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BSc/MSci Course Unit Examination

9th May 2012

10:00 12:30

SBC107 Analytical Chemistry


Duration: 2 h 30 minutes

YOU ARE NOT PERMITTED TO START READING THIS QUESTION PAPER UNTIL INSTRUCTED TO
DO SO BY AN INVIGILATOR.
Answer ALL questions of Section A, ONE Question from Section B and ONE Question from Section C.
Section A carries 60% of the marks, whilst Sections B and C each carry 20% of the marks.

A Periodic Table is provided. A marking scheme is provided for your guidance.

Graph paper is provided.


CALCULATORS ARE PERMITTED IN THIS EXAMINATION. PLEASE STATE ON YOUR ANSWER
BOOK THE NAME AND TYPE OF MACHINE USED.
COMPLETE ALL ROUGH WORKINGS IN THE ANSWER BOOK AND CROSS THROUGH ANY WORK
WHICH IS NOT TO BE ASSESSED.
IMPORTANT NOTE: THE ACADEMIC REGULATIONS STATE THAT POSSESSION OF UNAUTHORISED
MATERIAL AT ANY TIME WHEN A STUDENT IS UNDER EXAMINATION CONDITIONS IS AN
ASSESSMENT OFFENCE AND CAN LEAD TO EXPULSION FROM THE COLLEGE. PLEASE CHECK
NOW TO ENSURE YOU DO NOT HAVE ANY NOTES IN YOUR POSSESSION. IF YOU HAVE ANY
THEN PLEASE RAISE YOUR HAND AND GIVE THEM TO AN INVIGILATOR IMMEDIATELY.
PLEASE BE AWARE THAT IF YOU ARE FOUND TO HAVE HIDDEN UNAUTHORISED MATERIAL
ELSEWHERE, INCLUDING TOILETS AND CLOAKROOMS IT WILL BE TREATED AS BEING FOUND IN
YOUR POSSESSION. UNAUTHORISED MATERIAL FOUND ON YOUR MOBILE PHONE OR OTHER
ELECTRONIC DEVICE WILL BE CONSIDERED THE SAME AS BEING IN POSSESSION OF PAPER
NOTES. MOBILE PHONES CAUSING A DISRUPTION IS ALSO AN ASSESSMENT OFFENCE.
EXAM PAPERS CANNOT BE REMOVED FROM THE EXAM ROOM.

Examiners: Dr B C Parkin and Dr T S Sheriff

Queen Mary University of London, 2012

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SBC107 (2012)

Useful information:
1

R = 8.314 J K mol

0C = 273.2 K

79

81

12

13

Br is 50.69% abundant

Br is 49.31% abundant
C is 1.10% abundant

C is 98.90% abundant

H is 99.985% abundant

H is 0.015% abundant

The following information may be of use when answering Question 18:

Equation for calculating retention indices for temperature programming:




t ' - t '
R
R
i
z
I T = 100n
+ 100z

t
t
'
R'
( z+1) R z

Retention indices (for temperature programming), IT, for some common fragrance
compounds:
Citronellol

C10H20O

1212

Nerol

C10H18O

1234

Geraniol

C10H18O

1240

Terpineol

C10H16O

1198

Limonene

C10H16

1031

Terpineol

C10H16O

1159

Linalool

C10H18O

1101

Thujone

C10H16O

1116

Myrcene

C10H16

991

Ethyl heptanoate

C9H18O2

1094

Piperitone

C10H16O

1281

The following information may be of use when answering Question 19:

Ki IS =

Ci AIS
CIS Ai

A'
C 'i = C 'IS K i IS i
A'IS

SBC107 (2012)

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SECTION A
1.

0.328 g of sodium phosphate, Na3PO4, was dissolved in water and made up to 25.0 cm3 in a
volumetric flask. Determine the molar concentration of sodium ions, Na+, in the solution.
[3 marks]

2.

9.98 cm3 of a 5.00 mol dm3 aqueous solution of sodium hydroxide was required to fully
neutralise 1.63 g of a triprotic acid. Determine the molar mass of the acid.
[4 marks]

3.

Calculate the amount of sodium hydroxide in water as a %(w/w) for a 5.00 mol dm3 solution
which has a density of 1.18 g cm3.
[3 marks]

4.

Calculate the volume of 5.00 mol dm3 sodium hydroxide required to prepare exactly 100 cm3
of a 100 mM aqueous solution of sodium hydroxide.
[2 marks]

5.

Potassium permanganate (KMnO4) is not a primary chemical standard but solutions may be
standardised using weighed portions of sodium oxalate (Na2C2O4).
(a) Explain what is meant by the terms primary chemical standard and standardised. [4 marks]
(b) Determine the stoichiometry of the reaction between permanganate and oxalate. Hence
determine the concentration of potassium permanganate in a solution that required a mean
titre of 24.28 cm3 of KMnO4 when using 0.0200 g weighed portions of sodium oxalate.
[6 marks]

6.

The labels on two bottles containing colourless organic liquids fell off. One of the labels was
for ethanol and the other for 2-chlorophenol. State how these liquids can be correctly identified
by infra-red spectroscopy.
[4 marks]

7.

A sample of quinine sulfate in water absorbs 90.0% of an incident source of radiation at


251 nm when using a 1.00 cm cell. If the concentration of the sample was 5.00 ppm, calculate
the molar absorptivity () of quinine sulfate (Mr = 756.92 g mol1) in dm3 mol1 cm1. [4 marks]

8.

In liquid chromatography (LC) what is meant by the terms isocratic elution and gradient
elution?
[2 marks]

9.

In GCMS analyses, how is it possible to distinguish isomeric compounds in complex


mixtures?
[4 marks]

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SBC107 (2012)

10. This question relates to mass spectrometry.


(a) Define what is meant by the term resolving power.

[2 marks]

(b) In a mass spectrum showing the natural isotopes of Pb as an impurity in brass, the 208Pb
peak was found to have m1/2 = 0.1122 Da. Calculate the resolving power of the mass
spectrometer.
[4 marks]
11. Determine the molecular mass and nominal mass for C5H11Br. Why are the values slightly
different?
[5 marks]
12. In mass spectrometry of an organic compound, what information can be obtained from the M+
peak and from the M+1 peak.
[2 marks]
13. Briefly describe the factors that affect chromatographic column resolution.

[3 marks]

14. Using appropriate sketches, discuss the origin of asymmetric bandshapes in chromatographic
separations.
[8 marks]

SBC107 (2012)

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SECTION B
16. Answer all parts.
(a) Twenty iron tablets, containing FeSO47H2O, with a total mass of 24.268 g were ground
and 3.119 g of the powder was dissolved in HNO3 and heated to convert all the iron to
Fe3+. Addition of NH3 caused quantitative precipitation of Fe2O3xH2O, which was ignited
to give 0.2950 g of Fe2O3. What was the average mass of FeSO47H2O in each tablet?
[6 marks]
(b) Methylamine, CH3NH2, is a weak base, pKb = 3.36
(i) What species is the conjugate acid of methylamine? Determine the pKa value of this
acid. [pKw = 14.00]
[2 marks]
(ii) Determine the pH of a 0.200 mol dm3 solution of methylamine.

[5 marks]

(iii) A 100 cm3 aliquot of a 0.200 mol dm3 solution of methylamine is titrated against
0.500 mol dm3 HCl. Calculate the volume of HCl corresponding to the equivalence
point of the titration. Determine the pH of the methylamine solution at the equivalence
point and after the addition of 60.0 cm3 of HCl.
[7 marks]
17. Answer all parts.
(a) A sample of steel (0.506 g) was digested in acid and the solution made up to 100 cm3 with
distilled water. Aliquots (25.0 cm3) of this solution were transferred into two volumetric
flasks (100 cm3) labelled A and B. Flask A was made up to volume with distilled water.
To flask B was added 10.0 cm3 of a 260 ppm standard solution of Cr3+ which was then also
made up to volume with distilled water. The following absorbance results were obtained.
Solution A = 0.356, Solution B = 0.578
Use these results to calculate the % (w/w) of chromium in the steel sample.
[8 marks]
(b) Describe how infra-red spectroscopy can be used to distinguish between
(i) aliphatic and aromatic hydrocarbons;

[3 marks]

(ii) saturated and unsaturated hydrocarbons;

[3 marks]

(iii) aldehydes and ketones;

[2 marks]

(iv) the medicinal drug 1 and the recreational drug 2.

[4 marks]

OH
NHCH3

NHCH3

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SBC107 (2012)

SECTION C
18. Answer all parts.
(a) Explain what is meant by the terms accuracy and precision. How may these be determined
experimentally?
[4 marks]
(b) A 2% v/v solution of a personal hygiene product sample was dissolved in ethanol (EtOH)
and then subsequently analysed by GCMS, on an Agilent HP5 column, using a
temperature gradient of 10C per minute from 35225C. The following results were
obtained:
tR / min

M+ (m/z)

1.79

9.68

136

10.54

136

12.13

158

14.89

152

Compound
Unretained species (EtOH)

Additionally, a series of straight chained alkanes (2% v/v in EtOH) were prepared and
analysed by GC, under identical conditions. The following retention times were obtained:
Compound

tR / min

Unretained species (EtOH)

1.79

Nonane, C9H20

7.42

Decane, C10H22

9.84

Undecane, C11H24

12.16

Dodecane, C12H26

14.58

Tridecane, C13H28

17.00

(i) Determine the retention indices for the given temperature programme for compounds
14.
[8 marks]
(ii) Using the information given on page 2 of the exam paper, identify compounds 14.
[4 marks]

[Question 18 continued overleaf]

SBC107 (2012)

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(c) The following data were obtained for a GC analysis of a 50 M solution of linalool in
EtOH spiked with 100 M solution of internal standard (IS):
Injection

Peak Area (Linalool)/pAu s

Peak Area (IS)/pAu s

58400

120100

56750

117700

59100

122000

61580

122960

54690

115340

57000

119900

Determine the intra-assay precision and comment on the value obtained.

[4 marks]

19. Answer all parts.


(a) Briefly describe
chromatography.

the

difference

between

planar

chromatography

and

column
[4 marks]

(b) Define, using appropriate equations, what is meant by the following chromatography terms:
(i) distribution constant
[2 marks]
(ii) capacity factor
[2 marks]
(c) Substances C and D have retention times of 4.12 min and 6.57 min, respectively, on a 30
cm HPLC column. An unretained species (solvent) passes through the column in 1.54 min
and the internal standard, IS, elutes at 5.33 min.
(i) Determine the adjusted retention times of C, D and IS.
(ii) Calculate the selectivity factor between analytes C and D.
(iii) Calculate the relative retention of analytes C and D.

[3 marks]
[2 marks]
[4 marks]

(d) Analyte C was found to have a peak area of 46185 pAu s and the area of the peak
corresponding to the IS was 27930 pAu s. The concentration of IS was 30.00 ng mL1.
Given that the response factor, Ki/IS = 0.9800, determine the concentration of C in the
sample.
[3 marks]

________________________________________________________________________________
End of Paper