Beruflich Dokumente
Kultur Dokumente
6 SHIPWRECKS,
CORROSION AND CONSERVATION
1. The chemical composition of the ocean implies its potential role as
an electrolyte.
1.2.1 Identify the origins of the minerals in oceans as: leaching by rainwater from
terrestrial environments, hydrothermal vents in mid-ocean ridges.
Mineral ions in oceans come from two main sources: the leaching by rainwater from terrestrial
environments and hydrothermal vents in mid-ocean ridges. Rainwater washes over and leaches
mineral ions from rocks and soils in the process of weathering. These ions, including Ca 2+, Mg2+
and HCO32, are carried by the water-cycle into the sea. When seawater enters hydrothermal
vents in mid-ocean ridges, or when it cools mineral-rich magma, it also leaches out mineral ions.
1.2.2 Outline the role of electron transfer in oxidation-reduction reactions.
1.2.3 Identify that oxidation-reduction reactions can occur when ions are free to
move in liquid electrolytes.
Oxidation is the loss of electrons, reduction is the gain. In oxidation-reduction reactions, the
electron moves from the anode (the site of oxidation) to the cathode (the site of reduction).
Without this electron transfer, there will be no reaction.
Redox reactions can occur when ions are free to move in liquid electrolytes. An example of this is
the displacement of copper by zinc in a copper solution. Zinc metal comes in contact with copper
ions and u get electron transfer. Zinc loses electrons and becomes cations while copper cations
gain electrons. If the ions cannot move freely, for example two compartments separated by a very
fine semipermeable membrane that Cu2+ cannot penetrate, then the redox reaction will not occur.1
1.2.4 Describe the work of Galvani, Volta, Davy and Faraday in increasing
understanding of electron transfer reactions.
1.3.1 Process information from secondary sources to outline and analyse the
impact of the work of Galvani, Volta, Davy and Faraday in understanding electron
transfer reactions.
Luigi Galvani was an Italian physician in the eighteenth century. In the 1780s he undertook a
series of investigation into the twitching of frog leg muscles with a static electricity generator. He
also obtained twitching by pressing a brass hook into the frogs spinal cord and hanging the hook
on an iron railing. He concluded that animal tissue contained an electric fluid, through which a
force, animal electricity, could acted upon the tissue. This was the first example in our
understanding of electrolytes in electron transfer reactions.
Alessandro Volta was a contemporary of Galvani, who later refuted his theory of animal
electricity. He believed that the twitching of the frog legs were due to the two different metal
pieces holding the legs. In 1800, Volta made his most famous discovery, the voltaic pile, a stack
of silver and zinc discs separated by felt pads soaking in brine (salt solution). This discovery led
to our understanding of using electron transfer reactions to generate electricity.
Humphry Davy was inspired by work of other scientists who managed to electrolyse and
decompose water into hydrogen and water using a voltaic pile. This led to his electrolysis
experiments where he decomposed potassium hydroxide (potash) and molten sodium hydroxide
1
Credit where credit is due: this very good explanation was suggested by phenol. All kudos is owed to him.
-1-
(soda) into previously undiscovered elements, potassium and sodium. These investigations led to
our understanding of electron transfer reactions as the basis of electrolysis.
Michael Faraday was Davys laboratory assistant, and as a result continued Davys work on
electrolysis. He was the first person to define the laws of electrolysis and quantify electrolysis. He
also introduced the terminology used today such as electrolyte, cation and anion. His discoveries
led a better understanding of electron transfer reactions in electrolysis.
Fe(s)
O2(g) +
Fe2+(aq) +
H2O(l) +
2e
2e
2OH
E = + 0.44V
E = + 0.40V
Since the total potential of both half-equations is positive, the reaction is spontaneous. The Fe2+
ions and the OH ions form a green precipitate, Fe(OH) 2. Fe(OH)2 will oxide further in the
presence of oxygen and water to form Fe(OH) 3:
4Fe(s)
3O2(g)
6H2O(l)
4Fe(OH)3(s)
Fe(OH)3 will then dehydrate to form rust, Fe 2O32H2O. Therefore the overall equation for the
formation of rust is:
4Fe(s)
3O2(g)
4H2O(l)
-2-
Fe2O32H2O(s)
Fe(s)
O2(l)
Fe2+(aq) +
2H+(aq) +
2e
2e
H2O(l)
E = + 0.44V
E = +1.23V
-3-
CuSO4(aq):
Cu2+(aq)
H2O(l)
Cu2+(aq) +
2e
Cu
(goes
towards cathode)
H2O(l)
O2(g) + 2H+ + 2e
(bubbling at anode)
2e
-4-
3.3.1 Plan and perform a first-hand investigation and gather first data to identify
the factors that affect the rate of an electrolysis reaction.
Oxidation: I(aq) I2(aq) + e
E = 0.77V
Reduction: H2O(l) H2(g) + OH(aq) E = 0.83V
We use the amount of bubbling of hydrogen gas as
the indicator of the rate of electrolysis. The
equipment was set up as the diagram. The rate of
bubbling was measured on a scale of 1 to 5.
To show how concentration affected the rate, we
changed the potassium iodide solution to 2M.
To show how the nature of electrolyte affected the
rate, we changed to using molten potassium
iodide.
To show how the nature of electrodes affected the
rate, we used copper electrodes; then we used
cylindrical carbon electrodes instead of rectangular.
Surface alloys:
New paints:
4.2.2 Predict the metal which corrodes when two metals form an electrochemical
cell using a list of standard potentials.
Since corrosion is really the oxidation of a metal into its ionic form, when two metals of different
oxidation (electron-losing) potentials form an electrochemical cell, the one with the higher
oxidation potential will become the anode and corrode. The other will become the cathode, and
will be protected from corrosion.
4.2.3 Outline the process of cathodic protection, describing examples of its use in
both marine and wet terrestrial environments.
-5-
Fe(s)
Zn(s)
Fe2+(aq) +
Zn2+(aq) +
2e
2e
E = + 0.44V
E = + 0.76V
Since the oxidation potential of zinc is greater than that of iron, it will oxidise in preference (ie
become the anode) and render the iron as the cathode. Moreover, zinc, being a passivating
metal, will form an impervious layer of zinc oxide around the iron, giving further protection against
corrosion. Galvanised iron is used in marine environments such as galvanised nails and
terrestrial environments such as roofs and cars.
A similar principle is used in the process of using sacrificial anodes. A metal with greater oxidation
potential than iron is used so that it will oxidise in preference to iron. Zinc is usually chosen over
other metals (of greater oxidation potential) to decrease the rate of reaction and lengthen the life
of the anode. It is used in the hulls and propellers of ships and underground steel piping (a moist
terrestrial environment).
In the process of applied voltage, iron is connected to low voltage circuit, so that electrons are
pushed into it constantly, rendering it cathodic. This form of protection is usually used in
conjunction with the sacrificial anodes, in large ships, metal girders and some cars.
4.3.1 Identify data, gather and process information from first-hand or secondary
sources to trace historical developments in the choices of materials used in the
construction of ocean-going vessels with a focus on the metal used.
By 3000BC, some societies were constructing wooden ships. Wood was the most
common shipbuilding material until the nineteenth century.
Metals were used in some early ships, such as Viking longboats which had iron and
bronze fittings.
Around 1500AD the development of iron nails made it possible to connect wooden planks
to frames and bulkheads. This made the hull stronger and less flexible, but the nails
were susceptible to rapid corrosion.
By the 1800s composite ships were built using wooden planks over iron frames. The first
all iron ship was the British Vulcan, a passenger barge, launched in 1818. By 1870
more than 90% of the ships produced in the UK were iron.
Although they needed constant maintenance due to corrosion, iron ships had numerous
advantages over wooden ones: stronger, thus safer, more economical, easier to
repair, could be built larger, carry more cargo, travelled faster, was not susceptible to
fire from cannonball explosions.
By the late 1800s shipbuilders began to use steel alloys, which meant lighter and
stronger ships.
In the early 1900s the invention of electric welding meant faster and better construction of
steel ships.
-6-
-7-
10H+(aq)
8e
-8-
H2S(aq)
4H2O(l)
H+(aq)
HS(aq)
Hydrogen sulfide produced may interact with lead or silver to form black deposits of lead or silver
sulfide.
This type of bacteria flourishes in deep-ocean environments due to the lack of oxygen, and
therefore the lack of competition.
Acidic environments promote corrosion because:
Reduction:
Reduction:
O2(l) +
O2(g) +
2H+(aq) +
H2O(l) +
2e
2e
H2O(l)
2OH
E = +1.23V
E = + 0.40V
As can be seen, the reducing potential of oxygen and hydrogen ions are greater than that of
oxygen and water. Therefore the reduction of oxygen and hydrogen ions happen in preference,
and, because of the higher potential, at a faster rate. Therefore the rate of corrosion is
accelerated in acidic environments.
6.3.1 Perform a first-hand investigation to compare and describe the rate of
corrosion of metals in different acidic and neutral solutions.
Three equal-sized samples of iron were placed and submerged in three test tubes with the
following contents: one was 10mL distilled water, another was 10mL 0.5M hydrochloric acid, the
third was 10mL 1M hydrochloric acid. Each day the evidence of corrosion were observed and
recorded on a scale of 1 to 5.
4OH
2H2O(l) + O2(g) + 4e
2H2O(l) 4H+ + O2(g) + 4e
Cathode: 2H2O(l) + 2e H2(g) + 2OH
An alkaline electrolyte, NaOH, is used to prevent
the corrosion of the iron as iron is passivated in
solutions with a pH >8. The chlorine ions are slowly
-9-
extracted from the corroded metal and oxidised on the anode. Hydrogen gas formed at the
cathode helps loosen the corrosion and other concretions.
7.2.4 Identify the use of electrolysis as a means of cleaning and stabilising iron,
copper and lead artefacts.
7.2.5 Discuss the range of chemical procedures which can be used to clean,
preserve and stabilise artefacts from wrecks and, where possible, provide an
example of the use of each procedure.
When an artefact is extracted, such as iron, crystallisation of salt and acidic oxidation must be
avoided:
Acidic Oxidation:
Therefore, the artefact must be first stabilised by storing it in an inhibitive solution such as 2 to 5%
sodium hydroxide; this ensures no further damage to the artefact by acidic oxidation.
Crystallisation of the saturated solution is then avoided by the process of desalination, where the
object is submerged in fresh water; the salt within
wooden artefacts is diluted and leached out by
osmosis. A 5% solution of polyethylene glycol
(PEG) is added to the water to add support to
fragile wooden artefacts. An example of this
process is a wooden ship at the Maritime Museum,
which, because it could not be submerged, was
sprayed daily for ten years to desalinise it.
The artefact is then treated to remove concretions,
or deposits, of CaCO3. The concretions are Xrayed to find their size and position; they are
removed very carefully by chisel and hammer, or
by dental drills. A thin of concretion is left on which
will be removed by hydrogen gas during
electrolysis.
Electrolysis is used to reverse the process of corrosion: the corroded object is made into the
cathode, the anode is usually platinum and the electrolyte a solution of sodium hydroxide. For
example, a corroded silver fork can be restored as follows:
Any silver ions will be reduced back onto the cathode as silver metal and the hydrogen gas will
remove remaining concretions. Often this process is done with a mesh anode, wrapped around
the cathode.
- 10 -
The artefact is then preserved for display usually by a combination of protections: the artefact
would most often be varnished to prevent oxygen and water re-entering; it would be kept in a
display cabinet which regulates an isolated environment and a voltage applied to it for cathodic
protection.
7.3.1 Perform an investigation and gather information from secondary sources to
compare conservation and restoration techniques applied in two Australia maritime
archaeological projects.
The Vernon anchors which are on display outside the Maritime Museum were conserved and
restored in the 1980s. Electrolysis was not applied to the anchors because it required the removal
of the timber stocks (which could cause unnecessary damage) and also because the cast iron
was in sufficiently good condition.
In 1992, the preservation process removed the outer corrosion and protective paint by blasting
with copper slag then polished the surface with garnet. The iron was then treated with zinc epoxy
paint. The timber stocks were saturated with a zinc napthenate solution (which retards the growth
of organisms such as mould).
The Endeavour cannons, part of Captain Cooks famous ship were rediscovered in 1969 after
being jettisoned when the Endeavour was damaged in the Great Barrier Reef in June 1770. The
six cannons were then transported into a salt solution with 10% formalin to kill any bacteria
present. Hammers were used to remove hard coral concretions from the cannons.
The cannons were then placed in 2% NaOH solution to prevent acidic corrosion; then electrolysis
was applied in NaOH baths for many weeks. After the baths, the cannons were washed with fresh
water at each refreshing of the electrolyte. After electrolytic treatment, the cannons were washed
for 5 months to remove any remaining chloride and hydroxide using distilled water with chromate
ions (the chromic oxide formed is a surface protective layer).
The cannons were dried for 48 hours at 120C. They were then immersed in molten
microcrystalline wax (as a further protective layer) for 5 days to ensure maximum penetration of
wax.
While the Endeavour cannons required electrolysis because of its badly corroded condition, the
Vernon anchors did not. The cannons required many steps of treatment (stabilisation, removal of
concretions, electrolysis and surface protection), while the anchors required only two (removal of
concretions and surface protection).
- 11 -