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:
0 Ag Fe Au Cu (s) (s) (s) - -2+ 3+ ++ Ag e3e Fe+ Deterioration of metal Au Cu (aq) (aq) + 2e (aq)

-0.44 +1.50 +0.34 +0.80

Cathodic Reaction: 2H+(aq) + 2eO2 (g) + 2H2O (l) + 4eO2 (g) + 4H+(aq) + 4eOverall Reaction: Fe0(s) + 2H+(aq) Fe2+(aq) + H2 (g) Chemical 2Fe2+(aq) + 4OH-(aq) Atmospheric 2Fe2+(aq) + 2H2O (l) Combination H2 (g) Chemical 4OH-(aq) Atmospheric 2H2O (l) Combination 0.00 +0.40 +1.23 Eocell (V) +0.44 +0.84 +1.67

Which of these will oxidize copper? Silver? Gold?

2Fe0(s) + O2 (g) + 2H2O (l) 2Fe0(s) + O2 (g) + 4H+(aq)

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)

-0.83

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

(aq)

Eocell (V)
-0.39

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

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
O2 + 2H2O + 4eFe2+ + 2OH4OHOHFe(OH)2 RUST Hull of ship

Cathodic Region

4Fe(OH)2 + O2

2(Fe2O3H2O) + 2H2O

eFe2+ Fe Fe2+ + 2e-

Anodic Region

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 Shipboard Power

Paint Layer

Controller
Reference Electrode

Hull

Power Supply

e-

ePt Anode Insulation

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

O2 H2O

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

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.