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TOPIC FOUR

SHIPWRECKS, CORROSION AND CONSERVATION


Contextual Outline
Electrochemistry plays an important part in both theoretical and practical chemistry. Since the
discovery of its theoretical basis, knowledge and understanding of the reactions involved have
greatly increased. Today electrochemistry is used in a wide range of applications, from space
travel to pacemakers to the mobile phone battery.
The ocean represents a massive electrolyte and the effects of the saline environment can be
investigated and analysed from the perspective of prevention of corrosion and its effects. The
salvaging of iron ships that have sunk into deep-water environments requires consideration of
the effects of anaerobic environments on corrosion. Conservation of salvaged artefacts can
require electrolytic reactions.
This module increases students understanding of the history, applications and uses of
chemistry and current issues, research and developments in chemistry.
Galvanic cells Devices that utilise the chemical energy released by a spontaneous redox
reaction to perform electrical work
Electrolytic cells device that utilises electrical energy to force a non spontaneous redox
reaction
Features
Similarities

Anode This is where oxidation occurs, liberate electrons

Cathode This is where reduction occurs, electrons enter

Salt bridge electrolyte used in order to allow the migration of ions and to neutralise the
charges of the two cells

Differences

Anode Galvanic cell is negative where as electrolytic cell is positive. This is to attract the
electrodes out of the anode

Cathode Galvanic cell is positive where as electrolytic cell is negative.

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Section One
The chemical composition of the ocean implies its potential role as an
electrolyte

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Identify the origins of the minerals in oceans as :


o Leaching by rainwater from terrestrial environments
o Hydrothermal vents in mid ocean ridges

Nature of the Ocean


The oceans of the world contains many dissolved ions, making ocean water a good electrolyte
and thus able to conduct electricity through mobile ions. This enables electrochemical process
to occur when the ocean water is in contact with metal, leading to corrosion. The typical
salinity of sea water is 3.5% w/w. The major ions in seawater are chloride and sodium.
Most common salts in ocean water
Cations
Na

Anions
Cl-

Mg2+

SO42-

Ca2+

CO32-

K+

Br-

Origins of minerals in the oceans

Leeching by Rain water Physical and chemical weather of rocks and soils cause rivers to
carry dissolved minerals to the ocean. Water can seep through into underground aquifers
which can dissolve greater quantities of these under certain conditions

Hydrothermal vents in mid-ocean ridges - Mid ocean ridges occur near the boundaries of
some of the tectonic plates due to geothermal activity where magmatic fluids rises from the
mantle and solidify to form these ridges. Sea water is able to percolate down the ridges
fissures or cracks and heated to high temperatures. This enables considerable leeching and
released back into the ocean via convection currents at the hydrothermal vents.

Outline the role of electron transfer in oxidation-reduction reactions


Identify that oxidation-reduction reactions can occur when ions are free to
move in liquid electrolytes

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A redox reaction is a chemical reaction where an electron is transferred from one species to
another.

Oxidation involves a loss of electrons

Reduction involves the gaining of electrons

The reductant that gives away electrons is said to be oxidised


The oxidant that gains electrons is said to be reduced.
Electrons transfer can occur directly between reactants or from the oxidation reaction site
through a conductor to the reduction reaction site. Such conductors are usually electrolyte
solutions; substances that dissolve in order to form ions. It contains mobile ions that are able
to freely conduct electricity.
e.g.
Oxidation:
Reduction:

Mg(s)

Pb2+(aq) +

Mg2+(aq)

2e- Pb

2e(s)

The magnesium metal is said to have been oxidised while the lead ions are said to have been
reduced
Redox reaction: Mg(s) +

Pb2+(aq)

Mg2+(aq)

Pb

(s)

Describe the work of Galvani, Volta, Davy and Faraday in increasing


understanding of electron transfer reactions
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

Outline: Sketch in general terms, indicate the main features


Analyse: Identify components and the relationships among them, draw out and relate
implications.
Luigi Galvani (1737 98)
Outline:
Galvani is credited with the first generation of an electric current. Galvani conducted
many experiments in which he observed a muscle contraction with static electricity. Galvani
discovered he could also produce this contraction after joining two wires of different
metals (copper hook to iron railings) and placing the unjoined ends into the frog leg,
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without a source of electrostatic charge. He incorrectly interpreted his findings as the


discovery of animal electricity; where the animal tissue contained a vital force which activated
nerves and muscle when spanned by different metals
Analysis:

Galvani contributed to the understanding of electron transfer reactions by discovering the


generation an electric current through the conversion of chemical energy into
electrical energy through the contact of two metals

His work pioneered the area of science called electrophysiology which was based on the
connection between electricity and muscular contraction discovered by Galvani

Alessandro Volta (1745 1827)


Outline:
Volta demonstrated that it was the wires of different metals that generated the
electricity rather than animal electricity. Volta proposed metallic electricity to describe
the current produced in this experiment. He made the first DC battery by creating the voltaic
pile that consisted of alternating discs of zinc and silver that were each separated by
cardboard soaked in a salt solution. By connecting the metals at the top and bottom of the pile
using metallic wires, a small electric current was produced. This creation caused the rejection
of Galvanis animal electricity as Volta believed that it was contact between the metals that
created the electricity. Volta also experimented with a range of metals and showed that
the degree of twitch was related to the types of metals used
Analysis:

Volta contributed to the understanding of electron transfer electrons by constructing a


useable galvanic cell which was the first source of a direct electric current where it was a
way of supplying electricity from chemicals

His usage of an electrolyte showed the importance as it is a vital component in allowing the
flow of electricity. Similarly by connecting the top and bottom wires, he showed how a
complete circuit was necessary in order to complete this electron transfer reaction.

Voltas observation showed chemical energy within the metals related to the supply of
electricity as he observed varying degrees of effects when using different metals to
reproduce the muscle contraction

Humphry Davy (1778 1829)


Outline:
Davy was the first to recognise that the electric current was actually produce by the chemical
reactions between the two alternate metals in the voltaic pile. Davy then explored the
electrochemical application of the voltaic pile and electric batteries in using them to decompose
compounds; later to be known as electrolysis. This enabled him to separate a number of
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elements from their compound form and isolated alkali elements such as potassium, sodium,
magnesium, calcium, strontium and barium and recognised them as newly discovered
elements. With these electrolysis reactions, he was able to decompose water into hydrogen
and oxygen gas. Also Davy suggested that acids contain replaceable hydrogen
Analysis:

Davy work impacted on the understanding of electron transfer reactions by showing how it
can be used to cause chemical changes in electrolytic cells that involve an electron transfer.

His use of the Voltaic pile to perform his electrolysis experiments led many scientists to
investigate the electrochemical field and discover new elements and observe the
decomposition of many substances in order to gain a better knowledge of electron transfer
and the chemistry of electricity and electron transfer reactions.

Davy realised that galvanism was a purely chemical process that depended on the
oxidation of the surface of metals

Michael Faraday (1791 1867)


Outline:
Faraday continued and extended Davys experiments and found quantitative laws pertaining to
electrolysis. Faraday was able to develop an electrolytic device for measuring electric charge
that consisted of a cell in which sulfuric acid was electrolysed and oxygen gas collected with its
volume measured.
Faraday developed his first law by analysing the relationship between the quantity of electricity
transferred into an electrolytic cell containing solutions of metallic salts and the mass of metal
deposited on the cathode.
Faradays first law of electrolysis:
The mass of metal produced at the cathode in an electrolytic cell is directly proportional to the
quantity of electricity passing through the cell
m = kQ
Faradays second law of electrolysis:
This law demonstrates the connection between the mass of metal deposited at the cathode
during electrolysis and the electrochemical equivalent of the metal. This electrochemical
equivalent was directly related tot the relative atomic weight, A, of the metal and inversely to
its valency, v.
M = QA/Fv (F is faradays constant of 96487 Coulombs)
Analysis:
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Faradays major contribution to the understanding of electron transfer reactions was the
recognition that were was a quantitative relationship between the mole of substances
formed during electrolysis and the quantity of electricity involved.

Faraday also systemized the terminology used in electrochemistry for electrochemistry and
introduced new terms such as electrode, electrolyte, ions (cations and anions), anode and
cathode.

All four scientists, Galvani, Volta, Davy and Faraday made great contributions to the
understanding of electron transfer reactions. It is due to the collective efforts of many
scientists over the centuries (such as these four) that our knowledge has gradually been built
upon and consequently improved greatly. The impact of their work of each scientist is great,
regardless of their accuracy. Their development went from a spark creating contractions in leg
muscles, animal electricity, to the idea that the current was generated by the contact between
two metals in a wet electrolyte.
While Galvani may have interpreted his frog experiment wrongly, it was due to his discovery
that Volta set out to prove his own interpretation. This led to the invention of the voltaic pile.
This pile commenced Davys investigations into electrolysis where he discovered that the
chemical reactions between the two metals actually generated the current. Similarly, these
electrolysis experiments then influenced Faraday to investigate the relationship between the
amount of electricity used and the amount of substance produced. Each scientists works
helped the following to develop the understanding of electric current.

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Section Two
Ships have been made of metals or alloys of metals

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Account for the differences in corrosion of active and passivating metals

Corrosion this is the oxidation of a metal by environmental agents. It involves redox


chemical reactions, usually with oxygen (but not always). The presence of an electrolyte
solution in contact with the metal greatly accelerates the corrosive process
Types of corrosion

Uniform corrosion this occurs uniformly over a metal surface. It is caused by exposure of
a metal surface to oxygen and water or other corrosive media such as acidic rain

Pitting corrosion corrosion proceeds down a pit caused by scratches, cracks on the
metal surface

Active metals this term is commonly used for reactive metals that do not passivate
Reactive metals corrode more readily than less reactive metals. This is because they have low
ionization energy and hence gives away electrons more easily, thus corroding more easily.
Only a few metals such as gold or platinum are inert and do not corrode.
These metals (such as iron or magnesium) will be readily oxidized by oxygen and water as it
comes into contact with the metal surface, hence forming a layer of porous metal oxide. Moist
air can get pass the porous layer to attack the metal structure below it. In time, the whole
structure or metal is corroded
Passivating metals
These are metals which react with oxygen in the air to form a thin layer of the metal oxide on
the surface. The oxide layer is impermeable to air and water and prevents further corrosion.
The tightly bound non-porous oxide layer seals the surface and protects it from further contact
with air.
These metals tarnish and lose their shiny luster when exposed to air, but if the thin layer of the
metal oxide is removed by abrasion, the lustrous surface underneath can be observed.
Passivating metals Aluminium, Zinc, Lead, Chromium

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Identify iron and steel as the main metals used in ships

Iron and iron alloys such as steel are the major structural metals that have been used to
construct ships since the late 18th century. Pure sheet iron is very malleable and readily
wielded. Steel is harder than iron and has greater mechanical strength, and still can be wielded
while being ductile and malleable. These are the reasons why iron and steel are the main
metals used in ships

Identify the composition of steel and explain how the percentage


composition of steel can determine its properties

Steel is an alloy of iron with small amounts of carbon (no more than 2%) and varying amounts
of other elements. Generally, the presence of carbon makes the steel harder and more suitable
for other uses.
This is because in pure iron, the atoms can easily slide past each other relatively easy when a
force is applied, thus malleable and soft. If there are small amounts of different atoms present,
their different size disrupts the lattice and makes it difficult for adjoining regions to slide past
each other, thus becoming harder and more brittle.
Alloying metals optimize the mechanical properties of the steel or reduce the tendency to
corrode under different environmental conditions
For example adding:

Nickel increases its strength and hardness. This also improves corrosion resistance and
toughens low temperature steel

Tungsten improves the high temperature strength and hardness of steel

Molybdenum increases the tensile strength and hardness while improving corrosion
resistance in marine environments

Aluminium toughens steel and improves malleability

Vanadium increases shock resistance and improves tensile strength

Cobalt is added to permanent magnets to increase their hardness

Changing the properties of steel physically

Annealing (cooling slowly) this makes the carbon and iron in steel form large crystals,
which make it more ductile but not as hard

Quenching (cooling rapidly) the carbon in the steel is present as cementite crystals. Its
harder, but more brittle

Work hardening (Rolling and hammering) the tensile strength and hardness of the steel
is improved as the crystal grains are rearranged

Tempering the steel is repeatedly heated to a temperature below the melting point and
then cooled. This reduced the brittleness and improves tensile strength.
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Gather and process information from secondary sources to compare the


composition properties and uses of a range of steels

Type of Steel
Carbon steels

Composition

1. Mild Steel

1. 0.15 0.25 C

2. Structural Steel

2. 0.25 - 0.6 C

3. High carbon steel

3. 0.6 1.3 C

Properties

Uses

1.

1.

2.
3.

Cheap, ductile, easily wielded, soft

Most commonly used for

and malleable, corrodes fairly

construction such as car

quickly

bodies, ships, bridges,

Tougher than mild steel. Strong

buildings, roofing, pipes, buts

and malleable

and bolts

Increased hardness and strength,

2.

Beams and girders, railways

but lower ductility and more brittle

3.

Scissors, axes, knives

Cobalt Steel

73.5 Fe, 17 Co,

Improves magnetic properties

Magnets, jet engines

Chrome-vanadium

2.5 Cr, 8 W+C


98 Fe, 1 Cr, 0.2

Hard wearing and shock

Tools, grinders

Steel
Stainless Steel

V+C
80 Fe

resistant
Corrosion resistant, chemically

Kitchen skins and

At least 10 Cr

uncreative, hard and strong,

appliances, cutlery,

4 Ni

reduced brittleness

cookware, razor blades,

High Speed steel

0.1 1 C
75 Fe, 18W, 6

Hard at high temperatures

Drills, cutting tools

Titanium Steel

Cr+C
0.2-2 Ti, with

Very hard

Aircraft, armour plating

varying
quantities of
other metals
such as Cr, Ni, V

Describe the conditions under which rusting of iron occurs and explain the
process of rusting
Use available evidence to analyse and explain the conditions under which
rusting occurs

Rusting is the corrosion of iron


Process of rusting:
Anode:

Cathode:

Overall:

Fe(s)

Fe2+(aq)

O2(g)

2H2O(l)

2 Fe(s)

O2(g) +

2e-

4e-

2H2O(l)

0.44V

4OH-

4OH-

0.4V

Fe2+(aq)

0.84V (hence spontaneous)

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The iron ion reacts with the hydroxide iron to form iron (II) hydroxide 2Fe(OH)2
This further reacts with oxygen, forming hydrated iron (III) oxide, this is rust
4Fe(OH)2

O2(g)

Fe2O3 . H2O

+ H2 O

Conditions that promote Rusting

Presence of both O2 and H2O O2 is reduced with water as the electrolyte (note, water
alone or oxygen alone does not promote rusting)

Oxygen concentration the higher the DO concentration in the water, the greater the
chance of rusting

Presence of electrolyte Iron rusts more in salty water than in fresh water. The
presence of free ions such as sodium and chloride ions in the water film provides a
conducting pathway between the anodic and cathodic sites

Impurities such as carbon become cathodic sites. This promotes rusting at other sites
on the surface of the iron

Regions of mechanical Stress rust occurs more readily when under mechanical stress
e.g. cracked or stressed regions of the lattice contain iron atoms that are not strongly
bonded. These atoms form ions and more readily dissolve in the water film

Contact with less reactive metals The less active metal acts as the cathodic site and
the iron as the anodic site in a galvanic cell.

Acidic environments These promote rusting as the reduction potential is more positive.

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Identify data, select equipment, plan and perform a first hand investigation
to compare the rate of corrosion of iron and an identified form of steel

This experiment was also repeated with high speed steel. The mass before and after of all
steel/iron were weighed
Results:

It was found that the normal iron nail corroded faster

Evidence of rust were the brown red fail pieces attached or floating around

Mass change indicated rusting had occurred

The results indicated there was more corrosion on the iron screws than the stainless steel
screws. This was expected because of the composition of the stainless steel which contains
chromium and nickel, both make steel harder and more resistant to corrosion

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Section Three
Electrolytic cells involve oxidation reduction reactions

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Describe, using half-equations, what happens at the anode, and cathode


during electrolysis of selected aqueous solutions

Electrolysis this is the process in which a non spontaneous reaction is forced to take place
by applying an external power supply
Uses of electrolysis

Purify and extracting metals such as aluminium and copper

Clean corroded objects (e.g. to clean artifacts from shipwrecks so they can be preserved
and studied)

Electroplating covers a surface of an object with a particular metal to protect against


corrosion or to improve appearance

Electrolysis of water
Oxidation: 2H2O(l)
Reduction: 2H2O(l)

O2(g)

2e-

Redox reaction: 6H2O(l)

4H+(aq)

-1.23V

H2(g) + 2OH-(aq)

O2(g)

+ 4e-

2H2(g)

-0.83V

+ 4H+(aq) + 4OH-(aq)

E = -2.06V

The hydrogen ions and hydroxide ions react and cancel out the water and thus becoming
2H2O(l)

O2(g)

2H2(g)

Electrolysis of Potassium Iodide aqueous solution


Possible oxidation reactions:

H2O(l)

O2(g)

I-(aq)

I2 (g)

2H+(aq)
+

+ 2e-

e-

-1.23V
-0.54V

Because the oxidation of iodine ions is much higher, it will oxidize preferentially
Possible reduction reactions:

H2O(l)

e-

H2(g) + OH-(aq)

K(s)

(aq)

-0.83V
-2.94V

Because the reduction of water is much higher, it will reduce preferentially


Thus the overall redox equation is
I-(aq)

H2O(l)

I2 (g)

H2(g) + OH-(aq)

E = -0.54 0.83 = - 1.37V

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General rules

Sodium, potassium and magnesium ions are not reduced at the cathode as their potentials
are too high, unless it is a molten solution

Sulfate ions and nitrate ions are not oxidized at the anode

Anodes made of reactive metals may be oxidized preferentially if molecules or ions in


solution have a higher oxidation potential than the anode metal

Describe factors that affect an electrolysis reaction


o nature of electrolyte
o nature of electrodes
o effect of concentration

Nature of electrolyte
Aqueous solutions
Different ions are discharged at different voltages. Depending on the potentials of the ions,
water itself may be oxidized and/or reduced instead. For example, sodium iodide as above
Molten solutions
Although generally it is more expensive to electrolyse molten compounds than aqueous due to
the quantity of energy required to maintain the molten state, it is necessary in some cases if
the desired products are to be obtained. For example, the extraction of reactive metal such as
aluminium or sodium must be carried out by electrolysis in its molten state. If carried out in
aqueous solution, the product at the cathode would be hydrogen gas rather than aluminium as
the reduction potential of water is higher.
Reduction potential:
Al3+(aq)

2H2O(l)

3e2e-

Al(s)
H2(g) + 2OH-(aq)

- 1.66V
-0.83V

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Similarly the extraction of sodium is by electrolysis of molten sodium chloride


Cathode:

Na+(l)

e-

Anode:

2Cl-(aq)

Redox:

Na+(l)

Na(l)

Cl2(g)

2Cl-(aq)

-2.71V

2e-

-1.4V

Na(l)

Cl2(g)

Nature of electrodes
Inert electrodes
Graphite and Platinum electrodes are inert electrodes because they are unreactive and only
provide a pathway for the electron transfer in the electrode half reactions.

(replace zinc with copper)


For this reaction using platinum electrodes
Oxidation: H2O(l)
Reduction:
Redox:

Cu2+(aq)

H2O(l)

O2(g)

+
+

2e-

Cu2+(aq)

2H+(aq)

Cu(s)
O2(g)

+ 2e-

-1.23V
0.34V

2H+(aq)

Cu(s)

E = -0.99V

However if copper electrodes were used


Oxidation:

H2O(l)

Cu(s)

Cu2+(aq)

Reduction:

Redox:

O2(g)

Cu2+(aq)

Cu(s)

+
+

2H+(aq)

+ 2e-

2e-

2e-

Cu2+(aq)

-1.23V
- 0.34V

Cu(s)

Cu2+(aq)

0.34V

Cu(s)
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This is used in the purifying of blister copper where copper dissolves and returns at the
cathode. This is an example of electroplating, the process of using electrolysis to coat one
metal with a thin layer of another metal.
Concentration of Electrolyte
This can affect the products formed in an electrolysis reaction. By increasing the concentration,
it will increase the reduction/oxidation potential of the ions. For example, the difference
between a diluted and concentrated electrolyte of sodium chloride:
Possible reduction:

2H2O(l)

2e-

Na+(l)

e-

H2(g) + 2OH-(aq)

-0.83V

Na(l)

-2.71V

Possible Oxidation:

2H2O(l)

2Cl-(aq)

O2(g)
Cl2(g)

4H+(aq)

+ 4e-

-1.23V

2e-

-1.36V

Dilute solution
This will just be the electrolysis of water
Concentration solution
At high concentrations of chloride ions, the discharge of chlorine becomes more favourable and
hence produces chlorine at the anode.
Anode:
Cathode:

2Cl-(aq)

2H2O(l)

Redox: 2H2O(l)

Cl2(g)

2e

2Cl-(aq)

2e-

-1.36V

H2(g) + 2OH

Cl2(g)

(aq)

-0.83V

H2(g) + 2OH-(aq)

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Plan and perform a first-hand investigation and gather first hand data to identify
the factors that affect an electrolysis rate of reaction

Factors affecting an electrolysis reaction

Voltage high voltage increases the rate by increasing the current flow for a cell of fixed
resistance. The higher voltage may also lead to the formation of additional reaction
products

Surface area higher currents can flow then the surface area of the electrodes is
increased, this increases the rate of reaction

Separation the resistance to charge flow is reduced if the electrodes are close together,
thus the rate of reaction will increase if the separation decreases

Concentration of the electrolyte the presence of the ions as charge carriers is important
in the electrolytic process. Ions improve the conductivity of the solution. The higher the
concentration of ions, the greater the rate of electrolysis.

Two copper strips were cleaned with emery paper and weighed. They held a certain distant
apart and were submerged in 50ml of copper sulfate ensuring both electrodes were immersed
to the same depth. Electrical clips were attached to each electrode. The apparatus was
electrolysed for 30 mins. The electrodes were then weighed.
Part

Electrode

Separation

Width
Control
A
B
C
D
E

Concentration

Voltage

(M)
2
2
2
5
2
2

2
2
2
2
5
2

1
1
1
1
1
0.1

2
4
6
2
2
2

It was found that voltage was the biggest factor that affected electrolysis
Risks Copper sulfate is toxic if ingested or by contact -> splashing
High voltage electrocution

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Section Four
Iron and steel corrode quickly in a marine environment and must be
protected

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Identify data, gather and process information from first-hand or secondary sources
to trace historical developments in the choice of materials used in the construction of
ocean-going vessels with a focus on the metals used

Primitive
The earliest boats were constructed in prehistoric times from natural materials such as wooden
logs, bamboo, reeds and animal skins. Sewn hides were sometimes used to cover a wooden
frame. Such primitive vessels could travel only small distances across water.
Wooden ships
Wood was essentially the important material in the construction of boats for thousands of
years with nails of copper used to fasten the wooden planks together. With the arrival of
the Iron Age, the copper nails were replaced by iron nails and fastenings as iron was
stronger and cheaper.
Metal Sheeting
Timber had its limitations and needed to prevent attack of the wooden hulls from marine
organizes. Peoples knowledge of the use of metals increased and in the 17th century, lead
sheeting was introduced to make ship hulls more durable by covering them and preventing
attack from marine worms. Lead was a soft, malleable metal that could easily be attached to
the wood. However, lead caused corrosion to occur rapidly and was soon replaced by
copper sheeting in 1761. Despite its cost, copper is soft, malleable, and also has biofouling
properties as it is toxic to marine organisms. It inhibited growth of encrustations and barnacles
on the hull. However, copper was far too expensive to be used extensively in ship building.
A brass alloy (60% copper and 40% zinc) was developed to replace the copper
sheeting by George Muntz in 1832. This alloy was found to be stronger and could be used
to make thinner sheets and corroded slower than copper. It could be hot rolled to form large
flexible plates which could be attached to wooden hulls. Evidently, the discovery that metals
could be allowed gave humans the opportunity to manipulate the composition of substances to
produce desired properties.
Sheet Iron ships
As our methods of extraction became more sophisticated, more metals were discovered. Iron
was more difficult to extract than copper, and thus came after. The development of sheet
iron in the late 19th century led to the construction of the first sheet iron boats. Their
use as a wood replacement did not really develop until after 1955.
Although all iron ships needed to be regularly dry-docked and cleaned to remove rust and
barnacles, they had a number of advantages over wooden boats as they were more easily
shaped and welded. They were also stronger and safer that made it more economical because
it was more easily repaired than wooden boats. It could carry more cargo because they could
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be built longer and had more room inside as a result of the less bulky framework. They could
travel faster and used to as warships as it was much safer than a wooden ship, in which a shell
could set a wooden boat alight on impact. The development of the steam turbine driven by
petroleum fuels also contributed to the demise of wooden vessels.
The development of the steel economy during the 20th century led to the construction of vast
fleets of steel ships and tankers due to their strength and hardness. In the early 1990s, the
invention of electric wielding allowed much faster construction of steel ships. These ships were
lighter than sheet iron sheets and hence larger ships could be constructed. These ships were
also stronger and more corrosion resistant.
With the knowledge of alloying and increased knowledge of the properties of metals, the
incorporation of metals into steel has added advantageous properties such as greater strength
and minimal rusting. Aluminium alloys have been used in iron ships, as well as yachts and
rowboats since the 1890s. They are light and strong, allowing improvements in economy and
speed. They can also be welded and resist fatigue well. The aluminium oxide film does not
adhere well in a marine environment. Modern-day methods of corrosion prevention, such as
painting, tin-plating passivating and galvansing have also assisted in improving the quality of
ships constructed.
Our increasing knowledge of metals and alloys has played a major role in our search for
materials that we are increasingly better than the previous, and the traditional timber in
particular. This has resulted in the construction of better sea vessels. Current research into
copper-nickel allows and new paints hold further promise with greater developments
Impacts on society:

Better ships better means of transportation of cargo and good over long distances,
greater reliability

Technological advancements increased scientific knowledge, which can be applied to


other areas of interest

Impacts on the environment:

Larger ships more risk of oil spills which are difficult to clean up and dangerous to wild
life

Knowledge demand for these metals for shipbuilding is high, thus mining activity
increased.

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Identify the ways in which a metal hill may be protected including:


o Corrosion resistant metals
o Development of surface alloys
o New paints

Marine environments accelerate the corrosion of iron and steel very rapidly. The presence of
electrolytes promotes galvanic action when iron and other material come into contact.
However, they can be protected in a variety of ways:
Physical barrier - New paints
This includes painting or lacquering and is used for steel bridges and railings. It prevents
oxygen and moisture from coming into contact with the iron and so rust cannot form.
Disadvantages

If the paint is scratched or not in full coverage, the corrosive media can get through and
attack the underlying structure

Not easily maintained for underwater structures

Possible environmental pollution due to leeching of paints into waterways

However there have been newly developed polymer based paints that

Forms an impervious polymer layer that neither oxygen nor water can penetrate

The chemicals in the paints react with the surface layer of steel to form a highly insoluble
mineral which binds the paint and steel tightly. This effectively prevents any migration of
ions between the steel and the paint layers, hence preventing rusting

Examples are polturethane, Rustmaster


Plating Steel
Tin plating is commonly used in steel cans to provide a physical barrier to prevent rusting. The
tin oxidises to form a stable oxide layer. It has the advantage that it adheres more tightly to
the steel, but when scratched, this accelerates the rusting procedure.

-24-

Passivating the surface of the iron can allow it to form passivating layers. For example,
chromium alloy steel will naturally form one where as mild of structural steel can be passivated
by painting the surface with phosphoric acid.
Corrosion resistant metals
High chromium nickel stainless steels offer food corrosion resistance in marine environemtns
due to the formation of a passivating layer of chromium (III) oxide. Similarly, copper-nickel
allows are also used for pipes and sheathing in marine environments as a corrosion resistant
layer forms on the surface. These stainless steels, while corrosively resistant, are expensive
Surface alloys
This is used to protect the hull of a ship by forming a chromium nickel like surface layer on
ordinary steel. This can be produced using laser techniques where gaseous chromium and
nickel are bombarded and embedded as atoms to form a surface alloy. The surface behaves as
a stainless steel due to the strong metallurgical bonding and the passivating layer formed as
the chromium atoms react with oxygen.

Predict the metal which corrodes when two metals form an electrochemical cell
using a list of standard potentials

To predict which metal will corrode:

Select the reduction half equations for the two metals used in the electrochemical cell.

Reverse the half equation that has the most negative Eo value (the half equation of lowest
reduction potential) This equation will now represent an oxidation half reaction and will
have a positive Eo value

This metal will be the one that is oxidised and will be the metal that corrodes.
Thus the one with the more positive oxidation potential will preferentially corrode.
For example
Fe2+(aq)

2e-

Fe(s)

E = -0.45V

Sn2+(aq)

2e-

Sn(s)

E = -0.1V

In this case, iron will corrode preferentially

-25-

Outline the processed of cathodic protection, describing examples of its use in both
marine and wet and terrestrial environments
Describe the process of cathodic protection in selected examples in terms of the
oxidation/reduction chemistry involved

Cathodic protection
An effective and low maintenance methods of preventing corrosion is by making the protected
method a cathode.
There are 3 main types
1. Sacrificial anode
2. Impressed current
3. Galvanizing
Sacrificial anode
This is the process of attaching a metal that is more reactive and corrodes preferentially to
another. This process makes the metal desired the cathode.

Marine environments plates of metals which are more reactive than iron and its allows
(such as magnesium or zinc) are attached to the steel structure. When the two metals are
in contact, the more reactive metal becomes the anode and hence corrodes/sacrifices
preferentially to prolong the life of the steel structure. Examples include off shore oil rigs
and ship hulls

Wet terrestrial environments buried steel pipes, underground tanks and hot water
heaters are protected by sacrificial anodes. These sacrificial anodes do need to be
physically attached and can be connected by cables or wires. The salts in the soil acts as an
electrolyte to complete the circuit

Zinc is used over magnesium because magnesium corrodes too fast


Disadvantages

Requires regular replacement and checking

More expensive to maintain

Not practical for inaccessible structures such as underground tanks, pipelines

Anode: Zn(s)

Zn2+(aq) + 2e-

Cathode: O2(g)+ 2H2O(l) + 4e- 4OH-

Redox: 2Zn(s) + O2(g)+ 2H2O(l) Zn2+


(aq)

+ 4OH-26-

Impressed current
This process involves connecting the protected metal to a negative terminal of an external
voltage supply. This causes the metal to act as a cathode. An inert electrode is used as an
anode

Marine environments This applied voltage technique has been used in shipping, for
example, a boat with lightweight aluminium alloy hull with a corrosion resistant nickelaluminium-bronze alloy. The propeller must be further insulated from the aluminium hull
from a galvanic cell forming. Thus the hull, shaft and bearings are made cathodic by
connecting them to a DC power supply

Wet terrestrial environments Underground steel pipes or other steel structures or coastal
environments

Anode: H2O(l)
Cathode:

Fe2+(aq)

O2(g)

+ 2H+(aq)

2e-

+ 2e-

Fe(s)

Oyxgen in the water may also be reduced

-27-

Galvanising
This is the process where an iron structure is coated with zinc. This is achieved by dipping the
steel in molten zinc. It has a particular advantage where the layer of zinc, if scratched, is able
to repair itself and continue protecting the steel.
This is because:

Zinc is a moderately passivating metal. It develops a coating of hydroxide and carbonate


which protects the underlying zinc and this in turn protects the steel.

Zing being more reactive than Fe, offers cathodic protection (sacrificial anode)

Gather and process information to identify applications of cathodic protection and use
available evidence to identify the reason for their use and the chemistry involved.

The admiralty were the first users of cathodic protection as they prompted unvestigation into
the corrosion of the copper sheathing of the hulls of wooden naval ships. Davy experimented
with anodes of tin, iron and zinc to protect the copper. Zinc and iron were favored and were
continued to used when wooden hulls were superseded by iron and steel. The zinc anodes
were placed close to the circulating pipe inlets or stern gear as these areas proved to be the
most susceptible to corrosion.
Zn(s)

Zn2+(aq)

2e-28-

Edison tried to achieve cathodic protection of a ship at sea from trailing impressed current
anodes, but the materials and techniques made available to him proved to be inadequate. Most
early users of impressed current in sea water were concerned with attempts to affect
antifouling or to prevent the scaling that would occur in boilers when replenished with sea
water.
The extension networks of oil pipelines installed presented a vast corrosion problem. To an oil
company, a single leak from a pipeline can cause numerous losses such as

Loss of commodity

Property damage including fire

Expensive repair

Service interruptions

Contamination of water supplies

Loss of livestock

Various coatings and cathodic protection were applied to the worst sections where pipes had
been laid in corrosive soils. The cathodic protection was derived from zinc anodes or impressed
currents supplied by DC wind generators or by transformers and rectifiers from an AC power
supply.
From these early beginnings, cathodic protection has developed rapidly and its use has become
widesperead. New materials such as sacrificial allows of magnesium and aluminium and
superior impressed current anodes together with the developments in electrical and electronic
engineering has allowed great advances in techniques. It is now established as an essential
engineering service with a sound and comprehensive scientific background

Identify data, choose equipment, plan and perform a first hand investigation to
compare the corrosion rate, in a suitable electrolyte, of a variety of metals including
named modern alloys to identify those best suited for use in marine vessels

4 test tubes were set up with 25ml of 1M sodium chloride salt solution. Next 1x1cm iron,
stainless steel, mild steel, zinc, aluminium and iron pieces were cleaned using sand paper. Each
piece was weighed and added to different test tubes. The test tubes were stopped with a
stopper and left for a whole week, away from direct sunlight. After 7 days, each test tube was
emptied and the metal reweighed. The level of mass changes were compared
It can be concluded that aluminium was the best metal because it formed a passivating layer
Aluminium stainless steel bronze zinc mild steel iron

-29-

Plan and perform a first hand investigation to compare the effectiveness of different
protections used to coat a metal such as iron and prevent corrosion

Firstly iron 5 identical iron nails were gathered and 4 of them coated with paint, tin plated,
chromium alloyed and zinc plated. These coated ones were the independent variable while the
iron nail was the control. Each nail was placed in 100ml of 0.5M salt solution in a test tube and
sealed. The rate of corrosion was determined by measuring the mass of each nail over a period
of time. The results of the corrosion were compared and found that the iron nails with a
coating corroded less compared to the control.
The accuracy could have been improved by using more precise measuring instruments.
Reliability could have been improved by repeating the experiment under the same conditions
and comparing results.

-30-

Section Five
When a ship sinks, the rate of corrosion may be dependent on the final
depth of the wreck

-31-

Outline the effect of:


o Temperature
o Pressure
on the solubility of gases and salts

The main factors that affect the solubility of gases and salts are temperature and pressure
Gases
For gases such as
O2(g)

O2 (aq)

CO2(g)

CO2 (aq)

These are exothermic processes and by Le Chateliers principle

Increasing the temperature will decrease the solubility of the gas. Also the increasing
temperature increases the magnitude of the vibration that breaks the dispersion forces

Increasing the pressure would increase the solubility of the gas

Therefore the solubility of the gases in water is greatest at low temperature and high pressure
Salts

The solubility of salts increases as the temperature increases

The solubility of salts is unaffected by pressure as there are no gas molecules in the
dissolution process

Gases are less soluble than salt in water

Identify that gases are normally dissolved in the oceans and compare their
concentrations in the oceans to their concentrations in the atmosphere

The ocean water near the surface is generally saturated with the 3 gases below. This is
because there is good stirring (waves) of both the atmosphere near the surface which
facilitates the dissolution of gases.
The main gases soluble in water are

Nitrogen

Oxygen

Carbon dioxide

-32-

The concentration of gases in sea water is lower than in fresh water. This is because the
presence of ions interferes with the dispersion forces between the water and gaseous
molecules, reducing the solubility of the gases.
Gas

Concentration in the

Concentration at the surface

Oxygen
Nitrogen
Carbon dioxide

atmosphere at 20 C (ppm)
209400
780900
360

water at 20oC (ppm)


1 13
10 18
60 110

Table of relative abundance (% by volume)


Gas
oxygen
Nitrogen
Carbon dioxide

Atmosphere
20.9
78.1
0.036

Surface sea water


36
48
15

Total Ocean
6
11
83

Factors affecting the concentration of gases in the ocean

Partial pressure of the gas the greater the concentration of gases above the water
surface, the greater the shift in dissolution equilibrium and hence increasing concentration

Diffusion rate in water the speed of the movement of gaseous molecules into the water is
affected by the wave action and temperature of the air and the water. Wave action creates
smaller droplets which have a larger surface area, allow for faster diffusion

Ocean currents this affects temperature

Thus we can see that gases are less concentrated in the ocean than in the atmosphere. The
surface layers are usually saturated in atmospheric gases due to wave action. However, carbon
dioxide is an exception due to the hydrolysis of carbon dioxide to form carbonic acid
CO2(g) + H2O(l)

H2CO3

H+ + HCO3

2H+ + CO32

Compare and explain the solubility of selected gases at increasing depths in the
ocean

The concentration and solubility of gases in the ocean changes with increasing depth.
For oxygen:

At the surface this is relatively high due to the wave action and photosynthetic activity.
This is about 6.5ppm, but varies with temperature

At increasing depths the concentration is low even though the solubility is high. This is
because a net result of the following:
o

Plants that produce oxygen are only found in the top layer (50m) and light can
only penetrate through 150m of water.

-33-

As oxygen diffuses down, they are consumed by aerobic organisms for


respiration and decomposition which increase with depth.

There is no mixing between water on the top and water at the bottom since
there are no convection currents

Oxygen rich water from the poles is transported to great depths by deep, cold,
oxygen saturated ocean currents from polar regions

Temperature decreases with depth

For carbon dioxide this increases with increasing depth. Low concentrations of CO2 are due to
consumption of CO2 by photosynthetic plants. The concentration of carbon dioxide increases
with depth because there are fewer photosynthetic plants to use it up, but respiration and
decomposition processes continue to occur. However it does not reach a high level as it
precipitates out as calcium carbonate.
Nitrogen There is no significant production or removal processes so as depth increases, its
concentration does not change much from its surface value.

Predict the effect of low temperatures at great depths on the rate of corrosion of a
metal
Use available evidence to predict the rate of corrosion of a metal wreck at great
depths in the oceans and give reason for the prediction made

Factors affecting the rate of corrosion at great depths

Availability of oxygen

Temperature

Salinity

pH

The following conditions exist at great ocean depths

temperatures are very low (0 4 oC)

oxygen levels are very low (1 - 3ppm)

salinity levels may be higher than on the surface due to the cold

Predictions

Low temperatures should slow down the rate of corrosion as the interacting particles have
lower kinetic energies

Low oxygen levels should slow down corrosion as oxygen is necessary for the formation of
metal oxides such as rust

High salinity levels may promote corrosion, but the ocean is already highly saturated
-34-

Hence it would be expected that rusting and corrosion of shipwrecks on the deep ocean floor
such as the titanic to be very slow or less than those compared with similar wrecks on warmer,
shallow water off the coastline.

Perform a first hand investigation to compare and describe the rate of corrosion of
metals in different :
o Oxygen concentrations
o Temperatures
o Salt concentrations

Oxygen concentrations

3 iron nails were cleaned with emery paper and all weighed. They were placed into 3
separate test tubes
o

50 ml of water was then boiled to remove air and poured into one of the test
tubes. This was covered with a layer of oil and stoppered

Another nail was completely covered with distilled water and stoppered

Another nail partially covered with distilled water and stoppered

There were then reweighed and observations noted


Results:

Rust and Fe2+ present in all cases, but more so in the partially submerged one

The pH of the water were slightly acidic

Temperature

3 iron nails were cleaned with emery paper and all weighed. Each placed in different test
tubes. All nails were completely covered with distilled water and stoppered.
o

One test tube was placed in the fridge

One left in room temperature

One placed in incubator/oven

Results:

The one in the oven corroded more

Salt concentration

3 nails
o

One completely covered in distilled water

One with 40ml distilled water and 10ml of 0.1M salt solution, NaCl

One with 40ml distilled water and 10ml of 1M salt solution, NaCl

Results:

It was found that the one with the higher salt concentration corroded more as more mobile
irons promoted the corrosion process by acting as an electrolyte
-35-

Section Six
Predictions of slow corrosion at great depths were apparently incorrect

-36-

Explain that shipwrecks at great depths are corroded by electrochemical reactions


and by anaerobic bacteria

Despite the prediction that corrosion at great depths would be slow, the Titanic (sank in 1912)
was discovered in 1985 and found to be severely corroded at a depth of 3.7km.
Chemical analysis:

The long rust flows on the railings and hulls were rusticles and they consisted of FeO(OH)
(iron oxide hydroxide)

Other corrosion products from various metals and alloys present were found to consist of
o

Black metallic sulfides FeS on steel, PbS from leaded paint, Ag2S on cutlery

Magnetite grey or black rusticles that have further been reduced within the
ship

Hydrated magnetite on iron and steel

Verdigris on bras or bronze cabin fittings

Analysis of the slit clinging to the artifacts showed that it was moderately acidic , 4 5 pH

Investigation showed that some of the corrosion processes were caused by electrochemical
reactions, but a majority was caused by anaerobic bacteria.

Describe the action of sulfate reducing bacteria around deep wrecks

Sulfate reducing bacteria This is a type of anaerobic bacteria that grows wherever oxygen
content is low and reduces sulfate ions to sulfide ions in order to gain energy for their
metabolism. This facilitates the oxidation of metals such as the bodies of shipwrecks, hence
bacterial corrosion. They multiply rapidly around the titanic wreck and may have used the
textiles and wood of the ship as a food source
These anaerobic bacteria use sulfate ions from the seat water instead of oxygen for respiration.
The sulfate is reduced to sulfur and then to sulfide ions, eventually forming hydroxide sulfide.
This reaction occurs best in acidic environments
Oxidation: 4Fe(s)

Reduction: SO42-(aq)

Redox:

Fe2+(aq)

10H+(aq)

4Fe(s) + SO42-(aq)

8e-

+ 8e-

H2S

10H+(aq)

Fe2+(aq)

4H2O(aq)

H2S(aq)

4H2O(aq)

The hydrogen sulfide formed can react with various metal ions such as
Fe2+(aq

H2S(aq)

FeS(s)

+ 2H+(aq)
-37-

To release hydrogen ions, forming an acidic environment


Note: that the oxidation state of sulfur has been reduced from +6 in SO42 to 2 in H2S.

Explain that acidic environments accelerate corrosion in non-passivating metals

Acidic conditions can lead to accelerated corrosion in non passivating metals because it

The reduction potential of oxygen increases as it becomes a stronger oxidant in such


conditions

O2

2H2O

O2

4H

+
+

4e4e

4OH-

0.4V

2H2O

1.23V

It facilitates the reduction of sulfate ions and also oxidizes metals

e.g. Fe(s)

2H+(aq)

Fe2+(aq)

H2(g)

Sources of Hydrogen ions in deep water

As the concentration of CO2 increases with depth, the dissolved carbon dioxide produces an
acidic environment due to hydrolysis
o

CO2

+ H2 O

H2CO3

H+

HCO32-

Organic materials from wooden structures and dead tissue of living organisms are oxidized
by bacteria to produce acid
o

For example, carbohydrates are oxidized to form carbon dioxide and hydrogen
ions. This addition of carbon dioxide will also increase the acidity

Carbohydrate CO2

H+

Precipitations of metallic sulfides by hydrogen sulfide produces hydrogen ions

Hydrogen sulfide is also a weak acid

Hence the unexpected fast corrosion of the titanic is thought to be largely due to bacterial
action, accelerated by the reaction of an acidic environment around the wreck.

Perform a first hand investigation to compare and describe the rate of corrosion of
metals in different acidic and neutral solutions

A piece of steel was placed in a test tube half submerged in 1M of 30ml of hydrochloric acid
solution/. AN identical piece was placed in water under the same conditions. Two pieces of zinc
were set up in similar conditions. All metals were first weighed and left for 2 days in the
solution, then removed, cleaned and reweighed.

-38-

The mass loss from both zinc and iron in the acidic conditions were greater. This is because
when metals corrode, they form soluble metal irons which dissolve in the solution and do not
add towards the mass.

-39-

Section Seven
Salvage, conservation and restoration of objects from wrecks requires
careful planning and understanding of the behaviour of chemicals

Artefacts Objects from past human society


Conservation action taken to clean and stabilise material
Preservation action to protect against further deterioration once an object has been stabilised
Restoration action taken to return the object as much as possible to its original condition

-40-

Explain that artefacts from long submerged wrecks will be saturated with dissolved
chlorides and sulfates

Artefacts are objects produced by the work of humans; they have both historical and cultural
value.
Artefacts recovered from shipwrecks are saturated with mineral salts. Sulfate and chloride salts
are the major contaminants.

The cellular contents of wooden artifacts are leached out and replaced by salty solutions
that eventually fill the spaces between the cellulose and lignin fibers. Eventually the
cellulose breaks down due to the hydrolysis and action of bacteria.

Textiles and leather also absorb salts

Metal objects have sea water trapped inside of them in the microscopic pores

Describe the processes that occur when a saturated solution evaporates and relate
this to the potential damage to drying artefacts

When a salt solution such as sodium chloride evaporates, the solution becomes more
concentrated and eventually becomes saturated. As further water is removed, the salt
crystallizes and only the solid remains.
When artefacts are brought to the surface, they are stored in sea water. This is to stabilise the
artefact and prevent the salts crystallizing and damaging the structure of the artefact.
When a salt saturated artefact is allowed to dry out, the salt crystals grow and cause
weakening and distortion of the artefact, for example, leather may crack and shrink. Further
more, hydrochloric acid may form when corrosion products such as hydrated metal chlorides
are exposed to air. The acid formed will attach the artefact.

Identify the use of electrolysis as a means of removing salt

Desalination
This is the first process in removing salts. After being saked in sea water, the artefact ois
soaked in dilute solution of sodium hydroxide (0.5M) to allow diffusion of chloride atoms out of
the artefact (as OH- displaces Cl-) and also retards further corrosion. The solutions are changed
regularly as the salts are leached out. This procedure may lost for a long time and continues
until the concentration of chloride ions is very low. However the leaching process does not
proceed to completion due to the presence of insoluble basic iron chlorides
FeCl2

2 OH-

Fe(OH)2

2 Cl-41-

Electrolytic treatment
The remaining chlorides embedded in the fine pores and cracks are a serious problem because
it can accelerate further corrosion after the object has been cleaned and restored. This because
the hydroxyl chlorides can react slowly with water to form HCl
The removal of these chlorides salts may be achieved using electrolysis. The artefact becomes
the cathode in the electrolytic cell with a stainless steel mesh as the anode. This causes ions
(such as Cl-) to diffuse out of the artefact as they are attracted to the positive anode. An
electrolyte of dilute sodium hydroxide helps to passivate any iron in the artefact. Furthermore,
the hydrogen released at the cathode also provides a reducing environment for an iron
artefact.

Anode:

4OH-(aq)

Cathode:

Redox:

2H2O(l)

2H2O(l)

2H2O(l)
2e-

2 H2(g)

O2(g)

H2(g)

+ 4e+

2OH-(aq)

O2(g)

The electrolyte is replaced weekly in order to prevent the build up of chloride concentration

Identify the use of electrolysis as a means of cleaning and stabilising iron, copper
and lead artefacts
Discuss the range of chemical procedures which can be used to clean, preserve and
stabilise artefacts and where possible, provide an example of the use of each
procedure

Concretions - these are encrustations or a solid mass which bonds onto the surface of
another. They are often composed of calcium carbonate and magnesium hydroxide mixed with
sand and corrosion products. Deconcretion is the first stage in restoring an artefact (before
desalination)
-42-

The first step in restoring artefacts covered in concretions is to X-ray them to locate the
artefact. The concretion layers may then be mechanically removed with dental chisels or by
soaking in baths of weak acid to remove any calcium carbonate and magnesium hydroxide.
The chloride salts can then be removed
Iron and steel artefacts
Electrolysis
Following desalination, iron artefacts are then electrolytically cleaned in an alkaline solution.
The current in the electrolysis cell is adjusted to obtain a slow stream of hydrogen from the
cathode. At this point iron (III) oxide rust layers are reduced to black magnetite, which
stabilises the iron artefact.
The chloride ions in an iron artefact may be locked up in the form of basic iron chlorides such
as Fe(OH)Cl. Such compounds can be electrolytically reduced to form metallic iron and chloride
ions
Fe(OH)Cl(s)

2e-

Fe(s)

+ OH-(aq)

Cl-(aq)

Following the electrolytic bath, the iron artefact will then be rinsed with hot and cold deionised
water. This process continues until all chlorides have been removed
Cooks cannons were restored in this way.
Hydrogen furnace reduction
Alternatively, the iron artefact may be heat treated (400oC) in a reducing atmosphere of
hydrogen gas for a couple of days. This process converts iron (III) oxides or iron (II) chlorides
to metallic iron

Following heat treatment and cooling in an inert nitrogen atmosphere, the artefact is stored in
an alkaline solution to prevent aerial oxidation
In recent times, iron objects have usually been restored by a combination of reductive heating
and electrolytic removal of traces of chloride.

-43-

Coating
The iron artefact is finally coated with a clear polyurethane polymer or microcrystalline wax in
order to preserve it. Wax is used rather than other physical barriers because it does not alter
the appearance of artefacts and is also an easily reversible process
Copper artefacts
Copper and its alloys, bronze and brass do not corrode as badly in aerobic conditions because
it is a less active metal. Galvanic corrosion form surface layers of copper (I) chloride and
copper (II) hydroxychloride
In anaerobic environments, the action of SRB leads to the formation of copper (I) sulfide on
the surface. Later exposure to oxygen causes the corrosion layer to be oxidized to form black
copper (II) sulfide which stabilises the artefact.
They are cleaned by

chemical stripping; dissolving the surface deposits with a chemical solution and in this
case, dilute citric acid solution that contains a corrosion inhibitor of thiourea.

chloride salts can then be removed by desalination in sodium bicarbonate solutions or by


electrolytic cleaning, using sodium carbonate as the electrolyte as zinc and tin dissolve
slowly in sodium hydroxide

Finally they are coated with a clear acrylic lacquer.


Lead artefacts
This consists of cannonballs, sheeting and weights. Lead sulfide is a major corrosion product in
anaerobic marine environment. There will be very little concretion growing in lead objects as it
is a biocide.
The corrosion products of lead are stable when the artefact is recovered and hence immersing
it in 10% HCl will remove lead corrosion products and carbonate encrustations, but will not
cause damage to the metal underneath.
PbS(s)

2H+(aq)

Pb2+(aq)

H2S(g)

The artefact is then soaked in EDTA to dissolve the remaining insoluble lead compounds.
Leaching with water of electrolysis can be used to remove residual chloride. If electrolysis is
used, then sodium carbonate will be required.

-44-

Cathode: PbS(s) + H2O(l)

2e-

Pb(s)

+ HS-(aq)

OH-(aq)

Wooden Artefacts
After salvaging, wooden ships need to be kept moist and away from damaging sunlight.
Corroded iron nails were replaced with oak pegs with crustations removed by using brushes.
Polyethylene Glycol (PEG) was used to preserve it by spraying the ship. This PEG fills all the
cavities in the wood so stabilises it by restoring some of its strength and preventing further
degradation, Finally the object is air fried
Leather
Leather like all organic material must be kept wet once recovered. This is in order to regain
some of its original elasticity by gradually replacing sea water with other moisture. The first
step is the removal of large concretions using metal/wooden picks or toothbrushes. This may
be followed by the alternate bath of 2-5% solution of ammonium citrate. The leather should
then be soaked for at least 23 hrs in room temperature distilled water to removal any salts.
Due to its degraded structure, nylon or wooden blocks should be used for support. E.g. shoes
The item should then be submerged in 30% PEG for 2 weeks. The PEG diffuses through the
structure to keep it permanently supple. The leather is then rinsed in warm water and air
dried.

Perform investigations and gather information from secondary sources to compare


conservation and restoration techniques applied in two Australian maritime
archaeological projects

Endeavour Cannon
Background In 1969, six cast iron cannons were discovered beneath 200 years of coral. The
one on display has been conserved using oxidation-reduction techniques combined with
physical protection.
Preservation

The cannons were transported in sea water and then transferred to 10% formalin solution
to kill bacteria

Hammers were used to remove the hard coral with the cannons bores drilled

Electrolysis was used to remove the dissolved ions, mostly chloride where a circuit of
10amps were set up with the cannon as the cathode and a mild steel mesh the anode in a
2% sodium hydroxide electrolyte solution. The electrolyte solution was replaced continually
as the chloride concentration built up. After many weeks, the chloride concentration leveled
to 20ppm,

-45-

Then the cannons were washed extensively to remove any remaining chloride and
hydroxide. This took 5 months where distilled water with chromate ions were used. It
allowed for a protective layer to form

Eventually they were dried in an oven for 2 days at 120 degrees and immersed in a wax
bath

The original cast iron has been replaced in the recreated wooden stocks and roped off from
visitors
Vernon anchors
Background The ship Vernon was completed in 1839 and was moored off Cockatoo Island in
Sydney harbour as a reformatory for wayward and orphaned boys. Following their use on the
Vernon, the anchors continued to be used for mooring in other vessels.
Preservation

Outer corrosion and remains of protective paint were removed by furnace blasting and then
coating the surface with a protective metal.

In 1992, after earlier temporary treatments, the iron surface of the anchors were blasted
with copper slag and then garnet polished (a more refined process than sand blasting)

The timber stocks were masked for protection during the above treatments

The iron was then treated with a zinc epoxy paint which forms a hard, resinous surface

The timber stocks were saturated with a zinc napthenate solution in order to retard the
growth of organisms such as mould

Electrolytic treatment was not considered because

Treatment wouldve destroyed the timber stocks or required their removal, causing
unnecessary damage

The anchors were considered to be in sufficiently good condition to not require electrolytic
treatment to preserve the cast iron

A display and mounting system was built for the anchors which includes an aluminium mesh on
which the anchors rest. They are subjected to wind, rain, sun, hail and humidity.
Comparison

The Vernon Anchors are a good example of conservation by application of a protecting


coating (both physical and chemical) for the iron and anti-rot preservatives for the timber.
The wrought ion of the anchors is original from 1839 and the timber stocks date to 1905.
They have not been changed in an attempt to return them to new conditions

The cast iron cannon from the Endeavour has been conserved using redox techniques
combined with physical protection. While the metal cannon is original, the timber and
-46-

associated parts have been manufactured to copy how the cannon mightve looked like
back then.

-47-