and oxidized to water:

Anode: MH(s) + OH−(aq) → M(s) + H2O(ℓ) + e−
Overall: MH(s) + NiO(OH)(s) → M(s) + Ni(OH)2(s)
Lithium–Ion Batteries
Low mass, high energy density (3.4 V)
Layered electrodes improve Li+ migration. One type:
• Anode: treated graphite.
• Cathode: CoO2 (Co4+ ions between layers of O2-).
• A salt (e.g. LiPF6)/organic-solvent electrolyte.
If fully-charged, Li+ are inserted between graphene
layers (represented as C6 here) in the anode:

Anode: LiC6(s) → Li+ (electrolyte) + C6(s) + e-

Cathode: Li+(electrolyte) + e- + CoO2(s) → LiCoO2(s)
Overall: LiC6(s) + CoO2(s) → C6(s) + LiCoO2(s)
Fuel Cells
Converts bond energy into electricity.

Reactants are continually fed from an external source.

An H2/O2 fuel cell uses a proton-exchange membrane

Anode: 2 H2(g) → 4 H+(aq) + 4 e-

Cathode: O2(g) + 4 H+(aq) + 4 e- → 2 H2O(ℓ)
Overall: 2 H2(g) + O2(g) → 2 H2O(ℓ)

The proton-exchange membrane (thin plastic sheet):

• separates the cells
• allows the passage of H+ ions, but not e-
Fuel Cells
A PEM H2|O2 fuel cell generates ~1 V:
Electrolysis
Applied V can force a reaction to occur.
ΔrG° = +384 kJ/mol
2 NaCl(s) → 2 Na(s) + Cl2(g)
E° = −1.99 V
This reaction can be forced to occur in molten NaCl:

Cathode: 2 Na+(melt) + 2 e- → 2Na(ℓ)

Anode: 2 Cl-(melt) → Cl2(g) + 2 e-
2 Na+(melt) + 2 Cl-(melt) → Cl2 (g) + 2 Na(ℓ)

To generate Na(ℓ) and Cl2(g), the applied voltage must

exceed the negative cell potential.
However, melting NaCl takes lots of energy…
Electrolysis
Aqueous solutions? Other reactions can occur.
Consider KI(aq):
K+(aq) + e- → K(s) E° = -2.925 V
reductions

2 H2O(ℓ) + 2 e- → H2(g) + 2 OH-(aq) E° = -0.828 V

2 I-(aq) → I2(aq) + 2 e- E° = 0.535 V
oxidations

2 H2O(ℓ) → O2(g) + 4 H+(aq) + 4 e- E° = 1.229 V

The reduction with the most positive E occurs…

The oxidation with the least positive E occurs…
2 H2O + 2 I- → H2 + I2 + 2 OH-
Ecell = Ecathode - Eanode = -0.828 – 0.535 V = -1.363 V
Electrolysis

Brown = I2 ; Purple = OH- (phenolphthalein)

Electrolysis Summary
Metal ions are reduced when E°red > −0.8 V
• Na+, K+, Mg2+, Al3+ … will not reduce in H2O.

Anions can be oxidized if E°red < +1.23 V

• F- … will not oxidize in H2O.

In practice Erequired > E calculated. An overvoltage is needed.

(Cl-(aq) does oxidize to Cl2(g) E°red = +1.36 V)
 Reduction Half Reaction E° (V)
F2(g) +2 e- → 2 F-(aq) +2.87
H2O2(aq) + 2 H+(aq) + 2 e- → 4 H2O(ℓ) +1.763
Won’t oxidize Au3+(aq) + 3 e- → Au(s) +1.52
in water
MnO4−(aq) + 8 H+(aq) + 5 e− → Mn2+(aq) + 4 H2O(ℓ) +1.51
Cr2O72−(aq) +14 H+(aq)oxidation
+ 6 e− → 2 Cr3+(aq) + 7 H2O(ℓ) +1.358
Cl-(aq) will oxidize Cl (g) + 2 e- → 2 Cl-(aq) +1.358
2

O2(g) + 4 H+(aq) + 4 e− → 2 H2O(ℓ) +1.229

Br2(ℓ) + 2 e- → 2 Br-(aq) +1.066
Ag+(aq) + e- → Ag(s) +0.7991
2 H+(aq) + 2 e- → H2(g) 0
Zn2+(aq) + 2 e- → Zn(s) -0.763
2 H2O(ℓ) + 2 e− → H2(g) + 2 OH−(aq) -0.8277
Al3+(aq) + 3 e− → Al(s) -1.676
Won’t reduce Mg2+(aq) + 2 e− → Mg(s) -2.356
in water. reduction
Na+(aq) + e- → Na(s) -2.714
K+(aq) + e- → K(s) -2.925
Counting Electrons

Ag+(aq) + e- Ag(s) 1 mol e- ≡ 1 mol Ag

Cu2+(aq) + 2 e- Cu(s) 2 mol e- ≡ 1 mol Cu

Also charge = current x time

1 coulomb = 1 ampere x 1 second
1C =1As
Counting Electrons
Current (A)
charge = current x time

Charge (C)
use Faraday’s constant
Moles of e-
use stoichiometry

Moles of substance
oxidized or reduced

use molar mass

Mass of substance
oxidized or reduced
Counting Electrons
What mass of gold will be electroplated from aqueous
gold(III) chloride in 5.0 min by a 10.0 A current?

Au3+(aq) + 3 e- → Au(s)

60 s
Charge = (10.0 A)(5.0 min) = 3.0 x 103 C
1 min

1 mol e -
1 mol Au 197.0 g
3.0 x 10 C
3
= 2.0 g
96,485 C 3 mol e 1 mol Au
-
Counting Electrons
How long will it take to produce 14 g of Al from Al3+
(melt)? Assume a current of 500.0 A.

Al3+ + 3 e- → Al

14. g 1 mol Al 3 mol e- 96,485

= 1.50Cx 105 C
26.98 g 1 mol Al 1 mol e-

charge 1.50 x 105 C 2

Time = = = 3.0 x 10 s
current 500.0 A
Electrolytic Production of H2
2 H2O(ℓ) → 2 H2(g) + O2(g) E°cell= -1.24 V
O2 H2
~2 V needed
(overvoltage)

Energy to produce 1.0 kg of H2(g)?

1 mol H 2 2 mol e -
ne-= 103 g H2
2.02 g H2 1 mol H2
anode cathode
ne-= 9.9 x 102 mol e-
2V = 2 J/C
E = charge x voltage
- 9.65 x 10 C 2 J
4
= 9.9 x10 mol e
2
= 1.9 x 10 8
J
1 mol e
-
1C
Corrosion
Oxidation of metals by the environment.
Anode: M(s) → Mn+ + n e-
Cathode: often involve water and/or O2
O2(g) + 2 H2O(ℓ) + 4 e- → 4 OH-(aq)
2 H2O(ℓ) + 2 e- → 2 OH-(aq) + H2(g)
• Anode: exposed bare metal (cracks in coatings).
• Cathode: less-reactive areas (impurity sites, e.g.
metal sulfides or carbides).
The metal itself acts is the “wire”; ions dissolved in
moisture from the environment form a salt bridge.
Corrosion
Iron “rusts”
• Forms Fe2O3·2H2O
• Flakes off, exposing more iron.

Aluminum corrodes
• Forms Al2O3 (insoluble)
• Hard, thin layer.
• Protects Al from further corrosion.
Corrosion
Anode: 2[Fe(s) Fe2+ + 2 e-]
Cathode: O2(g) + 2 H2O(ℓ) + 4 e- 4 OH-(aq)
2 Fe(s) + O2(g) + 2 H2O(ℓ) 2 Fe(OH)2(s)

Converted to rust by oxygen:

4 Fe(OH)2(s) + O2(g) 2 Fe2O3·2H2O(s) + H2O(ℓ)
red-brown rust
Corrosion
Iron nails corroding:
• Blue = Fe2+ indicator
• Purple = OH- indicator

Stress points act as anodes corrode quickly.

Corrosion Protection
Anodic inhibition
• Paint or coat the surface.
• Form thin metal oxide coat:

2 Fe(s) + 2 Na2CrO4(aq) + 2 H2O(ℓ)

→ Fe2O3(s) + Cr2O3(s) + 4 NaOH(aq)
Insoluble
Insolublecoatings;
coating;
impervious to O2 and H2O
Corrosion Protection
Cathodic protection
Force another metal to corrode (use a sacrificial anode)
• Attach a more reactive metal which will corrode first.
• The protected metal acts as the cathode

Iron is galvanized (coated with Zn)

Corrosion Prevention
Galvanized Iron: Fe → Fe2+ + 2 e- E° = -0.44 V
More easily oxidized; Zn → Zn 2+
+ 2 e -
E° = -0.763 V
acts as the anode

Zn(OH)2 forms on the surface:

• It is Insoluble (Ksp,Zn(OH)2 = 1.2 x 10−17).
• It further slows corrosion