Module 3: Corrosion

Definition:

Corrosion is defined as the destruction or decomposition of metals and alloys by their surrounding

environment through chemical or electrochemical changes.

Note:

- Usually, metals undergo corrosion by oxidation (loss of electrons).

Types of Corrosion

1. Dry (or Direct) Chemical Corrosion:

- Caused by direct chemical attacks of dry gases like O2, Cl2, or SO2 present in the environment.

- Occurs through chemical reactions on the metal surface without the presence of moisture.

Example:

- Direct attack of metal by air (oxygen) to form oxide layers on the metal surface.

2. Electrochemical Corrosion:

- Occurs when a metal is placed in an aqueous medium (water) in the presence of moist air.

- Involves electrochemical reactions leading to corrosion.

Example:

- Rusting of iron.

Illustration (Electrochemical Corrosion):

- Example: Iron rod in aqueous conditions.

- The corrosion process includes oxidation at anode sites and reduction at cathode sites.
 Electrochemical Theory of Corrosion

Key Points:

- Corrosion is explained on the basis of galvanic cells formed on the metal surface.

- Minute galvanic cells develop where:

* Anode: Oxidation occurs.

* Cathode: Reduction occurs.

Oxidation Reaction (Anodic Reaction):

At the anode, the metal undergoes oxidation, releasing electrons.

Reaction: Fe -> Fe2+ + 2e- (Oxidation)

Reduction Reaction (Cathodic Reaction):

The electrons flow to the cathodic site, where oxygen is reduced in the presence of water.

Reaction: 1/2O2 + H2O + 2e- -> 2OH-

Corrosion Product:

The hydroxide ions formed react with Fe2+ ions, leading to the formation of rust.

Conditions for Cathodic Reactions:

1. Presence of Dissolved Oxygen (Neutral Electrolyte):

Reaction: O2 + 2H2O + 4e- -> 4OH-

2. Absence of Dissolved Oxygen (Deaerated Environment):

Reaction: 2H+ + 2e- -> H2 (gas)

3. Acidic Conditions:

Reaction: 2H+ + 2e- -> H2 (gas)

Overall Corrosion Process:

1. At Anode: Fe -> Fe2+ + 2e-

2. At Cathode: 1/2O2 + H2O + 2e- -> 2OH-

3. Formation of Rust:

- Ferrous hydroxide is formed: Fe2+ + 2OH- -> Fe(OH)2

- Further oxidation leads to hydrated ferric oxide (rust):

4Fe(OH)2 + O2 + 6H2O -> 4Fe(OH)3 -> Fe2O3 · xH2O (Rust)

 Differential or Galvanic Corrosion

Key Concept:

- When two dissimilar metals are in contact with each other, a potential difference is set up between the me

- The metal higher in the galvanic series acts as the anode and undergoes corrosion due to its lower electro

- The metal lower in the galvanic series acts as the cathode and is protected from corrosion due to its highe

Process Explanation:

1. Anodic Reaction:

At the anode, the metal (higher in the galvanic series) undergoes oxidation.

Reaction: Fe -> Fe2+ + 2e- (Oxidation)

2. Cathodic Reaction:

At the cathode, reduction occurs, and the cathodic metal is protected.

Reaction: Cu2+ + 2e- -> Cu (Reduction)

Example:

- Setup: Iron (Fe) and Copper (Cu) in a neutral, aerated solution of NaCl.

* Anode: Iron (Fe)

- Oxidation occurs, releasing Fe2+ ions into the solution.

* Cathode: Copper (Cu)

- Reduction occurs, depositing Cu from Cu2+ ions in the solution.

Summary:

- The flow of electrons from the anode to the cathode results in the corrosion of the anode.

- Diagram Description: The setup illustrates the flow of electrons from Fe (anode) to Cu (cathode) in

the electrolyte.
 Differential or Galvanic Corrosion: Examples

Key Explanation:

- Experimental Setup:

* Two dissimilar metals, Iron (Fe) and Copper (Cu), are placed in a neutral, aerated solution of sodium chl

* Fe (Anode): Acts as the anode due to its low electrode potential and undergoes corrosion.

* Cu (Cathode): Acts as the cathode due to its high electrode potential and remains free from corrosion.

1. Reaction at the Anode:

Fe -> Fe2+ + 2e- (Oxidation)

2. Reaction at the Cathode:

Cu2+ + 2e- -> Cu (Reduction)

Observation:

This type of corrosion is common when two dissimilar metals are in electrical contact within a

conductive electrolyte.

Additional Example:

- Setup:

* A piece of iron metal is combined with zinc and exposed to a corrosive environment.

* Zinc (Zn): Acts as the anode and undergoes corrosion.

* Iron (Fe): Acts as the cathode and remains free from corrosion.

Anodic Reaction: Zn -> Zn2+ + 2e-

Cathodic Reaction: Fe2+ + 2e- -> Fe

Electrons flow from zinc to iron, as illustrated in the diagram.

Diagram Description:

1. Iron and Zinc:

- Zinc serves as the anode, releasing electrons, while iron serves as the cathode, re

- A conductive electrolyte ensures the flow of ions between the two metals.

2. Iron and Copper:

- Similar reactions occur, with iron acting as the anode and copper as the cathode.
 Differential Aeration Theory of Corrosion

Key Concept:

- This type of corrosion occurs due to differences in the concentration of oxygen on different parts of the me

- The area with less oxygen acts as the anode and undergoes corrosion (oxidation).

- The area with more oxygen acts as the cathode and remains protected from corrosion.

Process Explanation:

1. Anodic Reaction:

Reaction: Fe -> Fe2+ + 2e- (Oxidation)

2. Cathodic Reaction:

Reaction: 1/2O2 + H2O + 2e- -> 2OH- (Reduction)

Example:

- Partially Immersed Iron Rod:

* When an iron rod is partially immersed in water:

- The portion inside the water is less aerated and acts as the anode (undergoes corrosion).

- The portion above the water is more aerated and acts as the cathode (protected from corrosion).

Diagram Description:

1. Anode:

- The less aerated portion of the metal surface (under water) undergoes oxidation.

- Reaction: Fe -> Fe2+ + 2e-

2. Cathode:

- The more aerated portion of the metal surface (above water) undergoes reduction.

- Reaction: 1/2O2 + H2O + 2e- -> 2OH-

Observation:

- According to this theory:

* Areas with less oxygen concentration on the metal surface are anodic and corrode.

* Areas with more oxygen concentration are cathodic and remain free from corrosion.
 Pitting Corrosion

Key Concept:

- Corrosion occurring in the form of pits or holes on a metal surface is known as pitting corrosion.

- This type of corrosion is explained by the differential aeration theory, where:

* Less aerated areas act as the anode and undergo corrosion.

* More aerated areas act as the cathode and remain protected.

Process Explanation:

1. Anodic Area:

The anodic area is smaller compared to the cathodic area. Corrosion is concentrated at the anode,

leading to localized pits or holes.

Reaction at Anode: Fe -> Fe2+ + 2e- (Oxidation)

2. Cathodic Area:

The cathodic area is larger, where electrons from the anode participate in reduction reactions.

Reaction at Cathode: 1/2O2 + H2O + 2e- -> 2OH- (Reduction)

Example:

- If the metal surface is partially covered by dust or sand and exposed to

moisture:

* The covered portion forms the anodic area (less oxygen) and undergoes

corrosion.

* The uncovered portion forms the cathodic area (more oxygen) and remains

free from corrosion.

Practical Examples of Pitting Corrosion:

1. Portion of a nail inside the wall: The portion inside the wall is less aerated (anode)

2. Cracked portions of metal surfaces: Cracks serve as anodic areas and are prone to

3. Paper pins inside paper sheets: Pins inside paper (less aerated) corrode while expo

4. Window rods in frames: The portion inside the frame is less aerated and corrodes.

Diagram Description:

- The metal surface covered by dust or sand becomes the anode and undergoes corro

- The uncovered portion of the metal surface becomes the cathode and is protected.
 Corrosion in Mild Steel Water Tanks and Ships

Key Concept:

- This type of corrosion is explained by the differential aeration theory, where:

* Less aerated areas (lower oxygen concentration) act as the anode and undergo corrosion.

* More aerated areas (higher oxygen concentration) act as the cathode and are protected.

Process Explanation:

1. Anodic Reaction:

Reaction: Fe -> Fe2+ + 2e- (Oxidation)

2. Cathodic Reaction:

Reaction: 1/2O2 + H2O + 2e- -> 2OH- (Reduction)

Examples of Corrosion:

1. Mild Steel Water Tanks:

- The less aerated portion (bottom or submerged parts) acts as the anode and corro

- The more aerated portion (near the surface) acts as the cathode and is protected.

- Commonly observed in water tanks used for storage.

2. Ships:

- The portion of the ship submerged in water is less aerated and acts as the anode,

- The portion of the ship above the water surface is more aerated and acts as the ca

Diagram Description:

- Anode: Represents the submerged part of the tank or ship with lower oxygen conce

- Cathode: Represents the part above the water level with higher oxygen concentratio