IMPERIAL COLLEGE LONDON

M.Eng EXAMINATION IN CHEMICAL ENGINEERING 2010

PART I

For Internal Students of Imperial College London

This paper is also taken for the relevant examination

for the Associateship

CHEMISTRY (PART I)
Tuesday 15th June 2010 10.00-12.00
Answer TWO questions (among 1-3) in full and part a) of the remaining question
(The maximum score is 100 marks)

THE EXAMINATION HAS FOUR PAGES IN TOTAL

WHICH INCLUDES THIS COVER SHEET
TURN OVER FOR QUESTIONS

Question 1
Cyclopentene is brominated with bromine at 298K in methanol.

1a)

What are the main reaction products (draw structures and give their IUPAC
names)? Discuss the mechanism that leads to their formation (show a curlyarrow representation). What by-products can you expect to observe in this
reaction (give a rationale for their formation)?
(20 marks)

1b)

If benzene is to be brominated under similar conditions a catalyst is required.

Explain the nature and the role of the catalyst. Using the HOMO-LUMO
concept as guiding principle for reactivity, explain why a catalyst is needed in
this case whereas no catalyst is required in the case of cyclopentene.
(10 marks)

1c)

For the bromination of anisole (methoxybenzene) the reaction goes

essentially to completion at 298K in ethanoic acid without a catalyst. Explain
why no catalyst is needed in this case. Identify the main reaction products in
this reaction and give a rationale for their formation.
(10 marks)

Question 2
You have been given the results of a study of the reaction of 2-bromo-2methylpropane with sodium iodide (NaI) in acetone. The report states that the
reaction goes to completion and that 62% conversion of 2-bromo-2-methylpropane
was obtained after 4 h reaction time at 323K. When the reaction was carried out at
310K, 17% conversion of the reactant was recorded after three days.

2a)

How long would it take to achieve 99% conversion of 2-bromo-2methylpropane if the reaction was carried out at the reflux temperature of
330K?
(20 marks)

2b)

What other reaction products could you expect to form from competitive
reaction pathways (particularly as the reaction temperature is increased)? Are
these potential alternative reactions going to limit the yield of your desired
product in this particular reaction?
(10 marks)

2c)

A co-worker has suggested speeding up the reaction even more by using

higher concentrations of 2-bromo-2-methylbutane and sodium iodide. He
claimed that much higher conversions could be reached in the same time. Do
you agree?
(10 marks)

Question 3

You are asked to design an extraction process to recover copper and nickel from
soil. Oxalate is being used as a coordinating agent in this process as it speeds up
the extraction of the metals from the soil.

3a)

Oxalate (C 2 O 4 2-) is a bidentate, chelating ligand. Sketch, how oxalate would

co-ordinate to a metal cation and describe how the chelating effect manifests
itself. Explain the chelating effect either through thermodynamic or through
kinetic principles (hint: compare oxalate with a monodentate ligand).

Assuming that at equilibrium the concentration of Cu2+ and Ni2+ in solution is

10-6M each, what pH would your extraction solution have to have if you
wanted to avoid the precipitation of copper and nickel hydroxides?
(20 marks)

3b)

Does oxalate hydrolyse to a significant extent at this pH?

(10 marks)

3c)

You are asked to consider sodium oxalate and ammonium oxalate as

potential extracting agents. Which of the two would be better?
(10 marks)

Physical constants at 25C:

NH 3 :

K b = 1.8x10-5

Cu(OH) 2 :

K SP = 4.8x10-20

Ni(OH) 2 :

K SP = 5.5x10-16

Oxalic acid - H 2 C 2 O 4 :

pK a1 = 1.20 and pK a2 = 4.09

4

IMPERIAL COLLEGE LONDON

M.Eng EXAMINATION IN CHEMICAL ENGINEERING 2011
PART I

For Internal Students of Imperial College London

This paper is also taken for the relevant examination

for the Associateship

CHEMISTRY
Friday 3rd June 2010 10.00-12.00

Answer TWO questions (among 1-3) in full and the a) part of the remaining question
(The maximum score is 100 marks)

THE EXAMINATION HAS FIVE PAGES IN TOTAL

WHICH INCLUDES THIS COVER SHEET
TURN OVER FOR QUESTIONS

Question 1

When 3,3-dimethyl-2-butanol is dehydrated using hot phosphoric acid the

following product mixture is obtained in 80% yield with the product
selectivities indicated below in parentheses
3,3-dimethyl-1-butene
2,3-dimethyl-2-butene
2,3-dimethyl-1-butene

1a)

(3%)
(64%)
(33%)

Considering the elementary steps in this reaction, write a curly-arrow

mechanism by which the formation of all three products can be
accounted for (write correct Lewis structures for all species).
(20 marks)

1b)

Sketch a free energy-reaction coordinate diagram for this reaction (pay

special attention to the correct size of activation barriers and relative stabilities
of the reaction intermediates and products) and give a detailed explanation for

(i)

The higher proportion of 2,3-dimethyl butenes observed in the

product mixture.

(ii)

The higher proportion of 2,3-dimethyl-2-butene over 2,3-dimethyl1-butene observed in the product mixture.
(10 marks)

1c)

Based on your mechanistic analysis, write a multi-step mechanism from which

you could derive a rate equation that you could test against experimental data.
Derive the expression for the rate of formation of 3,3-dimethyl-1-butene from
your mechanism (assume an irreversible overall reaction).
(10 marks)

Question 2
The solvolysis of 3-chloro-1-butene was measured in ethanol at 318 K with
simultaneous removal of the HCl product. You have measured a conversion of the
chloroalkene of 88.9% in 2 h reaction time. The half-life of the reactant was
previously determined as 17.33 h at 307 K.

2a)

What reaction temperature is required to achieve 99% conversion of 3-chloro1-butene in 2 h reaction time?
(20 marks)

2b)

You observe two ethers as the main products of this reaction. Explain the
formation of these two products (write a curly arrow mechanism) and give
their IUPAC names. How does the fact that two ethers are being formed help
you determine whether this is an S N 1 or S N 2 reaction? Why are elimination
side reactions not a serious problem in this conversion?
(10 marks)

2c)

Discuss the nature of the reaction intermediate in this reaction, particularly its
stability. Using the system (neglecting any further alkyl-substituents) and discuss the nature of
the HOMO and LUMO (energy and shape). What can you conclude about the
location of nucleophilic attack on the molecule? In what way do further alkylsubstituents influence the stability of the reaction intermediate?
(10 marks)

Question 3
You are asked to prepare an aqueous electroplating solution containing zinc at a pH
of 9.

3a)

What is the maximum concentration of zinc (assume the 2+ cation) that can
exist in solution without a precipitate forming?
(5 marks)
In order to get reasonable concentrations of the metal cation in solution you
decide to use citrate as a complex-forming agent. What would be the required
citrate concentration to permit a total of 0.1M of zinc in solution at that pH
(state all your assumptions)?
(15 marks)

3b)

Explain the relatively large complex formation constant of zinc-citrate

complexes through the principle of chelation. Give an explanation why
chelated complexes are more stable than non-chelated complexes using
acetic acid for comparison. Why is there no Zn(Cit) 3 complex observed?
(10 marks)

3c)

In order to be better able to control the pH during the electroplating process

you consider using a buffer. You can choose between a phosphate buffer, a
glycine buffer or a carbonate buffer (relevant hydrolysis constants are given in
the data sheet on the next page). Which of the three buffers would give you
the highest flexibility with respect to any pH change in the system?
Describe, how you would prepare the actual buffer using either phosphoric
acid, glycine or sodium bicarbonate and a strong acid or base, so that it can
buffer 0.1 mol/L of base with a maximum change of 0.05 pH units.
(10 marks)

Physical constants at 25C:

H 3 PO 4 :

K a1 = 7.1x10-3

K a2 = 6.3x10-8

Glycine:

K a1 = 4.47x10-3

K a2 = 1.66x10-10

K a3 = 4.5x10-13

(Glycine is an amino acid the K a2 refers to the deprotonation of

the amino group)
H 2 CO 3 :

K a1 = 4.5x10-7

K a2 = 4.7x10-11

Citric acid:

HO-C-(CH 2 -COOH) 2
COOH
K a1 = 7.1x10-4

K a2 = 1.7x10-5

Zn(OH) 2 :

K SP = 3x10-17

Zinc citrate

Zn(Cit)-

K f = 6.31x104

Zn(Cit) 2 4-

K f = 3.16x106

K a3 = 6.4x10-6

IMPERIAL COLLEGE LONDON

M.Eng EXAMINATION IN CHEMICAL ENGINEERING 2012
PART I

For Internal Students of Imperial College London

This paper is also taken for the relevant examination

for the Associateship

CHEMISTRY (PART I)
Monday 28th May 2012 14.00-16.00

Answer TWO questions (among 1-3) in full and part a) of the remaining question
(The maximum score is 100 marks)

For all questions explain your reasoning in detail.

THE EXAMINATION HAS FIVE PAGES IN TOTAL

WHICH INCLUDES THIS COVER SHEET
TURN OVER FOR QUESTIONS

Question 1
The reaction of p-nitro phenol with iodomethane in dimethylformamide (DMF) as
solvent has been studied at 25C in a small batch reactor using an excess of the
organic base TMGN (tetramethylguanidinonaphthalene) and was found to go to
completion.
Using initial concentrations of p-nitro phenol and iodomethane of 7x10-4 molL-1
the data in the table below were recorded.

1a)

Time (s)

10

20

40

70

Conversion (%)

17.7

30.1

46.3

63.3

75.0

Determine the overall order of reaction and the rate constant at 25C.
(15 marks)
Based on the reactants, solvent, and the kinetic analysis, what type of
reaction mechanism would you propose (drawing of a curly arrow
representation is not required)?
(5 marks)

1b)

In another experiment, the same reaction was studied without the base. It was
found to have the same overall reaction order but to occur at a much slower
rate. Based on these observations, write a multi-step mechanism for the
reaction in part 1a. Derive the overall rate law based on this mechanism
expressed through the reactant concentration. What interpretation of the
measured rate constant in part 1a can you give?
(10 marks)

1c)

If the reaction product from part 1a is further reacted with a mixture of nitric
acid and sulphuric acid, only one new product is formed. Identify this product
(draw the Lewis structure and give the IUPAC name) and explain its selective
formation (use a free energy reaction coordinate diagram in your explanation).
(10 marks)

Question 2
3-methylcyclopentene is reacted with HBr in acetic acid (ethanoic acid) as a solvent
at room temperature. You observe three main reaction products, which are
constitutional (structural) isomers of the bromoalkane.

2a)

Draw a curly-arrow mechanism that explains the formation of all three

products (give their IUPAC names). Which of the three reaction products
would you expect to be formed in the largest proportion and why?
(20 marks)

2b)

Use the HOMO-LUMO concept to explain the first step of this reaction (state
clearly which assumptions you make and what simplifications you use
drawing of MO diagrams is not required here).
Using appropriate bonding theories, discuss the nature of the reaction
intermediate that leads to the major reaction product in this reaction,
particularly its stability.
(10 marks)

2c)

If the reaction is carried out at somewhat higher temperatures, oxygencontaining by-products are obtained. Identify these by-products (give IUPAC
names) and explain their formation.
(10 marks)

Question 3
Raw cotton is bleached in an alkaline peroxide bath at pH 12 prior to
cotton contains large amounts of alkaline earth metal salts that can
when it is processed. At a liquor-to-fabric ratio of 10:1, raw cotton
average of 5.35x10-3 mol of Ca2+ ions per litre. Your process water
average 2x10-3 molL-1 of Ca2+. Calcium precipitates are however
because they give a greyish colour to the cotton.

3a)

its use. The

be released
releases an
contains on
undesirable

Is the liquor-to-fabric ratio sufficient to avoid the precipitation of any calcium

hydroxide (base your calculation on the solubility at the process temperature
of 80C)?
(10 marks)
You consider removing the calcium prior to bleaching at 25C with a chelate
wash at pH 7 using an aqueous solution of NTA (nitrilotriacetic acid, see
structural formula on data sheet, page 5) in the process water. Assume that
only the calcium in the complex can be washed out. What is the minimum
concentration of NTA that should be added per litre of process water at a
liquor-to-fabric ratio of 10:1 in order to avoid precipitation of the hydroxide in
the subsequent bleaching step at 80C?
(10 marks)

3b)

NTA has a limited stability in the alkaline peroxide solution and decomposes
in a pseudo first order process with a half-life of 120 minutes at 80C. The
bleaching process takes 5 hours. If you dont carry out the chelate wash, how
much NTA must be added in the bleaching step per litre of process water to
avoid precipitation of any hydroxide at the end of the reaction? Assume that
the process stream can be cooled instantaneously stopping the NTA
decomposition after reaction and that the complex formation constant is
independent of temperature.
(10 marks)

3c)

NTA is a chelating ligand. Explain why chelation leads to a higher complex

formation constant compared with monodentate ligands.
(10 marks)

Physical constants at 25C:

Nitrilotriacetic acid

H 3 NTA:

pK a1 = 1.54 pK a2 = 2.26 pK a3 = 9.55

Speciation equation:
[NTA3-]
[NTA]total

Ka1Ka2Ka3
+ 3

[H3O ] + Ka1[H3O+]2 + Ka1Ka2[H3O+] + Ka1Ka2Ka3

Ca(OH) 2 :

solubility at 80C is 0.0296g/100 cm3 water

CaNTA-:

log 10 K f = 6.4

IMPERIAL COLLEGE LONDON

M.Eng EXAMINATION IN CHEMICAL ENGINEERING 2013
PART I

For Internal Students of Imperial College London

This paper is also taken for the relevant examination

for the Associateship

CHEMISTRY (PART I)
Thursday 6th June 2013 10.00-12.00

Answer TWO questions (among 1-3) in full and part a) of the remaining question
(The maximum score is 100 marks)

For all questions explain your reasoning in detail.

THE EXAMINATION HAS FIVE PAGES IN TOTAL

WHICH INCLUDES THIS COVER SHEET
TURN OVER FOR QUESTIONS

Question 1
Methylcyclohexane is brominated in the liquid phase in a small-scale isothermal
photochemical reactor at 30C by irradiation with UV light to determine the
reaction kinetics.
Using an initial concentration of methylcyclohexane of 7.5x10-1 molL-1 and an
initial concentration of bromine of 5x10-2 molL-1 the data in the table below were
recorded. After one day all bromine had disappeared from the reaction mixture.

Time (min)
Bromine concentration
(mol L-1)

1a)

0.0500 0.0302 0.0153 0.0053

4
0.0002

Determine the order of the reaction with respect to bromine and the rate
constant at 30C.
(15 marks)
What additional experiment should you carry out to determine the reaction
order with respect to methylcyclohexane reliably? How would you work out the
true rate constant?
(5 marks)

1b)

Since the reaction was carried out in a small scale reactor you are concerned
that radical quenching on the reactor wall could falsify the kinetic experiments.
Assume that chain termination occurs exclusively through the following
elementary step
Br + Wall

Br-Wall

Was the experiment reported above controlled by this process? Explain your
reasoning.
(10 marks)

1c)

What would be the main product of the reaction listed above (give its IUPAC
name) and why? In your explanation refer to the relevant bonding theories
and the energetics of the process.
(10 marks)
2

Question 2
Toluene (methylbenzene) is reacted with 1-chloro-2-methylpropane in the presence
of AlCl 3 at room temperature. You observe three main reaction products, which are
constitutional (structural) isomers.

2a)

Draw a curly-arrow mechanism that explains the formation of all three

products and give their IUPAC names.
(11 marks)
Which of the three reaction products would you expect to be formed in the
smallest proportion and why?
(9 marks)

2b)

You are required to synthesise 1-n-butyl-4-methyl benzene from toluene.

Describe the sequence of reaction steps including all reagents that lead to this
product and identify the main by-product(s).
(10 marks)

2c)

Why is it preferable to carry out the reaction in part a) with an excess of

toluene at low temperature? What are the expected main products at higher
reaction temperature and lower relative toluene concentrations? Is the
reaction temperature and reactant ratio equally critical in the reaction in part
b)?
(10 marks)

Question 3
EDTA (ethylenediamine tetra acetic acid) is used in medicine to treat heavy metal
poisoning such as lead contamination by complexing lead cations, thereby
decreasing their bio-availability and speeding up their excretion.

3a)

Use a speciation diagram to explain at what pH EDTA complexation is most

efficient
(20 marks)

3b)

The actual complexation of heavy metals in the human body must be carried
out at a pH of 7.4. The maximum safe concentration of total EDTA in the
human body was reported as 3x10-2 mol L-1. How much of EDTA4- is available
at equilibrium for the complexation reaction if a single dose of the maximum
permissible EDTA concentration is administered?
(10 marks)

3c)

The blood pH in humans is regulated by several buffer systems, the most

important ones being the carbonate and the phosphate buffer. Define a buffer
and explain the action of the phosphate buffer system, identifying the main
species and writing corresponding hydrolysis equilibria. The blood pH is
regulated at a pH of 7.4 0.05. At what concentrations do the two main
species in the phosphate buffer have to be present in solution to give a buffer
capacity of 10-6 molL-1?
(10 marks)

Physical constants at 25C:

H 6 EDTA2+:

Ka 1
Ka 2
Ka 3
Ka 4
Ka 5
Ka 6

H 3 PO 4 :

Ka 1 = 7.1 x 10-3
Ka 2 = 6.3 x 10-8
Ka 3 = 4.2 x 10-13

H 2 CO 3 :

Ka 1 = 4.4 x 10-7
Ka 2 = 4.7 x 10-11

=1
= 3.16 x 10-2
= 1.02 x 10-2
= 2.14 x 10-3
= 6.92 x 10-7
= 5.50 x 10-11