Chemistry:

Shipwrecks, Corrosion & Conservation

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

1.1 Identify the origins of the minerals in oceans as leaching by rainwater from terrestrial environments & hydrothermal vents in mid-ocean ridges: Sea water contains about 35g salts/L (this varies with temperature; higher temperature, higher concentration of salt) 78% of the oceans salt is NaCl; 16% is Mg salts; 6% is K salts Main cations and anions in sea water: Cations Anions Sodium Chlorides Potassium Carbonates Calcium Sulfates Magnesium Bromides Leaching by rainwater from terrestrial environment: Rainwater seeps over the Earth, dissolving minerals from rocks and soils, and carries them via ground water or rivers into the oceans The ions dissolved vary according to the composition of the rocks/soil through which the water gets into (i.e. water that had moved through limestone would be high in calcium and carbonate ions) Hydrothermal vents in mid-ocean ridges: Hydrothermal vents occur where tectonic plates are separating (mid-ocean ridges) and at hot spots in plates. At these places, molten material is rising from the mantle Rocks form from cooling molten material which solidifies As the igneous rocks cool, they crack; allowing cold sea water to sink into the rocks and heat the water to about 350oC-400oC by the hot magma The water then expands and rises through the rocks, bringing insoluble sulfides of copper, zinc and iron into the oceans water. Soluble ions in the water include sodium, potassium, magnesium, chloride, sulfate and bromide 1.2 Outline the role of electron transfer in oxidation-reduction reactions: An oxidation-reduction reaction occurs between two substances when electrons are lost by one reacting species (reductant) and gained by another (oxidant) Oxidation involves the loss of electrons (OIL)
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Reduction involves the gain of electrons (RIG) Oxidation and reduction reactions occur simultaneously for each species that loses an electron, another species must gain an electron

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1.3 Identify that oxidation-reduction reactions can occur when ions are free to move in liquid electrolytes: Electrolyte: a liquid that can conduct electricity because they have ions free to move Electrons can be transferred in electrolytes, thus redox reactions can occur as the electrons are transferred from one species in the electrolyte to another Without the electrolyte, there would be no way for the ions in reactions to move away to make room for further reaction 1.4 Describe the work of Galvani, Volta, Davy and Faraday in increasing understanding of electron transfer reactions: Galvani: In his experiments on a dissected frog, he noticed that the muscle contracted when two different metals were in contact with both the spinal cord and the leg muscle of the frog He called this animal electricity Volta: Further investigated Galvanis effect and realised that the current was generated by the two metals, not the dead animal Volta then developed the first battery, a voltaic pile made of alternating zinc and copper disks with an electrolyte solution in between This enabled further experiments to be conducted by others such as Davy Davy: Davy used Voltas device to pass electricity through compounds, resulting in the decomposition of some compounds previously classified as elements, i.e. H2O, NaCl Made important discoveries in electrochemistry that led to corrosion protection for ships hulls Discovered several active elements including Na, K, Ca, Sr, Ba and Mg Faraday: Continued on from Davys experiments and extended them Quantified electrolysis by relating the quantity of electricity used in electrolysis to the valency and mass of the element produced Formulated laws of electrolysis Developed terminology we use today; anode, cathode, electrodes, ion, anions, cations The Significance of their Findings: They all advanced the knowledge and understanding of electrochemistry Galvanis, and later Voltas experiments led to the development of the first device for generating a continuous electric current the battery Davy then examined the decomposition by electrolysis and discovered several active elements Their combined work showed the relationship between chemical bonds and electricity They began the first step in understanding how electron transfer reactions work

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Ships have been made of metals or alloys of metals

2.1

Account for the differences in corrosion of active and passivating metals: Corrosion is the oxidation of metals and alloys due to chemicals in the environment The most common form of corrosion is the rusting of iron Causes many environmental problems, i.e. oil spills due to ship and pipelines corroding. It is expensive to have to constantly replace corroded materials. Also, the failure of metal parts can endanger lives. The corrosion of active metals: Generally, the more active the metal, the more quickly/easily it will corrode Metals higher up in the activity series are more susceptible to reacting with oxygen, water and dilute acids in the environment Active metals corrode easier because they lose electrons more readily The corrosion of passivating metals: Passivating metals are reactive metals that form an inactive, protective coating as a result of reaction with substances such as oxygen Chromium and aluminium are passivating metals. They react with the atmosphere, forming an oxide that is inert, non-porous and adheres to the surface o 4Cr(s) + 3O2(g) 2Cr2O3(s) o 4Al(s) + 3O2(g) 2Al2O3(s) If removed, the protective coating quickly reforms (provided oxygen is available) and protects the metal from further corrosion 2.2 Identify iron and steel as the main metals used in ships: The main metal used in the hulls of ships is iron, in the form of steel alloys Iron/steel is suitable for this use because it is strong, hard and malleable and it can be made relatively corrosion resistant by the use of alloyed elements (e.g. stainless steel)

2.3 Identify the composition of steel and explain how the percentage composition of steel can determine its properties: Steel is iron with <2% carbon and small amounts of other alloyed metals such as manganese, chromium, nickel, tungsten, molybdenum and others Steel has many uses, i.e. in household appliances, construction, cars, and ships. Each different use requires different properties. Therefore, different types and percentages of other added metals are required; e.g. chromium is added to prevent corrosion, manganese increases strength and malleability The effect on the properties of steel of lowering the carbon content o The less carbon there is in the steel, the more malleable it is. The higher the carbon content, the less malleable, but the steel is harder and stronger % carbon of steel Effect Use Low carbon (0.1-0.3%C) Easily welded, machined and shaped, Cars, ships more malleable. Medium carbon (0.3-0.6% C) Strong and malleable Buildings, railways High carbon (0.6-1.3% C) Hard, strong, tends to be brittle. Small tools, i.e. hammer Resists wear. Not very malleable. heads, axes and scissors.
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2.4 Gather and process information from secondary sources to compare the composition, properties and uses of a range of steels: Composition Properties Uses Stainless steels have > 10.5% Corrosion resistant, hard, Sinks, cutlery, electrical chromium content and strong, aesthetically pleasing, appliances possibly nickel, manganese, very malleable silicon and <0.3% carbon content High carbon steels (0.6-1.3% Increased hardness, resistant Tools such as axes, carbon) and <4% chromium to wear and abrasion hammerheads, gears and axels Steel with added tungsten and Very hard steels, resistant to High-speed cutting and drilling cobalt abrasion, can with hand heat tools Steels with molybdenum Malleability increased, easily Pressure vessels, construction alloyed welded, strong and very hard industry Element added Nickel Effect Increases strength, especially at low temperature. Increases ductility and resistance to corrosion. Increases hardness, resistance to wear and corrosion. Increases strength and hardness. Decreases brittleness. Increases resilience Increases hardness, even when hot Increases strength and hardness at high temperatures. Increases resistance to corrosion. Can be easily welded. Decreases brittleness. Increases strength and shock resistance Uses Bus and truck gears, cams and crankshafts.

Chromium Manganese

Gears, axels, ball bearings, tools Riffle barrels, gears, axels

Silicon Tungsten Molybdenum

Springs High-speed cutting tools Aircraft industry, pressure vessels, car axels

Vanadium

Bearings, tools, axels

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2.5 Describe the conditions under which rusting of iron occurs and explain the process of rusting: Rusting is the process by which iron reacts, when exposed to oxygen and water (which acts as an electrolyte), to form hydrated iron (III) oxide (rust; Fe2O3.xH2O(s)) o Rust is an orange-brown, crumbly, porous compound o Note: high humidity in the air is sufficient moisture for rusting Rusting can be accelerated by: o Acidic conditions o The presence of an electrolyte o Impurities in the iron (i.e. carbon or other metals with lower reactivity than iron) o Iron in contact with less reactive metals, such as copper o Electrical contact between the iron and another less reactive metal (i.e. copper) o Mechanical stresses in the iron o Increased temperature The electrochemical process of rusting: Anode: Iron is oxidised to iron (II) ions: o Fe(s) Fe2+(aq) + 2 Cathode: Oxygen dissolved in water is reduced and forms hydroxide ions: o O2(g) + 2H2O(l) + 4 4OH-(aq) The iron and hydroxide ions form iron(II) hydroxide: o Fe2+(aq) + 2OH-(aq) Fe(OH)2(s) The iron(II) hydroxide oxidises to hydrated iron(III) oxide (rust): o 4 Fe(OH)2(s) + O2(g) 2(Fe2O3.H2O)(s) + 2H2O(l) The overall equation for the formation of rust can then be written as: o 4Fe(s) + 3O2(g) + 2H2O(l) 2(Fe2O3.H2O)(s) 2.6 Use available evidence to analyse and explain the conditions under which rusting occurs: Role of water in rusting: Water acts as an electrolyte during rusting, transferring ions from the anode to the cathode. The rate of rusting is accelerated by the presence of salt water, because it has more dissolved ions in it and consequently a more efficient electrolyte. The need of oxygen during rust: Oxygen is reduced in the cathode reaction. It is the electron acceptor and thus is essential for rusting to occur. Effect of pH on rusting: Acidic pH accelerates corrosion as H+ ions accept electrons readily, forming hydrogen atoms. High pH (alkaline conditions) reduces rusting by inhibiting the reduction of oxygen to hydroxide ions. Temperature and rusting: As temperature increases, collisions between reactants become stronger and more frequent. Higher temperature = more rusting Mechanical stresses: (bends/cracks) Weakens the iron lattice, so oxidation occurs more easily at these weak points and rusting is accelerated. Effect of impurities in iron or alloys in the iron: Less active metals increase the rate of corrosion of iron as an electrochemical cell is set up in which the iron is the anode and hence rusting will occur faster. The presence of non active metals such as silicon can accelerate rusting by causing internal stresses in the iron metallic lattice.
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Electrolytic cells involve oxidation-reduction reactions

3.1 Describe, using half-equations, what happens at the anode and cathode during electrolysis of selected aqueous solutions: Electrolysis is the decomposition of a substance by passing electric current through it; chemical reactions occur due to a voltage being applied A brief description of a typical electrolytic cell: o A container with an electrolyte and two electrodes. The electrodes are connected by an external circuit containing a battery (or some other form of power source). The positive terminal is the anode & the negative terminal is the cathode (think physics) o Inert electrodes include carbon, platinum and stainless steel The electrolysis of aqueous copper sulfate: At the cathode: o Cu2+ + 2 Cu Eo = 0.34 V At the anode: o 2H2O O2 + 4H+ + 4 Eo = 1.23 V The overall reaction: o 2Cu2+(aq) + 2H2O(l) 2Cu(s) + O2(g) + 4H+(aq) Eototal = 0.89 V Therefore, the electrolysis of CuSO4(aq) requires a minimum voltage of 0.89V; - Note: the negative sign shows that the reaction isnt spontaneous Hence in the electrolysis of copper sulphate solution, copper is produced at the cathode and oxygen gas forms at the anode 3.2 Describe factors that affect an electrolysis reaction; effect of concentration, nature of electrolyte, nature of electrodes: Effect of concentration: When the concentration of the electrolyte is not 1mol/L the electrode potentials are different and the standard potential tables cannot be used to predict the reactions occurring The more concentrated the electrolyte, the faster the rate of reaction as the electrolyte becomes a better conductor of electricity Effect of the nature of the electrolyte: Molten electrolytes with inert electrodes can yield only one product at each electrode. For example, molten magnesium bromide would discharge magnesium metal and bromine gas. In aqueous solution there is also the possibility that water will be one of the reactants at one, or both, electrodes in preference to other reactions. Effect of the nature of the electrodes: The size of the electrodes: The surface area of the electrodes in contact with the electrolyte affects the rate of reactions. The greater the area, the faster reaction rate. The distance between the electrodes: The distance affects the rate of reaction also. The closer the electrodes are to one another, the faster the electrolysis. The composition of the electrodes: It influences the products formed as the anode may oxidise in preference to the electrolyte. Inert electrodes, like platinum, stainless steel and carbon, will not affect the products, but metals such as Zn, Ni, Cu, Fe, may be oxidised.

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

4.1 Identify the ways in which a metal hull may be protected including; corrosion resistant metals, development of surface alloys, new paints: The need for protection against corrosion: Ships hulls are in an environment in which they are very susceptible to corrosion. The presence of salt water, oxygen, mechanical stress and alloyed metals in the steel all increase the likelihood of corrosion. Physical protection: Placing a barrier between the water and oxygen and iron can prevent corrosion Examples include organic paints, polyurethanes and epoxy resins Although, metal parts underwater are harder to maintain because of chemical leaching and physical abrasion/chipping Coating with other metals: This also sets up a physical barrier Tin plating can also be effective by excluding oxygen and water, however, if the tin coating is damaged and iron is exposed, it will rust rapidly because iron is more reactive than tin Sacrificial electrodes: Coating with a more active metal also affords protection Galvanised iron is iron with a layer of zinc. The zinc oxidises in preference to the iron, thereby acting as a sacrificial anode. Passivating the metal: Alloying steel with corrosion-resistant or passivating metals gives it protection Nickel alloy steel forms a protective (passivating) layer of nickel(II) oxide - used in ship hulls Cathodic Protection: By impressing a small current through the metal, it can be protected from corrosion New paints: Development of a new water-based polymer paint, Rustmaster Pro The paint cures in air forming an impenetrable barrier to both air and water vapour Additives in the paint also react with the steel forming a layer which prevents the crucial movement of ions and so rusting cannot occur Surface alloys: Typically, chromium and nickel ions bombard a steel surface at high temperatures The ions are allowed to bond to the steel to form a harder, more corrosion-resistant surface The steel surface forms a passivating layer as the chromium or nickel reacts with oxygen

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4.2 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: When humans took to the seas thousands of years ago; used wood to stay afloat, which was protected from rotting by using animal fats and shark oils About 500 years ago; used lead sheeting to cover the wood to prevent wood-boring shipworms from attacking the wood later replaced by copper sheeting o Copper was used as it was a biocide (a chemical substance capable of killing living organisms in this case; marine worms) Copper sheeting was later replaced by bronze sheeting wasnt as expensive, was stronger and corroded more slowly Other parts of the ship had metal parts even before the hull e.g. anchors, rudders, cannons were commonly made of iron, bronze and other metals By the late 18th century, iron was the mainly used for most ship building o Preventing the iron from rusting caused some problems But there were advantages to using iron in ships: o Iron is stronger and safer to withstand an impact o Could be shaped more easily than wood, and could be welded together o Could build longer ships with less bulky framework o Easier and less costly to repair ships, and they last longer Eventually, iron gave way to steel, a more versatile, stronger and durable alloy of iron. This is the main metal used on ships today. Small boats have been made out of aluminium because of its lightness and durability 4.3 Predict the metal which corrodes when two metals form an electrochemical cell using a list of standard potentials: General rule: the metal with the lowest standard potential (Eo) will corrode (be oxidised) The less active metal - the weaker reductant - becomes the cathode The more active metal will be the anode and corrode E.g. in a reaction between magnesium and iron, magnesium becomes the cathode as it is more negative than iron in the standard potentials 4.4 Outline the process of cathodic protection, describing examples of its use in both marine and wet terrestrial environments: Cathodic protection is the process of protecting iron structures from corrosion by making the iron structure become the cathode in an electrochemical cell For example, a buried steel pipe or storage tank can be protected by connecting it to a more reactive metal, such as zinc or magnesium. The sacrificial anode will corrode at a faster rate than it would have by itself, while the steel pipeline becomes the cathode and corrodes at a slower rate than it would have by itself Cathodic protection in marine environments: Ships lumps of zinc are attached to outboard motors or to the hulls of ships Oil rigs Metal pylons, bridges, wharfs
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Cathodic protection in wet terrestrial environments: Underground fuel storage tanks Steel pipes and pylons 4.5 Describe the process of cathodic protection in selected examples in terms of the oxidation/reduction chemistry involved: Sacraficial anodes: Metals more active than iron (an Eo value less than that of iron) are attached to the iron structure in order to set up a galvanic cell. They are corroded away in preference to the iron and need to be regularly replaced. Zn and Mg are commonly used. For example: A galvanic cell is set up with the Zn as the anode and the iron structure as the cathode The Zn is oxidised at the anode and corrodes preferentially while the iron is protected Dissolved oxygen is reduced at the cathode If Fe2+ ions form, some electrons may be diverted to reduce these ions Hence, iron (Fe) is cathodically protected o Anode: 2Zn(s) 2Zn2+(aq) + 4eEo = 0.76 V o Cathode: O2(aq) + 2H2O(l) + 4e- 4OH-(aq) Eo = 0.34 V o Overall: 2Zn(s) + 2H2O(l) + O2(aq) 2Zn2+(aq) + 4OH-(aq) Eo = 0.76 + 0.34 = 1.10 V Impressed electric currents: An external direct electric current connected to the metal being protected (negative end) and an inert electrode (positive end) Electrons flow to the iron, preventing formation of Fe2+ ions For example - cathodic protection system for reinforced concrete on a bridge: At the anode water can be oxidised: o 2H2O O2(g) + 4H+ + 4eEo = 1.23 V In marine environments, with a plentiful supply of chloride ions, these ions are oxidised in preference to the water: o 2Cl- Cl2(g) + 2eEo = 1.36 V 4.6 Gather and process information to identify applications of cathodic protection, and use available evidence to identify the reasons for their use and the chemistry involved: Applications of sacrificial anodes and impressed currents: Ships hulls are normally protected by sacrificial anodes as are rudders and propellers. Accessible steel structures commonly use sacrificial anodes Structures that are buried such as fuel storage tanks and pipelines use impressed currents. Modern naval vessels have built-in impressed current systems Reasons for the use of sacrificial anodes and impressed currents: Zinc plates attached are used as these are cheaper to set up than impressed currents and can be easily replaced as the zinc is used up Underground structures, however, require impressed current systems because the anodes cannot be reached to replace them; where as an electric current can be easily monitored and maintained from the surface.
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5 When a ship sinks, the rate of decay and corrosion may be dependent on the final depth of the wreck

5.1 Outline the effect of temperature and pressure on the solubility of gases and salts: With increasing ocean depth, temperature decreases and pressure increases. As temperature decreases: The solubility of salts decreases The solubility of gases increases As pressure increases: The solubility of salts remains largely unaffected The solubility of gases increases 5.2 Identify that gases are normally dissolved in the oceans and compare their concentrations in the oceans to their concentrations in the atmosphere: The main gases dissolved in ocean waters are nitrogen, oxygen, argon and carbon dioxide The percentage composition of gases in the air at equilibrium with those dissolved in sea water: Gas Concentration in the atmosphere Concentration in sea water N2 78.08% 62.6% O2 20.95% 34.3% Ar 0.934% 1.6% Co2 0.033% 1.4% 5.3 Compare and explain the solubility of selected gases at increasing depths in the oceans: Oxygen (O2) and Carbon Dioxide (CO2): Rate of photosynthesis: o Confined to the upper 150m of the ocean where light can penetrate o Thus less oxygen as a result as ocean depth increases Rates of respiration and decomposition: o Organisms, through respiration, release CO2 as one of their waste products o The breakdown of organic materials releases carbonates into the environment o Respiration and decomposition processes increase with increasing depth, thus increase of CO2 and carbonates as depth increases Calcium carbonate (CaCO3) formation and dissolution: o Many organisms remove carbon dioxide from sea water in forming shells and other exoskeletons. In slightly acidic environments this process can be reversed. o Hence the lack of CO2 in sea water Oxygen use by animals and plants: o Animals & plants remove oxygen dissolved in sea water for use in cellular respiration o Thus, reduced oxygen concentration mainly near the surface

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5.4 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 reasons for the prediction made: Conditions at great depths: Very low temperatures, around 4oC Very low oxygen levels, around 2ppm Salinity levels are higher than at the surface Sea water is slightly alkaline, pH 8 Predictions that can be made: Low or zero oxygen levels and low temperatures should inhibit corrosion o Oxygen is needed for rusting and reaction rates are reduced at low temperatures The water is not acidic, thus less reason for steel to react and corrode Higher salinity (salt) levels would have negligible effect since the ocean water is already saline and this would enhance corrosion in any event It was expected that shipwrecks in deep ocean water should corrode fairly slowly, if at all
6 Predictions of slow corrosion at great depths were apparently incorrect

6.1 Explain that ship wrecks at great depths are corroded by electrochemical reactions and by anaerobic bacteria: Note: The term anaerobic means living or active in the absence of oxygen. Account for the presence of anaerobic bacteria in the ocean: Anaerobic bacteria grow wherever the oxygen content is very low and an organic food source is available They grow in the seabed, utilising organic material as their food source. They dont require oxygen for respiration, but use the sulfate ions in the sea water instead They are able to withstand the low temperatures and high pressures at great depths. They thrive around wrecks where there is a source of organic material; i.e. textiles, wood Assess the role of electrochemical cells and anaerobic bacteria in the corrosion of shipwrecks at great depths: Anaerobic bacteria use sulfate ions in sea water for respiration and they thrive around wrecks using organic materials as food Electrochemical cells occur as iron and other metals are present in salt water (an electrolyte). They would be slow to operate in the freezing temperatures at great depths, however, the growth of anaerobic bacteria stimulates the rate of reaction of the cells by utilizing any H2 produced and providing a source of H2S to react with any cations The reaction of H2S with cations results in acidic conditions which accelerate corrosion Thus both electrochemical cells and anaerobic bacteria contribute enormously to the rapid corrosion of shipwrecks at great depths

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6.2

Describe the action of sulfate reducing bacteria around deep wrecks: Anaerobic sulfate reducing bacteria(SRB) use sulfate ions, from sea water, during respiration The action of SRB reduces the sulfur in the sulfate ion: This produces the cathode half-reaction: SO42-(aq) + 10H+(aq) + 8e H2S(aq) + 4H2O(l) The anode half-reaction: Fe(s) Fe2+(aq) + 2eAs Fe2+ ions are formed at anodic sites, they can react with the H2S from the bacteria, forming iron sulphide (FeS) and H+ ions: Fe2+(aq) + H2S(aq) FeS(s) + 2H+(aq) Thus producing an acidic environment, increasing the rate of corrosion around the wreck Note: It is these bacteria, as a consequence of this process, that led to the rapid decay of the Titanic, since it sank in 1912. These bacteria also cause extensive decay to the organic materials around the wreck.

6.3 Explain that acidic environments accelerate corrosion in non-passivating metals: Passivating metals: Passivating metals such as aluminium and chromium have a protective coating of the oxide on their surface and these metals will not corrode as long as the coating remains intact Non-passivating metals: In neutral solutions: o The anode reaction is: Fe(s) Fe2+(aq) + 2eo The cathode reaction is : O2(g) + 2H2O(l) + 4e- 4OH-(aq) In acidic conditions: o The anode reaction is: Fe(s) Fe2+(aq) + 2eo The cathode reaction is: 2H+(aq) + 2e- H2(g) o The reduction of H+ ions has a lower reduction potential and proceeds more easily than the reduction of oxygen, therefore corrosion is accelerated Note: The pH of sea water is about 8 (basic)

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

7.1 Explain that artefacts from long submerged wrecks will be saturated with dissolved chlorides and sulfates: Artefacts are objects from past human societies. o They may be obtained from buried cities, tombs, shipwrecks, etc. i.e. (from shipwrecks): anchors, bells, cannons, , jewellery, money, etc. How do submerged objects become saturated with dissolved chlorides and sulfates? o Chlorides and sulfates are the most common anions found in sea water. Any object submerged for sometime will become saturated with ions from the sea water. o This occurs for metal objects, glass objects, and organic materials such as leather and textiles 7.2 Describe the processes that occur when a saturated solution evaporates and relate this to the potential damage to drying artefacts: When a salt solution evaporates, the salts form crystals: o If salts become impregnated into the structure of an artefact and it is allowed to dry out, the salts will form crystals. As the crystals expand, they cause pressure within the artefacts structure, weakening the object. o As a consequence of this process, ceramic objects and glass may break or crack; leather materials become hardened and stained; metal objects corrode more rapidly. Actions taken by conservators to ensure that damage to the artefact is avoided when it is recovered from a shipwreck: Conservators first record information about the site, where the artefact was found and its environment (documentation and research). When the object is to be raised from the surface, conservators: o Wash the object free from silt and sand, then store it in a slightly basic solution to prevent drying out and stop further corrosion o (Back in the laboratory) Remove concretions of calcium carbonate, corrosion products, sand and marine life that may be attached to the surface of the object o Repeated washing in alkaline solutions to desalinate: During desalination the object is placed in a series of baths with decreasing concentrations of NaCl. In this process the chloride concentration in the wash water is monitored. This can be done by using a chloride specific electronic probe. As ions are removed from the object, the chloride concentration in the following washes drops. The desalination process stops when the chloride ion concentration reduces to 50ppm. o Possible electrolysis to remove deep-rooted salts o Stabilise and preserve to protect from further corrosion

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7.3

Identify the use of electrolysis as a means of removing salt: Electrolysis can be used to free the chloride ions from the insoluble compounds into the solution since chloride ions enhance corrosion, they all need to be removed Initially a low current is used to draw out negative ions (chlorides and sulfates) which become attached to the inert anode. Later a high voltage current is used which generates bubbles of hydrogen gas at the cathode which help to remove/loosen any remaining concretions. o Note: electrolysis removes deeply embedded chloride ions See 7.2 dot point (above) for desalination process.

7.4 Identify the use of electrolysis as a means of cleaning and stabilising iron, copper and lead artefacts: Electrolysis is a more efficient method of removing chloride ions from metal artefacts Uses a dilute alkaline solution (such as 2% NaOH solution) as the electrolyte which is regularly changed over extended periods. The artefact is the cathode and an inert steel electrode is the anode. Reaction at the anode: Two reactions are possible, depending on voltage used and concentration of the electrolyte: o 4OH-(aq) 2H2O(l) + O2(g) + 4eo 2H2O(l) 4H+(aq) + O2(g) + 4eReaction at cathode: 2H2O(l) + 2e- 2OH-(aq) + H2(g) Iron artefacts: Fe(OH)Cl(s) + 2e- Fe(s) + OH-(aq) + Cl(aq) Chloride and hydroxide ions are caused to migrate out of the artefact towards the anode by this electrolysis Note: electrolytic reduction can take days or weeks to complete 7.5 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: Procedure Method Example of use
Electrophoresis Impregnating polymers into wood Heat treatment of iron artefacts Acid baths Wax coatings/ lacquers Object is placed in an electrolyte between inert electrodes. A small current is applied. Wooden object is soaked in natural plant resins/polyethylene glycol (PEG) until the polymer penetrates and sets in the object. Object is heated in an electrical furnace in an atmosphere of hydrogen. Iron chlorides and oxides are reduced to iron. Soak object in a dilute acid bath. Apply a thin coating of grease, wax or lacquer appearance unchanged. Can be used to clean silver and lead artefacts Used to restore strength and stabilise wooden objects Helps to restore the structure of badly corroded objects. e.g. FeO(s) + H2(g) Fe(s) + H2O(g) Cleaning copper artefacts: dissolve corrosion layers in dilute citric acid Preserve objects from further corrosion for display i.e. a museum Page | 15

7.6 Perform investigations and gather information from secondary sources to compare conservation and restoration techniques applied in two Australian maritime archaeological projects: The Endeavour Cannon: The coral growth concretions on the cannon were carefully removed by chipping away Then electrolysis was used over many weeks to remove chlorides and to reduce oxide formation converts much of the iron hydroxides and oxides back to iron Once completed, the cannons were washed in pure water and dried in hot air Coated in a molten microcrystalline wax to prevent further corrosion and give the metal an attractive lustre HMS Sirius Anchor: Concretions were carefully removed by chipping away with hammer and chisel The anchor was fitted with a cathode rod and placed into a tank of water 150kg of NaOH was added to prepare the treatment solution (pH of 14) Anode sheets were assembled to fit the shape of the anchor Electrolytic treatment was undertaken with a current flow of 10 amps Once completed, the anchor was washed with pure water, dried and an appropriate corrosion inhibitor was applied A clear acrylic lacquer was used as a finishing top coat The wooden stock and iron ring were restored and fitted to the anchor to illustrate what it would have looked like when it was in actual use

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Practicals to cover:
(2.) 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 (3.) Plan and perform a first-hand investigation and gather first-hand data to identify the factors that affect the rate of an electrolysis reaction (4.) 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.) 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 (5.) Perform a first-hand investigation to compare and describe the rate of corrosion of materials in different oxygen concentrations, temperatures and salt concentrations (6.) Perform a first-hand investigation to compare and describe the rate of corrosion of metals in different acidic and neutral solutions

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