USNA Chemistry Department

CORROSION
LECTURE
 What is Corrosion?
Corrosion is the oxidation of a metal due to an
ELECTROCHEMICAL reaction. The oxidizing agent is
most often O2 (atmospheric corrosion) or H+ (chemical
corrosion) or both.

Why is it a problem?
Financial - $350 Billion Dollar Annual Problem in U.S.
(4.25% of GNP) Department of Defense spends $6 –
8 Billion
 Recipe for corrosion
Active metal

Water

Oxygen
(atmospheric corrosion)

Acid
(chemical corrosion)

Salt

High temperature
 Chemical vs. Atmospheric Corrosion
(H+ vs. O2)
Eo red (V)
Anodic Reaction:
Fe0
Ag
Au(s)(s)
Cu Fe
Ag
2+
Au+2+3+
Cu (aq)
(aq)
+
+ +
+2e
e- - -Deterioration
3e
2e - of metal -0.44
+1.50
+0.34
+0.80
(s)(s) (aq)
(aq)

Cathodic Reaction:
2H+(aq) + 2e- H2 (g) Chemical
0.00
O2 (g) + 2H2O (l) + 4e -
4OH -
(aq) Atmospheric
+0.40
O2 (g) + 4H+(aq) + 4e- 2H2O (l) Combination
+1.23
Which of these will oxidize copper? Silver? Gold?
Overall Reaction:
Eocell (V)
Fe0(s) + 2H+(aq) Fe2+(aq) + H2 (g) Chemical
2Fe0(s) + O2 (g) + 2H2O (l) 2Fe2+(aq) + 4OH-(aq) Atmospheric +0.44
2Fe0(s) + O2 (g) + 4H+(aq) 2Fe2+(aq) + 2H2O (l) Combination +0.84
+1.67
 Why won’t iron corrode in pure (degassed) water?

Eo (V)
Anodic Reaction:
Fe0(s) Fe2+(aq) + 2e- -0.44
Cathodic Reaction:

2H2O (l) + 2e- H2 (g) + 2OH-(aq) -0.83

Overall reaction: Eocell (V)

Fe0(s) + 2H2O (l) Fe2+(aq) + H2 (g) + 2OH-(aq) -0.39

What metals will corrode in pure (degassed) water?

Any sufficiently active metal Eored < -0.83 V

(alkali metals, alkaline earth metals, aluminum, manganese)

Example of Atmospheric Corrosion

Corrosion on wing of Navy aircraft

F/A-18C Hornet

Why does corrosion of an airplane

occur primarily while the plane is on
the ground?

How might this corrosion be

minimized?
 Example of Chemical Corrosion
Nuclear Reactor Vessel Head Degradation
• February 16, 2002, Davis-Besse Nuclear Power Station in Oak Harbor, Ohio

Boric Acid leak from control rod

drive mechanism led to chemical
corrosion of reactor vessel head
Serious potential for loss of
reactor coolant access
 Corrosion of a Ship’s Hull
Anodic and Cathodic Regions
O2 Hull of ship

O2 + 2H2O + 4e- 4OH- Cathodic Region

OH-
Fe2+ + 2OH- Fe(OH)2 RUST

4Fe(OH)2 + O2 2(Fe2O3·H2O) + 2H2O Anodic Region

e -

Fe2+

Fe Fe2+ + 2e-

Electrons Migrate from

Anodic to Cathodic Region
 STRESS CORROSION
2Fe0(s) + O2 (g) + 2H2O (l) → 2Fe2+(aq) + 4OH-(aq)
anode Nail is embedded in a gel.

Gel contains phenolphthalein

and ferricyanide ion.

Phenolphthalein turns pink in

basic solution.

Ferricyanide reacts with Fe2+

to produce a blue color.

cathode
STRESS CORROSION
 Example of Stress Corrosion
Aloha Flight 243 (28 APR 1988)

Lesson:

Frequent inspections
to detect signs of stress!
 Preventing Corrosion

Salt

High pH (> 9)
 Preventing the Corrosion of Iron
(cathodic protection/sacrificial anode)

Sacrificial anode
 Applications of Cathodic Protection

• Galvanized Steel
Zinc coating

• Sacrificial Anodes
Ship Hulls
Subs (free flooding areas)

Los Angeles Class Sub

Arleigh-Burke Destroyer
 Impressed Current Cathodic
Protection
Paint
Shipboard Power
Shipboard Power Layer

Controller
Reference
Electrode

Hull
e-
e-
Power Supply
Pt Anode

Insulation
 Galvanic Corrosion
(contact between unlike metals;
opposite of cathodic protection)

O2
H2O

Copper Iron
Cathode: Anode:
O2 + 2H2O + 4e- → 4OH- Fe → Fe2+ + 2e-
GALVANIC CORROSION
There are some leaks in Sampson Hall. Upon
inspection it turns out that copper (Cu) was attached to
lead (Pb) on the roof. I guess it turns out when they
are mixed with water (H2O) or air (N2, O2, CO2, etc) there
is some kind of reaction that breaks down the
properties of the copper and lead.