Year 3 & 4 Chemistry

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Table of Contents
Particulate Nature of Matter ........................................................ 4
Particulate Nature of Matter .............................................................................. 5

Elements, Mixtures and Compounds ......................................... 7 Experimental Design and Purification Techniques ................ 10
Separation Techniques ................................................................................... 11 Identifying Gases ............................................................................................ 13 Experimental Design ...................................................................................... 14

Formulas, Equations, Stoichiometry and Mole Concept ....... 16
Common Ions ................................................................................................. 17 Formulae ........................................................................................................ 18 Stoichiometry and the Mole Concept .............................................................. 20

Atomic Structure and Chemical Bonding ................................ 22
Atomic Structure ............................................................................................. 23 Chemical Bonding .......................................................................................... 26 Types of Bonding ............................................................................................ 28 Ionisation Energy ............................................................................................ 31

Acids, Bases and Salts .............................................................. 34
Acids ............................................................................................................... 35 Bases .............................................................................................................. 37 pH and Indicators ........................................................................................... 38 Oxides ............................................................................................................ 39 Preparation of Salts ........................................................................................ 40

Chemical Energetics .................................................................. 42
Chemical Energetics ....................................................................................... 43 Positive ∆H (Endothermic) .............................................................................. 44 Negative ∆H (Exothermic) .............................................................................. 45 Fuel Cell.......................................................................................................... 46 Hydrogen as a Fuel ........................................................................................ 47

Reaction Kinetics ....................................................................... 48 Redox Reactions ........................................................................ 51 Periodic Table ............................................................................. 54
Periodic Table ................................................................................................. 55 Trends in Periodic Table ...................................Error! Bookmark not defined. Group Trends ...................................................Error! Bookmark not defined.

Qualitative Analysis ................................................................... 64
Physical Tests to Identify Substances ............................................................ 65 Identification of Cations .................................................................................. 67 Identification of Anions ................................................................................... 69 Identification of Gases .................................................................................... 70 Types Of Reactions ........................................................................................ 71 www.noteacademy.wordpress.com

Reactivity Series of Metals and their Extraction ..................... 72
Reactivity Series of Metals ............................................................................. 73 Alloys .............................................................................................................. 77 Corrosion and Rusting .................................................................................... 78 Extraction of Metals ........................................................................................ 80 Extraction of Iron ............................................................................................ 81 Recycling of Metals ........................................................................................ 83

Electrolysis ................................................................................. 84
Electrolysis ..................................................................................................... 85 (Example) Electrolysis of Molten Lead(II) Bromide (PbBr2) ............................ 86 Factors Affecting Electrolysis ...........................Error! Bookmark not defined. Summary of Electrolysis Reactions ................................................................ 91 Applications of Electrolysis (Purification/Refining of Metals) .......................... 93 Applications of Electrolysis (Electroplating) .................................................... 94 Applications of Electrolysis (Aluminum Manufacturing) .................................. 95

Chemical Equilibria .................................................................... 96
Chemical Equilibria ......................................................................................... 97 Haber Process ................................................................................................ 99 Contact Process ........................................................................................... 100

Organic Chemistry ................................................................... 102
Fossil Fuels .................................................................................................. 103 Petroleum ..................................................................................................... 104 Cracking ....................................................................................................... 105 Organic Chemistry ........................................................................................ 106 Writing Carbon Compounds ......................................................................... 107 Alkanes ......................................................................................................... 109 Alkenes ......................................................................................................... 110 Alcohols ........................................................................................................ 112 Carboxylic Acids ........................................................................................... 114 Redox Reactions in Organic Chemistry ........................................................ 116 Isomerism ..................................................................................................... 117

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Particulate Nature of Matter

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Particulate Nature of Matter

States of Matter Five States of Matter – Solid, Liquid, Gas, Plasma, Bose-Eistein Condensate

Kinetic Particle Theory All matter is made up of small particles that cannot be seen using the naked eye. There are spaces between particles in all matter. Particles are in constant random motion. Particles posses kinetic energy that changes with temperature. The average kinetic energy of all particles is directly proportional to the absolute temperature.

Particles in Solid, Liquid and Gas In a solid, the particles are packed very closely in a regular arrangement, the forces of attraction between particles are very strong and the particles vibrate about fixed positions. In a liquid, the particles are packed closely in an irregular arrangement, the forces of attraction between particles are strong and the particles undergo vibration and translation. In a gas, the particles are far apart in an irregular arrangement, the forces of attraction between particles are weak and the particles undergo vibration and translation; they move randomly at high speeds.

Difference between Evaporation and Boiling Evaporation occurs any time. Boiling occurs only at boiling point. Evaporation only occurs on the liquid surface. Boiling occurs throughout the liquid. No bubbles are observed in evaporation. Bubbles are observed in boiling. Evaporation occurs slowly. Boiling occurs rapidly. The lower the boiling point of a liquid, the faster the liquid evaporates.

Brownian Motion Brownian Motion shows that the movement of gas and liquid molecules is continuous and random.

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These movements of the molecules occur due to the collisions of the molecules with other surrounding molecules.

Diffusion Diffusion occurs when there is a movement of particles from a region of higher concentration to a region of lower concentration to achieve equilibrium in concentration. Only occurs in liquids and gases, but occurs faster in gases than in liquids. The rate of diffusion increases when the molecular mass decreases. The rate of diffusion increases when the temperature increases.

Changes in State A change in state 1. is reversible 2. is a physical change involving the gain or loss of energy by particles 3. is achieved by changing the pressure or temperature of the matter 4. involves changing the forces of attraction and distance of particles Solid to Liquid – Melting (Endothermic) Liquid to Solid – Freezing (Exothermic) Liquid to Gas – Evaporation/Boiling (Endothermic) Gas to Liquid – Condensation (Exothermic) Solid to Gas – Sublimation (Endothermic) Gas to Solid – Reverse Sublimation/Deposition (Exothermic)

Pure Substance A pure substance has a fixed melting and boiling point. A pure substance only gives one spot on chromatogram. The presence of an impurity in the substance causes the melting point to decrease and the boiling point to increase. The melting and boiling points melts and boils respectively over a range.

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Elements, Mixtures and Compounds

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Elements, Mixtures and Compounds

Definitions An element is a substance that is made up of only one kind of atom. It cannot be split into simpler substances. (e.g. silver, helium) A compound is a substance that contains two or more elements chemically joined together. (e.g. table salt, water) A mixture is a substance containing two or more substances physically joined together but not reacted with one another chemically. (e.g. salt water, air)

Similarities between Elements and Compounds Made of atoms Pure substances Fixed melting and boiling points

Differences between Elements and Compounds Elements consist of one kind of atom, while compounds consist of many kinds of atoms Elements are either metallic or non-metallic, while compounds combines metallic and non-metallic, or many non-metallic Elements cannot be chemically split into simpler substances, while compounds can be decomposed into elements or simpler substances

Similarities between Compounds and Mixtures Made of more than one kind of atom

Differences between Compounds and Mixtures Compounds can be separated into components chemically (e.g. electrolysis), while mixtures can be separated into components physically (e.g. distillation) Compounds have fixed boiling and melting points, while mixtures have a range of boiling and melting points www.noteacademy.wordpress.com

Compounds have different chemical properties from constituents while mixtures have the same properties as their elements Compounds are elements combined in fixed proportions by mass, while mixtures are elements combined in varied proportions Compounds are combined in such a way that chemical reaction occurs while mixtures are combined in such a way that chemical reaction occurs

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Experimental Design and Purification Techniques

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Separation Techniques

Filtration Insoluble solid from a solid/liquid mixture. e.g. filter sand from sand and water mixture

Crystallization Dissolved pure solid from an impure solution. Thermally stable solute (e.g. copper(II) sulfate and solution) Dissolve solute until saturation, then heat, then cool, then pat between filter paper. e.g. crystallize sugar from cane syrup

Sublimation Pure solid from a mixture of solids. e.g. sublime iodine from a iodine and sand mixture

Evaporation Solute will remain, Solvent will evaporate. (e.g. obtaining sodium chloride from sodium chloride solution)

Decanting Separating a mixture of liquid and a heavy solid (i.e. pouring the liquid out)

Centrifugation Separate small amounts of suspension. The suspension of solid in liquid is poured into a centrifuge tube, then spin around very fast in a centrifuge. The spinning motion forces the solid to the bottom of the tube. The liquid can be poured off from the solid.

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Simple Distillation Pure liquid from a solution with dissolved solids. e.g. distil pure water from seawater

Fractional Distillation Two or more miscible liquids with slightly different boiling points. The water enters nearer to the beaker while the water exits nearer to the fractional column so that the coolest part of the condenser is nearer the outlet and all the remaining vapor can be condensed. The liquids are distilled according to their boiling points, with the liquid with the lowest boiling point (most volatile) being distilled first. e.g. distil different fractions from crude oil

Separating Funnel Separating immiscible liquids. e.g. separating oil from water (or other organic compounds)

Paper Chromatography Substances based on different solubility. The retention factor value (Rf value) of a substance is the distance moved by the solution up the paper divided by the distance moved by the solvent. It is less than one. For separation of colorless compounds, locating agents are used. e.g. separate and indentify both coloured and colourless mixtures such as drugs and dyes

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Identifying Gases

Chlorine Pale yellow gas evolved. The moist blue litmus paper turns red and then bleaches.

Hydrogen Effervescence observed. Colorless gas evolved. The gas extinguishes the lighted splint with a ‘pop’ sound.

Oxygen Effervescence observed. Colorless gas evolved. The gas relights the glowing splint.

Sulphur Dioxide Colorless gas evolved. Turns acidified purple potassium manganate (VII) solution colourless. (or Turns acidified orange potassium dichromate(VI) solution green.)

Carbon Dioxide Effervescence observed. Colorless gas evolved. A white precipitate is formed when bubbled in limewater, Ca(OH)2.

Ammonia Colorless and pungent gas evolved. The moist red litmus paper turns blue.

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Experimental Design

Measurement Physical Quantity Time Temperature Mass Volume (Liquid) Volume (Gas) Measuring Apparatus Stopwatch Mercury/Alcohol Thermometer Beam Balance/ Electronic Balance Burette/Pipette/Measuring Cylinder Gas Syringe SI Unit Second (s) Kelvin (K) Kilogram (kg) Cubic meter (m3) Cubic meter (m3)

K = degrees Celsius + 273.15 ∆ K = ∆1 degree Celsius Smaller volumes are usually measured in cubic centimetres (cm3) or cubic decimetres (dm3). 1000cm3 = 1dm3

Measuring volume of gas Use Gas Syringe, Delivery Tube, Test Tube, Beaker, Stopper, U-Tube Depends on solubility in water and density compared to air 1. Displacement of water (if gas is not soluble in water) e.g. hydrogen, oxygen, nitrogen, methane 2. Downward Delivery (if gas is more dense than air and soluble in water) e.g. chlorine, carbon dioxide, sulphur dioxide, hydrogen chloride, nitrogen dioxide 3. Upward Delivery (if gas is less dense than air and soluble in water) e.g. hydrogen, ammonia

Drying Agents 1. Anhydrous Copper(II) Sulfate tests for water/water vapour. In the presence of water, the white crystals become blue (hydrated copper(II) sulfate). 2. 3. 4. 5. 6. Anhydrous Sodium Sulphate, Na2SO4 Concentrated Sulfuric Acid, H2SO4 Calcium oxide, CaO (not for acidic gases like SO2, CO2, Cl2) Anhydrous Calcium Chloride, CaCl2 (not for ammonia) Silica Gel

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Measuring Liquids 1. Measuring Cylinder (100cm3) (0 decimal points) 2. Pipette (25cm3) (1 decimal point) 3. Burette (50cm3) (2 decimal points) Note: A beaker is not used to measure; scale lines are approximate.

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Formulas, Equations, Stoichiometry and Mole Concept

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Common Ions

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Formulae

Ionic Formula Can be obtained by ‘crisscrossing’ the charges between the interacting ions. Sodium Chloride Na+ ClNaCl Calcium Bromide Ca2+ BrCaBr2 Aluminium Oxide Al3+ O2Al2O3

Chemical Equations and State Symbols 1. Write the reactants and products 2. Balance the equation by writing a number in front of the compounds. Ensure that there are the same number of each type of atoms before and after reaction 3. Add the state symbols to each chemical

Ionic Equations An ionic equation is an equation that shows specifically which atoms/ions/molecules take part in the reaction. Spectator ions are free ions present at the start and at the end of a reaction. (i.e. remains unchanged by the reaction). The aim of an ionic equation is to eliminate the spectator ions. 1. 2. 3. 4. Write the balanced chemical equation Add the state symbols to each chemical Write out the free ions in aqueous solution* Cancel away corresponding spectator ions on left hand side and right hand side of the equation 5. Write down the un-cancelled formulas give the ionic equation *Substances in solid, liquid or gaseous state do not form free ions. *Substances that are covalently bonded do not form free ions.

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Note that the net charge on both sides of the equation is balanced.

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Stoichiometry and the Mole Concept

For all calculations, the answer should be in 3 significant figures.

Relative Atomic Mass Percentage of mass of an element in a compound = (total atomic mass of the element in the compound) / (total molecular mass of the compound) x 100% = (total mass of the element in the compound) / (total mass of the compound) x 100%

Mole Concept The number of particles in a mole ix 6 x 1023. The unit is mole and the symbol is mol. Number of moles = (mass in grams) / (molecular mass) 1 mole of hydrogen = 1 g 1 mole of calcium = 40.08 g 0.5 mole of calcium = 20.04 g 1 mole of oxygen = 2 moles of oxygen atoms 1 mole of sodium chloride = 1 mole of sodium atoms and 1 mole of chloride atoms

Empirical Formula Empirical Formula refers to the simplest whole number ratio formula found by experiment. (e.g. The empirical formula of C6H12O6 is CH2O) Molecular Formula refers to the chemical formula that shows the total number and kinds of atoms in a molecule. Molecular formula = n x Empirical Formula e.g. C6H12O6 = 6 x CH2O

Structural formula Molecular formula – C4H10 Empirical formula – C2H5 www.noteacademy.wordpress.com

Structural formula – CH3CH2CH2CH3 (or the drawn out form)

Gas Volume One mole of any gas at room temperature and pressure occupies 24dm3. 1 mole of gaseous oxygen = 24dm3 = 24000cm3 1 mole of gaseous calcium = 24dm3

Limiting Reactants A limiting reactant in a chemical reaction limits the amount of product that can be formed. The chemical reaction stops when the limiting reactant is completed used up. A reactant that is in excess remains behinds.

Concentration of Solutions Concentration in (mol/dm3) = (number of moles of the substance in mol) / (volume of the solution in dm3)

Percentage yield Percentage yield (%) = (actual yield) / (theoretical yield) x 100%

Percentage purity Percentage purity (%) = (actual amount of a compound) / (total amount of sample) x 100%

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Atomic Structure and Chemical Bonding

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Atomic Structure

Neutron, Proton and Electron Neutron - Neutral , 1 atomic mass unit Proton - Positive +1 , 1 atomic mass unit Electron - Negative , no mass

s, p, d, f subshells 4 subshells: s, p, d, f Each subshell has orbitals. Each orbital contains 2 electrons each. Electrons fill subshells with lowest energy first. The nucleus is positioned in the middle of the outer energy shells. s orbital – 1 orbital p orbital – 3 orbitals d orbital – 5 orbitals f orbital – 7 orbitals Lithium – 1s2 2s1 Beryllium – 1s2 2s2 Boron – 1s2 2s2 2p1 Carbon – 1s2 2s2 2p2 Nitrogen – 1s2 2s2 2p3 Oxygen – 1s2 2s2 2p4 Flourine – 1s2 2s2 2p5 Neon – 1s2 2s2 2p6 Sodium - 1s2 2s2 2p6 3s1 Magnesium – 1s2 2s2 2p6 3s2 Aluminum – 1s2 2s2 2p6 3s2 3p1 Silicon – 1s2 2s2 2p6 3s2 3p2 Phosphorus – 1s2 2s2 2p6 3s2 3p3 Sulfur – 1s2 2s2 2p6 3s2 3p4 Chlorine – 1s2 2s2 2p6 3s2 3p5 Argon – 1s2 2s2 2p6 3s2 3p6 Potassium – 1s2 2s2 2p6 3s2 3p6 4s1 Calcium – 1s2 2s2 2p6 3s2 3p6 4s2 Scandium – 1s2 2s2 2p6 3s2 3p6 3d1 4s2 Titanium – 1s2 2s2 2p6 3s2 3p6 3d2 4s2 Vanadium – 1s2 2s2 2p6 3s2 3p6 3d3 4s2 Chromium – 1s2 2s2 2p6 3s2 3p6 3d4 4s2 www.noteacademy.wordpress.com

Manganese - 1s2 2s2 2p6 3s2 3p6 3d5 4s2 Iron - 1s2 2s2 2p6 3s2 3p6 3d6 4s2 Cobalt - 1s2 2s2 2p6 3s2 3p6 3d7 4s2 Nickel - 1s2 2s2 2p6 3s2 3p6 3d8 4s2 Copper - 1s2 2s2 2p6 3s2 3p6 3d9 4s2 Zinc - 1s2 2s2 2p6 3s2 3p6 3d9 4s2 4p1 Gallium - 1s2 2s2 2p6 3s2 3p6 3d9 4s2 4p2 Germanium - 1s2 2s2 2p6 3s2 3p6 3d9 4s2 4p3 Arsenic - 1s2 2s2 2p6 3s2 3p6 3d9 4s2 4p4

Proton Number, Nucleon Number
Y

X where Y is mass number/nucleon number (protons + neutrons)

ZX where Z is proton number/atomic number (protons/electrons)

Proton Number / Atomic Number is the number of protons in the nucleus. Nucleon Number / Mass Number is the sum of protons and neutrons. The number of protons is equal to the number of electrons, for an element without any charge.

Relative Atomic Mass/ Relative Molecular Mass Reference: 1/12 of a carbon-12 atom Relative Atomic Mass (Ar) = Average mass of one atom of element/ mass of 1/12 of a carbon-12 atom Relative Molecular Mass (Mr) = Sum of Ar of atoms in molecule

Isotope and Ion Isotopes are atoms of an element that have the same atomic number but different mass number. Isotopes have the same proton number but different nucleon number. They have the same number of electrons; hence they have the same chemical properties. There are two types of isotopes – radioactive (radioisotopes) and non-radioactive isotopes. An ion is when an atom loses or gains an electron and becomes electrically charged.

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Mass Spectrometer Mass Spectrometer determines 1. Relative masses of isotopes 2. Relative abundance of isotopes 3. Number of isotopes

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Chemical Bonding

Octet Rule Octet Rule: Most atoms end up with octet structure (8 valence electrons) after forming a compound Exceptions: Helium (duplet), Octet Expanders Atoms reach configuration of unreactive noble gas atom to give compound stability. Minimal amount of energy is used to form such compounds.

Electronegativity Pauling scale: measure of the tendency of an atom to attract a bonding pair of electrons. 0.0 ≤ ∆ EN ≤ 0.5: Non-Polar Covalent 0.5 ≤ ∆ EN ≤ 2.0: Polar Covalent (covalent with ionic characteristics) 2.0 ≤ ∆ EN ≤ 4.0: Ionic

Van der Waals Forces Forces of attraction between slightly positively-charged area of one molecule and slightly negatively-charged area of another molecule. Occurs when electron charge cloud around molecule is asymmetrical. Interaction between polar molecules: when in a molecule, one atom is more electronegative.

Hydrogen Bonding Hydrogen bonding occurs when hydrogen is covalently bonded to oxygen/nitrogen/fluorine. Bigger molecules have greater intermolecular forces between themselves than smaller molecules (i.e. iodine has a higher melting point than chlorine).

Coordinate/Dative Bonding Covalent bond in which shared pair of electrons is provided by only one of bonded atoms. One is the donor, the other is the acceptor. www.noteacademy.wordpress.com

e.g. H+ + H2O  H3O+ H2O has two lone pairs of electrons

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Types of Bonding

There are three types of bonding – Ionic Bonding, Covalent Bonding, Metallic Bonding

Ionic Structure 1. Ionic Bonding: Non-metal and Metal 2. Solid ionic compound has a giant lattice structure. The cations and anions are held together by strong electrostatic attraction in a repeated and regular arrangement. 3. High melting and boiling point. The ions are held together by strong electrostatic forces of attraction between the positive and negative ions. Therefore, it requires a lot of energy to break these strong ionic bonds. 4. Conducts electricity in the liquid and molten state. In the liquid and molten state, the positive and negative ions can move freely. These ions can carry charges to conduct electricity. 5. Soluble in water. Water molecules are polar molecules. Therefore, they can interact with the lattice and weaken the ionic bonds. This causes the ions to separate, hence the compound dissolves

Simple Molecular Structure 1. Covalent Bonding: Non-metal and Non-metal 2. Low melting and boiling point. The molecules are held together by weak intermolecular forces of attraction. Therefore, it requires little energy to break the weak covalent bonds. 3. Does not conduct electricity in any state. The simple molecular structure does not have any free moving ions or electrons to carry the charge to conduct electricity. 4. Soluble in organic solvents. It contains non-polar molecules, which can interact with the non-polar organic solvents. 5. Exceptions: HCl and NH3 conduct electricity because they form ions when dissolved in water.

Macromolecular Structure www.noteacademy.wordpress.com

1. Covalent Bonding: Non-metal and Non-metal 2. High melting and boiling point. The atoms are held together by strong covalent bonds in a lattice structure. Therefore, it requires a lot of energy to break these strong covalent bonds. 3. Only graphite conducts electricity. The 3 carbon atoms are bonded covalently to 3 other carbon atoms in the graphite lattice. Therefore, there fourth valence electron is delocalized within each layer, which can carry charges to conduct electricity. 4. Diamond is hard because of its tetrahedral structure. 5. Insoluble in all solvents. 6. Examples are graphite, diamond, SiO3, SiO2, Sn

Metallic Structure 1. Metallic Bonding: Metals 2. High melting and boiling point. The atoms are held together by strong electrostatic forces of attraction between the positive metal ions and the sea of delocalized electrons. Therefore, it requires a lot of energy to break these strong metallic bonds. 3. Conducts electricity in all states. In a metallic structure, there are delocalized sea of electrons that can carry the charge to conduct electricity. 4. Insoluble in all solvents. 5. Malleable and ductile. The closely packed metal ions form a regular arrangement in which planes of ions lie upon one another. When forces are applied to a metal, these planes of ions move across one another, causing a change in shape, but the mobile electrons still continue to move freely, thus the metallic bonds are still present. 6. Good conductor of heat. When heated, the positive metal ions vibrate more quickly. These ions transfer their energy to the mobile electrons, which transmit their energy quickly to other parts of the metal.

Organic Solvents Hexane – C6H14 Benzene – C6H6 www.noteacademy.wordpress.com

Ethanol – C2H6O Cyclohexane – C6H12 Chloromethane* – CH3Cl Tetrachlromethane* – CCl4 *Chloromethane and tetrachlromethane are CFCs, which are banned in laboratories.

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Ionisation Energy

The ionisation energy is the minimum energy required to remove an electron from the ground state of the isolated gaseous atom. 1st ionisation energy - 1s22s22p2 2nd ionisation energy - 1s22s22p1 3rd ionisation energy - 1s22s2

Trends Across the period, the first ionization energy typically increases. Across the period, the number of electron shells remains the same, while the number of protons increase. Therefore, the outermost electron is more strongly attracted to the nucleus, and hence, more energy is required to remove the valence electron. Down the group, the first ionization energy typically decreases. Down the group, the number of electron shells increases. Therefore, the outermost electron is more weakly attracted to the nucleus, and hence, less energy is required to remove the valence electron.

Explanation Technique The 3rd electron is located in the outermost electron shell while the 4th electron is located in the second outermost electron shell. There is a stronger force of attraction in the second outermost electron shell than the outermost electron shell because it is located nearer to the nucleus of the atom. Therefore, the 3rd electron requires less energy to remove than the 4th electron. The 3rd electron is located in the p orbital while the 4th electron is located in the s orbital. As the p orbital is located further away from the nucleus than compared to the s orbital, it requires less energy to remove the electron in the p orbital than in the s orbital.

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Volumetric Analysis

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Volumetric Analysis Common Indicators Methyl Orange Phenolphthalein Acid Red Colourless End Point Orange Pink Alkali Yellow Pink

Solution of known concentration: Standard solution/titrant Solution of unknown concentration: Titrant Titration graphs?

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Acids, Bases and Salts

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Acids

Acids Acids are substances that produce hydrogen ions, H+ (aq), when dissolved in water. The hydrogen ions are responsible for the acidic properties of acids.

Important Experiment When hydrogen chloride gas or citric acid solid is dissolved in non-polar solvents such as toluene, they do not exhibit acidic properties (like turning litmus red or reacting with carbonates to produce carbon dioxide) because their molecules do not ionize. Thus, it is the presence of H+ ions in aqueous solutions that give these acids the acidic properties.

Strong and Weak Acids The higher the amount of H+ ions that dissociate in water, the stronger the acid. Strong acids dissociate nearly or completely in water while weak acids dissociate partially only. Note: A strong acid can be diluted while a weak acid can be concentrated.

Monobasic vs Dibasic Acids Monobasic acids have one replaceable hydrogen atom per molecule and form one salt. (e.g. HCl  H+ + Cl-) Dibasic acids have two replaceable hydrogen atoms per molecule and form two salts. (e.g. H2SO4  2H+ + SO42- and H2SO4  H+ + HSO4-)

Physical Properties 1. 2. 3. 4. Tastes sour Turns (moist) blue litmus paper red pH value of less than 7 Good conductors of electricity

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Chemical Properties 1. Reacts with metals to form salt and hydrogen gas 2. Reacts with metal carbonates and hydrogencarbonates to form salt, carbon dioxide and water 3. Reacts with bases to form salt and water 4. Reacts with sulfites (SO32-) to form salt, water and sulfur dioxide

Examples of Acids Common Name Hydrochloric Acid Nitric Acid Sulfuric Acid Carbonic Acid Acetic Acid Chemical Name Aqueous Hydrogen Chloride Aqueous Hydrogen Nitrate Aqueous Hydrogen Sulfate Aqueous Hydrogen Carbonate Aqueous Ethanoic Acid Formula HCl HNO3 H2SO4 H2CO3 CH3COOH Description Strong acid, monobasic Strong acid, monobasic Strong acid, dibasic Weak acid, dibasic Weak acid, monobasic

Applications of Neutralisation 1. 2. 3. 4. 5. Controlling the pH of Soil Treatment of Indigestion Treatment of Insect Stings Treatment of Industrial Wastewater or Waste gases Egg Dyeing

Neutralisation is an exothermic reaction.

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Bases

Bases are metal oxides/hydroxides (not all bases are soluble in water). Alkalis are soluble bases. They dissociate to form hydroxide ions, OH- (aq), when dissolved in water. The hydroxide ions are responsible for the alkaline properties of the base.

Strong and Weak Alkalis The higher the amount of OH- ions that dissociate in water, the stronger the alkali. Strong alkalis dissociate nearly or completely in water while weak alkalis dissociate partially only. Note: A strong alkali can be diluted while a weak alkali can be concentrated.

Physical Properties 1. 2. 3. 4. 5. Tastes bitter Turns (moist) red litmus paper blue Alkalis have pH more than 7 Good conductors of electricity Feel soapy and slippery

Chemical Properties 1. Reacts with acids to form salt and water 2. Reacts with ammonium salts to form salt, water and ammonia 3. Reacts with some salts to produce insoluble hydroxides

Examples of Alkalis Common Name Caustic Soda Caustic Potash Slaked Lime Limewater Ammonia Solution Chemical Name Sodium Hydroxide Potassium Hydroxide Calcium Hydroxide Aqueous Ammonia Formula NaOH KOH Ca(OH)2 NH3 Description Strong Alkali Strong Alkali Strong Alkali (slightly soluble in water) Weak Alkali

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pH and Indicators

The pH scale is a measure of acidity and alkalinity of aqueous solutions using a scale of numbers from 0 – 14. It uses a logarithmic scale. (i.e. pH 1 has 10 times more hydrogen ion concentration than pH 2) From 0 to 14, the universal indicator turns red, orange, yellow, green, blue, purple. Other indicators include: Universal Indicator, methyl orange and phenolphthalein.

Calculation of pH Calculation: pH = -log10[H+] where [H+] is the concentration of hydrogen ion in mol dm-3

e.g. 0.01 moles of HCl is added to water to make 1 dm3 of solution. Assuming the HCl is completely ionized, what is the pH of the solution? [H+] = 0.01 mol dm-3 = 1 x 10-2 mol dm-3 pH = -log10[H+] = -log10[1 x 10-2] = 2

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Oxides

Types of Oxides 1. Acidic oxide: a non-metallic oxide React with bases to form salts Examples: CO2, SO2, NO2 2. Neutral oxide: a non-metallic oxide Do not react with acids or bases Examples: CO, NO, H2O Most non-metallic monoxides are neutral oxides 3. Basic oxide: a metallic oxide React with acids to form salts Examples: Na2O, CaO, CuO 4. Amphoteric oxide: a metallic oxide React with both acids and bases to form salt Examples: PbO, Al2O3, ZnO There are only 3 amphoteric oxides (LAZ – Lead, Aluminum, Zinc) All amphoteric oxides are insoluble in water Hydroxides behave like metal oxides. Only Pb(OH)2 and Zn(OH)2 are amphoteric.

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Preparation of Salts

Salts A salt is an ionic compound formed by replacement of one or more hydrogen ions of an acid by a metallic ion/ammonium ion. A salt can be either soluble or insoluble in water.

Solubility Rules All nitrates, Group I and ammonium compounds are soluble. All chloride, iodides, bromides are soluble except LS. All sulfates soluble except LBC. All carbonates, hydroxides, oxides are insoluble except Group I and ammonium. LS = Lead(II), Silver LBC = Lead(II), Barium, Calcium

Salt Preparation (Soluble Salt) Soluble Base/Carbonate + Soluble Acid = Titration (Soluble Salt) Insoluble Base/Carbonate + Soluble Acid = Excess Base (Filtration) (Insoluble Salt) Soluble Base/Carbonate + Soluble Acid = Precipitation

Filtration Method 1. Add excess base/carbonate into the acid, stirring and heating until no more can dissolve. 2. Filter off the excess base. 3. Heat the salt solution obtained until about one-third its volume, to saturate it. 4. Leave it to cool. 5. Crystals of salt would appear. Filter them off. 6. Dry the crystals between sheets of filter paper.

Titration Method

1. Titrate the corresponding acid and base/carbonate with a suitable indicator. Note the end-point. 2. Repeat titration without indicator. www.noteacademy.wordpress.com

3. 4. 5. 6.

Heat the salt solution obtained until about one-third its volume, to saturate it. Leave it too cool. Crystals of salt would appear. Filter them off. Dry the crystals between sheets of filter paper.

Precipitation Method 1. Mix 2 aqueous solutions, one containing the cation and the other containing the anion, that make up the salt. 2. Filter the mixture. 3. Wash the residue with distilled water. 4. Dry the residue (salt) between sheets of filter paper.

Acid + Metal Method Unsuitable for: 1. Lead(II), Copper(II), Silver Salts Lead, Copper and Silver are unreactive metals. They do not react with dilute acids to form salts. 2. Insoluble Salts The thin layer of the insoluble salt forms on the surface of the metal, thus preventing the metal from further reacting with the acid. The reaction is thus incomplete, leaving most of the metal unreacted. 3. Group I Salts Group I metals react with both the acid and water. Thus, although some salt would form, the corresponding hydroxide will also form.

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Chemical Energetics

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Chemical Energetics

Types of Energy Conversion 1. Chemical reactions involving heat/light change 2. Chemical reactions involving electrical change (electrical cells/electrolysis) 3. Nuclear reactions

Enthalpy Change (∆H) Energy that is stored in bonds is known as enthalpy. Enthalpy change, ∆H, is defined as the amount of heat released or absorbed when a chemical reaction occurs at a constant pressure. Bond energy is the heat required to break one mole of molecules into their individual atoms. ∆H = Hp - Hr ∆H = bond breaking - bond breaking Hr = enthalpy of reactants Hp = enthalpy of products

Energy Profile Diagrams Activation energy of a reaction is defined as the minimum energy that must be overcome in order for a chemical reaction to take place. It is the difference between the energy of the reactants and the peak of the energy profile diagram.

Breaking and Forming Bonds Bond breaking is endothermic because heat energy must be taken in by the reactants to overcome the existing bonds to form new products. Bond forming is exothermic because heat energy is released when new bonds are formed in the product. Bond energy is the amount of energy required to make or break a chemical bond. The stronger the bond, the higher the bond energy.

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Positive ∆H (Endothermic)

Enthalpy of products is more than enthalpy of reactants. The total energy change in bond formation is less than in bond breaking. Heat energy is absorbed from the surroundings by the reacting system. Results in the cooling of its surrounds and a rise in temperature of the reacting system.

Examples of Endothermic Reactions 1. Change in State heat + H2O (l)  H2O (g) (melting and boiling) 2. Dissolving some salts in water heat + NH4Cl (s)  NH4Cl (aq) 3. Decomposition of compounds (thermal decomposition) heat + CuCO3 (s)  CuO (s) + CO2 (g) 4. Reactions between acids and hydrogencarbonates Headache tablets 5. Photosynthesis (takes in light energy, not heat) light energy + 6 CO2 (g) + 6 H2O (l)  C6H12O6 (aq) + 6 O2 (g)

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Negative ∆H (Exothermic)

Enthalpy of products is less than enthalpy of reactants. The total energy change in bond formation is more than in bond breaking. Heat energy is released from the surroundings by the reacting system. Results in the warming of its surrounds and a drop in temperature of the reacting system.

Examples of Exothermic Reactions 1. Change of state H2O (l)  H2O (s) + heat (condensation) H2O (g)  H2O (l) + heat (freezing) 2. Dissolving of some salts Na2CO3 (l)  Na2CO3 (aq) + heat 3. Combustion 2 H2 (g) + O2 (g)  2 H2O (l) + heat 4. Neutralisation Heat is due to the combination of H+ and OHH+ (aq) + OH- (aq)  H2O (l) + heat 5. Metal Displacement Zn (s) + Cu2+ (aq)  Zn2+ + Cu (s) + heat 6. Respiration C6H12O6 (aq) + 6 O2 (g)  6 CO2 (g) + 6 H2O (l) + heat 7. Diluting Concentrated Sulfuric Acid www.noteacademy.wordpress.com

Fuel Cell

A fuel cell is an electrochemical cell that operates like a battery. It will continue to produce electrical energy and heat as long as the fuel is being continuously added. It consists of two platinum electrodes, which sandwich the electrolyte. Hydrogen is fed to the anode while oxygen is fed to the cathode, generating electricity, water and heat.

Anode: 2H2  4H+ +4eCathode: O2 + 4H+ + 4e-  2H2O Net reaction: 2H2 + O2  2H2O (∆H = -242 kJ/mol) H2 is oxidized at anode, causing electrons to be released. Electrons flow out of the cell through an external circuit and return to the cathode, creating current. O2 is reduced at cathode by absorbing returning electrons. The electrodes do not deteriorate chemically, so fuel can supply continuous electrical energy, given a constant hydrogen supply. www.noteacademy.wordpress.com

Hydrogen as a Fuel

Advantages 1. Burns cleanly in air, producing only steam, compared to carbon monoxide and carbon dioxide from other fuels 2. Produces at least twice as much heat energy per gram burnt as compared to other common fuels

Disadvantages 1. Low boiling point of -252 degrees Celsius, so it cannot be stored, transported and used as easily as liquid fuels

Manufacturing 1. Cracking of Heavy Petroleum Fractions Cracking is the process whereby complex organic molecules are broken down into simpler molecules.

2. Steam Reforming Mixture of steam and methane is passed over a catalyst. H2O + CH4  CO + 3H2 CO is reacted with more steam to give more hydrogen. H2O + CO  CO2 + H2 H2 is separated from the CO2 by passing mixture through an alkali, which absorbs CO2.

Usages 1. As a fuel in big rockets 2. Fuel cells (Experimental cars use about 400 small fuel cells) 3. Ammonia manufacturing (Haber Process)

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Reaction Kinetics

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Reaction Kinetics

The rate of reaction depends on the frequency of effective collisions between reactant particles. It refers to how fast a particular reaction is taking place. The activation energy is the minimum amount of energy required for all colliding particles before a reaction will occur. The activation energy is there because all chemical reactions require the breaking of bond between atoms, since bonds have to be broken before new ones can be formed. When the activation energy is high, the reaction is slow, because only a few of the collisions give particles sufficient energy to produce a reaction. When the activation energy is low, the reaction is fast, because many collisions give particles sufficient energy to produce a reaction.

Factors that Increase Rate of Reaction 1. At higher temperature, the particles have more kinetic energy to move faster. Thus, the particles collide with each other harder, resulting in increased reaction rate. 2. At a higher concentration, there are more particles per unit volume. Thus, the particles are closer to each other and the frequency of collisions increases, resulting in increased reaction rate. 3. At higher pressure (in gaseous reactants), the particles are in closer proximity, thus colliding more frequently, resulting in increased reaction rate. 4. The smaller the particle, the surface area for reaction is larger. Thus, the area of contact between the reactants increases, and the number of collisions per unit time also increases. (Stirring helps to break large solid particles into smaller particles) 5. A catalyst provides an alternative pathway, which has a lower activation energy. (A catalyst speeds up the reaction but itself is not chemically reacted. Its mass remains the same before and after the reaction.)

Rate of reaction is monitored by (one of the product has to be gas)

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Rate of reaction = Change in property / Time Taken 1. Decrease in mass of reaction mixture 2. Increase in volume of gas formed 3. The steeper the slope of the graph, the faster the reaction. The reaction rate is fastest at the start of the reaction, when the reactants are at their highest concentration. The gradient decreases with time, hence the rate of reaction decreases with time. When the gradient is zero, the reaction has stopped.

Other methods (without one of the products having to be gas) 1. Changes in amount of reactant/product using titration 2. Changes in intensity of colour (reactant or product must be a coloured substance) 3. Changes in pressure in a close reaction vessel 4. Change in temperature

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Redox Reactions

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Redox Reactions

Oxidation and Reduction A redox reaction is when oxidation and reduction occurs simultaneously in a complementary manner. A substance is oxidized when it loses electrons or its oxidation number increases. A substance is reduced when it gains electrons or its oxidation number decreases. OIL RIG = Oxidation is Lost; Reduction is Gain Oxidized substance = Reducing agent Reduced substance = Oxidizing agent

Half Equations Half Equations = An equation that shows oxidation or reduction e.g. Zn (s) + 2H+ (aq)  Zn2+ (aq) + H2 (g) Oxidation: Zn (s) Zn2+ (aq) + 2eReduction: 2H+ (aq) + 2e- H2 (g)

Oxidation Number Oxidation number = Charge that atom would have if it is an ion Exceptions to usual oxidation numbers: O- (peroxides), H- (metal hydrides e.g. NaH)

Tests for reducing agents Using aqueous potassium manganate (VII); KMnO4 needs to be acidified. Purple MnO4- permanganate ion will turn into colourless Mn2+ manganese ion 1. 1cm3 of potassium manganate (VII) solution is poured into a test tube, followed by 1cm3 of dilute sulfuric acid. 2. A few drops of this acidified potassium manganate is added to the unknown solution. 3. If the purple MnO4- solution turns colourless, then the MnO4- has been reduced to Mn2+

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4. This means that the unknown substance caused the reduction and was hence a reducing agent Using aqueous potassium dichromate (VI); K2Cr2O7 needs to be acidified. Orange Cr2O72- dichromate ion will turn into green Cr3+ chromium ion Same method as above is used.

Test for oxidizing agents Using aqueous potassium iodide, KI Colourless I- iodide ion will turn into brown I2 iodine molecule 1. A few drops of aqueous potassium iodide is added to the unknown solution. 2. If the colourless I- solution turns into brown, then the I- has been oxidized to I2 3. This means that the unknown substance caused the oxidation and was hence a oxidizing agent

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Periodic Table

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General Information The Periodic Table is an arrangement of elements in the order of increasing proton/atomic number. Horizontal row is called a period. (Note that Hydrogen is in Period 1) Vertical row is called a group. (Note that Groups are only written in Roman Numerals) There are four main classes of elements, from left to right; they are metals, transition metals, metalloids, and non-metals.

Elements in the same group 1. 2. 3. 4. Same number of valence electrons Form ions and compounds with similar formulae Tend to have similar chemical properties Elements go from metals to non-metals, from left to right

Elements in the same period 1. Same number of shells

Nuclear Charge 1. Actual nuclear charge = atomic/proton number = sum of all protons in nucleus of the atom 2. Shielding electrons = electrons not in valence shell of atom Shield outer shell electrons from attraction force of nuclear charge 3. Effective nuclear charge (Zeff) = Actual nuclear charge - Number of shielding electrons = Resultant charge acting on valence shell electron

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Summary of Trends in Periodic Table Down the Group Atomic Radius Ionisation Energy Melting and Boiling Points (Metals) Melting and Boiling Points (Non-Metals) Electronegativity Shielding Electrons Effective Nuclear Charge Increases Decreases Decreases Increases Decreases Increases Constant Alkali Metals Increases Low Decreases Low Increases All silvery Across the Period Decreases Increases Increases Constant Increases Noble Gases Increases Very Low Increases Low All colourless

Density Density Melting and Boiling Points Melting and Boiling Points Reactivity Colour of Elements

Halogens Increases Increases Low Decreases Darker

Properties of Metals 1. 2. 3. 4. 5. 6. Usually solids at r.t.p (except Hg) High m.p. and b.p. (except Group I) Good conductors of heat and electricity Usually shiny, ductile, malleable and possess great tensile strength Oxides usually basic or amphoteric Always form cations

Properties of Non-Metals 1. 2. 3. 4. 5. 6. Often gases at r.t.p. (except C, S, Si) Low m.p. and b.p. (except C and Si) Poor conductors of heat and electricity (except graphite, C) Usually dull and soft Oxides usually acidic/ neutral Usually form anions

Trends for Shielding Electrons 1. Number of shielding electrons increases down a group 2. Number of shielding electrons remains the same across a period Trends for Effective Nuclear Charge

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1. Effective nuclear charge remains the same down a group 2. Effective nuclear charge increases across a period

Trends for Electronegativity 1. Measured on Pauling scale Fluorine is most electronegative (value of 4.0) 2. Electronegativity decreases down a group 3. Electronegativity increases across a period For smaller atoms, electrons used in bonding are closer to the nucleus. Hence, there is a greater attractive force, and a greater ability to polarize. Hence, smaller atoms have higher electronegativity, and greater polarizing power.

Trends for Ionisation Energy 1. Ionization energy measures the energy required to remove one electron each from one mole of gaseous atoms of an element 2. Ionization energy decreases down a group With more electron shells down a group, valence electron become further away from nucleus. Hence, the force of attraction between the valence electron and the nucleus decreases, resulting in a decrease in ionisation energy. 3. Ionization energy increases across a period The effective nuclear charge increases across the Period (due to increasing number of protons and constant number of shielding electrons), the force of attraction between the nucleus and the valence electrons increases, resulting in an increase in ionisation energy

Trends for Atomic Radius 1. Atomic radius measures the distance between 2 nuclei in solid state, divide by 2 (by X-ray diffraction). For non-metallic elements in molecular form, measure distance between nuclei of covalently bonded atoms. 2. Atomic radius increases down a group Going down a group, a shell of electrons is added for each element, so atoms get larger.

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3. Atomic radius decreases across a period The atoms become smaller due to increasing number of protons and constant number of shielding electrons. Thus, the positively charged nucleus exert a greater force of attraction on the valence electrons, pulling these electrons in towards the nucleus, so that the atoms decreases in size from left to right across the period. Trends for Melting and Boiling Points 1. Melting and boiling points are affected by force of attraction between particles in substance (bond strength). 2. Melting and boiling points decrease down a group (Metals) For metals with larger atoms, delocalized free electrons are further away from positive nuclei, hence the force of attraction between them decreases. Therefore, it is easier to break the electrostatic forces, resulting in a lower melting and boiling point. 3. Melting and boiling point increases down a group (Non-Metals) For non-metals with larger molecules, there is a larger surface for interaction, hence the intermolecular forces of attraction increases. Therefore, it is harder to break the intermolecular forces of attraction, resulting in a higher melting and boiling point.

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Group I Elements (Alkali Metals)

Physical Properties 1. Shiny, silvery, soft metals that are easily cut by razor blades 2. Must be stored in oil as they are easily tarnished in air Chemical Properties 1. Uses their outermost s-orbital electrons for bonding 2. Low density (Li, Na, K float on water) 3. Density increases down the group 4. Low melting and boiling points 5. Melting and boiling points decreases down the group 6. Colour of flame are Lithium – red; Sodium – yellow; Potassium – lilac; Rubidium – red; Cesium – blue Reactivity Reactivity increases down the group. The reactivity of alkali metals depends on its ability to lose its outershell electrons. Down the group, the atomic radii increases, and hence the number of shells increases down the group while the effective nuclear charge remains the same. Therefore, the force of attraction between the outershell electrons and the positive nuclei is less, and hence it is easier to remove the outershell electrons down the group. Chemical Reactions 1. Alkali Metal + Water  Alkali + Hydrogen Gas 2Li + 2H2O  2LiOH + H2

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Group VII Elements (Halogens) Physical Properties 1. Colours of elements get darker down the group 2. Poisonous

Chemical Properties 1. Exists as diatomic molecules (F2, Cl2, Br2, I2, At2) 2. Density increases down the group 3. Low melting point and boiling point 4. Melting and boiling points increases down the group 5. Halogens more soluble in organic solvents than water, and form distinctive coloured solutions Reactivity Reactivity decreases down the group. The reactivity of halogens depends on its ability to accept one electron to complete their outershell. Down the group, the atomic radii increases, and hence the number of shells increases down the group while the effective nuclear charge remains the same. Therefore, the force of attraction between the outershell electrons and the positive nuclei is less, and hence it is harder to attract electrons to complete its outershell

Chemical Reactions 1. Halogen + Alkali Metal  Metal Halide 2Na + Cl2  2NaCl 6. Halogen + Metal  Ionic Salt (Halogen as Oxidising Agent) Cl2 + 2Na  2NaCl 7. Halogen + Non-Metal  Covalent Molecule Cl2 + H  HCl 8. Halogen + Alkalis  Salt + Water

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Br2 + NaOH  NaBr +NaOBr + H2O 9. Halogen + Water  Acid 1 + Acid 2 Cl2 + H2O ⇌ HCl + HOCL 10. Halogen + Hydrogen  Hydrogen Halide (Gas) Cl2 + H2  2HCl 11. Displacement Reaction
(Redox Reactions) 2NaI + Cl2  2NaCl + I2 More reactive halogen will displace a less reactive halogen from a solution of its salt

Functions 1. Fluorine is used in toothpaste to prevent tooth decay. 2. Chlorine is used to sterilise water by killing bacteria. 3. Iodine is used as mild antiseptic solution.

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Group O Elements (Noble Gases) Physical Properties 1. Colourless gases at room temperature and pressure 2. Not flammable 3. Provides an inert environment

Chemical Properties 1. Monoatomic 2. Unreactive because of their noble gas electron configuration (Note: do not use the phrase “inert gas”) 3. Low melting point and boiling point 4. Melting and boiling points increases down the group 5. Density increases down the group Functions 1. Helium is used to fill balloons. 2. Neon is used in advertising signs and fluorescent lights. 3. Argon is used in bulbs and to provide an inert environment for steel welding.

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Group II Elements (Alkali Earth Metals) Physical and Chemical Properties 1. Denser and harder than Alkali Metals 2. Higher melting point than the alkali metal in the same period 3. Reactive, but not as reactive as Alkali Metals

Transition Metals Physical and Chemical Properties 1. Located in the central block of the Periodic Table (Sc to Zn form the first row). Uses d-orbital electrons for bonding. 2. Hard, tough, strong, malleable, and ductile 3. Good conductors of heat and electricity 4. High density 5. High melting and boiling point (except mercury) 6. Not very reactive 7. Formed coloured compounds and ions in solution (except zinc, which is colourless) 8. Variable oxidation states, hence they are good catalysts in biological and industrial reactions (due to their ability to be oxidised and reduced easily)

Functions 1. Vanadium (V) oxide is used as a catalyst in the Contact Process. 2. Iron is used as a catalyst in the Haber Process. 3. Nickel is used as a catalyst in the manufacture of margarine from vegetable oils.

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Qualitative Analysis

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Physical Tests to Identify Substances

pH pH test is used to determine the acidity and alkalinity of a substance. However, the pH test cannot be used to identify an unknown substance without other tests.

Colour Most substances can be identified by their distinctive colour. Colour White Blue Green Dirty Green Pale Green Orange Yellow Pale Yellow Greenish Yellow Purple Colourless Black Reddish Brown Compound Most Na+, K+, Ca2+, Zn2+, Al3+, Pb2+, NH4+ Compounds All Cu2+ Compounds except CuO, CuCl2, CuCO3 All Ni2+ Compounds, All Cr3+ Compounds, CuCO3, CuCl2 Fe(OH)2 All Fe2+ Compounds, FeSO4 K2Cr2O7, Pb3O4 PbI2, ZnO (yellow when hot, white when cooled) AgI Cl2 gas KMnO4 Most gases (e.g. O2, CO2) CuO, C, MnO2, I2, Metal powder like Fe filings Fe(OH)3, Cu (reddish brown/pink/brown) Liquid Cu2+ (aq) Compounds I2 (aq), Br2 (aq) K2Cr2O7 (aq) FeCl3 (aq) KMnO4 (aq) Co(NO3)2 (aq) I2 dissolved in organic solvent

Colour Blue Brown/Reddish Brown Orange Yellow/Brown Purple Pale Red Violet

Smell Most gases are odourless. For example, oxygen, hydrogen and carbon dioxide are odourless.

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Other gases have very distinguishing smell. For example, ammonia gas has a pungent smell, sulfur dioxide smells of burnt matches and chlorine gas has a choking odour.

Solubility in Water The solubility test is very useful If an unknown substance is soluble in water, it may be sodium chloride but it cannot be silver chloride or barium sulfate as they are insoluble.

Flame Test Oxygen relights a glowing splint. Carbon dioxide extinguishes a burning split. Hydrogen extinguishes a burning splint with a ‘pop’ sound.

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Identification of Cations 1. Cations are positively charged ions, which are usually derived from metals. 2. Cations react and form precipitates with alkalis. 3. From the colour of the precipitate (insoluble metal hydroxides) and whether the precipitate is soluble in excess alkali, the cations can be identified. 4. Cations are identified using two types of test reagents a. Aqueous sodium hydroxide b. Aqueous ammonia Testing Using Aqueous Sodium Hydroxide (NaOH) Sodium hydroxide dissociates into sodium ions and hydroxide ions in water. NaOH (aq)  Na+ (aq) + OH- (aq) 1. Add a few drops of NaOH (aq) to the sample salt solution. 2. Observe for any changes (formation of precipitates, effervescence) 3. Add NaOH (aq) in excess until no further change is observed (dissolution of precipitate) Cation Ca2+ Pb2+ Al3+ Zn2+ Cu2+ Fe2+ Fe3+ NH4+ Precipitate formed White, Ca(OH)2 White, Pb(OH)2 White, Al(OH)3 White, Zn(OH)2 Blue, Cu(OH)2 Dirty Green, Fe(OH)2 Reddish Brown, Fe(OH)3 No Precipitate Solubility in Excess Insoluble Dissolves, Colourless Solution Dissolves, Colourless Solution Dissolves, Colourless Solution Insoluble Insoluble Insoluble -

Lead hydroxide, zinc hydroxide and aluminum hydroxide are amphoteric hydroxides. They react with excess sodium hydroxide to form complex salts that are soluble in water. Lead(II) ions can be distinguished from aluminum(III) ions by the addition of chlorine ions. Lead(II) chloride is insoluble while aluminum(III) chloride is soluble. Lead(II) ions can be distinguished from aluminum(III) ions by the addition of aqueous potassium iodide. Pb2+ ions form bright yellow lead(II) iodide, while Al3+ has no visible reaction.

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The green precipitate of iron(II) hydroxide turns brown in contact with air due to the slow oxidation of Fe2+ to Fe3+ by oxygen. This is a possible source of error during qualitative analysis. To test for ammonium, NH4+, warm the mixture. Pungent ammonia gas should evolve and it will turn damp red litmus paper blue. Ammonium does not need the aqueous ammonia test.

Testing Using Aqueous Ammonia (NH3) Ammonia dissociates partially to form ammonium and hydroxide ions in water. NH3 (g) + H2O (l)  NH4+ (aq) + OH- (aq) 1. Add a few drops of NH4OH (aq) to the sample salt solution. 2. Observe for any changes (formation of precipitates, effervescence) 3. Add NH4OH (aq) in excess until no further change is observed (dissolution of the precipitate) Cation Ca2+ Pb2+ Al3+ Zn2+ Cu2+ Fe2+ Fe3+ NH4+ Precipitate formed No Precipitate White, Pb(OH)2 White, Al(OH)3 White, Zn(OH)2 Light Blue, Cu(OH)2 Green, Fe(OH)2 Reddish Brown, Fe(OH)3 No reaction Solubility in Excess Insoluble Insoluble Dissolves, Colourless Solution Dissolves, Deep Blue Solution Insoluble Insoluble No Reaction

Only zinc hydroxide and copper(II) hydroxide dissolve in excess aqueous ammonia because they form soluble complex ions in excess aqueous ammonia. Aqueous ammonia is a weak base and does not have enough OH- ions to form the Ca(OH)2 precipitate.

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Identification of Anions 1. Anions are negatively charged ions, which are usually derived from nonmetals. 2. The tests used to identify anions are specific and yield distinct results for different anions. 3. Anions are usually identified using four types of test reagents. a. Aqueous silver nitrate/nitric acid b. Aqueous barium nitrate/nitric acid c. Aqueous lead(II) nitrate/nitric acid d. Aqueous sodium hydroxide/aluminum foil Observations of Anion Tests Anion CO32ClISO42NO3Test Add dilute hydrochloric acid. Add dilute nitric acid, followed by aqueous silver nitrate. Add dilute nitric acid, followed by aqueous lead(II) nitrate. Add dilute nitric acid, followed by aqueous barium nitrate. Add aqueous sodium hydroxide, followed by a small amount of aluminum powder or Devarda’s alloy. Warm the mixture. Observation Carbon dioxide gas is produced. The gas forms a white precipitate with limewater. White precipitate AgCl is formed. Yellow precipitate PbI2 is formed White precipitate BaSO4 is formed. Pungent ammonia gas is produced. The gas turns damp red litmus paper blue.

NO3- cannot be used in above tests, since the reagents are nitrates.

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Identification of Gases

Identification Test for Gases using Colour and Odour Gas H2 O2 CO2 NH3 SO2 Cl2 I2 HCl NO2 Colour Colourless Colourless Colourless Colourless Colourless Greenish Yellow Violet Colourless Brown Odour Odourless Odourless Odourless Pungent Smell of Burnt Matches Choking Odourless Choking Pungent

Identification Test for Gas using Specific Chemical Tests Gas NH3 CO2 Cl2 H2 O2 SO2 HCl Observation Gas turns damp red litmus paper blue Gas forms a white precipitate when bubbled in limewater Gas turns damp blue litmus paper red, then bleaches Gas extinguishes lighted splint with a ‘pop’ sound Gas relights a glowing splint Reacts with acidified potassium dichromate (VI) to turn orange K2Cr2O7 to green Gas turns damp blue litmus paper red; Reacts with NH3 to produce dense white fumes

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Types Of Reactions 1. Precipitation Reaction (forming a solid) 2NaOH (aq) + ZnCl2 (aq)  Zn(OH)2 (s) + 2NaCl (aq) 2. Acid-Base Reaction H2SO4 (aq) + 2NaOH (aq)  Na2SO4 (aq) + 2H2O (l) 3. Redox Reaction Metal + Non-Metal: 2Na + Cl2  2NaCl Combustion: C + O2  CO2 Displacement: Cl2 + 2KI  2KCl + I2 Others: 2FeCl2 + Cl2  2FeCl3 4. Decomposition CuCO3  CuO + CO3 5. Complex Formation Zn(OH)2 (s) + 2NaOH (aq)  Na2Zn(OH)4 (aq) Zn(OH)2 dissolves in NaOH to form an aqueous complex salt (sodium zincate).

How to know if two aqueous compounds will react? If you switch the ions around and a gas/pure liquid/solid would form, there is a driving force for reaction. Hence, it will react.

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Reactivity Series of Metals and their Extraction

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Reactivity Series of Metals

Reactivity Series of Metals

Please Stop Calling Me A Zombie I Love Hot Cute Sexy Girls PSCMAZILHCSG Interpreting the Reactivity Series The higher a metal in the series, the more reactive it is. The more reactive 1. The greater the tendency it has to form a positive ion 2. The more difficult it is to be extracted 3. The more susceptible it is to react with oxygen and water

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Displacement Reactions Relating to the Reactivity Series

A metal higher in the series can displace any metal below it. Thus, a more reactive metal can be used to extract a less reactive metal from its salts.

Reaction of a more reactive metal with aqueous salt solution of a less reactive metal A salt of the more reactive metal will be formed. The less reactive metal will be precipitated. e.g. Mg (s) + CuSO4 (aq)  MgSO4 (aq) + Cu (s) The more reactive magnesium displaces the less reactive copper.

Reaction of a more reactive metal with a less reactive metal oxide An oxide of the more reactive metal will be formed. The less reactive metal will be precipitated. e.g. Zn (s) + CuO (s)  ZnO (s) + Cu (s) The more reactive zinc displaces the less reactive copper.

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Determining the Reactivity of a Metal The reactivity series of metals can be established by studying their reactions with oxygen, water or acids.

Reaction with Oxygen Most metals react with oxygen to form metal oxides. e.g. 2Mg (s) + O2 (g)  2MgO (s) K to Mg reacts rapidly with oxygen. Al to Cu reacts slowly with oxygen. Ag to Pt does not react at all with oxygen.

Reaction with Water Most metals react with cold water or steam to form either hydroxides or oxides and hydrogen. For K to Ca, the reaction occurs violently with water. Metal + Cold Water  Metal Hydroxide + Hydrogen Gas e.g. 2Na (s) + 2H2O (l)  2NaOH (aq) + H2 (g) For Mg to Fe, the reaction is much slower with water. Metal + Steam  Metal Oxide + Hydrogen Gas e.g. Zn (s) + H2O (g)  ZnO (s) + H2 (g) For Sn to Pt, the reaction does not occur at all with water.

Reaction with Dilute Acids Most metals react with dilute acids (sulfuric acid and hydrochloric acid) to produce salt and hydrogen gas. K to Ca reacts violently with dilute acids. e.g. 2Na (s) + 2HCl (aq)  2NaCl (aq) + H2 (g) Mg to Pb reacts slowly with dilute acids. e.g. Pb (s) + H2SO4 (aq)  PbSO4 (s) + H2 (g) Cu to Pt does not react with dilute acids because they are less reactive than H+ ions.

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Thermal Decomposition of Metal Carbonates

The more reactive a metal, the higher the temperature need for the decomposition of its carbonates.

Thermal Decomposition For K and Na carbonates, they are unaffected (heat stable). For Ca to Cu carbonates, they decompose to form metal oxide and carbon dioxide. Ag2CO3 decomposes readily to form silver, carbon dioxide and oxygen.

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Alloys

Pure metals are soft and malleable because the metal atoms are arranged in neat and regular rows, which slide across one another easily when force is applied. An alloy is a mixture of two or more metals (or carbon). It is made by melting components together and solidifying the mixture. The components must be soluble in one another when molten and should not separate into distinct layers when solid. Alloying makes a metal harder and stronger because the regular rows of atoms are disrupted by other atoms of different sizes, so atoms cannot slide across one another easily.

Steel Steel (alloy of iron) is the most important allow. Its properties are dependent on its carbon content, the presence of other metals and heat treatment (tempering). Possible additives 1. Carbon (as carbon content increases, hardness and brittleness increases) 2. Cobalt (highly magnetic steel for permanent magnets) 3. Tungsten (high-speed steel, stays very hard at high temperatures) 4. Manganese (hard and tough steels, used in rock drills) 5. Silicon (spring steels) 6. Molybdenum (Resist acid corrosion) Mild Steel 1. 99.0% - 99.5% Fe 2. 0.15% - 0.25% C 3. Harder and stronger than iron, more malleable and ductile, withstands great stress and strain 4. Used for construction for car bodies, machinery, steel rods to reinforce concrete Stainless Steel 1. 90.0% - 95.0% Fe 2. 5.0% - 10.0% Cr and Ni 3. Variable C 4. Hard, resistant to corrosion, attractive in appearance 5. Used for cutlery, surgical instruments, chemical plants

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Corrosion and Rusting

Corrosion of Metals When a metal reacts, its atoms become ions, and the metal eventually disappears to form another compound. Corrosion is the gradual destruction of the metal due to reaction with air, water or other chemicals. Formation of oxides on the surface of the metal can be advantageous and disadvantageous. Aluminum 1. Thin, non-porous layer, adheres to metal, prevents corrosion by oxygen and water 2. Can be protected further by anodizing (making oxide layer thicker), an electrolysis process 3. During anodizing, dyes can be introduced, which are absorbed onto the oxide layer. 4. Similar to magnesium Other Metals (e.g. sodium) 1. Oxide layer is porous, so oxygen and water continue to penetrate, attack and corrode the metal underneath 2. Oxide layer tends to fall off, exposing fresh metal surface to air 3. To prevent this, sodium is stored under oil

Rusting Rusting is the corrosion of iron. It needs both air and water to occur. When iron is in contact with water containing dissolved oxygen, redox reactions take place. 1. Fe (s)  Fe2+ (aq) + 2eElectrons transferred to oxygen and water molecules to form hydroxide ions. 2. O2 (g) + 2H2O (l) + 4e-  4OH- (aq) In the presence of oxygen, further oxidation occurs. Iron(II) ions oxidizes to Iron(III) ions. 3. 4Fe2+ (aq) + 4H+ (aq) + O2 (aq)  4Fe3+ + 2H2O (l) Iron(III) ions react with OH- to form Iron(III) hydroxide, which is a form of rust. Fe(OH)3 eventually changes to hydrated Fe2O3 . nH2O, which is a form of rust

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Conditions Speeding Up Rusting 1. Air from sea and polluted air (e.g. containing dissolved SO2) tend to speed up rusting. This is because water contains other dissolved ionic substances, e.g. NaCl (aq), and dilutes acids. This provides mobile ions, which speed up rusting. 2. When iron is in contact with another substance that is less reactive than it, it speeds up rusting. This is because Fe loses electrons to other metals, so oxidation occurs more quickly.

Prevention of rusting To prevent rusting, a protective layer is applied to the substance. Examples include paint, oil, grease, tin plating, chromium plating (i.e. covering with a thin layer of less reactive metal). The disadvantages are that when oil/grease is rubbed off or paint/plating is scratched, the exposed iron begins to rust and eventually the whole piece of iron rusts.

Sacrificial Corrosion Sacrificial corrosion is when iron is connected to a more reactive metal so that the other metal corrodes preferentially. In presence of oxygen and water, the other metal forms ions more easily, so the iron atoms remain. As long as some part of the other metal is in contact with iron, it gives protection, since both are conductors and movement of electrons occur easily. Examples include 1. Galvanizing (galvanized iron is iron covered with a thin layer of zinc) 2. Iron pipes connected to blocks of magnesium 3. Blocks of magnesium/zinc attached to sides of ships

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Extraction of Metals

Extraction Process 1. Most metals are found in the ground as compounds known as minerals (e.g. bauxite, which is aluminum oxide). These minerals are mostly impure. 2. Ores that are rich in a mineral will take the name of the mineral (e.g. aluminum ore rich in aluminum oxide is known as aluminum oxide/bauxite) 3. Minerals must first be separated from other worthless compounds in the ore, usually by physical methods. 4. The pure metal is then extracted from the mineral. Less reactive metals extracted by chemical reactions, usually by heating the metal oxides with coke, which is a form of carbon, obtained from coal. 5. More reactive metals from stable compounds with strong bonds, and the extraction requires a lot of energy. Hence, electrolysis is used to extract them.

Extraction of Metals in Reactivity Series For K to Al, extraction by electrolysis. For C to Pb, extraction by carbon reduction. For H to Pt, extracted by reduction in hydrogen gas.

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Extraction of Iron

Iron is extracted from iron ore called iron(III) oxide, known as haematite, in a blast furnace.

Purpose of coke (C) is to produce carbon monoxide (CO), the reducing agent, which reduces Fe2O3 to Fe C + O2  CO2 C + CO2  2CO Fe2O3 + 3CO  2Fe + 3CO2

Purpose of limestone (CaCO3) is to produce lime (CaO), which removes acidic impurities (e.g. sand) CaCO3  CaO + CO2 CaO + SiO2  CaSiO3 (slag)

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Purpose of heat is to combust coke into carbon dioxide, to melt iron and slag and ensure they separate at the bottom, to decompose limestone and to facilitate all reactions, which occur faster with more heat.

Input at the bottom – Hot air to supply oxygen Input at the top – Haematite, Coke, Limestone Output at the top – Hot air to remove waste gases, which are mainly nitrogen and carbon dioxide (nitrogen from hot air; does not react in furnace). Output at bottom – Molten iron, which solidifies as pig iron (contains up to 5% of carbon and is brittle, with little industrial uses) Output at bottom – Slag (CaSiO3), which floats on top of molten iron, and is used for road construction.

Iron Pig iron can be re-melted with scrap iron, and then cooled in molds of required shapes to form cast iron. It is brittle, and cannot be welded or forged. It is used for making objects that do not require high tensile strength (e.g. stoves, lamp posts) Wrought iron is obtained by heating cast iron with haematite. It is the purest commercial form of iron, with only 0.1% carbon. It is soft but tough, and malleable. 90% of pig iron produced is converted into steel. The impurities are removed by oxidation with oxygen. Following that, quantities of carbon and other metals are added to the pure molten iron to obtain the desired composition.

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Recycling of Metals

Metal ores are a finite resource, and needs to be recycled.

Economic Advantages 1. Metals are profitable to recycle and companies pay people and business for used metals. This money often goes to charity. 2. It is cheaper to recycle than to go through the entire process of mining and refining.

Environmental Advantages 1. Preserves natural supply of ore 2. Process of recycling creates much less pollutants and greenhouse gases than mining 3. Discarded metals, after incineration, produces methane and carbon dioxide 4. Reduces scrap metal land fill areas

Social Advantages 1. Money earned from recycled metal often goes to charity

Disadvantages 1. Collection and sorting of domestic materials to be recycled can be expensive, time-consuming and requires energy 2. People steal metal from each other to recycle and get money.

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Electrolysis

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Electrolysis Electrolysis is the conduction of electricity by an ionic compound (electrolyte), when molten or dissolved in water, leading to decomposition of the electrolyte. This is different from electrochemical cells, whereby the current is generated by a chemical change. Electrolysis uses current to bring about chemical change. Electrolytic apparatus includes two electrodes immersed in an electrolyte, along with a connection to a battery.

Electrolyte Electrolyte is a compound which is molten or in a solution, and conducts electricity by movement of ions to electrodes. A strong electrolyte can conduct large currents, due to high percentage of ionization. A weak electrolyte does not ionize completely, so it does not readily conduct electricity. This is different from a metal conductor, which conducts electricity in a solid or liquid state, due to the movement of electrons from atom to atom.

Electrodes Electrodes are conductors by which an electric current leaves or enters the electrolyte. A cathode is a negative electrode. It is connected to the negative terminal of the battery. A reduction occurs here as the cations gain electrons and the electrons enter the electrolyte. In general, metals or hydrogen gas are produced here. An anode is a positive electrode. It is connected to the positive terminal of the battery. An oxidation occurs here as the anions lose electrons and the electrons leave the electrolyte. In general, non-metals (except hydrogen) are produced here. RED CAT = Reduction at Cathode AN OX = Oxidation at Anode

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(Example) Electrolysis of Molten Lead(II) Bromide (PbBr2)

When the battery is connected, electrons are pumped from anode to cathode. Pb2+ ions migrate to cathode to undergo reduction. Metallic lead (Pb) is produced. Pb2+ + 2e-  Pb Br- ions migrate to anode to undergo oxidation. Bromide molecules (Br2) are produced. 2Br-  Br2 + 2eDue to the high temperature, Br2 escapes as gas.

Overall chemical equation PbBr2 (l)  Pb (l) + Br2 (g)

Ionic Equation Pb2+ (l) + 2Br- (l)  Pb (l) + Br2 (g)

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Electrolysis of Aqueous Electrolyte

Factors affecting order of ease of discharge of ions via electrolysis 1. When electrolyte is an aqueous state, there are more than two types of ions present. Water also ionizes to give H+ and OH-. The presence of additional ions (H+ and OH-) in the aqueous solution affected the potential release of the ions of the electrolyte. Hence, they compete with cation and anion to be discharge.

Factors affecting the order in which ions are selectively discharged 1. Relative position of the ion in the reactivity series 2. Concentration of ions in the electrolyte 3. Nature of the electrodes used

Things to Note 1. Alternating currents (a.c.) cannot be used instead of direct current (d.c.), as electrodes would keep changing in polarity. Hence, there will be no fixed cathode and anode, and the ions would not migrate. Therefore, there will be no discharge. 2. Electrolysis of NaCl (aq) tends to produce Cl2 at anode; O2 is produced when NaCl concentration is low. 3. Production of O2 4OH-  O2 + 4eOxygen is more soluble in water than hydrogen.

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Relative position of the ion in the reactivity series

Ease of positive ion in gaining or ease of negative ion in losing electron (electrochemical series) Electrochemical series is opposite from the reactivity series. Less reactive ions will be charged first.

For example, when H+ and Na+ are present, we say that H+ ions are gain electrons more readily than Na+ ions, so H+ is preferentially discharged. This is the primary factor determining preferential discharge.

Example Electrolysis of dilute sodium chloride sodium, NaCl (aq), that contains Na+, H+, Cland OH- ions (inert electrodes used). Cathode: 2H+ (aq) + 2e-  H2 (g) H+ is less reactive than Na+. Therefore, H+ ions will be preferentially discharged. Anode: 4OH- (aq)  2H2O (l) + O2 (g) + 4eOH- is less reactive than Cl-. Therefore, OH- ions will be preferentially discharged.

NaCl (aq) does not participate in this electrolysis process. It aids in the decomposition of water.

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Concentration of ions in the electrolyte The more concentrated ions will be discharged first. The influence of concentration is only effective when rival ions are closely positioned in series.

Example Electrolysis of concentrated sodium chloride sodium, NaCl (aq), that contains Na+, H+, Cl- and OH- ions (inert electrodes used). Cathode: 2H+ (aq) + 2e-  H2 (g) H+ is less reactive than Na+. Therefore, H+ ions will be preferentially discharged. Anode: 2Cl- (aq)  Cl2 (g) + 2eAlthough OH- is less reactive than Cl-, Cl- ions are preferentially discharged because of their high concentration.

Na+ ions are not selectively discharged because they are so reactive that increasing their concentration is not sufficient to reverse the order of discharge. On the other hand, the order of discharge can be reversed for Cl- ions because they are not very reactive.

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Nature of electrodes (inert or reactive)

Inert electrode materials such as graphite or platinum are non-reactive and are not affected by the ions surrounding them. However, the order of discharge can be affected when reactive electrodes such as copper or silver as used.

Example Electrolysis of aqueous copper(II) sulfate solution, CuSO4 (aq), that contains Cu2+, H+, SO42- and OH- ions using copper electrodes (reactive electrodes are used). Cathode: Cu2+ (aq) + 2e-  Cu (s) Cu2+ is less reactive than H+. Therefore, Cu2+ ions will be preferentially discharged. Anode: Cu (s)  Cu2+ (aq) + 2eOH- and SO42- are not discharged because the Cu atoms lose electrons more readily than OH- and SO42-. As a result, the copper anode oxidizes itself to form Cu2+ ions.

The copper anode loses mass while the cathode gains mass. There is no change in the colour of the electrolyte solution (blue). Note: If aqueous copper(II) sulfate is electrolyzed using carbon electrodes (inert), the electrolyte will turn lighter blue and more acidic.

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Summary of Electrolysis Reactions Electrolyte Molten PbBr2 (l) H2O (l) (a few drops of H2SO4 (aq) can be added to increase conductivity) Dilute H2SO4 (aq) Conc. HCl (aq) Conc. NaCl (aq) Conc. NaCl (aq) CuSO4 (aq) Cathode Carbon Platinum Product at Cathode Pb (l), molten lead H2 (g), hydrogen gas Anode Carbon Platinum Product At Anode Br2 (g) O2 (g)

Platinum Carbon Carbon Mercury Carbon

H2 (g), hydrogen gas H2 (g), hydrogen gas H2 (g), hydrogen gas Na, metallic sodium* Cu, copper

Platinum Carbon Carbon Carbon Carbon

O2 (g) Cl2 (g) Cl2 (g) (conc. effect) Cl2 (g) (conc. effect) O2 (g) (may react with electrode to form CO2 at high temperatures) Anode dissolves (Cu atoms give up electrons more readily than SO42- or OH-) I2 (aq) (higher concentration) (conc effect)

CuSO4 (aq)

Copper

Cu, copper

Copper

KI (aq)

Carbon

H2 (g), hydrogen gas

Carbon

Electrolyte Molten PbBr2 (l) H2O (l) (a few drops of H2SO4 (aq) can be added to increase conductivity) Dilute H2SO4 (aq) Conc. HCl (aq) Conc. NaCl (aq) Conc. NaCl (aq) CuSO4 (aq) CuSO4 (aq) KI (aq)

Effect on Electrolyte -

Electrolyte becomes more acidic (conc. of acid increases) Electrolyte becomes more dilute Electrolyte becomes alkaline with NaOH (aq) Electrolyte becomes more dilute Electrolyte becomes acidic with H2SO4 (aq) Conc. of electrolyte remains unchanged. Electrolyte becomes alkaline with KOH (aq)

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*Metallic sodium immediately dissolves in mercury, as it tends to associate with sodium, so Na+ discharge requires less energy.

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Applications of Electrolysis (Purification/Refining of Metals)

Using Copper refining as an example For example, to refine a piece of impure copper (blister copper, 98% pure) Impure copper is made the anode; a piece of pure copper is used as the cathode. Electrolyte is CuSO4 (aq) or a solution of a copper salt. During electrolysis, copper atoms of anode lose electrons, as the electrodes are reactive, causing copper atoms to lose electrons more readily than SO42or OH-. Ions of copper migrate to cathode and form pure copper (copper is deposited at cathode). Anode: Cu (s)  Cu2+ (aq) + 2eCathode: Cu2+ (aq) + 2e-  Cu (s) Anode becomes smaller while cathode becomes bigger. Concentration of CuSO4 (aq) remains unchanged. Impurities are left on anode, and fall off to collect below anode. Often contain valuable silver/gold.

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Applications of Electrolysis (Electroplating) Electroplating is coating a metallic object with a thin layer of a metal by electrolysis. The purpose is to make the metal more attractive for a decorative finish, and for protection against corrosion. (e.g. copper plating, tin plating for food cans, silver and gold plating)

Using Silver coating as an example For example, coating a steel spoon with silver. Object is to be electroplated is made the cathode; metal used to plate is anode. Electrolyte must contain metal ions of the anode metal. During electrolysis, anode dissolves and ions migrate to cathode where they are discharged and deposited as a layer on the object. Electrolyte remains unchanged in concentration. Anode: Ag (s)  Ag+ (aq) + eCathode: Ag+ (aq) + e-  Ag (s)

Note Usually many articles are plated at once. Series of plating may be necessary. Chromium does not adhere well to steel. Steel is coated with copper for adhesion, then nickel for sacrificial protection against corrosion, then chromium. To electroplate a non-conducting metal, it is sprayed with metallic paint or coated with graphite powder.

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Applications of Electrolysis (Aluminum Manufacturing)

Aluminum is extracted from an ore called bauxite, which contains Al2O3, mixed with impurities like iron(II) oxide, Fe2O3, and SiO2, silica. Bauxite is purified to obtain pure aluminum oxide, also known as alumina, from which electrolysis produces pure aluminum. It is treated with sodium hydroxide to purify. Alumina has a high melting point of 2045 degrees Celsius. It is expensive and dangerous to carry out electrolysis at that temperature. Therefore, molten cryolite, Na2AlF6, sodium hexafluoroaluminate(III), is used as a ‘solvent’, mixed with the molten Al2O3 to reduce melting point. Cryolite’s melting point is 950 degrees Celsius.

Anode: 2O2- (e)  O2 (g) + 4eCathode: Al3+ (l) + 3e-  Al (l)

Problems 1. Expensive, requires a lot of electricity 2. Since temperature is high, oxygen gas attacks carbon anodes to form gaseous products, mainly carbon dioxide gas. Hence, the anodes are burned away and must be replaced regularly.

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Chemical Equilibria

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Chemical Equilibria

Reversible Reactions Some reactions can proceed two ways, forward and backward. For example, when ammonium chloride is heated, it decomposes to form ammonia gas and hydrogen chloride gas. When cooled, the gases combine to form ammonium chloride. NH4Cl (s) ⇋ NH3 (g) + HCl (g) Left to right arrow: Forward reaction. Right to left arrow: Backward reaction. This is called reversible reactions. Definition: A chemical reaction that results in an equilibrium mixture of reactants and products. These reactions tend not to go into completion. The mixture of reactants and products are obtained no matter how long the reaction carries on. Dynamic Equilibrium When concentration of reactants and products are constant, the mixture is at equilibrium. Chemical equilibrium is dynamic, and the reaction does not stop (i.e. the rate of forward reaction equals to the rate of backward reaction). It only exists in a closed system. The substances do not escape or enter a reaction container. The equilibrium state is independent of the direction from which it is approached (whether you start with only reactants or products, the end concentration of each will be the same).

Le Chatelier’s Principle If a chemical system at equilibrium undergoes changes in the conditions under which it has been established, then the chemical system responds by minimizing the effect of the changes. For example, if pressure is increased, the side of the reaction with less pressure will be favored.

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Note: A catalyst increase speed of both forward and backward reactions, hence it does not affect the yield of the product.

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Haber Process

The Haber Process is the process to manufacture ammonia. After collection of ammonia gas, the ammonia gas is condensed into liquid. N2 (g) + 3H2 ⇋ 2NH3 (g) Ammonia is used to make nitrogenous fertilizers, but it may cause water pollution. For example, ammonium nitrate reacts with alkalis to produce ammonia. The Haber Process is efficient because the products and catalysts are plentiful and cheap, there is no waste products and the heat from the reaction keeps the catalyst chamber hot. Iron is a catalyst for the Haber Process.

Reactants 1. Nitrogen gas from air 2. Hydrogen from cracking oil

Conditions 1. 200 atmospheres a. 4 moles of gas on the left side, 2 moles of gas on the right b. By Le Chatelier’s principle, if pressure increases, the system responds by speeding up the forward reaction such that pressure is reduced. Hence, more ammonia is produced. c. Conditions are not more than 200 atm because beyond 200 atm, the cost of increasing pressure exceeds the potential benefit from additional yield of ammonia 2. 450 degrees Celsius a. The reaction is exothermic ((∆H = -184 kJ/mol) b. Lower temperatures produces higher yield of ammonia c. However, low temperatures result in slower rates of reaction d. 450 degrees Celsius is the optimum temperature, with optimum yield at optimum speed

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Contact Process

The Contact Process is the process to manufacture sulfuric acid. Sulfuric acid is used to make fertilizers and detergents.

Reactants 1. Sulfur dioxide gas a. Burn sulfur in air S (s) + O2 (g)  SO2 (g) b. Heat sulfide ores in excess of air (must be purified to avoid catalyst poisoning; removal of catalyst catalytic properties) 2ZnS (s) + 3O2 (g)  2SO2 (g) + 2ZnO (s)

2. Oxygen gas (must be purified to avoid catalyst poisoning)

First Step Sulfuric dioxide gas is added to oxygen gas to form sulfur trioxide gas. 2SO2 (g) + O2 (g) ⇋ 2SO3 (g) Purpose of this step is to form sulfuric trioxide gas. Condition has to be that it is 450 degrees Celsius for the catalyst vanadium (V) oxide to be used. Platinum is a better catalyst but it is expensive and poisonous.

Second Step Sulfur trioxide gas is added to concentrated sulfuric acid to form oleum (disulfuric acid). SO3 (g) + H2SO4 (l)  H2S2O7 (l) Purpose of this step is to dissolve SO3. Water is not used, as the reaction would be highly exothermic, producing acidic vapor or mists.

Third Step Oleum is reacted with water to produce sulfuric acid. www.noteacademy.wordpress.com

H2S2O7 (l) + H2O (l)  2H2SO4 (l)

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Organic Chemistry

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Fossil Fuels

Natural gas (mostly methane), coal, petroleum are sources of energy. There is a limited supply – petroleum and natural gas may only last for 50 more years, and coal only 250 more years. Combustion in excess of these fossil fuels will produce water and carbon dioxide gas, which are pollutants, and heat, which contributes to global warming. If there is insufficient air provided during combustion, carbon monoxide, which is a poisonous gas, and soot are produced.

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Petroleum

Petroleum is the mixture of hydrocarbons, which are molecules that are made of only carbon and hydrogen. Petroleum is in the liquid form because they are more viscous (flow less easily). Liquids burn less easily and with a smoky flame.

Fractional Distillation The mixture of hydrocarbons must first be refined to make useful fuels and chemicals. The first step is fractional distillation. All fractions are insoluble in water and burn in air. As the boiling point increases, the molecules get bigger (more carbon atoms).

Types of hydrocarbons Name Uses Boiling Point (degrees Celsius) below 25 35-75 70-170 170-250 250-340 340-500 above 500 Carbon atoms per molecule 1-4 5-10 8-12 10-14 15-25 19-35 above 70

Petroleum gas Petrol Naphtha Kerosene Diesel Oil Lubricating Oils Bitumen

Fuel for cooking Fuel for motor vehicles Feedstock for chemical industry Fuel for jet aircraft and oil stoves Fuel for diesel engines Lubricants and polishes Making road surfaces

Competition for Oil Most petroleum is used to make fuel for burning, while some is used to make substances like plastics and chemicals. Since the supply of petroleum is limited, many believe that it is wasteful to burn it as a fuel, and say that it should be reserved for making chemicals. If not, there will be a shortage of chemicals and it may not be possible to produce plastics, drugs etc.

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Cracking Cracking is the breaking of large hydrocarbon molecules into smaller molecules. It is important, as heavy fractions from fractional distillations are less in demand than lighter fractions. (e.g. lubricating oil can be converted into petrol to meet demand) Upon cracking, products always contain an alkene, may contain hydrogen, carbon and other alkanes. After cracking, the mixture of products is separated by fractional distillation.

Types of Cracking 1. Thermal cracking is when alkanes are heated to 800-850 degrees Celsius under high pressure. 2. Catalytic cracking is when alkanes are passed over catalysts alumina (aluminum trioxide) and silica (silicon dioxide) at 300 degrees Celsius.

Applications of Cracking 1. Changing heavy fractions to lighter fractions to meet demand 2. Changing naphtha into alkenes 3. Making hydrogen gas.

Chemical Conversion Changing hydrocarbons from petroleum or from cracking into useful chemicals like detergents, plastics, alcohols and drugs.

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Organic Chemistry

Organic Chemistry is the study of chemistry of carbon compounds.

Properties of Carbon Compounds (in general) 1. Can contain O (common), H, N, halogens, P, S, some metals 2. Covalent 3. Non-polar (do not ionize in solution) 4. Insoluble in water, except molecules which contain polar group (molecules like glucose and ethanol) 5. Mix well with non-polar solvents (tetrachloromethane) 6. Lower melting point and boiling point than inorganic compounds 7. Thermally unstable and decompose into smaller/simpler molecules when heated 8. Inflammable and burn exothermically in excess air to form carbon dioxide and water 9. Reactions involving organic compounds are slower; Need heating, mixing and catalysts 10. Carbon atoms can form 4 single covalent bonds in a tetrahedral arrangement 11. When burnt in insufficient air, it forms carbon mononxide and carbon (soot) due to incomplete combustion

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Writing Carbon Compounds

Homologous Series A group of compounds, which have a regular structural pattern according to a general formula (e.g. CnH2n) Have similar physical and chemical properties, with gradual changes as size and mass of molecules increases.

Nomenclature Names of organic compounds have roots, suffixes and as many prefixes as necessary. Roots (derived from longest unbranched carbon chain) 1. 1 carbon: meth2. 2 carbons: eth3. 3 carbons: prop4. 4 carbons: but5. 5 carbons: pent6. (The following are: hex-, hept-, oct-, non-, dec-) Suffixes 1. Alkanes: -ane 2. Alkenes: -ene 3. Alcohol: -ol 4. Carboxoylic acid: -anoic acid Prefixes (Alkyl/Alkane Groups) 1. Replace hydrogens 2. Named after parent alkane 3. Methyl (CH3), Ethyl (C2H5), Propyl (C3H7), Bulyl (C4H9) 4. If more than one prefix is needed, place in alphabetical order 5. When more than one of the same subtituent group is present, add di-, tri-, tetra6. Others; bromo, chloro etc. Prefixes (Positions/Numbers) 1. Number all carbons in longest chain, starting from carbon nearest to main functional or substituent group Prefixes (Alkene Double Bonds) 1. Position double bond indicated as a number before the –ene

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Functional Group Atom, radial (group of atoms) or bond common to a homologous series. Determines main chemical properties of series.

Formulas General formula shows the common patterns (e.g. CnH2n) Empirical formula shows the simplest ratio of the compound. It indicates the relative numbers of each kind of atom. Molecular formula shows the actual numbers of each kind of atom. Structural formula indicates how the atoms are arranged. It does not necessarily imply a flat molecule.

Saturation A saturated organic compound contains atoms joined by a single covalent bond. An unsaturated organic compound contains atoms joined by double or triple bonds.

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Alkanes

Properties of Alkanes 1. Saturated hydrocarbons 2. Main constituent of petroleum 3. General formula: CnH2n+2 4. Gases or liquids at room temperature a. Methane, ethane, propane, butane are all gases at r.t.p. 5. Chemically inert, except for a few reactions, mainly combustion and substitution with chlorine

Combustion In excess of oxygen, carbon dioxide and water is produced. CH4 + 2O2  CO2 + H2O In limited oxygen, carbon monoxide and water is produced. 2CH4 + 3O2  2CO + 4H2O

Substitution with Chlorine In sunlight (UV is a catalyst) Mixture of products (each hydrogen atom can be replaced)

Methane + Chlorine  Chloromethane + Hydrochloric Acid

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Alkenes

Properties of Alkenes 1. Unsaturated hydrocarbons, one carbon-carbon double bond 2. General formula: CnH2n (for those with one C=C double bond) 3. Gases and liquids (mostly liquids) at r.t.p. a. Ethene (ethylene, propene, butane are all gases at r.t.p. 4. More reactive than alkanes due to C=C double bond 5. Reactions include addition of hydrogen, water, bromine and potassium manganate (VII), combustion

Addition of hydrogen (hydrogenation) Nickel is a catalyst. Produces alkanes (for those with one C=C)

(Hydrogenation of Ethene) Ethene + Hydrogen  Ethane Hydrogenation is important in making margarine. Vegetable oil is polyunsaturated (many C=C bonds), so vegetable oil is in the liquid state. Hydrogenation creates a more ‘solid’ substance.

Addition of water (hydration) High temperature (300 degrees Celsius, water is steam) High pressure (60 atmospheres) Phosphoric acid is a catalyst.

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(Hydration of Ethylene) Ethylene + Water  Ethanol

Addition of bromine Test for unsaturation (test for alkene). When liquid bromine is shaken with an alkene, brown colour of bromine is decolourised.

Addition of potassium manganate (VII) Acidified KMnO4 is decolourised (purple to colourless) by an alkene.

Polymerization Small alkenes can link together (polymerize) to form a long chain. Ethene  Polyethene

Combustion In excess of oxygen, carbon dioxide and water is produced. In limited oxygen, carbon monoxide and water is produced. For complete combustion using a Bunsen burner, the air hole has to be open and there should be a non-luminous flame. The luminous flame is due to incomplete combustion (the presence of soot causes a orange/yellow flame). Lower percentage mass of carbon is better for burning. For example, ethane (86% C) burns with a yellower and sootier flame than ethane (80% C).

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Alcohols

Properties of Alcohols 1. Contain hydroxyl (OH) group. Suffix: -ol a. 2 OH groups: -diol; 3 OH groups: -triol 2. General formula: CnH2n+1OH 3. All alcohols are colorless liquids at r.t.p. 4. Methanol, ethanol, propanol, butanol are soluble in water 5. Uses of ethanol a. Solvent b. Alcoholic drinks c. Fuel for some motor vehicles 6. Reactions include combustion, dehydration, oxidation, esterification

Combustion In excess of oxygen, carbon dioxide and water is produced. C2H5OH + 3O2  3H2O + 2CO2 In limited oxygen, carbon monoxide and water is produced.

Dehydration Heating With concentration H2SO4 (dehydrating agent)

(Dehydration of Ethanol) Ethanol + Sulfuric Acid  Ethylene + Water

Oxidation

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By oxidizing agents (e.g. acidified K2Cr2O7 or O2 in air) Beer or where left exposed to air becomes sour due to formation of ethanoic/acetic acid. Forms carboxylic acid. C2H5OH + 2[O]  H2O + CH3COOH (Oxidation of Ethanol) Ethanol + Oxygen  Water + Ethanoic Acid [O] represents oxygen from oxidizing agent.

Esterification React with carboxylic acids to form ester and water.

Preparation of Ethanol (from ethane) C2H4 + H2O  C2H5OH Ethane + Water  Ethanol Phosphoric acid is a catalyst. Conditions are 300 degrees Celsius and 60 atmospheres. Mixture of steam and ethane are passed over the catalyst.

Preparation of Ethanol (by fermentation) C6H12O6  2C2H5OH + CO2 Glucose  Ethanol + Carbon Dioxide Catalytic conversion of glucose into ethanol by enzyme zymase in yeast. It occurs in an anaerobic environment.

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Carboxylic Acids

Properties of Carboxylic Acids 1. Contain carboxyl (COOH) group. Suffix: -anoic acid. a. 2 COOH group: -dioic acid 2. General formula: CnH2n+1COOH (n ≥ O) a. Methanoic acid (HCOOH), ethanoic/acetic acid, propanoic acid, butanoic acid b. Vinegar is a solution of ethanoic acid in water 3. All carboxylic acids are liquid at r.t.p. 4. All carboxylic acids do not dissociate completely in water because they are weak acids 5. Uses of ethanoic acid a. Manufacture esters, which are used as solvents b. Manufacture insecticides, drugs 6. Reactions include acid reactions, esterification Acidic Properties (CH3COO- ‘ion’) 1. Carboxylic Acid + Base  Salt + Water 2. Carboxylic Acid + Some Metals  Salt + Hydrogen 3. Carboxylic Acid + Carbonate  Carbon Dioxide + Salt + Water

Esterification Ester is a colourless liquid with a sweet smell. It is used as solvents, for flavouring and for perfume. Carboxylic Acid + Alcohol ⇋ Ester + Water (Backward reaction is hydrolysis) Concentrated hydrochloric acid is a catalyst. Heating Naming of esters 1. First word: from alcohol -yl 2. Second word: from acid –oate 3. e.g. Methanoic acid + Butanol  Butyl Methanoate + Water www.noteacademy.wordpress.com

Preparation of Ethanoic Acid (from ethanol) Ethanol is oxidized by air or acidified potassium dichromate (VI)

Preparation of Ethanoic Acid (from methane) Methane is used to manufacture methanol and carbon monoxide. These two products are reacted together in the presence of a catalyst to form ethanoic acid.

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Redox Reactions in Organic Chemistry

Oxidation Gain of oxygen atom Loss of hydrogen atom

Reduction Loss of oxygen atom Gain of hydrogen atom

Oxidation of Alcohol When an alcohol is oxidized, it gains an oxygen atom and loses hydrogen atoms. e.g. CH3CH2OH + 2[O]  CH3COOH + H2O Ethanol + Oxygen  Ethanoic Acid + Water

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Isomerism

Isomers are molecules with same molecular formula but different arrangement of atoms in space (different physical and chemical properties).

Structural Isomerism (Chain Isomerism) Branching in carbon chains Name Pentane (C5H12) Structure

2-methylbutane (C5H12)

2, 2-dimethylpropane (C5H12)

Structural Isomerism (Position Isomerism) Basic carbon skeleton remains unchanged, but important groups move around. Name Structure

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1-bromopropane (C3H7Br)

2-bromopropane (C3H7Br)

Functional Group Isomerism Molecules are in different homologous series. Name Propanoic acid (C3H6O2) Structure

Methyl Ethanoate (C3H6O2)

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The End Year 3 & 4 Chemistry
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Last updated: 29 May 2012, 9:30PM

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