Corrosion may be defined as chemical degradation or metal destruction by a chemical or electro-chemical process (reaction) with its environment, which is called corrosion. Corrosion will happen when these three things combine:
- Water
- Metal
- Oxygen
In water system, the principal factors affecting the corrosion of iron are:
- Potential difference
- Dissolved solids (electrolyte)
- Depolarize (presence of O2)
- CO2-free mineral acid and PH factors
Corrosion Theory
The existence of potential differences within a metal or between two metals will cause chemical reactions at the cathode and the anode.
Explanation
For understanding let us consider a simple cell in which two electrodes are present i.e. (anode and cathode). One of iron and the other of copper and both are in water. When two electrodes are connected by wire a closed circuit is completed connecting two electrodes externally by wire and internally by the electrolyte (H2O). Electrons will move from Iron (Fe) towards copper (Cu) because iron (Fe) is anode. This production of electrons is due to the following reaction:
At the Anode:
Fe → Fe++ + 2e-
At Cathode
H2O → H+ + –OH
2H+ + 2e → H2
In the above reaction, iron (Fe) is dissolved in H2O as Fe++ (anode reaction), and H2 gas is liberated at the cathode (cathodic reaction). The Fe++ Combines with -OH to form Fe(OH)2. This process stops sometimes due to the formation of a thin film of H2 gas on the Cathode (Copper) which prevents the flow of electrons in an external circuit (from anode to cathode). If oxygen is present in water, then it combines with H+ at the cathode to form water,
4H+ + O2 → 2 H2O
This reaction of O2 with 4H+ prevents the formation of film (layer) over the cathode. Thus, in the presence of O2, the cross-reaction enhances the anodic-cathodic reaction and increases the corrosion rate.
In presence of Oxygen (O2), corrosion product Fe(OH)3 is formed by oxidation reaction,
4Fe (OH)2 + O2 + 2H2O → 4Fe(OH)3
4Fe (OH)3 is insoluble and becomes precipitate.
Corrosion Mechanism:
As described earlier corrosion is an electrochemical process in which an electrical potential difference develops between two metals or different parts of a single metal. Thus, voltage can be measured when metals are electrically connected to standard electrodes. The electrical potential may be more or less than standard. The voltage is expressed as either positive (+) or negative (-). So, the difference in potential allows current to pass through the metal causing reactions are anodic and cathodic sites. These sites constitute corrosion cells.
The anode is the region of lower potential and conversely, the cathode is the region of higher potential. Theoretically, therefore we can assume that if two metals are connected one is of lower potential is anode and the other is of higher potential the cathode.
Single Corrosion Cell:
- Anodic Corrosion cell
The anodic corrosion reaction is done by the dissolution of metal.
Fe → Fe++ + 2e
- Anodic Corrosion cell
The electron migrates through the metal to the cathode area where it reacts in any of several ways depending upon acidity and reaction in water.
- Reduction of water
2H2O + 2e → H2 + 2OH
- Reduction of H+ ions in acidic solution
H2O → H+ + OH
2H+ + 2e → H2
- Oxygen-reduction occurred in aerated acidic solution
O2 + 4H+ + 4e → 2H2O
- Oxygen reduction of water normally occurs in aerated water
O2 + 2H2O + 4 e → 4(OH-)
- Ferric ion reduction occurs in an acidic medium
Fe+3 + e → Fe+2
Negative charge ions such as OH- ions are produced at the cathode and positive (+) charge at anode will move towards cathode.
OH- ions will combine with Fe+ ions which are produced at the anode.
Fe+2 + 2(OH-) → Fe(OH)2
Fe(OH)2 is produced which has very low solubility and remains in white flocs. These flocks rapidly oxidize to Fe(OH)3.
4Fe(OH)3 + O2 + 2H2O → 4Fe(OH)3
Dehydration of this product leads to the formation of the corrosion product in red rust.
2Fe(OH)3 → Fe2O3 + 3H2O
Depolarization:
It has been noted that sometimes the cathodic reaction is reduced due to the formation of hydrogen gas in a cathode which prevents the flow of electrons in the external circuit (from anode to cathode).
Hydrogen gas from the barrier for corrosion reaction and the corrosion reaction stops. This is possible only if oxygen is not present in the media.
H2 + O2 → 2(OH)
If O2 is present in the media it will react with H2 gas and depolarization occurs. This is said to be a depolarization reaction and O2 acts as depolarization.
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