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:
Ag
Fe
Au0(s)
Cu
(s)
(s)

- -3+ ++e2e
Ag
Fe
Au+2+
Cu
(aq)
(aq)
(aq) + 3e Deterioration of metal

-0.44
+1.50
+0.34
+0.80

Cathodic Reaction:
2H+(aq) + 2e-

0.00

H2 (g) Chemical

O2 (g) + 2H2O (l) + 4eO2 (g) + 4H+(aq) + 4e-

4OH-(aq) Atmospheric
2H2O (l) Combination

Which of these will oxidize copper? Silver? Gold?

Overall Reaction:
Fe0(s) + 2H+(aq)
2Fe

(s)

Fe2+(aq) + H2 (g) Chemical

+ O2 (g) + 2H2O (l)

2Fe0(s) + O2 (g) + 4H+(aq)

2Fe

2+

(aq)

+ 4OH (aq) Atmospheric

-

2Fe2+(aq) + 2H2O (l) Combination

+0.40
+1.23
Eocell (V)
+0.44
+0.84
+1.67

Why wont 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)

Overall reaction:
Fe0(s) + 2H2O (l)

Fe2+(aq) + H2 (g) + 2OH-(aq)

-0.83
Eocell (V)
-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 Ships Hull

Anodic and Cathodic Regions
O2

Hull of ship

O2 + 2H2O + 4e-

Cathodic Region

4OHOH-

Fe2+ + 2OH4Fe(OH)2 + O2

RUST

Fe(OH)2

2(Fe2O3H2O) + 2H2O

Anodic Region

Fe2+
Fe

Fe2+ + 2e-

Electrons Migrate from

Anodic to Cathodic Region

STRESS CORROSION
2Fe0(s) + O2 (g) + 2H2O (l)
anode

2Fe2+(aq) + 4OH-(aq)
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
Shipboard Power

Paint
Layer

Shipboard Power

Controller
Reference
Electrode

Power Supply

e-

e-

Hull

Pt Anode
Insulation

Galvanic Corrosion
(contact between unlike metals;
opposite of cathodic protection)
O2

Copper
Cathode:
O2 + 2H2O + 4e- 4OH-

H2O

Iron
Anode:
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.