AQAY Mark scheme ALLIANCE GCE Chemistry Unit CHM5SECTION A Answer all the questions in the spaces provided. ‘You are advised to spend about 1 hour on this section. 1 (@ The following reaction occurs in the hightemperature preparation of titanjum(IV) chloride. TiO,(5) + C(s) +2Ch(g) > TAC) + CO,g) (i) Use the data given below to calculate the standard enthalpy change and the standard entropy change for this reaction. {Substance Ti0,(s) cs) CL@) Ta, | CO, AH{/kI mol” 940 0 0 804 -394 SOK" mol” 49.9 57 223 252 214 hs — DAUs wadants Standard enthalpy change b Trae ales (- Sow — dae) Sheng Hee cho -156 (KT nel wore UES Come aorta? ‘s Allows + 258 @) marke Alles maxowt for +187 ii) Calculate the temperature at which this reaction ceases to be feasible. Awake Gan locus ua AP The, Zevalen Dom alanmn. Akane rey Se ow ~ 256 Koo TE o negabioe Femeraton gotn rar 2 TE °C used Laconctly max % Rive nal oenaline aur of Here Crone tg dla! eo(b) In the industrial extraction of titanium, TiCl, is reduced to titanium in an inert ute atmosphere. mak shecte seh “A 4 €€ iF Gj) Write an equation for this reduction process. a B . : atlas ° ayoe Tide + tha —> Ghee OT res 9 Oe — . x Denah shew,” (i) Explain why itis essential to exclude air when this reduction takes place. Penaline vt i : ; ofles prededs or Th ee or 1 it tt “ ~ Seas OF Naor hy tacts wilh cnyaen, nittoyan er aie marks) (c)_ Write an equation for the reaction of TiCl, with water. Tice AHO —P TRO, 4 Get (Tore stele syneele) © allow VCoH), ola. Ate (mark) or Tiloble (Hol, ck 6 Hip asad or TH wio bet mvet be belencat wa eb orless TURN OVER FOR THE NEXT QUESTION oe nade syels o Tum over > 32 Hark on Eee an KE Mateo Cell emf Large blocks of magnesium are bolted onto the hulls of iron ships in an attempt to prevent the iron being converted into iron(II), one of the steps in the rusting process. ‘Use the data below, where appropriate, to answer the questions which follow. ENV Mgi*(aq) +2e” == Mg(s) -237 Fe*(aq) +2e° == Fe(s) 0.44 0,(g) + 24,00) +40" == 40H (aq) +0.40 (a) Calculate the em. of the cell represented by Mg(s)IMg™(aq)lIFe”*(aq)|Fe(s) under standard conditions. Write a half-equation for the reaction occurring at the negative electrode of this cell when a current is drawn. rAd (v) ce if = mgabive ‘ Cell emf. bad lv € ue ; ngatioe value aise Half-equation:.. (2 marks) . Ta - Deduce how the emt of the cell Mg(s)IMg”*(aq)IIFe*(aq)IFe(s) changes when the concentration of Mg” is decreased. Explain your answer. } ) Change in emf Explanation .. E__dgoseses... (3 marks) re Ko ‘or guns roe perenoa or Lonne vente AQ me (c) Calculate a value for the emf. of the cell represented by Pt(s)|OH (aq)!02(g)llFe**(aq)IFe(s) and use it to explain why iron corrodes when in contact with water which contains dissolved oxygen. ate an fo Explanation ok 8.8 oo QAI... De one Yeadon ote. Sy. the (2 marks) We Te eek G1 Bek onal ne vale geen but ce tu woth @ and) ve emt = Revo 58 oO ca) @ xIww ‘Lane 3 (a) Dons aller Charge franster State fhe origin of the colour of transition-metal complexes. buoys ind glullade A ©) Dttenet) oxdalin (Defharertl legends [Dieter] Change! Do nok allow | glape Change 3... as lan answer Change 2 (3 marks) ‘You are provided with a 1.00 mol dm’® solution of iron({III) ions and a visible-light spectrophotometer (colorimeter), Outline a plan for experiments using this solution and this apparatus which would enable you to determine the coneentration of ispn(JH1) ions in a selution of unknown centration, CRasaavete ENS)” of levpani © Beds ee sol ‘Tum over so4 Consider the reaction sequence below. Colourless solution Dilute . Na,$,0,(e) c NH(aq) Colourless NaBr(aq) . Cream net AgC\(s) ———» solution ———» precipitate A Bea: KCN(aq) Colourless solution D (a) Identify the silver-containing species in A, give its shape and state a use for it in organic chentictry. Dllow nae lout penalise coubradic! Hark Specs ad Bekore ta Hark ube sabarak ely () - @” Identify the cream pretipitate B and the silver-containing species in C. Précipitate B Silver-containing species in C .. i)’ Write an equation for the reaction in which the silver-containing species in C is formed from B and explain the use of this reaction in photographic processing. : ‘ sotograph To Tes (oe be Equation Explanation (©) Identify the silver-containing species in D, and state one use of solutions containing this, species. Species saperedely, UE ~ (2 marks) (@ What can be deduced about the outer electronic configuration of silver in each of the species A,C and D from the fact that all the species are colourless? Te ae. 9 folk A shell ot chow mat howe a Su 3a port vally felled a shelh Rot ik, Werte: KUM outer eball” (i mark) mareea Be WoT alloio wackine with baste offer than water 5 (@)_@_ Write an equation o show why aqueous chromium(ID) chloride is acd Atos leet — [er(yole{t x Ho. —= [er(Avo s(ou) |" + Hyo* a) ve te att or “Ler(dioye SP Lee Ws (oul tt ~ Explain why aqueous chromium(I]) chloride is ‘more acidic than aqueous chromium(II) chloride: danny: vor charge tesizerobin Atreity of cheat @ maO-H loonde (bree wel feo. ss (marks) Leow ox Aen (Max 2 fen 3) (b) The addition of sodium hydroxide or of sodium carbonate to aqueous chromium(III) chloride results in the formation of the same green precipitate. (i) Identify this green precipitate.’ ’ Sr (WO) s Cots on CeCOv)s ar Colotlly Hic wle | a) OF Mame, Charomiven (tit) lyase xcke COST (ii) State the role shown by both sodium hydroxide and sodium carbonate in the formation of this green precipitate. tar 3 shecten pain cho NoT allerli 5 Cnet nuceobli (iii) Identify the gas-evolved when carbonate ions react with aqueous chromium(III) ions and write an equation for the reaction occurring. @ bee penatiae Iaond” (4 marks) (©) State the reagents which could be used to convert aqueous chromium( 1M) ions into chromate(VI) ions. ¢ 4 6 44 to, {Se of Score @) (2 marks) nao Na,O, scores (2) 3 Do nek allo “alkaline, @F ORT or WH, 61 Turn over >6 (a) State what is meant by the term co-ordinate bond. eed Neckve Bik slechrne Lom ovelenk loud ove abou Mask posts Sepsatela, (2 marks) 4 Bronsted-Lowry acid ) O Alove or election pach accebler o (2 marks) (b) Define the terms Bronsted-Lowry acid and Lewis acid. fo Lewis acid .. (©) State what is meant by the term bidentate ligand. ott of athaduant chron pos @ ot o OR donates ted) parm of tlechrenn (@)_ State how the co-ordination number of cobalt(II) ions in aqueous solution changes when ‘an excess of chloride ions is added. Give a reason for the change. Change in co-ordination number Danek Chloride | allow Morne er Ch Suggest why the enthalpy change for the following reaction is close to zero. [Co(NH,),* +.3NH,CH,CH,NH; —> [Co(NH,CH,CH,NH,),J* + 6NH, bende ©) ‘(2 marks) (0 Deduce the formula of the compound formed when ethane-1,2-diamine is treated with an excess of hydrochloric acid. ° Nu oe (NA CHECH, Huy) Alles Cr Wyo NaCl, ond NHSet CH eH WHA cr act 62 Leave MaRct Laneweave Manin SECTION B “Answer alll of the questions below in the space provided on pages 11 to 20 of this booklet. 7 A.4.54g sample of PCI, was heated in a sealed flask at 525K. Partial decomposition occurred as shown by the equation below. PCL(g) == PCL(g) + Ch(s) ‘At equilibrium, 45.0% of the PCls had dissociated and the total pressure in the flask was 91.9kPa. (a) Calculate a value for the equilibrium constant K, of this reaction at 525K. (9 marks) (b) In the gaseous state, both PCI, and PCI, exist as molecules. In the solid state, PCI, is ionic and made up of two species both of which contain phosphorus. Sketch and name the shape of the PCL, molecule and that of the PCI, molecule. Suggest a formula and a shape for each of the two ionic species present in solid PCl, (6 marks) 8 The reaction scheme below shows the conversion of epoxyethane into sodium ethanedioate. oO 2NaOH HCO Cth ae compoundX ———» (COOH), ———> Na,C,0, (@) Identify compound X. State the reageants and conditions required to convert X into ethanedioic acid. Draw the structure of the anion in sodium ethanedioate. (4 marks) (6) The addition of sodium ethanedioate to an aqueous solution containing [Co(H,0),)”* jons results in the formation of a more stable complex ion. Draw the structure of the complex ion formed and explain, in thermodynamic terms, why this substitution reaction occurs. (4 marks) (©) @ Sketch the pH curve for the titration of ethanedioie acid with aqueous sodium hydroxide. Write equations for the reactions which occur during this titration. (i)_A.25.0em sample of a solution of ethanedioic acid was found to react with exactly 382 cm? of a 0.145 mol dm™ solution of sodium hydroxide. Calculate the concentration of the ethanedioic acid solution. ‘What volume of sodium hydroxide solution: would have been required if the solution titrated had been sodium hydrogenethanedioate, NaHC,O,, of the same concentration rather than ethanedioic acid? (7 marks) = ‘Turn over Be!9 (a) The reaction between aqueous persulphate ions, S,0§ (aq), and iodide ions, I(aq), is 10 ) @) (o) catalysed by Fe” (aq) ions. Suggest why this reaction has a high activation energy. Write equations to explain the catalytic action of Fe*(aq) ions. Suggest why V*"(aq) ions will also act as a catalyst for this reaction but Mg™*(aq) ions will not. (6 marks) Outline a mechanism for the reaction between benzene and ethanoyl chloride and explain why AICI, acts as a Lewis acid catalyst for this reaction, Predict, with an explanation in each case, the suitability of FeCl, and of NH,Cl to act as a catalyst for this reaction. (9 marks) P and Q are oxides of Period 3 elements. Oxide P is a solid with a high melting point. It does not conduct electricity when solid but does conduct when molten or when dissolved in water. Oxide P reacts with water forming a solution with a high pH. Oxide Q is a colourless gas at room temperature. It dissolves in water to give a solution with a low pH. (i) Identify P. State the type of bonding present in P and explain its electrical conductivity. Write an equation for the reaction of P with water. Identify Q. State the type of bonding present in Q and explain why it is a gas at room temperature. Write an equation for the reaction of Q with water. (9 marks) R is a bydroxide of a Period 3 element. It is insoluble in water but dissolves in both aqueous sodium hydroxide and aqueous sulphuric acid (@ Give the name used to describe this behaviour of the hydroxide. (ii) Write equations for the reactions occurring. (6 marks) i) Suggest why R is insoluble in water. END OF QUESTIONS ueQuestion 7 NB Mark NOW awarded for calculating pPCig not pPClg = pCl2 a (2) pital moles of PCIg = 4.54/208.5 (1) = 0.0218 (AE i Mr PCs wrong) ‘Atequilibrium moles PClg = 0.0218 x 55/100 (1) = 0.01198 (allow 0.012) NB Award 2 marks @ inital moles POs missing but equilbrium moles POIs correct) Either moles PCig or moles Clg = 0.0218 x 45/100(1) = 0.00980 NB This can also be determined by subtraction NB If mole PCig * Moles Qlp award max 4 forthe following Inkial moles PCs (1) Equilorium moles PCs (1) Partial pressure = Total pressurex mole traction (stated or used correctly) (1) Kp defined or used correctly (1) Total moles in system = 0.03158 (Allow 0.032) (1) [NB Mark this consequentially to equilibrium moles of PCI, PClg plus Ciz) partial pressure =Total pressure x mole fraction (stated or used correctly) (1) pPCls = 91.9 x 0.01199/0.03161 (1) = 34.91034.5 NB Mark consequentialy to equilibrium moles Cis and total number of moles pPClg = pClz = 91.9 x 0.00981/0.03161 (1) = 28.52 Kp = pPCIg x pCl2/pPCis (defined or used correctly) (1) NB Donot alow t [ J included here = 28.522/34.86 = 23.3 1023.9 (KPa) (1) NB Mark consequentialy fo partial pressures determined above NB Ignore units even if incorrect {b) PClg_ Pyramidal or Tetrahedral (1) Sketch a) R “41 a ba NB Mark sketch and name separately 'NB I! clearly pyrinidl,aliow shketch withou lone eleSctron pair PCig Trigonal bipyramidal 4) ‘Sketch a Ke a) “ P—Cl aw cl NB Mark sketch and name separately Formulae ofions —-PClg* and PCig- (1) Shapes Tetrahedral and Octahedral (1) OR PCig* and stated as tetrahedral (1) PCig- and stated as octahedral (1) 65Question 1 1 ACTERNATWE magi TeriEme. Cam ipatés coud AMPROMA THE Arersg Tint wang Umm) Ere. 66 Pag oS Py 8 itary e ° ° at €a0 a('-«) ae ax rene roues = 0(/t%) sing Ts meTHOD woe. out AA TH Foucsutg Seotery fowts : EE) ree fancran file + MPay w w (Aa) 0 Panera My + men anctoat 06 OED A tr) pee py 9 pense 2 met fine (Hide panbeil presmee of Pele = 09TH WT -Greg7 © (Fa): * pebil prostere of Pap oc 2 O.8l03 x WT “CD C1 . GD (eh) CY @Question 8 (a) (b) (cy) (oni) Identity of A; ; Sthane-1,2-diol or 1,2 dihydroxyethane or ethylene glycol or formula (1) NB Do NOT allow OHCH2CH2OH unless a correct name also given KoCr207/ dilute H2SO4 or dilute HCI or K2Cr207/H+ (1) NB. Oxidising agent must be a reagent NB Do not allow concentrated HaSO4 Reflux (ignore temperature if given) or warm of heat a) NB ita temperature given on is onn it must be ator below 200°C Anion o 0 Wow ¢-C aN 0 o (1) NB Do NOT allow C2042- NB Ignore lone pairs of fectrons Structure; correct co-ordination (1) bonding through six correct oxygen (1) (Score 2 or 0) [NB Not essential io show double bonds i.e. C=O in structure Explanation; Substitution produces more molecules or particles or more disorder (1) Entropy change is positive (1) pH curve; two steps shown 0) NB Axes not essential but I given must be correct for graph as drawn Volume NaOH(aq) added Equations; HyC204 + OH- + HC2Og + HO a) HC204- + OH- > C2042 + HzO a) NB Alowone for HjCp04 + 20H —» Cy0,2- + 2H,0 NB Allow molecular equations" 2.64 x 10°3 82 x 103 Moles of NaQH 0.145 x 18.2/1000 (1) Moles acid (2.64 x 10°3) #2 (1) = NB Mark CE at this point i moles NaOH not divided by 2 Concentration of acid = 1.32 x 10-3 x 1000/25 = 0.0528 0r 0.05278 (1) NB. Mark concentration consequential to correct moles acid Volume NaOH if NaHC20 4 used = 18.2/2 = 9.1 (1) 07Question 9 (@) (b) High Ea: $20g2- repels Ir or both ions negative 2Fe2+ + S20g2 — 2Fe3+ + 2S042- (1) 2FeS+ + 2b > 2Fe2+ + Ip (1) 'NB ignore addtional incorrect equations ‘Vanadium is a transition element or Magnesium is not a transition element (1) Vanadium has variable oxidation states (1) Magnesium only forms Mg2+, or has only one oxidation state (1) NB Score two Marks for “Only vanadium has variable oxidation states” AIClg + CKCOCHg — AICI” + CH3CO+ (1) ety 9 em ces iis cs > 4 ‘ Or: 2 + Of}, o mals ct. o CH (ae ke HOt Ge OF u ° +Ht Y H+ + AIClg- -> AICIg + HCI a) Lewis acid: AICig accepts electron pair (1) NB Penalise incorrect acy! chioride by one mark NB Penalise chloroethane by two marks i.e. first equation mark, attack on benzene mark NH4Cl: Not a catalyst (a) Fei: A catalyst ” has a low energy vacant shell ‘or has spaces or vacancies in d shell ‘or has a partially filled d shell ‘or able to accept an electron pair ‘or can from FeCl4- a) a) 6Question 10 (ay) qi) Deductions onic Ions not free to move in the solid state Tons free to move when motten or in aqueous solution Identity of P; _Naz0_ or sodium oxide NB If a formula given this must be correct Equation: Nag0 + Hg0 + 2NaOQH Deductions ~ Covalent yi) covarolecular forces are weak or van der Waals forces, or dipole -dipole NB Any answer including a relerence to hydrogen bonding is incorect Identity of @; SO2 ° or Sulphur dioxide Equation; SO2 + H20 > H2S03 NB Allow max one for SOg . Amphoteric Equation with NaOH ‘A\(OH)3 + NaOH — NaAl(OH)4 OR —AI(OH)g(H20)3 + OH" —> [AKOH)4(H20)2I" + H20 OR AI(OH)3 + OH — [AKOH)4} R identified as A(OH)3 or A(OH)3(H20)3 A balanced equation 4 he akon qotore wt coat Ruin apts OF oad (NB Allow equation mark it ‘M(OH)3 given in a balanced equation Equation with H2SO4 2AIOH)3 +3H2804 -> Alg(SO4)3 + 6H20 OR AM(OH)3(H20)3 +H*+ —[AlOH)2(H20)4] * + H20 'NB Allow equations with six co-ordinate Aluminium and up to six H20 ligands NB Alow equation mark # MOH)ggiven in a balanced equation Correct Al species as product Abalanced equation Large lattice eneray or strong covalent bonds or AHsoln is very positive or AGis positive oF cum of tydration energies less than covalent bond energies o q {i (1) a) a) q & a) a) (iy (4) (1)