Anderson Junior College

H2 Chemistry 9647 2015 JC2 Prelim Paper 3 Suggested Solutions

Section A

1 (a) (i) Electrophilic addition [3]

R1 R1 R1
slow fast
C CH2 R2 C CH2 R2 C CH3
R2
  H Cl
H Cl
Cl

[1]: type of reaction

[1]: structure of carbocation intermediate, correct label of slow/fast
[1]: correct dipoles, lone pairs and curly arrows

(ii) [1]

In step 1, the more stable (tertiary) carbocation intermediate ( ) is

formed instead of a (primary) carbocation ( ).

Alkyl groups exert an electron–donating effect, helping to disperse the positive [1]
charge on the carbocation, stabilising it.

[1]: need to show clearly which carbocation is more stable – in drawing or words
[1]: correct explanation (do not accept H atom attaches itself to the double–
bonded C atom already carrying a larger number of H atoms)

(b) (i) There are only 6 electrons around the central B atom of borane (incomplete [1]
octet) / there is an empty (p) orbital on boron.

(ii) R1 R1 H [2]
C CH2 R2 C C H
R2
H BH3
B 
H  H

Not required
“favours formation of anti–Markovnikov product.” and the structure of the
intermediate showing presence of –BH3–
 B atom is the electrophilic centre.

[1]: electrophilic B atom attaches itself to the double–bonded C carrying fewer

both H atoms
[1]: correct dipoles on B–H bond and curly arrow

(iii) O.N. of C bonded to –BH2 changes from –3 to –1. [1]

H2O2 acts as an oxidising agent. (awarded only if 1st mark is correct) [1]

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 (iv) [1]
HO
OH

(c) (i) X [1]

X

X = Cl, Br, I, OH

(ii) Step I: suitable halogen X2, in inert solvent / cold KMnO4, dil. H2SO4 [1]
chosen halogen should correspond with proposed structure of H provided in
(c)(i)

Step II: NaOH in ethanol, heat (under reflux) / excess conc. H2SO4, 180 oC [1]

(iii) Heat separate samples of G and isoprene with acidified KMnO4. [1]

G decolorises purple KMnO4 without effervescence. [1]

Isoprene decolorises purple KMnO4 along with effervescence.

(d) (i) P4O10(s) + 6H2O(l) 4H3PO4(aq) [1]

ignore wrong state symbols

(ii) For Al2O3, aluminum oxide is insoluble in water. pH = 7. [1]

For MgO, magnesium oxide dissolves sparingly in water to give a white [1]
suspension of Mg(OH)2. pH = 9.

MgO(s) + H2O(l) Mg(OH)2(s) [1]

(accept )

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2 (a) (i) Brønsted–Lowry acid is a proton (H+) donor. [1]

(ii) H2SO4 HSO4– + H+ [1]

HSO4– SO42– + H+

(accept for 1st step)

(iii) [H+] = 10 mol dm–3 [1]

[HSO4–] = 10 mol dm–3

2
(iv) [H ][SO4 ] [1]
Ka = 
[HSO4 ]

(v) Let the [H+] from 2nd stage be x.

(10  x)(x)
= 1.0 x 10–2
(10  x)
Since x << 10, (10 + x)  10 and (10 – x)  10 [1]
x = 0.0100 mol dm–3

[H+]total = 10 + 0.0100 [1]

= 10.01 mol dm–3

Alternative
(10  x)(x)
= 1.0 x 10–2
(10  x)
10x + x2 = 0.1 – 0.01x
x2 + 10.01x – 0.1 = 0
solving by GC, x = 0.00998

[H+]total = 10 + 0.00998
= 10.0 mol dm–3

You may find the use of ICE table helpful.

HSO4–(aq) H+(aq) + SO42–(aq)

–3
initial conc. / mol dm 10 10 –
change in conc. / mol dm–3 –x +x +x
conc. at eqm / mol dm–3 10 – x 10 + x x

(vi) [SO42–] = 0.0100 mol dm–3 (accept 0.00998 mol dm–3) [1]

[HSO4–] = 10 – 0.01
= 9.99 mol dm–3

(vii) HSO4– is a very weak base because its tendency to accept a H+ proton is very [1]
low since H2SO4 is completely ionised / a strong acid.

Kw
or Kb (HSO4–) = is very small as H2SO4 is a strong acid and its Ka is
K a (H2 SO 4 )
large.

Hence HSO4– is a stronger acid than it is a base as Ka (HSO4–) = 1.0 x 10–2 >> Kb
[1]
(HSO4–).

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 (b) (i) Anode: 2SO42– S2O82– + 2e or 2H2SO4 H2S2O8 + 2H+ + 2e [2]

Cathode: 2H+ + 2e H2
(do not accept 2H2O + 2e H2 + 2OH–)

(ii) H2S2O8 + 2H2O 2H2SO4 + H2O2 [1]

(iii) H2S2O8 + H2O H2SO4 + H2SO5 [2]

H2SO5 + H2O H2SO4 + H2O2

[1]: each correct step

(iv) O [3]
H O O S O H
O
HOO = 104.5o (accept 104o – 105o)
OOS = 104.5o (accept 104o – 105o)
SOH = 104.5o (accept 104o – 105o)
OSO = 109.5o (accept 109o)

[1]: correct displayed structure

[1]: each correct bond angles wrt O and S (ignore repeated bond angle)

(v) O.N. of S in H2S2O8 and H2SO5 = +6 [1]

(c) decomposition of H2O2: 2H2O2 2H2O + O2 [2]

H2O2 + 2H+ + 2e– 2H2O Eo = +1.77 V

O2 + 2H+ + 2e– H2O2 Eo = +0.68 V
Mn3+ + e– Mn2+ Eo = +1.49 V

(Step 1: 2Mn2+ + H2O2 + 2H+ 2Mn3+ + 2H2O) Eocell = +0.28V

3+
(Step 2: 2Mn + H2O2 2Mn + O2 + 2H+)
2+
Eocell = +0.81V

Since Ecell > 0, both reactions are feasible. Hence Mn2+ acts as a homogeneous
catalyst in the two–step reaction by providing an alternative pathway with lower
activation energy via the intermediate Mn3+(aq).

[1]: suitable choice of Eo wrt Mn2+ (accept MnO4–/Mn2+ but not MnO2/Mn2+)
[1]: appropriate attempts to show Eocell > 0 (i.e. ignore numerical error if method and
conclusion is correct)
(award only the 2nd mark if Mn3+ is used as catalyst instead)

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3 (a) (i) high temperature and low pressure [1]

(ii) 68 [2]
n(PH3) = = 2.00 mol
[31.0  3(1.0)]

pV = nRT
nRT
V=
p
2.00(8.31)(800)
=
3.36  107
= 3.96 x 10–4 m3
= 396 cm3

[1]: correct volume in m3

[1]: correct conversion from m3 to cm3

(iii) PH3 behaves non–ideally and volume calculated in (a)(ii) is smaller than the [2]
volume of the container.

under high pressure,

the volume of the PH3 molecules is not negligible / significant. Hence the actual
free volume between the gas molecules is smaller.

[1]: recognise that PH3 is behaving non–ideally and volume is smaller

[1]: correct explanation

(b) (i) 1 3 [1]

P4(s) + H2(g) PH3(g)
4 2

(with correct state symbols, accept if just use P)

(ii) By Hess’s Law, [2]

1 3
Hfo = (–3012) + (–286) – (–1291)
4 2
= +109 kJ mol1

[1]: correct application of Hess’ Law

[1]: correct answers with units

(iii) Cl is more electronegative than H. Hence the H–Cl bond is polar and the bond [1]
has ionic character which results in extra bond strength.

The electronegativity of P and H are similar, hence the bond energy of the P–H
bond is just the average of the H–H and P–H bond energies.

(c) (i) nucleophilic substitution [1]

(ii) It acts as a base. [1]

(iii) H CH3 [2]

C C
H 1 2 CH
3

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 oxidation number of
C1: –2
C2: 0

[1]: each correct answer

(iv) [2]
H CH3 H CH3
H C C CH3 C C Ph3P O
H CH3
Ph3 P O

[1]: both curly arrows correctly shown (allow 4 )

[1]: correct by–product

(d) Step V: NaOH(aq), heat (under reflux) [5]

Step VI: K2Cr2O7, dilute H2SO4, warm with (immediate) distillation

CH2OH
K:

O
C H
L:

+ –
M: Ph3P–CHPh

[1] each

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4 (a) (i) H H [2]
H O O H
H C C C C Cl
H H H H

[1]: correct diol

[1]: correct displayed formula shown

(ii) OH [2]
CH3 C C C2H5
H CH3
 
The yield of carbocation Q is smaller as it is a less stable carbocation due to 1
less electron donating alkyl group to help disperse the positive charge on the
carbocation.

[1]: correct structure of Q

[1]: correct explanation

(iii) OH [1]
CH3 C C H more stable
OH OH intermediate
H CH2Cl
CH3 C C H
OH
H CH2Cl
CH3 C C H less stable
intermediate
H CH2Cl
followed by

H O
CH3 C C H
OH CH2Cl shift
CH2Cl
CH3 C C H
H O
H CH2Cl H shift
CH3 C C CH2Cl
H

[1]: correct carbonyl compound

(b) (i) O H OH H OH H [3]

CH3 C C CO2H CH3 C C CO2H CH3 C C CH2OH
CH3 H CH3 H CH3

R S T
[1] each

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 Not required
R and S react with Na2CO3.
 presence of –CO2H
 likely presence of 1o in T (due to reduction of –CO2H in R)
R, S and T give yellow ppt with I2/OH–.
 presence of CH3COR or in R and CH3CH(OH)R in S and T (S and T are
formed from the reduction of R)
From these 2 pieces of information, you can deduce the structure of R as the
remaining 2 C atoms must be branched in order for R to be chiral.

(ii) CH3 CH3 [2]

HO O HO

NH NH

V W
[1] each

Not required
V and W react with sodium metal.
 likely presence of (2o) alcohol (due to reduction of ketone in U)
Only W reacts with HCl(aq).
 presence of basic amine group in W (infer from the molecular formula and
structure of U)
From these 2 pieces of information and from the loss of 1 O atom and gain of 4
H atoms (U W), you can deduce the structure of W. (or by comparing W
with V)
Other cues include “LiAlH4 is the more powerful of the two” and “behaves
differently towards the two reducing agents”.

(iii) Add 2,4–dintrophenylhydrazine to separate test–tubes containing U and V. [2]

U gives an orange ppt but no orange ppt observed for V.

(accept use of anhydrous PCl5 / SOCl2 or K2Cr2O7, dil H2SO4)

[1]: correct test

[1]: correct observation

(iv) Compound U is neutral but ethylamine is basic. Lone pair on the N of U is [2]
delocalised into the C=O, hence it is not available to accept the H+ ion.
In ethylamine, the electron donating ethyl group bonded to N makes the lone pair
more available to accept the H+ ion, hence it is more basic.

[1]: correct relative basicity

[1]: correct explanation

(c) LiAlH4 + 4H2O LiOH + Al(OH)3 + 4H2 [1]

LiOH + Al(OH)3 + 4H+ Li+ + Al3+ + 4H2O [1]

(d) (i) nucleophilic addition [2]

(Generation of nucleophile: LiAlH4 LiAlH3+ + H–)

 

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 H OH
 O O OH
slow fast
CH3CH2 C CH3 CH3CH2 C CH3 + OH
 C
CH3CH2 CH3 H H

[1]: correct dipoles on the carbonyl C and O and correct curly arrows
[1]: correct intermediate and product, (slow/fast steps clearly indicated)

(ii) Since the butanone molecule is trigonal planar with respect to the carbonyl [1]
carbon atom, the nucleophile has equal probability of attacking it from either side
of the molecule.
This generates equimolar mixture of the enantiomers / alcohol formed via
nucleophilic addition mechanism and gives an optically inactive racemic mixture
which does not rotate plane–polarised light.

(iii) Absence of electron deficient C atom / polarised bond or same electronegativity [1]
between 2 C atoms and not susceptible to nucleophilic attack by H–.

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5 (a) (i) [I2 ]CCl 4 [1]
D=
[I2 ]water
0 .102
= = 85
0 .00120
OR
[ I 2 ]water 0 .00120
D= = = 0.0118
[ I 2 ]CCl 4 0 .102

(ii) When the [I–] increases, by Le Chatelier’s Principle, the position of equilibrium [1]
shifts to the right, to decrease the concentration of I–, hence favouring the
forward reaction. This results in a decrease in the fraction of I2.

(iii) [I2 ]CCl 4 0.085 [1]

85 = =
[I2 ]water [I2 ]water

0 .085
[I2]water =
85
= 0.001 mol dm–3

(iv) Since [I2]total = [I2(aq)] + [I3–(aq)] [2]

0.01 = 0.001 + [I3–(aq)]
[I3–(aq)] = 0.009 mol dm–3

I2(aq) + I–(aq) I3–(aq)

–3
initial conc. / mol dm 0.0232 –
change in conc. / mol dm–3 – 0.009 + 0.009
conc. at eqm / mol dm–3 0.001 0.0142 0.009

[1]: correct [I3–(aq)]

[1]: correct [I–(aq)]

(vi) 0.009 [2]

Kc =
(0.001)(0.0142)
= 634 mol–1 dm3

[1]: correct answer

[1]: correct units

(b) (i) A = Co(OH)2(H2O)4 (accept Co(OH)2) [1]

(ii) [Co(NH3)6]3+ + e– [Co(NH3)6]2+ Eo = +0.11V [2]

O2 + 2H2O + 4e– 4OH– Eo = +0.40V

Eocell = +0.40 – (+0.11)

= +0.29V > 0

Hence yellow–brown solution B changes to red–brown solution C as the

[Co(NH3)6]2+ is oxidised to [Co(NH3)6]3+.

[1]: correct choice of Eo (O2 + 4H+ + 4e– 2H2O not accepted)

[1]: correct Eocell calculated (allow ecf)

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 (iii) When concentrated HCl is added to an aqueous solution of Co2+, ligand [2]
exchange occurs where Cl– displaces H2O ligands, forming the blue [CoCl4]2–.

[Co(H2O)6]2+ + 4Cl– [CoCl4]2– + 6H2O

Addition of water will cause the position of equilibrium to shift to the left,
reforming the pink [Co(H2O)6]2+.

[1]: correct equation (accept [CoCl6]4–)

[1]: correct explanation

Note: Addition of water will result in decrease in concentration of the ions.

Position of equilibrium will shift to the left as it will result in an increase in no. of
ions, reforming the pink [Co(H2O)6]2+ as shown by the equation
[CoCl4]2 + 6H2O [Co(H2O)6]2+ + 4Cl

(recall: the effect of decreasing pressure on system will cause P.O.E. to shift to
the side with more gaseous particles so as to increase the pressure)

(c) (i) In the presence of ligands, [3]

 the partially–filled 3d orbitals of Co3+ are split into two levels (non–
degenerate) with a small energy gap E
 When light passes through, photons/energy equal to red light is absorbed.
 An electron promotes from a lower energy d orbital to a
vacant/unfilled/partially filled higher energy d orbital, i.e. d–d transition,
 The green colour of the complex F is complementary to red absorbed.

[1]: partially filled 3d–orbital; small energy gap

[1]: d–d transition
[1]: absorption of red (complementary to green)

(ii) Number of moles of free Cl– per mole of complex [2]

= 2 x number of moles of PbCl2 precipitated per mole of complex

F: 0.5 mol of PbCl2 precipitated

 1 mol of free Cl– and 2 mol of Cl– as ligand per mol of complex
 cation is [Co(NH3)4Cl2]+
 the 2 Cl– ligands must be at 180o to each other / cannot be 90o away from
each other (no net dipole)

+
NH3

Cl NH3

CoIII

H3N Cl

NH3
F

[1]: correct formula for complex ion

[1]: for structure with lone pairs and correct net charge

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 (d) (i) The energy gap E between the two sets of d–orbitals is greater than the [1]
repulsion energy, favouring the pairing of electrons.

[1]: for comparison of energy gap E and repulsion energy between electrons

(ii) Ni2+ ion: 1s2 2s2 2p6 3s2 3p6 3d8 [2]

Ni2+ ion in [NiCl4]2– Ni2+ ion in [Ni(CN)4]2–

energy

energy gap E

energy gap E

d–orbitals of metal d–orbitals of metal

ion in tetrahedral ion in square
complex planar complex

In [NiCl4]2–, there are 2 unpaired electrons in the d–orbitals. Hence it is

paramagnetic.
In [Ni(CN)4]2–, there are 0 unpaired electrons in the d–orbitals. Hence it is non–
paramagnetic.

[1]: correct electronic configuration / no. of d–orbital electrons for Ni2+

[1]: correct placement of electrons

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