SPS 5903

SEMINAR RESEARCH PROPOSAL

Removal of Heavy Metal from aqueous solution by
using
Poly(Acrylonitrile-Acrylic Acid) Amidoxime
MASTER OF SCIENCE
CHEMICAL ENGINEERING
UPM

SPS 5903
SEMINAR RESEARCH
PROPOSAL

Name:
Nur Amirah Binti Mohd Zahri
Matric No.: GS39436
Chairman: Prof. Dr. Luqman Chuah Abdullah
Int. Members: Dr. Siti Nurul Ain Binti Jamil
Dr. Mohsen Nourouzi Mobarekeh
Ext. Member: Dr. Sim Jia Huey
Approved by,
Prepared by,

(Prof. Luqman Chuah

(Nur Amirah Binti Mohd
Abdullah)
Zahri)
Chairman Supervisor

Process Flow
PART
Synthe
1
sis
PART
2
PART
3
PART
4

Modificat
ion

BET analysis

CHNS, SEM & BET analysis

Adsorptio
n&
Regenerat
ion

On going

RSM/WN
N

Not Started yet

+
Acrylonitrile

Acrylic Acid

Poly(Acrylonitrile-Arcylic
Acid)

H2NOH

+ Hydroxylamine
(Amidoxime)

Scheme 1: The conversion of

nitrile group to amidoxime group
in Poly(Acrylonitrile-Arcylic Acid)
Horzum et. al., 2012

Introducing Arcylic
Acid to
Acrylonitrile
If only Homo-Poly(acrylonitrile)
High polarity
Nitrile-nitrile dipolar
interactive
Not porous

When arcylic acid being added,

polymer will become
More hydrophobic
High in porousity

PART 1:
Synthesis

Table 1: Calculated Data of Percentage Yield

Ratio of Copolymer
(Acrylonitrile:Arcylic
Acid)

Percentage of
Yield (%)

Homo-Polyacrylonitrile
(Homo-PAN) 100:0

72.66

97:3

64.16

95:5

71.00

93:7

72.15

Speed of stir: 200 rpm, Temperature:

40oC
90:10
62.88

74

72.66

72.15

72

71.00

70

Percentage of Yield (%)

68
66
64.15

64

62.88

62
60
58
56
100:0

97:3

95:5

93:7

90:10

Ratio of copolymer (Acrylonitrile:Arcylic Acid)

Graph 1: Percentage of Yield Polymerization

Synthesis

Homo-PAN (100:0) has the most high yield

When Arcylic Acid (AA) being added for the following ratio the yield
drop
Lower comonomer: degree dissociation high so yield become
low
As increase comonomer: degree dissociation low so yield
increasing
Certain level comonomer: decrease in the conc. in carboxylate ion

Introducing
Hydroxylamine
hydrchloride
(Amidoxime
group) to
Poly(AcrylonitrileArcylic Acid)

High adsorption affinity to metal

ions. Saeed et al 2008

Only take place at nitrile groups

to convert into amidoxime
groups

545.17

546.39

394.33

513.51

368.05
365.28

520.97

319.05
246.15

249.33

204.25

194.94 203.29

96.39

50.91

3780

3280

2780

2280
1780
Wavenumber (cm-1)

60.67
1280

780

Graph 2: Infrared Spectra (FTIR) of different method

modification

There is 4 different method have been tried to convert CN to C=N by

using hydroxylamine Method 2 & 4 completely successful.
Further the experiment with Method 2 because of:-simplicity of step
compare to method 4
simplicity of step compare to method 4

280

Table 2: IR spectra for different modification

method

Function
al Group

C=N

C=O

OH
stretch

OH
bend

N H2

NO

Frequenc
ies
Range
(cm-1)

16401670

1580
1900

3400
2400

950-910

34003500

16001530
13901300

Method
1

1640.0

1640.0

3190.01

3190.01

Method
2

1642.03

1642.03

3332.65

928.28

3332.65

1386.78

Method
3

- But
CN
(2243.41
)

1581.62

3358.15

3358.15

1581.62

Method
4

1642.62

1642.62

3168.41

3168.41

1387.50

Unmodified :
Completed
Modified : Waiting
Scanning
electron
Microscopy
(SEM)

Unmodified :
Completed
Modified : Completed
Fourier
Transform
Infrared
Spectra (FTIR)

ANALYSI
S
Brunauer
EmmettTeller
(BET)

Unmodified :
Waiting
Modified : Waiting

CHNS
elemental
analysis

Unmodified :
Completed
Modified : Waiting

SEM analysis
95:5

97:3

100:0

* 134.6nm

93:7

* 130.2nm
* Average polymer bead size

* 177.9nm

* 158.6nm

90:10

* 160.0 nm

FTIR analysis
732.5

723.44
694.44

665.85

642.63

589.38
577.28
579.31
541.86
499.33

520.61

476.67
442.53

329.75

309.59

341.04
268.86

238.73
169.45

177.33
105.07
46.54

3700

3200

2700

2200

1700

1200

700

Wavenumber (cm-1)

Graph 3: Infrared Spectra (FTIR) of Poly(Acrylonitrile-Arcylic Acid) and

Poly(Acrylonitrile-Arcylic Acid) Amidoxime for different ratio copolymer

200

Table 3: IR spectra for unmodified and amidoxime

modified

Function
al Group
Frequenc
ies
Range
(cm-1)

C=N/
CN

16401670
22002300

OH
stretch

C=O

1580
1900

3400
2400

OH
bend

950-910

N H2

NO

34003500

16001530
13901300

AMIDOXIME MODIFIED
100:0

1642.76

1642.76

3326.11

918.78

3326.11

1386.54

97:3

1642.67

1642.67

3323.21

922.43

3323.21

1386.64

95:5

1639.15

1639.15

3197.59

918.96

3458.98

1376.40

93:7

1642.34

1642.34

3322.10

915.34

3322.10

1386.12

90:10

1643.44

1643.44

3331.90

927.66

3331.90

1386.85

UNMODIFIED
100:0

2244.13

2932.73

97:3

2244.45

1732.16

2935.01

95:5

2244.81

1729.79

2933.70

93:7

2244.16

1729.36

2933.39

CHNS analysis
Table 4: CHNS Poly(Acrylonitrile-Arcylic Acid)

Samp
le

Carbon (%)

Analys
is

100:0 63.59

Hydrogen
(%)

Nitrogen (%)

Sulphur (%)

Calculat
ed

Analys
is

Calculat
ed

Analys
is

Calculat
ed

Analysis

Calculat
ed

56.80

6.77

4.86

24.51

22.09

1.01

5.97

97:3

61.21

56.31

6.43

4.87

24.07

21.27

2.07

5.93

95:5

59.89

55.98

6.32

4.87

20.90

20.74

3.10

5.90

93:7

63.27

55.66

6.85

4.87

21.10

20.19

0.06

5.87

90:10

59.7

55.18

6.42

4.88

19.37

19.40

0.21

5.82

70
carbon analysis
carbon calculated
hydrogen analysis
hydrogen
calculated

60

nitrogen analysis
nitrogen
calculated
50

sulphur analysis
sulphur calculated

Percentage of C, H, N, S (%)
40

30

20

10

0
100:0

97:3

95:5

93:7

Ratio of Copolymer (Acrylonitrile: Arcylic Acid)

90:10

References
Horzum, N., Shahwan, T., Parlak, O., & Demir, M. M.
(2012). Synthesis of amidoximated
polyacrylonitrile fibers and its application for
sorption of aqueous uranyl ions under continuous
flow. Chemical Engineering Journal, 213, 4149.
doi:10.1016/j.cej.2012.09.114
Saeed, K., Haider, S., Oh, T.-J., & Park, S.-Y. (2008).
Preparation of amidoxime-modified
polyacrylonitrile (PAN-oxime) nanofibers and their
applications to metal ions adsorption. Journal of
Membrane Science, 322(2), 400405.
doi:10.1016/j.memsci.2008.05.062

Thank
You