Corrosion I Objectives

1. Identify oxidation-reduction reaction pairs present in corrosion situation.

Corrosion I Objectives
1. Identify oxidation-reduction reaction pairs present in corrosion situation.

2. List and define the basic types of corrosion.

Corrosion
Example:

Zn + 2HCl ZnCl2 + H2
Chlorine only peripherally involved

Zn + 2H+ Zn 2+ + H2

Example
2 Reactions Oxidation: (Anodic RXN)

Zn Zn2+ + 2e-

Example
2 Reactions Oxidation: (Anodic RXN) Reduction: (Cathodic RXN) Zn Zn2+ + 2e-

2H+ + 2e- H2

Example
Oxidation:

(Anodic RXN) Reduction: (Cathodic RXN)

Zn Zn2+ + 2e2H+ + 2e- H2

Key Principle - Rate of Reduction = Rate of Oxidation

All corrosion falls into Ox-Red pair groups Oxidation RXN (Free Electron):

M M+n +ne(From metal to its ion)

All corrosion falls into Ox-Red pair groups

Oxidation RXN (Free electrons): M M+n +ne(From metal to its ion) ie: Ag Ag+ + eAl Al3+ + 3e>>>Produces Electrons

Reduction Reactions (Consume electrons)

Hydrogen Evolution: 2H+ + 2e- H2

Reduction Reactions (Consume electrons)

Hydrogen Evolution: Oxygen Reduction (acid): O2 +4H+ +4e- 2H20 2H+ + 2e- H2

Reduction Reactions (Consume electrons)

Hydrogen Evolution: Oxygen Reduction (acid): O2 +4H+ +4e- 2H20 Oxygen Reduction (neutral or basic): O2 + 2H2O + 4e- 4OH2H+ + 2e- H2

Reduction Reactions (Consume electrons)

Hydrogen Evolution: Oxygen Reduction (acid): O2 +4H+ +4e- 2H20 Oxygen Reduction (neutral or basic): O2 + 2H2O + 4e- 4OH Metal Ion Reduction: M3+ + e- M2+ 2H+ + 2e- H2

5 Reduction Reactions (Consume electrons)

Hydrogen Evolution: Oxygen Reduction (acid): O2 +4H+ +4e- 2H20 Oxygen Reduction (neutral or basic): O2 + 2H2O + 4e- 4OH Metal Ion Reduction: Metal Deposition: M3+ + e- M2+ M+ + e- M 2H+ + 2e- H2

Note:
Reactions can be controlled from either side (OX/ RED). Example: Add oxygen gas to an acid Oxygen reduction is available to consume electrons.

Note:
Reactions can be controlled from either side (OX/ RED). Example: Add oxygen gas to an acid Oxygen reduction is available to consume electrons. Higher Rate of Oxidation

Note:
Reactions can be controlled from either side (OX/ RED). Example: Add oxygen gas to an acid Oxygen reduction is available to consume electrons. Higher Rate of Oxidation Acids with oxygen are worse than acids without.

Polarization: What controls rate of RXN

Two Types 1. Activation Polarization 2. Concentration Polarization

Activation
Four steps in reduction process: 1. 2. 3. 4. Adsorption Conduction of eDiffusion H2 Evolution

Concentration
Diffusion of reducing species controls rate

Passive Behavior
Some metals cease to be reactive under the right conditions 1. Active Behavior

2. Passive Behavior
3. Transpassive

Types
1. Uniform Attack -Measured in mpy (mils per year) -Easy to manage

Types
2. Galvanic Coupling

-Dissimilar metals or environments create electrical potential -Will have anode and cathode

Terminology
Anode Oxidized Active Cathode Reduced Passive

Types
3. Localized Corrosion a. SCC (Stress Corrosion Cracking)

Types
3. Localized Corrosion a. SCC (Stress Corrosion Cracking) b. ESC (Environmental Stress Cracking)

Types
3. Localized Corrosion a. SCC (Stress Corrosion Cracking) b. ESC (Environmental Stress Cracking) c. Inter-granular Attack - Fe at grain boundaries in Al -Cr23C6 in Stainless -Hydrogen Embrittlement

Types
3. Localized Corrosion a. SCC (Stress Corrosion Cracking) b. ESC (Environmental Stress Cracking) c. Inter-granular Attack - Fe at grain boundaries in Al -Cr23C6 in Stainless -Hydrogen Embrittlement d. Pitting

Types
3. Localized Corrosion e. Crevice Corrosion - Filiform if under coatings

Types
3. Localized Corrosion e. Crevice Corrosion - Filiform if under coatings f. Corrosion Fatigue

Galvanic Example
Zn Anode Oxidized Active
Cathode Reduced Passive

Pt

Galvanic Potential Example

Dry Cell Battery Vcell = 1.5 Volts

Calculation of Cell Potential

p.568: Table Pt 2+ + 2e- Pt Mg 2+ + 2e - Mg

Table +1.2V -2.363V

Calculation of Cell Potential

p.568: Table Table Pt 2+ + 2e- Pt +1.2V Mg 2+ + 2e - Mg -2.363V Actual Mg Mg 2+ + 2e - (oxidation) Pt 2+ + 2e - Pt

Actual +2.363V +1.2V

Calculation of Cell Potential

p.568: Table Pt 2+ + 2e- Pt +1.2V Mg 2+ + 2e - Mg -2.363V Actual Mg Mg 2+ + 2e - (oxidation) Pt 2+ + 2e - Pt Total Mg + Pt 2+ + 2e - Mg 2+ + 2e - + Pt

Actual +2.363V +1.2V Total +3.563V

EMF Values
1. (+) Potential means rxn will proceed as written. (-) Potential means opposite rxn occurs.

2. The more positive rxn will proceed as written