Question Mark Question Mark Question Mark

1(a) 4 4(b) 1 8 7
1(b) 4 4(c) 1 9 9
2(a) 5 4(d) 1 10(a) 4
2(b) 5 4(e) 1 10(b) 4
2(c) 5 4(f) 1 11 8
3(a) 1 5 8 12 6
3(b) 4 6(a) 3 13 2
3(c) 1 6(b) 2 14 2
4(a) 1 7 6 15 4

Question 1

a) 4 marks In the boxes provided below, rank the following species from best (1) to worst (4)
nucleophile for performing an SN2 reaction.

species O O
F3C O O
OH
O O2 N

Conjugate -7.8 4.8 13 7.2

b) 4 marks In the boxes provided below, rank the following species from best (1) to worst (4) base for
performing an E2 reaction.

species
N N O
N
N
Conjugate acid pKa 36 11 12 17
Question 2 15 marks

Alkyl halides can undergo substitution reactions (via SN1 or SN2 mechanisms) and/or elimination
reactions (via E1, E2 or E1cB mechanisms). Illustrate your understanding of these pathways in the
following three examples by:

i) indicating the reaction mechanism(s) favoured by the particular type of substrate,

N H

DMF solvent

b)
H
H
Br
K O
O

N H

DMF solvent
c)
H
H
OH conc. HCl (aq)

Question 3
The pesticide, carbaryl, has a pKa of 12.02 and can be degraded by base-catalysed hydrolysis
(aqueous/methanol, pH 10, 293 K).
O
CH3
O N
H
OH

1 mark (a) indicate the acidic proton

O
CH3
O N
H
OH

4 marks (b) using the arrow formalism, predict the products of hydrolysis

O
CH3
O N
H
OH
 1 mark (c) Justifying your choice, classify the reaction mechanism as SN1, SN2, E1, E2 or E1cB.

Question 4 6 marks
Consider the reaction profiles A-D shown below and answer the following questions

a) What type of mechanism is occurring in profile B?

b) In profile C, which product Y or Z would be favoured under conditions of high temperatures and
long reaction times?
c) In profile B, would changing the solvent from water to ethanol result in an increase, a decrease,
or no change in the rate of disappearance of starting material?

d) In profile A, is transition state N best considered early or late?

e) In profile C, which product is favoured under conditions of kinetic control?

f) In profile D, what term is given to Q?

Question 5 8 marks

Using arrow notation to show the movement of electrons, predict the product(s) of the following
reaction.

Classify the mechanism of this reaction as one or more of SN1, SN2, E1, E2 or E1cB mechanisms

OH O
H NaOH, ∆
H CH3
H
H

Derive an expression for the rate law consistent with your classification of the mechanism.
Question 6

(a) 3 marks In the box below, using arrow notation to show the movement of electrons, give the
structures of the 3 other resonance contributors to the overall hybrid of the phenoxide ion.

1 2 3

(b) 2 marks Briefly explain why p-nitrophenol is more acidic than phenol itself.
Question 7 6 marks

Treatment of chlorobenzene with NaOH and water at high temperature and pressure gives phenol
via a benzyne intermediate. Similar treatment of o-chlorotoluene gives two regioisomeric products.
Complete the Scheme below by inserting the structures of the reactive intermediate and products in
the boxes provided.

Cl
o
NaOH, 300 C

reactive intermediate

H 2O H2O

Question 8 7 marks

Explain the trends and differences among and between the stepwise stability constants of the
ammine complexes of Ni(II) and Cu(II) ions.

log Kn 1 2 3 4 5 6
Ni (II) 2.7 2.2 1.7 1.1 0.6 0.03
Cu (II) 4.1 3.5 2.9 2.1 0 0
Question 9 9 marks

Sketch the d-orbital energy level diagram for trans-[Co(NH3)4(CN)2]+, label the d-orbitals and show
the d-electron occupancy.

Question10

[Cr(H2O)6]2+ and [Cr(CN)6]2¯both contain Cr(II) ions and are paramagnetic with effective magnetic
moments of around 4.9 and 3.4 B.M respectively.

4 marks (a) Explain the origin of the paramagnetism of these two ions and for the difference in their
magnetic moments.

4 marks (b) [Cr2(CH3CO2)4] also contains Cr(II) ions but is effectively diamagnetic. Account for the
magnetism of this dimer.
Question 11 8 marks

The pictures below show the ligand-field spectrum of the [Cr(OH2)6]2+ion, which shows a single
absorption at around 14000 cm¯1, and of the [Ti(OH2)6]3+ ion, which shows two overlapping
absorptions at about 18000 and 19900 cm¯1.

Explain why the ligand-field spectrum of [Cr(OH2)6]2+ consists of only one absorption whilst that of
[Ti(OH2)6]3+ consists of two overlapping absorptions.
Question 12 6 marks

At room temperature, the rate constant for water exchange for Cr2+(aq) is around 109 s¯1 whilst that
for Cr3+(aq) is around 10¯6 s¯1.

Assuming that the water exchange reaction occurs via a dissociative mechanism in both cases,
account for the lability of Cr(II) and the inertness of Cr(III).

Question 13 2 marks

The ligand field splitting, Δo (10Dq), and the mean pairing energy, P, for the cation, [Mn(OH2)6]3+,
are 15,800 cm¯1 and 28,000 cm¯1, respectively. Is the cation, [Mn(OH2)6]3+, expected to be high-spin
or low spin?
Question 14 2 marks

Will neither, either or both the high and low spin configurations of the cation, [Mn(OH2)6]3+ be
subject to a Jahn-Teller distortion?

Question 15 4 marks

Is the [FeCl4]2¯ dianion expected to be tetrahedral or square planar?