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TITANIC – Resting or Reacting?

The famous Titanic shipwreck has been submerged 4km below the surface of the North
Atlantic Ocean for nearly 100 years. Scientists believed that a number of factors typical of a deep
ocean environment would keep the Titanic in relatively good condition until the technology required
to salvage it was developed. However, in 1985 when the technology became available and the Titanic
wreck was first explored, scientists were surprised at what they discovered. The Titanic had corroded
far beyond what they had imagined, contrary to their predictions. The scientists didn’t yet know about
one other factor that heavily contributed to the corrosion of the Titanic. All the subsequent research
concerning the Titanic has contributed to explaining why the scientists’ predictions were incorrect.

The hull of the Titanic is made of steel which is an alloy of mostly iron and about 0.2-1.7%
carbon for strength (Broad, 1998; Wikipedia, 2008). Iron is an active metal, which means that when it
corrodes, the by-products of corrosion do not form a protective coating on the metal to prevent further
corrosion. Instead, when iron rusts, the iron oxide (Fe2O3) forms a porous crust that is permeable to
water. This allows more water to come in contact with the un-corroded iron underneath the rust layer,
causing it to continue to rust. Passive metals such as copper and aluminium form a protective layer of
corrosion that prevents the metal from further rusting. However because of porous rust, iron can
continue to rust until there is no pure metal left.

The most rusting occurred where the iron was under mechanical stress in places such as joins,
bends and rivets. When iron is under stress, the Fe atoms are less closely bonded so it becomes easier
for them to be oxidised by the dissolved oxygen in the water. In the following redox reaction (the
rusting of iron where oxygen is present), iron is the anode and oxygen is the cathode – electrons are
transferred from the iron to the oxygen – oxidising the iron and reducing the oxygen.

Fe(s)  Fe2+(aq) + 2e- Iron oxidation half-reaction

Oxygen reduction half-reaction


O2(g) + 2H2O(l) + 4e-  4OH-(aq)
Redox reaction
2Fe(s) + O2(g) + 2H2O(l)  2Fe2+(aq) + 4OH-(aq)
Synthesis reaction
2Fe2+(aq) + 4OH-(aq)  Fe(OH)2(s)
Second oxidation of iron
4Fe(OH)2(s) + O2(g)  2Fe2O3(s) + 4H2O(l) corrosion product is rust
(Charles Sturt University, 2004)
This sort of rusting occurs most easily in warm temperatures where oxygen, water and salts or
impurities are present. It is universally accepted that ocean temperature decreases with depth as
pressure increases. Also, gas solubility increases while salt solubility decreases as temperature
decreases. At 4km below the ocean’s surface, with the water temperature being near freezing and little
oxygen or salt dissolved in the water, any chemical reactions would be hindered. Based on this
information, scientists in the 1910’s predicted that the Titanic would corrode only very slowly.
However, the one factor they were not aware of at the time was “iron-eating” bacteria (Charles Sturt
University, 2004).

At great depths of the ocean (below 1000m), lives anaerobic sulfate-reducing bacteria (also known as
“iron-eating” bacteria). The bacteria is said to be “iron-eating” because it reduces sulfate as the first of
several chemical reactions that contribute to the corrosion of iron. Sulfate ions are plentiful in sea
water which the abundant sulfate-reducing bacteria feed on and produce hydrogen sulfide (H2S) as a

© Sarah Don, Australia, 2008


result. The equation below shows the reduction reaction caused by the sulfate-reducing bacteria. The
oxidation number of sulfur has changed from +6 to -2, hence sulfur has been reduced.
+6 -8=-2 +2 -2=0
SO42- + 10H+ + 8e-  H2S + 4H2O

The pH of seawater is typically 8, however as ocean depth increases, the solubility of carbon dioxide
(CO2) increases, causing the water to become more acidic as shown in the following chemical
equation.

H2O + CO2  H2CO3

The corrosion of iron occurs more rapidly in acidic water, which counteracts the effect that the depth
and low temperature of the ocean has on slowing the corrosion of the Titanic wreck. Some areas of
the water surrounding the Titanic was found to be of a pH of as low as 4. Also, the higher
concentration of hydrogen ions (made available by the dissolved hydrogen sulfide in the water)
contributes to the corrosion of iron as shown in the following equations.

Fe(s)  Fe2+(aq) + 2e-


Two half-reactions of galvanic corrosion of iron
2H+(aq) + 2e-  H2(g)

Fe(s) + 2H+(aq)  Fe2+(aq) + H2(g) (Charles Sturt University, 2004)

The sulfate-reducing bacteria are then able to


convert the hydrogen gas (H2) into hydrogen ions
(H+) which then chemically react to reduce the
sulfate ions in the water, and more iron is
consequently ionised.

On the Titanic, researchers have found what


are called rusticles – icicle-shaped rust formations as
pictured in figure 1. These rusticles provide an ideal
environment for the sulfate-reducing bacteria to live.
Also, the hydrogen sulfide (H2S) produced by the
sulfate-reducing bacteria dissociates into its ions in
 Figure 1 – Rusticles on the bow of the Titanic
the sea water and the sulfide ions (S2-) form a (Gould, 2006).
precipitate with the iron ions (Fe2+) in the water as
shown in the following equations.

H2S(aq)  2H+ + S2- Hydrogen sulfide dissociating into ions

Fe(s) + 2H+  Fe2+ + H2(g) Oxidation of iron

Synthesis reaction of iron and sulfide ions


Fe2+ + S2-  FeS(s)

The resulting iron sulfide (FeS) forms insoluble deposits similar to the rusticles, although they have a
black and less porous appearance than rust. The precipitation of iron sulfide isolates more H+ ions,
making them available for involvement in the oxidation of more iron. This, in turn, increases the rate
at which the steel hull of the Titanic rusts.

© Sarah Don, Australia, 2008


One other relatively minor – however still considerable – factor in the increased corrosion rate
of the Titanic is due to organic material aboard the ship. Because the Titanic was a luxury vessel, it
was largely fitted out with interior wooden panelling. As the cellulose in the wood on the titanic
shipwreck breaks down, the oxygen released further contributes to the corrosion of the iron hull. The
released oxygen fuels normal rusting reactions and also feeds the aerobic bacteria which produce by-
products that decrease the pH of the water surrounding the Titanic. (Charles Sturt University, 2004)

Sulfur-reducing bacteria was not the only extra contributing factor involved in the faster-than-
expected rate of corrosion of the Titanic, though it was the most significant. Normal rusting in the
presence of oxygen and dissolved salts in the seawater still played a large role in the corrosion of the
Titanic, however slowed. At the Titanic’s current rate of decay, scientists have predicted that the
wreck will have completely rusted away all of the steel of the hull within the next 75-90 years (Gould,
2006). The discovery of the anaerobic bacteria has allowed scientists to adjust their methods of
predicting the corrosion rate of shipwrecks depending on their associated environmental conditions
far below the ocean’s surface. For the era in which the Titanic sank, with the established scientific
knowledge of marine corrosion, scientists made logical predictions. However the unknown factor of
the anaerobic sulfur-reducing bacteria caused their predictions to be found inaccurate. Therefore,
because the environmental conditions at 4km below the surface of the ocean favour spontaneous
corrosion, the Titanic is rusting at a much faster rate than was first thought.

© Sarah Don, Australia, 2008


BIBLIOGRAPHY

Broad, W. (1998) Faulty Rivets Emerge as Clues to Titanic Disaster, The New York Times,
http://query.nytimes.com/gst/fullpage.html?res=980CE1DB133AF934A15752C0A96E958260&sec=
&spon=&pagewanted=all (18/05/08)
Charles Sturt University (2004) Shipwrecks, Corrosion and Conservation: 1. The ocean as an
electrolyte, http://www.hsc.csu.edu.au/chemistry/options/shipwrecks/ (18/05/08)
Charles Sturt University (2004) Shipwrecks, Corrosion and Conservation: 2. Corrosion of iron and
its alloys, http://www.hsc.csu.edu.au/chemistry/options/shipwrecks/2728/ch961Dec2_03.htm
(18/05/08)
Charles Sturt University (2004) Shipwrecks, Corrosion and Conservation: 3. Electrolytic cells,
http://www.hsc.csu.edu.au/chemistry/options/shipwrecks/2730/ch963Dec2_03.htm (18/05/08)
Charles Sturt University (2004) Shipwrecks, Corrosion and Conservation: 4. Marine environment
protection, http://www.hsc.csu.edu.au/chemistry/options/shipwrecks/2731/ch964Dec2_03.htm
(18/05/08)
Charles Sturt University (2004) Shipwrecks, Corrosion and Conservation: 5. Rate of decay and
corrosion, http://www.hsc.csu.edu.au/chemistry/options/shipwrecks/2732/ch965Dec2_03.htm
(18/05/08)
Charles Sturt University (2004) Shipwrecks, Corrosion and Conservation: 6. Corrosion at great
depths, http://www.hsc.csu.edu.au/chemistry/options/shipwrecks/2733/ch966Dec2_03.htm (18/05/08)
DeAngelis, M. (2005) Deep divers explore Titanic shipwreck, CDNN - Cyber Diver News Network,
http://www.cdnn.info/news/industry/i050906.html (29/04/08)
Gould, M. Et.Al (2006) Chemistry in Use – Book 2, McGraw Hill Education, Australia.
Miles, K.A. & Peters II, C.F (2001) The Science of Titanic, and How to Wreck the Shipwreck,
http://starryskies.com/Artshtml/dln/11-00/titanic.pt1.html (05/05/08)
National Geographic Society Press Release (2004) Scientists Return to the Titanic,
http://usinfo.state.gov/journals/itgic/0404/ijge/gj09b.htm (12/05/08)
Vector Corrosion Technologies (2005) Impressed Current Cathodic Protection, http://www.vector-
corrosion.com/impcurrent_main.html (14/05/08)
Vector Corrosion Technologies (2005) Corrosion Basics: Understanding the Different Types of
Corrosion that Affect Concrete, http://www.vector-corrosion.com/corr_basics.html (01/05/08)
Wikipedia, (2008) Cathodic protection, http://en.wikipedia.org/wiki/Cathodic_protection (30/04/08)
Wikipedia, (2008) Carbonic acid, http://en.wikipedia.org/wiki/Carbonic_acid (18/05/08)
Wikipedia, (2008) RMS Titanic, http://en.wikipedia.org/wiki/RMS_Titanic (18/05/08)
Wikipedia, (2008) Steel, http://en.wikipedia.org/wiki/Steel (18/05/08)
Wikipedia, (2008) Rust, http://en.wikipedia.org/wiki/Rust (18/05/08)

© Sarah Don, Australia, 2008