UNIVERSITY OF PESHAWAR

INSTITUTE OF CHEMICAL SCIENCES

Two step modification of chitosan using glycidylmethacrylate and 2
aminoethanethiol for cations removal from aqueous solution
Prof. Dr. Claudio Airoldi
Fortaleza
September / 2012
Materials used for removal of heavy metals
Cellulos, Chitina, Chitosan, Coal , Zeolites
Synthetic: Ion exchange resin, Chelanting resin
Natural:
Low cost
High availability
Principally obtained as a byproduct and industrial waste
No need much process of regeneration for reuse
High cations sorption capacity
Interaction with metal ions

Figura 6. Model of complexation of copper with chitosan
Chelation, Electrostatic attraction, ion exchange,
1- obtained chemically modified chitosan with glycidylmethacrylate and
then reaction with defferent amines.
2- characterization of materials obtained by various techniques.
3- Study sorption capacity of the modified chitosan for divalent cations.
4- Apply Langmuir, Freundlich and Temkin models to obtained sorption
data at equilibrium.
Objectives
5- Apply linear and nonlinear regression method to determine
parameters of isotherms.

6- Langmuir model will be used in four different forms carried out
sorption study.

Modification of chitosan with glycidylmthacrylate
Water
353 K, 2 h
O
O
O
CH
3
O
O
HO
O
OH
NH
2
O
HO
O
H
3
C
O
O
HO
O
OH
NH
Experimental
Q-gly
Figura 7. Modification of chitosan with glycidylmethacrylate
Modification of Q-gly with 2-Aminoethanethiol
O
HO
O
H
3
C
O
O
HO
O
OH
NH
H
2
N
SH
+
O
HO
O
H
3
C
O
O
HO
O
OH
NH
HS
NH
Figure 8. Reaction of Q-gly with 2-Aminoethanethiol
QAT
Et
3
N,

333 K
Ethanol, 72 h

Elemental analysis of carbon, hidrogen and nitrogen

Infrared Spectroscopy

13
C NMR

Inductive couple plasma atomic emission spectrometry (ICP) -
Determination of cations content of supernatant

Characterization
Amostra C/% N/% S/% C/mmolg
-1
N/mmolg
-1
S/mmolg
-1
C/N
Q 40,63 7,39 - 33,86 5,27 - 6,42
Q-gly 44,04 5,89 - 36,66 4,20 - 8,73
QAT 40,99 6,38 1,81 34,15 4,56 0,56 7,48
Table 1. Percentages of carbon (C) and nitrogen (N), number of moles for
chitosan and its derivative and the corresponding molar ratio (C/N)
Elemental Analysis
Results
Figura 1. Infrared spectroscopy of chemical modified chitosan QAT
Results
2550-2600 cm
-1
: v S-H
674 cm
-1
: v C-S
4000 3500 3000 2500 2000 1500 1000 500
35
40
45
50
55
60
65
70
75
80
T
r
a
n
s
m
i
t
t
a
n
c
e

/

%
Wave number / cm
-1
O
HO
O
H
3
C
O
O
HO
O
OH
NH
10
11
12
13
9
8
7
2
1
3
4
5
6
250 200 150 100 50 0
Chemical Shift / ppm
Q
Q-gly
Figura 2.
13
C NMR spectra of chitosan and chitosan chemically modified with
glycidylmethacrylate Q-gly
Results
Q
105 ppm - C1
75 ppm C3 e C5
84 ppm - C4
62 e 58 ppm - C6 , C2
23 e 175 ppm CH
3
e C=O
Q-gly
125, 137 ppm C=C
19 e 169 ppm CH
3
e C=O
250 200 150 100 50 0
Q-gly
QAT
Chemical Shift / ppm
O
HO
O
H
3
C
O
O
HO
O
OH
NH
HS
NH
1
2
3
4
5
6
7
8
9
10
11
12
13
14
QAT
Results
Figure 3.
13
C NMR of chemical modified chitosan Q-gly and QAT
48 ppm C-N
22 ppm C-SH
400 600 800 1000 1200
Temperature / K
Q
QAT
300 400 500 600 700 800 900 1000 1100 1200 1300
20
30
40
50
60
70
80
90
100
M
a
s
s

/

%
Temperature / K
Q
QAT
Thermogravimetry
Results
Figure 4. TG and DTG for os biopolymers Q and QAT.
Q - 570 K
QAT - 549 K
Aplication of chemically modified chitosan
Sorption of Cu
2+
, Ni
2+
, Pb
2+
e Cd
2+
from aqueous solution.
20 mg of solid
25,0 cm
3
of aqueous
solution of divalents
cations
7,0 x 10
-4
a
8,0 x 10
-3
mol dm
-3

4h a 298 1 K
Batch method
Figure 4. Langmuir sorption isotherm and
its linear form for Cu
2+
sorption on chitosan
(QCAD) at 298 1 K.
( ) m n n N
s i f
/ =
n
i

number of moles in initial solution
n
s
number of moles in supernatant
m mass in gram, of sorbents
0 1 2 3 4 5 6 7 8 9 10 11 12
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
1,1
1,2
Cs / mmol dm
-3
N
f

/

m
m
o
l

g
-
1
0
2
4
6
8
10
C
s
/
N
f

/

g

d
m
-
3
Models
Results
Isotherm Nonlinear form Linear form Plot

Langmuir type 1


Langmuir type 2

Langmuir type 3

Langmuir type 4
bCs
NsbCs
Nf
+
=
1
Nsb Ns
Cs
Nf
Cs 1
+ =
Cs Vs
Nf
Cs
Ns Cs Nsb Nf
1 1 1 1
+
|
.
|

\
|
=
Cs
Vs
Nf
1 1
Cs
Nf
b
Ns Nf +
|
.
|

\
|
=
1
Cs
Nf
Vs Nf
bNf bNs
Cs
Nf
=
Nf Vs
Cs
Nf
N
s
Maximum sorption capacity
N
f
- number of moles sorbed
Cs concentration of supernatant
b - constant
Temkin
Freundlich
Cs
n
K Nf f log
1
log log + =
b
RT
nT =
2
1
exp ) (
1
fcali
m
i
i f N N
P m
SE

=

=
Standard Error

=
1
2
exp
2
) (
i
fcali
fcali i f
N
N N
x Chi-Square Test

n
fCs K Nf
1
=
T
n
TCs K Nf
1
) ln( =
1 1
ln ln
f T s
T T
N K C
n n
= +
Table 2. Number of moles sorbed (Nf), parameters of the Langmuir (Ns and b),
equation, correlation coefficients (r) and standard errors (SE) for the interaction of
divalent metals with chemically modified chitosan at 298 1 K.


Biopolmero

M

Nf (mmol g
-1
)

N
S
(mmol g
-1
)

b

r
Q
Cu

Pb

Cd

Ni
1,40

1,19

1,35

1,29
1,46

1,22

1,12

1,43
3,38

2,70

3,75

1,30
0,998

0,998

0,992

0,997

QAT

Cu

Pb

Cd

2,39

1,49

0,69

2,52

1,73

0,83

2,12

0,21

0,69

0,999

0,997

0,995
Isotherm Constant Type I Type II Type III Type IV
Langmuir
Nf (mmol g
-1
)

1,40

1,40

1,40

1,40
Ns (mmol g
-1
) 1,46 1,58 3,60 3,73
b (g mmol
-1
) 3,38 2,20 0,43 0,414
R
2
0,998 0,986 0,945 0,945
SE 0,060 0,066 0,83 0,87

2
0,030 0,056 2,67 2,87
Freundlich K
f
(mmol g
-1
) 0,97
n 4,13
R
2
0,810
SE 1,53

2
9,76
Temkin K
T
(mmol dm
-3
) 70,55
b (kJ mol
-1
) 0,599
R
2
0,861
SE 0,29

2
0,42
Table 3. Number of moles sorbed (Nf), parameters of the Langmuir (Ns and b), the Freundlich (n and K
f
),
and the Temkin (n
T
and K
T
) equations, correlation coefficients (r) and standard errors (SE) for interaction of
Cu
2+
with chitosan, a 298 1 K, using linear method.
Material Isoterma Constante Tipo I Tipo II Tipo III Tipo IV
QAT
Cu
2+

Nf (mmol g
-1
) 2,39 2,39 2,39
2,39
Ns (mmol g
-1
) 2,520,01 2,420,01 2,490,05
2,490,26
b (g mmol
-1
) 2,120,01 2,42,01 2,250,02 2,240,14
r
2
0,999 0,984 0,966 0,962
SE 0,053 0,080 0,057 0,057

2
0,026 0,037 0,026 0,026
Pb
2+

Nf (mmol g
-1
) 1,49 1,49 1,49
1,49
Ns (mmol g
-1
) 1,730,13 1,760,02 1,740,03
1,760,01
b (g mmol
-1
) 0,210,01 0,200,09 0,210,24 0,200,01
r
2
0,997 0,989 0,973 0,973
SE 0,032 0,032 0,031 0,031

2
0,010 0,009 0,009 0,009
Cd
2+

Nf (mmol g
-1
) 0,65 0,65 0,65
0,65
Ns (mmol g
-1
) 0,830,10 0,920,04 0,880,03
0,920,02
b (g mmol
-1
) 0,690,03 0,550,06 0,600,15 0,570,05
r
2
0,995 0,992 0,940 0,940
SE 0,026 0,028 0,022 0,028

2
0,007 0,007 0,006 0,007
Table 4. Number of moles sorbed (Nf), parameters of the Langmuir (Ns and b), the Freundlich (n and K
f
),
and the Temkin (n
T
and K
T
) equations, correlation coefficients (r) and standard errors (SE) for interaction of
Cu
2+
, Pb
2+
and Cd
2+
with QAT, at 298 1 K, using linear method.
Table 5. Number of moles sorbed (Nf), parameters of the Langmuir (Ns and b), the Freundlich (n and K
f
), and
the Temkin (n
T
and K
T
) equations, correlation coefficients (r) and error for the interaction of divalent metals
with chitosan at 298 1 K using nonlinear method.

Isoterma Constante Cu(II)
Langmuir
Nf (mmol g
-1
)

1,40
Ns (mmol g
-1
) 1,52
b (g mmol
-1
) 2,62
R
2
0,974
SE 0,054

2
0,002
Freundlich K
f
(mmol g
-1
) 1,01
n 5,0
R
2
0,812
SE 0,14

2
0,021
Temkin K
T
(mmol dm
-3
) 70,36
b (kJ mol
-1
) 4,13
R
2
0,875
SE 0,12`

2
0,014
Table 6. Number of moles sorbed (Nf), parameters of the Langmuir (Ns and b), the Freundlich (n and K
f
), and
the Temkin (n
T
and K
T
) equations, correlation coefficients (r) and error for the interaction of divalent metals
with chitosan QAT, at 298 1 K using nonlinear method.

Isoterma Constante Cu(II) Pb(II) Cd(II)
Langmuir

Nf (mmol g
-1
)

1,49

0,65 2,39
Ns (mmol g
-1
) 2,520,03 1,740,02 0,860,03
b (g mmol
-1
) 2,080,11 0,210,01 0,650,08
r
2
0,994 0,994 0,977

2
0,002 0,0009 0,0005
Freundlich K
f
(mmol g
-1
) 1,450,06 0,490,04 0,360,02
n 3,620,37 2,920,29 2,640,36
r
2
0,943 0,938 0,914

2
0,031 0,010 0,002
Temkin K
T
(mmol dm
-3
) 30,485,26 2,150,29 5,601,21
b (kJ mol
-1
) 2,180,09 2,670,12 4,990,40
r
2
0,983 0,982 0,961

2
0,008 0,002 0,001
Chitosan chemically modifiedNitrogen and sulfur Lewis basic centers
characterization
Final Consideration
Chitosan Cu
2+
> Cd
2+
> Pb
2+
Modified chitosan showed high sorption capacity for Cu
2+
in comparison with
other cations.
Langmuir model type 1 is more adequate to describe experimental data than
other three models, the Freundlich and the Temkin models.
Four different linear forms of Langmuir model gave different values of errors.

AKNOWLEDGEMENT
Mehrabani
Shukriya
Shukran
Obrigado
Thanks