Oil, Plastics & The Earth Key Notes Fossil fuels formed millions of years ago from the

remains of living things (coal from plants and natural gas and oil from sea creatures) - they were gradually buried by layers of rock which stopped them rotting The buried remains were put under pressure and chemical reactions heated them up, gradually changing into fossil fuels Some oil and natural gas was covered by cap rock which is impermeable (not letting them through) They can be removed from the ground by drilling through the rock

Crude oil is a mixture of compounds called hydrocarbons they only contain hydrogen and carbon atoms, joined together by chemical bonds There are different types of hydrocarbon, but most of the ones in crude oil are alkanes The alkanes are a family of hydrocarbons that share the same general formula: CnH2n+2 The general formula means that the number of hydrogen atoms in an alkane is double the number of carbon atoms, plus two E.g. methane is CH4 and ethane is C2H6

Alkane molecules can be represented by displayed formulae in which each atom is shown as its symbol (C or H) and the chemical bonds between them by a straight line

As the alkane chain increases in length the properties change longer chains mean the following: Less ability to flow (more viscous) Less flammable Less volatile Increased boiling points

Alkanes are saturated hydrocarbons this means that their carbon atoms are joined to each other by single bonds This makes them relatively un-reactive, apart from their reaction with oxygen in the air during combustion (they do burn well)!

Hydrocarbons have different boiling points, and can be either solid, liquid or gas at room temperature: Small hydrocarbons with only a few carbon atoms have low boiling points and are gases Hydrocarbons with between 5 and 12 carbon atoms have medium boiling points and are usually liquids Large hydrocarbons with many carbon atoms have high boiling points and are solids Some of the 21st centurys most important chemistry involves chemicals that are made from crude oil they are used for fuels in cars; warming of homes; making electricity etc When oil prices rise it affects us all countries that produce crude oil can have an affect on the world economy by the price charged for oil Crude oil originates as a dark, smelly liquid which is a mixture of lots of different chemical compounds it is not much use straight out of the ground (there are too many substances in it, all with different boiling points). As such it needs to be refined Although we can get useful substances from oil, crude oil itself has no uses. In order to make crude oil into useful substances we first have to separate the mixture into molecules of similar size this is done in an oil refinery Crude Crude oil is a mixture of different sized hydrocarbons the exact composition depends upon where the oil comes from but typically it contains a lot of big molecules

Distillation is a process that can be used to separate a pure liquid from a mixture of liquids it works when the liquids have different boiling points Fractional distillation differs from distillation only in that it separates a mixture into a number of different parts, called fractions A tall column is fitted above the mixture, with several condensers coming off at different heights The column is hot at the bottom and cool at the top substances with high boiling points condense at the bottom and substances with low boiling points condense at the top Like distillation, fractional distillation works because the different substances in the mixture have different boiling points

The main fractions include refinery gases, gasoline (petrol), naphtha, kerosene, diesel oil, fuel oil, and a residue that contains bitumen These fractions are mainly used as fuels, although they do have other uses too

Hydrocarbons with small molecules make better fuels than hydrocarbons with large molecules because they are volatile, flow easily and are easily ignited In order for it to be useful to us, crude oil is broken down in oil refineries into its component parts (fractions), which can then be used for many different purposes Fractions that are produced by the distillation of crude oil can go through a process called cracking, producing smaller hydrocarbons Crude oil often contains too many large hydrocarbon molecules and not enough small hydrocarbon molecules to meet demand - this is where cracking comes in Fuels made from oil mixtures containing large hydrocarbon molecules are not efficient (they do not flow easily and are difficult to ignite)

Cracking is an example of a thermal decomposition reaction Shorter chain hydrocarbons are in greater demand because they burn easier, and they can be made from long chain hydrocarbons via cracking

The products of cracking include alkenes (for example ethene and propene) The alkenes are a family of hydrocarbons that share the same general formula: CnH2n The general formula means that the number of hydrogen atoms in an alkene is double the number of carbon atoms, e.g. ethene is C2H4 and propene is C3H6 Alkene molecules can be represented by displayed formulae, in which each atom is shown as its symbol (C or H) and the chemical bonds between them by a straight line

Alkenes are unsaturated hydrocarbons they contain a double bond, which is shown as two lines between two of the carbon atoms The presence of this double bond allows alkenes to react in ways that alkanes cannot (they can react with oxygen in the air, so they could be used as fuels) They can be used to make ethanol (alcohol) and polymers (plastics): two crucial products in today's world

Alkanes are saturated every carbon atom has already used all four of its bonds to join to four other atoms: no other atoms can be added (it is full up) Alkenes are unsaturated have a double bond that could instead become two single bonds: this means that other atoms can be added Alkanes and alkenes can be distinguished between due to this double bond

When bromine water is added to an alkane nothing happens When bromine is added to an alkene the red colour of the bromine disappears

Plastics are polymers (huge molecules which are made up of lots of smaller molecules (monomers) which have been joined together) Different types of plastics can be made by using different monomers these plastics can have very different properties Nylon was the first commercially successful synthetic polymer a thermoplastic (softens when heated) silky material originally used in toothbrushes and later as tights Alkenes can be used to make polymers polymers are very large molecules made when many smaller molecules join together, end-to-end The smaller molecules are called monomers

Polymer: Poly(ethene) - polythene Many ethene monomers can join end-to-end to make poly(ethene) or polythene Initially the C=C double bond of the ethene must be broken, and then the molecules can be added together

Different polymers can be made by using different monomers these polymers can have very different properties Polymers have properties that depend on the chemicals they are made from, and the conditions in which they are made polymers have many uses, including: Waterproof coatings Fillings for teeth Dressings for cuts Hydrogels for making soft contact lenses and disposable nappy liners Shape memory polymers for shrink-wrap packaging

One of the useful properties of polymers is that they are unreactive, so they are suitable for storing food and chemicals safely, but this property makes it difficult to dispose of polymers Most polymers, including poly(ethene) and poly(propene) are not biodegradable meaning that micro-organisms cannot break them down, so they may last for many years in rubbish dumps However, it is possible to include chemicals that cause the polymer to break down more quickly carrier bags and refuse bags made from such degradable polymers are already available Polymers can be burnt or incinerated they release a lot of heat energy when they burn and this can be used to heat homes or to generate electricity

There are problems with incineration as carbon dioxide is produced, which adds to global warming Toxic gases are produced unless the polymers are incinerated at high temperatures

Many polymers can be recycled reducing the disposal problems and the amount of crude oil used It is crucial different polymers are separated from each other first, and this can be difficult and expensive to do Many polymers can be recycled reducing the disposal problems and the amount of crude oil used Some modern plastic bags are now being made from biodegradable polymers such as cornstarch which will increasingly provide useful replacements for the main polymers currently used

Ethanol is the type of alcohol found in alcoholic drinks such as wine and beer Ethanol is also useful as a fuel for use in cars and other vehicles, it is usually mixed with petrol Ethanol can be manufactured by reacting ethene (from cracking crude oil) with steam phosphoric acid is used as a catalyst: Ethene + Steam Ethanol

C2H4+ H2O C2H5OH In the reaction ethanol is the only product the process is continuous as long as ethene and steam are fed into one end of the reaction vessel, ethanol will be produced These features make it an efficient process, but as ethene is made from crude oil, which is a non-renewable resource, it cannot be replaced once it is used up and it will run out one day Ethanol can also be made via fermentation sugar from plant material is converted into ethanol and carbon dioxide Enzymes found in single-celled fungi (yeast) are the natural catalysts that can make this process happen (this is a renewable resource): C6H12O6 2C2H5OH + 2CO2 It is possible to make fuel for vehicles using vegetable oils biodiesel is the name given to any fuel made from vegetable oils (and they can be added to any diesel engine) Biodiesel is made by treating vegetable oils to remove some unwanted chemical during production other useful products form, including a solid waste material which can be used as cattle feed and glycerine (used in soap manufacture) Biodiesel is a very clean fuel it also breaks down about five times faster than conventional crude oil diesel, advantageous if spilt It also burns much more cleanly, making far less sulfur dioxide and other pollutants It also has a major atmospheric advantage as crops are used to make the fuel it is carbon neutral (all the carbon released by the fuel burning was originally absorbed by the plant from the atmosphere in the first place)

Biodiesel therefore makes little contribution to the greenhouse gases in the atmosphere

Biodiesel is however not without is problems: There are costs related to its production machinery which harvests this biodiesel requires fuel itself, so this counts to the atmospheric cost It also requires crops ethical issues arise over using crops for fuel when famine is still widespread throughout the world There is also a great amount of financial reward to producing biodiesel areas of tropical rainforest are being cleared in huge amounts to grow this money-making crop, leaving vast areas having their natural flora and fauna destroyed forever Combustion is the chemical reaction which takes place when a substance burns The substance reacts with oxygen, releasing energy (heat and light) Combustion is extremely important (>90% of the worlds energy comes from combustion reactions (e.g. fossil fuels such as coal, natural gas and petrol) Combustion is exothermic - heat is released to the surroundings This can also be called an oxidation reaction, as it involves oxygen being added to the fuel the carbon and hydrogen in the fuels are oxidised The fuel you use will result in different combustion reactions taking place A good supply of oxygen is needed for a fuel to burn completely and release as much energy as possible

If there is a plentiful supply of oxygen we get complete combustion However, if there is not enough oxygen then the fuel will not burn completely, wasting both the fuel and reducing the energy released If there is not enough oxygen we get incomplete combustion Complete combustion: carbon + oxygen carbon dioxide Incomplete combustion: carbon + oxygen carbon monoxide

Levels of carbon dioxide in the atmosphere are increasing in no small part due to the increased burning of fossil fuels As carbon dioxide levels in the atmosphere increase so the reaction between carbon dioxide and seawater increases producing insoluble carbonates and soluble hydrogen-carbonates In this way the sea acts as a buffer however this buffering system is put under increasing strain as we burn more fossil fuels

Normally the Earth absorbs heat and emits heat at the same rate, causing the temperature to remain constant Certain gases, like CO2 and methane, act like a greenhouse they let heat in but do not let it out meaning the more CO2 and methane there is, the hotter planet will become

Acid rain has a higher than normal acid level (a low pH) Acid rain may contain weak solutions of carbonic, sulfuric acid, and nitric acids Where it falls over a prolonged period it can cause damage to the environment Global dimming is also a major concern due to the burning of hydrocarbons - tiny particles that are released when fuels are burned cause global dimming (like global warming, this process may change rainfall patterns around the world) The amount of sunlight reaching the Earths surface has decreased by about 2% every ten years, because more sunlight is being reflected back into space the particles from burning fuels reflect sunlight, and they also cause more water droplets to form in the clouds This makes the clouds better at reflecting sunlight back into space

One impact of burning fossil fuels is that the products of combustion can be very harmful to the environment Sulfur dioxide and carbon dioxide are the two biggest gases which cause environmental problems, as well as carbon monoxide and the oxides of nitrogen Sulfur can be removed from fuels before they are burnt, such as the fuels used for most vehicles Sulfur dioxide can also be removed from the waste gases after combustion, both in factories and vehicles (using a catalytic converter) Car exhaust systems have catalytic converters these convert carbon monoxide into carbon dioxide Carbon Monoxide + Nitrogen Oxide Nitrogen + Carbon Dioxide 2CO + 2NO N2 + 2CO2 Catalytic converters also convert nitrogen oxides into nitrogen and oxygen as well as complete the oxidation of un-burnt hydrocarbons to carbon dioxide and water Nitrogen Oxides Nitrogen + Oxygen Hydrocarbon + Oxygen Carbon Dioxide + Water There are a variety of alternatives to fossil fuels, and one of the most promising is using hydrogen as a fuel Hydrogen and oxygen will react together releasing energy their only by-product being water The problem at the moment is getting the hydrogen it can be split from water, but requires energy to do so (currently from burning fossil fuels)!

Biofuels such as biodiesels and ethanol are produced from plant material however is it right to grow crop for fuel when many of the worlds population remain hungry? There are a variety of alternatives to fossil fuels, and one of the most promising is using hydrogen as a fuel Hydrogen and oxygen will react together releasing energy their only by-product being water the problem at the moment is getting the hydrogen it can be split from water, but requires energy to do so (currently from burning fossil fuels)! Biofuels such as biodiesels and ethanol are produced from plant material however is it right to grow crop for fuel when many of the worlds population remain hungry? Plant oil extraction is relatively simple, involving two steps: Crush the plant Remove the oil by pressing or via distillation

Molecules of vegetable oils consist of glycerol and fatty acids: Glycerol has three carbon atoms Fatty acids have long chains of carbon atoms

Three long chains of carbon atoms are attached to a glycerol molecule (with its three carbon atoms) together they combine to make one molecule of vegetable oil

Thee long fatty acid chains stop vegetable oils dissolving in water The fatty acids in some vegetable oils are saturated, and only have single bonds between their carbon atoms Saturated oils tend to be solid at room temperature, and are sometimes called vegetable fats instead of oils lard is an example of a saturated oil The fatty acids in some vegetable oils are unsaturated, and have double bonds between some of their carbon atoms Unsaturated oils tend to be liquid at room temperature, and are useful for frying food they can be divided into two categories: Monounsaturated fats have one double bond in each fatty acid Polyunsaturated fats have many double bonds

The carbon-carbon double bonds in unsaturated oils can be detected using the elements bromine or iodine these elements react with the double bonds in the oils, and the more double bonds there are, the more bromine or iodine is used up Unsaturated fats can be tested for using a simple test with bromine water bromine water is a dilute solution of bromine, which is normally orange-brown in colour which becomes colourless when shaken with an alkene, or with unsaturated fats When shaken with alkanes or saturated fats, its colour remains the same

During hydrogenation, vegetable oils are hardened by reacting them with hydrogen gas at about 60C (this increases their melting point) a nickel catalyst is used to speed up the reaction the double bonds are converted to single bonds by the hydrogenation This causes unsaturated fats to be made into saturated fats

Saturated vegetable oils are solid at room temperature, and have a higher melting point than unsaturated oils This makes them suitable for making margarine, or for commercial use in the making of cakes and pastry The temperature that a liquid boils at depends on the size of the forces between its molecules the bigger these forces the higher the liquids boiling point The molecules in vegetable oils are much bigger than water molecules (so their boiling point is much higher) Cooking food causes permanent changes to occur to the food cooking in vegetable oils causes different reactions to the food as the temperature is so much higher (often the food cooks more quickly, turns a different colour on the outside and becomes crisper) Also cooking in oil can cause the food to absorb some of that oil meaning the energy content of the food is much higher (one reason why fried food can be bad for you)!

Vegetable oils are important nutrients and provide a lot of energy. Vegetable oils are also used as fuels for vehicles (some of this biodiesel is made from waste cooking oil and rapeseed oil with benefits as these fuels are carbon neutral) It can be questioned how ethical it is to use food crops in this way, instead of using them for feed when famine is still a global problem Vegetable oils do not dissolve in water if a mixture of oil and water is shaken, then left to stand, eventually a layer of oil will form on the surface of the water Emulsifiers can be added to the oil and water, causing an emulsion to form (a mixture of the two) Emulsions are more viscous than oil or water on their own, and contain tiny droplets of one of the liquids spread through the other liquid

Immiscible liquids do not mix together, e.g. oil floats on the surface of the water when mixed. If you shake oil and water together then leave them to stand, tiny droplets of oil float upwards they join together until eventually the oil is floating on the water again

This is not a useful property when concerned with foods which often contain both oil and water (such as salad cream) without a binder to hold the two together they would keep separating

Emulsifiers are molecules that have two different ends: A hydrophilic end (water-loving) that forms chemical bonds with water but not with oils A hydrophobic end (water-hating) that forms chemical bonds with oils but not with water

The hydrophilic 'head' dissolves in the water and the hydrophobic 'tail' dissolves in the oil In this way, the water and oil droplets become unable to separate out the mixture formed is called an emulsion An emulsion is a mixture of oil and water An emulsifier is a specific molecule able to bind the two ends so they stick together (i.e. the oil and water bind) E.g. Lecithin is an emulsifier which binds the emulsion of water and oil

Emulsions are thicker than oil or water and have many uses that depend on their special properties Emulsions can provide better texture or coating ability and appearance

Examples of oil droplets in water: Egg yolk Milk Ice cream Salad cream Mayonnaise

Examples of water droplets in oil: Margarine Butter Skin cream Moisturising lotion

Partially hydrogenated vegetable oils may contain trans fats these are thought to cause health problems such as heart disease in humans, and food manufacturers are being encouraged to reduce the amount of them in our food The Earth is almost a sphere, consisting of four main layers Crust relatively thin and rocky Mantle has the properties of a solid, but can flow very slowly Outer core made from liquid nickel and iron Inner core made from solid nickel and iron

The average density of the Earth is much higher than the crust, meaning the inner core must be very dense solid nickel and iron

Why does the Earth look the way it does has it always looked this way and will it remain? The Earth's crust and upper part of the mantle are broken into large pieces called tectonic plates these are constantly moving at a few centimetres each year Although this rate is not great, over millions of years the movement allows whole continents to shift thousands of kilometres apart called continental drift The plates move because of convection currents in the Earth's mantle, driven by the heat produced by the decay of radioactive elements and heat left over from the formation of the Earth Where tectonic plates meet, the Earth's crust becomes unstable as the plates push against each other, or ride under or over each other Earthquakes and volcanic eruptions happen at the boundaries between plates, and the crust may crumple to form mountain ranges The theory of plate tectonics and continental drift were proposed at the beginning of the last century by a German scientist, Alfred Wegener Before his time it was believed that the planet's features, such as mountains, were caused by the crust shrinking as the Earth cooled after it was formed

It took more than 50 years for Wegeners theory to be accepted because it was difficult to work out what the mechanism was that could make whole continents move, and it was not until the 1960s that enough evidence was discovered to support the theory fully Alfred Wegener suggested that the continents looked like they fit together He also noted they have similar rock patterns and fossil records these two pieces of evidence led him to believe that there was once a single land mass, and form the tectonic theory The massive amounts of heat generated through radioactive decay in the core power convection currents in the mantle causing the crust to move, as well as the spreading of the sea floor at plate boundaries as new crust is formed both key discoveries and proof of Wegeners theory

Plate tectonics explained why earthquakes and volcanoes were concentrated in specific places - around the boundaries of moving plates

The match in shape between the east coast of South America and the west coast of Africa suggests both were once part of a single continent There are similar patterns of rocks and similar fossils on both sides of the Atlantic - including the fossil remains of land animals that would have been unable to swim across an ocean The Earth was formed about 4.5 billion years ago its early atmosphere was probably formed from the gases given out by volcanoes It is believed that there was intense volcanic activity for the first billion years of the Earth's existence the early atmosphere was probably mostly carbon dioxide, with little or no oxygen There were smaller proportions of water vapour, ammonia and methane As the Earth cooled down, most of the water vapour condensed and formed the oceans It is thought that the atmospheres of Mars and Venus today, which contain mostly carbon dioxide, are similar to the early atmosphere of the Earth

The proportion of oxygen went up because of photosynthesis by plants

The proportion of carbon dioxide went down because: It was locked up in sedimentary rocks, such as limestone, and in fossil fuels It was absorbed by plants for photosynthesis It dissolved in the oceans The burning of fossil fuels is adding carbon dioxide to the atmosphere faster than it can be removed meaning the level of carbon dioxide in the atmosphere is increasing As oxygen levels rose atmospheric ammonia (NH3) reacted with oxygen (O2) to form water (H2O) and nitrogen (N2) Also, living organisms, including denitrifying bacteria, broke down nitrogen compounds releasing more nitrogen into the atmosphere And so the atmosphere headed towards a composition that has remained fairly constant for the last 200 million years Oxygen normally exists as pairs of atoms (O2) Oxygen can, however, turn into another form that has three atoms joined together: this is ozone (O3) as oxygen levels rose, so did the amount of ozone This layer of ozone in the atmosphere filters out harmful ultraviolet rays from the sun this will have allowed new organisms to evolve and survive

The Earth's atmosphere has remained much the same for the past 200 million years The main gas is nitrogen and oxygen (the gas that allows animals and plants to respire and fuels to burn) is the next most abundant gas These two gases are both elements and account for about 99% of the gases in the atmosphere the remaining gases, such as carbon dioxide, water vapour and noble gases such as argon, are found in much smaller proportions

The early Earth was very different to the one we know today it was hotter and the atmosphere consisted mostly of carbon dioxide, with other gases such as ammonia and methane

There are two possible origins for these molecules: They were produced by the conditions on Earth at the time, or They came from somewhere else, such as another planet in our solar system or further out in space Over many millions of years these molecules joined with other molecules, becoming gradually more complex and dependent on each other The process of evolution by natural selection eventually led to all of the different living things that we see on Earth today Sometime between about 4.1 billion years ago when the Earths crust began to solidify, and 3.5 billion years ago life began Most biologists subscribe to the hypothesis that life developed on Earth from nonliving materials that became ordered into molecular aggregates these eventually became capable to self-replication and metabolism In the ancient environment the origin of life was evidently possible (conditions were very different, with more intense lightning; volcanic activity; meteorite bombardment; and UV radiation) One hypothesis suggests the first organisms were products of a chemical evolution in four stages: 1. The abiotic (non-living) synthesis and accumulation of small organic monomers such as amino acids and nucleotides from a primordial soup 2. The joining of these monomers into polymers (including proteins and nucleic acids) 3. The aggregation of abiotically produced molecules into droplets (protobionts) with chemical characteristics different from their surroundings 4. The origin of heredity

It is not possible to be certain how life on Earth began because: Earth is about 4,500 million years old There is evidence living things existed on Earth at least 3,500 million years ago No-one was there to record how life began

The best we can do is study simple organisms and the chemistry of living things to work out scientific theories The main theory is that living things developed from molecules that could copy themselves, rather as DNA does It is not known how life began on the Earth because there is not enough evidence available An experiment by Miller and Urey in 1952 tried to recreate the conditions which may have been present in the Earths atmosphere around 3 billion years ago They used a sealed and sterile glass flask with the gases ammonia, methane, hydrogen and water vapour inside they then passed electrical sparks (simulating lightning) through the gases for a week

When they analysed the mixture they found many carbon compounds had formed inside the flask (from the methane gas)

Some of these compounds were found to be amino acids (used to make proteins) This suggests the first life forms may have been bacteria able to utilise the methane and ammonia to live