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AS/JUN 2012/CHM580

UNIVERSITI TEKNOLOGI MARA FINAL EXAMINATION

COURSE COURSE CODE EXAMINATION TIME

SPECTROCHEMICAL METHODS OF ANALYSIS CHM580 JUNE 2012 2 HOURS

INSTRUCTIONS TO CANDIDATES 1. 2. 3. This question paper consists of seven (7) questions. Answer ALL questions in the Answer Booklet. Start each answer on a new page. Do not bring any material into the examination room unless permission is given by the invigilator. Please check to make sure that this examination pack consists of: i) ii) iii) the Question Paper an Answer Booklet - provided by the Faculty a three - page Appendix 1

DO NOT TURN THIS PAGE UNTIL YOU ARE TOLD TO DO SO This examination paper consists of 6 printed pages
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QUESTION 1 a) What are the requirements for radiation sources to be useful for spectrometers? (3 marks) b) Describe how a photomultiplier tube works. (4 marks)

QUESTION 2 a) The ultraviolet (UV) spectrum of acetone shows absorption maxima at 166, 189 and 279 nm. What type of transition is responsible for each of these bands? (3 marks) b) The three molecules listed in the table below give similar UV absorption spectra However, the A.max is progressively shifted to a longer wavelength. Explain the shift. Molecule Ethene CH2CH2 buta-1,3-diene CH2CHCHCH2 hexa-1,3,5-triene CH2CHCHCHCHCH2 Wavelength of maximum absorption (nm) 171 217 258 (4 marks)

QUESTION 3 a) Discuss all types of 'interferences' that can occur in atomic spectrometry. (12 marks) b) i) Describe the operation of a pneumatic nebulizer and electrothermal vaporizer as sample introduction methods for atomic absorption spectrophotometry (AAS). (6 marks) ii) What is the main advantage and limitation of each sample introduction technique? (2 marks) c) Why are atomic emission methods with an inductively coupled plasma (ICP) excitation source better suited for multi-element analysis? (4 marks)
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d) Chromium (Cr) in an aqueous sample was determined by pipetting 10.0 mL of the unknown into each of five 50.0 mL volumetric flasks. The volumes (indicated below) of standard containing 12.2 ppm Cr were added into the flasks and each solution was made up to volume. The plot gave a linear equation of y = 0.0088x + 0.2022 Unknown volume (mL) 10.0 10.0 10.0 10.0 10.0 i) Standard volume (mL) 0.0 10.0 20.0 30.0 40.0 Absorbance 0.201 0.292 0.378 0.467 0.554 (4 marks) ii) Calculate the concentration in ppm of Cr in the sample. (2 marks) iii) Name the method of calibration and why it is used in the analysis above. (2 marks)

Sketch a labeled calibration curve.

QUESTION 4 a) Why are high intensity sources such as xenon arc lamps and lasers typically used in fluorescence experiments where as deuterium and tungsten halogen lamps are adequate for most UV-visible absorption experiments? (4 marks) b) Explain why many molecules that demonstrate significant UV-visible absorption do not fluoresce. (4 marks)

QUESTION 5 a) What causes a bond in a molecule to be infrared (IR) active? (3 marks)

b) What is the advantage of using an interferometer in recording IR spectra?

(3 marks)

c) i) Compare Stokes line and Rayleigh scattering.

(6 marks)

ii) Which of these two lines will be more intense? Explain.

(2 marks)

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QUESTION 6 a) What do you understand from the term NMR spectroscopy? (3 marks) b) Describe the most common type of magnet used with high resolution NMR spectrometers. What is the advantage of this magnet? (2 marks) c) Describe two factors that affect the proton chemical shift values. (4 marks) d) In NMR spectroscopy, what are the advantages of using a magnet with a high magnetic field? (2 marks) e) Explain why C-13 NMR is always done on a FT-NMR. (2 marks) f) Propose the molecular structure for an unknown molecule with a molecular formula C7H1202. The IR spectrum of the molecule shows many peaks including sharp peaks at 3030 cm"1 and 1620 cm"1; and a strong absorption band at 1730 cm"1. The 1H NMR and 13 C NMR spectra for this unknown are shown below. (10 marks)
1

H NMR spectrum

6-H 1-H 6 2-H ilk

3- H

I I.
4

4
ppm

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13,C

NMR spectrum

ppm QUESTION 7 a) A mass spectrometer block diagram with major components is shown below;
Sample

i) What is the function of component B? (3 marks) ii) Why must all components of mass spectrometers except the signal processor and readout be in the vacuum system? (2 marks) CONFIDENTIAL

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b)

Distinguish the samples to be used in electron impact (El) ionization and electrospray ionization (ESI). (2 marks) The following are two mass spectra of amphetamine obtained from two different types of ionization. With reasons, determine the type of ionization used for each spectrum. (2 marks)

c)

00-i
755025-

44

Spectrum A

C\ U ^Y
91

NH2

w
c
CD

i, '

51
r*

40

65 ,.l

77

120
. .. 1

134

I
80

'I '

60

100

120

I "

140
{M+HJ* 136.1126

i
1
100-,
Spectrum B

a:
7550250 40

KJ

N* H

119

60

"ir
80

100

120

1 140

mlz

END OF QUESTION PAPER

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APPENDIX 1(1)

AS/JUN 2012/CHM580

INFRARED ABSORPTION TABLE BONDING OR GROUP C-H C-H TYPE OF COMPOUND Alkane Alkane FREQUENCY RANGE, crn 1 2960 - 2850 1340 1485-1445 1470-1430 3080 - 3020 995 - 985 730 - 665 980 - 960 3300 3100-3000 670 770 - 730 870 - 735 865 - 760 3650 - 3590 3600 - 3200 (broad) 3300 - 2500 (broad) 1400-1000 800 - 600 600 - 500 500 3500 - 3300 1220-1020 1360-1250 2260-2210 1680-1620 2260-2100 1600-1580 1300-1000 1750-1680 1780-1710 1750-1735

TYPE OF VIBRATION Stretching Bending (CH) (-CH2-) (-CH3) Stretching Bending (monosubstituted) (disubstituted, cis) (disubstituted, trans) Stretching Stretching Bending (benzene) (monosubstituted) (disubstituted) (trisubstituted) Stretching (free O - H ) (H-bonded) Stretching Stretching Stretching Stretching Stretching Stretching Stretching Stretching Stretching Stretching Stretching Stretching Stretching Stretching Stretching Stretching Stretching Stretching

C-H C-H

Alkene Alkene

C-H C-H

Alkyne Aromatic

C-H

Aromatic

O-H

Alcohol, phenol

O-H C-F C-CI C-Br C-I N-H C-N C-N C=N C =C CsC C =C C-0

Carboxylic acid

C=0

Amine Amine (aliphatic) Amine, aromatic Nitrile Alkene Alkyne Aromatic ring Alcohol, ether, Carboxylic acid Ester Aldehyde, ketone Carboxylic acid Ester

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APPENDIX 1(2)

AS/JUN 2012/CHM580

APPROXIMATE 1H CHEMICAL SHIFT RANGES (ppm) FOR SELECTED TYPES OF PROTON R-CH3 0.7-1.3 R-N-C-H 2.2-2.9

I
R - CH2 -R 1.2-1.4

I
2.0-3.0

R-S-C-H

I
R3CH 1.4-1.7

I
I-C-H

2.0-4.0

I
I
0

R-C=C-C-H

1.6-2.6 0

I
Br-C-H

2.7-4.1

I
II
0

I
II I
2.1-2.4

I
CI - C - H

3.1-4.1

R-C-C-H,

H-C-C-H

I
2.1 - 2 . 5

I
I

II I

II

RO - C - H, HO - C - H

3.2-3.8

RO-C-C -H, HO-C-C-H

I
2 . 1 - 3.0 0

I
I
3.5-4.8

I
N=C-C-H

I
II I
02N - C - H 2.3-2.7 1.7-2.7 R-C-O-C-H

I
4.1-4.3

fyi-H
R-C=C-H R-S-H

I
F-C-H 4.2-4.8

I
1.0-4.0

R-C=C-H

4.5-6.5

R-N-H

0.5-4.0

I
R-O-H 0.5-5.0

O
0

6.5-8.0

II
R-C-H 0

9.010.0

^y 0 - H
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4.0-7.0

II
R-C-OH

11.012.0

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APPENDIX 1(3)

AS/JUN 2012/CHM580

O-T-"
R-CH 3
R2 - CH3

0 3.0-5.0 R-C-N-H

II

5.0-9.0

APPROXIMATE 13C CHEMICAL SHIFT VALUES (ppm) FOR SELECTED TYPES OF CARBON

8-30 15-55 20-60 0-40 25-65

C^C

65-90 100-150 110-140 110-175 0 155-185

c=c
C^N

R3 CH3

C-I C-Br

0
0

II
O R - C - NH2

II

R-C-OR.R-C-OH C-N 30-65 155-185

C-CI

35-80

O R - C - CI

II

160-170

C-0

40-80

II

II

185-220

R-C-R, R-C-H

CONSTANTS Speed of light Plank's constant Avogadro's number 3.00 x 108 ms'1 6.63 x 10"34 J s 6.02 x 1023 particles mol'1

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