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By the end of this section, you will be able to:
  • Define corrosion
  • List some of the methods used to prevent or slow corrosion

Corrosion is usually defined as the degradation of metals due to an electrochemical process. The formation of rust on iron, tarnish on silver, and the blue-green patina that develops on copper are all examples of corrosion. The total cost of corrosion in the United States is significant, with estimates in excess of half a trillion dollars a year.

Statue of liberty: changing colors

The Statue of Liberty is a landmark every American recognizes. The Statue of Liberty is easily identified by its height, stance, and unique blue-green color ( [link] ). When this statue was first delivered from France, its appearance was not green. It was brown, the color of its copper “skin.” So how did the Statue of Liberty change colors? The change in appearance was a direct result of corrosion. The copper that is the primary component of the statue slowly underwent oxidation from the air. The oxidation-reduction reactions of copper metal in the environment occur in several steps. Copper metal is oxidized to copper(I) oxide (Cu 2 O), which is red, and then to copper(II) oxide, which is black

2Cu ( s ) + 1 2 O 2 ( g ) Cu 2 O ( s ) ( red )
Cu 2 O ( s ) + 1 2 O 2 ( g ) 2CuO ( s ) ( black )

Coal, which was often high in sulfur, was burned extensively in the early part of the last century. As a result, sulfur trioxide, carbon dioxide, and water all reacted with the CuO

2CuO ( s ) + CO 2 ( g ) + H 2 O ( l ) Cu 2 CO 3 (OH) 2 ( s ) (green)
3CuO ( s ) + 2CO 2 ( g ) + H 2 O ( l ) Cu 2 ( CO 3 ) 2 (OH) 2 ( s ) (blue)
4CuO ( s ) + SO 3 ( g ) + 3H 2 O ( l ) Cu 4 SO 4 (OH) 6 ( s ) (green)

These three compounds are responsible for the characteristic blue-green patina seen today. Fortunately, formation of the patina created a protective layer on the surface, preventing further corrosion of the copper skin. The formation of the protective layer is a form of passivation, which is discussed further in a later chapter.

This figure contains two photos of the Statue of Liberty. Photo a appears to be an antique photo which shows the original brown color of the copper covered statue. Photo b shows the blue-green appearance of the statue today. In both photos, the statue is shown atop a building, with a body of water in the background.
(a) The Statue of Liberty is covered with a copper skin, and was originally brown, as shown in this painting. (b) Exposure to the elements has resulted in the formation of the blue-green patina seen today.

Perhaps the most familiar example of corrosion is the formation of rust on iron. Iron will rust when it is exposed to oxygen and water. The main steps in the rusting of iron appear to involve the following ( [link] ). Once exposed to the atmosphere, iron rapidly oxidizes.

anode: Fe ( s ) Fe 2+ ( a q ) + 2 e E Fe 2+ /Fe ° = −0.44 V

The electrons reduce oxygen in the air in acidic solutions.

cathode: O 2 ( g ) + 4 H + ( a q ) + 4 e 2 H 2 O ( l ) E O 2 /O 2 ° = +1.23 V
overall: 2Fe ( s ) + O 2 ( g ) + 4H + ( a q ) 2 Fe 2+ ( a q ) + 2 H 2 O ( l ) E cell ° = +1.67 V

What we call rust is hydrated iron(III) oxide, which forms when iron(II) ions react further with oxygen.

4 Fe 2+ ( a q ) + O 2 ( g ) + ( 4 + 2 x ) H 2 O ( l ) 2 Fe 2 O 3 · x H 2 O ( s ) + 8 H + ( a q )

The number of water molecules is variable, so it is represented by x . Unlike the patina on copper, the formation of rust does not create a protective layer and so corrosion of the iron continues as the rust flakes off and exposes fresh iron to the atmosphere.

A grey rectangle, labeled “iron,” is shown with thin purple layers, labeled “Paint layer,” at its upper and lower surfaces. A gap in the upper purple layer at the upper left of the diagram is labeled “Cathodic site.” A blue droplet labeled “water” is positioned on top of the gap. A curved arrow extends from a space above the droplet to the surface of the grey region and into the water droplet. The base of the arrow is labeled “O subscript 2” and the tip of the arrow is labeled “H subscript 2 O.” A gap to the right and on the bottom side of the grey region shows that some of the grey region is gone from the region beneath the purple layer. A water droplet covers this gap and extends into the open space in the grey rectangle. The label “F e superscript 2 positive” is at the center of the droplet. A curved arrow points from the edge of the grey area below to the label. A second curved arrow extends from the F e superscript 2 positive arrow to a rust brown chunk on the lower surface of the purple layer at the edge of the water droplet. A curved arrow extends from O subscript 2 outside the droplet into the droplet to the rust brown chunk. The grey region at the lower right portion of the diagram is labeled “Anodic site.” An arrow extends from the anodic site toward the cathodic site, which is labeled “e superscript negative.”
Once the paint is scratched on a painted iron surface, corrosion occurs and rust begins to form. The speed of the spontaneous reaction is increased in the presence of electrolytes, such as the sodium chloride used on roads to melt ice and snow or in salt water.

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Source:  OpenStax, Chemistry. OpenStax CNX. May 20, 2015 Download for free at http://legacy.cnx.org/content/col11760/1.9
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