08N-1

A-Level Solutions Chemistry

2008 Nov (9746) Paper 1

1. [08N P1 Q01 Moles]

B
24000
10 02 . 6 1
23


At r.t.p., volume of 1 mol of gas = 24 dm
3

mol of O
2
in 1 cm
3
=
3
10 24
1

mol
no. of O
2
molecules = nL
=
3
10 24
1

6.02

10
23

Hence, option B. (ans)
Step-by-Step

2. [08N P1 Q02 Relative Masses] [99N P3 Q01]

A argon

Since density of 'atmospheric N
2
' is higher than
that of chemically pure N
2
, the gas that causes
this discrepancy would, therefore, be one of
higher mass than N
2
. [M
r
: N
2
= 28; Ar = 39.9;
He = 4; CH
4
= 16; Ne = 20.0] (ans)
Step-by-Step

3. [08N P1 Q03 Atomic Structure]

C 1s
2
2s
2
2p
6
3s
2
3p
6
3d
1
4s
2


Element (X) in C has 3 valence electrons and
would lose all 3 valence electrons most easily
to achieve a stable octet configuration (forming
X
3+
ion). (ans)
Step-by-Step

4. [08N P1 Q04 Atomic Structure]

D
40
K
40
Ca


In the decomposition, a neutron is converted to
a proton ( mass number remains unchanged
since there is no change in total no. of neutrons
and protons) and an electron ( atomic no.
increases by 1). Hence, the process is
described by K
40
19
Ca
40
20
. (ans)
Step-by-Step
5. [08N P1 Q05 Atomic Structure]
[04J P1 Q05] [93J P4 Q02]

C N

has 8 electrons. On losing an electron, it

forms N which has 7 electrons (configuration
1s
2
2s
2
2p
x
1
2p
y
1
2p
z
1
) and so, has a half-filled
set of p orbitals. (ans)
Step-by-Step

6. [08N P1 Q06 Bonding]

N atoms numbered

1 and 3 2 and 4
C ionic co-ordinate

Chlorophyll is a chlorin pigment, and has a
Mg
2+
ion at the centre of the chlorin ring.
N-1 and N-3 form
ionic bonds with
Mg
2+
, while N-2
and N-4 form
co-ordinate (or
dative covalent)
bonds with Mg
2+
.
(ans)



Step-by-Step

7. [08N P1 Q07 Chemical Equilibria]

A 0.17


2NO
2
(g) 2NO(g) + O
2
(g)
initial atm, p 0 0
eqm atm, p a a

a
Since pressure at equilibrium is 20 % greater
than initial pressure,
(p a) + a +

a =
100
120
p a = 0.4

p
Hence, at equilibrium
2NO
2
(g) 2NO(g) + O
2
(g)
eqm atm, p 0.4

p 0.4

p

0.4

p
= 0.6

p = 0.2

p
mole fraction of O
2
in equilibrium mixture,
x =
p p p
p
2 . 0 4 . 0 6 . 0
2 . 0
+ +
= 0.17 (ans)
Step-by-Step
N

Mg
2+
N

N
N C C
C
C
H
H
C

C
H

C C
C
C C
C
C
C
R
R
C
C
R
R

C
C
R
H
C C
R
H
R

H
C
C
O
R
08N-2

A-Level Solutions Chemistry
8. [08N P1 Q08 Solids]

copper iodine
D cations molecules

Copper has a giant metallic structure lattice
particles are metal cations. Iodine has a simple
molecular structure lattice particles are
discrete I
2
molecules. (ans)
Step-by-Step

9. [08N P1 Q09 Energetics]

A burning an element in oxygen

When an element is burnt in oxygen, the
enthalpy change (enthalpy change of
combustion, H
c
) is always negative
(i.e. exothermic). (ans)
Step-by-Step

10. [08N P1 Q10 Entropy]

H S G
C + +

The phrase instant 'cold packs' suggests that
the reaction is endothermic; i.e. H is positive.
When the pack is squeezed, NH
4
NO
3
(s)
dissolves in the water suggests that the reaction
is spontaneous; i.e. G is negative. Dissolution
of NH
4
NO
3
(s) is accompanied by an increase
in entropy (less orderly); i.e. S is positive.
Hence, option C. (ans)
Step-by-Step

11. [08N P1 Q11 Ionic Equilibria] [93N P4 Q10]







K
a
, the acid dissociation constant, is only
affected by changes in temperature. It is not
affected by changes in volume, V. (ans)
Step-by-Step
12. [08N P1 Q12 Chemical Equilibria]

C The enthalpy change is zero.

When the equilibrium constant is independent
of temperature, it suggests that the reaction is
neither exothermic nor endothermic; i.e.
enthalpy change, H = 0. (ans)
Step-by-Step

13. [08N P1 Q13 Kinetics]

D
10
2
1


Since half-life, t

, of iodine-131 is 8 days,
80 days 10

t

have elapsed.
fraction of isotope that remained = (
2
1
)
10

or
10
2
1
. (ans)
Step-by-Step

14. [08N P1 Q14 Periodicity]

D V

HCl (produced when the chloride of R is
hydrolysed) gives a white precipitate of AgCl
with AgNO
3
(aq).
Ag
+
(aq) + Cl

(aq) AgCl(s)
mol of Cl

from chloride of R = mol of Ag
+

= 0.30

1000
100

= 0.030 mol
0.010 mol of chloride of R 0.030 mol of Cl


or 1 mol of chloride of R 3 mol of Cl


However, the low b.p. (76

C) suggests that the
chloride of R is not an ionic compound, i.e. R
is not a Group III element. Hence, R is a
Group V element which forms two chlorides,
RCl
3
and RCl
5
. RCl
3
gives 3 mol of HCl when
mixed with water. (ans)
Step-by-Step
D
0
K
a

V
08N-3

A-Level Solutions Chemistry
15. [08N P1 Q15 Group II]

A Some of the barium hydroxide had reacted
with carbon dioxide in the air to from solid
barium carbonate.

In the titration, the reaction is
Ba(OH)
2
.8H
2
O + 2HCl BaCl
2
+ 10H
2
O
The titres were lower than expected suggests
that the solution contains less Ba(OH)
2
than
expected. This is because when the prepared
solution was left in an open beaker, some
Ba(OH)
2
has reacted with CO
2
(g) in the air to
form solid BaCO
3
(in an acid-base reaction).
Ba(OH)
2
+ CO
2
BaCO
3
+ H
2
O (ans)
Step-by-Step

16. [08N P1 Q16 Group VII]

boiling point electron affinity
C increases less negative

Boiling point of Group VII elements increases
from Cl
2
to I
2
due to stronger intermolecular
van der Waals' forces as the number of
electrons increases from Cl
2
to I
2
.
From Cl to I, electron affinity becomes less
negative due to the increase in atomic size and
hence, weaker attraction for the additional
electron. (ans)
Step-by-Step

17. [08N P1 Q17 Transition Elements]

B 1s
2
2s
2
2p
6
3s
2
3p
6
3d
6


26
Fe has electronic configuration: [Ar] 3d
6
4s
2

(where [Ar] is 1s
2
2s
2
2p
6
3s
2
3p
6
). In forming
ions, electrons are removed from the 4s orbitals
first before the 3d orbitals.
Electronic structure of Fe
2+
is [Ar] 3d
6
4s
0
.
(ans)
Step-by-Step
18. [08N P1 Q18 Transition Elements]

C Fe
2
O
3


The formation of chromium(VI) compounds
from chromium(III) involves oxidation.
Al
2
O
3
: Al
3+
+ 3e

Al E
o
= 1.66 V
CuO: Cu
2+
+ 2e

Cu E
o
= +0.34 V
Fe
2
O
3
: Fe
3+
+ e

Fe
2+
E
o
= +0.77 V
ZnO: Zn
2+
+ 2e

Zn E
o
= 0.76 V
From the list, the best oxidising agent is Fe
2
O
3

(most positive E
o
value). (ans)
Step-by-Step

19. [08N P1 Q19 Hydrocarbons]

A It is an sp
2
sp
2
overlap.

Each carbon atom in buta-1,3-diene is sp
2

hybridised. Hence, the covalent bond
between C2 and C3 are formed by the overlap
of sp
2
hybrid orbitals. (ans)
Step-by-Step

20. [08N P1 Q20 Alkenes]




Option B will not give a good yield of 1,2-
dibromocyclohexane because the second step
involves a free-radical substitution reaction
which is not stereospecific and so, a mixture of
substitution products is obtained. (ans)
Step-by-Step

21. [08N P1 Q21 Alkanes]

C CH
3
CH
2
CH
3
+ Cl

The relevant bond energies (in kJ mol
1
) are:
CCl CH
Bond energy 340 410
CCl bond is weaker than CH bond. Hence,
homolytic fission of CCl bond occurs and
products formed are CH
3
CH
2
CH
3
and Cl

.
(ans)
Step-by-Step
Br
2
, hv

HBr

B
08N-4

A-Level Solutions Chemistry
22. [08N P1 Q22 Halogen Derivatives]

A BrCH
2
CH
2
CH
2
CH
2
Br

Compound X is a halogenoalkane,
BrCH
2
CH
2
CH
2
CH
2
Br.






(ans)
Step-by-Step

23. [08N P1 Q23 Halogen Derivatives]
[92J P4 Q24]

A 0

PCBs contain only aryl Cl (i.e. Cl attached
directly to benzene ring) which are resistant to
hydrolysis. Hence, no Cl atoms will be
removed by hydrolysis. (ans)
Step-by-Step

24. [08N P1 Q24 Alcohols]

C CH
3
(CH
2
)
10
O(CH
2
CH
2
O)
10
H

A possible formula of the non-ionic detergent
made by the reaction of excess epoxyethane
with a C
11
alcohol is



(ans)
Step-by-Step

25. [08N P1 Q25 Alcohols] [03J P1 Q29]

reagent Y solution Z
C concentrated H
2
SO
4
dilute NaOH

When ethanol is heated with an excess of
concentrated H
2
SO
4
(Y) at 170
o
C, it undergoes
dehydration to give ethene.





The impure ethene is then bubbled into dilute
NaOH (Z) to remove any excess acid. (ans)
Step-by-Step
26. [08N P1 Q26 Carbonyl Compounds]




Reaction of CH
3
COCH
3
(a ketone) with HCN
involves the use of a homogeneous catalyst,
NaCN(aq) the catalyst is in the same physical
state as the reactants. (ans)
Step-by-Step

27. [08N P1 Q27 Acid Derivatives]







CH
3
COCl reacts with the phenol functional
group to give the corresponding ester.





(ans)
Step-by-Step

28. [08N P1 Q28 Esters]

C (CH
3
)
2
CHCO
2
CH
2
CH
3


Acid hydrolysis of ester X gives a carboxylic
acid and an alcohol. The yellow precipitate
obtained with alkaline aqueous iodine (positive
iodoform test) suggests that the alcohol
contains a CH
3
CH(OH) group. Hence, X is
(CH
3
)
2
CHCO
2
CH
2
CH
3
.
















(ans)
Step-by-Step
KCN
in ethanol
reduction
BrCH
2
CH
2
CH
2
CH
2
Br
NCCH
2
CH
2
CH
2
CH
2
CN
H
2
N(CH
2
)
6
NH
2
H C C H
H OH
H H
c.H
2
SO
4
heat
+ H
2
O H C C H
H H
B CH
3
COCH
3

HCN

CH
3
OH

C
CH
3
CN
C
OCH
3
OH
CH
2
CH=CH
2
OCH
3
OH
CH
2
CH=CH
2
CH
3
COCl
OCH
3

OCOCH
3
CH
2
CH=CH
2
(CH
3
)
2
CHC
OCH
2
CH
3
O
+ CH
3
CH
2
OH (CH
3
)
2
CHC
OH
O
acid hydrolysis
X
Hydrolysis of ester:
CH
3
CH
2
OH + 4I
2
+ NaOH


CHI
3
+ HCO
2

Na
+
+ 5HI
yellow ppt
Iodoform test:
C
11
alcohol
CH
3
(CH
2
)
10
O(CH
2
CH
2
O)
10
H
excess
epoxyethane
08N-5

A-Level Solutions Chemistry
29. [08N P1 Q29 Amino Acids]


total number of
positive charges
total number of
negative charges
C 2 0

At pH 2 (acidic), the basic NH
2
group would
react with the H
+
ions present to give a salt.
The product formed is



(ans)
Step-by-Step

30. [08N P1 Q30 Amino Acids]

D HO
2
CCH
2
CH(CH
3
)NH
2

Proteins in the body are built from

-

amino
acids (or 2-aminocarboxylic acid). The amino
acid in D is a 3-aminocarboxylic acids.
(ans)
Step-by-Step

31. [08N P1 Q31 Bonding]

1 The C=S bond is more polar than the
C=Se bond.

2 The C=O bond is more polar than the
C=S bond.


CO
2
, COS and COSe are all linear in shape.
Down Group VI, electronegativity of the
elements decreases from O to Se.
i.e. electronegativity: O > S > Se
bond polarity: C=O > C=S > C=Se
This accounts for the overall polarity of COS
being less than that of COSe. (ans)
Step-by-Step

32. [08N P1 Q32 Energetics]

1 NH
3
(g) + HCl(g) NH
4
Cl(s)

At 298 K (or 25

C), carbon exists in the solid
state, C(s), which therefore rules out option 2.
Option 3 is ruled out because at 298 K, water
exists as H
2
O(l) and not, H
2
O(g). (ans)
Step-by-Step
33. [08N P1 Q33 Electrochemistry]

1 E
o
cell
= 0.77 V.

2 The left hand electrode is the negative
electrode.


H
+
+ e

2
1
H
2
E
o
= 0.00 V
Fe
3+
+ e

Fe
2+
E
o
= +0.77 V
E
o
cell
= E
R
o
E
L
o

= +0.77 0.00
= +0.77 V
At the left hand electrode, oxidation takes
place and so, it is the negative electrode.
2
1
H
2
H
+
+ e

Under standard conditions, concentrations of
Fe
3+
and Fe
2+
in the right hand solution should
be 1.0 mol dm
3
. (ans)
Step-by-Step

34. [08N P1 Q34 Kinetics] [96N P4 Q34]

1 The rate equation for the reaction can be
written: rate = k

[H
2
O
2
]

[I

].
2 The reaction is zero order with respect to
acid.

Comparing expt 1 and 2: [I

] and [H
+
]
constant, when [H
2
O
2
] triples, the initial rate is
also tripled. first order w.r.t. H
2
O
2
.
Comparing expt 2 and 3: [H
2
O
2
] and [H
+
]
constant, when [I

] doubles, the initial rate is

also doubled. first order w.r.t. I

.
Comparing expt 3 and 4: [H
2
O
2
] and [I

]
constant, when [H
+
] doubles, the initial rate
remains unchanged. zero order w.r.t. H
+
.
rate equation is rate = k

[H
2
O
2
]

[I

].
rate constant, k =
] I ][ O [H
rate
-
2 2

From expt 1, k =
0.010 0.010
10 2
-6

= 0.02 dm
3
mol
1
s
1

Hence, k 2.0

10
1
dm
3
mol
1
s
1
(ans)
Step-by-Step
NH
3
+

CH
2
CH
NH
3
+

CO
2
H
HO
2
CCH
2
CH(CH
3
)NH
2

1 2 3
08N-6

A-Level Solutions Chemistry
35. [08N P1 Q35 Periodicity]

1 The cation has a greater nuclear charge
than the anion.

Group II cation has charge 2+, while Group
VII anion has charge 1. Hence, configuration
1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6
suggests that the
Group II element has (36+2) = 38 electrons (or
proton no. 38), while the Group VII element
has (36 1) = 35 electrons (or proton no. 35).
The smaller size of the cation is due to the
greater nuclear charge which results in the
same number of electrons being attracted more
strongly by the nucleus. (ans)
Step-by-Step

36. [08N P1 Q36 Group VII]

2 There is an increase in reducing power in
the sequence X

, Y

and Z

.
3 The reaction 2Z

(aq) + Y
2
(aq) Z
2
(aq) +
2Y

(aq) occurs.

X
2
(aq) + 2e

2X

(aq) +1.36 V
Y
2
(aq) + 2e

2Y

(aq) +1.07 V
Z
2
(aq) + 2e

2Z

(aq) +0.54 V
E
o
value becomes less positive suggests a
decrease in oxidising power

: X
2
> Y
2
> Z
2
.
reducing power increases: X

< Y

< Z

.
2Z

(aq) + Y
2
(aq) Z
2
(aq) + 2Y

(aq)
E
cell
o
= E
R
o
E
L
o
= +1.07 (+0.54)
= +0.53 V (> 0, reaction is feasible)
Hence the reaction occurs. (ans)
Step-by-Step

37. [08N P1 Q37 Halogen Derivatives]
[02J P1 Q39] [93J P4 Q37]

1 The reaction is an example of nucleophilic
substitution.
2 Between X and Y the CHal bond will be
lengthening.
3 The energy difference between X and Z
represents the activation energy.

Halogenoalkanes undergo nucleophilic
substitution. The energy profile shows a one-
stage process involving the formation of an
intermediate Z. Between X and Y the CHal
bond will be lengthening as COH is gradually
formed.





The energy difference
between X and Z
represents the activation energy. (ans)
Step-by-Step

38. [08N P1 Q38 Alcohols]

1 The hydrocortisone molecule has 7 chiral
centres.
2 When treated with an excess of hot
concentrated acidified KMnO
4
,
hydrocortisone will produce a compound
with 2 carboxylic acid groups.

Hydrocortisone has seven chiral centres
(indicated by *

):







With excess hot conc. KMnO
4
, the 1 alcohol
group, 2 alcohol group and C=C are oxidised
to give the product:







(which has 2 carboxylic acid groups).
With hot acidified K
2
Cr
2
O
7
, only the alcohol
groups are oxidised. The product formed is:








(which has 3 carbonyl groups). (ans)
Step-by-Step
C Hal
+
OH

..
slow


C Hal OH
fast
C OH

+ Hal

O
CH
3

OH
C
CH
2
OH
CH
3
HO
*
* *
H H
H
*
O
*
*
*
O
CH
3

OH
C
CO
2
H
CH
3
O
H H
H
O
HO
2
C O
O
CH
3

OH
C
CO
2
H
CH
3
H H
H
O
O
08N-7

A-Level Solutions Chemistry
39. [08N P1 Q39 Aldehydes]







Option 2 involves the reaction of aldehyde
group with CH
3
O

nucleophile (from CH
3
OH).









Option 3 involves the reaction of aldehyde
group with phenylhydrazine.








(ans)
Step-by-Step
40. [08N P1 Q40 Proteins]

1 CH
2
CONH
2









In each of the above, the amino group forms
hydrogen bonding and hence, the cross-link to
stabilise the tertiary structure of a protein.
(ans)
Step-by-Step

[08N P1 MCQ Key]

Q. Key Q. Key Q. Key Q. Key
1 B 11 D 21 C 31 B
2 A 12 C 22 A 32 D
3 C 13 D 23 A 33 B
4 D 14 D 24 C 34 B
5 C 15 A 25 C 35 D

6 C 16 C 26 B 36 C
7 A 17 B 27 C 37 A
8 D 18 C 28 C 38 B
9 A 19 A 29 C 39 C
10 C 20 B 30 D 40 A

Step-by-Step
- H
2
O
N N
H
C
CH
3
H

+ H
2
N N
H
C O
CH
3
H

CH
3
CH=NNH 3
H
OCH
3
O
O
2
NH
NH
2
2 CH
2
CH
2
CH
2
NHC
N
3 CH
2

H

OCH
3
H
OCH
3
O
O
H
O
OH
O
H
O
OH
HO
OCH
3
-

H
2
O
08N-8

A-Level Solutions Chemistry
2008 Nov (9746) Paper 2

1. [08N P2 Q01 Hydroxy Compounds]

(a)
(i)

(ans)

(ii)




(ans)

(b)
(i) Gas A is ethene, C
2
H
4
. (ans)

(ii) The purple acidified KMnO
4
solution is
decolourised. (ans)

(c) The three functional groups are:
phenol
secondary alcohol, and
primary amine. (ans)

(d)
(i)
[Reaction of phenol

]


(ans)

(ii)
[Acid-base reaction
of phenol

]

(ans)

(iii)
[Oxidation of
secondary alcohol

]

(ans)

(iv)
[Acid-base reaction
of amine]
(ans)
Step-by-Step
2. [08N P2 Q02 Solubility Product]

(a)
(i) K
sp
= [Ag
+
]

[Br

] (ans)

(ii) [Ag
+
] = [Br

] = [AgBr]
K
sp
= (7.1

10
7
)

(7.1

10
7
)
= 5.0

10
13
mol
2
dm
6
(1 d.p.) (ans)

(b)
(i) G
o
ppt
= 2.303RT

log

K
sp

= 2.303

8.31

298

log

(2.0

10
10
)
= 55310 J mol
1

= 55.3 kJ mol
1
(1 d.p.) (ans)

(ii) G

o
= H

o
T S

o

S

o
=
T
G H
o o


=
298
) 3 . 55 ( 0 . 66
=
298
7 . 10

= 0.03591 kJ mol
1
K
1

= 35.9 J mol
1
K
1
(1 d.p.) (ans)

(iii) S

o
is negative suggests that there is a
decrease in entropy due to the formation of an
ordered lattice as the precipitate forms. (ans)

(c) G
o
ppt
= 2.303RT

log

K
sp

= 2.303

8.31

298

log

1.006
= +14.8 J mol
1
(1 d.p.)
Since G
o
ppt
is positive, precipitation will not
occur, i.e. AgF is soluble in water. (ans)
Step-by-Step
H
H O C C O H
H
H
H
OH
OH Br
Br Br
CH(OH)CH
2
NH
2
O

Na
+
O

Na
+
CH(OH)CH
2
NH
2
OH
OH
CH(OH)CH
2
NH
3
+
Cl

OH
OH
C
CH
2
NH
3
+
O
H
H O C C O H
H
H
H
H
H O C C O H
H
H
H

hydrogen
bonding

+
08N-9

A-Level Solutions Chemistry
3. [08N P2 Q03 Carbonyl Compounds]

(a) Products are



(ans)
(b)
(i) E
cell
o
= E
R
o
E
L
o

= +1.52 (+0.70)
= +0.82V (ans)

(ii)



(ans)


(iii) To reduce quinone, the reducing agent must
have a E

o
value less positive than +0.70 V.
SO
4
2
+ 4H
+
+ 2e

SO
2
+ 2H
2
O E

o
= +0.17 V
SO
2
(g) is a suitable reducing agent. (ans)

(c) Reagent used is NaBH
4
. (ans)

(d)
(i) reagent: 2,4-dinitrophenylhydrazine
observation: orange precipitate formed. (ans)

(ii) reagent: neutral FeCl
3
solution
observation: violet/purple coloration. (ans)

(iii) reagent: aqueous Br
2
solution
observation: brown Br
2
(aq) decolourised
(with quinol, white ppt and steamy fumes of
HBr are also observed) (ans)
Step-by-Step
4. [08N P2 Q04 Transition Elements]

(a) Cu 1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
1

Cu
2+
1s
2
2s
2
2p
6
3s
2
3p
6
3d
9
(ans)

(b)
(i) B is Ag(NH
3
)
2
Cl. (ans)

(ii) CuCl
2
(aq): [Cu(H
2
O)
6
]
2+
(ans)
C: [Cu(NH
3
)
4
(H
2
O)
2
]
2+
. (ans)

(c)
(i) D CuCl
2
+ 2HCl H
2
CuCl
4
(ans)
E CuCl
2
+ Cu + 2HCl 2HCuCl
2
(ans)

(ii) D [CuCl
4
]
2
(ans)
E [CuCl
2
]

(ans)

(iii) Ligand exchange occurs. (ans)

(iv) tetrahedral in shape. (ans)

(v) +1 oxidation state. (ans)

(d)
(i) reduction occurs. (ans)

(ii) F is CuCl. (ans)

(e)
(i) mole ratio Cu : F : K =
5 . 63
5 . 21
:
0 . 19
7 . 38
:
1 . 39
8 . 39

= 0.338

:

2.036

:

1.018
= 1 : 6 : 3
empirical formula of G is CuF
6
K
3
. (ans)

(ii) +3 oxidation state. (ans)

(f)
(i) Cu
+
1s
2
2s
2
2p
6
3s
2
3p
6
3d
10

Cu(I) in E and F has no empty or partially
filled d-orbitals. Hence, d-d* electron
transitions cannot occur which accounts for
both E and F being colourless. (ans)

(ii) Cu
3+
1s
2
2s
2
2p
6
3s
2
3p
6
3d
8

Cu(III) in G has empty d-orbitals. Hence, d-d*
electron transitions can take place and the light
energy not absorbed is seen as the colour of the
complex. (ans)
Step-by-Step
CH
3

CHCO
2
H
CH
3

CO
2
H
CO
2
H
and
OH HO 5 + 2MnO
4

+ 6H
+

O O 5 + 2Mn
2+
+ 8H
2
O
08N-10

A-Level Solutions Chemistry
2008 Nov (9746) Paper 3

1. [08N P3 Q01 Group VII / Halogenoalkanes]

(a) Bond energy (of dissociation) is the energy
required to break one mole of a covalent bond
between two atoms in the gaseous state. (ans)

(b)
(i) This reaction can be carried out by heating the
hydrogen halides. (ans)
[or by inserting a hot wire/glass rod into a test
tube of the gas.]
(ii) Down Group VII, the hydrogen halides, HX, is
increasingly easy to decompose. (ans)

(iii) 2HCl H
2
+ Cl
2

H = 2

E
HCl
E
HH
E
ClCl

= (2

431) 436 244
= +182 kJ mol
1
(ans)

2HI H
2
+ I
2

H = 2

E
HI
E
HH
E
II

= (2

299) 436 151
= +11 kJ mol
1
(ans)

(iv) Down the group, less energy is needed for the
reaction. As the size of the halogen increases,
the HX bond becomes longer and weaker and
so, breaks more easily. (ans)

(c) Electrophilic addition. (ans)
Mechanism: electrophilic addition with the
positive end of the polarised X
+
X

as
electrophile.











(ans)

(d)
(i) boiling point: C
2
H
5
Cl < C
2
H
5
Br < C
2
H
5
I
Boiling point increases from C
2
H
5
Cl to C
2
H
5
I
due to stronger intermolecular van der Waals'
forces as the number of electrons increases
from C
2
H
5
Cl to C
2
H
5
I. (ans)
(ii) bond polarity: CCl > CBr > CI
Bond polarity decreases from CCl to CI due
to decrease in electronegativity from Cl to I.
(ans)

(iii) reactivity towards nucleophilic reagent:
C
2
H
5
Cl < C
2
H
5
Br < C
2
H
5
I
Reactivity towards nucleophilic reagent
increases from C
2
H
5
Cl to C
2
H
5
I due to the
decrease in strength of CX bond. (ans)

(e) P is a tertiary bromide (chiral carbon indicated
by *)


(ans)

The four alkenes are:










I and II are geometrical isomers. (ans)

NB. Q is a tertiary alcohol since it does not react
with hot, acidified Na
2
Cr
2
O
7
(aq); i.e. not oxidised.
Hence, P is a tertiary alkyl halide (chiral carbon
indicated with *). HBr can be eliminated from P in
three possible ways:












Step-by-Step
slow
+
XX
C
C
H
H H
H
carbocation
+ X


C
C
H
H
X
H
H
fast
C
C
H
X H
H
H X
+ X


C
C
H
H
X
H
H
CH
3
C C C CH
3

Br
CH
3
H

H
H

CH
3
*
(i)
(i)
CH
3
H

CH
3

CH(CH
3
)
2

C=C

exists as geometrical isomers
(iii) (ii)
(iii)
H

H

CH
2
CH
3
CH(CH
3
)
2
C=C
(ii)
CH
3
CH
2
CH
3
CH
3

CH
3

C=C

CH
3
H

CH
3
CH(CH
3
)
2
C=C
CH
3
H

CH
3

CH(CH
3
)
2

C=C

I II
H

H

CH
2
CH
3
CH(CH
3
)
2
C=C
CH
3
CH
2
CH
3
CH
3

CH
3

C=C

III IV
CH
3
CH
2
C CHCH
3

Br
CH
3
CH
3
*
08N-11

A-Level Solutions Chemistry
2. [08N P3 Q02 Electrolysis / Alkanes]

(a) Products at the cathode: H
2
(g) and NaOH(aq)
(ans)
Overall reaction is:
2RCO
2

Na
+
+ 2H
2
O H
2
+ RR + 2CO
2

+ 2NaOH (ans)

(b) charge, Q = I t = (2.0

40

60) C
= 4800 C
=
96500
4800
F = 0.0497 F
2RCO
2

Na
+
RR + 2CO
2
+ 2e

From equation, 2 F 1 RR
or 0.0497 F (
2
1

0.0497) mol of RR
mol of C
2
H
6
= (
2
1

0.0497) mol
M
r
of C
2
H
6
= (2

12.0) + (6

1.0) = 30.0
mass of C
2
H
6
= (
2
1

0.0497)

30.0
= 0.746 g (ans)

(c) Since A is a mono-carboxylic acid,
mol of A = mol of NaOH
= cV
= 0.100

1000
4 . 11
= 1.14

10
3
mol
mass of 1.14

10
3
mol of A = 0.100 g
mass of 1 mol of A =
3
10 14 . 1
100 . 0

= 87.7 g
M
r
of A = 87.7 (ans)

Possible structure of A:
(ans)
(d) Using the ideal gas equation,
pV = nRT =
r
M
m
RT (since n =
r
M
m
)
M
r
of C =
pV
mRT
=
6 5
10 87 10 01 . 1
380 31 . 8 20 . 0

= 71.9 (ans)
Molecular formula of C is C
5
H
12
. (ans)
(e)
(i) P
2
O
5
+ 3H
2
O 2H
3
PO
4
(ans)
CO
2
+ 2NaOH Na
2
CO
3
+ H
2
O (ans)

(ii) mass of H
2
O = 1.55 g
mol of H
2
O =
r
M
m
=
0 . 16 ) 0 . 1 ( 2
55 . 1
+
=
0 . 18
55 . 1

= 0.0861 mol (ans)

mass of CO
2
= 3.03 g
mol of CO
2
=
r
M
m
=
) 0 . 16 ( 2 0 . 12
03 . 3
+
=
0 . 44
03 . 3

= 0.0689 mol (ans)

(iii) mol of H in D = 2

mol of H
2
O
= 2

0.0861 = 0.172 mol
mol of C in D = mol of CO
2

= 0.0689 mol
H

:

C ratio in D = 0.172

:

0.0689
= 2.5 : 1
= 5 : 2
molecular formula of D is C
4
H
10
. (ans)

(f) Possible structures:



(ans)

(g) Structures of F, G and H:






(ans)


F is a symmetrical alkane since it gives only
two isomeric monobromo compounds when
reacted with Br
2
under u.v. light; i.e. H atoms
in only two different chemical environments.
H has a chiral carbon atom indicated by *.
(ans)
Step-by-Step
CH
3
CH
2
CH
2
C
O
OH
CH
3
CH
2
CH
2
CH
2
CH
2
CH
3

alkane E
CH
3
CH
2
CO
2
H
acid B
CH
3
CH CHCH
3
;
CH
3
CH
3
F is CH
3
CH C CH
3

CH
3
CH
3
G is
Br

CH
3
CH CHCH
2
Br
CH
3
CH
3
H is
*
08N-12

A-Level Solutions Chemistry
3. [08N P3 Q03 Acid Derivatives]
(a)
(i) Reaction I: HCN + trace amount of NaOH;
10 20

C (ans)

(ii) Reaction II: H
2
O/H
+
[or dilute H
2
SO
4
(aq)];
heat (ans)

(b) HA H
+
+ A

(where HA lactic acid)

From the above equation, [H
+
] = [A

]
and since the degree of dissociation is very
small, [HA]
eqm
= [HA]
initial
K
a
=
[HA]
] ][A [H
+

K
a
=
0.20
] H [
2 +

[ H
+
]
2
= (0.20)(1.38

10
4
)
[H
+
] = 5.25

10
3
mol dm
3
pH = log
10
[H
+
]
= log
10
(5.25

10
3
) = 2.28 (ans)

(c)
(i) A buffer solution is a solution whose pH
remains almost unchanged on dilution or when
small amounts of acid or base are added to it.
(ans)
(ii) pH = pK
a
+ log
10
[acid]
salt] [

= log
10
K
a
+ log
10
[acid]
salt] [

= log
10
(1.38

10
4
) + log
10
20 . 0
30 . 0

= 4.04 (ans)

(iii) CH
3
CH(OH)CO
2

+ H
+
CH
3
CH(OH)CO
2
H
(added)
(ans)

(d)
(i) Ester functional group is present in PLA. (ans)

(ii) Hydrolysis might occur during biodegradation
of PLA. (ans)
(e)
(i) Reaction III: aq. NaOH, heat;
followed by acidification (say,
with aq. H
2
SO
4
). (ans)

(ii) Structures for K and L:





(ans)

In J, the Cl atom attached to C=O (i.e. acyl
chloride) is much more reactive due to the
electron-withdrawing effect of C=O group.
(ans)

(f) The two chemical tests are:
1. Add 2,4-dinitrophenylhydrazine to each
compound separately and warm.
Compound M gives an orange precipitate. No
such precipitate is observed with N. (ans)
2. Add Tollens' reagent to each compound
separately and warm.
Compound M gives a silver mirror. No such
silver mirror is observed with N. (ans)

[or warm with Fehling's solution only M gives a
red precipitate; or add Na
2
CO
3
only N gives
brisk effervescence of CO
2
(g); or add Na(s) only
N gives effervescence of H
2
(g).]
Step-by-Step
O
N C
2
H
5

CH
3
CHC
H
Cl
K
O
N C
2
H
5

CH
3
CHC
H
NH
2

L
08N-13

A-Level Solutions Chemistry
4. [08N P3 Q04 Bonding / Energetics]

(a) molecular formula of vapour: Al
2
Cl
6
(ans)





(ans)

(b) With a few drops of water, steamy white fumes
of HCl(g) evolved and a white solid, Al
2
O
3
(s),
remains.
2AlCl
3
(s) + 3H
2
O(l) Al
2
O
3
(s) + 6HCl(g)
[or Al
2
Cl
6
+ 6H
2
O 2Al(OH)
3
+ 6HCl

]
With a large amount of water, AlCl
3
undergoes
hydrolysis to give a weakly acidic solution.
AlCl
3
+ 6H
2
O [Al(H
2
O)
6
]
3+
+ 3Cl


[Al(H
2
O)
6
]
3+
[Al(H
2
O)
5
(OH)]
2+
+ H
+
(ans)

(c) When Na
2
O(s) is added to a solution of litmus
in water, a blue solution is obtained as Na
2
O(s)
dissolves readily in water to give an alkaline
solution (pH 13). (ans)
Na
2
O(s) + H
2
O(l) 2NaOH(aq) (ans)

(d)
(i)
(ans)

(ii) Mg
3
N
2
+ 6H
2
O 2NH
3
+ 3Mg(OH)
2
(ans)
The white insoluble solid is Mg(OH)
2
.
M
r
of Mg
3
N
2
= (3

24.3) + (2

14.0) = 100.9
M
r
of Mg(OH)
2
= 24.3 + 2

(16.0

+

1.0) = 58.3
mol of Mg(OH)
2
= 3

mol of Mg
3
N
2

= 3

9 . 100
0 . 2
= 0.0595 mol
mass of Mg(OH)
2
= 0.0595

58.3
= 3.47 g (ans)
[or Mg
3
N
2
+ 3H
2
O 2NH
3
+ 3MgO
in which case, mass of MgO = 2.40 g]
(e)
(i) Factors affecting magnitude of lattice energy:
ionic charge the bigger the ionic charge, the
bigger (more exothermic) is the lattice energy;
ionic radius the smaller the ionic radius, the
bigger (more exothermic) is the lattice energy;
arrangement of ions in the crystal (crystal
structure) but this effect is small.
(ii) Since lattice energy
) r (r
q q
-
-
+

+
+
,
the lattice energies of the oxides of Group II
elements decrease down the group as the size
of the cation, M
2+
, increases down the group.
(ans)
(iii) Since lattice energy
) r (r
q q
-
-
+

+
+
,
the lattice energy of Mg
3
N
2
is larger than that
of MgO due to the bigger charge of N
3
ions
(compared to O
2
ions). (ans)
Step-by-Step

5. [08N P3 Q05 Group II / Acid Derivatives]

(a) Two reactions in which iron or its compounds
behaves as a catalyst:
1. N
2
(g) + 3H
2
(g) 2NH
3
(g)
with finely divided iron, Fe(s), as
heterogeneous catalyst.
2. 2I

(aq) + S
2
O
8
2
(aq) I
2
(aq) + 2SO
4
2
(aq)
with Fe
3+
(aq) as homogeneous catalyst. (ans)

(b) Mg(NO
3
)
2
.6H
2
O MgO + 2NO
2
+
2
1
O
2

+ 6H
2
O (ans)
(c)
(i) HNO
3
+ 2H
2
SO
4
NO
2
+
+ 2HSO
4

+ H
3
O
+

(ans)

(ii) Type of reaction: nitration via electrophilic
substitution mechanism with NO
2
+
as the
electrophile.
Step 1: Production of electrophile, NO
2
+
.
HNO
3
+ 2H
2
SO
4
NO
2
+
+ 2HSO
4

+ H
3
O
+

Step 2: The NO
2
+
electrophile is attracted to
the delocalised electron system in benzene to
form an unstable intermediate.





Step 3: Expulsion of a proton from the
intermediate and the stable delocalised system
of benzene is retained.




(ans)
Mg
2+
3 N
3
2
slow
NO
2
+
H

NO
2
+
carbocation intermediate
NO
2
+ H
2
SO
4
+ HSO
4

fast
H
NO
2
+
Al
2
Cl
6
dimer
Al
Cl Cl
Cl Cl
Al
Cl
Cl
08N-14

A-Level Solutions Chemistry
(d) Synthesis of T from R:


















(ans)

(e)
(i) The four functional groups in aspartame are:
carboxylic acid, amine, amide and ester. (ans)

(ii) The three compounds are:
CH
3
OH,











(ans)
(iii) Structural formulae of compounds formed:
cold HCl (aq) :






(ans)

CH
3
COCl :








(ans)
Step-by-Step

HO
2
C CH
CH
2
N H

O
C
O
C
CH

CH
2
N
H
OCH
3
CH
3
C
O
HO
2
C CH
CH
2
NH
3
+
Cl

O
C
O
C
CH

CH
2
N
H
OCH
3
O
C
CH

CH
2
H
2
N
O

Na
+
Na
+

O
2
C CH
CH
2
NH
2
O
C
O

Na
+

and

c. HNO
3

OCH
2
CH
2
CH
3

R
(i) Sn + HCl (small amount)
(ii) aq. NaOH
OCH
2
CH
2
CH
3
O
2
N
NH
2

T
OCH
2
CH
2
CH
3
O
2
N
NO
2

S