UNIVERSITY OF CAMBRIDGE LOCAL EXAMINATIONS SYNDICATE Joint Examination for the Higher School Certificate " and General Certificate ot Education Advanced Level CHEMISTRY ‘9253/3, 9256/3 PAPER 3 Mulliple Choice Friday 28 NOVEMBER 1999 1 hour Additional maten, Data Booklet Electronic catsulator andior Mathematical tables Multiple Choice answer sheet Soft clean ere ser Soft pencil (tye B or HB is recommended) TIME 4 hour INSTRUCTIONS TO CANDIDATES De not open this booklet until you are told to do so. Write your tame, Centre number and candidate number on the answer sheet in the spaces provided unless this has already besin done for you. Thiere are forty questions. in this paper. Answer all questions, For each question, there are four possible answers, A, B, Cand D. Choose the one you consider correct and recard your choice in soft pencil on the separate answer sheet. Read very carefully the ir.structions cn the answer sheet. INFORMATION FOR CANDIDATES Each correct answer will score one mark. A mark will not be deducted for a weong answer, ‘A Data Booklet is provided. Mathematical tables are available. You may yse a calculetor. Any rough working should be done in this booklet. This question paper consists of 16 printed pages. Ww) aKaAs66'4 EST : [Turn over2 Section A "For each question there are four possible answers, A, B, C, and D. Choose the one you consider to be correct. In 1892, Lord Rayleigh made ‘atmospheric nitrogen’ by removing oxygen from the atmosphere. He found the density of this nitragen to be 1.2572 gdir~“.at s.t.p. Chemically pure nitrogen has a density of 1.2505gdm~ at s.t.p. Which gas was present in ‘atmospheric nitrogen’ to cause this discrepancy? argon helium methane coo Db neon Which equation is used to define the first ionisation of bromine? A Brg) —> Br-(g)-e B Brig) —-~ Br'(g) +e" © 38r,(g) —> Br(g)-e D_ 3Br,(9) —> Br'(g)+e~ ‘The reaction of hydrogen sulphide with sulphur dioxide gives sulphur" as one of the products H,S(aq) == S(s) + 2H*(aq) + 2e~ SO,(aq) + 4H*(aq) + 4e" == S(s) + 2H,0()) How many moles of hydrogen sulphide ate needed to react with sulphur dioxide to produce 1 mol of sulphur? * + . a A 3mol B §mol Cc $mot D 2mol: 3 4 The elements radon (Fin), francium (Fr) and radium (Ra) have consecutive proton numbers in the Periodic Table, ' . What is the order of their first ionisation energies? " ~ | least i endothermic = > Fr Ra : Fr Rn Ra: Fr oy. Rn Ra a 5 Ethanol is much more soluble in water than is ethyl ethanoate. Which statement helps to account for this? A Ahydrogen bond iorms between the hydrogen of the -OH group in ethanol and the hydrogen of a water molecue. ‘ B__ Ahydrogen bond torms betwéen the hydrogen of the ~OH group in ethanol and the oxygen of a water molecule. Ethanol is a pola: molecule, but ethyl ethanoate is non-polar. D___Ethanot is able to sissociate into hydrogen ions and ethoxide ions, bu: ethyl ethanoate is not able to dissociate. c sen woe [Turn overA ae Trimethylamine, Me,N, reacts with boron trifluoride, BF,, to form a compound -of formula Me,N.BF,, {the symbol Me = CHa] How may this reaction be written in terms of the shapes.of the reac’ants and products? Me Me. Y Me : Ne nae F- —+ A * | LF F— . vr Me Me Benen i "s Bo Me. VT oMe + FO gb RO ee _ Ne F 27 Bs, FOL YF - Me Me. .f Me Me “NO Me. T Me + — c Ne e ~Me ve 7 Me." Me + a Do SNe Under which set of conditions does a real gas most closely obey the ideal gas laws? A high pressure and low temperature B low pressure and high temperature € low pressure and low temperature D standard temperature and pressure10 4 5 In @ syringe experiment, 0.10g of a gas is found to occupy 83.1 cm, measured at standard pressure (1.0 x 10° Pay and 27°C. Whaat is the relative molecular mass of the gas? . 0.10 x 8.31 x27 0.10 x 8.31 x 27 R10 x 10x 63.4 4.0.x 10° x 83.1 x 10° 0.10 x 8.31 x 300 0.10 x 8.31 x 300 1.0.x 105 x 83.1 1.0.x 105 x 83,1 x 108 From which of the following reactions can the bond energy of the C — F yond be determined by using only the standard enthalpy change of the reaction? A CF,(g) —> Cig) = 4Fig) B CF,(¢) —> CF() + F,(9) C CF,(s) —> CF, (s) D_ 2F,(g) + C(s) —> CF,(g) The graph shows the variation of pH during the titration of an aqueous alkal’ with an aqueous acid of similar concentration. pH : 0 = volume of aqueous acid added What could be the alkali and acid in this titration? [ [ata acid . A | NH(aq) | CHJCO,H(aq) B | NH,(aq) | HCl(aq) © | NaOH{aq) | CH{CO,H(aq) D | NaoHiaq) | HCHaq) “ese von [Turn over" 6 Methanol is manufactured industrially by the catalytic reaction shown, CO(g) + 2H,(g) —> CH,OH(g) ; AH -92 kJ mor i hae bp The operating 2onditions are: 250°C; a pressure between 50 atm and 100 atm; a copper-based catalyst. ‘Which factor influences the choice of these conditions? &. The catalyst increases the equilibrium yiald of methanol BL At lower pressures, the rate of formation of methanol increases G © Ai lower temperatures, the equilibrium yield of methanol increases. “No Atlower temperatures, the rate of formation of methanol incrozses. 12 13 14 In which units could the rate constant of a first-order reaction be expressed? A st B mols mol dm? s DB mol dm$ s+ The following species contain the same number of electrons, In which order do their radii increase? [| erated —~Trageat] 1 radius an) radius B Ar Kr le Kt 5 Barium sulphate occurs naturally as barite, which is « solid ore. Magnesium sulphate, however, occurs mainly in solution. Why is this? ‘A Barium ions are less readily hydrated than magnesium ions. B Bajfurysulphate has a stronger crystalline lattice. C Barium sulphate is more resistant to oxidation than magnesium sulphate D Magnesium sulphate is hydrolysed by naturally acidic solutions, but barium sulphate is not e500 09916 16 7 18 19 7 What are the products of the thermal decomposition of magnésium nitrate? ‘A magnesium nitride and oxygen B magnesium oxide and nitrogen C magnesium oxide, nitragen and oxygen D_ magnesium oxide, nitrogen dicxids’ and oxygen Why is silicon tetrachloride readily hydrolysed whereas carbon tetrachloride is not? A ASi-Clbond is more polar than a C - Cl bond. B_ASi-Clbondis weaker than a C - Cl bond. © Silicon can use available d orbitals whereas carbon cannot D_ The d orbitals of carbon are filled whereas those of’silicon are not. ‘A weedtkiller can be prepared by heating a bleach solution. . . h anacio 8, enacts Nacio, bleach weedkilier What are the oxidatior: states of chlorine in these three compounds? A +t 45 B+ +5 ! cH 47 Do 42 4 47 . Which'atom has three unpaired elentrons? A Al B Sc ec cr D Co Nitrogen dioxide and sulphur dioxide have some properties in common. Which property is shown by one of these compounds, but not by the other? ‘A forms ‘acid-rain’ B sia reducing agent C__is‘insoluble in water: 7 D is'used as a food-preservative 2565 909 +: [Turn over20 vat 22 ; 8 Tetramethyl-lead{(IV) increases the rate of the reactior of methane with chlorine. CH,(g) + Cl(g) —> CH,Cl(g) + HCIg) . Why can tetramethy/-lead(IV) behave in this way? A Itis a source of methyl radicals. B Itreleases. CHS(g) C _ Itreacts with chloromethane’and prevents equilibrium being established, he D Metal jons catalyse the reaction. The drug cortisone has the formula shown, {In addition to those chiral centres marked by an asterisk (*),.how many other chiral centres are present in the cortisone molecule? Ao B41. ¢c2 D3 Smoke from a bonfire contains a compound that causes irritation to the eyes. This, compound feadily decolourises aqueous bromine and produces a precipitate of silver when bubbled into Tollens’ reagent. What is a possible structure of the compound? ne A B c D CH, = CHCH,OH — CH,==CHCHO l ,—CH,CHO 2 sewn9 23 What Is the correct s2t of conditions for the conversion of benzene into nitrobenzene? temperature 8 & A | dilute HNO, B | concentrated 4NO, © | concentrated 4NO, and concentrated H,SO, D | concentrated NO, and concentrated H,SO, 24 A possible mechanien of the hydrolysis of 2-chloro-2-methylpropane is s:iown, CH, CH, ee cr, _slow ee + or ar CH . CH, : CH, CH,— rr + OH est CH,—C —OH a . e Which diagram represents the reaction profile for this mechanism? A 8 c D > > > > & B & PL EU BU 5 5 5 5 reaction pati reaction path reaction path reaction path 25 Which inorganic reagent may be used to distinguish between phenol and methanol? A alkaline aqueous I, B aqueous NaHCO, © K,Cr,O, in dilute H,S0, D Na vase wae [Turn ever26 The following compounc! can be used as a photographic developer. 10 OH O OH Which reaction does it give? A B c It forms a dye when mixed with phenylamine. It gives an orange precipitate with 2,4-dinitrophenylhydrazine. Itforms a salt with aqueotis sodium hydroxide. CO,H Itis oxidised to 0 by aqueous alkaline potassium manganate(V1l). CO,H 22560 909De 4 - 27. The first stage in the synthesis of Antipyrine, a diug used in reducing fever, is the reaction between compound P and phenylhydrazine CH,COCH,CO,CH,CH, + eo NHNH, ——~ @ P phenylhydrazine ‘ What is the product (1 of this first stage? A CH,COCH,CONH —{ C) » B ©- NACH,CO,CH,CH, : , © CH,COCH,cc ~ T is -83kJ mol as Wo0 ts 1 t0 3 may be (you may find it helpful to put.a tick against {Turn over14 32 Some standard redox potentials ate given below. Br, + > Br +4.07V 10% +7Ht+ Se” = Cr ¥5H,O + 1.33 $CL, +e == Cl +1.36V MnO; +8H'+5e> == Mn?* + 4,0. +152V Which oxidations are theoretically possible under standard conditions? 1 chloride ions by acidified manganate(V1l) ions 2 chloride iors by bromine _ 3 manganate({l) ions by acidified dichromate(V1) ions 33 Which suggested mechanisms are consistent with the experimentally obtained rate equations? rate equation suggested mechanism + 1 rate = KINOF[H,] | 2NO(g) + H,(g) 1", N,0(g) + H,0(@) | N,0(@) + H,(g) —88'_, n,(@) + HO | slow | 2 rate = k,[F,) [1p] H,(9) — 2H(g) +1, —85t_, ang) “, 2H(g) = 2HB4(g) + 0,(g) S”_, aHBro(g) | [ HBrofe) « HEr(@) et. H,0(@) + Bra) 34 Which’statements about GeCl, are correct? 1 Itis covalently bonded with van der Waals’ forces between molecules. 2 Its molecule is tetrahedral in shape. 3 Its molecule undergoes nucleophilic substitution by bases. 22869 Wo8© The responses A to D shold be selected on the basis of 36 37 3B 15 | > i 7 a | | 41,2and3 tand2 2and3 1 only are only are only are is + 4 correct correct correct correct 7 Lo ——_|. st No other combination of statements is used as a correct response. The hexa-aquairon(II) ion hydrolyses as shown, [Fe(H,0),)*(aq) + H,0(l) == [Fe(H,0),OH]*"(aq) +H,0'/aq) Which statements are correct? 1 The correspondirig iron(I1) ion, [Fe(H;0),]**, is less likely to undergo hydrolysis. . 2 The iron undergces a change in oxidation state. 3. This hydrolysis is favoured by low pH values. Which mixtures, on heating, produce the gas ND.,? [D = jH, an isotope of hydrogen] 1 CaO{s) and ND,Clis) 2 CH,CN and NaOD in D,0. 3 NDH,Cland NaOD in D,0 Which compounds mey be prepared fram C,H.CHBrCH, by the action of sodium hydroxide under different conditions? 1 C,H.CO,Na 2 O,H,CH(OH)CH, 3 CyH,CH=CH,” How can the rate of reaction between ethanal and aqueous hydrogen cyanide be increased? 1 by inadiation witt ultraviolet light 2 bya rise in temperature 3 _ by the addition of a small quantity of aqueous sodium cyanide ese 28 {Turn over16 39. A suri protection cream contains the following ester as its active ingredient. CH,CHs ~CH=CHCO,CH,CH CHO —~ ~CH,CH,CH,CH, What are the products of its partial or total hydrolysis ky aqueous sodium hydroxide? 1 CH,CH,CH,CH,CH(CH,CH,)CH,OH 2 cHo—~ ())cn=c460;n0 : 3 chH,O @ CO; Nat 40 Dopamine is a rug used in the treatment of Parkinson's disease: NHS HO. C) CH,CH “CO,H HO Which statements about this compound are correct? 1 Itcan exist in optically active forms. , 2 One mole ean react with three moles of sodium hydroxide to form a salt. 3 Itcan exist as a 2witterion in aqueous solution, esa wes