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SEPT 2013

CHAPTER 2: STRUCTURE OF THE ATOM 2.1 MATTER


1. Matter : Any substance or material that occupies space and has mass. Exists as a solid, liquid or gas (3 states of matter). Made up of particles. 3 kinds of particles atoms, molecules, ions Can be divided into elements and compound. Particles Atoms Description Smallest particles of an element that retain the chemical properties of the element. Examples : Sodium atom (Na) Zinc atom (Zn) Helium atom (He) Particles composed of two or more atoms. Can be with the same or different atoms Examples : Same atoms Oxygen gas (O2) Different atoms Ammonia (NH3) Charged particles positive or negative Positive charged ion (Cation) Zinc ion (Zn2+) Negative charged ion (Anion) Chloride ion(Cl-) Descriptions Particles made up of the same atoms only. Can be in the form of atom or molecules. Cannot be split into two or more simpler substance by chemical means. Examples: - Metallic Copper(Cu), Iron(Fe), Gold(Au) - Non-metallic Oxygen(O2), Sulphur(S8) Particles made up of two or more elements. Can be molecules or ions. Examples: - Molecules Water (H2O) Sulphur trioxide (SO3) Tetrachloromethane (CCl4) - Ions Sodium chloride (Na+, Cl-) 2

Molecules

Ions

Matter Elements

Compounds

Iron(III) oxide (Fe3+, O2-) Calcium chloride (Ca2+, Cl-) 2. Changes in states of matter Matter can change its state. Reversible changes. Exists in 3 states, solid, liquid and gas. SOLID LIQUID GAS

Boiling point

Melting point

During the changes, the following do not change: - Mass of particles - Size of particles - Type of particles Velocity of the particle increases when - Temperature increases - Kinetic energy increases 3

Sublimation can only happen to : - Ammonium chloride (NH4Cl) - Solid carbon dioxide / Dry ice (CO2) - Iodine (I2) Differences between solid, liquid and gas (Kinetic Theory Of Matter): (Essay) States of matter Arrangement of particles Particles motion Solid compact, orderly manner Vibrate, rotate in a fixed position Very low Fixed Liquid Loosely packed, disorderly manner Move freely Moderate Not fixed (follow the shape of container) Fixed Average Medium Gas very far apart, random motion Move freely and randomly High Not fixed (follow the shape of container) Not fixed High Very weak

Particles Kinetic energy Shape

Volume Rate of diffusion Attractive forces between particles

Fixed Low Very strong

3. Experiment (PeKa) a. Heating curve of naphthalene/acetamide Diagram:

Graph:

AB: Solid BC: Solid + Liquid CD: Liquid

DE: Liquid + Gas EF: Gas

Explanation: AB: When the solid is heated, heat energy is absorbed. This causes the particles to gain kinetic energy and vibrate faster. BC: The temperature remains constant because the heat energy absorbed by the particles is used to overcome the forces between particles so that the solid can turn into a liquid. At this temperature, both solid and liquid are present. CD: The particles in liquid naphthalene absorb heat energy and move faster. During the heating of naphthalene: - Water bath is used (ensure uniform heating, naphthalene is flammable) - Naphthalene is stirred continuously (ensure an even heating) Water bath: For heating a substance which is less than 100C. Oil bath: For heating a substance which is more than 100C. Latent heat of fusion: heat required to convert solid to liquid without a change in temperature. b. Cooling curve of naphthalene/acetamide Diagram:

Graph:

PQ: Gas QR: Liquid + Gas RS: Liquid

ST: Solid + Liquid TU: Solid

Explanation: RS: When the liquid is cooled, the particles in the liquid lose their kinetic energy. They move slower as the temperature decreases. ST: The temperature of naphthalene remains constant because the heat loss to the surroundings is balanced by the heat energy given off during freezing. TU: The particles in solid naphthalene release heat energy and vibrate slower. During the cooling of naphthalene: Boiling tube containing naphthalene is placed in a conical flask. (to minimize heat loss which may affect the accuracy of freezing point air trapped in conical flask is poor conductor of heat) Stirred by using thermometer (to ensure even cooling)

Super cooling

i.

ii.

Condition in which the temperature of a cooling liquid drops below the normal freezing point. Occurs when conical flask is not used in the experiment.

2.2 ATOMIC STRUCTURES


1. Historical development of the structure of atom a) John Dalton

- All elements made up of small indivisible particles called atoms. - Atoms made up of tiny particles which cannot be created or destroyed. - Atoms of same element same mass - Atoms of different elements different mass - Atoms join together to form larger molecules or compounds (in simple ratio) - Weakness: Atoms are not the simplest particles bigger than proton, neutrons and electron Atoms can be destroyed or breakdown radioisotopes Atoms of same element have different mass isotopes

b) J.J. Thomson

- Plum pudding model. - Electron embedded in a sphere of positive charge. - Electron spreads randomly throughout the positive charge. c) Ernest Rutherford

- All positive charge of an atom is concentrated in the nucleus contain protons. - Mass of atom is located in a small area (nucleus). - Number of protons = number of electron d) Neils Bohr

- Electrons of atom are arranged and move around the nucleus in orbital called electron shells. - Nucleus contains protons. - The orbital has various radius form the nucleus. 9

e) Sir James Chadwick

- Discovered neutrons which are located in the nucleus. - The neutral particle has the same mass as protons. 2. Atomic Structure Made up of subatomic particles; protons, electrons and neutron. Nucleus situated at the centre of atom. has positive charge, protons. Neutrons may also present. Electrically neutral. (Number of proton = Number of electrons) Have electrons which move around the nucleus in its shells. Mass of proton = mass of neutron Nucleus contributes a lot of mass in an atom. Subatomic particles Proton Neutron Electron Symbol p n e Relative atomic mass (RAM) 1 1 Charge + neutral

3. Electron Configuration Maximum number for each shell: First shell : 2 electrons Second shell : 8 electrons Third shell : 8 electrons Forth shell : 2 electrons Valence electron = electrons found in the outermost shell of an atom.

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4. Atomic number & Mass number Atomic number = proton number Nucleon number = proton number + number of neutrons Mass number = Nucleon number

2.3 KINETIC THEORY OF MATTER


1. According to the Kinetic Theory Of Matter, Matter consists of tiny and discrete particles. Particles always move randomly. There are forces of attraction between the particles. Particles gain kinetic energy and move faster when heated. Particles lose kinetic energy and move slower when cooled. Can be proven by using 2 experiments: Diffusion and Brownian movement. 2. Diffusion Occurs when particles of a substance move in between the particles of another substance. Random movement of particles from a high concentration region to a lower concentration region. Happens in three states of matter; solid, liquid and gas. Occurs most rapidly in gases, followed by liquid and solid. Particles diffuse from one medium to another. Rate of diffusion increases with the temperature. Rate of diffusion decreases when the mass of matter increases. Diffusion in gases:

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Diffusion of liquid:

(Blue) Diffusion of solid:

Jelly

3. Brownian movement

Random movement that is shown when colliding with other particle. Can only be observed under a light microscope. Supports the Kinetic Theory Of Matter.

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2.4 ISOTOPES
1. Atoms of same element with the same number of protons but different number of neutrons. Uses Isotopes Carbon-14 determination of age of carbon-containing artifacts as a biological tracer, for example, in studies of photosynthesis biological tracer, for example, in studies of photosynthesis Detect location of leaks in water pipes, studies of body electrolytes location of leaks in water pipes cancer treatment as tumour cells tend to be more susceptible to radiation than other cells lung ventilation studies Medical tracer used to locate brain tumours and problems with the lungs, thyroid, liver, spleen, kidney, gall bladder, skeleton, blood pool, bone marrow, salivary to detect infection Medical tracer treat the thyroid gland &amp used in the diagnosis of adrenal medulla for imaging suspected neural crest and other endocrine tumours used in imaging to monitor thyroid function detect adrenal dysfunction Enriched as a fuel for most nuclear reactors 13

Oxygen-18 Sodium-24

Magnesium27 Cobalt-60

Krypton-81

Technetium99

Iodine-131

Iodine-123

Uranium-235

Americium241 Phosphorus32

Domestic smoke alarms Treatment of excess red blood cells

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CHAPTER 3: CHEMICAL FORMULAE AND EQUATIONS 3.1 Formula and Chemical Equations
1. Reasons of comparing relative atomic mass(R.A.M, Ar) with one carbon-12 atom: Solid and easily handled. Most abundant carbon isotope. Easily available. Used as a reference standard in spectrometer. 2. Formulae: MASS OF SUBSTANCE, g

M.M.

M.M.

M.V. VOLUME OF SOLUTION, cm3 M.V. NA NA NO. OF PARTICLES, atoms NO. OF MOLES, mol

3.2 The Mole and the Volume of Gas


1. 2. Avogadros Constant, NA Number of particles in one mole of substance. 6.02 1023 Standard Temperature and Pressure (S. T. P.) Temperature = 0C 15

3.

Pressure = 1 atmosphere / atm Molar volume of 1 mole of gas = 22.4dm3 or 22400cm3 Room condition (R. T. P.) Room temperature = 25C Pressure = 1 atmosphere / atm Molar volume of 1 mole of gas = 24dm3 or 24000cm3

3.3 Molecular Formula and Empirical Formula


1. Molecular formula: actual number of atoms in each element that present in a molecule of the compound. 2. Empirical formula: simplest whole number ratio of atoms of each element in the compound. 3. Empirical formula =
4. Example : Glucose M.F.: C6H12O6

E.F.: CH2O 5. Determining empirical formula by using table form: Element Mass/Percentage x No. of mole y( Ratio Empirical formula 4. Experiment for empirical formula: For higher reactivity of metal (Mg, Zn, Ca, Al)

Crucible with lid

Metal tape

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Precaution: - Lift the lid at intervals to allow oxygen gas to enter for combustion of metal. - Lid is closed immediately after it is lifted to prevent white fume from escaping to the surroundings. - Stop heating the metal when it is started to glow. Reactive metal: both reactant and products are solid and thus, the individual mass of metal and oxygen cannot be determined. For lower reactivity of metal (Cu, Sn, Pb, Ag)

Chemical used to dry hydrogen gas: Anhydrous cobalt chloride / anhydrous calcium chloride. Hydrogen gas is flowed through the apparatus throughout the experiment to prevent the air for entering it.

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CHAPTER 4: PERIODIC TABLE OF ELEMENTS 4.1 INTRODUCTION TO PERIODIC TABLE

1. Classifications of elements with the same chemical properties are placed in the same group. 2. Elements in: Group 1 Alkali metals Group 2 Alkali earth metals Group 3 12 transition elements Group 17 Halogens Group 18 Noble gases Group 1, 2, transition elements and 13 metals Group 15, 16 and 17 non metals Same group same chemical properties and valence electrons No. of 1 2 3 4 valence electrons Group 1 2 13 14 3. Historical Development of the Periodic Table i. Antoine Lavoisier 5 6 7 8/2

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16

17

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Classify elements into 4 groups which are gases, metals, non-metals and metal oxide. Not accurate heat and light are included as gases. ii. Johann W. Dobereiner Classify elements with the same chemical properties into groups of three (triads). Discover relationship between R.A.M. in each triad. (Middle R.A.M. = average R.A.M.) iii. John Newlands Arrange elements in order of increasing nucleon number (mass number) in horizontal rows. Each row has 7 elements. Law of Octaves every eighth element have similar chemical properties. Only accurate for the first 16 elements. Discover the existence of periodic pattern. iv. Lothar Meyer Volume of an atom = of an element Graph of volume of atoms against their R.A.M. Show the properties of elements recur periodically. v. Dmitri Mendeleev Arrange element in order of increasing atomic mass. Left gaps for elements yet to be discovered. vi. Henry G. J. Moseley i. Different element with high energy electrons & measured the frequency of the X-ray emitted by inert gases elements. ii. Graph of square root of frequency against proton number. a) Group 18 elements Noble Gases Made up of Helium (He), Neon (Ne), Argon (Ar), Krypton (Kr), Xenon (Xe), Radon (Rn). Exist in monoatomic form. Has stable electron arrangement (outermost shell filled with the maximum number of electrons). Chemically unreactive (do not share, donate or accept electrons). Duplet Helium, Octet other noble gases. Physical properties: Colourless gaseous state at room temperature. 19

Low boiling and melting point (weak Van der Waals forces / intermolecular forces of attraction. Do not conduct electricity. Low density (atoms are far apart). Going down the group, Melting & Boiling point Atomic size Forces of attraction between atoms Heat energy Density Atomic mass Uses: Helium Fill airship, bicycle tyres of Olympic cyclist & meteorological balloons. Exist in the gas in divers oxygen tank. Neon Advertising boards / lights. Electric discharge through glass tubes produces a red light. Argon Electric light bulb. Carrier gas in gas-liquid chromatography. Krypton Laser light Flash lamps of a light house Radon For cancer treatment. Xenon For flash lamp. b) Group 1 elements Alkali metals Made up of Lithium (Li), Sodium (Na), Potassium (K), Rubidium (Rb), Cesium (Cs), and Francium (Fr). Has 1 valence electron. Very reactive to become positive ions (easily to donate valence electron). Physical properties: Soft metal with shiny and silvery surfaces (can be cut by knife). Good electric and heat conductor. Less dense than water.

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When going down the group, Melting and boiling point Metallic bond Decreases Forces of attraction Atomic size Increases Density Number of occupied shell Chemical properties: Have same chemical properties. Electropositivity: measurement of ability of an element to lose an electron and form a positive ion. Good reducing agent. Can be oxidised easily. Going down the group, reactivity / electropositivity increases. Safety precautions when handling Group 1 elements: Kept in paraffin oil. Use forceps to take them. Wear safety goggles & gloves. Reactions: a) Alkali metal + water Hydroxide solution produced will turn red litmus paper red. Products: metal hydroxide + hydrogen gas Alkali metal Cold water Lithium Sodium Potassium 2Li + 2H2O 2LiOH + H2 Moves slowly with hiss sound. 2Na + 2H2O 2NaOH + H2 Moves quickly and randomly with loud hiss sound. 2K + 2H2O 2KOH + H2 Burns with reddish-purple light, jumps, hiss and pop sound.

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b) Alkali metal + oxygen Products: metal oxide (white powder). When metal oxide dissolves in water, it turns phenolphthalein indicator red (presence of OH- ions alkaline)

4Li + O2 2Li2O Burns slowly with red light. Sodium 4Na + O2 2Na2O Burns quickly and brightly with yellow light. Potassium 4K + O2 2K2O Burns very quickly and brightly with reddish-purple light. c) Alkali metal + halogen gas (Chlorine & Bromine) Products: metal halides (metal bromide / chloride white powder) Lithium

Halogen

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Lithium Sodium Potassium

2Li + Cl2 2LiCl / 2Li + Br2 2LiBr Burns slowly with reddish flame. A white solid is obtained. 2Na + Cl2 2NaCl / 2Na + Br2 2NaBr Burns brightly with a yellowish flame. A white solid is obtained. 2K + Cl2 2KCl / 2K + Br2 2KBr Burns very brightly with a purplish flame. A white solid is obtained.

4.2 HALOGEN
1. Group 17 elements (Halogens) Made up of fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and astatine (At). Exist in diatomic molecules. Non metal. Physical properties: Heat and electrical insulator. Low melting and boiling point (weak forces between the molecules). When going down the group, Atomic size Van der Waals forces Heat energy used to overcome forces Boiling and melting point Colour of halogen darker. 2. Chemical properties: Same chemical properties (same valence electrons 7) High electronegativity When going down the group, Reactivity/electronegativity Van der Waals forces Tendency to accept electron Solubility Atomic size Distance between the nucleus and outermost shell Reaction: Halogen + water Product: two acids. 23

Halogens act as bleaching agent, except iodine water. In general, X2 + H2O HX + HXO, where X is halogen. Chlorine water Turn blue litmus paper red then decolourise it. Prepared from the reaction between potassium manganate (VII) chips with concentrated hydrochloric acid. 16HCl + 2KMnO4 2MnCl + 8H2O + 5Cl2 Cl2 + H2O HCl + HClO Products: Hydrochloric acid + Hypochlorous acid (bleaching agent). Greenishyellow gas dissolves quickly to form a light yellow solution. Bromine (liquid) Br2 + H2O HBr + HBrO Products: Hydrobromic acid + hypobromous acid (bleaching agent). Reddishbrown liquid dissolves slowly, forming a brownishyellow solution. Iodine (solid) I2 + H2O HI + HIO Products: Hydroiodic acid + hypoiodous acid (bleaching agent). Very little purplishblack solid dissolves, forming a light yellow solution. Halogen + Sodium hydroxide solution, NaOH. Products: Sodium halide + Sodium halite(I) + Water In general, X2 + 2NaOH NaX + NaOX + H2O, where X is halogen. Chlorine (gas) Cl2 + 2NaOH NaCl + NaOCl(sodium chlorate) + H2O Greenish-yellow gas dissolves quickly to form a colourless solution. Bromine Br2 + 2NaOH NaBr + NaOBr(sodium bromate) + H2O Reddish-brown liquid dissolve averagely to form a colourless solution. Iodine I2 + 2NaOH NaI+ NaOI(sodium Iodate) + H2O Purplish-black solid dissolves slowly to form a colourless solution. Halogen + Iron (Fe) Product: iron(III) halides (brown solid) Apparatus set up: Chlorine

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/ Lime soda

Soda lime: mixture of calcium hydroxide and sodium hydroxide (absorb excess halogen gas) Iron wool is heated strongly until red hot. Concentrated hydrochloric acid is added to potassium manganate (VII) through a thistle funnel (to produce chlorine gas). In general, 3X2 + 2Fe 2FeX3, where X is a halogen. Chlorine 3Cl2 + 2Fe 2FeCl3 Iron wool burns lights up strong and bright. Brown solid is formed. Bromine 3Br2 + 2Fe 2FeBr3 Iron wool glows moderately bright and less vigorously. Brown solid is formed. Iodine 3I2 + 2Fe 2FeI3 Iron wool glows dimly and slowly. Brown solid is formed. 3. Precaution: Halogens are poisonous gas. Must be handled in fume chamber. When handling halogens. Safety goggles and gloves must be used. Fluorine is a radioactive substance, astatine is radioactive. 25

4.3 Elements in a Period


1. Period: horizontal row in the Periodic Table. 2. There are 7 periods in the modern periodic table. 3. When it goes across the period from left to right: Electronegativity Proton number Increases Valence electrons Non-metallic properties Nuclei attraction on valence electrons Atomic size Electropositivity Decreases Metallic properties (Metallicity) Na2O MgO Al2O3 SiO2 P4O10 SO2 Cl2O7 Element Acidic oxides Characteristics Basic oxides Amphoteric (Alkali) oxides 4. Amphoteric oxides: react with both acids and alkalis, have base and acidic properties. ( acid, alkali) 5. Sodium, Magnesium and Aluminium : Metal Strong metallic bonds High melting and boiling points High strength of metallic bond 6. Silicon High melting and boiling points Has strong covalent bond, forming a 3-dimensional gigantic network.

7. Uses of semi-metals/metalloids(element with properties intermediate between those of metals and non-metals) Silicon and Germanium makes diodes and transistor/switch Conductivity increases with temperature. Important in microelectronic industry

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8. Transition Element Elements between Group 3 until Group 12. Metals Show metallic properties: Shiny surface Ductile Malleable Can withstand high tension High melting and boiling point High density (big atomic mass despite small radius) Electric and heat conductor Form coloured compounds or ions Transition elements Colour 3+ Chromium ion, Cr Green 2+ Iron(II) ion, Fe Green 3+ Iron(III) ion, Fe Brown 2+ Copper(II) ion, Cu Blue 2Chromate ion, CrO 4 Yellow 2+ Manganese ion, Mn Pink 2+ Cobalt ion, Co Pink 2+ Nickel ion, Ni Green 2Manganate ion, MnO 4 Purple 2Dichromate ion, Cr2O 7 Orange Act as catalyst to speed up the reaction. Iron, Fe Haber process (producing ammonia, NH3). Platinum, Pt Ostwald process (producing nitric acid, HNO3). Nickel, Ni manufacture of margarine. Vanadium (V) oxide, V2O5 Contact process (producing sulphuric acid, H2SO4). Form complex ions. Polyatomic anion/cation consisting of more than 2 metal ions with other group bonded to it. Examples hexacyanoferrate (II) [Fe(CN)6]4 Tetramine copper (II) [Cu(NH3)4]2+

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Have different oxidation number. Iron, Fe - +2, +3, +1 Manganese - +1, +2, +3, +6, +7 Nickel - +2, +3 Chromium - +2, +3, +6 Give colour to precious stone. Presence of ions in a solution can be confirmed by using sodium hydroxide solution, NaOH / ammonia solution, NH3. The ions of transition elements will react with hydroxide ion, OH - to form coloured solution / precipitate. Precious stone Emerald Ruby Sapphire Amethyst Colour Green Red Blue Purple Transition elements Nickel, Iron Chromium Iron, Titanium Iron, Manganese

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CHAPTER 5: CHEMICAL BONDS 5.1 Formation of Chemical Bonds


1. Ionic bond Metal element reacts with non-metal element. Metal element (Group 1, 2, and 13) Non-metal element (Group 16 and 17) Metal elements donate electrons and produce positive ions. Non-metal elements will accept electrons to achieve a stable electron configuration and produce negative ions. These ions will attract each other by a strong electrostatic force of attraction (ionic bond). Examples: sodium chloride, magnesium oxide, lithium oxide. Elements which are reacting Metal M Non-metal X + Group 1, M Group 15, M3Group 1, M+ Group 16, M2Group 1, M+ Group 17, MGroup 2, M2+ Group 15, M3Group 2, M2+ Group 16, M2Group 2, M2+ Group 17, MGroup 13, M3+ Group 15, M3Group 13, M3+ Group 16, M2Group 13, M3+ Group 17, M Sodium chloride, NaCl Formula of ionic compound M3X M2X MX M3X2 MX MX2 MX M2X3 MX3

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4.2 Covalent Bonds


1. Formed by non-metal elements form Group 14, 15, 16, and 17. 2. Atoms of non-metals will combine to donate one, two or three valence electrons to be shared. 3. 3 types of covalent bonds: Single sharing one pair of electrons Double sharing two pair of electrons Triple sharing three pair of electrons 4. These will form covalent compound. 5. Examples: Chlorine molecule, Cl2 (Single)

Water molecule, H2O (Single)

Carbon dioxide molecule, CO2 (Double)

Nitrogen molecule, N2 (Triple)

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Non-metal elements which combined Element P Element Q 4+ Group 14, P Group 17, QGroup 14, P4+ Group 16, Q2Group 15, P3+ Group 17, QGroup 16, P2+ Group 17, Q6. Physical properties of ionic compounds: High melting and boiling point Conducts electricity

Molecular Formula PQ4 P2Q4 / PQ2 PQ3 PQ2

Soluble in water, insoluble in organic solvents Able to ionize in water. Has strong electrostatic force of attraction Need a lot of heat energy to overcome the forces Arranged in lattice structure in solid state Contain free-moving ions that carry charges 7. Physical properties of covalent compounds: Low melting and boiling points Has weak Van der Waals forces less heat energy is needed. Insoluble in water, soluble in organic solvent Cannot conduct electricity Do not contain free-moving ions that carry charges

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8. Giant molecules covalent compounds: Strong covalent bonds combine all atoms in a three-dimensional lattice structure. Have high melting and boiling point Unable to conduct electricity. Examples: silicon, graphite, silicon oxide, diamond, protein 9. Covalent compound as organic solvents Water Dissolves all types of food sugar and salt Dissolves food substances in the body Cleanses or gets rid of dirt Organic solvent Ethanol preparation of shellac, lacquer, paint, cosmetic and perfumes Petrol / kerosene cleans greasy and oily dirt stains Propanone nail varnish Chlorofluorocarbon cleans circuit board of computer

5.4 Comparisons between ionic and covalent bond


Ionic compound NaCl, MgO, ZnCl2, CuO High has strong electrostatic forces of attraction (A lot of heat energy is needed) Soluble in water, insoluble in organic solvent. Conduct electricity in both molten and aqueous state contain free moving charged ions. Non volatile Properties Examples Melting and boiling points Covalent compound O2, CO2, H2O, N2, Cl2 Low has weak intermolecular forces of attraction (Little heat is needed) Soluble in organic solvent, insoluble in water. Do not conduct electricity.

Solubility

Electrical conductivity

Volatility

Volatile

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Ionic compound Examples

Covalent compound Simple Giant

Metal Cu, Zn, Na, Ca, Pt, Ni, Mg High in Insoluble in both

Low High Insoluble in Insoluble organic both solvent, soluble in water Electrical Conduct in Does not Does not conductivity molten state or aqueous solution Volatility No Yes No

M/P & B/P Solubility

High Soluble in water, insoluble in organic solvents

Conduct in solid or liquid

No

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CHAPTER 6: ELECTROCHEMISTRY 6.1 Electrochemistry


1. Electrochemistry: study of the interconversion of chemical energy and electrical energy. 2. Electrolyte: chemical substances that can conduct electricity in molten or aqueous form. Examples: Molten potassium iodide, KI Molten lead(II) chloride, PbCl2 Molten aluminium oxide, Al2O3 Sulphuric acid solution, H2SO4 Copper sulphate solution, CuSO4 Sodium chloride solution, NaCl 3. Non-electrolyte: chemical substances that cannot conduct electricity either in molten or aqueous form as they have no free-moving ions. Examples: Sulphur Wood Molten sugar Naphthalene Covalent compounds except ammonia and hydrogen chloride 4. Conductor: substances that can conduct electricity in liquid or solid state (not regarded as electrolyte as they are not decomposed) Copper Iron Platinum Silver 5. Electrolysis: process whereby a compound is separated into its constituent elements when an electric current passes through an electrolyte. Electrical energy chemical energy

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Set up of apparatus: Electrolysis of molten compound

Electrolysis of aqueous solution

6. 2 types of electrodes: a) Active electrode - do not react with electrolytes - do not involve in chemical reactions - Carbon, platinum and graphite electrodes b) Inert electrode - react with electrolytes - involves in chemical reactions - Copper, silver, or mercury electrodes 7. Anode: electrode that connect to the positive terminal of battery. 8. Cathode: electrode that connect to the negative terminal of battery. 9. Anion: negatively charged ions and attracted to anode. 10.Cation: positively charged ions and attracted to cathode. 11.Half equation: Positive ions (Cations) Negative ions (Anions) + K +eK 2F - 2e F2 + 2F- F2 + 2e Na + e Na Ca2+ + 2e Ca 2Cl- Cl2 + 2e Mg2+ + 2e Mg 2I- I2 + 2e Al3+ + 3e Al 4OH- 2H2O + O2 + 4e Zn2+ + 2e Zn 2O2- O2 + 4e Fe2+ + 2e Fe 2Br- Br2 + 2e Sn2+ + 2e Sn Pb2+ + 2e Pb 2H+ + 2e H2 Cu2+ + 2e Cu Ag+ + e Ag 35

12.Electrolysis of molten compounds Metal Sodium Lead Nickel Copper Gas Bromine Iodine Chlorine Oxygen Hydrogen Observation Shiny grey solid is formed. Shiny grey solid is deposited. Shiny grey solid is formed. Brown deposit is formed. Observation Brown gas is produced. (pungent smell) Purple gas is produced. Yellowish-green gas is produced. Colourless gas bubbles are formed. (effervescence) Colourless gas bubbles are formed. (effervescence) Test for Hydrogen gas, H2 A lighted splinter is placed near the mouth of the test tube containing oxygen gas. A pop sound is produced.

Test for Oxygen gas, O2 A glowing splinter is placed near the mouth of the test tube containing oxygen gas. It will light up.

6.2 Electrolysis of Aqueous Solution


1. Aqueous solution: Produced when solute is dissolved in water. Electrolyte containing cations, anions, H+ and OH- ions. 2. During electrolysis of aqueous solution: 2 cations are attracted to cathode (-). 2 anions are attracted to anode (+). Only one of the four ions will be chosen to be discharged at anode and cathode. 3. Factors affecting which ions are chosen to be discharged: Position of ions in the electrochemical series (ECS) Concentration of ions in the solution Type of electrodes used

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4. Position of ions in the electrochemical series (ECS) Cations K Na Ca Mg Al Zn Fe Sn Pb H Cu Ag Kalau Nak Cari Minum Air Zappel Free Sila Pergi Hotel Curi Agar F SO42NO3ClBrIOH-

Anions Father Say Nothing Can Buy Indian Oranges

The lower the position of the ion, the higher the tendency of the ions to be discharged. Sulphate ion, SO42- and nitrate ion, NO3- cannot be discharged. 5. Concentration of ions The anions in a lower concentration solution will be chosen to be discharged. (diluted) The cations in a higher concentration solution will be chosen to be discharged. Diluted 0.0001, 0.001, 0.01 dm-3 Concentrated 0.1, 1.0, 2.0 dm-3 K+ and Na+ cannot be discharged even if their concentration of the solution is high. 6. Types of electrodes used Inert electrodes: Carbon, graphite and platinum (Both of these electrodes do not react with the electrolytes or products of electrolysis) Active electrodes: Silver, copper and nickel (Active anode ionises and concentration of cations in the electrolyte does not change)

6.4 Application of Electrolysis


1. Electroplating of metals Objectives: to prevent corrosion / to improve appearance. Plating metals: gold (Au), Platinum (Pt), Chromium (Cr), copper (Cu), Silver (Ag), & Nickel (Ni). 37

Conditions: Object to be plated cathode Electroplating metal anode Electrolyte used must contain the metal ions. Surface of electroplating metal must be cleaned. Set-up apparatus:

2. Extraction of metals Reactive metals (Na, Ca, Mg, Al) are extracted from their ores compounds using electrolysis. These metals cannot be extracted by reduction using carbon. a) Extraction of aluminium metal from bauxite (aluminium oxide)

Cryolite is added to bauxite to lower the temperature of bauxite from 2000C to 950C. Bauxite dissociates. Al2O3 2Al3+ + 3O2 Half equation at cathode : Al3+ +3e Al 38

Half equation at anode : 2O2- O2 + 4e Overall equation : 4Al3+ + 6O2- 4Al + 3O2 Carbon electrodes react with the oxygen gas to produce carbon dioxide. Hall Heroults Process. b) Extraction of sodium metal from sodium chloride Iron : cathode Carbon : anode Set up apparatus:

Calcium chloride is added to lower the melting point of sodium chloride. Half equation at cathode : Na+ + e Na Half equation at anode : 2Cl- Cl2 + 2e Overall equation : 2Na+ + 2Cl- 2Na + Cl2 Downs Process 3. Purification of metals Impure metal containing impurities can be purified. Conditions: Impure metal : anode Pure metal : cathode Electrolyte used must contain the metal ions.

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Set-up apparatus:

Observation: Copper anode becomes thinner and the impurities are deposited below it. Copper cathode becomes thicker. Intensity of blue solution remains the same. Rate of formation of copper(II) ions of anode = rate of discharge of copper(II) ions of cathode. Concentration remains the same. Half equation at anode : Cu Cu2+ +2e Half equation at cathode : Cu2+ + 2e Cu

6.5 Voltaic Cell


1. Simple voltaic cell Uses two metal plates being immersed in an electrolyte (must contain one of the metal ions). Two different metals used must have different positions in the electrochemical series. Voltage can be measured by using voltmeter. The further the distance between those two metals in electrochemical series, the higher the voltage produced. Higher position of metal will donate electrons more easily to form positive ion and become a negative terminal (anode). Lower position of metal will accept electrons from the electrolyte to form metal and become a positive terminal (cathode). This results in the thinning and thickening of the plates. Unstable and will decrease rapidly.

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2. Daniell cell Produces more stable cell voltage. Cell built with two pieces of different metal immersed in a salt solution of their respective metals. Porous pot: to complete the circuit by allowing the transition of ions and separate both solutions. Porous pot can be replaced by salt bridge. Salt bridge: consists of filter paper soaked with a concentrated salt solution such as sodium chloride, potassium chloride, potassium nitrate, ammonium chloride and dilute sulphuric acid. Weaknesses: Electrolyte can spill out easily. Difficult to carry around. Voltage produced decreases quickly due to the polarity of the cell(formation of gas bubbles around the electrodes)

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3. Examples of voltaic cells:

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4. Advantages and disadvantages of voltaic cells:

5. Comparison between electrolytic cell and voltaic cell:

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6.6 Construction of Electrochemical Series through Cell Potential Difference


1. Procedure: 30cm3 of 1 moldm-3 copper(II) sulphate solution is added into a beaker. A piece of magnesium tape and copper metal are cleansed with sand paper and immersed into copper(II) sulphate solution. Both pieces of metals are connected to a voltmeter using wires as shown in the diagram. The voltmeter reading is recorded. The positive and negative terminals are determined. The procedure is repeated by using zinc, iron, lead, aluminium and copper metal. 2. More electropositive metal : negative terminal 3. The further apart two metals are in the ECS, the higher the voltage of the cell.

6.7 Construction of Electrochemical Series through Displacement Reaction


1. Metal which is more electropositive (placed higher) in the ECS will displace other metals less electropositive (below it) from its salt solutions. 2. Summary: Solution Copper(II) salts Metal (Cu2+) Copper ~ Lead Yes Iron Yes Zinc Yes Magnesium Yes Lead(II) salts (Pb2+) No ~ Yes Yes Yes Iron(II) salts (Fe2+) No No ~ Yes Yes Zinc salts (Zn2+) No No No ~ yes Magnesium salts (Mg2+) No No No No ~

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Chapter 7: Acids and Bases 7.1 Acids and Bases


1. Acid Chemical substance that dissociate in water to produce hydrogen ions, H+ or hydroxonium ions, H3O+. Depicted as proton donors (H+). Strength of acid depends on the degree of dissociation/ionization. 3 types of acids: Monoprotic acid (HCl, HNO3) Diprotic acid (H2SO4) Triprotic acid (H3PO4) Physical properties: Sour in taste pH value: less than 7 Turns blue litmus paper red. Conducts electricity (has free-moving ions). Chemical properties: Acid + metal salt + hydrogen gas Hydrogen gas can be tested by using a glowing splinter. Less reactive metals (Pb and Cu) are not suitable for the reaction. Acid + carbonate salt salt + water + CO2 gas CO2 gas turns lime water chalky/milky/cloudy. Acid + alkali (base) salt + water Neutralisation reaction. Non-organic/mineral acid (strong acid) a. Sulphuric acid, H2SO4 b. Hydrochloric acid, HCl c. Nitric acid, HNO3 d. Carbonic acid, H2CO3 e. Phosphoric acid, H3PO4 f. Sulphurous acid, H2So3 a. b. c. d. e. f. g. Organic acid (weak acid) Methanoic acid, HCOOH Ethanoic acid, CH3COOH Lactic acid (sour milk) Citric acid (citrus fruit) Ascorbic acid (vit. C) Ethanediodic acid, H2C2O4 Formic acid (insect bites)

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Strong acid Dissociate completely into hydrogen ions in water. Degree of dissociation is 100%. Produces higher concentration of hydrogen ions and lower pH value. Eg: Hydrochloric acid Sulphuric acid Nitric acid

Weak acid Dissociate partially into hydrogen ions in water. Degree of dissociation is <100%. Produces lower concentration of hydrogen ions and higher pH value. Eg: Ethanoic acid Methanoic acid Citric acid

2. Water and acidic properties Acid shows its acidic properties in the presence of water. Acid will ionise to form hydrogen ions that are responsible for the acidic properties. Acid cannot be ionized in an organic solvent. Acid Hydrogen chloride Condition Dissolved in methylbenzene (non-acid) Observation Inference No changes in the colour Does not show of litmus paper. Bulb does acidic properties. not light up. Does not conduct electricity as there are no free moving ions. Blue litmus paper turns Show acidic red. Bulb lights up. properties. Conduct electricity as there are free moving ions.

Aqueous solution (acid)

3. Bases Chemical substances that can neutralise an acid to produce salt and water (Neutralisation process). Most are not soluble in water. Soluble bases are called alkali. Eg: zinc oxide, ZnO copper(II) oxide, CuO magnesium hydroxide, Mg(OH)2 46

4. Alkali Chemical substance that dissociate in water to produce hydroxide ion, OH-). Have alkaline properties as the formation of freely moving hydroxide ions in water. Eg: Sodium hydroxide, NaOH Aqueous ammonia, NH3 Potassium hydroxide, KOH Calcium hydroxide, Ca(OH)2 Physical properties: Feel soapy when in touch Bitter in taste Turns red litmus paper blue Has a pH >7 Conducts electricity Chemical properties: Acid + Alkali Salt + Water (neutralization) Alkali + ammonium salt salt + water + ammonia gas 5. Water and alkaline properties Alkaline properties only can be shown in the presence of H2O (presence of free-moving ions). Ionic compound NaOH, KOH, Ca(OH)2 Cannot show their properties in organic solvent. Ionisation of alkali produces hydroxide ions in water. Covalent compound NH3 Can dissolve in both water and organic solvent (trichloromethane). Only show its properties in water. Conduct electricity only in water. There is no mobile ion in organic solvents.

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7.2 The Strength of Acids and Alkalis


Strong alkali Dissociate completely into hydroxide ions in water. Degree of dissociation is 100%. Produces higher concentration of hydrogen ions and higher pH value (pH 14). Eg: Sodium hydroxide, NaOH Potassium hydroxide, KOH Weak acid Dissociate partially into hydrogen ions in water. Degree of dissociation is <100%. Produces lower concentration of hydroxide ions and low pH value. Eg: Magnesium hydroxide, Mg(OH)2 Aqueous ammonia, NH3 Calcium hydroxide, Ca(OH)2

1. pH concept To measure acidity and alkalinity of a solution. From pH 0 14 pH 7 : the concentration of H+ ions = the concentration of OH- ions

2. Acid base indicator Indicator Litmus paper / litmus solution Phenolphthalein Methyl orange Universal indicator Bromothymol blue Acid Red Colourless Red Red/orange/yellow Yellow Alkali Blue Pink Yellow Green Blue Neutral Purple Colourless Orange Blue/purple/violet Green

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3. Concentration / molarity

No. of moles =
1000cm3 = 1dm3

/ /

Concentration =

4. Standard solution: solution which has a known concentration. Prepared by using volumetric flask. Dilution method:

7.4 Neutralisation
1. Neutralisation

Titration method Reaction between an acid and a base to produce salt and water. Acid + Base Salt + Water H+ ions from acid will react with OH- ions from the alkali to produce water molecules. H+ + OH- H2O (ionic equation) Neutral solution produced pH 7. Titration: method used to determine the molarity of a solution by using another solution with a known molarity. 49

End point: all the ions dissociated from acid and alkalis have reacted completely to form water molecules. (neutral, pH 7) The water molecules dissociated into ions and thus do not conduct electricity. Formula:

=
Graph:

(ratio of acid and alkali)

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CHAPTER 8: SALTS 8.1 Salts


1. Salts Ionic compound that is formed when H+ ions in an acid is replaced by a metal ion or ammonium ion. Neutral [ pH 7 phenolphthalein (colourless)] Neutral in term of electrical charges. Can be produced through neutralisation process. Examples: Acids Hydrochloric acid HCl X chloride Nitric acid HNO3 X nitrate Sulphuric acid H2SO4 X sulphate Carbonic acid HCO3 X carbonate Phosphoric acid H2PO4 X phosphate Ethanoic acid CH3COOH X ethanoate 2. Solubility of salts Type of salts Solubility in water Sodium, potassium & ammonium All are soluble except oxide, salts hydroxide and carbonate Nitrate, ethanoate salts All are soluble Chloride salts All are soluble except PbCl2, AgCl, HgCl2 Sulphate salts All are soluble except PbSO4, BaSO4, CaSO4 Carbonate, oxide & hydroxide salts All are insoluble except sodium, potassium & ammonium Lead(II) salts All are insoluble except Pb(NO3)2 and Pb(CH3COO)2 ***Lead hallides such as lead(II) chloride, lead(II) bromide and lead(II) iodide are insoluble in cold water but soluble in hot water. ***Lead(II) nitrate is soluble in both cold and hot water. 3. Preparation of soluble salts except soluble salts of sodium, ammonium and potassium Acid + alkali salt + water Acid + metal salt + hydrogen Acid + base salt + water Acid + metal carbonate salt + water + carbon dioxide 51

4. Preparation of soluble salts of sodium, ammonium and potassium i. Titration of an acid and alkali (Neutralisation) ii. Crystallization (Heating) iii. Recrystallization (Filtration) 5. Crystals Formed when a saturated salt solution is cooled down. Physical characteristics: Fixed geometrical shape Flat surfaces, straight edges and sharp corners Fixed angle between two adjacent surfaces Hard and brittle Colour of crystal depends on the ions in the crystals. Salt / metal oxide Solid Copper(II) salts Copper(II) carbonate Copper(II) sulphate, copper(II) nitrate, copper(II) chloride Copper(II) oxide Iron(II) salts Iron(II) sulphate, Iron(II) nitrate, Iron(II) chloride Iron(III) salts Green Blue Black Light green Colour Aqueous solution Insoluble Blue Insoluble Light green

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Iron(III) sulphate, Iron(III) nitrate, Iron(III) chloride Zinc oxide Lead(II) oxide Magnesium oxide, aluminium oxide Potassium oxide, sodium oxide, calcium oxide 6.

Brown Yellow (hot) White (cold) Brown (hot) Yellow (cold) White White

Brown / Green brownish Insoluble Insoluble Insoluble Colourless

8.2 Qualitative Analysis of Salts


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1. Test for gases: Gases Colour Oxygen, O2 Hydrogen, H2 Colourless Colourless

Smell -

Carbon dioxide, CO2 Ammonia, NH3

Colourless

Colourless

Pungent

Chlorine, Cl2

Greenish yellow

Pungent

Hydrogen chloride, HCl Sulphur dioxide, SO2

Colourless

Pungent

Colourless

Pungent

Nitrogen dioxide, NO2

Brown

Pungent

Confirmation test Light up glowing splinter Lighted splinter is placed near the mouth of the test tube. A pop sound is produced. Damp blue litmus Bubbled through paper turns red lime water. It will turn milky. Damp red litmus Forms dense paper turns blue white fumes with hydrogen chloride gas. Damp blue litmus Tested by using paper turns red, litmus paper. then decolourises / bleaches it. Damp blue litmus Forms dense paper turns red white fumes with ammonia. Damp blue litmus Decolourise paper turns red purple colour of potassium manganate(VII) solution / changes orange potassium dichromate(VI) solution Damp blue litmus Tested by using paper turns red litmus paper.

Effect on damp litmus paper -

2. Production of gases: Gases

Production 54

Oxygen, O2 Hydrogen, H2 Carbon dioxide, CO2 Ammonia, NH3 Chlorine, Cl2

Heating a chlorate(V) or nitrate salt Acid-metal reaction Heating a metal carbonate or acid-carbonate reaction Heating a mixture of ammonium salt and alkali Heating a mixture of manganese(IV) oxide and concentrated hydrochloric acid Hydrogen chloride, HCl Heating a common salt and concentrated sulphuric acid Sulphur dioxide, SO2 An acid-sulphite reaction Nitrogen dioxide, NO2 Heating a nitrate salt 3. Action of heat on salts Carbonate salts

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Nitrate salts

Sulphate salts i. Group 1 and 2 sulphate salts do not decompose when heated. ii. The sulphates of heavy metals decompose into metal oxides and sulphur trioxide when heated except iron(II) sulphate which release sulphur dioxide gas. iii. Ammonium sulphate sublimates at first and decompose into ammonia and hydrogen sulphate when further heating. 56

Chloride salts i. All are stable to heat except ammonium chloride. ii. Ammonia gas emerges first, then followed by hydrogen chloride. 4. Test for anions

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5. Confirmatory tests

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6. Tests for cations

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CHAPTER INDUSTRY

9:

MANUFACTURED

SUBSTANCES

IN

9.1 Sulphuric Acid


1. Uses: To manufacture fertilizers To manufacture detergent To manufacture pesticides To manufacture synthetic fibres (boat, wall) To manufacture paint To manufacture metal oxide As an electrolyte (lead-acid accumulator) 2. Contact process
Step I Step II

Sulphur, S

Sulphur dioxide, SO2


Step III

Sulphur trioxide, SO3

Sulphuric acid, H2SO4

Oleum, H2S2O7

Catalyst: Vanadium(V) oxide Temperature: 450C - 550C Pressure: one atmosphere (atm)

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Step I i. Production of sulphur dioxide ii. S + O2 SO2 Step II i. Production of sulphur trioxide ii. 2SO2 + O2 2SO3 iii. High % of SO2 is converted into SO3. Step III i. SO3 + H2SO4(concentrated) H2S2O7 (oleum) ii. H2S2O7 + H2O 2 H2SO4

9.2 Ammonia
1. Main uses: To manufacture fertilizers As a cooling agent in refrigerator To produce nitric acid (Ostwald process) To make explosives To prevent coagulation of latex To produce ammonium chloride 2. Haber process Nitrogen, N2 + Hydrogen, H2

Ammonia, NH3

Excess N2 and H2 61

Catalyst: Iron powder Promoter: Aluminium oxide Temperature: 450 550

Pressure: 200 500 atm

3. Nitrogen gas is obtained from fractional distillation of liquid air. 4. Source of hydrogen gas: Reaction between steam and heated coke (carbon) Reaction between steam and natural gas (methane) 5. Equation: N2 + 3H2 2NH3 6. Ratio of nitrogen gas to hydrogen gas 1 : 3

9.3 Alloy
1. Advantages of alloying: Increase the hardness/strength of metal Prevent corrosion/rusting Improve appearance of metal 2. Physical properties: Ductile can slide over when external force is applied.

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Malleable slide into new positions in the empty spaces of alloy. High boiling and melting points High density Good conductor of electricity Composition 99% iron 1% carbon 74% iron 18% chromium 8% nickel 90% copper 10% tin Properties Hard Uses For construction, bridges, vehicles, tools, heavy machinery For crockery, kitchenware and machine parts For kitchenware, ship propellers, decorative ornaments and art crafts. For musical instrument, electrical connecter, decorative ornaments

Alloy Carbon steel

Stainless steel

Rust resistant

Bronze

Hard & shiny

Brass

70% copper 30% zinc

Hard & shiny

Magnalium Duralumin

Pewter

70% aluminium 30% magnesium 95% aluminium 1% magnesium 4% copper 97% tin 3% lead and antimony 50% tin 50% lead Copper, nickel

Light & hard Light & hard

Hard & shiny

Solder Cupro-nickel

Hard, shiny and low melting point Hard, shiny and corrosion resistant

For mugs, candlesticks, decorative ornaments and souvenirs. For soldering electrical wires and metal pipes For coins

9.4 Synthetic Polymers


1. Polymers: large long-chain molecules formed by joining together many identical repeating sub-units called monomer. 2. Polymerisation: chemical process by which the monomers are joined together into chain-like molecule called polymer. 3. Natural polymer: polymer obtained from animals and plants. 63

4. Advantages of synthetic polymers Strong and light Cheap Able to resist corrosion Inert to chemical reactions Easily moulded or shaped and be coloured Can be made to have special properties Name(s) Monomer Properties Polyethylene ethylene soft, waxy solid low density CH2=CH2 (LDPE) Polyethylene ethylene rigid, translucent high density CH2=CH2 solid (HDPE) Polypropylene propylene atactic: soft, elastic (PP) different CH2=CHCH3 solid grades isotactic: hard, strong solid Poly(vinyl vinyl chloride strong rigid solid chloride) CH2=CHCl (PVC) Poly(vinylidene vinylidene dense, high-melting chloride) chloride solid (Saran A) CH2=CCl2 Polystyrene styrene hard, rigid, clear (PS) CH2=CHC6H5 solid soluble in organic solvents Polyacrylonitrile acrylonitrile high-melting solid (PAN, Orlon, CH2=CHCN soluble in organic Acrilan) solvents Polytetrafluoroeth tetrafluoroethylen resistant, smooth ylene e solid (PTFE, Teflon) CF2=CF2 Poly(methyl methyl methacrylate) methacrylate (PMMA, Lucite, CH2=C(CH3)CO Plexiglas) 2CH3 Poly(vinyl acetate) vinyl acetate (PVAc) CH2=CHOCOC H3 hard, transparent solid

Uses film wrap, plastic bags electrical insulation bottles, toys similar to LDPE carpet, upholstery pipes, siding, flooring seat covers, films toys, cabinets packaging (foamed) rugs, blankets clothing non-stick surfaces electrical insulation lighting covers, signs skylights latex paints, adhesives 64

soft, sticky solid

cis-Polyisoprene natural rubber Polychloroprene (c is + trans) (Neoprene)

isoprene CH2=CHC(CH3)=CH2 chloroprene CH2=CHCCl=CH2

requires vulcanization for practical use tough, rubbery solid synthetic rubber oil resistant

soft, sticky solid

9.5 Glass and ceramics


1. Properties of both glass and ceramics: Main component: silica or silicon dioxide, SiO2 Hard but brittle Inert towards chemicals Insulator of heat and electricity withstand compression but not stretching Can be easily cleaned Low cost of production 2. Differences between glass and ceramics: Glass transparent , ceramic opaque Glass cannot withstand high temperature, ceramics can withstand high temperature 3. Type of glass:

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4. Special purpose glass and ceramics I. Photochromic glass II. Conducting glass produced by adding tin(IV) oxide (conduct electricity) used to make LCD. III. Super conductor ceramics used to make light magnets, electrical generators & electric motors

9.6 Composite Materials


1. New material produced from a complex mixture of two or more materials with different physical properties.

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/ Optical fibres

~ THE END ~ ~ febianhenry_96 ~


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