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WORKBOOK ANSWERS AQA A-level Chemistry Inorganic and organic chemistry 2 This Answers document provides suggestions for some of the possible answers that might be given for the questions asked in the workbook. They are not exhaustive and other answers may be acceptable, but they are intended as a guide to give teachers and students feedback. Inorganic chemistry Topic 4 Properties of period 3 elements and their oxides 1a 4Na + O2 → 2Na2O 2Mg + O2 → 2MgO 4Al + 3O2 → 2Al2O3 Si + O2 → SiO2 P4 + 5O2 → P4O10 S + O2 → SO2 Remember that it is the oxide formed on reaction of the element with oxygen. Phosphorus and sulfur form two oxides. It is P4O10 and SO2 that form on reaction with oxygen. 1b SO2 / sulfur dioxide The ionic (Na2O, MgO, Al2O3) oxides are solids as is the giant covalent oxide SiO2. P4O10 is a solid as well due to the van der Waals forces between the molecules, but SO2 is a gas as it is a small molecule with weak intermolecular forces between the molecules. 2a Basic 2b Bonding: ionic Structure: ionic lattice 2c Na2O + H2O → 2NaOH 2d Na2O + H2SO4 → Na2SO4 + H2O Sodium, magnesium and aluminium form ionic compounds with oxygen. The oxides of sodium and magnesium are basic oxides. Aluminium oxide is amphoteric. © Alyn G. McFarland and Nora Henry 2016 Hodder Education 1 MgO + H2O → Mg(OH)2 3a 3b i MgO + 2HCl → MgCl2 + H2O ii MgO + H2SO4 → MgSO4 + H2O 4a Al2O3 + 6H+ → 2Al3+ + 3H2O 4b Al2O3 + 2OH− + 3H2O → 2Al(OH)4− 4c Aluminate(III) or aluminate ion 5a Bonding: covalent Structure: giant/macromolecular 5b 2NaOH + SiO2 → Na2SiO3 + H2O Sodium silicate 6a Bonding: covalent Structure: simple/molecular 6b P4O10 + 6H2O → 4H3PO4 Phosphoric(v) acid 6c P4O10 + 12NaOH → 4Na3PO4 + 6H2O Sodium phosphate(V) 6d P4O10 + 6MgO → 2Mg3(PO4)2 The oxidation state is important in the IUPAC name of an acid or its salt at this level. Remember to include it when needed and also to recognise it. 7a SO2 + H2O → H2SO3 Sulfuric(IV) acid SO3 + H2O → H2SO4 Sulfuric(VI) acid 7b SO2 + CaO → CaSO3 7c SO3 + 2NaOH → Na2SO4 + H2O The difference between sulfuric(IV) acid and sulfuric(VI) acid is important, as is the difference between sulfate(IV) and sulfate(VI) ions. Make sure you look for the oxidation state as this is important. © Alyn G. McFarland and Nora Henry 2016 Hodder Education 2 Topic 5 and 6 Transition metals and reactions of ions in aqueous solution 1 Answer is C The coordination number is the number of coordinate bonds between the ligand(s) and the central metal atom or ion. EDTA4− is a hexadentate ligand, so one ion forms six coordinate bonds. The other ligands are monodentate so each forms a single coordinate bond with the central metal atom or ion. 2 Answer is A All contain 24 electrons as iron has an atomic number of 26, so the number of electrons in a 2+ ion should be 24. This is an important way to check this. Add up the superscript numbers. Transition metal atoms lose their 4s electrons first. The most obvious distractor here is C as this would imply that iron atoms would lose their 3d electrons to form the 2+ ion. 3a Answer is A 3b Answer is D 3c Answer is E 3d Answer is E 3e Answer is C The shapes and coordination number of complexes are important. Create a list of complexes with shape, coordination number, oxidation state of the transition metal atom or ion and colour of any complex you are supposed to remember. 4a A = [Al(H2O)6]3+ B = [Cu(H2O)6]2+ C = [Fe(H2O)6]2+ 4b [Al(H2O)6]3+ + 3OH− → Al(OH)3(H2O)3 + 3H2O 4c [Cu(NH3)4(H2O)2]2+ 4d [Fe(H2O)6]2+ + CO32− → FeCO3 + 6H2O 4e Carbon dioxide The reactions of ions in aqueous solution can be used to identify the complex. Make sure you know the identity of any precipitates and be able to write equations for the reactions. © Alyn G. McFarland and Nora Henry 2016 Hodder Education 3 Exam-style question Oxidation state is +3 1a Coordination number is 6 Shape is octahedral Brown precipitate 1b Does not redissolve in excess sodium hydroxide solution 1c [Fe(H2O)6]3+ + 3OH− → Fe(OH)3(H2O)3 + 3H2O 1d Brown precipitate Bubbles of gas 2[Fe(H2O)6]3+ + 3CO32− → 2Fe(OH)3(H2O)3 + 3CO2 + 3H2O 1e 1f i = 410 × 10−9 m ΔE = ii hc l = 6.63 ´10-34 ´ 3 ´108 1.989 ´10-25 = = 4.85 × 10−19 J 410 ´10-9 410 ´10-9 For yellow solution it is bigger Smaller means larger ν and larger ΔE iii Any two from the list below: identity of the metal/type of ligands/coordination number/oxidation state of the metal or charge on the ion/shape of the complex This type of question on one particular complex tests your knowledge of many different parts of this section. The observations and equations for the reaction of [Fe(H2O)6]2+, [Fe(H2O)6]3+, [Cu(H2O)]2+ and [Al(H2O)6]3+ with sodium hydroxide solution, ammonia solution and sodium carbonate solution are important. Remember that 3+ ions form the hydroxide precipitates with sodium carbonate solution. The answer to (f)(i) using the other wavelength given (480 nm) would be 4.14 × 10−19 J. Try the calculation backwards as well to make sure you can work out the wavelength from the given value of ΔE. © Alyn G. McFarland and Nora Henry 2016 Hodder Education 4 Variable oxidation states and catalysts 1 Answer is A The substance that could carry out a reduction of vanadium must be on the right-hand side of the half-equations, so it cannot be iodine. Sulfur dioxide being oxidised to sulfate(VI) ions has a potential of −0.17 V. Adding this to each of the potentials for the vanadium half-equations gives +0.83 V (so +5 to +4 is feasible), +0.17 V (so +4 to +3 is feasible) and −0.42 V (so +3 to +2 is not feasible), so sulfur dioxide reduces vanadium from +5 to +3 but not to +2. Zinc being oxidised from Zn to Zn2+ has a potential of +0.76 V and this means that zinc will reduce vanadium from +5 to +2 as all of the reactions are feasible. Iodide ions being oxidised to iodine has a potential of −0.54 V, so adding to each of the potentials for the vanadium half-equations gives +0.46 V (so +5 to +4 is feasible), 0.20 V (so +4 to +3 is not feasible) and −0.80 V, so +3 to +2 is also not feasible. Iodide ions would reduce vanadium from +5 to +4 but no further. 2a Colourless to pink This titration is self-indicating, so the last drop of the purple potassium manganate(VII) solution added does not decolourise but changes the colourless solution to pink. Mn 2+, Fe2+ and Fe3+ ions have a very pale colour in solution compared to the intense colour of manganate( VII). 2b 5Fe2+ + MnO4− + 8H+ → 5Fe3+ + Mn2+ + 4H2O ratio of Fe2+ : MnO4− = 5:1 2c Moles of MnO4− = 14.25 ´ 0.0248 = 3.534 × 10−4 mol 1000 Moles of Fe2+ in 25 cm3 = 3.534 × 10−4 × 5 = 1.767 × 10−3 mol Moles of Fe2+ in 1 dm3 = 1.767 × 10−3 × 40 = 0.0707 mol Mr of FeSO4.7H2O = 277.9 Mass of FeSO4.7H2O = 0.0707 × 277.9 = 19.6 g Using given ratio of 4:1 answers are 3.534 × 10−4 mol , 1.414 × 10−3 , 0.0565 mol , 277.9 and 15.7 g Often a ratio or numerical answer will be given to enable you to carry on with the rest of the question and make sure you do this. The ×5 is from the ratio and ×40 is to multiply from 25 cm 3 to 1 dm3. Remember to give your answer to three significant figures. This question could have asked for the degree of hydration of hydrated iron(II) sulfate using the initial mass (19.6 g) and the final titre. Check that you would get 7 (or 6.96 which is what is obtained using the 19.6 g). It is only the last couple of steps in the calculation that are different. Check it out below. Moles of MnO4− = = 3.534 × 10−4 mol Moles of Fe2+ in 25 cm3 = 3.534 × 10−4 × 5 = 1.767 × 10−3 mol Moles of Fe2+ in 1 dm3 = 1.767 × 10−3 × 40 = 0.0707 mol © Alyn G. McFarland and Nora Henry 2016 Hodder Education 5 Mr of FeSO4.xH2O = 19.6 0.0707 = 277.2 Mr of xH2O = 277.2 − (55.8 + 32.1 + 4 × 16.0) = 125.3 x = 125.3 / 18.0 = 6.96 (i.e. 7) 3a S2O82− + 2I− → 2SO42− + I2 3b 2Fe2+ + S2O82− → 2Fe3+ + 2SO42− 2I− + 2Fe3+ → I2 + 2Fe2+ Reactions can occur in either order 3c Homogeneous catalysts are in the same state as the reactants All ions here in solution/aqueous This reaction is commonly used as an example of homogeneous catalysis. Make sure you know the ionic equations for the main reaction and the catalysed reactions. 4 moles of MnO4− = 9.25 ´ 0.214 = 1.98 × 10–3 mol 1000 Ratio of FeC2O4 : MnO4− = 5:3 moles of FeC2O4 in 25 cm3 = 1.98 ´10-3 × 5 = 3.3 × 10-3 3 moles of FeC2O4 in 250 cm3 = 3.3 × 10-3 × 10 = 0.033 mol Mr of FeC2O4.xH2O = 5.93 = 179.7 0.033 Mr of xH2O = 179.7 – (55.8 + (2 × 12.0) + (4 × 16.0)) = 35.9 x = 35.9/18.0 = 1.99 so x = 2 The most difficult part of this calculation is the ratio of FeC2O4 : MnO4– = 5:3. It is important you remember this or can work it out and sometimes the question will take you through the halfequations and the ionic equations and working out the ratio. If you remember the overall ratio then you know where you are going with the question. Both the Fe 2+ and C2O42– ions react with MnO4−. Try repeating the calculation with an average titre of 8.40 cm3. This should give x = 3. This is not a true value but allows you another chance to do the calculation. © Alyn G. McFarland and Nora Henry 2016 Hodder Education 6 Exam-style questions 1a i 5C2O42− + 2MnO4− + 16H+ → 10CO2 + 2Mn2+ + 8H2O This equation can be worked out from the two half-equations by multiplying the top one by 2 and the bottom one by 5 to get 10e− in each. The equations when added together form the ionic equation. ii C oxidation state changes from + 3 to + 4 C is oxidised Mn oxidation state changes from + 7 to +2 Mn is reduced Make sure you can clearly identify the element being oxidised and the element being reduced using oxidation states. This was first met at AS but often forms parts of the A-level papers. iii Bubbles of gas Purple solution Changes to colourless You can use an equation to determine the observations expected during a reaction even if you have never seen the reaction. In this case carbon dioxide is produced so bubbles should be seen in the solution. Also manganate(VII) ions are purple in solution and Mn2+ ions are virtually colourless. You should know this from manganate(VII) titrations. 1b i Two negative ions repel each other/high activation energy ii Production of Mn2+ Autocatalysis by Mn2+ 4Mn2+ + MnO4− + 8H+ → 5Mn3+ + 4H2O 2Mn3+ + C2O42− → 2Mn2+ + 2CO2 iii Manganate(VII) ions are coloured/purple Colorimetry Using solutions of known concentration/calibration curve iv Ions are used up This reaction is often used as an example of autocatalysis, as it shows the Mn2+ ions being formed that catalyse the reaction. This is why the reaction is slow initially as it has no catalyst present. As the Mn2+ ions are formed in the reaction the reaction rate increases. You may be asked to sketch this shape of graph based on your knowledge of the reaction. © Alyn G. McFarland and Nora Henry 2016 Hodder Education 7 Organic chemistry Topic 7 Optical isomerism 1 Answer is C Optical isomers have a chiral centre which is a carbon with four different atoms or groups attached. 2 Answer is C It its good practice to quickly sketch out the isomers of C4H10O butan-1-ol, butan-2-ol, 2methylpropan-1-ol and 2-methylpropan-2-ol. Butan-2-ol has a chiral centre, and therefore stereoisomers, hence the total is 5. 3 a, c, d and e have optical isomers b and f do not First decide if the structures have chiral centres. You may need to draw the structure out. 4a Rotates the plane of plane polarised light 4b Remember to find the chiral centre, with four different groups attached, then draw two threedimensional structures, arrange the four groups on the structure and draw a mirror image. 4c Mixing equal amounts of the same concentration of two enantiomers No effect on plane polarised light One isomer rotates plane polarised light in one direction, the other rotates plane polarised light in the opposite direction and the effect cancels © Alyn G. McFarland and Nora Henry 2016 Hodder Education 8 Topic 8 Aldehydes and ketones 1a Propanone 1b Ethanal 1c Pentan-3-one 1d Butanal 1e 3-methylpentanal 1f Pentan-2-one 1g Propanal 1h 2-methylpropanal 1i 4-methylpentanal 1j Methanal 1k 2-bromo-4-methylhexanal 1l Hexan-2-one 2a (a) and (g) (e) and (l)/(i) (c) and (f) 2b C7H13OBr 3 Answer is C 4a CH3CH2CHO + 2[H] → CH3CH2CH2OH Reduction of an aldehyde produces a primary alcohol, in this case propan-1-ol 4b Heat under reflux propan-1-ol 4c Hydride ion 4d 4e CH3COCH3 or © Alyn G. McFarland and Nora Henry 2016 Hodder Education 9 An isomer has the same molecular formula (C3H6O) and a different structure hence propanone is the isomer. © Alyn G. McFarland and Nora Henry 2016 Hodder Education 10 Topic 9 Carboxylic acids and derivatives Carboxylic acids and esters 1a Ethyl ethanoate 1b Pentanoic acid 1c Butanoic acid 1d 3-hydroxypropanoic acid 1e Methyl butanoate 1f Propanoic acid 1g Propyl butanoate 1h Propyl methanoate 2 Answer is D There cannot be a straight-chain ketone with two carbon atoms as the C=O has to be in the middle of a molecule, so the simplest straight-chain ketone is propanone C3H6O. 3a 2CH3CH2COOH + Mg → (CH3CH2COO)2Mg + H2 3b 2CH3COOH + Na2CO3 → 2CH3COONa + H2O + CO2 3c CH3CH2CH2COOH + NaOH → CH3CH2COONa + H2O 3d CH3COOH + CH3CH2CH2OH ⇌ CH3COO CH2CH2CH3 H2O 3e CH3CH2COOH + CH3OH ⇌ CH3CH2COOCH3 + H2O Remember that acid + metal gives salt and hydrogen, acid and base gives salt and water and that acid and carbonate gives salt and water and carbon dioxide. The salts are -anoates. Carboxylic acids react with alcohols to give esters. Esters are named as alkyl carboxylates where the alkyl name comes from the alcohol and the carboxylate name comes from the carboxylic acid from which they are formed. 4a Name: propane-1, 2, 3-triol © Alyn G. McFarland and Nora Henry 2016 Hodder Education 11 4b 4c 4d Heat with methanol © Alyn G. McFarland and Nora Henry 2016 Hodder Education 12 Acylation 1 Answer is D An acid chloride reacts with an alcohol at room temperature. In this case the ester formed is propyl ethanoate. It is not a reversible reaction. 2a Nucleophilic addition–elimination 2b N-methylpropanamide Exam-style questions 1 Answer is A Always make sure you number from one side; this eliminates answers B and C. The smallest combination of numbers is chosen, hence D is incorrect. 2 Answer is C An optically active compound has a chiral centre; a carbon with four different atoms or groups attached. A and D do not have chiral centres. Tollens’ reagent is only reduced by aldehydes. C is an aldehyde with a chiral centre. 3 Answer is C The structure is an acyl chloride and it reacts with alcohols to form esters, in a reaction where HCl is removed. 4a CH2O The empirical formula is the simplest ratio. C16H32O2 is the molecular formula so the empirical formula is CH2O 4b © Alyn G. McFarland and Nora Henry 2016 Hodder Education 13 5a CH3CHO + HCN → CH3CHOHCN 5b 2-hydroxypropanenitrile 5c Nucleophilic addition 5d i ii CH3CH=CHCHO Remember that en means that a double bond is present and that it is on position 2 6a CH3OH + CH3CH2COOH ⇌ CH3CH2COOCH3 + H2O 6b Catalyst 6c H bonds between molecules of propanoic acid These are stronger than the dipole–dipole attractions between methyl propanoate When explaining the difference in boiling points in molecular covalent substances, always refer to intermolecular forces. 6d Goes to completion No heat or catalyst needed 6e C2H5COONH3 C2H5CH2OH C2H5COONa © Alyn G. McFarland and Nora Henry 2016 Hodder Education 14 Topic 10 Aromatic chemistry 1a C6H5COOC2H5 + HNO3 → C6H4NO2COOC2H5 + H2O 1b Conc sulfuric acid Conc nitric acid 1c Moles of ethyl 3-nitrobenzoate = 5.85/195.0 = 0.03 For 70% yield this (0.03 × 100)/70.0 = 0.043 moles Ratio 1:1 0.043 moles ethyl benzoate = 0.043 × 150.0 = 6.45 g 1d Substitution of NO2 at different positions forms different isomers / multiple substitution or nitration can also occur 1e To remove impurities Dissolve in minimum amount of hot ethanol / methanol Filter while hot and allow (filtrate) to cool and crystals to form Suction filtration to separate crystals 1f Between filter papers / cool oven / desiccator 1g Sharp m.pt compare to 42°C 2a Benzene is more stable than cyclohexatriene Expected enthalpy of hydrogenation of C6H6 is 3(−120) = −360 kJ mol−1 Actual value is less because of delocalisation, which makes benzene more stable 2b Cyclohexatriene orange → colourless Benzene stays orange © Alyn G. McFarland and Nora Henry 2016 Hodder Education 15 Topic 11 Amines 1a Ethylamine/aminoethane 1b N-methylpropylamine The prefix N is used to show that the alkyl groups are attached to the main chain via the nitrogen atom. 1c Phenylamine 1d N-methylethylamine 1e 2-aminopropane 1f 2,4-diaminopentane The prefix diamino is used if a compound contains two amino groups. 1g 1,3-diaminopropane 1h Diethylamine 1i 2-aminopropanoic acid 1j N,N-diethylpropylamine 2a i CH3CH2NH2 + HCl → CH3CH2NH3Cl ii 2CH3NH2 + H2SO4 → (CH3NH3)2SO4 iii C6H5NH2 + HNO3 → C6H5NH3NO3 iv CH3CH2NH2 + H2O → CH3CH2NH3+ + OH− v CH3CH2NH3Cl + NaOH → CH3CH2NH2 + NaCl + H2O i Ethylamine as the electron-donating alkyl group releases electrons to the N, meaning the lone pair is more able to accept a proton ii Ammonia as in phenylamine the lone pair on N becomes delocalised into the pi system so the electron density on the N is less and the lone pair is less available to accept a proton iii Butylamine as it has a larger electron-donating group 2b Remember that aliphatic amines are more basic than ammonia, which in turn is more basic than aromatic amines. © Alyn G. McFarland and Nora Henry 2016 Hodder Education 16 Exam-style questions Answer is A 1 First calculate the number of moles of 4-hydroxyphenylamine (10.9/109.0 = 0.1). Moles of paracetamol produced = 0.1. Multiply this by the formula mass, 151.0, to get 15.1 g if the yield is 100%. The yield is 80% so the answer is 15.1 × 0.8 = 12.1 g. 1,3-dinitrobenzene 2a The NO2 group is nitro. There are two of them, so dinitro is used in the name. The position of the nitro groups must be given; remember to place commas between numbers and a hyphen between a number and word. 1,2-dinitrobenzene or 1,4-dinitrobenzene 2b The position of the NO2 group can change to give an isomer, a different structure with the same molecular formula. 2c i NO2+ HNO3 + 2H2SO4 → NO2+ + 2HSO4− + H3O+ ii Electrophilic substitution Be careful that the + is on the N and that the arrow comes from the ring. The horseshoe must not extend beyond C2 to C6. iii 2d Manufacture of explosives / formation of amines / organic synthesis H2/Ni or H2/Pt or Sn/HCl or Fe/HCl 3a Phenylethanone + 3b CH3COCl+ AlCl3 ® CH3 C O+ AlCl4- 3c © Alyn G. McFarland and Nora Henry 2016 Hodder Education 17 4a A nucleophile is a lone pair donor. Amines have a lone pair on the nitrogen and so can act as nucleophiles. 4b CH3CH2CH2Br + 2NH3 → CH3CH2CH2NH2 + NH4Br 4c Quaternary ammonium salt Topic 12 Polymers 1 Answer is C A and B would both form condensation polymers; A would form a polyamide polymer and B would form a polyester polymer. D would form an addition polymer. The alcohol groups in HO(CH2)2OH and the amino groups in H2N(CH2)4NH2 cannot react to form a polymer. 2a or other appropriate Any proper repeating unit is correct such as all the ones shown below. They are shown in different colours to show you that the repeating unit can start from any part in the polymer structure. There are six possible repeating groups based on where you start from in the structure of the polymer. 2b Benzene-1,4-dicarboxylic acid Benzene-1,4-diamine Kevlar Clothing / bullet-proof vests © Alyn G. McFarland and Nora Henry 2016 Hodder Education 18 Topic 13 Amino acids, proteins and DNA 1a 2-amino-4-methylpentanoic acid 1b 2,6-diaminohexanoic acid 1c 1d At low pH the NH2 groups and COOH groups are protonated. All NH2 groups are protonated. 2a i ii Adenine © Alyn G. McFarland and Nora Henry 2016 Hodder Education 19 2b iii Thymine iv Condensation Cisplatin is [Pt(NH3)2Cl2] Coordinate bonds between nitrogen atom in guanine and cisplatin DNA cannot be replicated/copied Cells which are replicating are killed Topic 14 Organic synthesis 1 Route A uses KCN In ethanol (or aqueous) Intermediate is butanenitrile or CH3CH2CH2CN Lithal/LiAlH4 or H2 In dry ether for lithal or Ni/Pt/Pd for H2 Route B uses NH3 Excess NH3 It is important to be able to process the organic reactions you have met. Make sure you think through the reactions. In Route A the carbon chain is lengthened so the reaction of the halogenoalkane with KCN provides an extra carbon atom in the chain. The nitrile produced is then reduced using either lithal or hydrogen to form the amine. The longer chain halogenoalkane in Route B reacts directly with ammonia to form the amine. The conditions required in each step are necessary. These questions are a great way to revise your organic chemistry. Topic 15 Nuclear magnetic resonance spectroscopy 1 Answer is C As the molecule is symmetrical, the 1H nuclei in the two CH3 groups are chemically equivalent and so occur at the same chemical shift. As there are no 1H nuclei bonded to the middle carbon atom, there is no spin‒spin splitting, so there is only one singlet in the spectrum. 2 Answer is C The first thing to consider here is the number of chemical environments. A and B have four chemical environments whereas the spectrum shows only three sets of peaks which would indicate three environments. C and D have three environments of 1H nuclei. In order of increasing chemical shift, C would produce a triplet, a singlet and then a quartet as shown in the spectrum. D would produce a triplet, a quartet and the singlet would be at the highest value. © Alyn G. McFarland and Nora Henry 2016 Hodder Education 20 3 L is 2-methylbutanal 3-methylbutanal is not optically active and the only one which has four different groups bonded to the same carbon atom is 2-methylbutanal. Be able to work out that C2H5, CH3 CHO and H are the different groups. M is 2-methylbut-2-en-1-ol or 2-methylbut-1-en-1-ol or 3-methylbut-1-en-1-ol. Or any other appropriate structure Any correct E‒Z isomer would be accepted but these are the answers accepted. N is pentan-3-one. This is the only ketone that has three peaks in its 13C NMR spectrum. Topic 16 Chromatography 1a For spot 1 Rf = 2.5/8 = 0.3125 For spot 2 Rf = 5/8 = 0.625 For spot 3 Rf = 6.1/8 = 0.7625 Rf values are calculated by dividing the distance moved by the spot by the distance moved by the solvent. 1b The most polar substance is 1 Slowest movement in non-polar solvent and held by polar stationery phase The silica gel support is the stationary phase and is polar and so polar substances are held by the stationary phase. © Alyn G. McFarland and Nora Henry 2016 Hodder Education 21