SHIPWRECKS, CORROSION AND CONSERVATION 1.

Chemical composition of the ocean implies its potential role as an electrolyte

Identify the origins of the minerals in oceans as: leaching by rainwater from terrestrial environments,
hydrothermal in mid-ocean ridges Minerals are defined as solid, naturally occurring substances with a definite chemical formula and general structure. Minerals are classified as oxides, sulfides, sulfates, silicates, or carbonates. There are two major sources of the salts (which form minerals) in oceans, these include: o Leaching by rainwater through the environment: When rain water percolates through soil or rocks, it dissolves ions and then carries them into the ocean via rivers or ground water Mainly, sodium, magnesium, chloride and sulfate are dissolved in this way, and since rain water is acidic, it also picks up hydrogen carbonate. o Hydrothermal vents Mid-ocean ridges are totally submerged mountain ranges on ocean floors These usually exist on the boundaries of tectonic plates that make up the earths crust. These ridges often have fissures and cracks in the rocks Sea water can percolate through cracks and fissures in mid-ocean ridges As it does so, it becomes superheated by the magma it approaches (typically 350 C) These are then called hydrothermal vents. As water is forced with great pressure back into the ocean and since salts have higher solubilities at higher temperatures, by convection (movement of liquid from area of high heat to lower heat), these pass through crack and dissolves ionic substances The water dissolves many ions as it is forced back through the cracks. When it reaches the cold water, some ions (especially sulfides of transition metals such as iron, copper, and manganese) crystallise out, but others stay in solution (like chlorides and sulfates of magnesium, calcium, sodium and potassium)

Outline the role of electron transfer in oxidation-reduction reactions

Redox reactions are reactions that involved the transfer of electrons from one species to another Oxidation is the loss of electrons, reduction is the gain. In oxidation-reduction reactions, the electron moves from the anode (the site of oxidation) to the cathode (the site of reduction). Redox reactions can occur when ions are free to move in liquid electrolytes. o Example: displacement of copper by zinc in a copper solution. Zinc metal comes in contact with copper ions and electron transfer. Zinc loses electrons and becomes cations while copper cations gain electrons. In some redox reactions however, the oxidation half reaction occur at different location from where the reduction half reaction occurs. In such cases there is flow of electrons through the metal joining the locations and flow of ions through the solution connection the two locations. o This is especially the case for corrosion in the ocean.

Identify that oxidation-reduction reactions can occur when ions are free to move in liquid
electrolytes In oxidation-reduction reactions electrons move from reductant undergoing oxidation to the oxidant undergoing reduction. An redox reaction will ONLY occur if ions are free to move (i.e. electrolyte) and a electrochemical cell is produced Sea water is an electrolyte solution in which ions are free to move.

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Describe the work of Galvani, Volta, Davy and Faraday in increasing understanding of electron transfer & Process information from secondary sources to outline and analyse the impact of the
work of Galvani, Volta, Davy and Faraday in understanding electron transfer reactions Luigi Galvani: o An Italian physician in the 1780s he undertook a series of investigation into the twitching of frog leg muscles with a static electricity generator. He concluded that animal tissue contained an electric fluid, through which a force, animal electricity, co uld acted upon the tissue o He also obtained twitching by pressing a brass hook into the frogs spinal cord and hanging the hook on an iron railing. o Galvani, studying the connection between life and electricity through investigations involving connecting a nerve and muscle of a frog with two dissimilar metals, concluded that electricity was generated by the animal itself. o Impact: This was the first example in our understanding of electrolytes in electron transfer reactions. In this experiment, Galvani created a galvanic cell (in which an electron transfer reaction occurs), although his interpretation of his observations was incorrect and he did not understand the electron transfer process. His foundational work provoked Volta to research further into electrochemistry. Volta o Was an existing at the same time as Galvani, proposed that, in Galvanis experiment, electricity was generated by the o Contact between metals in the moist electrolyte of the frogs bodily fluids thus refuting his theory of animal electricity. o He (incorrectly) believed that the twitching of the frog legs were due to the two different metal pieces holding the legs. In 1800, Volta supported this hypothesis by the invention of the Voltaic cell, a stack of silver and zinc discs separated by felt cardboard pads soaking in brine (salt solution). This relies on an electron transfer reaction to operate. o Impact: Although Volta did not realise that an electron transfer reaction, as opposed to contact between metals, was what was creating electricity, his work was significant in that it facilitated Davys experimentation with electrolysis (another form of electron transfer reaction) and stimulated further research into electrochemistry (such as the construction of a useable galvanic cell; the first source of direct electrical current). Humphry Davy: o Explained correctly that chemical reactions resulted in creation of electricity in the Voltaic cell, and not between two different metals. o He also recognised that the reaction bringing about this current, where decomposition reactions (is the separation of a chemical compound into elements or simpler compounds), he used the understanding from this to create electrolysis apparatus and to decompose water into hydrogen and oxygen (further proving water is compound not element). o He developed improved versions of Volta's pile to decompose many substances. He electrolysed molten salts to isolate metals such as sodium, potassium, and calcium. o Impact: Through his experiments, he concluded that it was electrostatic forces that held together the elements of compounds, precursory to ionic theory developed by Arrhenius and the understanding that it was the movement of electrons that caused current and oxidation-reduction reactions that generated electricity He used electrolysis to decompose compounds, isolate elements, and show in chemical reactions there was a definite connection between reaction and electricity. These investigations led to our understanding of electron transfer reactions as the basis of electrolysis. Michael Faraday: o He preformed studies to relate the amount of substance produce to the quantity of electricity that passed. Thus developed two major laws of electrolysis based on experimental evidence. The first states: the amount of product of electrolysis is proportional to the quantity of electrical charge that has flowed through the circuit. (Q=It)

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The second states: the masses of substances produced are proportional to the molar masses of each substance

Impact: Allowed the electron transfer reaction of electrolysis to be understood quantitatively His discoveries supported the suggestion made later that electricity consisted of small particles (electrons), contributing to the understanding of particle theory and electron transfer that we have today. He was the first person to define the laws of electrolysis and quantify electrolysis. He also introduced the terminology used today such as electrolyte, cation and anion. His discoveries led a better understanding of electron transfer reactions in electrolysis.

2. Ships have been made of metals or alloys of metals

Account for the differences in corrosion of active and passivating metals

Corrosion: the degradation (through oxidation) of a metal, so that it loses strengths and becomes unable to fulfil its intended purpose. o The most common type of corrosion is known as rusting. A passivating metal is a reactive metal that readily forms an unreactive, impervious surface coating (usually an oxide), by the reaction with oxygen or water. It protects the metal from further reaction (i.e. corrosion). o An example of an passivating metal is aluminum, it forms a layer of aluminum oxide 4Al (s) + 3O2 (g) 2Al2O3(s) Prevents oxygen going through the rest of the aluminum metal, hence no further corrosion. Other metals in include Zinc (Zn) {the passivation of Zinc is called galvanising}, Chromium (Cr) which forms Cr2O3, and stainless steel (which also contains chromium to passivate through).

Note: some non-metals such as copper also form a protective layer of oxide (or carbonate) but these are not termed passivating, as they are not reactive metals. An active metal is a reactive metal, such as magnesium or sodium, that does not passivate (i.e. form a protective coating against further reaction). Most are located in the first two columns of the periodic table.

Identify iron and steel as the main metals used in ships

Since 1860s ocean-going ships have been made from steel and iron. They both have the advantages of being hard, high mechanical strength, and can be welded.

Identify the composition of steel and explain how the percentage composition of steel can determine its properties & Gather and process information from secondary sources to compare the
composition, properties and uses a range of steels Alloys are partial or complete solid solution of one or more elements. In general, alloys are harder than pure metals, as the presence of differently sized atoms interrupts the orderly structure of the metal lattice, preventing atoms in the lattice from sliding over each other. In general there are 2 different types of alloys o Homogeneous: meaning the presence of different atoms is evenly spread out o Heterogeneous: meaning the presence of different atoms is not evenly spread out Steel is an alloy of iron, carbon (no more than 2%), and often varying amounts of other metals. An increase in any of the element metals leads to different types of steel. The choice of steel for a specific purpose depends on the properties necessary for that purpose as well as the environment the alloy will be exposed to.

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Element Aluminium Nickel Tungsten Vanadium

Property effects Steel becomes easily shaped, and forms passivating layer High corrosion resistant High strength at high temperatures Wear resistance

Composition, properties and uses of a range of steels o NOTE: the rest of the composition is made up of IRON

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: the most common form of corrosion that involves redox reactions o It produces red hydrated iron oxide (Fe2O3.H2O) Conditions for rusting: o Iron: the metal to be oxidised. o Water: acts as an electrolyte to connect the anodic and cathodic sites, and is also reduced (discussed below). o Both oxygen and water are necessary: O2 and H2O are needed because together they are reduced to form hydroxide ions.

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Impurity sites in the iron: these are needed to act as cathodes, where the reduction (gain of electrons) of O2 can occur. This is clearly seen through the slow process of rusting in pure iron, it doesnt have good reducing surface Conditions that affect rusting: o Salt water: Salt water accelerates rusting because it is an electrolyte and therefore more conductive than fresh water o Concentration of oxygen: Oxygen concentration pushes equilibrium to the right therefore increasing the amount of hydroxide produced, increases the chances for the formation of iron oxide Reduction: O2 (g) + 2H2O (l) + 4e 4OH (aq) Furthermore the oxygen is needed to form rust, i.e. it receives electrons from iron oxide (gets reduced). So an increase in oxygen concentrations increases all the above rates. o Mechanical stress: When iron is under stress, example at bends, sharpened joins or edges, the stress disrupts the metallic lattice orderly crystal structure of iron, hence becomes distorted 2+ and this makes it easier for individual Fe atoms to break away from the crystal as Fe ions. o Acidic electrolyte: In the process of rusting, when iron is oxidised, water is reduced. The reaction is: o O2 (g) + 2H2O (l) + 4e 4OH (aq) By Le Chateliers principle, as [OH-] becomes small (i.e. the electrolyte becomes more acidic), the equilibrium will favour the forward reaction and hence the corrosion of iron. o Temperature: As with all chemical reactions, corrosion occurs more rapidly at higher temperatures, as high temps. increase rates of collision o Contact with other metals: If iron is in contact with metals that are weaker reductants, such as tin or copper, it rusts more readily as less active metals act as cathodic sites. This process is called galvanic corrosion. Process of rusting:

When iron metal is in contact with oxygen AND water (sometimes in the form of moisture), at anodic 2+ sites, iron atoms oxidise (i.e. lose electrons) to form Fe ions. o Oxidation: Fe (s) Fe (aq) + 2e E = + 0.44V The electrons from this half-reaction flow to the cathodic sites, usually an impurity such as carbon (i.e. where reduction (gain of electrons) can take place)
2+

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o o o

There, the electrons reduce the oxygen dissolved in the thin film of moisture on the irons surface OR in the water touching the iron (if the iron is submerged)

Reduction: O2 (g) + 2H2O (l) + 4e 4OH (aq) E = + 0.40V Note: in order for this galvanic cell to continue to operate, there has to be a migration of ions through the moisture layer from one location to the other. This migration of ions is to preserve the electrical neutrality (for the flowing of electrons that are needed for reduction/oxidation reactions). This is why salt solutions are ideal, as they provide an ample supply. Simplified rusting formula:

o 4Fe (s) + 3O2 (g) + 2H2O (l) 2(Fe2O3.H2O) (s) 3. Electrolytic cells involve oxidation-reduction reactions

Describe, using half-equations, what happens at the anode and cathode during electrolysis of
selected aqueous solutions Galvanic Cell Chemical Electrical energy Produces electrical current Spontaneous reaction Anode is NEGATIVE () Cathode is POSITIVE (+) E0 is positive (electricity produced) Anode= oxidation, cathode = reduction Electron flow= oxidation reduction Electrolysis of concentrated NaCl solution o Diagram: Electrolytic Cell Electrical Chemical energy Requires an input of electrical current Reaction is forced Anode is POSITIVE (+) Cathode is NEGATIVE () E0 is negative (electricity required) Anode= oxidation, cathode = reduction Electron flow= oxidation reduction

Equations: Oxidation: 2Cl (aq) Cl2(g) + 2e (bubbles of Cl2 formed) Reduction: H2O(l) + e 1/2H2 + OH (bubbles of H2 formed) Redox: 2H2O(l) + 2Cl (aq) H2(g) + 2OH (aq) + Cl2(g) Electrolysis of molten NaCl o Diagram:

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Equations: Oxidation: 2Cl (l) Cl2(g) + 2e + Reduction: Na (l) + e Na(l) + Redox: 2Na (l) + 2Cl (l) Cl2 (g) + 2Na(l) Electrolysis of dilute NaCl solution (same as electrolysis of water) o Diagram:

Equations: Oxidation: 2H2O (l) Reduction: 2H2O (l) + 2e Redox: 2H2O (l)
-

4H + O2 (g) + 4e 2H2 (g) + 2O2 (g)

H2 (g) + 2OH

Electrolysis of CuSO4 o Diagram:

Equations: 2+ Oxidation: Cu (aq) + 2e Cu(s) + Reduction: H2O 1/2O2(g) + 2H (aq) + 2e 2+ + Redox: Cu (aq) + H2O(l) Cu(s) + 1/2O2 + 2H (aq)

Describe factors that affect an electrolysis reaction (concentration, electrolyte, electrodes)

Effect of concentration of certain ions present (ie electrolytes): o ALL standard potential tables are measured at 1mol/L electrolyte solutions. o By varying the concentration of certain ions in an electrolyte (for example adding more salt to increase the concentration of chloride ions present in the sample), CHANGES the potentials. o For example, in the standard potential table the following occurs at 1mol/L o 2Cl
(aq)

Cl2 (g) + 2e
+

E = 1.36 V
-

2H2O (l) 4H + O2 (g) + 4e E = 1.23 V HOWEVER, if the Cl (aq) concentration is increase, the E may well increase to 1V; hence this will in favour instead of water.

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Similarly, if the Cl (aq) concentration is decreased, the E will decrease even further, hence favouring the water oxidation. Nature of electrolyte: o Products vary according to the nature of electrolytes. o For example in molten electrolytes, there exists only 2 substances (the anions and cations); hence the yield is a product at each electrode. For example, the electrolysis of molten NaCl, others include magnesium chloride (MgCl2) which yields magnesium and chlorine gas. o However, electrolytes that consist of aqueous solutions may result in water being reacted at the electrodes in preference to the other alternatives (that are wanted). o For example, an aqueous solution of magnesium chloride would yield hydrogen gas at the cathode rather than magnesium. This occurs because the E value for the reduction of water to hydrogen, has a LOWER numerical value that that for the reduction of magnesium ions 2+ (Mg ). o And again at the cathode (though depending on the concentration) the oxidation of water to oxygen has a lower numerical value (-1.23V) than chloride ions into chlorine gas (-1.26V), so it will preferably oxidise. o This happens when there are two species present that have similar tendencies to be oxidised or reduced; that is their standard electrode potentials are similar. Nature of electrodes o Reactions that are out using inert electrodes, will simply act as conductors, or a site where oxidation and reduction can take place, IN PREFERENCE to the electrolyte. o For example, in the electrolytic refining of copper, blister copper is used as the anode and the cathode is pure copper. The blister copper electrode oxidises, while layers of pure copper build up around the inert cathode. o At the anode the reaction is Cu(s) Cu (aq) + 2e , however if another inert electrode is added (i.e. there are now 2 inert electrodes), the anode reaction simply becomes 2H2O (l) 4H (aq) + O2 (g) + 4e , this is because there is no other solid wishing to be oxidised except water (remember copper sulfate exist as ions in the solution).
+ 2+ -

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

Identify the ways in which a metal hull may be protected including corrosion resistant metals,
development of surface alloys, new paints Corrosion resistant metals: o A common way to protect a metal is simply using one that does not corrode in the first place, that is use a substitute material. o This is done in buildings and parts on the ship, where aluminium has nearly completely replaced all steel in windows, and door frames. Aluminium can form a passivating layer, hence protecting the iron. o Other examples include, stainless steel (that does not corrode) has replaced carbon steel, where it is able to take in high heat (heat favours any chemical reaction and induces rusting). Another reason is that they can passivate (form chromium (III) oxide which doesnt allow oxygen to react with bare metal), that is to form a protective layer of oxide which prevents rusting. Development of surface alloy: o One method is through the use of stainless steel-like properties on the surface of a metal hull. It would be able to resist rusting, as the bare metal under it is not exposed. This is done by bombarding a hull with ions of chromium and nickel The metal ions are formed in a high temperature gaseous discharge ( plasma) and are directed onto the surface of ordinary steel where they become embedded as atoms and so form a surface alloy This stainless steel surface resists corrosion. New paints: o Painting a steel object protects it from oxygen and water and hence from corrosion.

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This is an inexpensive and potentially effective method. However, the paint needs regular maintenance (which is a nuisance for submerged steel objects) and can pollute the environment by leaching out chemicals. Polymer-based paints, such as Rustmaster pro, are a fairly recent development. When applied to steel, a polymer layer impervious to water and oxygen is formed. Additives in the paint also react with the steel to form an intermediate layer of highly insoluble ionic layer pyroaurite. This ionic layer is tightly bonded to the steel surface and extends well into the polymer layer. It prevents the movement of ions hence rusting. This paint is effective, does not require maintenance as frequently, and does not release chemicals into the environment. Phosphate coatings are used on steel parts for corrosion resistance, or as a foundation for subsequent coatings or painting. It serves as a conversion coating in which a dilute solution of phosphoric acid and phosphate salts is applied via spraying or immersion, chemically reacts with the surface of the part being coated to form a layer of insoluble, crystalline phosphates i.e. it forms iron (III) phosphate, which is insoluble and adheres to the iron tightly, forming a protective layer

Predict the metal which corrodes when two metals form an electrochemical cell using a list of
standard potentials In a galvanic cell the metal that corrodes (oxidises), is the one that has the highest oxidation potential (this can be obtained by flipping the reduction potential table values). This is because, the one with higher oxidation potential is the one that wants to OXIDISE MOST.

Outline the process of cathodic protection, describing examples of its use in both marine and wet
terrestrial environments Cathodic protection (also known as galvanic protection): o the process of protecting a metal, by making a metal the cathode (reduction, ie gains electrons) of an galvanic cell (electrochemical cell) in order to prevent its oxidation. o Marine and terrestrial environments, forms of cathodic protection such as galvanised steel, sacrificial anodes and applied voltage are used.

Describe the process of cathodic protection in selected examples in terms of the oxidation/reduction
chemistry involved Sacrifical electrodes (more specifically anodes): o A sacrificial electrode is usually a bloke of zinc or magnesium (or anything that will preferably oxidise in preference to iron). This is done by the galvanic action, the more reactive metal, in this case (Mg or Zn) oxidise sacrifices preferentially t o the iron, giving up electrons to the iron +2 and so preventing iron oxidising to form Fe . o o Fe(s) Fe
2+ (aq) 2+

+ 2e

E = + 0.44V

Zn(s) Zn (aq) + 2e E = + 0.76V Since the oxidation potential of zinc is greater than that of iron, it will oxidise in preference (i.e. become the anode) and render the iron as the cathode +2 If any Fe ions did form, they would be reduce, that is be converted back to iron solid (Fe (s)) by the electrons given up by Zn or Mg. Zn (s) + Fe (aq) Zn (aq) + Fe (aq) Note: since the action is galvanic, it is essentially a galvanic cell. However galvanic cells require an electrolyte (i.e. solution containing free ions that make it electrically conductive), so too does sacrificial electrodes. Hence the medium should be sea water/moist earth, such that the build of +2 Mg ions is balanced, and electrons can flow without resistance from the solid block of Mg to the iron.
2+ 2+ 2+

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Also Mg should not be used in moist ground, as it can react with water violently and deteriorate it much quicker.

Applied voltages (also known as impressed current/voltage): o Another form of cathodic protection is to use an inert (i.e. non-sacrificial) anode such as platinum-coated titanium. A suitable voltage is applied between it and the metal wanted to be protected, rendering it cathodic (i.e. hull of ship, or underground pipes). o This voltage forces electrons into potentially active sites on the steel hull and so prevents oxidation. o Fe (aq) + 2e Fe (s) E = + 0.44V However because there may be extra electron flow from the voltage source, water (as moisture) may also react Anode at : 2H2O 4OH Cathode: 2H2O (l)
(l) 2+

+ 2e

H2(g) + 2OH 4H
+ (aq) +

(aq)

OR O2 (aq) + 2H2O

(l)

+ 4e

O2 (g) + 4e

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 Wood was the most common shipbuilding material until the nineteenth century. Metals were used in some early ships: o Viking longboats which had iron and bronze fittings to cover oak planks. o Greeks and Romans using iron to replace the weaker copper. Around 1500AD Lead and then copper sheeting was fixed to the hull of ships to prevent biofouling by marine organisms, iron nails made it possible to connect. o This made the hull stronger and less flexible, but the nails were susceptible to rapid corrosion. o Copper nails were used in their place. The first all iron ship was the British Vulcan, a passenger barge, launched in 1818. By 1870 more than 90% of the ships produced in the UK were iron. Although they needed constant maintenance due to corrosion, iron ships had numerous advantages over wooden ones o stronger, thus safer, more economical, easier to repair, could be built larger, carry more cargo, travelled faster, was not susceptible to fire from cannonball explosions. By the late 1800s shipbuilders began to use steel alloys, which meant lighter and stronger ships. o Iron was the preferred metal because it was readily available by that time, and because of its hardness, and strength. o However, the process of making steel was unsophisticated and difficult to control, resulting in high amounts of carbon (0.2%), sulfur (0.1-0.2%), and phosphorus (0.1%) and a very brittle steel, especially at low temperatures.

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In the early 1900s the production of steel improved after World War II, when manufacturers were able to remove sulfur and phosphorus from steel, and the invention of electric welding meant faster and better construction of steel ships. o Companies experimented with the addition of elements such as manganese, o Ships became more durable and tougher, but much less brittle. Other developments in the twentieth-century included the progressive improvement in steel alloys, incorporating aluminium, chromium, titanium, zinc and nickel. o Modern steels are lighter, stronger and more corrosion-resistant than before. Other developments at this time: o Bronze (alloys of copper and tin) was used instead of steel as propellers (because they resist corrosion even when exposed to rapidly moving, highly aerated water). o Aluminium, being resistant to corrosion and extremely light, was used in the superstructures and fittings in ships. o Stainless steel, being extremely resistant to corrosion but very expensive, was used in fittings and equipment of ships. The metal predominantly used in ships is still steel, primarily because of the abundance and low cost of iron, and the tensile strength, and malleability of steel. o Improved methods of protecting steel from corrosion are constantly being developed.

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 Uses and applications: o Sacrificial anodes are often used for accessible steel structures, for example: Ships hulls, rudders and propellers Water tanks (above ground). o Impressed current systems are used for: Underground steel structures (because sacrificial anodes would not be able to be replaced) such as pipelines and fuel storage tanks. Ship hulls, rudders and propellers. Reasons for use: o Both effectively prevent the corrosion of iron. o Both are easily maintained; maintenance is simply replacing corroded sacrificial anodes. o Both are relatively inexpensive corrosion prevention methods, although impressed current systems can be expensive to set up. o Impressed current systems release no pollutants (whereas sacrificial anodes release metal ions). o Impressed current systems allow the consistent prevention of corrosion of buried steel structures.

5. When a ship sinks, the rate of decay may be dependent on the final depth of the wreck

Outline the effect of temperature and pressure on the solubility of gases and salts
Gases Increase in temperature Increase in pressure And vis versa Decrease solubility Increase solubility Salts Generally increases Nothing

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

Gas

Concentration in the

Concentration in ocean (at surface)

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atmosphere Oxygen Nitrogen Carbon dioxide 21% -5 1.5 x 10 mol/L 79% -2 3.3 x 10 mol/L 0.04% -5 1.5 x 10 mol/L Up to 8.5ml/L 2.8 x 10-4 mol/L Very little low solubilty -4 5.6 x 10 mol/L Up to 46ml/L -5 1.4 x 10 mol/L

Compare and explain the solubility of selected gases at increasing depths in the oceans
Carbon dioxide o Carbon dioxide has a higher concentration in sea water (16%) than its concentration in the atmosphere would lead one to expect. This is due to the fact that carbon dioxide can react with water to form carbonic acid. o Carbon dioxide is consumed near the surface of the ocean in the photosynthesis of plants. Further down, it is still produced by the processes of respiration and decomposition, but there are few plants to consume it, so its concentration is much higher. It also has a very high solubility under the conditions present in very deep sea water (low temperature, high pressure). Nitrogen o Nitrogen makes up approximately 48% of the gas dissolved in water at the oceans surface, compared to 78% of the gas in the atmosphere (v/v). Even though nitrogen is not very soluble in water, it has a high concentration in water due to its high partial pressure. Because there are few processes that remove or create nitrogen in the ocean, its concentration does not change heavily with depth. Oxygen o Near surface: As well as being diffused from the atmosphere, oxygen is produced in water by the photosynthetic action of phytoplankton. Since they require light to photosynthesise, they are only found in the top 100 metres of the ocean. o 100-1000m below surface: Oxygen is still consumed in the process of respiration, but is not as readily replenished by contact with the atmosphere and photosynthesis. o Below 1000 metres: Deep ocean currents bring some oxygen-rich water from the surface. Oxygen makes up approximately 36% of dissolved gases at the surface, compared to 21% of the atmosphere (v/v). It has a greater concentration in the ocean because it is more soluble than nitrogen, and because it is produced by phytoplankton. 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 The predicted effect of low temperatures at great depths on the rate of corrosion is that the corrosion would be slow, for two reasons: o All chemical reactions (including equilibrium reactions) slow down at low temperatures, meaning slower reaction and less corrosion. Note: yes the 'exothermic' reaction is favoured in the equilibrium reaction, and would be the reaction that is created, however it is at an unbelievable slow rate. o Another reason is, which is probably the most important; lack of light, this will mean the lack of living organisms at that depth due to photosynthesis to produce oxygen: A low dissolved O2 concentration would mean a less corrosion: O 2 is required for corrosion to occur and low levels mean a slower reaction and less corrosion.

6. Predictions of slow corrosion at great depths were apparently incorrect

Explain that ship wrecks at great depths are corroded by electrochemical reactions and by anaerobic bacteria & Describe the action of sulfate reducing bacteria around deep wrecks

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Before the shipwrecked Titanic was discovered, it was predicted that the ship would corrode very slowly because of the low temperature, low salt concentration, and low concentration of dissolved oxygen. However, the ship was found to be corroded extensively due to a number of factors. For shipwrecks in deep ocean water, some of the corrosion is caused by the normal electrochemical process of iron oxidising and reacting to form rust. However most of the corroision is by anaerobic (requiring no oxygen) sulfate-reducing bacteria. They respire (obtain energy) by reducing sulfate to sulfur. An example, is the bacteria Desulfovibrio family. o SO4 (aq) S (s) S (aq) For these reactions to occur they need electrons (as the above are all reducing reactions), this comes from organic compounds such as carbohydrates (i.e. CH2O) that oxidise and release electrons. o CH2O (aq) + H2O (l) CO2 (g) + 4H + 4e Hence the bacteria allow the corrosion process to occur even in the absence of oxygen.They tend to populate shipwrecks because they provide an excellent source of nutrients, and allow the corrosion process to occur even in the absence of oxygen. o The SUM reduction reaction is: o o o o SO4
2(aq) 2+ 2-2

+ 5H2O (l) + 8e

HS

(aq)

+ 9OH

(aq)

SO4 (aq) + 10H+ (aq) + 8e The oxidation reaction is: 4Fe (s) 4Fe Net ionic equation:
22+ (aq)

H2S (aq) + 4H2O (l)

+ 8e

(it has been multiplied by 4 so we can balance electrons)

2+ -

4Fe (s) + SO4 (aq) + 5H2O (l) 4Fe (aq) + HS (aq) + 9OH (aq) 2+ The Fe then react with HS and OH (aq) to form insoluble FeS and Fe(OH)2 4Fe (aq) + HS (aq) + 7OH (aq) FeS (s) + 3Fe(OH)2 (s) + H2O (l) Upon adding the above 2 reactions, and cancelling one H2O on each side, the overall reaction is:
22+ -

4Fe (s) + SO4 (aq) + 4H2O (l) FeS (s) + 3Fe(OH)2 (s) + 2OH (aq) This form to form insoluble black iron (II) sulfide and iron (II) hydroxide along the steel (if there is oxygen this hydroxide will become converted to rust). These compounds combine to form finger growths, that are reddish-brown known as resticles. Rusticles also contain many other compounds such as calcium carbonate (CaCO 3).

Explain that acidic environments accelerate corrosion in non-passivating metals

Now in rusting, the normal reduction reaction, at the cathode is: o O2(g) + 2H2O(l) + 4e 4OH E = + 0.40V + When working with acidic solutions, the half reaction is usually put in terms of H , rather then OH . This is done by adding 4H to each side of the equation above, then 'convert' 4OH + 4H 4H2O(l). Then cancel 2 H2O from each side to obtain:
+ + +

o O2(l) + 4H (aq) + 4e H2O(l) E = +1.23V Both equations represent the same thing, oxygen reducing into water; all that changes is how the acidity of the equation is represented. Now there are 2 reasons for why acidity accelerates corrosion. o The half reaction above has a standard potential of 0.4V; this is the value at [OH ] = 1 mol/L, as the acidity increases (i.e. the concentration of OH decreases), the following occurs. For -7 example a pH of 7, [OH ] = 1.0 x 10 mol/L, the non-standard electrode potential is 0.81V, at -11 the pH = 4. At pH 3, [OH ] = 1.0 x 10 mol/L, it is 0.99V. Thus the fact that the electrode potential increases means that the half reaction has a greater tendency to occur as acidity increases. o By Le Chateliers principle, looking at equation 2 above (doesn't really matter), as the electrolyte becomes more acidic, [OH ] becomes small, hence the equilibrium will favour the forward reaction and hence the corrosion of iron.

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

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Explain that artefacts from long submerged wrecks will be saturated with dissolved chlorides and
sulfates Aretefacts are objects from past human societies, they are valued as they provide insight into history. When long-submerged objects have been recovered, they are generally in very poor condition. o Wooden artefacts will usually have all their cellulose eaten away, and there pores will impregenated with salts and other ions such as chlorides and sulfates occupy the pores of an artefact (microscopic in the case of metals) and saturate the object. o Since most artefacts, are usually metals, which are cations, they will ALSO attract anions in their reactions by precipitation. Describe the processes that occur when a saturated solution evaporated and relate this to the potential damage to drying artefacts When a solution of a solid such as sodium chloride (NaCl) is evaporated, the solution becomes more concentrated, as there is less water to dilute the solution. The water evaporates and hence the salt remains. Eventually it becomes saturated with salts, the water is removed, and the solid starts to crstyallise until the solid structure forms. This formation of solid salt crystals throughout porous objects causes an increase in pressure, thus cracking and damage by distorting the shape of the object, or even reaction that can further accelerate corrosion.

o 4FeCl2 (aq) + 10H2O (l) + O2 (g) 4Fe(OH)3 (s) + 8HCl (aq) o 4FeCl2(s) + 4H2O(l) + O2(g) 2Fe2O3(s) + 8HCl(aq) Identify the use of electrolysis as a means of removing salt Artefacts that have long been submerged, will often carry a huge amount of salt content. One method of removing these salts is to leach them out of the object. The process involves putting the object in fresh distilled water for a period of weeks -months, depending on how high the concentration of salt is. The action involves osmosis, where molecules move from an higher of higher concentration (the object) to an area of lower solute concenctration (the water bath). Water is regularly changed to accelerate this process. Generally, dilute sodium hydroxide (NaOH) is used then distilled water, as it speeds the removal of -) chloride (though it doesnt not matter). It does this because the hydroxide ion (OH can replace chloride (Cl ) in iron, which exists as Fe(OH)2, this will be removed by further means. MOST chloride is SOLUBLE and present as iron (ii) chloride (FeCl2) or iron (iii) chloride (FeCl3) or copper (ii) chloride (CuCl2). HOWEVER, There are some salts are extremely hard to remove by these conventional means, they are insoluble hydroxy chloride salts. If the object is iron they include Fe(OH)Cl, or if copper Cu(OH)Cl. These chlorides react with water and oxygen to form rust and hydrochloric acid which even further expediting the corrosion process: o Fe(OH)Cl (s) + H2O (l) Fe(OH)2 (s) + HCl (aq)

o 4Fe(OH)Cl (s) + 6H2O (l) + O2 (g) 4Fe(OH)3 (s) + HCl (aq) o Similarly for copper compounds. A more efficent way of removing chloride from such objects, is through electrolysis. Identify the use of electrolysis as a means of cleaning and stabilising iron, copper and lead artefacts Conservation: Cleaning, stabilisation and preservation of an artefact to prevent further deterioration, involving as little interventive treatment as possible. Restoration: Returning an artefact to a condition as similar to its original as possible. The metal object is made the cathode (such that it reduces, gains electrons), and through this the salts (or even if theres any iron (ii) hydroxide that is wanting to form rust) can accept electrons, then following occurs: o o Fe(OH)2 (s) + 2e
-

Fe (s) + 2OH

(aq) (aq)

Fe(OH)Cl (s) + 2e

Fe (s) + OH

+ Cl

(aq) 2+ (aq)

The above reactions can basically be represented as Fe

+ 2e

Fe (s)

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This means that the salt (or iron(ii) hydroxide) is converted to solid iron, which builds up on the object as that is the cathode (site of electron acceptance), and the rest of the ions flow into the solution. This effectively means, salt is removed, and the needed part of that salt is used to repair the worn object. 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 Artefacts from ships include anything that was used on that ship, it can include wooden objects, lead , copper, metal etc. However the main things are often restored as: Silver artefacts o Generally silver doesn't corrode, until the Desulfovibrio bacteria reduce sulfate to sulfide, the following reaction can occur: o o SO4 (aq) + 10H+ (aq) + 8e H2S (aq) + 4H2O (l) Then the silver solid reacts with dihydrogen sulfide to form insoluble silver sulfide. 2Ag (s) + H2S (aq) Ag2S (s) + H2 (g) Silver sulfide forms as relatively firm layer on the object and prevents it from corroding, also this layer further becomes covered by calcium carbonate (also known as concretions). They form by the following precipitaiton reaction: Ca + CO3 CaCO3 (aq) The layers of concretions (which can become very thick) are removed by dissolving them in acid. CaCO3 (s) + 2HCl (aq) CaCl2 (aq) + H2O (l) + CO2 (g) After these have been removed, it will leave black objects (as there is black silver sulfide remaining) , it will be too abrasive to clean the the silver sulfide by acid, as the silver can also react with acid and damage engravings and embossings, something so fragile as coins need to have as much detail as can be. The formation of silver sulfide can be reversed by making the corroded object the cathode in an electrolysis cell The reduction (cathode): Ag2S (s) + 2e 2Ag (s) + S (aq) An inert electrode is used as the site of oxidation (such as platnium or stainless steel), also a solution of sodium hydroxide is chosen as it facilitates (makes easier) the reduction reaction to occur. Hence the oxidation (anode): 2H2O (l) 4H (aq) + O2 (g) + 4e In this way, the silver sulfide is converted back to silver which embeds back to the object, with little damage to the markings on the object. If further stabilisation is required, clear laquer is applied (though not necessary). Note: silver chloride (AgCl) salt , or any other types of insoluble salts , rarely forms on silver.
+ -2 2+ 22-

Iron o

o o

Iron artefacts are usually covered in concretions of calcium carbonate or coral, which is usually removed mechanically carefully by a hammer (MRI magnetic resonance image can be used to display this layer). The piece is saturated with soluble chlorides and sulfates, and covered in insoluble iron compounds such as hydroxides, oxides, and hydroxychlorides. Desalination, which is the removal of salts from an object, is done through the washing of the object for extended periods of time. Usually dilute (~0.5mol/L of sodium hydroxide, or carbonate or bicarbonate). The reason for this, is it includes the fact that it makes the solution more alkaline hence inhibiting further corrosion, as it is favoured in acidic environment However the main reason is the fact that they accelerate the removal of chloride ions this is done by the reaction Fe(OH)Cl (s) + X (aq) Fe(OH)X (s) + Cl (aq) 2 The X can be OH , HCO3 or CO3 , when this form with iron, it can be removed be electrolysis, at least stopping the damaging of chloride. Electrolysis can be performed to remove soluble (the ones that are left) and insolubes chlorides compounds.
-

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The metal object is made the cathode (such that it reduces, gains electrons), and through this the salts (or even if theres any iron (ii) hydroxide that is wanting to form rust) can accept electrons, Then following occurs: FeCl2 (aq) + 2e
-

Fe (s) + 2Cl

FeSO4 (aq) + 2e

Fe(OH)2 (s) + 2e

Fe(OH)Cl (s) + 2e

(aq) -2 Fe (s) + SO4 (aq) Fe (s) + 2OH (aq) Fe (s) + OH (aq)

+ Cl

(aq) 2+ -

The above reactions can basically be represented as Fe (aq) + 2e Fe (s) This means that the salt (or iron(ii) hydroxide) is converted to solid iron, which builds up on the object as that is the cathode (site of electron acceptance), and the rest of the ions flow into the solution. This effectively means, salt is removed, and the needed part of that salt is used to repair the worn object. At the cathode, when the voltage is abit higher then normal the following reaction occurs: 2H2O (l) + 2e 2OH (aq) + H2 (g) The following reaction causes the production of hydrogen bubbles at the cathode, which helps loosen any remaining concretions.
-

Copper o Copper artefacts do not corrode badly because copper is unreactive and poisonous to marine organisms. However, they do form surface layers of CuCl2 and Cu(OH)Cl. The surface of the artefact is cleaned by chemical stripping; it is placed in a 5-10% citric acid and 1-2% thiourea (a corrosion inhibitor) mixture to dissolve surface deposits. Chlorides can be removed by soaking in sodium hydrogen carbonate or pure water. Electrolysis can be performed with sodium carbonate electrolyte (NaOH damages alloys of copper). o Then following occurs at the cathode (reduction): o CuCl2 (aq) + 2e
-

Cu (s) + 2Cl

(aq) (aq)

Cu(OH)Cl (s) + 2e Cu (s) + OH (aq) + Cl Then following occurs at the anode (oxidation):
-

o Lead o

2H2O (l) + 2e 2OH (aq) + H2 (g) The following reaction causes the production of hydrogen bubbles at the cathode, which helps loosen any remaining concretions. The artefact is washed and coated with crystalline wax or clear acrylic lacquer. Lead artifacts have few concretions because lead is poisonous to marine organisms (but still can form). Lead oxidises slowly to form insoluble: PbS, 2PbCO3.Pb(OH)2, PbCl2, or Pb(OH)Cl (You can check this with solubility rules). Usually lead artifacts include cannon balls, weights, and lead sheeting. PbS and CaCO3 concretions are removed with 10% hydrochloric acid: PbS (s) + H (aq) Pb (aq) + H2S (aq) Other insoluble lead compounds are removed with 5% EDTA solution in an ammoniaammonium buffer; EDTA forms complexes with lead ions, allowing the insoluble compounds to dissolve. Electrolysis can be used to remove hydroxychlorides with sodium carbonate electrolyte. Then following occurs at the cathode (reduction): PbCl2 (aq) + 2e
+ 2+

Pb (s) + 2Cl

(aq) (aq)

Pb(OH)Cl (s) + 2e Cu (s) + OH (aq) + Cl Then following occurs at the anode (oxidation):
-

2H2O (l) + 2e 2OH (aq) + H2 (g) The lead is finally washed with H2SO4 and distilled water, and is then dried thoroughly and coated with crystalline wax.

Wood o When wood is immersed in sea water, there is rapid decay, wood worms known as toredo worms and various bacteria, fungi attack the wood, quickly eating its useful c ellulose and

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o o o

o o

leaving the lignin behind (which is what maintains its shape). Special circumstances can however slow down the process: If the wreck or object is buried in silt or mud, which excludes the worms and aerobic bacteria, this reduces the rate. If the water is very cold, unsalted, and not in great water current movement (ie near the 0 ocean floor reaches 4 C, and 0.4% of salt such as the Baltic sea, the water movement over the wreck restricts the inflow of fresh oxygen for bacteria). When long submerged wooden objects, they are very fragile (due to missing cellulose), and the salt is dangerously damaging if it is left to dry, at it allows to shrink, wrap and split. Wooden artifacts are first cleaned of silt and mud by spraying them with cold water for an extended period of time and gently brushing them. The water impregnating the wood is replaced by poly(ethylene glycol), which is a inert wax (or oil as well), a polymer soluble in water with the structure (-CH2-CH2-O-)n- note: different values of 'n' vary the properties such as viscosity (sticky) and melting points, hence why it can be called a wax or oil. This fills all the cavities (i.e. missing cellulose) in the wood and stabilizes it by restoring some of its structural strength and stopping further degradation. Final the object is dried to remove residual water and coated with higher melting point poly(ethylene glycol) wax.

Perform an investigation and gather information from secondary sources to compare conservation and restoration techniques applied in two Australia maritime archaeological projects Endeavour cannons Cannon was stored in mixture of seawater and 10% formalin (to kill bacteria). Coral was removed mechanically with hammers Cannon was placed in a 2% NaOH solution (to prevent acidic corrosion). It was electrolysed 2 with a current density of 10A/m , with cannon as cathode and mild steel as anode. After the baths, the cannons were washed with fresh water at each refreshing of the electrolyte (The electrolyte was replaced after two weeks, then weekly until chloride concentration stabilised at 20 ppm.) Cannon was placed in distilled water with -3 chromate ions (8.7 x 10 mol/L) to remove chlorides and hydroxides and form a protective layer of iron oxide and chromic oxide. o Cannon was dried for two days at 120 C, and then immersed in crystalline wax (as a further o protective layer) for five days, at 135 C to ensure maximum penetration of wax. Wax was cooled to just above melting point. Vernon anchors Surface corrosion and remains of protective paint were removed by blasting (smoothing rough surface) with copper slag. Iron was treated with zinc epoxy paint. Timber components were saturated with zinc naphenate solution to prevent growth of organisms Electrolysis was not applied to the anchors because it required the removal of the timber stocks (which could cause unnecessary damage) and also because the cast iron was in sufficiently good condition. The anchors are supported by an aluminium mesh (cathodic protection).

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