A.

Periodic Table

A0. Summary of Periodic Trends (adapted from http://www.seab.gov.sg/aLevel/20102011Syllabus/9647_2011.pdf)

A-1. Redox rules that you absolutely must not forget Oxidation Reduction OIL (e-) RIG (e-) Loss of H Gain of H Gain of O Loss of O A1. Definitions Actual Nuclear Charge (Z) Effective Nuclear Charge (Zeff) Shielding Electrons (S) Proton number of atom

Drawing (thats right) courtesy of Daniel Siew (RI4H10)

RI 2010 Year 4 Chemistry Speed Revision Notes v7: A Learner-Outcome/Referencebased Approach in 7495 words and 11 sheets best used as a supplement alongside your Chemistry file (there are
things which Ive omitted because theyre relatively simple or easy to derive. Ive tried to cover everything in the EOY SoW though. Im pretty sure reading these 11 pages will be sufficient to jog your memory and help you with rote-memorising stuff like QA! Brevity: Wits soul.)

CC BY-NC-SA 3.0 (SIN) DISCLAIMER: Use these notes at your own risk. Questions? Comments? Errata? Send to: ADVANCE GRATITUDE to: Mr Ong, for the help and guidance Friends and batchmates who liked the MYE/Y3 EOY10 incarnation and helped with content/proofreading Daniel Siew for the dove drawing Sources, (hopefully) credited where appropriate (most content is paraphrased from the worksheets) The Gentle Reader, for reading this. My apologies if the notes sound a little self-indulgent ._. List of Topics A. Periodic Table B. Salt Preparation C. Qualitative Analysis D. Metal Reactivity E. Metal Extraction F. Electrolysis G. Chemical Energetics H. Reaction Kinetics I. Chemical Equilibria J. Organic Chemistry K. Others

A3. Oxides (hydroxides behave the same way) Basic Amphoteric Metals ZAP: Zn, Al, Pb Group I and II, transition metals Basic Amphoteric Acidic

Acidic Non-metals CO2, SO2, SO3, NO2, SiO2, P4O10

Neutral Other non-metals CO, NO, O2 ^^

Reacts with converse CaO (s) + 2HCl (aq) CaCl2 (aq) + H2O (l) ZnO (s) + 2HCl (aq) ZnCl2 (aq) + H2O (l) ZnO (s) + 2NaOH + H2O Na2Zn(OH)4 (aq) SO2 (g) + 2NaOH (aq) Na2SO3 (aq) + H2O (l) SiO2 (s) + hot conc.1 2NaOH (aq) Na2SiO3 (aq) + H2O (l)

Yields H+ (aq)/OH- (aq) CaO (s) + H2O (l) Ca(OH)2 (aq) CO2 (g) + H2O (l) H2CO3 (aq) SO2 (g) + H2O (l) H2SO3 (aq) SO3 (g) + H2O (l) H2SO4 (aq) NO2 (g) + H2O (l) HNO3 (aq) P4O10 (s)2 + 6H2O (l) 4H3PO4 (aq)

1 2

Else your flasks will start to dissolve in NaOH. Phosphorous pentoxide can react with carboxylic acids: P4O10 + RCO2H P4O9(OH)2 + [RC(O)]2O. AARGH Summary: Acidic/basic oxides (1) react with alkalis/bases to form a salt, or (2) form an acid/alkali in water.

Resultant +ve charge acting on a valence shell electron Zeff = Z S Electrons not in the valence shell of the atom they shield the outer shell electrons from the attraction force of +ve nuclear charge 1st I.E. Measure of energy (usually in kJ/mol) required to remove one electron from one mole of X (g) A2. Periodic Trends Across a period Down a group (L R) Decreases Metallic character Decreases (higher Increases (more Atomic radius electron shells) Zeff greater electrostatic attraction between e- and +ve nucleus) Decreases (for Ionic Increases (more radius isoelectronic ions electron shells) as proton number increases)1 1st I.E.2 Increases (higher Decreases (increasing distance Zeff more of valence e- from energy required to nucleus) ionise) Z Increases (higher Increases (higher proton number) proton number) S Constant Increases (more e-) Zeff Increases (since Constant (but Z increases but S distance prevails remains constant) down group, e- lost more readily 1 Isoelectronic = same electronic configuration. P3- with electronic configuration 2.8.8 obviously isnt going to be smaller than Al3+ with 2.8 2Smaller I.E. easy e- loss OIL easily oxidised

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A4. Group Characteristics M.p./b.p. Group I Alkali Metals Decreases down group (more electron shells greater distance between positively charged nuclei and negatively charged sea of delocalised electrons weaker electrostatic forces of attraction less thermal energy needed to overcome forces decrease in m.p./b.p.) +1 Reactive (reactivity increases down group; more electron shells greater distance between nucleus and valence electrons lower I.E. higher reactivity) Good reducing agents; easily oxidized (OIL, low I.Es) see A2 Catalytic Property None MnO2 (s): 2H2O2 2H2O (l) + O2 (g) Fe (s): Haber Process (NH3 (g)) Ni (s): Hydrogenation Cu2+ (aq): Acid + zinc Pt (s): Petroleum cracking High density solids Appears as hard, coloured metals Transition Metals Group VII Halogens Increases down group (more electron shells larger surface area larger IM forces more thermal energy needed to overcome increase in m.p./b.p.) Group VIII Noble Gases Increases down group (more electron shells larger surface area larger IM forces more thermal energy needed to overcome increase in m.p./b.p.)

A5. Halogens More reactive halogens will displace less reactive halogens from their aqueous halide solutions. In terms of reactivity, F > Cl > Br> I, e.g.: Cl2 (g) + 2Br- (aq) 2Cl- (aq) + Br2 (aq) Colour in organic solvent Cl2 Colourless Colourless Br2 Brown Orange I2 Brown Violet A6. Miscellaneous stuff Same group same number of valence electrons same charge as ions (mostly) Same period same number of electron shells By the way Colour as (aq)

Oxidation State Reactivity

Variable Moderately reactive; see reactivity series!

-1 (usually) Reactive (reactivity decreases down group; more electron shells greater distance between nucleus and outer electron shells lower E.A. lower reactivity) Good oxidizing agents; easily reduced (RIG, high electron affinity - E.A.) None

0 Mostly unreactive due to stable octet structures [NOT completely filled valence shells! Look at Kr; its 4th shell isnt full (2.8.18.8), and neither is Xes 5th shell (2.8.18.18.8)]

None

Appearance and Density

Low density solids Appears as soft, silvery metals

With water Bonding

Forms corresponding hydroxide (alkali) Metallic (positively charged nuclei in a sea of negatively charged delocalized electrons)

No reaction (but an aqueous solution of its ions is usually coloured) Metallic (positively charged nuclei in a sea of negatively charged delocalized electrons)

Range from gases (F2, Cl2) to liquids (Br2) to solids (I2) Colour darkens down group (F2: yellow; Cl2: greenish; Br2: brown; I2: black/purple) Dissolves (this is different from formation of halide ions X- (aq)) Intramolecular: Covalent; diatomic molecules Intermolecular: van der Waals IM forces of attraction (instantaneous dipole-induced dipole interaction)

Colourless gases

Monoatomic molecules Intermolecular: van der Waals IM forces of attraction (instantaneous dipole-induced dipole interaction)

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B. Salt Preparation
B1. Solubility Rules Soluble Nitrates Chlorides Sulphates Group I salts Ammonium salts Insoluble Oxides Hydroxides Carbonates

B3. Decision Flowchart (visual version of B5) Given that we need to produce salt XY (where X is the cation and Y is the anion): Is XY soluble? Yes No Precipitation by XNO3 (aq) + NaY (aq)

B4. Caveats You can try reacting acids with metals to create certain Group II (Mg, Zn) salts but this is not recommended to prepare the following: Insoluble salts Salts of unreactive metals (Pb, Cu, Ag) Group I salts A thin layer of the insoluble salt will form on the metal, hence preventing further reactions between the metal and the acid. Reaction thus ends prematurely. Being unreactive, they will not react with the acid.

CaO, SrO, BaO Ca(OH)2, Sr(OH)2

PbCl2, AgCl CaSO4, BaSO4, PbSO4

Is X2O or X2CO3 soluble?

Solubility of Group II oxides and hydroxides increases down the group. Mg is stubborn. B2. Methods of Salt Preparation Precipitation 1. Mix two relevant aqueous solutions 2. Filter to obtain residue salt 3. Wash residue with distilled water 4. Dry residue between sheets of filter paper Titration 1. Titrate with suitable indicator till endpoint is reached 2. Repeat titration without indicator 3. Heat obtained solution to 1/3 volume (for saturation) 4. Leave to solution to cool 5. Filter to obtain residue salt 6. DO NOT WASH (else it will dissolve) 7. Dry residue between sheets of filter paper Excess Base 1. Add excess base/carbonate into acid, stirring and heating until no more can dissolve 2. Filter off excess base to obtain filtrate 3. Heat filtrate to 1/3 volume (for saturation) 4. Leave to solution to cool 5. Filter to obtain residue salt 6. Dry residue between sheets of filter paper

Yes Titration of XOH (aq) with HY (aq)

No Excess base: add excess X2O (s) or X2CO3 (s) with HY (aq)

Group I metals react with both the acid and the water in the acid, thus giving you the relevant soluble Group I hydroxide mixed with the relevant salt

B5. Summary of Salt Preparation Approach (textual version of B3) Grey boxes denote desired products. Latter two cases consider the scenario where you have to obtain a salt XZ given a related salt XY. Anion (-) Cation (+) Method Product Byproduct Contributor Contributor Titration Excess Base Precipitation acid (aq) acid (aq) solution (aq) sodium carbonate Na2CO3 (aq) acid HZ (aq) nitric acid Insoluble salt XZ from base XY [HNO3, Precipitate] HNO3 (aq) sodium salt solution NaZ (aq) + + + + + + alkali (aq) base (s) solution (aq) soluble compound XY (aq) insoluble carbonate XCO3 (s) base XY (s) soluble nitrate XNO3 (aq) soluble salt (aq) soluble salt (aq) insoluble salt (s) insoluble carbonate XCO3 (s) soluble salt XZ (aq) soluble nitrate XNO3 (aq) soluble salt XZ (aq) + + + + + + water H2O (l) excess base (s) solution (aq) sodium salt solution NaY (aq) carbon dioxide + water CO2 (g), H2O (l) acid reaction byproduct CO2 (g), H2O (l) or H2 (g) sodium nitrate NaNO3 (aq)

Soluble salt XZ from soluble compound XY [Na2CO3, Acid]

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C1. Cation Tests To distinguish between Al3+ and Pb2+, KI should be added. Al3+ cations form AlI3 which dissolves; yielding no ppt. Pb2+ ions form yellow ppt PbI2. Ppts marked with (soluble) dissolve when corresponding excess base is added. Solutions are colourless save for Cu2+ + NH3 (aq) (a dark blue solution). Cation NaOH (aq) NH3 (aq) NH4+ Gas evolved: NH3 Cu2+ Light blue ppt (insoluble) Light blue ppt (soluble, dark blue soln) Fe2+ Dirty green ppt (insoluble) Fe3+ Reddish brown ppt (insoluble) Zn2+ White ppt (soluble) Ca2+ White ppt (insoluble) No ppt Pb2+ White ppt (soluble) White ppt (insoluble) Al3+ White ppt (soluble) White ppt (insoluble) C2. Anion Tests For all tests, acidify the sample by adding HNO3 first in order to remove any CO32-, UNLESS the anion to be tested for is NO3- (adding HNO3 invalidates the test by introducing NO3- anions). Anion Reagents to add Result CO32HNO3 Effervescence of CO2 ClAgNO3 White ppt AgCl IPb(NO3)2 Yellow ppt PbI2 NO3NaOH (aq), Al (s), Gas evolved: NH3 SO42Ba(NO3)2 White ppt BaSO4 Standard carbonate ion reaction: 2H+ (aq) + CO32- (aq) CO2 (g) + H2O (l) For the intrepid, heres the reaction for the identification of NO3- (aq): 8[Al(OH)6]3-(aq) + 3NH3(g) 3NO3-(aq) + 8Al(s) + 18H2O(l) + 21OH-(aq) C3. Gas Tests Gas NH3 CO2 Cl2 H2 O2 SO2 Test and Results Turns damp red litmus paper blue (1) Forms white ppt when bubbled into limewater (2) Extinguishes lighted splint Bleaches damp litmus paper Extinguishes lighted splint with a pop Relights glowing splint (1) Reduces acidified orange Cr2O72- (aq) to green Cr3+ (2) Reduces acidified purple MnO4- (aq) to pink Mn2+

C. Qualitative Analysis

C4. (extra) Notes on Gas Tests This can be skipped; its for understanding(since when did that become sidelined? Oh, right. Mugging.) NH3 CO2 CO2 (g) + Ca(OH)2 (aq) white ppt CaCO3 (s) + H2O (l) NH3 (g) + H2O (l) NH4+ (aq) + OH (aq) With prolonged bubbling: CO2 (g) + CaCO3 (s) + H2O (l) Ca(HCO3)2 (aq) This would explain why it turns damp red litmus paper blue. Ca(HCO3)2 is not a compound that you can actually extract by evaporation. Its just freefloating Ca2+ (aq), CO2 (aq), CO32 (aq) and HCO3 (aq). Either way, its colourless, so prolonged bubbling makes the white ppt (CaCO3) disappear. Cl2 SO2 An example of the oxidation of SO2 (g) and reduction of Cr2O72- (aq) in acidic Cl2 (l) + H2O (l) HCl (aq) + HClO (aq) This explains why damp blue litmus paper turns red media: Cr2O72- (aq) + 2H+ (aq) + 3SO2 (g) 2Cr3+ (aq) + 3SO42- (aq) + H2O (l) Note: Acidified KMnO4 (aq) and K2Cr2O7 (aq) test for reducing agents. Just first. Cl2 is a very strong oxidising agent and thus oxidises the litmus dyes in litmus paper, hence because a gas makes orange acidified K2Cr2O7 (aq) solution turn green doesnt mean that it MUST be SO2. effectively bleaching it. C5. Explanations of (less intuitive results in) C1 (there actually isnt anything left to saymost stuff here probably isnt tested.) Explanations paraphrased from http://home.clara.net/rod.beavon/cations.htm (a very good site IMHO) Some aqueous metal cations exist as their aqua complexes e.g. Cu2+ (aq) can be written as [Cu(H2O)6]2+ (aq). Hooray for d orbital awesomeness! Then again, please just stop at the simple equations (e.g. Cu2+ (aq) + 2OH- (aq) Cu(OH)2 (s)) for the examinations, or else the examiner will kill you for acting smart (theres A-levels for that to happen, la la) NH4+ Consider aqueous ammonias dissociation reaction: NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq) By LCP, the addition of NaOH (aq) and the subsequent increase in [OH- (aq)] will cause the equilibrium to shift to the left, hence increasing [NH3 (aq)] which is then liberated from the solution upon heating. Cu2+ + NaOH (aq): light blue ppt insoluble in xs [Cu(H2O)6]2+ (aq) + 2OH- (aq) Cu(OH)2 (s) + 6H2O (l) 2[Cu(H2O)6]2+(aq) + 2OH-(aq) + SO42- (aq) Cu(OH)2CuSO4(s) + 12H2O (l) + NH3 (aq): light blue ppt, soluble in xs to give dark blue solution [Cu(H2O)6]2+ (aq) + 2OH- (aq) Cu(OH)2 (s) + 6H2O (l) [Cu(NH3)4(H2O)2]2+(aq) +2OH-(aq) then again the number of H2O variesFYI only Cu(OH)2 (s) + 4NH3(aq) + 2H2O(l) Fe2+/ + NaOH (aq) or NH3 (aq): dirty green (II) / brown (III) ppt insoluble in xs. Fe doesnt form complexes with NH3 (aq). Fe3+ (II): [Fe(H2O)6]2+(aq) + 2OH-(aq) Fe(OH)2(s) + 6H2O(l) (III): Apparently, aqueous iron (III) ions exist as [Fe(H2O)5OH]2+ after protonating water: [Fe(H2O)6]3+ (aq) + H2O (l) [Fe(H2O)5OH]2+ (aq) + H3O+ (aq). Fe(OH)3 (s) + 6H2O(l) [Fe(H2O)6]3+(aq) + 3OH-(aq) Zn2+ + NaOH (aq): white ppt, soluble in xs to give colourless solution [Zn(H2O)6]2+(aq) + 2OH-(aq) Zn(OH)2(s) + 6H2O(l) Zn(OH)42-(aq) Zn(OH)2(s) + 2OH-(aq) + NH3 (aq): white ppt, soluble in xs to give colourless solution [Zn(H2O)6]2+(aq) + 2OH-(aq) Zn(OH)2(s) + 6H2O(l) [Zn(NH3)4]2+(aq) + 2OH-(aq) soluble! note: distinct from the NaOH (aq) reaction Zn(OH)2(s) + 4NH3(aq) Ca2+ + NaOH (aq): white ppt, insoluble in xs Ca2+ (aq) + 2OH- (aq) Ca(OH)2 (s) [OH-(aq)] is too low in NH3 (aq) to make Ca(OH)2 precipitate (it isnt too soluble; waiting will get you limewater: Ca(OH)2 (aq).) Pb2+/ + NaOH (aq): white ppt, soluble in xs to give colourless + NaOH (aq): white ppt, soluble in xs to give colourless solution solution Al3+ Pb2+(aq) + 2OH-(aq) Pb(OH)2(s) [Al(H2O)6] 3+(aq) + 3OH-(aq) Al(OH)3 (s) + 6H2O(l) Pb(OH)2(s) + 2OH-(aq) [Pb(OH)4]2-(aq) Al(OH)3(s) + 3OH- (aq) [Al(OH)6]3-(aq) + NH3 (aq): white ppt, insoluble in xs + NH3 (aq): white ppt, insoluble in xs Pb2+(aq) + 2OH-(aq) Pb(OH)2(s) Al3+(aq) + 3OH-(aq) Al(OH)3(s) Pb doesnt form complexes with NH3(aq), and NH3(aq) is not Al does not form complexes with NH3 (aq), and NH3 is not strong enough a base to react with amphoteric Pb(OH)2(s) strong enough a base to react with amphoteric Al(OH)3(s)

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D. Metal Reactivity
D1. Reactivity Series (Reactivity w/) Metal Cl2, Cold water P S C M A C Z I T L H C M K Na Ca Mg Al C Zn Fe Sn Pb H Cu Hg MCl MOH Reactivity w/ Steam HCl/ H2SO4 MO MCl/ MSO4 O2, M2O (lim. O2), M2O2 (xs O2) Burn MO D2. Reactivity Series (Thermal Stability/Solubility) Metal Thermal Stability MO MOH MCO3 MNO3 P S C M A C Z I T L H C M S G P K Na Ca Mg Al C Zn Fe Sn Pb H Cu Hg Ag Au Pt M MO MOH MO MCO3 MO + CO2 MNO2 + O2 MO + NO2 + O2 Solubility MO MCl MOH Insol. Sol. (except PbCl2, dissolves in hot water) D3. General Trends Down the reactivity series: I.E. Increases Ease of oxidation (OIL) Decreases Reactivity Decreases Strength as reducing agent Decreases More reactive metals will displace the cations of less reactive metals from their aqueous solution (see A5) e.g. Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s) D4. On oxide layers Porous Na Fe Oxide layer falls off and exposes more metal to oxidation/corrosion Non-porous Mg Al Oxide layer is nonporous and protects from further corrosion (disallows penetration of water and oxygen)

Surface MO -

M + CO2 + O2

M + NO2 + O2

Insol.

S Ag G Au P Pt D1 (alt). Reactivity
credits to Theophi (4P10) for the mnemonic!

D2 (alt). Thermal Stability

Al oxide layers can be anodized to make them thicker and hence better protect the metal. Anodizing involves the introduction of dyes, hence also colouring it. D5. Electric Cells (a.k.a. Galvanic cells) An electric (or galvanic cell) comprises two electrodes (metals of different reactivities) immersed in an electrolyte containing free mobile ions (doesnt matter what kind). Due to the differing reactivity (and hence ease of electron gain/loss) of the two electrodes, a potential difference is set up. More reactive metal (M) Anode (since ox.) Oxidised (OIL) M (s) M+ (aq) + eM+ enters electrolyte e- enters electrode, flows into wire Negative electrode Less reactive metal (Y) Cathode (since red.) Reduced (RIG) Y+ (aq) + e- Y (s) e- flows from wire out of electrode to reduce Y+ (aq) in electrolyte Positive electrode Substance produced (reduced form of cation in electrolyte; e.g. H+ (aq) produces H2 (g))

D6. Examples of Galvanic Cells Seriously, any mobile ions in solution will do for an electrolyte Salt bridges (typically filter paper dipped in KNO3 or) maintain electrical neutrality that was previously caused by e- flow (ions of salt bridge flow to areas of charge imbalance)

Using electrolyte containing metal cations of one of the electrodes

Using acid electrolyte

Using two electrolytes and a salt bridge

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E. Metal Extraction
E1. Alloys Alloy Bronze Brass Steel Constituents Copper, tin Copper, zinc Iron, carbon

E4. Iron Extraction & the Blast Furnace diagram adapted from worksheet

E5. Rusting and Corrosion Rusting Corrosion of iron Corrosion Gradual destruction of any metal due to reaction with air, water or other chemicals For iron to rust, it needs (1) water and (2) oxygen. Mechanics Red. (RIG): 0.5O2 (g) + H2O (l) + 2e- 2OH- (aq) Ox. (OIL): Fe (s) Fe2+ (aq) + 2eRedox: Fe (s) + 0.5O2 (g) + H2O (l) Fe(OH)2 (s) Further Ox. (OIL): Fe2+ (aq) Fe3+ (aq) + eFe3+ (aq) + 3OH- (aq) Fe (OH)3 (s)

Adapted from image found at http://www.spaceflight.esa.int/impress/text/education/Solidificati on/Question_Solidification_Phase_Diagram_13.html

-------- [1]

Pure metals tend to be soft and malleable, since the metals are arranged in neat regular rows that slide across each other easily when a force is applied. Hence, alloying a metal with another substance (another metal, or carbon) disrupts these regular rows, preventing them from sliding easily and hence increasing the resultant mixture (alloy)s strength and hardness. E2. Steel The hardness and brittleness of steel increases as the carbon content increases. Lower carbon steels are softer and more easily shaped. Alloy Composition Features Uses Mild Steel Fe: 99 -99.5 % Hard, strong, Car bodies, C: 0.15 -0.25% malleable, machinery, ductile; can steel rods to withstand reinforce great stress concrete and strain Stainless Fe: 90-95% Hard; resistant Cutlery, surgical Steel Cr/Ni: 5-10% to corrosion; instruments, C: variable attractive chemical appearance plants E3. Methods of Metal Extraction P S C M A C Z I T L H C M S G P Electrolysis Smelting Heat/Physical with coke Extraction Electrolysis: Reactive metals form stable compounds with strong bonds. Thus, extracting reactive metals from their compounds would require a lot of energy, and electrolysis is thus used. Smelting with coke: Less reactive metals can be extracted by heating the relevant metal oxide with coke (carbon is more reactive and can hence displace the metal from oxygen), which will reduce the metal.

Conditions that speed up Rusting (1) Water contains dissolved ionic substances (e.g. seawater, acid) Rusting is like a galvanic cell; waters the electrolyte XD

List of substances Coke C (s) Haematite Fe2O3 (s) (iron ore) iron (III) oxide Hot air Lime CaO (s)

Used for CO generation Substrate Provides a supply of oxygen

Right: Presence of free mobile ions in water (i.e. electrolyte) speeds up electron transfer

Reacts with and removes acidic impurities (e.g. SiO2) Limestone CaCO3 (s) Produces lime after thermal decomposition Slag1 Byproduct; used to make CaSiO3 (s) calcium silicate roads 1 Floats on top of Fe (l) so it can be easily collected Why do we need? CO (g) C (s) + O2 (g) CO2 (g) CO2 (g) + C (s) 2CO (g) Fe2O3 (s) + 3CO 2Fe + 3CO2 (g) CaO (s) CaCO3 (s) CaO (s) + CO2 (g) CaO (s) + SiO2 (s) CaSiO3 (s) The obtained iron (termed pig iron) has 5% C by weight and is too brittle to be of industrial use it can be processed to produce cast iron (low tensile strength applications e.g. stoves) and wrought iron (0.1% C; soft, tough, malleable), or steel (by oxidising pig irons impurities with oxygen)

(2) Iron is in contact with less reactive metal This will speed up reaction [1] earmarked above under Mechanics. Recall that higher reactivity greater ease of electron loss Hence, iron will lose electrons to copper: Fe + Cu2+ Fe2+ + Cu
(The formation of Cu2+ is a mystery we will solve later. Possibly corrosion? Meh)

Rust Prevention can be achieved by (1) Applying a protective coating (paint/oil/grease/tin/chromium) Problems: Coating will be ineffective even if a tiny bit is scratched off (and a tin coating will make iron rust even faster; recall that tin is less reactive than iron) (2) Sacrificial corrosion (i.e. connecting a more reactive metal to iron) In this case, the more reactive metal is more likely to lose electrons in the oxidising environment created by the presence of water and oxygen, and the iron atoms are hence not oxidised. Since both substances are metals, electrons flow readily within and between them and a connection between iron and the more reactive meal is sufficient (i.e. no need to coat the whole thing). Example: underwater pipes with magnesium, iron cans with galvanized zinc coating

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F. Electrolysis

F3. Summary Table (well, supposedly) Mat. = Material of electrode, Pdt. = Product, R = Reason (see F2) adapted from the worksheet Electrolyte PbBr2 (l) H2O (l)5 dil. H2SO4 (aq) conc. HCl (aq) conc. NaCl (aq) CuSO4 (aq) Cathode (negative electrode) Site of Reduction (of cations) Cations Pb2+ (l) H+ (aq) H+ (aq) H+ (aq) Na+ (aq), H+ (aq) Na+ (aq), H+ (aq) Cu2+ (aq), H+ (aq) Cu2+ (aq), H+ (aq)
1

F1. Definitions and Basics Electrolysis is the conduction of electricity by an ionic compound (electrolyte), when molten or dissolved in water, leading to the decomposition of the electrolyte. Since stuffing carbon electrodes into a huge crystal of NaCl and passing current through the electrodes wont get you anything, electrolysis shows that ions are held immobile in an ionic lattice, and are mobile only when molten or in solution. Thats just what the scope wanted me to tell you. Caveat: Oxidation occurs at the anode, and reduction occurs at the cathode! Forget this not! F2. Determining substances preferentially discharged Three things come into play: (1) Reactivity Less reactive species usually get preferentially discharged. Consider potassium and gold: potassium is reactive and loves to lose an electron so it would rather stay as K+ (i.e. not liberated), whereas gold is unreactive and would rather stay as Au rather than lose an electron to become Au+ (i.e. Au+ discharged! Au+ reduced at cathode) (2) Concentration (and the eponymous concentration effect, or CE) Species in high concentration usually get preferentially discharged, though reactivity is a more important factor. This is usually relevant only when the two ions we want to compare are of similar reactivity. Consider the electrolyte NaCl (aq) (ions present: Na+, H+, Cl-, OH-) When CE works: Cl-, OH- are of similar reactivity, [OH-(aq)] > [Cl-(aq)] OH- (aq) discharged as O2 (g) at anode (+ve electrode) When CE fails: [Na+ (aq)] > [H+(aq)] , but H+ is less reactive H+ (aq) discharged as H2 (g) at cathode (-ve electrode) (3) Nature of electrode Inert electrodes (e.g. platinum and carbon, which are attacked only by liberated chlorine and oxygen respectively) dont affect discharge, but certain reactive electrodes do. Example: Cu electrodes in CuSO4 (aq): Instead of considering SO42(aq) or OH- (aq) to lose electrons and get oxidised (OIL) and discharged at the +ve electrode (anode), Cu at the anode undergoes the reaction Cu (s) Cu2+ (aq) + 2e- since Cu loses electrons more readily than SO42- (aq) or OH- (aq). Example: Hg cathode in NaCl (aq): Usually H+ gets preferentially discharged, but Na and Hg tend to amalgamate and hence less energy is needed to discharge Na+ over H+, therefore Na+ is reduced and discharged.

Anode (positive electrode) Site of Oxidation (of anions) R 1 3 1 1 Anions Br- (l) OH- (aq) SO42- (aq), OH- (aq) Cl- (aq) , OH- (aq) Cl- (aq) , OH- (aq) Cl- (aq) , OH- (aq) SO42- (aq), OH- (aq) SO42- (aq), OH- (aq) Mat. C Pt Pt C C C C Cu Pdt. Br2 (g) O2 (g) O2 (g) Cl2 (g) Cl2 (g) Cl2 (g) O2 (g)6 (anode dissolves) R 1 2 2 2 1 3 -

Effect on electrolyte

Mat. C Pt Pt C C Hg C Cu

Pdt. Pb (l) H2 (g) H2 (g) H2 (g) H2 (g) Na/Hg Cu (s) Cu (s)

More acidic1 More dilute2 More alkaline3 More dilute4 More acidic1 Concentration unchanged

[H+ (aq)] increases since [H2O(l)] decreases as OH- (aq) is discharged at anode 2 [HCl (aq)] decreases since Cl- (aq) is discharged at anode 3 Water usually has only a small [OH-(aq)] from auto-ionisation, but as H+ (aq) and Cl- (aq) are discharged at the cathode and anode respectively, [Na+ (aq)] and [OH- (aq)] increase electrolyte becomes more alkaline. 4 [NaCl (aq)] decreases since Na+ (aq) and Cl- (aq) are discharged at the cathode/anode respectively 5 Catalytic amounts of H2SO4 (aq) usually added to increase the poor conductivity of water (a weak electrolyte) 6 This O2 (g) can cause the C anode to burn up (more prevalent at high temperatures) F4. Preferential Discharge Chart F6. Electroplating Species at the bottom tend to get Object to be electroplated is made the cathode preferentially discharged first as per F2. (where cations of electroplating material are discharged). K+ Metal used for electroplating is made the anode. Ca2+ Consider the use of silver for electroplating: Na+ Cathode: Ag+ (aq) + e- Ag (s) Mg2+ FAnode: Ag (s) Ag+ (aq) + eAl3+ SO42From worksheet The discharged electroplating material is deposited as a Zn2+ NO3layer on the electroplated object. Fe2+ ClRationale for adding cryolite F7. Extraction of Aluminium Sn2+ BrM.p. of Al2O3 = 2065oC (too high to be costPb2+ ICarbon cathode (reduction, RIG): Al3+ (l) + 3e- Al (l) H+ OHeffective/safe) Carbon anode (oxidation, OIL): 2O2- (l) O2 (g) + 4eCu2+ M.p. of Na3AlF6 = 950oC Overall: 4Al3+ (l) + 6O2- (l) 4Al (l) + 3O2 (g) Ag+ Al2O3 Na3AlF6 electrolyte mixture can Au+ remain liquid (i.e. contain free mobile ions) Process at a temperature lower than 2065oC Bauxite (aluminium ore) F5. Electrolysis for Refining Purification1 Impure metals (e.g. copper) are made Alumina (Al2O3 (s)) Problem of carbon anodes the anode and electrolysis is carried Melting, solvation in cryolite (Na3AlF6) (as per F3 fn.6) out. Pure metal accumulates on the Al2O3 Na3AlF6 electrolyte mixture Oxygen gas discharged attacks carbon cathode (which itself is the desired pure Electrolysis anode at high temperature: metal). Aluminium (and O2(g) liberated) C (s) + O2 (g) CO2 (g) Cathode: Cu2+ (aq) + 2e- Cu (s) Hence, carbon anodes must be frequently Anode: Cu (s) Cu2+ (aq) + 2e1 Bauxite + hot NaOH (aq), filter replaced. Impurities collect below the anode as filtrate: sodium aluminate; residue: Fe2O3 (s) anodic sludge. Sodium aluminate + dil. Acid Al(OH)3 (s) Al(OH)3 (s) + heat Al2O3 (s)

RI 2010 Year 4 Chemistry Speed Revision Notes v7: A Learner-Outcome/Reference-based Approach in 7495 words and 11 sheets

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G. Chemical Energetics

G1. Exothermic and Endothermic Reactions diagrams adapted from http://schools-wikipedia.org/images/58/5853.png.htm Exothermic Reaction Endothermic Reaction

G4. Hydrogen as a fuel if this wasnt in the scope, no one would have known that this had to do with Chemical Energetics XD Pros and cons (+) Burns cleanly in air, forming H2O (g) (+) High energy released per gram: H2 125kJ/g; CH4 61kJ/g (-) Low b.p. (-252oC), hard to transport/store Production (1) Cracking (see X) (2) Steam Reforming H2O (g) + CH4 (g) cat. CO (g) + 3H2 (g) H2O (g) + CO (g) cat. CO2 (g) + H2 (g) H2 (g) separated from CO2 (g) by passing mixture through alkali (reacts with acidic CO2 (g)) Uses of hydrogen (1) As a fuel in rockets or fuel cells (2) Manufacture of NH3 (g) in Haber process, hydrogenation of margarine (vegetable oil) G5. Hydrogen-Oxygen Fuel Cells diagram adapted from worksheet Definitions NOTE: Fuel cells are electric/galvanic cells that produce current, and are NOT electrolytic cells! Fuel cells use a fuel to react with atmospheric oxygen to directly produce electrical energy. Reactions Anode (oxidation, OIL): 2H2 (g) 4H+ (aq) + 4eCathode (reduction, RIG): O2 (g) + 4H+ (aq) + 4eOverall: 2H2 (g) + O2 (g) 2H2O (g)

Ereactants > Eproducts Ereactants < Eproducts H = negative H = positive Energy released to environment Energy absorbed from environment Bond making Bond breaking Think about itif you need to add energy to break bonds (bond breaking is endothermic), then the logical converse is that bond making is exothermic. Hurrah! Expressions for enthalpy change H = Eproducts Ereactants H = Ebond breaking Ebond making G2. Useful algebraic manipulation of standard enthalpy changes Multiplying Reversing A (l) + B (l) AB (l) PQ (g) P (g) + Q (g) H = +500kJ/mol P (g) + Q (g) PQ (g) H = -500kJ/mol 2A (l) + 2B (l) 2AB G3. Some standard enthalpy changes (SECo = Standard Enthalpy Change of) Assume all reactions occur at standard state/conditions 1atm, 298K Hr SECoReaction 1mol of reactions occurs Hf SECoFormation 1mol of substance formed in standard state from constituent elements in their standard states Hc Hm Hvap Hat Hlat Hi.e. Hsol SECoCombustion SECoFusion SECoVapourisation SECoAtomisation Lattice enthalpy First IE Enthalpy of solution 1mol of substance completely combusted 1mol of substance from (s) to (l) 1mol of substance from (l) to (g) 1mol of substance from standard state to individual (g) atoms Hf of 1mol of ionic compound from gaseous ions 1mol of e- removed from 1mol of (g) atoms 1mol of substance dissolved in water

2H2O (g)

H = -500kJ/mol H = -1000kJ/mol

Mechanism Electrodes are usually carbon (cheap, and the O2 (g) produced isnt hot) or platinum (amazing efficiency but costly). Fuel cell works like a battery (produces current), but since electrodes are inert, they do not deteriorate chemically constant fuel supply = constant electrical energy!

Variable Variable (sometimes for elements in standard state bonds must be broken first, so this isnt always ve as per bond making) Always ve (burning releases energy) Always ve (fusion, the opposite of melting, releases energy) Always +ve (requires energy) Always +ve (requires energy) Always ve (bond making release energy) Always +ve (requires energy) Variable (-ve for acids)

RI 2010 Year 4 Chemistry Speed Revision Notes v7: A Learner-Outcome/Reference-based Approach in 7495 words and 11 sheets

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H. Reaction Kinetics
H0. Preamble Frequency of effective collisions (right orientation, above minimum energy) reaction rate Minimum energy needed is known as activation energy (Ea). high Ea = slow reaction rate (less molecules have sufficient energy to react, reaction proceeds slower) low Ea = fast reaction rate (more molecules have sufficient energy to react, reaction proceeds faster) The Maxwell-Boltzmann distribution curve (Graph A) shows the number of gas molecules that posses a certain amount of energy, over a range of possible energies. As you can see, most of the molecules have an intermediate amount of energy. The area under a section of the curve gives the number of gas molecules with energies falling within that range (think integration!)

H2. Catalysts Definition Catalysts lower the Ea of a reaction and Catalysts can be poisoned by molecules other hence enable the reaction to proceed to than the intended reactant molecules that are equilibrium more quickly. Catalysts are preferentially adsorbed/permanently attached not consumed or used up during the to the catalyst surface, hence reducing the reaction. Biological catalysts are called number of available active sites and catalytic enzymes. activity. Catalyst Definition Example Homogeneous1 Same state as reactants H2SO4 (aq) in water electrolyte Heterogeneous1 Different state as reactants MnO2 (s) in H2O2 (l) decomposition 1 Not to be spelled as homogenous or heterogenous; those have different meanings. Examples (not exhaustive! Includes our variable oxidation state transition metal friends from A4) Catalyst Reaction Product Ti/Al compound (s) Low-P polymerisation polyethene Fe (s) Haber Process NH3 (g) V2O5 (s) Contact Process H2SO4 (aq) Zeolite1 or Pt (s) Catalytic cracking gasoline Ni (s) Hydrogenation Margarine Zymase enzyme (yeast) Fermentation Wine MnO2 (s) H2O2 (l) decomposition O2 (g) Cu2+ (aq) Acid + zinc Zinc salt + H2 (g) 1 Microporous, aluminosilicate minerals (thanks, Wikipedia!) Basically, very large surface area. Mechanism (not strictly relevant; still) Catalysts provide a different pathway of reaction. For example, reactant molecules can collide with them to form an intermediate which breaks down into the (restored) catalyst and the product.
Diagram from the worksheet (AARGH NOTEMAKING BURNOUT)

Diagram adapted from http://www.webchem.net/notes/how_far/kinetics/maxwell_boltzmann.htm

Diagram from http://www.physchem.co.za/OB12-che/catalysis.htm

Diagram from http://www.physchem.co.za/OB12-che/catalysis.htm

Graph A

Graph B

Graph C

H1. Factors affecting rate of reaction: to increase the rate of reaction, we can: Increase T (see Higher temperature Graph B) particles have higher KE particles move faster, collide harder more particles have E > Ea increased frequency of effective collisions Usually, increasing the temperature by 10K will double the reaction rate Increase Higher concentration concentration more particles/unit volume [] particles closer, increased frequency of collision increased frequency of effective collisions Increase P (for Higher pressure gaseous particles closer, increased frequency of collision reactants) increased frequency of effective collisions Increase Increased surface area surface area of Increased area of reactant reactants Increased frequency of collision/unit time increased frequency of effective collisions Use of catalyst Catalyst (see Graph C) Lowers Ea of reaction (usually by providing collision site; see H2) increased frequency of effective collisions Increasing catalyst amount will increase reaction rate up to a point (after which catalyst > substrate)

H3. Investigating the effect of a given variable on the speed of a reaction -.To monitor the rate of reaction, measure: mass of reaction mixture volume of gas evolved amount of product/reactant titrating samples of reaction mixture removed at fixed intervals colour intensity w/ colorimeter (one of the reactants/products must be coloured) pressure in closed reaction vessel (when amount of gaseous products amount of gaseous products) temperature

RI 2010 Year 4 Chemistry Speed Revision Notes v7: A Learner-Outcome/Reference-based Approach in 7495 words and 11 sheets

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I. Chemical Equilibria
Chemical reactions that can proceed both forward and backward1. Look out for as opposed to Example: NH4Cl (s) NH3 (g) + HCl (g) Equilibrium A state in which the concentration of the reactants and products are constant (and the forward and backward reactions are still occurring). 1 Strictly speaking, all chemical reactions are reversible; just that the equilibrium constant Kc is so high for the forward reaction that the reaction virtually goes to completionbut hey, thats beyond the scope of this test. I2. Le Chateliers Principle (LCP; a.k.a >) our UG friends are not amused. If a system at equilibrium is subjected to a small change, the equilibriums response is to shift so as to minimize the effect of the change. Well, that probably isnt intuitive enough, so a few case studies would come in handy! (1) concentration Consider A + B C+D By LCP, removing A or B will cause the equilibrium to shift left the system converts some C and D to replenish A and B. By LCP, adding A or B will cause the equilibrium to shift right the system converts some A and B to C and D to maintain the ratios of the amounts of each species. (2) temperature (now is a good time to be familiar with Section G) Consider A + B C Hr = +500kJ/mol This reaction is endothermic (takes in energy), so we can rewrite it as: A + B + heat C Now, by treating heat as a reactant, we have generalized the temperature case to the concentration case! By LCP, removing heat (i.e. cooling the system) will cause the equilibrium to shift left, and adding heat (i.e. warming the system) will cause the equilibrium to shift right. (Of course, you can rewrite A + B C Hr = -500kJ/mol as A+B C + heat) (3) pressure For this to make sense, at least one of the products/reactants should be a gas. Consider A (g) + 2B (g) 4C (g) + 8D (g) As you can see, the RHS has a greater amount of gas (12mol) as compared to the LHS (3mol). When a closed reaction vessel is under pressure, it tries to dissipate this excess pressure. This is normally done by reducing the amount of gas in the system. By LCP, increasing pressure will cause the equilibrium to shift to the left, and decreasing pressure will cause the equilibrium to shift to the right. I1. Definitions Reversible Reaction I3. Contact Process Reactions (1) S (s) + O2 (g) SO2 (g) (2) 2SO2 (g) + O2 (g) 2SO3 (g) (3) SO3 (g) + conc. H2SO4 (aq) H2S2O7 (aq)* (4) H2S2O7 (aq)* + H2O (l)2 conc. 2H2SO4 (aq) 450oC Conditions (bolded step) Catalyst: V2O5 (s) vanadium (V) oxide *Oleum, more accurately described as nSO3H2O or H2SO4nSO3. H2S2O7 is actually its empirical formula it merely describes SO3 (g) dissolved in conc. H2SO4 (aq). Dissolving SO3 (g) in water gives a fine mist of H2SO4 (g) that is difficult to manage (thanks, Wikipedia!) 2 Im assuming T is a lot lower than 100oC at this point. I4. Haber Process Reactions 3H2 (g) + N2 (g) 2NH3 (g) Hr = -92kJ/mol Conditions 450oC 200atm Catalyst: Fe (s) N2 (g) comes from the air (78% N2, oh yeah!). H2 (g) comes mainly from petroleum cracking. Elucidating the rationale of said conditions for the Haber Process
(5 syllables! Score!)

Given the reaction: 3H2 (g) + N2 (g) 2NH3 (g) Hr = -92kJ/mol and applying the concepts presented in I2 (2), we rewrite this as such: 2NH3 (g) + heat 3H2 (g) + N2 (g) temperature LCP tells us that we should carry out the reaction at low temperatures to maximize NH3 (g) concentration pressure Looking at the amount of gas on each side, we see that LHS > RHS (4mol > 2mol). Hence, LCP tells us that we should carry out the reaction at high pressure to maximize NH3 (g) concentration. Kinetic considerations Since a higher temperature generally connotes a faster rate of reaction, it would be reasonable to assert that a low temperature entails a slower rate of reaction. (At this juncture it is worth noting that equilibria position and reaction rate are two unrelated parameters of a reaction). Based on this alone, we should carry out the reaction at high temperatures. Economic considerations It is very expensive to maintain high pressure systems; hence low pressure industry setups are preferred. In the interests of cost, as well as considerations in terms of kinetics and equilibria, scientists/engineers have settled on the 450oC/200atm configuration. (not something too slow/expensive like 60oC/1000atm) This is what could have been:

From http://www.ausetute.com.au/haberpro.html

RI 2010 Year 4 Chemistry Speed Revision Notes v7: A Learner-Outcome/Reference-based Approach in 7495 words and 11 sheets

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J. Organic Chemistry!

J1. Fractional Distillation of Petroleum Fractions that condense higher up the column are displayed higher. Fraction C B.p. Uses Petroleum gases 1-4 Below r.t. Bottled gas for gas cookers Petrol/gasoline 5-10 35-75 Motor vehicle fuel Naphtha 8-12 70-170 Petrochemical feedstock Kerosene/Paraffin 10-14 170-250 Jet aircraft fuel, oil stove fuel Diesel oil 15-25 250-340 Diesel engine fuel Lubricating oil 19-35 340-500 Engine lubricant, wax/polish making Bitumen >70 >500 Road surfacing Higher up the column Explanation of Trends (vice versa lower down the column) Smaller molecules/Mr Smaller molecules (and Mr) Smaller surface area Weaker van der Waals IM forces of attraction Low m.p./b.p. Volatile Less thermal energy needed to overcome IM forces Low m.p./b.p./lower viscosity volatile Less viscous Flammable (evaporate more easily) more flammable J2. Definitions Homologous A group of compounds with a general formula, similar series chemical properties and a gradation in physical properties as a result of increase in the size and mass of molecules General formula e.g. alkynes: CnH2n-2 Molecular formula e.g. ethanol: CH3CH2OH alternatively (though I dont like this one): C2H6O Displayed formula e.g. butanol: J3. Saturation, unsaturation and degrees of unsaturation* (*not in syllabus) Alkanes are saturated hydrocarbons, whereas alkenes and alkynes are unsaturated hydrocarbons. Given a random hydrocarbon like C20H38 and further information that all the bonds in that molecule are either single or double bonds, we can actually figure out the number of double bonds in the molecule. Using the general formula for alkanes (CnH2n+2), we would expect 2x20+2 = 42 H atoms. However, we are short of 42-38 = 4 H atoms. This tells us that there are 4/2 = 2 C=C double bonds, because: For every 2 less H atoms as would be expected from an alkane of that number of carbons , there is one degree of unsaturation (1 degree a C=C bond, 2 degree CC bond or 2 C=C bonds). J5. cis-trans isomerism* since double J4. Cracking of alkanes always yields at least one alkene molecule. Possible bonds arent rotatable like single bonds products are alkenes (always), alkanes, H2 (g) and C (s). Alkane alkene + alkane cistransAlkane alkene + H2 (g) opposite side same side Alkane alkene + alkane + C (s) of double bond

J6. Summary of tested chemical transformations For the purposes of demonstration, Ive used specific molecules to illustrate the related reactions. Ive also omitted byproducts. Meh.

- Oxidation reactions can be written as CH3CH2OH (aq) + 2[O] CH3COOH (aq) + H2O (l). - Depending on how long you let the reaction proceed, you can get multi-substituted chloroalkanes. * As a strong oxidising agent, KMnO4 (aq) will oxidise ROH to RCOOH directly. K2Cr2O7 (aq) will oxidise ROH to RCHO (aldehyde) first; upon prolonged oxidation, the RCOOH will be obtained. Of course, atmospheric oxygen will also do the job (albeit slowly). For this examination, treat KMnO4 (aq) and K2Cr2O7 (aq) as equals. * Bromine water (Br2 (aq)) reacts with alkenes to give bromohydrins as a major product and disubstituted alkanes as a minor product (for ethene, it will give 2-bromoethanol). Solvent is important! For this examination, take it that bromine water + alkene 1,2-dibromoalkene. *The oxidation of alkenes isnt actually tested. You can get cool stuff like the epoxide, ethylene oxide (C2H4O), from Ag catalysed oxidation of ethene. Depending on the substituents of an alkene (2x -H, -CH3 & -H, 2x -CH3), the (two; not necessarily similar) products of oxidative cleavage are also different (CO2 (g) and H2O (l), carboxylic acid and ketone respectively) J7. Miscellaneous noteworthy (wow, first pun! And were on the last page!) information - Meth-, eth- (= acet-), prop-, but- (after this its easy) - Polymerisation: Stuff like ethene can polymerise to become poly(ethene)/polythene - Reaction of alkenes with bromine water: Alkenes decolourise bromine water; e.g. ethene with Br2 (aq) yields 1,2-dibromoethane (major product; just state this in the examination) and 2-bromoethanol (minor product) - Esters: can be used as solvents/flavouring! Wow! (ethanol can be used as a solvent too) BTW ethers (R-O-R) esters. - Hydrogenation: of unsaturated vegetable oils to saturate them is done for the manufacture of margarine. (removal of double bonds including bent cis- isomers less kinked molecules stronger van der Waals IM forces of attraction more thermal energy needed to overcome higher m.p. solid state at r.t.p.!)

RI 2010 Year 4 Chemistry Speed Revision Notes v7: A Learner-Outcome/Reference-based Approach in 7495 words and 11 sheets

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