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EH/JAN 2013/CHE515

UNIVERSITI TEKNOLOGI MARA FINAL EXAMINATION

COURSE COURSE CODE EXAMINATION TIME

INSTRUMENTAL CHEMISTRY FOR ENGINEERS CHE515 JANUARY 2013 2 HOURS

INSTRUCTIONS TO CANDIDATES 1. 2. 3. This question paper consists of three (3) 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 make sure that this examination pack consists of: i) ii) iii) the Question Paper a three-page Appendix an Answer Booklet - provided by the Faculty

DO NOT TURN THIS PAGE UNTIL YOU ARE TOLD TO DO SO

This examination paper consists of 5 printed pages
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CONFIDENTIAL QUESTION 1 (P01,C01,C1,C4)

EH/JAN 2013/CHE515

Public Media has reported that a Flooding Retention Pool located at Commercial Area of City X is now exposing to the heavy metals contaminants and volatile organic compounds (VOC) which is carcinogenic to human health and aquatic life. Interestingly, there are a lot of Tilapia fish that can be found in the pool and it has attracted the people who love fishing. As a final year student, to fulfil the research project requirement, you are instructed by your supervisor to investigate the content of those heavy metals and VOC in the Tilapia fish from the pool. Identify and justify the use of two analytical techniques together with an appropriate sample preparation and measurement that you would pursue to determine the concentration of both pollutants in the Tilapia fish. Conclude your finding with the national or international standard and regulations of the heavy metals and VOC whether it is suitable to be served as delicious meal or harmful for the human life. (15 marks)

QUESTION 2 (P01, P03, C02, C2, C3, C4) a) Describe the significance of the molar absorbtivity.e in the Beer-Lambert equation by using an appropriate assumption of high and low concentrations. (6 marks) b) A solution of a dye absorbs light at wavelength of 480 nm, and for this absorption, the the molar absorbtivity.e is 18600 dm 3 mor 1 crrf 1 . A sample of the dye of unknown concentration is placed in a cuvette of path length 1 cm and the measured absorbance is 0.18. Calculate the concentration of the solution. (2 marks) c) 2-methylpentanal and 4-methyl-2-pentanone are isomers. Identify and justify which of these compounds correspond to the IR spectroscopy data and mass spectra in Figure 1 and Figure 2 presented below:

2-methylpentanal

4-methyl-2-pentanone

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EH/JAN 2013/CHE515

IOC " 80" &

0)
4-*

0)

,> '4-*
CH

60" " * 40" ' 20" . 0.0^i 0.0 rI 1 M 20 1 'IjM'i 40 | " | H ' | '! t k-i 60 80 1l^-i 100 r. 1 120

a >

m/z Figure 1: Mass spectra for unknown compound (source:http//webbook. nist.gov/chemistry)

10080i
(/> c

s
c
a> > ra a>

esA
40-1 201 O.OH r-^V 1 M^t 20 40 1 4"S 1 ' * t " i (fJI 60 80 1 1 1 1 1 1f 100 120

m/z
Figure 2: Mass spectra for unknown compound(source:http//webbook. nist.gov/chemistry). (7 marks)

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EH/JAN 2013/CHE515

QUESTION 3 (P03, C02, C1.C4,) Consider the following experimental reaction scheme and justifiably compounds, which correspond to the data provided:
H 2 0, H 2 S0 4 CH3MgCI, ether

identify the

A
1.NaNH 2 , NH3 2. CH,Br

*~
HgS0 4

B
H30+

*~

KMnO

D
H,0 +

+ F

a) Compound A: 1 H NMR 13 C NMR IR UV-Vis

C5H8 5 2.15 (2H, t), 1.9 (1H), 1.55 (2H, sext) and 1.00 (3H, t) 5 84, 68, 22, 20 and 13 2940 and 2120 cm'1 hmax 165 nm and e 8000 (4 marks)

b) Compound B: C5H10O 1 H NMR 5 2.39 (2H, t), 2.13 (3H), 1.6 (2H, sext) and 0.93 (3H, t) 13 C NMR 5 208, 45, 29, 17 and 13 IR 1717 cm"1 UV-Vis 195nmande 1000 (4 marks) c) Compound C: C 6 Hi 4 0 1 H NMR 5 2.04 (1H), 1.44 (2H, t), 1.38 (2H, sext), 1.20 (6H) and 0.93 (3H, t) 13 CNMR 5 71,46, 29, 18 and 15 IR 2963 cm"1 (broad) (4 marks) d) Compound D: C6H10 1 H NMR 5 2.08 (2H, t), 1.78 (3H), 1.5 (2H, sext) and 0.97 (3H, t) 13 CNMR 5 79,75, 23, 21,14 and 3 IR 2940 and 2120 cm"1 UV-Vis Amax 165 nm and e 8000 (4 marks)

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EH/JAN 2013/CHE515

e) Compound E: C4H802 1 H NMR 5 11.51 (1H), 2.33 (2H, t), 1.68 (2H, sext) and 0.98 (3H,t) 13 CNMR 6 180, 36, 18 and 13 IR 2970 (broad) and 1712 cm"1 UV-Vis Amax 205 nm and e 60 (4 marks)

END OF QUESTION PAPER

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APPENDIX 1

EH/JAN 2013/CHE515

Table 1 Infrared Correlations

Functional Group Characteristic Absorption(s) (cm"1) 2950 - 2850 (m or s) 1425 -1475 (m) 3100-3010 (m) 1680-1620 (v) 995 - 985 (s) 940 - 900 (s) -3300 (s) 2260-2100 (v) " -3030 (v) Aromatic C-H Bending 860 - 680 (s) Aromatic C=C Bending Alcohol/Phenol O-H Stretch Carboxylic Acid O-H Stretch 1700-1500 (m,m) 3550 - 3200 (broad, s) i ' Absorption peaks above 3000 cm"1 are frequently diagnostic of unsaturation Notes Alkane C-H bonds are fairly ubiquitous and therefore usually less useful in determining structure.

Alkyl C-H Stretch

Alkenyl C-H Stretch Alkenyl C=C Stretch Alkenyl C-H Bend Alkynyl C-H Stretch Alkynyl CfC Stretch Aromatic C-H Stretch

3000 - 2500 (broad, v) Primary amines produce two N-H stretch absorptions, secondary amides only one, and tertiary none.

Amine N-H Stretch

3500 - 3300 (m)

Nitrile C^N Stretch Aldehyde C=0 Stretch Ketone C=0 Stretch Ester C=0 Stretch Carboxylic Acid C=0 Stretch Amide C=0 Stretch Amide N-H Stretch C-O-C Stretch

2260 - 2220 (m) 1740-1690 (s) 1750-1680 (s) 1750-1735 (s) 1780-1710 (s) 1690-1630 (s) 3700 - 3500 (m) 1000-1300 (s) The carbonyl stretching absorption is one of the strongest IR absorptions, and is very useful in structure determination as one can determine both the number of carbonyl groups (assuming peaks do not overlap) but also an estimation of which types.

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APPENDIX 2

EH/JAN 2013/CHE515

Table 2 UV Absorption Maxima

Name Acetylide Aldehyde Alkynyl Amine ! Chromophore Wavelength [nm]S Molar extinction, e! | j j|_ -C=C -CHO -C5C-NH2
e lzene

175-180 210 !|_ 160-170 195 j { J

6,000 1,500 8000 2,800 j

^H? '

40

.1. ? I

C
|

274
210 290 285-400 208 200-210

j
) j j j ] | _ j j j j j I j
t[_

_2000
6200 1100 3-25 300 50-70 5,500 _ 50_ 1,000 1,000 12 __ 30-0__ 10J30-2000 strong 190-210 _ |

Aromatic-Alcoholj Aromatic-Amine Azo Bromide Carboxyl Disulphide _ Ester Ether Ketone Nitrate Nitrile Nitrite Nitro Alkenyl-Chloridej j |[ ![ [ j j _ _| I

-OH -NH -N=N-Br -COOH -S-S-COOR -O>C=0 -ON0 2 -C=N -ONO -N0 2 =C-CI

! | j

194 205 185 195 270 , 160

|[

220-230 210 180

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APPENDIX 3

EH/JAN 2013/CHE515

O
i

Aromatic?
1

J. r T T K^OT2
i 1

_L X J_ I Ethers Sulfides Sst. dfcsnes BOCH RS-CH. . R-H ,

i ii 1 i 1

RCH=CHR-

Alcohofc HOCHi

-iRCsCH
IRJOCR-CH

FhO-CHf JHH

H Ar-CHn . Cl-CH. I-CH.

Br-CRtEsters RCOjCH^
H
H

O ^R-tt-CH -iNC-CH

I-

RCQjH
WIDH-

AmwfeRCONH

ROH -RjHH
-

I
12JD

1
I1JD

1
IOJD

1
9D

1
gJO

1
7J0

1
6JD

1
5J0

1
4JD

1
3JD

1
2J0

1
1J0

0J0 p p m t f }

Figure 1 1H NMR Chemical Shifts

J_ Aldehydes, RCH=Q Ketones, R 2 C O

j_

R2C=CH2i RHC=CHRiR 2 C=CH 2 1 1

1 i2^i C-N0 2
i

C-Cl
i

C-I
1

C-Br

C-H Saturated Alkanes

1

Aromatics Heteroaromatics
i 1 i

C-NR2 C-OH
^ ^

H1

C-SR , C-Ar
I 1

Caiboxylic Acids i

R-C0 2 H 1

i RC=N ,

C^DR
H

R-C0 2 R" Esters t R-CONR2 Amides i 1

Sulfondes,Sulfones p~ S C ^ R M C=CR
I 1 H

C-C=C, O n HC-C-R

~~r
200 150 100 50 0.0 ppm(5)
13 Figure 2 " C NMR Chemical Shifts

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