Suggested Answers Section A 1 (a) Number of protons & number of neutrons in the nucleus of an atom (1) (b) (c)

Particle Mass /g Relative charge (i) (ii) Proton 1.6725 1024 +1 Neutron 1.6748 1024 0 Electron 0.0009 1024 -1
17 8

1m 1m

O (1 ) (1 )

1m

as shown in the table 1.6725 1024 + 0.0009 1024 = 1.6734 1024 g 1m

(iii) (iv) (d)

1.6734 1024

6.0225 1023

= 1.0078 g

1m 1m

Other isotopes present

1600 1400 1200 (1)

First ionisation 1000 1 energy/kJ mol 800 600 400 200 0 Na Mg Al Si P

below Mg Al
(1)

S below P and Cl 1m (1) but above Si

1m

Cl

Ar

(ii) increases Explanation for Al: (1) e removed from (3) p or e or orbital is higher in energy level or better shielded than (3)s or p electron is shielded by 3s electrons Allow e is further away Mark independently Or 1m

Explanation for S: e removed from (3)p electron pair or repulsion between paired e (reduces energy required) Mark separately If used d rather than p orbital only get (explanation marks)

1m

(10m)

2 (a)

Rate = k[PH2O2]n[OH]m By substituting the values of rate, [PH2O2] and [OH] from the results of experiments 1and 2: 1m

3=3 n=1

The reaction is first order with respect to phosphinate ion.

1m

(b)

(a) Rate = k[PH2O2]n[OH]m

By substituting the values of rate, [PH2O2] and [OH] from the results of experiments 3and 4: 1m 4 = 2m m=2 The reaction is second order with respect to hydroxide ion. 1m 1m 1m 1m

(c) (d) (e)

The overall order of reaction is third order. The rate equation is rate = k[PH2O2] [OH]2
By substituting the values of rate, [PH2O2] and [OH] from the results of experiment 1 in the rate equation

1m

(f)

By substituting the values of k, [PH2O2] and [OH] into the rate equation: Rate = 4 x 0.6 x (3.0)2 = 21.6 dm3 min1

1m 1m

(10m)

The chlorides of Group 14 are CCl4, SiCl4, GeCl4, SnCl4, PbCl4, (a) (i) (ii) State the type of hybridization present in the above tetrachloride sp3 Name the shape of each molecule. Tetrahedral The tetrachloride from the above that is totally not hydrolysed in water is CCl4 , Water molecules cannot form dative bonds with CCl4 Because carbon atom does not have 2d orbitals. PbCl4 ,has the highest boiling point. It has the strongest dispersion forces (temporary induced dipole) because it is the largest molecule. Why is carbn tetrachloride used in extinguishers? Chemically inert (not reactive/passive) / Its denser vapour sinks excludes oxygen and puts the fire off (i) (ii) Name one of the compounds : Lead (IV) tetrachloride Why is this compound that you choose thermally unstable? The Pb-Cl bond length is the longest and the weakest 1m 1m

(b)

(i)

1m 1m 1m 1m

(ii)

(c)

1m 1m 1m 1m (10m)

(d)

(iii) Write an equation for the decomposition. PbCl4 (s) PbCl2(s) + Cl2 (g)

(a)

(i) (ii)

secondary alcohol

1m

H3C CH

CH3 2m OCOCH3 + HCl (1 mark )

CH3

(1 mark )

(iii) 1m H3C CH O CH3

CH3 (iv) (b) (i) (ii) (iii) (iv) (v) No, because it is a secondary alcohol and not a phenol aqueous NaOH/KOH and boil under reflux nucleophilic substitution (SN1 or SN 2 ) NaOH in ethanol, heat the mixture elimination reaction hydroxide ions act as a base to remove all the H+ ions from the haloalkane molecule. Section B 5 (a) (i) More 63Cu atoms than 65Cu atoms (1) (idea of more abundant 63Cu isotope - NOT just reference to peak heights) Electron from electron gun / high speed electron / high energy electron 1 (accept electron gun fired at) [NOT bombarded with electrons] knock electron off (Cu atom) / idea of loss of e / appropriate equation 1 (Mark independently) (iii) Identity of the ion = 63Cu2+or equivalent (1) [NOT 63.0 - penalise this error once only] 1 Explanation for the m/e value : m/e = 63/2 (=31.5) or equivalent (1) (1) 1m (1) 1m 1m 1m 1m 1m 1m 1m 1m 1m (10m)

(ii)

1m

More energy needed to remove second electron OR 1 63 2+ Cu statistically less likely to remove second electron (Idea that not many 63Cu2+ ions formed OR explains why few are formed e.g. more energy needed) (1)

1m

(b) (i)

(ii) (iii)

If 63Cu not given, can only award M2 & M3 Notes on [If 65 used, lose M1 and M2] [If mass number missing from identity but appears in explanation, penalise M1 but allow M2 if earned] TOTAL = 6 MARKS 105 (allow 104106) (1) 4 electron pairs round O (1) tetrahedral (or 109) (1) lone pairs repel more than bonding pairs (1) angle < 109 (or less than tetrahedral angle) (1) hydrogen bonding (1) F more electronegative than H, thus will pulls electrons from H (1) Prediction > 105 (or increases) (1) Explanation lone pair more like bonding pair does not repel so strongly (1) TOTAL = 9 MARKS

(6m)

1m 1m 1m 1m 1m 1m 1m 1m 1m (9m)

(a )

(i)

Diagram: fuel cell

eanode cathode

oxygen gas carbon electrodes ethanoic NaOH beaker + 2 carbon electrodes: Anode : carbon electrode + ethanoic NaOH solution Cathode : carbon electrode with oxygen gas flowing in + NaOH aq Electrons flow from anode to cathode (ii) Function of oxygen : oxidized ethanol to ethanoic acid Function of NaOH : as electrolyte

1m 1m 1m 1m 1m 1m 1m 1m (8m) 1m 1+1

(iii) At Anode : C2H5OH + H2O CH3COOH + 4e + 4H+ At Cathode: O2 + 2H2O + 4e 4OHEmf = + 0.4 (+ 0.2 ) = + 0.20 V (b ) (i) (ii) State Hesss law: The overall enthalpy change is equal to the sum of the enthalpy changes for the individual steps in a reaction. N2H4(l) + O2 (g) N2(g) + 2H2O (l)

(iii)

Enthalpy change = 4(-242.7) (-19.57 + 2 x 50.63) = -1052 kJ mol-1 The reaction is violently explosive because the reaction is very exothermic, a lot of heat is given off.

1m 1m 1m 1m (7m ) 1m 1m

(a)

When aluminium reacts with chlorine gas, aluminium chloride, Al2Cl6, is formed (i) Draw the structural formula of aluminium chloride. Cl Al Cl (ii) (iii) Cl Cl Al Cl Cl

2Al(s) + 3Cl2(g) Al2 Cl 6 (s) State one important use of aluminium chloride Catalyst in alkylation of benzene to increase the rate of reaction When 1.0 g of aluminium was used, 2.3 g of aluminium chloride.was produced. Calculate the percentage yield of the product. 2 moles Al produce 1 mole Al2 Cl 6 54 g Al produce 267 g Al2 Cl 6 1g Al produce 267/54 = 4.9 g Al2 Cl 6 % yield = 2.3/4.9 x 100 = 46.9

1m

1m

(iv)

1m 1m 1m 1m 1m

(b)

The solution contains the complex ion Al(H2O)6 3+ and chloride ion. The complex ion undergoes hydrolysis to produce excess of hydronium ions making its pH<7, acidic. Al(H2O)6 3+ + H2O [Al(H2O)5(OH)] 2+ + H3O+ When an aqueous solution of aluminium chloride is added with sodium hydroxide solution until the sodium hydroxide is in excess. White preciptate is formed. The precipitate is aluminium hydroxide Al(H2O)6 3+ (aq)+ 3OH-(aq) Al(H2O)3(OH)3 (s)+ 3H2O(l)

(c)

1m 1m

The preciptate dissolve in excess of sodium hydroxide solution to form soluble 1m aluminate ion. Al(H2O)3(OH)3 (s ) + OH-(aq) [Al(H2O)2(OH)4] (aq) + H2O(l) 1m (max: 3 marks ) Aluminum is oxidized to aluminium oxide. And thus the oxide act as a protective layer to the aluminium inside. 1m

This is done by placing the aluminum as the anode in electrolysis. 4Al (s)+ 3O2 (g) 2Al2O3(s) 1m 1m 8 (a) Why are transition elements coloured? -In the presence of ligands, the 3d orbitals are split into different energy levels /d-d splitting occurs (can illustrate). -The electrons from a lower 3d orbitals absorb energy from light and are excited/promoted to a higher energy level. -however, only certain wavelengths in the visible spectrum is absorbed. The unabsorbed wavelength corresponds to the colour of the solution of complexes. -the difference in energy of the d-orbitals determines the wavelength of light absorbed and hence its colour. What determines its colour? Strength of the ligands, oxidation state of metals ions, Geometry of the complexes affects splitting of d orbitals and hence the colour of the complexes. (b) (i) The addition of the SCN- displaces the H2O ligands, forming the bloodred [Fe(SCN)(H2O)5]2+ complex ion Since SCN- is a stronger ligand. However when F- is added, it displaces the SCN- and H2O ligands to form the colourless [FeF5 (H2O)]2- ion since F- is a stronger ligand. [Co (H2O)6]2+ + 4Cl- [CoCl4]2- + 6H2O Pink blue According to Le Chateliers principle, the addition of water causes the equilibrium to shift to the left, colour changes fro blue to pink. 4NH(g) +5O2(g) 4NO (g) + 6 H2O 2NO(g) + O2 2NO(g) 4NO2(g) + O2(g) + 2 H2O(l) 4HNO3(aq) From the equations, 4 moles of ammonia gives 4 moles of NO 4 moles of No gives 4 moles of NO2 4 moles of NO2 gives 4 moles of nitric acid Thus, 1 mole ammonia gives 1 mole nitric acid 17 g of ammonia gives 63 g of nitric acid Hence, 1 kg of ammonia gives 63/17 x 1 = 3.71 kg of nitric acid. 1m 1m 1m

1m

1m 1m (5max) 1m 1m 1m (3m) 1m 1m (2m) 1m 1m

(ii)

(c)

(i)

(ii)

1m 1m 1m (5m)

(15 m) 9 (a ) This process involves the hydrolysis of chlorobenzene and sodium hydroxide at 300 C and 150atm Cl + 2NaOH O-Na+ + NaCl + H2O 1m 1m 1m 1m 1m 1m 1m

Phenol is obtained by adding acid to the products of hydrolysis. O-Na+ + HCl (b ) OH + NaCl

The C* is the carbon atom attached to the OH group. The (+) enantiomer rotates the plane of polarization clockwise while the (-) enantiomers rotates the plane of polarization anti-clockwise.

(c)

(i) CH3 CC CH3 Br Br (1) (ii) CH3 CC CH3 Cl H (1) (iii) CH3 CH3 C- C

CH3 CH2 - CH2 C CHBr - CH2Br (1) H OH

2m

CH3 CH2 - CH2 C CHCl CH3 (1) H Cl (1) CH3 CH2 - CH2 C CH(OH) CH2(OH) (1) H OH OH OH (1) (1) CH3 CH3 C=C CH3 H O- C-CH2CH3 CH2 - CH2 C CH = CH2

3m

2m

(iv)

1m

O (1) (15m)

10

(a) (b)

CH3OH +

CH3CH2COOH

CH3CH2COOCH3 + H2O NOT acylation

1m 1m

(nucleophilic) addition-elimination

Any 3m (i) faster/not reversible/bigger yield/purer product/no(acid) (catalyst) required (ii) anhydride less easily hydrolysed or reaction less violent/exothermic no (corrosive) (HCl) fumes formed or safer or less toxic/dangerous expense of acid chloride or anhydride cheaper (d) (i) (ii) C8H8O2 1m

(c)

1m 1m

2m

(e)

(i) (ii) (iii)

electrophilic addition CH3 -CH=CH-CH3 must show C=C nucleophilic substitution (1)

1m 1m

Max 3m

(15m) END OF ANSWER SCHEME