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Corrosion I Objectives. Identify oxidation-reduction reaction pairs present in corrosion situation. Corrosion I Objectives. Identify oxidation-reduction reaction pairs present in corrosion situation. List and define the basic types of corrosion. Corrosion. Example:
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Corrosion IObjectives Identify oxidation-reduction reaction pairs present in corrosion situation.
Corrosion I Objectives • Identify oxidation-reduction reaction pairs present in corrosion situation. • 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) Zn Zn2+ + 2e- • Reduction: • (Cathodic RXN) 2H+ + 2e- H2
Example Oxidation: (Anodic RXN) Zn Zn2+ + 2e- Reduction: (Cathodic RXN) 2H+ + 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+ + e- Al Al3+ + 3e- >>>Produces Electrons
Reduction Reactions (Consume electrons) Hydrogen Evolution: 2H+ + 2e- H2
Reduction Reactions (Consume electrons) Hydrogen Evolution: 2H+ + 2e- H2 Oxygen Reduction (acid): O2 +4H+ +4e- 2H20
Reduction Reactions (Consume electrons) Hydrogen Evolution: 2H+ + 2e- H2 Oxygen Reduction (acid): O2 +4H+ +4e- 2H20 Oxygen Reduction (neutral or basic): O2 + 2H2O + 4e- 4OH-
Reduction Reactions (Consume electrons) Hydrogen Evolution: 2H+ + 2e- H2 Oxygen Reduction (acid): O2 +4H+ +4e- 2H20 Oxygen Reduction (neutral or basic): O2 + 2H2O + 4e- 4OH - Metal Ion Reduction: M3+ + e- M2+
5 Reduction Reactions (Consume electrons) Hydrogen Evolution: 2H+ + 2e- H2 Oxygen Reduction (acid): O2 +4H+ +4e- 2H20 Oxygen Reduction (neutral or basic): O2 + 2H2O + 4e- 4OH - Metal Ion Reduction: M3+ + e- M2+ Metal Deposition: M+ + e- M
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: Adsorption Conduction of e- Diffusion H2 Evolution
Concentration Diffusion of reducing species controls rate
Passive Behavior Some metals cease to be reactive under the right conditions Active Behavior Passive Behavior Transpassive
Types 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 Cathode Oxidized Reduced Active Passive
Types • Localized Corrosion • SCC (Stress Corrosion Cracking)
Types • Localized Corrosion • SCC (Stress Corrosion Cracking) • ESC (Environmental Stress Cracking)
Types • Localized Corrosion • SCC (Stress Corrosion Cracking) • ESC (Environmental Stress Cracking) • Inter-granular Attack • - Fe at grain boundaries in Al • -Cr23C6 in Stainless • -Hydrogen Embrittlement
Types • Localized Corrosion • SCC (Stress Corrosion Cracking) • ESC (Environmental Stress Cracking) • Inter-granular Attack • - Fe at grain boundaries in Al • -Cr23C6 in Stainless • -Hydrogen Embrittlement • Pitting
Types • Localized Corrosion • e. Crevice Corrosion • - Filiform if under coatings
Types • Localized Corrosion • e. Crevice Corrosion • - Filiform if under coatings • f. Corrosion Fatigue
Galvanic Example Zn Anode Oxidized Active Pt Cathode Reduced Passive
Galvanic Potential Example Dry Cell Battery Vcell = 1.5 Volts
Calculation of Cell Potential p.568: Table Table Pt 2+ + 2e- Pt +1.2V Mg 2+ + 2e - Mg -2.363V
Calculation of Cell Potential p.568: Table Table Pt 2+ + 2e- Pt +1.2V Mg 2+ + 2e - Mg -2.363V Actual Actual Mg Mg 2+ + 2e - (oxidation) +2.363V Pt 2+ + 2e - Pt +1.2V
Calculation of Cell Potential p.568: Table Pt 2+ + 2e- Pt +1.2V Mg 2+ + 2e - Mg -2.363V Actual Actual Mg Mg 2+ + 2e - (oxidation) +2.363V Pt 2+ + 2e - Pt +1.2V Total Total Mg + Pt 2+ + 2e - Mg 2+ + 2e - + Pt +3.563V
EMF Values (+) Potential means rxn will proceed as written. (-) Potential means opposite rxn occurs. The more positive rxn will proceed as written