UNIVERSITY OF CAMBRIDGE INTERNATIONAL EXAMINATIONS

GCE Advanced Subsidiary Level and GCE Advanced Level

MARK SCHEME for the October/November 2009 question paper for the guidance of teachers

9701 CHEMISTRY
9701/42 Paper 42 (A2 Structured Questions), maximum raw mark 100

This mark scheme is published as an aid to teachers and candidates, to indicate the requirements of the examination. It shows the basis on which Examiners were instructed to award marks. It does not indicate the details of the discussions that took place at an Examiners meeting before marking began, which would have considered the acceptability of alternative answers. Mark schemes must be read in conjunction with the question papers and the report on the examination.

CIE will not enter into discussions or correspondence in connection with these mark schemes.

CIE is publishing the mark schemes for the October/November 2009 question papers for most IGCSE, GCE Advanced Level and Advanced Subsidiary Level syllabuses and some Ordinary Level syllabuses.

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Mark Scheme: Teachers version GCE A/AS LEVEL October/November 2009

Syllabus 9701

Paper 42 [1] [1] [1] [3]

(a) Sulfates become less soluble down the group both lattice energy and hydration (are involved) but hydration energy decreases more than lattice energy or HE becomes less than LE or HE decreases whereas LE is almost constant (due to cationic radius increasing)

(b) (i) n(CO) = pV/RT = 1.01 105 140 103/(8.31 450) = 3.78 or = 140 (273/450) / 22.4 = 3.79 [1] [1] [1] [1] [4] (c) (i) from data booklet, 1st IE = 502; 2nd IE = 966; sum = 1468 kJ mol1 so 460 = 1468 + 180 + 279 200 + 640 + LE 460 = 2367 + LE LE = 2827 kJ mol1 ( 1 for each error) (ii) LE of BaS should be smaller than that of BaO, since S2 is bigger than O2.

allow= 140 (298/450) / 24.0 = 3.86 (ii) n(BaSO4) = n(CO)/4 = 0.945 moles (or 0.9475) If RTP used answer is 0.966 (iii) Mr = 233, so 0.945 mol = 0.945 233 = 220g 100 220/250 = 88(.07)% (or 0.9475 mol 220.8g 88(.3)%) If RTP used answer is 90(.0)%

[3] [1] [4] [Total: 11]

UCLES 2009

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Mark Scheme: Teachers version GCE A/AS LEVEL October/November 2009

Syllabus 9701

Paper 42 [1]

(a) ethylamine > NH3, but phenylamine < NH3

in ethylamine, the alkyl group donates electrons to the N, making lone pair more available [1] in phenylamine, the lone pair is delocalised over the ring, so is less available [1] [3]

(b) halide chloride bromide iodide observation when AgNO3(aq) is added white ppt cream ppt (pale) yellow ppt observation when dilute NH3(aq) is added dissolves no reaction / slightly dissolves no reaction observation when concentrated NH3(aq) is added dissolves dissolves no reaction [1] [1] [1] [3] (c) (i) [Ag+(aq)] = Ksp = (5 1013) = 7.1 (7.07) 107 mol dm3

[1]

(ii) AgBr will be less soluble in KBr, due to common ion effect or equilibrium is shifted to the left / or by Le Chateliers principle [1] [2] (d) (i) Kc = [Ag(RNH2)2+]/[Ag+][RNH2]2 units are mol2 dm6 (ii) assume that most of the Ag+(aq) has gone to the complex, then [Ag+(aq)] = 7.1 107 [Ag(NH3)2+] = 0.1 and [NH3] = {[Ag(NH3)2+]/(Kc[Ag+])} = {0.1/(1.7 107 7.1 107)} = 0.091 mol dm3 [1] [1] [1] [1]

(iii) When R = C2H5, Kc is likely to be greater, since the ethyl group will cause the lone pair on N to be more available / nucleophilic / increases basicity [1] [5] [Total: 13]

UCLES 2009

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Mark Scheme: Teachers version GCE A/AS LEVEL October/November 2009

Syllabus 9701

Paper 42

(a) Any two from: high(-ish) density of metal variable oxidation states ability to form complexes formation of coloured compounds incomplete d subshell high m.p. / b.p.

[1] + [1] [2]

(b) equ: MnO4 + 8H+ + 5Fe2+ Mn2+ + 5Fe3+ + 4H2O method: Take a known volume of Fe2+(aq)/in a pipette and place in (conical) flask Add an excess of (dil) H2SO4 Titrate until end point is reached and note volume used End point is first permanent pink colour Repeat titration & take average of consistent readings any 3 points

[1]

[3] [4]

(c) (i) 2 MnO4 + 5 SO2 + 2 H2O 2 Mn2+ + 5 SO42 + 4 H+

[2] [1] [2] [1]

+7

+4

+2

+6

(ii) 1 Cr2O72 + 6 NO2 + 2 H+ 2 Cr3+ + 6 NO3 + 1 H2O

+6

+4

+3

+5

([2] marks for each equation: [1] for balancing of redox species, [1] for total balancing: i.e. H2O and H+) [6] (d) Fe3+ is a homogeneous (catalyst) Fe3+ oxidised I (and is reduced to Fe2+) Fe2+ reduces S2O82 (and is oxidised to Fe3+) or equations showing this

any two points

[2] [2] [Total: 14]

UCLES 2009

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Mark Scheme: Teachers version GCE A/AS LEVEL October/November 2009

Syllabus 9701

Paper 42 [1] [1] [2] [1] [1] [1] [3]

(a) The energy required to break.... .....1 mole of bonds in the gas phase

(b) HCl: nothing happens AND HI: purple fumes (at a low temperature) purple is iodine formed (or in an equation: 2HI H2 + I2) H-X bond energy becomes smaller/weaker down the group

(c) data needed: F-F = 158 Cl-Cl = 244 6 E(Cl-F) 328 = 3158 + 244 E(Cl-F) = +174 (kJ mol1) [2] [2] [Total: 7] 5 (a) compound A B C D E all 5 correct [3] (4 correct: [2], 3 correct: [1]. <3 correct: [0]) [3] (b) reaction I: Cl2 + AlCl3 / FeCl3 / Fe / or bromides of Al or Fe reaction II: Cl2 + heat / light / uv / hf [1] [1] [2] [1] [1] [1] [1] [1] [1] [6] [Total: 11] all carbon atoms can be coplanar not all carbon atoms coplanar

(c) (i) H is C6H5CH2Cl (ii) reaction III: KMnO4 + heat (+ OH) reaction V: NaOH in water + heat reaction VI: conc H2SO4 + heat (iii) reaction III: oxidation reaction V: hydrolysis or nucleophilic substitution

UCLES 2009

Page 6 6 (a) L M N Q P J K is is is is is is is

Mark Scheme: Teachers version GCE A/AS LEVEL October/November 2009 CH3CH2Br CH3CO2H CH3CH2NH2 CH3CH2CO2H CH3CH2CH2NH2 CH3CH2CONHCH2CH3 CH3CONHCH2CH2CH3

Syllabus 9701

Paper 42

[7] [7] [1] [1] [1] [3] [1] [1] [2] [1] [1] [2] [Total: 14]

(b) reaction I: KCN, heat NOT H+ OR HCN aq negates reaction II: SOCl2 or PCl5 or PCl3 BUT aq negates reaction IV: H2 + Ni or LiAlH4 or NaBH4 NOT Sn + HCl

(c) reaction IV: reduction reaction VI: nucleophilic substitution or condensation reaction

(d) (i) amide (ii) amine

(a) Primary: Secondary: Tertiary:

Covalent bond (ignore amide, peptide etc.) Diagram showing peptide bond: (-CHR-)CONH(-CHR-) Hydrogen bonds (NOT between side chains Diagram showing N-HO=C

[1] [1] [1] [1]

Two of the following: hydrogen bonds (diagram must show H-bonds other than those in -helix or -pleated sheet e.g. ser-ser) electrostatic/ionic attraction, Van der Waals/hydrophobic forces/bonds, (covalent) disulphide (links/bridges) [1] + [1] Suitable diagram of one of the above (for disulphide: S-S not S=S or SH-SH) [1] [max 6]

(b) Substrate binds to the active site of the enzyme Interaction with site causes a specific bond to be weakened, (which breaks) Or change in shape weakens bond(s) / lowers activation energy

[1] [1] [2] [1] [1] [2] [Total: 10]

(c) Non-competitive inhibition Rate never reaches Vmax

UCLES 2009

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Mark Scheme: Teachers version GCE A/AS LEVEL October/November 2009

Syllabus 9701

Paper 42 [1] [2]

(a) Ratio of the concentrations of a solute / distribution of solute [1] in two immiscible liquids

(b) Kc =

[pesticide in hexane] [pesticide in hexane] hence 8.0 = [pesticide in water] 0.0050 - [pesticide in hexane]

[1]

Therefore [pesticide in hexane] x = 0.040 8x Hence x = 0.0044(g)

[1] [2] [1] [1] [1] [3] [1] [1] [1] [1] [4] [Total: 11]

(c) (i) Ratio would be 3 : 1 (ii) Each chlorine at could be 35Cl or 37Cl Only way of getting M+4 is for both chlorines to be 37Cl (1 in 9 chance) Ratio of peaks M M+2 M+4 9 6 1

(d) (i) Accept dioxins and furans (without specifying) (ii) PCBs (but dont penalise non-specified dioxins and furans) (iii) Allow : pollution control / environmental legislation / removal of dioxins and furans / mill closed down (owtte) (iv) Five

UCLES 2009

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Mark Scheme: Teachers version GCE A/AS LEVEL October/November 2009 nanosphere diameter 1 cell diameter 2

Syllabus 9701

Paper 42

(a) Length of DNA 3

Both marks for correct sequence, [1] for cell smaller than DNA [2] (b) (i) Gaps in structure of shaft much smaller, hence less prone to fracture / more flexible (ii) Composites and carbon nanotubes less dense than metal (of comparable strength) [1] [1] [2]

(c) Wavelength of infrared energy is longer than that of light [1] Gaps between nano-sized particles allow light to pass through, but reflect infrared energy [1] [2] (d) (i) Resistance to corrosion / reaction (ii) Ability to kill bacteria / prevent bacteria multiplying (iii) Very much larger surface area means they dissolve more readily [1] [1] [1] [3] [Total: 9]

UCLES 2009