1 Answers to Paper 1 (Set 1) 1 11 21 31 41 B B A D B 2 12 22 32 42 D A C D B 3 13 23 33 43 C D B A A 4 14 24 34 44 B B B C A 5 15 25 35 45 C C D C D 6 16 26 36 46 C B D B C 7 17 27 37 47 A C C D B 8 18 28 38 48 A C D C B 9 19 29 39 49 B D C D C 10 20 30 40 50 D A B A D

Answers to Paper 2 (Set 1) 1. (a) 1.00 mol dm-3 1 atm/101kPa (b) Equilibrium position displaced to the left Becomes negative/decreases (c) (i) to allow transfer of electrons/provide a reaction surface (ii) emf = +1.52 (+1.09) = +0.43V

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

(iii)

2Br(aq) Br2(aq) + 2e [1] 2BrO3(aq) + 12H+(aq) + 10e Br2(aq) + 6H2O(l) 2BrO3 (aq) + 10Br(aq) + 12 H+(aq) 6Br2(aq) + 6H2O)l)

[1] [1]

[10 marks] 2. (a) (i) For a reaction A + B products Rate = k[A]a[B]b [1] Order of reaction = a + b [1] @The sum of the powers of their concentration in the rate equation (ii) more effective collisions @ more particles having energy equal or greater than activation energy [1] (iii) concentration increases by 0.54/0.18 @ 3 times Rate increases by a factor 9 = 32 second order reaction with respect to SO2 (b) (i) 3Cl2 + 6NaOH 5NaCl + NaClO3 + 3H2O (ii) Cl2 : 0; NaCl : -1; NaClO3 : +5 [1] [1] [1] [1]

[1]

(iii) Disproportionation [1] Cl2 undergoes oxidation and reduction simultaneously [1] [10 marks]

2 Cu : 1s22s2 2p6 3p6 3d10 4s1 [1] 2+ 2 2 6 6 9 Cu : 1s 2s 2p 3p 3d [1] (b) (i) [Ag(NH3)2]Cl [1] 2+ (ii) [Cu(NH3)4] [1] (c) (i) CuCl2 + 2HCl H2CuCl4 [1] 2(ii) [CuCl4] [1] (iii) Square planar [1] (iv) Copper(I) chloride [1] + 10 (v) -E contain Cu ion which have a full d electronic configuration. [1] - No d-d transition is possible [1] 3. (a)

4. (a)(i) Q=

CH3

R=

CCl3

S=

COOH

T=

COCl

U=

CONH2

[1+1+1+1+1] (ii) Step I : CH3X , AlX3 at r.t. X = halogens (Cl) [1] [1] [1] [1] [1]

Step III : excess aqueous sodium hydroxide; reflux / boil Step IV : SOCl2 @ PCl5, room temperature (b) Reagent : excess aqueous ammonia Condition : heat

3 5. (a)

Mean mass of an atom/ isotope relative to 1/12 mass of 12 C atom or 12 C taken as 12.000 [1] @ in the form of equation (ii) Ar = (46x0.0802) + (47x0.0731) + (48x0.7381) + 49x0.0554) + (50x0.0532) [1] = 47.93 @ 47.9 (3 or 4 S.F.) [1] (i) (b) Solvent has low bp or weak intermolecular forces or evaporates quickly [1] Solvent needs energy to evaporate/latent heat of vaporization [1] Energy taken from the skin (and so cools) [1] Fragrance/perfume/molecules slowly spreads through the room by random movement/diffusion [1]

(c) (i) a non volatile solute distribute itself between 2 immiscible solvents at constant temperature [1] - in such a way that the ratio of concentration of that solute in one solvent to the other is always a constant [1] (ii) In benzene ethanoic acid exists as dimer [1] In water, it exists as monomer [1] @If the answer given is :the molecular state of the solute in both the solvent must be the same. (1 mark only) (iii) Ether [1] has a reasonably high partition coefficient (K) [1] hence a large proportion of iodine in the aqueous solution will dissolve in it [1] ether is the most volatile solvent among the three [1] hence can be removed by gentle warming, leaving behind the pure iodine crystals. [1] **(if answer given is methylbenzene 2nd & 3rd marks) Total: 16 marks Max: [15 marks] 6. (a) Average heat required when 1 mole of covalent bonds between 2 atoms are broken in the gas phase. (b) Consider CH4 + F2 CH3F + HF H = bonds broken - bonds formed = {+412 + (+158)} {(+484) + (+562)} = - 476 kJmol-1 For CH4 + Cl2 CH3Cl + HCl H = {+412 + (+242)} {(+338) + (+431)} = -115 kJmol-1 Much lower energy for F2 because bond is weaker Due to repulsive forces between fluorine atoms stronger [1] [1] [1] [1] [1]

[1] [1] [1]

4 6 (c) F (aq) + H2O (l) +57 F (aq) H = +57 - (-13) = +70 kJmol-1 + H+(aq) HF(aq) + OH (aq) -13 + OH(aq) [1]

[1]

This is an endothermic reaction [1] Therefore if T increases, equilibrium right so as to absorb heat [OH ] increases pH = 14 pOH pH increases [1] [1] [1]

[1]

[15 marks]

7. (a) (i) - Al2Cl6 [1] - dot-and- cross diagram [1] - Two AlCl3 molecules dimerise via dative bonding [1] - One of the chlorine atoms in each AlCl3 donates one lone pair of electrons to the other electron-deficient aluminium atom [1] - The bond between the rest of the aluminium atoms and chlorine atoms is covalent bonding. [1] (ii) - AlCl3 + 6H2O [Al(H2O)6]3+ + 3Cl[1] - [Al(H2O)6]3+ + H2O [Al(H2O)5OH]2+ + H3O+ [1] - A clear, weakly acidic solution is formed because due to the high charge density // high polarizing power of Al3+ ions. [1] 3+ - The Al ions are able to weaken the H-O bond in the datively bonded water molecules and cause them to give up H+ ions. [1] - Hydrolysis occurs [1] (b) add hot water to the powders separately. [1] - If it dissolves (and forms an alkaline solution), then the powder is MgO. [1] - If it is insoluble in water, it could be Al2O3 or SiO2. [1] - Next, add HCl to the powder [1] - If it dissolves the powder is Al2O3. [1] - If it is insoluble in the acid, it is SiO2. [1] Total: 16 marks Max: 15 marks

5 8. (a) The thermal stabilities of the hydrogen halides decreases from HF to HI [1] - Down the group, the atomic radius of the halogens increases thus the bond length of H-X increases [1] - The bond strength of H-X decreases from HF to HI. [1] (b) (i) Kstab = [Fe(CN)63-] [Fe(H2O)63+][CN-]6 [1]

Units: dm18 mol -6

[1]

(ii) Since Kstab [Fe(CN)6]3- >> Kstab [Fe(SCN)]2+ [1] 32+ - [Fe(CN)6] is more stable than [Fe(SCN)] [1] - Thus, the predominant complex formed is [Fe(CN)6]3[1] (c)(i) CaCO3 CaO + CO2 [1] - CaO + H2O Ca(OH)2 [1] (ii) To reduce the acidity of soil [1] (iii) - As Group 2 is descended, the temperature required to decompose the carbonates increases. [1] This is because down the group, -the size of Group 2 cations increases [1] - the charge density of the cations decreases [1] 2- the polarising power of the cations towards the CO3 decreases [1] 9. (i) At s.t.p, 1 mole of gas ------ 22.4 dm3 or 22400cm3 100 cm3 = 100/22400 = 4.46x 10-3mol R.M.M of J = 0.250 = 56.1 -3 4.46 x 10 (CH2)n = 56.1 14n = 56.1 n=4 Molecular formula of J = C4H8 (ii) Isomers of J : CH2=CHCH2CH3 , H3C CH3 C =C cis H H [1] [1]

[1] [1]

CH2=C(CH3)CH3 H3C H C=C trans H CH3 [1+1+1+1] [1]

(iii) K : CH2=CHCH2CH3

L : BrCH2CH(OH)CH2CH3 [1] [O] CH2=CHCH2CH3 CO2 + H2O + CH3CH2COOH + KMnO4,/H

[1]

6 CH2=CHCH2CH3 + HBr CH2=CHCH2CH3 + Br2 (iv) CH2Br C H OH 10. (a) RNH2 + H2O RNH3+ + OHThe smaller the pKb, the stronger the baseor vice-versa C2H5 C2H5 OH
H2O

CH3CH(Br)CH2CH3 BrCH2CH(OH)CH2CH3 CH2Br C H

[1] [1]

[1+1]

[1] [1]

Order of increasing base strength : aniline < 4-methylaniline < methylamine [1] The strength of base depends on the stability of the conjugate acids formed. [1] Aniline is the weakest base because : - lone pair electrons of N atom can be delocalised into the benzene ring. [1] - the conjugate acid formed, is the least stable [1] Methylamine is the strongest base because : - methyl group is an electron donating group/ +I effect [1] - it increases the electron density of N atom causing the lone pairs to be more easily donated to a proton. @ the methyl group stabilizes the conjugate acid [1] 4-methylaniline is a stronger base than aniline because of the presence of methyl group which is an electron donating group. [1] - the stability of the conjugate acids CH3NH3+ > CH3 (b)
-NH3 +

>

NH3+
CH3 Conc HNO3 O2N

[1]

CH3Cl, AlCl3

[1]

[1]

conc H2SO4 < 55oC [1]

CH3

[1] [1] HCl

Sn in conc

H2N

CH3

[1]