Oxide layer of iron cannot protect iron

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Discussion Overview

The discussion centers on the effectiveness of the oxide layer of iron in protecting it from corrosion, comparing it to the protective layers formed by aluminum and zinc. Participants explore the structural differences in the corrosion products and the implications for rust formation, as well as factors that influence the rusting process.

Discussion Character

  • Technical explanation
  • Debate/contested
  • Experimental/applied

Main Points Raised

  • Some participants argue that the oxide layer of iron, specifically rust, is permeable and does not form a coherent diffusion barrier due to its layered structure, which includes hydrated ferric oxide and magnetite.
  • Others note that the hydroxides and oxyhydroxides of iron are not stable and are soluble, which contributes to the ineffectiveness of rust as a protective layer.
  • One participant mentions that alloying iron with chromium and nickel can produce stainless steels that resist rust formation through the formation of protective oxides.
  • There is a question about how aqueous ionic substances accelerate the rusting process, with a participant explaining that they act as electrolytes, facilitating electron transfer and speeding up oxidation reactions.
  • A participant raises questions about the specific locations on an iron nail where rusting occurs first, suggesting that the presence of certain substances may influence this pattern.

Areas of Agreement / Disagreement

Participants express differing views on the protective capabilities of the oxide layer of iron compared to those of aluminum and zinc. There is no consensus on the effectiveness of rust as a protective barrier, and the discussion includes multiple competing perspectives on the factors influencing rust formation.

Contextual Notes

Participants reference the Pilling-Bedworth ratio as a relevant concept, indicating that the discussion may depend on specific definitions and structural considerations of oxides. The influence of electrolytes on rusting is also noted, but the exact mechanisms remain partially unresolved.

primarygun
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Why the oxide layer of iron cannot protect iron from corrosion like aluminium and zinc?
 
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While the corrosion products of aluminum and zinc are dense and impervious (ceramic) oxides, rust on iron, is quite permeable - both to air as well as moisture. The reason the rust does not form a coherent diffusion barrier is, in large part due to the fact that rust typically has 3 layers.

The outer layer, with easy access to oxygen and water, is usually hydrated ferric oxide or even ferric hydroxide. Then there's an intermediate layer of magnetite (Fe3O4), and finally layers of ferric and ferrous oxides. This variation in composition, and the attendant lattice mismatch makes rust quite porous, and hence ineffective as a diffusion barrier.

You may have noticed that it's quite easy to scrape off or chip off rust, but impossible to do the same with aluminum oxide.
 
Adding to what Gokul43201 wrote, the hydroxides and oxyhydroxides of Fe are not very stable - they are soluble - nor are they structurally strong.

Iron has to be alloyed to resist rust formation - usually with Cr and Ni - to produce 'stainless steels'. The Cr (primarily) and Ni form protective oxides.

You may also want to look at the Pilling-Bedworth ratio which is a relationship between the structure of the oxide compared to the metal.

See - http://www.corrosion-doctors.org/HotCorrosion/Pilling.htm

or google on "Pilling-Bedworth".
 
Last edited by a moderator:
How does presence of aqeuous ionic substance speed up the process?
Why does rusting occur on the tip and the tail of an iron nail first?
(shown by potassium hexacyanoferrate)
 
Last edited:
well an aqeuous ionic substance will speed up the rusting process because, for the most part, they are electrolytes (at least the ones you are talking about anyway). they make it easier for electrons to be conducted from substance to substance, speeding up the oxidation reaction, afterall, all oxidation is, is an atom loosing an electron...

leo ger
loose electron OXIDATION
gain electron REDUCTION

depending on what is loosing or gaining the electron, it will gain either a positive or negative charge and then be attracted to the opposite charge.

so in the case of Iron (III) Oxide, the Iron is oxidized since it looses an electron (actually 3 in this case, since it has a positive charge of 3) and gains a positive charge, and the oxygen gain an electron since it has a negative charge, then the two are then attracted together. this whole process is sped up when the electrons can transfer easier, for example in the presence of an electrolyte.
 

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