Suggested Solns for Nov 2008

Tay L. K

Paper 1
1.

2.

3.

4.

5.

6.

7.

8.

9.

10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20.

21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40.

Paper 2
1
(a) (i)
H

C O

H
H
Ethane-1,2-diol

(ii)

dO
d+ H
Hydrogen Bond

O
dH
d+

(b) (i)
(ii)
(c)

H d+
O d-

H
H
H
H
C

Hydrogen Bond
H d+
O
d-

Ethene (CH2CH2)
Purple solution turned colourless.

(Primary) amine, (secondary) alcohol, phenol

(d) (i)

CH(OH)CH2NH2
Br

Br

Br

OH
OH

(ii)

CH(OH)CH2NH2

O-Na+
O-Na+

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Suggested Solns for Nov 2008

(iii)

Tay L. K

O
H2NH2CC

OH
OH

(iv)

CH(OH)CH2NH3+Cl-

OH
OH

(a)

(i)

Ksp= [Ag+][Br-]

(ii)

Ksp of AgBr = (7.1 10-7)2 = 5.0 10-13mol2 dm-6

DGqppt = 2.303RT logKsp
=2.303 (8.31J K-1 mol-1)(298K)(log 2.0 10-10 )= -55.3 kJ mol-1

(b) (i)

DGqppt = DHqppt - TDSqppt

-55.3 kJ mol-1 =-66.0 kJ mol-1 - (298K)DSqppt

(ii)

DSqppt = - 0.0359 kJ mol-1 K-1= - 35.9 J mol-1 K-1

(iii) The system leads to greater disorderliness.
(c)

DGqppt = 2.303RT logKsp

=2.303 (8.31J K-1 mol-1)(298K)(log 1.006 )= +14.8 kJ mol-1 ( not energetically feasible)
Since DGqppt >0, thus the precipitation reaction is not spontaneous and thus AgF is soluble in
water in 298 K.

(a)
H3C

H3C
CHCH
H3C

CH2CH2OH

O
CHC

CH2

OH

H3C

CH2COOH

COOH

OR
CH3

COOH

-2-

COOH
(Produced only under
prolonged heating)

Suggested Solns for Nov 2008

(b) (i)

Tay L. K

Eqcell = +1.52V - (+0.70V) = + 0.82V

(ii)

OH
5

+ 2MnO4- + 6H+

+ 2Mn2+ + 8H2O

HO

(iii) Sulphur dioxide.

From Data Booklet, SO42- + 4H+ +2e- SO2 + 2H2O

Eq = +0.17V

Eqcell = +0.70 V - (+0.17V) = + 0.53V > 0 (spontaneous)

(c)

LiAlH4, dry ether, heat under reflux

(d) (i)
(ii)

Reagent: 2,4-dinitrophenylhydrazine at room temperature

Observation: Yellow or orange precipitate
Reagent: neutral FeCl3 at room temperature
Observation: Purple or violet complex

(iii) Reagent: Aqueous bromine at room temperature

Observation: Aqueous bromine decolourised or reddish brown bromine water turned
colourless and white precipitate is formed.
4

(a)

Cu: 1s2 2s2 2p6 3s2 3p6 3d10 4s1

Cu2+: 1s2 2s2 2p6 3s2 3p6 3d9

(b) (i)

(c)

[Ag(NH3)2]+

(ii)

CuCl2(aq): [Cu(H2O)6]2+
C: [Cu(NH3)2]+

(i)

CuCl2(aq) + 2HCl(l)
OR

[CuCl4]2-(aq) + 2H+(aq)

[Cu(H2O)6]2+(aq) + 4Cl-(aq)
blue

[CuCl4]2-(aq) + 6H2O(l)
yellow

CuCl2(aq) + Cu(s) + 2HCl(l) 2[CuCl2]- (aq) +2H+( aq)

(ii)

D: [CuCl4]2-(aq)

E: [CuCl2]- (aq)

(iii) ligand exchange reaction

(iv) Tetrahedral
(v)
(d) (i)
(ii)

+1
Redox reaction
CuCl

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Suggested Solns for Nov 2008

(e)

(i)
Mass percentage
Mole ratio

Simplest mole
ratio
(ii)
(f)

(i)

(ii)

Tay L. K
Cu

21.5

38.7

39.8

21.5
63.5

38.7
19.0

39.8
39.1

= 0.3386

= 2.0368

= 1.0179

Oxidation state of copper in G = - (-6 +3) = +3

3d-orbitals are fully filled, thus there is no vacancy in the upper d-orbitals.
No visible light energy is absorbed as it is not energetically feasible to promote
electrons from d-orbitals of lower energy level to d-orbitals of higher energy level, thus
both E and F are colourless.
The d-orbitals are split into two energy levels by ligands
Vacancies are present in the upper d-orbitals as Cu+ has the electronic configuration
of 1s2 2s2 2p6 3s2 3p6 3d8.
Visible light energy is absorbed to promote electrons from lower to upper d-orbitals

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Suggested Solns for Nov 2008

Tay L. K

Paper 3
1
(a) Bond energy is the energy change in breaking one mole of covalent bonds between 2
atoms in the gaseous state.
Bond energy value of a particular bond is obtained by considering average bond
dissociation energies of that particular bond in a variety of molecules.
(b)

(i)

Insert a hot glass rod or hot inert metal rod into vessels containing different gaseous
hydrogen halides separately.

(ii)

The extent of this reaction increases down the group.

(iii)

When X = Cl,
DHr =SBonds Broken - S Bonds Form = [2(431) - (436+244)] kJ mol-1= +182 kJ mol-1
When X = I,
DHr =SBonds Broken - S Bonds Form = [2(299) - (436+151)] kJ mol-1= +11 kJ mol-1

(iv)

Since there is no increase no. of gaseous products for the reaction when X = Cl or I,
therefore DS for the reactions when X = Cl or I is similar in magnitude.
Since DG = DH - TDS, the more negative DG is, the more spontaneous the forward
reaction. As TDS are of similar magnitude for the reactions when X = Cl or I, DH for the
reaction when X = I is more exothermic than that when X = Cl based on answers in
(b)(iii). Thus, the extent of reaction is greater when X = I than X = Cl based on answer
in (b)(ii).

(c)

Name of mechanism: Electrophilic Addition

(d)

(i)

The trend in the boiling points of the halogenoethanes is as follows: C2H5I > C2H5Br >
C2H5Cl. The halogenoethanes are covalent polar simple molecules. During boiling,
intermolecular interactions in the form of induced dipole-induced dipole (id-id)
interactions are overcome. The effect of id-id interactions outweighs the effect of
permanent dipole-permanent dipole (pd-pd) interactions The electron cloud sizes
increases from C2H5I to C2H5Br to C2H5Cl and the polarisability of the electron cloud
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Suggested Solns for Nov 2008

Tay L. K

sizes increases correspondingly too. Thus the strength of id-id interactions increases in
the same manner.
(ii)

The electronegativity values of the halogen atoms increases from I to Br to Cl. Since
the polarity of the C-X bonds depends on the electronegativity difference between the
bonding atoms. Hence the polarity of the bonds increases from C-I to C-Br to C-Cl
bond.

(iii)

The reactivities of the three compounds towards nucleophiles decreases from C2H5I to
C2H5Br to C2H5Cl as these halogenoethanes undergo nucleophilic substitution which
involves breaking of C-X bond. Quoting from Data Booklet,
Bond

Energy / kJ mol-1

C-Cl

340

C-Br

280

C-I

240

Since the C-Cl bond is the strongest and the shortest due to its greatest extent of
overlapping of orbitals, thus its reactivity towards nucleophiles is the weakest.
(e)
Compound P

Compound Q

CH3

H3C
CH
H3C

CH3

H3C

CBr

COH

CH
H3C

CH2CH3

CH2CH3

4 different isomeric alkenes produced from

dehydrohalogenation of Compound P
H3C

CH

H3C

H3C

CH
C

CH3CH2

H3C

(a)

C
CH2CH3

H3C

H3C

H
C

H3C

H3C
CH3
Cis isomer

CH3

H3C

CH
C

CH3
C

H
H3C
Trans isomer

The products at cathode are hydrogen gas, H2and hydroxide ions, OH-.
Overall equation:
2R-CO2- +2H2O R-R +2CO2 + H2 + 2OH-6-

Suggested Solns for Nov 2008

(b)

Tay L. K

Charge, Q = It= (2.0A)(4060s)=4800 C

Amount of electrons =

4800C
= 0.0497mol
96500Cmol -1

Amount of ethane formed = 0.0497 mol 2 = 0.0249 mol

Mass of ethane formed = 0.0249 ( 2 12.0 + 6 1.0) = 0.746 g.
(c)

Amount of acid A in 0.100g = Amount of NaOH reacted =

11.4
dm 3 0.100moldm -3
1000

=1.14 10-3 mol

Mr of A = 0.100g 1.14 10-3 mol = 87.7
Possible molecular formula = C4H8O2 (Mr = 88.0)

(d)

PV=nRT
(1.01 105 Pa)(87 10-6 m3) = (

0.200 g
)(8.31J K-1 mol-1)(380K)
Mr

Mr of C = 71.9
Molecular formula = C5H12 (72.0)

(e)

(i)
(ii)

(iii)

3H2O(l) + P2O5(s) 2H3PO4(aq)

CO2(g) + 2NaOH(aq) H2O(l) + Na2CO3(aq)

1.55 g
= 0.0861mol
18.0
3.03g
Amount of carbon dioxide =
= 0.0689mol
44.0

Amount of water =

1 mol of water gives 2 moles of H atoms, thus

H : C ratio
= 2 amt of H2O: amt of CO2
= 2 0.0861 mol : 0.0689
=5:4
Since formula of alkane is Cn H2n+2, thus molecular formula of compound D is C4H10.

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Suggested Solns for Nov 2008

Tay L. K

(f)

(g)

Alkane F is a symmetrical alkane.

(a)
(b)

(i)

HCN, NaCN, 10-20C or HCN, NaOH, 10-20C

(ii)

Dilute HCl, heat

Let lactic acid be HA

HA
A- + H+

[ A - ][ H + ]
Ka =
[ HA]
Assume [HA] 0.20 mol dm-3 since x << 0.20 where 0.20 - x 0.20
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Suggested Solns for Nov 2008

1.38 10-4 =

Tay L. K

x2
0.20

[H+] = x = 5.25 10-3 mol dm-3

pH = -lg [H+] = 2.28 (3 s.f.)
(c)

(i)

(ii)

A buffer solution is either a mixture of weak acid and its conjugate base or a
mixture of weak base and its conjugate acid capable of minimal changes in pH
on dilution or on addition of small quantities of strong acid or alkali.

pH = pK a + lg

(iii)

[ A- ]
0.30
= - lg(1.38 10 -4 ) + lg
= 4.04
[ HA]
0.20

O
+

O
O-

OH

+
OH

OH

lactate ion
(d)
(e)

lactic acid

(i)

Ester linkage

(ii)

Acidic or alkaline hydrolysis

(i)

Reagents & conditions : NaOH (aq), heat, followed by acidification with H2SO4 at room
temperature

(ii)

Compound J
Chlorine Atom 1
Carbon Atom 1

Cl
C

H3C

Carbon Atom 2

C
H

O
Chlorine Atom 2
Cl

Chlorine atom 2 is more reactive than chlorine atom 1. The C atom bonded to chlorine
atom 2 is bonded to another highly electronegative O atom, thus it has a greater d+
charge than that bonded to chlorine atom 1. This implies that the C-X bond where X is
the chlorine atom 2 is more polar than that when X is chlorine atom 1, thus the
breaking of C-X is easier for chlorine atom 2.
Carbon atom 1 is sp3 hybridised, thus the molecular shape about this carbon atom is
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Suggested Solns for Nov 2008

Tay L. K

tetrahedral. Carbon atom 2 is sp2 hybridised, thus the molecular shape about this
carbon atom is trigonal planar.The approach of the nucleophile towards carbon atom 2
is easier as it is planar and has less steric hindrance compared to carbon atom 1.
(f)

Test 1: Na(s) at room temperature

Observations
M: No observable change
N: Efferversence of colourless and odourless gas that extinguishes lighted splint with pop
sound is observed.
Test 2: 2,4-dinitrophenylhydrazine
Observations
M: Yellow/orange precipitate observed.
N: No yellow/orange precipitate observed.

(a)

Al2Cl6

(b)

2AlCl3(s) + 3H2O(l) Al2O3 (s) + 6HCl(g)

White solid that is insoluble in water is Al2O3 due to its highly exothermic lattice energy.

AlCl3 (s) + 6H2O [Al (H2O)6]3+ (aq) + 3Cl- (aq)

[Al(H2O)6]3+ (aq) [Al(H2O)5(OH)]2+ (aq) + H+(aq)
OR
[Al(H2O)6]

3+

(aq) + H2O (l) [Al(H2O)5(OH)]

2+

(aq) + H3O (aq)

(Appreciable
hydrolysis)

AlCl3 undergoes substantial hydrolysis due to polarising power of high charge density
Al3+ to give a weakly acidic solution.
(c)

Na2O(s) + H2O(l) 2NaOH (aq)

White solid of sodium oxide is observed to dissolve in water to form a strongly alkaline
solution that turns solution of litmus blue.

(d)

(i)

Ionic Bonding is present in Mg3N2.

(ii)

Mg3N2(s) + 3H2O(l) 3MgO(s) + 2NH3(g)

Amount of magnesium nitride in 2.0g =

2. 0
= 0.0198mol
3 24.3 + 2 14.0

Amount of MgO formed = 3 0.0198 = 0.0595 mol

Mass of MgO (white solid) formed = 0.0595 (24.3 + 16.0) = 2.40g

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Suggested Solns for Nov 2008

(e)

(i)
(ii)

Tay L. K

Charge of ions and ionic radii of ions

Lattice energy, L. E.

q+ qr+ + r-

Down the group, L.E. becomes less exothermic to a much greater extent (the
increase in r+ + r- is very significant since r- << r+)
(iii)

The more exothermic the lattice energy, the more stable the compound is.

L.E. a

q+ qr+ + r-

As ionic radius of N3- is larger than O2-, L.E. of MO is more exothermic than the L.E. of
Mg3N2. The more energetically stable MgO is relative to Mg3N2, the more likely the
decomposition will proceed. Though N3- is larger than O2-, the greater ionic radius of
N3- outweighs the effect of the greater charge.
5

(a)

Example of Homogeneous catalysis: reaction between peroxodisulphate ions and

iodide ions catalysed by Fe2+ or Fe3+.
Uncatalysed reaction:
Eqcell = 2.01 - 0.54 = 1.47 V > 0 V
S2O82 (aq) + 2I (aq) 2SO42 (aq) + I2(aq)
Reaction catalysed by Fe3+:
Step 1

Fe3+(aq) + I (aq) Fe2+ (aq) + I2 (aq)

Eqcell = 0.77 0.54 = +0.23 V > 0

Step 2

Fe2+(aq) + S2O82 (aq) Fe3+ (aq) + SO42 (aq)

Eqcell = 2.01 0.77 = +1.24 V > 0

Example of Heterogeneous Catalysis: Use of Fe or Fe2O3 in Haber Process

N2(g) + 3H2(g) 2NH3(g)
OR
Example of Homogeneous catalysis: reaction between peroxodisulphate ions and
iodide ions catalysed by Fe2+ or Fe3+.
Uncatalysed reaction:
Eqcell = 2.01 - 0.54 = 1.47 V > 0 V
S2O82 (aq) + 2I (aq) 2SO42 (aq) + I2(aq)
Reaction catalysed by Fe2+:
Step 1

Fe2+(aq) + S2O82 (aq) Fe3+ (aq) + SO42 (aq)

Eqcell = 2.01 0.77 = +1.24 V > 0

Step 2

Fe3+(aq) + I (aq) Fe2+ (aq) + I2 (aq)

Eqcell = 0.77 0.54 = +0.23 V > 0

Example of Heterogeneous Catalysis: Use of Fe or Fe2O3 in Haber Process

N2(g) + 3H2(g) 2NH3(g)
(b)

Mg(NO3)2. 6 H2O (s) MgO (s) + 2NO2 (g) + O2 (g) + 6 H2O(g)

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Suggested Solns for Nov 2008

(c)

(i)

Tay L. K

The weaker nitric acid functions as a base in the highly acidic sulphuric acid medium
(protonation of nitric acid), releasing the nitronium ion, NO2+, which acts as the
electrophile.
HNO3 + 2H2SO4
NO2+ + H3O+ + 2HSO4Note that kinetic studies indicate the overall rate-determining step is the one involving
the attack of NO2+ on the benzene ring, i.e. rate = k[C6H6][NO2+]. Concentrated nitric
acid contains very little of the nitronium ion, NO2+ and hence it has hardly any effect
on benzene in the absence of sulphuric acid.

(ii)

Name of mechanism: Electrophilic substitution

Step 1: Electrophilic attack
The p electrons in the benzene ring act as a source of electrons to attract the
electrophilic NO2+.
NO2
H

+ NO2+

Step 2: Loss of proton

NO2

H
+

slow

NO 2

O S OH
O

HSO4

fast

+ H2SO4
(regenerated)

(d)

Stage 1 (from R to S) : Dilute nitric acid, warm

Stage 2 (from S to T) : Tin (Sn) and concentrated HCl, heat under reflux

(e)

(i)

Carboxylic acid group, (secondary) amine group, Amide group, ester group

(ii)

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Suggested Solns for Nov 2008

Tay L. K

(iii)

~~~~The End~~~~

-13-