Page 4

Mark Scheme A LEVEL JUNE 2005

Syllabus 9701

Paper 4

(a)

Ka = [RCO2-][H+]/[RCO2H]

[1] Part (a): [1]

(b)

(i)

The more chlorine atoms in the molecule, the stronger the acid,

[1]

due to the electron-withdrawing (inductive) effect of Cl... [1] either...stabilising the anion, or spreading (-) charge more, or...weakening the O-H bond in the acid, or...increasing ionisation, orfacilitates H+ donation orcausing the equilibrium RCO2H RCO2- + H+ to lie further to the right. Mark is conditional on reference to the effect of presence of chlorine. [1] (ii) [H+] = (0.1 x 1.4 x 10-3) = pH = -log10(0.0118) (iii) pKa = -log10(5.5 x 10-2) = = 0.0118 (mol dm-3) allow 0.012 1.93 1.26 Allow 1.9 or 1.92 Allow 1.3 e.c.f. [1] [1] [1] Part (b): [6] (c) (i) (ii) Cl2(aq) AlCl3 or UV negates Electrophilic substitution or addition-elimination [1] [1]

Nucleophilic substitution or electrophilic substitution on OH group If neither mark is awarded, could give salvage mark for substitution x2 [1] (iii) add Br2(aq) phenol decolourises it, or gives a white ppt. add FeCl3(aq) phenol give a purple colour add NaOH(aq) phenol dissolves add UI solution phenol goes yellow/orange (A stays green) add diazoniumto solution in OHphenol gives orange/red colour (in each case, A give no reaction) or: or: or: or: add Cr2O72-/H+/warm A changes colour from orange to green add MnO4-/H+/warm A changes from purple to colourless add PCl5/POCl3/PCl3/SOCl2 A gives fumes A gives fruity smell add CH3CO2H + conc. H2SO4 Either: or: or: or: or:

(in each case, no change with phenol) Test + reagents [1] Both observations [1] Part (c): [5] Total: [12]

University of Cambridge International Examinations 2005

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Page 5

Mark Scheme A LEVEL JUNE 2005

Syllabus 9701

Paper 4

(a)

(i) (ii)

Electrophilic substitution or nitration HNO3 + H2SO4 (both) conc., and at 50C T 60C

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

(iii)

NO2+
H NO2
etc.

H or

NO2

Any on NO2 or H negates H+

[1] [1] Part (a): [6]

(b)

(i) (ii)

Reduction Sn/Fe/Zn/SnCl2 + HCl/H+/H2SO4 (but not conc. H2SO4) or H2 + Ni/Pt (not LiAlH4)

[1] [1] Part (b): [2]

(c)

PCl5/PCll3/SOCll2/POCl3

(+ heat)

aq negates

[1] Part (c): [1]

(d)

(i) (ii)

An amide, not peptide Heat with H3O+ or heat with OH-(aq)

[1]

Or warm (not heat/reflux) with aqueous amidase/peptidase/protease not enzyme/trypsin/chymotrysin/pepsin/papain etc. [1] Part (d): [2] Total: [11]

University of Cambridge International Examinations 2005

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