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D.H. Lister & W.G. Cook: UN1001: Reactor Chemistry and Corrosion Section 1: Introduction To Corrosion
D.H. Lister & W.G. Cook: UN1001: Reactor Chemistry and Corrosion Section 1: Introduction To Corrosion
What is corrosion? Usually, it is the reaction of a metal with its environment: e.g. rusting of iron: 4 Fe + 3 O2 + 2 H2O 4 FeOOH (lepidocrocite) BUT: at high temperature the corrosion of iron can produce: 3 Fe + 4 H2O Fe3O4 (magnetite) + 4 H2 Sometimes, non-metals are said to corrode: e.g. degradation of graphite moderator in a CO2 cooled nuclear reactor C + CO2 2 CO (may be inhibited by addition of CH4)
Discussion points:
1. 2. 3. 4. 5. Other examples of metal corrosion? Do buildings corrode (brick, stone, concrete)? What about erosion? - is it a corrosion phenomenon? Can corrosion be desirable? Other types of corrosion (e.g., plastic, wood, etc.)?
Why does metal corrode? Energy is released as material proceeds towards natural state i.e. the thermodynamically stable state. Thus, rusting of iron is a reversion towards the (hydrated - usually) ore; e.g., if lepidocrocite is dehydrated, we get: 2Fe OOH Fe2O3 (haematite) + H2O Corrosion, especially of metals, is usually an oxidative process i.e. the metal loses electrons: wa a th m l h t re e eta e.g., 4 Cu + O2 2 Cu2O o id tio sta x a n tes? Zn + 2HCl ZnCl2 + H2
5whataretheion
The rows on the periodic chart are periods. The columns are groups. Elements in the same group have similar chemical properties. e.g. Group 8 are all gases and are relatively inert, hence they are called the NOBEL GASES.
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Valence describes the possible number of electrons an ion will pick up or donate. The valence state a particular compound is in is also called its oxidation state.
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The Group A elements are classified as having a single oxidation state (usually); The transition metals can have multiple oxidation states: 10
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What about the magnetite formation reaction? 3 Fe + 4 H2O Fe3O4 + 4 H2 3 iron, 8 hydrogen and 4 oxygen atoms are on each side.
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Corrosion reactions are actually electrochemical reactions that proceed through the transfer of charge (electrons). Consider the oxidation state of the atoms in the previous corrosion reaction. Fe (metal) O oxidation state = 0 other possible oxidation states = +2 and +3 oxidation state = -2 (always)
Therefore the 3 positive iron atoms must combine to balance the 8 negative charges of the oxygen atoms how? 14
Fe(2+)Fe2(3+)O4(2-)
So in order for this reaction to proceed, 8 electrons had to be released from the iron. The release of electrons is called oxidation. For the system to remain balanced, the electrons need to be consumed this is done in a reduction reaction. The combination of reduction and oxidation reactions is called a redox reaction. What is the reduction reaction in this example? 15
We typically break redox reactions into their two separate reactions that may be added together to obtain the overall reaction. Thus: 3 Fe Fe2+ + 2 Fe3+ + 8 eoxidation 4 H2O + Fe2+ + 2 Fe3+ + 8 e- Fe3O4 + H2 reduction What we generally find is several intermediate steps may occur with the basic reaction being: Fe Fe2+ + 2 e2 H+ + 2 e- H2 16
/2 O2-
M + Z/4 O2
MOZ/2
For example, the corrosion of zinc in hydrochloric acid is the net result of two electrochemical reactions: Zn Zn2+ + 2 e2 HCl + 2e- H2 + 2 Cl- (2 H+ + 2 e- H2) Zn + HCl H2 + ZnCl (Zn+ + Cl-) Question: which is the reduced species?
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