M11-P1 Materials from the Earth 6th International Junior Science Olympiad (IJSO) Dr. Yu-San Cheung yscheung@cuhk.edu.hk Department of Chemistry The Chinese University of Hong Kong 1 Natural Resources(天然資源) • • • • Naturally occurring substances Considered valuable in their relatively unmodified (natural) forms Values: depending on the amount available and the demand A commodity is generally considered a natural resource when the primary activities associated with it are extraction and purification, as opposed to creation. • Examples of natural resources: Air, water, and soil Biological resources - plants and animals Raw materials (like minerals) Space and land Energy (like wind, geothermal(地熱的), tidal(潮汐的), and solar energy) http://en.wikipedia.org/wiki/Natural_resources http://www.ecofriendlykids.co.uk/NaturalResourcesEarth.html 2 Renewable Resources(再生資源) • They can restock (renew) themselves, be used indefinitely if they are not over-harvested. • If consumed at a rate that exceeds their natural rate of replacement, the standing stock will diminish and eventually run out. • Examples of living renewable resources: • trees (forests and woodlands) and crops • fish and livestock • Examples of non-living renewable resources: • fresh water • fresh air • Flow renewable resources (or simply “flow resources”): renewable, but needing no regeneration or re-growth e.g., wind, tidal, and solar energy http://en.wikipedia.org/wiki/Natural_resources http://www.ecofriendlykids.co.uk/NaturalResourcesEarth.html 3 Non-renewable Resources (非再生資 • A non-renewable resource is a natural resource that cannot be re-made, re-grown, or regenerated on a scale comparative to its consumption. • Fossil fuels, such as coal, petroleum, and natural gas are often considered non-renewable resources, as they do not naturally re-form at a rate that makes the way we use them sustainable. 4 http://en.wikipedia.org/wiki/Natural_resources Natural Resources and Their Products • Forests: timber (for building houses, boats, decks, and furniture; and making paper) • Mines: metal products, fossil fuels, salts, jewelry, gravel (for building roads and concrete) • Aquaculture(水產養殖): fishes, shrimps, crabs, etc. 5 http://www3.iptv.org/exploremore/land/issues/iss_natu/natural_resources.cfm Minerals and Their Chemical Components Exercise: Find out the major chemical content in various types of minerals 6 “Periodic Chart.pdf” in http://www.mii.org/ Common Minerals and Their Uses Exercise: Find out the uses of some common minerals. 7 http://www.mii.org/commonminerals.html Cement & Concrete Cement: 水泥 Concrete:混凝土 Cement: • made from limestone, calcium, silicon, iron, and aluminum, plus lesser amounts of other ingredients • When water is added to cement, a chemical process occurs as it dries, allowing it to harden. Concrete: • cement + aggregates (e.g., sand, stone) • Important and widely-used construction material • Strengthened by steel-rod skeleton • Annual production: about 6 billion tons (~1 ton each person on the Earth) • Life: 50,000 years 8 http://www.wisegeek.com/what-is-the-difference-between-concrete-and-cement.htm Recycling(循環) Recycling is the reprocessing of materials into new products. It can save energy and reduce air pollution. Exercise: Find out the environmental effects of recycling. http://en.wikipedia.org/wiki/Recycling 9 Recycling (循環) • • • • • • • • • • • Aggregates and concrete Crushed and used as aggregates for new concrete Batteries Difficulty: so many types of batteries Some old types contain mercury and cadmium Lead-acid battery (mostly used in automobiles): containing lead Biodegradable waste Electronics waste (recovering metals) Various types of metals (e.g., _________________________________) Paper Glass Plastic Rubber Textiles Timber 10 http://en.wikipedia.org/wiki/Recycling Metals In chemistry: • A metal is an element that readily loses electrons to form positive ions (cations) and the cations are surrounded by a sea of electrons • Most metals form ionic bonds with non-metals [but not always, e.g., in Pb(C2H5)4, there is Pb–CH2CH3 covalent bond] Physical properties: • Electrical conducting • Some hard, some soft, some being liquid + + + + + 11 http://en.wikipedia.org/wiki/Metal Alloys(合金) • Alloy: a homogeneous mixture of two or more elements, at least one of the elements is a metal, the resulting mixture has metallic properties. • An alloy usually has properties (physical and chemical) different from those of its components. Example The major component of steel is iron and steel is stronger than iron. If chromium is added, we have stainless steel which can resist corrosion. 12 http://en.wikipedia.org/wiki/Alloy Examples of Alloys • • • Carbon steel: iron + carbon (higher carbon content, stronger but more brittle) Low carbon steel: ~0.05 – 0.3% carbon content Ultra-high carbon steel : ~1 – 2% carbon content Stainless steel: steel + chromium (> 10%) Brass: copper + zinc (typically ~30 – 35%) • Bronze: copper + tin (typically 12%) • Rose gold: gold + copper: for jewelry 24k: 100% gold (18k: 75% gold) (k = “karat”) • Solder: Conventional: Sn60/Pb40 (60% tin + 40% lead) Lead-free: e.g., SnAgCu (tin + silver + copper); different SnAgCu compositions: different melting points http://en.wikipedia.org/wiki/Carbon_steel http://en.wikipedia.org/wiki/Stainless_steel http://en.wikipedia.org/wiki/Brass http://en.wikipedia.org/wiki/Bronzes http://en.wikipedia.org/wiki/Rose_gold 13 http://en.wikipedia.org/wiki/Solder http://en.wikipedia.org/wiki/List_of_alloys Energy Resources • Solar energy • Wind energy • Water-related: • • • • • hydro power pumped-storage tidal power wave power Geothermal energy Biomass energy Garbage energy Nuclear energy Fossil fuels 14 http://home.clara.net/darvill/altenerg/index.htm Generation of Electrical Energy(電能) • Electrical energy is easily transported (from power plants to individual customers) • Electrical energy is versatile • Majority of energy available from Nature: in the form of kinetic energy and heat energy • Kinetic energy electrical energy • Heat energy kinetic energy of steam kinetic energy of magnet/metal electrical energy 15 Faraday‘s Law(法拉第定律) of Induction • In effect: Changing magnetic field electrical current http://hyperphysics.phy-astr.gsu.edu /Hbase/electric/farlaw.html • That is, kinetic energy electrical energy 16 Turbine(渦輪機) • Flow of fluid (acting on blazes) rotation of shaft • Kinetic energy of fluid kinetic energy of shaft electrical energy 17 http://en.wikipedia.org/wiki/Turbine Solar Energy(太陽能) • Energy from the Sun • The Sun is a nuclear reactor, 150 million km away. Only a small fraction of light energy and heat energy (1 part in 1010) reaches the Earth, but it is a huge amount to the Earth. Increasing wavelength Ultra-violet(UV) “light” Visible Infra-red (IR) Absorbed and becoming heat energy • Solar cell: light energy electrical energy • Water-heating system: heat energy heat energy of water • Solar furnaces: heat energy heat energy of gas kinetic energy of gas electrical energy http://home.clara.net/darvill/altenerg/solar.htm 18 Exercise: How is solar energy used for heating water in Hong Kong? Example: http://www.cuhk.edu.hk/greencampus/en/communication/sc_sp ring07.pdf 19 Wind Energy(風能) • Energy from wind • Ancient application: sailing • Used since Middle Ages: windmill • Electricity generation: wind turbine electricity (reverse of electric fan operation) Propeller blades Wind Gearbox & generator in housing which can be rotated to face the wind Tower 20 http://home.clara.net/darvill/altenerg/index.htm Hydro Power(水力) • Energy from the flow of water: (potential energy of water kinetic energy of water …) • Ancient application: corn grinding, sailing, war • Used nowadays to generate 20% of the world’s electricity Dam Reservoir Turbine Generator 21 http://home.clara.net/darvill/altenerg/index.htm Pumped Storage Reservoirs • They are not facilities or methods to generate electrical power. They are a way of storing energy so that it can be released quickly when needed. • Demand for electrical power changes throughout the day. When the demand is low, extra power not used is wasted. • A facility is needed which can store excess energy produced, and can release the stored energy immediately. Pumped storage reservoirs can do the job. Turbines & Pumps Top Reservoir Lower Reservoir 22 http://home.clara.net/darvill/altenerg/index.htm Tidal Power(潮汐能) • Tide: water movement, containing kinetic energy • Twice a day • 8 sites in Britain, generating 20% of energy needed • ~20 potential sites in the world • Largest one: northern France Tide coming in Tide going out 23 http://home.clara.net/darvill/altenerg/index.htm Off-shore Station http://www.swanturbines.co.uk/ http://www.marineturbines.com/technical.htm 24 Wave Power • Wave: generated by wind on sea surface • Method: reverse of a swimming pool wave machine Air flowing in and out Water level going up and down 25 http://home.clara.net/darvill/altenerg/wave.htm Geothermal Energy(地熱能) • The centre of the Earth: ~6000 C hot enough to melt rock • A few km down the surface: > 250 C • Used for thousands of years in some countries for cooking and heating • If hot enough to produce steam electricity • If not: heating Power station Cold water down Hot water down Hot region 26 http://home.clara.net/darvill/altenerg/geothermal.htm Biomass(生物量) • Energy from organisms (usually plants) • Example: burning of wood for heat and light • Extraction of fuel: ethanol by fermentation: corns / canes cane sugar ethanol • Biodiesel: a fuel made from vegetable oil that runs in any unmodified diesel engine. Triglycerides (三酸甘油酯) (Esters of glycerol with long-chain fatty acids) 27 Triglycerides Biodiesel NaOH + CH3OH Glycerol Glycerol part Fatty acid portions Methyl esters of fatty acid (Biodiesel) 28 Biodiesel Recipe: Biodiesel from New Oil http://www.dancingrabbit.org/biodiesel/newoil.php Use of Biodiesel in automobiles Example: 1994 Dodge: 100,000 miles on 100% Rapeseed (芥花籽) 29 Garbage Energy • Burning garbage: generating heat energy, but serious pollution (e.g., dioxin) • Bacterial action: generating landfill gas (mainly methane, CH4) 30 Basis of Nuclear Physics & Nuclear Power 31 Testing your knowledge on: molecules, atoms, and subatomic particles • A molecule consists of two or more _____ of the same or different elements. Examples: ____________________________ • Atoms are the smallest particles of an element. • Sub-atomic particles: particles that constitute atoms. ___________ ___________ ___________ Which of these sub-atomic particles make up nuclei? 32 Testing your knowledge on: molecules, atoms, and subatomic particles Compare the sizes of: molecules, atoms, and nuclei. Exercise (fill-in-the-blank): Isotopes are atoms of the same _______ but having different numbers of ________ in their ________. 33 Nuclides(核素) A nuclear species characterized by specific values of the atomic number (no. of protons) and the mass number (no. of protons and neutrons) 1 1H 2 1H 12 6C 13 6C 34 Radioactive(放射性)Substances Nuclei of some atoms, e.g., 40K, are unstable. They undergo spontaneous transformation into more stable atoms. The substance is called radioactive. Such a transformation process is called radioactive decay. It is usually accompanied by emitting particles and energy collectively called radiation. 35 Radioactivity(放射現象) The phenomena of radioactivity was discovered in 1896. This radiation was later shown to be separable by electric (or magnetic) fields into three types: alpha (a), beta (b) and gamma (g) rays. Radioactive material b ray Electric plate (positive) + – g ray a ray Lead block Electric plate (negative) Luminescent screen 36 Stability of Nuclides(核穩定性) • Unstable nuclei are radioactive • Nuclei consist of proton(s) & neutron(s) (except __________) • Forces inside the nuclei: (1) Repulsive Coulomb force: between protons (2) Attractive nuclear force: between proton & proton, neutron & neutron, proton & neutron • Stability depends on the balance of the two forces 37 Radioactive Decay Products • Alpha particle (helium-4 nucleus, 4He2+) • Beta particle (electron) • Gamma ray / X-ray (electromagnetic radiation) • Neutron 38 Interaction of Radiation with Cells • Ionization and atomic excitation causing molecular rearrangement or formation of free radicals • Alteration of molecules leads to malfunction of physiological processes which depend on the chemical structure Examples: inhibition of cell division, denature of enzymes, mutation of genetic materials 39 Rate of Radioactive Decay • Half-life (t1/2): the time it takes for half of its original amount to decay 1 ½ ¼ 1/8 1/16 …. After n half-lives, is left. For example, after 10 halflives, 1/(210) = 1/1024 (about 0.1%) is left. 1/(2n) 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 10 20 30 40 50 60 70 80 90 100 40 Half-lives of Some Radionuclides Each radionuclide has a characteristic t1/2 Radionuclide 81Kr 38K 73Se 131I 60Co 137Cs 14C 129I 235U 40K Half-life 13 seconds 7.6 min 7.2 hr 8 days 5.3 yr 30 yr 5730 yr 17 million yr 703 million yr 1260 million yr 41 Sources of Radiation Natural Radiation • cosmic rays • terrestrial radiation (including radon) • food & drinks (40K within body) Artificial Radiation • • • • medical instruments leakage/disposal radioactive fallout (weapon testing) consumer products, e.g., smoke detectors, “glow in the dark” watches 42 Nuclear Fuel(核燃料) 235U +n 139Ba + 94Kr Ba + 3n n U 235 Characteristics: n • Bombarded by neutron Kr • Chain reaction: Ba n an U 235 This neutron starts the chain Kr reaction But not every neutron can hit 235U Ba n 1 neutron in, 3 neutrons out. n nucleus. The reaction may eventually stop. n n U 235 n n n Kr Ba n U 235 n n Kr http://home.att.net/~cat4a/nuclear_III.htm 43 Enriched Nuclear Fuel(核燃料) To make the chain reaction self-sustaining, we need to use: (1) uranium enriched in 235U (2) super critical mass of the fuel Natural uranium: 238U Enriched: 2-3% in (99.3%) & 235U 235U (0.7%) (>85% for bomb) Methods: centrifugation, diffusion, and electromagnetic isotopic separation. 44 Critical Mass(臨界質量) Critical mass: sphere of 600 kg for 15% Higher 235U 235U (~40 cm diameter) percentage: larger/smaller critical mass Neutron reflector: larger/smaller critical mass 45 http://en.wikipedia.org/wiki/Image:Critical_mass.svg Nuclear Power Plant(核能發電廠) http://science.howstuffworks.com/nuclear-power2.htm Containment Structure Steam Generator Steam Line Reactor Turbine Control Rods Generator Cooling Tower Pumps Cooling Water Condensor Neutron absorber (e.g., boron, cadmium) 46 http://hyperphysics.phy-astr.gsu.edu/hbase/nucene/control.html Other Nuclear Fuels Plutonium-239 & Uranium-233 47 Nuclear Fusion(核聚變) Heavy nuclei favor fission. Light nuclei favor fusion. Examples of nuclear fusions: 2H + 3H 4He + n 2H + 2H 3He + n 2H + 2H 3H + p 48 http://en.wikipedia.org/wiki/Nuclear_fusion Human-made Nuclear Fusion In order for a nuclear fusion to occur, two nuclei must be brought close enough. But the repulsion between nuclei is huge. Nuclei must contain high enough energy. Human-made nuclear fusion: through nuclear fission in nuclear bomb 49 Nuclear Fusion(核聚變) in Nuclear Power Plant Nuclear fusion: more energy released than fission But … once started, nuclear fusion is out of controlled and cannot be stopped. Nuclear fusion for power generation: to be developed. Other advantages of fusions over fissions: • less hazardous products • source more available (natural abundance of 2H: 0.015%) 50 Accidents of Nuclear Power Plants • Three Mile Island, USA (1979) • Chernobyl, Ukraine, in former USSR (1986) Leakage of highly radioactive materials On the whole, non-nuclear large-scale industrial accidents result in higher tolls. 51 Nuclear Weapons & Nuclear Power Plants A nuclear power plant does not aim to make nuclear weapons. But the materials can be used for nuclear weapons. Concerns: • 235U: needs extra work to enrich its percentage • 329Pu: created in a uranium reactor, the percentage of which is high enough for nuclear weapons In addition to making a nuclear bomb (which can really explode), the waste can also used for “dirty bomb”. More about nuclear proliferation: http://en.wikipedia.org/wiki/Nuclear_proliferation 52 Advantages & Disadvantages Advantages • No CO2 is emitted • No air is needed Disadvantages • In case of accident, the damage is serious • Using and producing materials, which are the source for nuclear weapons • Disposal of nuclear waste: waste cannot be “destroyed” 53 Fossil Fuels(化石燃料) Industrial Revolution: increases in the use of fossil fuels Steam engines (late 1700s): needed fuels chemical energy (stored in _______) heat energy (of _______) kinetic energy (of _______) kinetic energy (of _______) to run machines, cars, etc. 54 What are fossil fuels? Plants, animals, and microorganisms (living millions of years ago) death Remains buried and subjected to high temperatures and pressures in Earth’s crust Primarily hydrocarbons, CxHy “Fossil fuel” sometimes also includes non-biological source such as tar sand, which is known as mineral fuel. 55 Types of Fossil Fuels(化石燃料) • • • • • Coal Petroleum (oil) Natural gas Tar sands and oil shale Methane hydrate 56 Carbon Cycle Exercise: Find out the carbon distribution in the Nature from internet. Atmosphere ( Vegetation ( Soils ( ) ) Fossil Fuels & Cement Production ( ) ) Marine Biota ( ) Surface Ocean ( ) Deep Ocean ( Dissolved Organic Carbon ( ) Sediments ( ) ) 57 http://en.wikipedia.org/wiki/Image:Carbon_cycle_diagram.jpg Heat Energy Units • BTU (British Thermal Units) = 1054 – 1060 J • Quad: quadrillion BTU = 1015 BTU • Total U.S. energy use: ~100 Quad in 2005 • A barrel of oil (bbl): ~6 million BTU • 100 Quads: 17 billion barrels of oil (1 bbl = 42 gallons) http://en.wikipedia.org/wiki/British_thermal_unit http://www.opm.state.ct.us/pdpd2/energy/flows94.htm 58 Coals(煤) • • • • Plant remains covered by water and mud Readily combustible Black or brownish black in color Mainly composing of carbon, with an assortment of other elements (e.g., sulfur) Most abundant of all fossil fuels, the largest single source of fuel for the generation of electricity world-wide One of the major sources of carbon dioxide emissions 59 http://en.wikipedia.org/wiki/Coal Worldwide Coal Production Exercise: Find out the worldwide coal production, coal reserves, and major coal exporters. 60 Processing of Coal Other than being burnt directly, coal can be further processed to obtain higher-quality fuel. • Liquefaction: coal liquid fuels e.g., gasoline or diesel • Gasification: C + steam + O2 synthesis gas (CO + H2) • Coking (~ 1000 oC): driving off volatile substances to form coke 61 Petroleum(石油)(Oil, Crude Oil) • Compression and heating of ancient organisms • Buried at the ocean bottom, where O2 was insufficient to oxidize all the organic materials 62 Oil Producing and Consuming Countries Exercise: Find out the major oil producing and consuming countries around the world. 63 Petroleum(石油) • Hydrocarbon, mostly alkane (saturated CxHy): C5H12 to C18H38 Shorter hydrocarbon: natural gas Longer hydrocarbon: paraffin wax • High energy density, easy transportability, relatively high abundance • Source of raw material for many chemical products 64 Oil Refinery: Separating Components of Different Molecular Weights Exercise: Find out various oil refinery products and their usages. Very detailed flowchart: http://en.wikipedia.org/wik i/Image:RefineryFlow.png 65 http://en.wikipedia.org/wiki/Oil_refinery Cracking(裂解) • Breaking down long carbon chains • By heating & with catalysts • e.g. CH3CH2CH2CH3 CH2=CH2 + CH3CH3 66 Knocking of Gasoline(汽油) • Gasoline is burnt to produce energy in a combustion engine (e.g., of a vehicle) • Some gasoline start to burn before they are ignited by sparks. • This premature ignition produces a “knocking” sound. So it is sometimes called “knocking”. • Consequences of knocking: power loss and engine wearing 67 http://en.wikipedia.org/wiki/Octane_rating Octane Rating • Different gasoline have different anti-detonation • Octane rating: a measure of the anti-detonation (or autoignition resistance) of gasoline and other fuels used in spark-ignition internal combustion engines. 68 http://en.wikipedia.org/wiki/Octane_rating Octane Rating iso-octane: set at 100 n-heptane: set at 0 A mixture of iso-octane and n-heptane: x% (by volume) in iso-octane, “octane rating”: x. Example: 84 liters of iso-octane + 16 liters of n-heptane 84% (by volume) in iso-octane 16% (by volume) in n-heptane Octane Rating: 84 It is found that 1-pentene has the same “knocking” property as this mixture, so we say that the octane rating of 1-pentene is 84. 69 Octane Rating Octane rating can be smaller than 0 and larger than 100. e.g., n-octane: -10 benzene: 101 ethane: 108 Octane rating for gasoline for vehicles: 85-90. 70 http://en.wikipedia.org/wiki/Image:09-03-06-Octane.jpg Anti-knocking Agent Tetra-ethyl lead (TEL): • Added to gasoline to increase octane rating • About 0.05% of TEL in gasoline • Pb(CH2CH3)4, mostly covalent in nature, not containing Pb4+ and CH2CH3– How it works: • Knocking causes formation of radicals, e.g., CH3, from gasoline • Chain reaction: these radicals destroy other gasoline molecules • Pb(CH2CH3)4 Pb(CH2CH3)3 + CH2CH3 (or Pb + 4 CH2CH3 ?) These radicals from TEL and remove radicals from gasoline Sometime literatures say that Pb + O2 PbO2 and the PbO2 reacts with the radicals from gasoline Other anti-knocking agents (also called octane enhancers): methanol & ethanol 71 Problems of Leaded Gasoline • Lead is toxic to humans • It poisons Rh and Pt catalysts in catalytic converters (which convert NOx and VOC emitted from pipes of vehicles into harmless substances) Rh = rhodium Pt = platinum Both are metals with catalytic property 72 Natural Gas(天然氣) • Formation process: similar to that of petroleum • Components: (%) methane (CH4): 70 – 90 ethane (C2H6): 5 – 15 propane (C3H8), butane (C4H10): < 5 CO2, N2, helium, and hydrogen sulfide (H2S): balance Exercise: Find out the major natural gas producing and consuming countries around the world. 73 Tar Sand • Also called “oil sand” (actually more appropriate) • A mixture of extremely heavy crude oil, sand or clay, and water. • Natural material, nothing to do with tar (man-made) • Worldwide sources: Canada, Venezuela, and USA. 74 http://en.wikipedia.org/wiki/Tar_Sands Oil Shale(油頁岩) • A fine-grained sedimentary rock containing significant traces of kerogen (a solid mixture of organic chemical compounds) that have not been buried for sufficient time to produce conventional fossil fuels. • When heated to a sufficiently high temperature a vapor is driven off which can be distilled to yield a petroleum-like shale oil, a form of non-conventional oil, and combustible shale gas. • Can be burnt directly as a low-grade fuel for power generation and heating. • Can be used as a raw material in the chemical and construction materials industries. • Reserve: mainly in North America 75 http://en.wikipedia.org/wiki/Oil_shale Methane Hydrate (Methane Ice) • Ice that contains a large amount of methane within its crystal structure • Total amount: 500-2500 billion tons of carbon (carbon for all fossil fuel reserves: 5000 billion tons) • Natural gas hydrates (NGH) vs. liquefied natural gas (LNG) in transportation: NGH: stable up to −20 C LNG: stable up to −162 C Therefore, there is some interest in converting natural gas into NGH rather than LNG for transportation. 76 http://en.wikipedia.org/wiki/Methane_hydrates