H2 Chemistry 2009 A-level Paper 3 mark scheme

1 (a) Primary structure in haemoglobin is formed with

unique sequence of α-amino acids
linked by peptide linkages.
The secondary structure found in haemoglobin are formed when the long
polypeptide chain folds into the shape of a α-helix.
The coil structure is held together by hydrogen bonding
between O atom in the C=O group of one amino acid residue and the H atom
in the N-H group of another amino acid residue (4 amino acid apart) along the
same polypeptide chain.
The tertiary structure of haemoglobin refers to the 3D arrangement / irregular
contortions formed by the folding of the secondary structural elements (α-helix)
formed as a result of interactions between side groups of amino acid residues.
These interactions include hydrogen bonds, disulfide bonds, ionic bonds and
van der Waals’ forces.
Quaternary structure of haemoglobin consists of 4 polypeptide chains made of
two α-subunits and two β-subunits, each with an associated heme group.
These polypeptide chains form the complete protein maintained by the same
forces that are responsible for tertiary structure.
Diagrams can be used to support explanation
(b) (i)

(ii) The van der Waals’ forces / induced dipole – induced dipole interactions
between the side chains cause the Hb-S molecules to aggregate.
Do not accept hydrophobic interactions.
(iii) There is repulsion between the
negatively charged glutamate (glutamic acid residue).

(c) (i)
Kc =
[ Hb(O2 ) 4 ]
[ Hb][ O2 ] 4
mol-4 dm12
(ii) Since [Hb(O2)4] = [Hb]
 1
Kc =
[ O2 ] 4
1 −4
= = 3.00 ×10 20 mol dm 12
(7.6 ×10 ) −6 4

(iii)
Kc =
[ Hb(O2 ) 4 ] = 99
[ Hb][ O2 ] 4 [ O2 ] 4
99 99
[O2 ] = 4 =4 20
= 2.40 ×10 −5 moldm −3
Kc 3.00 ×10

(d)
Kc =
[ MbO2 ]
[ Mb] [O2 ]
[ MbO 2 ]
7.6 x 10-6 x 7.6 x 10-6 =
[ Mb ]
[ MbO 2 ]
= 7.6
[ Mb ]
[MbO2] : [Mb] = 7.6 : 1
7.6
% of MbO2 in Mb-MbO2 mixture = x 100% = 88.4 %
8.6

2 (a) (i) -2
(ii)
O.N. Compound
0 H2CO
H2C(OH)2
+2 CO
HCOOH
+4 CO2
H2CO3

(iii) Product Reagents and conditions for conversion

H2CO acidified potassium dichromate(VI), heat with distil
H2C(OH)2 Acidified potassium dichromate(VI), heat with distil

CO Limited O2, heat

HCOOH Acidified potassium dichromate(VI), heat
CO2 Acidified potassium manganate(VII), heat
or Excess O2, heat
H2CO3 Acidified potassium manganate(VII), heat

(b) (i) Q = mc∆T = 200(4.18)(30) = 25080J = 25.08kJ

no of mol of ethanol = 1.50/46 = 0.0326 mol
 ∆Hc = -(25.08/0.0326) = -769 kJ mol-1
(ii) The experimental value is less exothermic due to heat loss to the surrounding /
copper can

(c) (i) Bonds broken = 1(C-H) + 1(C-O) + 1/2(O=O) = 410 + 360 + 1/2(496) = 1018kJ
Bonds formed = 1(C=O) + 1(O-H) = 740 + 460 = 1200kJ
∆H = +1018 – 1200 = -182 kJ mol-1
(ii)

∆Hc ethanal = + 182 – 1367 = – 1185 kJ mol-1

(iii) Less exothermic as combustion of ethanoic acid requires the breaking of the
(strong) C-O and O-H bonds, that do not occur in ethanal.
OR
Combustion enthalpy of ethanal (which is more oxidized than ethanol) is less
exothermic than that of ethanol, combustion of even more oxidized ethanoic acid
will be even less exothermic.

(d) (i) D: E:

CH3CH2CH2CH2OH H

CH3CH2 C CH3

F: G: OH

H OH

CH3 C CH2OH CH3 C CH3

CH3
In any sequence CH3
For every 2 correct – 1 m
(ii) D – primary, E – secondary, F – primary, G - tertiary
(iii) E is chiral
(iv) E gives CH3CH2COO- and CHI3
(v) E gives CH3CH2COCH3

3 (a) • Mg (s) + ½ O2 (g)  MgO (s)

 • P4 (s) + 5O2 (g)  P4O10 (s) or P4 (s) + 3O2 (g)  P4O6 (s)

• 1/8 S8 (s) + O2 (g)  SO2 (g)

Do not accept SO3 as the product upon combustion
Accept P and S instead of P4 and S8.
Any 3 correct – 2 m
Any 2 correct – 1 m
Otherwise – 0 m
Observation:
Magnesium burns with a brilliant white light in air to form white solid MgO.
White phosphorus P4 reacts spontaneously with oxygen, and burns with a white
flame, producing dense white fumes, which then condense to give white solids of
phosphorus (III) oxide (P4O6) & phosphorus (V) oxide (P4O10).
Sulphur burns with a blue flame to form colourless SO2.
Any 3 underlined observations – 2 m
Any 2 underlined observations – 1 m
Otherwise – 0 m
(b) P4O10 (s) + 6H2O (l) → 4H3PO4 (aq)
SO2 (g) + H2O (l) → H2SO3 (aq)
Colour in universal indicator:
H3PO4 – red (more acidic)
H2SO3 – red / orange (less acidic)

(c) (i) 22 .5 × 0.100

no. of mol of NaOH in 25.0 cm3 = = 0.00225 mol
1000
100
no. of mol of NaOH in 100 cm3 = × 0.00225 = 0.00900 mol
25
(ii) 5 10 .0 × 0.0200
no. of mol of H2O2 in 25.0 cm3 = × = 0.000500 mol
2 1000
100
no. of mol of H2O2 in 100 cm3 = × 0.000500 = 0.00200 mol
25
(iii) no. of moles of Na2O2 = no. of moles of H2O2 = 0.00200mol
no. of moles of NaOH reacted with Na2O2 = 2 x 0.00200 = 0.00400 mol
no. of moles of NaOH reacte with Na2O = 0.00900 – 0.00400 = 0.00500 mol
no. of moles of Na2O = ½ x 0.00500 = 0.00250 mol

(d) (i) The initial rate is inversely proportional to the time taken.
Do not accept “the faster the reaction, the shorter the time”.
(ii)
experiment number initial rate / s-1
1 0.0303
 2 0.0100
3 0.0149
4 0.0200
Comparing experiments 2 & 3, when [KI] increases by 1.5 times, initial rate
increases by 1.5 times.
First order w.r.t. [KI].
Comparing experiments 2 & 4, when [H2O2] doubles, initial rate also doubles.
First order w.r.t. [H2O2].

Comparing experiments 1 & 2 (or any other pairs)

rate 1 k (15 )(10 )( 5) n 0.0303
= n
=
rate 2 k (5)(10 )(10 ) 0.0100
n =0
Zero order w.r.t. [HCl].
(iii) rate = k[H2O2][KI]
Units of rate constant = mol-2 dm6 s-1 (since initial rate calculated has units of s-1 )
Accept units of mol-1 dm3 s-1.

4 (a) Ideal gas particles have no / negligible volume as compared to the vol of gas it
occupies.
Do not accept ideal gas has no /negligible volume.
Ideal gas particles have no / negligible force of attractions.
Intermolecular collisions are elastic or no loss of energy after particles collide.
Do not accept random collisions.

(b) (i) CH4 molecules are non polar molecules attracted by induced dipole – induced
dipole interactions / weak van der Waals’ forces.
NH3 molecules are attracted by stronger hydrogen bonds which require more
energy to overcome.

(ii) When methane is liquefied, the molecules are more strongly attracted and/or
arranged in a more regular manner, hence the system becomes more orderly.
Entropy decreases or Change in entropy is negative.
Do not accept entropy is negative.

(iii) ∆ G = ∆ H – T∆ S
0 = +23300 – (273 – 33) ∆ S
∆ S = + 97.1
J mol-1 K-1
Accept correct answer in kJ mol-1K-1
(c) (i) Basicity: C2H5NH2 > NH3 > C6H5NH2
Ethylamine contains electron donating C2H5 group which makes the lone pair
electrons on nitrogen more available for protonation in water, hence most basic.
Phenylamine is the least basic as the lone pair electrons delocalize into the
benzene ring, making them least available for protonation in water.

(ii) [OH − ]2
Kb =
[ ethyla min e]

[OH-] = (0.1) ( 6.4 x 10 −4

)

= 8 x 10-3 mol dm-3

pOH = - lg (8 x 10-3) = 2.10
pH = 11.90
CH3 O H
(iii)
CH 3 C C N C2H5

H Br

Br NH2

Br

Br
(d) (i) Nucleophilic substitution
CH3CH2CH2 C CH2CH2CH2CH2Br
(ii)
H

1,5-dibromooctane
H H
(iii) H CH2CH2CH=CH2
C C C C
CH3CH2 CH2CH2CH=CH2 CH3CH2 H

H H H CH2CH=CH2
C C C C
CH3CH2CH2 CH2CH=CH2 CH3CH2CH3 H

Give consequential marks but no marks are given if the molecular formula is not
 C8H14.

5 (a) Volatility decreases down the group for halogens.

Colour intensity increases down the group for halogens
OR
Halogens becomes darker down the group.
Cl2: yellowish green gas (not yellow gas)
Br2: reddish brown liquid
I2: black solids

(b)
KCl + H2SO4  HCl + KHSO4
KBr + H2SO4  HBr + KHSO4
2 HBr + H2SO4  SO2 + Br2 + 2H2O
KI + H2SO4  HI + KHSO4
2HI + H2SO4  SO2 + I2 + 2H2O
6 HI + H2SO4  S + 3I2 + 4H2O
White fumes of HCl produced
White fumes of HBr produced.
Some reddish-brown fumes
produced.
White fumes of HI produced.
Dense I2 violet vapour produced.
Rotten egg smell of H2S detected.

8HI + H2SO4  H2S + 4I2 + 4H2O

1 m for each equation in bold.

1 m for each observations in bold.

(c) Lone pair electrons on O atom delocalizes into the benzene ring,
causing the ring to be more electron rich and hence
attracts electrophile easily or more reactive or requiring less harsh condition.
 L P
K
(d) CH3
CH 2Cl CH 2OH
CH3

Cl2 + AlCl3 Cl2 sunlight aq NaOH

heat
Electrophilic Free radical
substitution substitution Nucleophilic
substitution
Cl Cl
Cl

NaCN in ethanol
Nucleophilic substitution

CH2COOH
CH 2CN

N dil H2SO4
M
Hydrolysis

Cl Cl

Accept any position of Cl on ring

CH2COOH CH2OH
O

conc H2SO4
Cl CH2C OCH2 Cl
+
heat
Condensation Q
or
esterif ication + H2O
Cl Cl

N P

1 m for each correct structure – 6 m

1 m for each correct type of reaction – 5 m
Do not double award nucleophilic substitution
Total 11 m max 9 m