Use of cellulose acetate-tin (lV) phosphate composite (CA/TPC) in highly effective removal
and recovery of heavy metal ions
Suriti Sharma1; Navin Chandra Kothiyal1,*; Bhim Singh Rathore2; Sumit Sharma1,**
1
Department of Chemistry
Dr. B.R. Ambedkar National Institute of Technology, Jalandhar, 144011Punjab, India
* E-mail: kothiyalnc@nitj.ac.in;
**sumit24nitj@gmail.com
Tel.: +91-9417274496; Fax 0181-2692204
2
Department of Chemistry,
Shoolini University, Solan 173212, Himachal Pradesh, India
1.Statistical analysis
In order to see which process parameters were statically significant and to find out any significant variation in the
experimental values with respect to the various experimental conditions statistics of analysis of variance (by using
Post-hoc test) was performed for the current experimental data. In this study, F-test was employed to determine
which process parameter has a more significant effect on the removal efficiency of metal ions [56]. ANOVA test
was being carried out by using the statistics software (SYSTAT version 7.0).The extent of significant difference
between the experimental data and the data calculated from model were examined by chi-square test. The chi-square
test statistic is basically the sum of the squares of the differences between the experimental values and values
obtained by calculating from respective models, with each squared difference divided by the corresponding values
obtained by calculating from the models.
χ2 = ∑
[(qe −qe,m )]2
(qe,m )
Where qe,m is equilibrium adsorption capacity obtained by calculating from the model and qe is experimental values
of the equilibrium adsorption capacity. If data from the model are similar to the experimental data, χ2 values will be
a small, while if they differ, χ2 values will be large. The equilibrium isotherm, kinetic, and thermodynamic
parameters have been evaluated by using ORIGIN version-8 software.
2. Batch study
The AAS was calibrated against standard chromium, nickel and zinc solutions i.e. 1, 2, 4 and 6 mg/dm3 before
detecting residual concentration and (AAS) calibration was checked after measuring every10 samples. All of the
adsorption results were corrected by blank tests in which no adsorbent was added into the metal solutions. In view of
the refinement and accuracy of the experimental data, all the batch experiments run thrice under the identical
conditions and the mean values were used in analyzing the final data. The accepted experimental error for the
average data was not more than ± 5 %. F-test values for the interaction between system conditions i.e. agitation
time (10 to 420 min), initial metal concentrations (1.0 to 15 mg/dm3) and temperature (298 to 313 K) for Cr3+, Ni2+
and Zn2+ uptake are listed in Tables S1,2 (a-c), respectively.
1
Table-S1(a) Significant variation for the interaction between agitation time and temperature conditions for Cr 3+ uptake
ANOVA test
Sum-of-Squares
D.F a
Mean-Square
F-ratio
P
(Agitation time + Temperature)
110.4
2
26.3
12.7
0.0001
Error
136.2
40
5.9
Total
246.6
42
32.2
a
Degree of freedom
Table-S1 (b) Significant variation for the interaction between agitation time and temperature conditions for Ni 2+ uptake
ANOVA test
Sum-of-Squares
D.F a
Mean-Square
F-ratio
P
(Agitation time + Temperature)
108.1
2
21.7
15.117
0.0001
Error
125.3
33
2.6
Total
233.4
35
24.3
a
Degree of freedom
Table-S1(c) Significant variation for the interaction between agitation time and temperature conditions for Zn 2+ uptake
ANOVA test
Sum-of-Squares
D.F a
Mean-Square
F-ratio
P
(Agitation time + Temperature)
105.2
2
29.783
11.1
0.0001
Error
124.4
29
2.679
Total
229.6
31
32.462
a
Degree of freedom
Table-S2(a) Significant variation for the interaction between initial metal concentration and temperature conditions for Cr 3+
uptake
ANOVA test
(Metal concentration + Temperature)
Error
Total
a
Degree of freedom
D.F a
Sum-of-Squares
6590.838
4632.876
11223.714
2
20
22
Mean-Square
1647.709
231.644
1879.353
F-ratio
7.113
P
0.001
Table-S2(b) Significant variation for the interaction between initial metal concentration and temperature conditions for
Ni 2+ uptake
ANOVA test
Sum-of-Squares
D.F a
Mean-Square
F-ratio
P
(Metal concentration + Temperature)
7804.2
2
1951.062
12.857
0.000
Error
3034.9
20
151.748
Total
10839.1
22
2102.81
a
Degree of freedom
Table-S2(c) Significant variation for the interaction between initial metal concentration and temperature conditions
for Zn 2+ uptake
ANOVA test
Sum-of-Squares
D.F a
Mean-Square
F-ratio
P
(Metal concentration + Temperature)
7602.2
2
1776.2
12.157
0.000
Error
3784.9
20
148.8
Total
11387.1
22
1952.8
a
Degree of freedom
12
10
11
9
10
8
9
7
7
6
6
5
t/qt
t/qt
8
5
4
4
3
3
2
2
1
1
0
0
0
100
200
300
400
500
0
600
100
308 K
300
400
500
600
time (min)
time (min)
298 K
200
298 K
313 K
Fig.S1 (a) Pseudo second order reaction kinetic for Cr 3+adsorption
(AD, 10.0 g; initial pH, 6.0; initial concentration of Cr 3+, 15 mg/dm3)
308 K
313 K
Fig.S1 (b) Pseudo second order reaction kinetic for Ni 2+ adsorption
(AD, 10.0 g; initial pH, 3.0; initial concentration of Ni 2+, 15 mg/dm3)
2
10
0.45
9
0.40
8
0.35
7
0.30
6
RL (-)
t/qt
0.25
5
4
0.20
0.15
3
2
0.10
1
0.05
0
0.00
0
100
200
300
400
500
4
6
8
298 K
10
12
14
16
18
3
Co (mg/dm )
time (min)
308 K
298 K
313 K
Fig.S1 (c) Pseudo second order reaction kinetic for Zn 2+ adsorption
(AD, 10.0 g; initial pH, 6.0; initial concentration of Zn 2+, 15
mg/dm3)
308 K
313 K
Fig.S2 Plot of separation factor (RL) versus initial Cr3+, Ni2+ and Zn2+
metal ion concentration (AD, 10.0 g; initial pH, 3-6; agitation
time,1h and 2h)
0.30
0.25
0.25
0.20
0.20
1/qe
1/qe
0.15
0.15
0.10
0.10
0.05
0.05
0.00
0
5
10
15
0
20
2
4
308 K
8
10
12
14
16
18
1/Ce
1/Ce
298 K
6
298 K
313 K
Fig.S3 (a) Langmuir Isotherm for Cr 3+ adsorption (AD, 10.0 g;
initial pH, 3.0; agitation time, 1h)
308 K
313 K
Fig.S3 (b) Langmuir Isotherm for Ni 2+ adsorption (AD, 10.0 g;
initial pH, 6.0; agitation time, 2h)
3
20
0.35
1.6
0.30
1.4
0.25
1.2
log qe
1/qe
0.20
0.15
1.0
0.8
0.10
0.05
0.6
0.00
0
2
4
6
8
10
-1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
12
log Ce
1/Ce
298 K
308 K
298 K
313 K
Fig.S3(c) Langmuir Isotherm for Zn2+ adsorption (AD, 10.0 g;
initial pH, 6.0; agitation time, 2h)
308 K
313 K
Fig.S4 (a) Freundlich Isotherm for Cr 3+ adsorption (AD, 10.0 g;
initial pH, 3.0; agitation time, 1h)
1.8
1.7
1.6
1.6
1.5
1.4
1.4
1.3
1.2
1.1
log qe
Log qe
1.2
1.0
0.9
1.0
0.8
0.8
0.7
0.6
0.5
0.6
0.4
0.3
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
1.5
2.0
Log Ce
298 K
308 K
0.4
-1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
log Ce
313 K
298 K
Fig.S 4(b) Freundlich Isotherm for Ni 2+ adsorption (AD, 10.0 g;
initial pH, 6.0; agitation time, 2h)
308 K
313 K
Fig.S4(c) Freundlich Isotherm for Zn 2+ adsorption (AD, 10.0 g;
initial pH, 6.0; agitation time, 2h)
4
34
32
40
30
28
26
24
30
qe (mg/g)
22
qe
20
18
16
14
20
12
10
10
8
6
4
0
2
-5
-4
-3
-2
-1
0
1
2
3
-3
4
-1
0
1
2
3
308 K
313 K
298 K
Fig.S5(a) Temkin isotherm model for Cr 3+ adsorption
(AD, 10.0 g; initial pH, 3.0; agitation time, 1h)
308 K
313 K
Fig.S5 (b) Temkin isotherm model for Ni 2+ adsorption
(AD, 10.0 g; initial pH, 6.0; contact time, 2h)
45
40
35
qe (mg/g)
30
25
20
15
10
5
0
-2.5 -2.0 -1.5 -1.0 -0.5 0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
ln Ce
298 K
4
In Ce
ln Ce
298 K
-2
308 K
313 K
Fig.S5 (c) Temkin isotherm model for Zn 2+ adsorption
(AD, 10.0 g; initial pH, 6.0; agitation time, 2h)
Fig.S 6(a) Plot of ln kc vs.1/T for Cr 3+ adsorption
(AD, 10.0 g; initial pH, 3.0; agitation time, 1h)
5
3.0
3.5
2 mg/dm3
5 mg/dm3
10 mg/dm3
12 mg/dm3
15 mg/dm3
2.5
2.0
1.5
2 mg/dm
3
5 mg/dm
3
10 mg/dm
3
12 mg/dm
3
15 mg/dm
2.5
1.0
2.0
0.5
1.5
0.0
1.0
-0.5
ln kc
ln kc
3
3.0
-1.0
-1.5
0.5
0.0
-2.0
-0.5
-2.5
-1.0
-3.0
-1.5
-3.5
-4.0
3.10
3.15
3.20
3.25
3.30
-2.0
3.10
3.35
1000/T
3.15
3.20
3.25
3.30
3.35
1000/T
Fig.S6 (b) Plot of ln kc vs.1/T for Ni2+ adsorption
(AD, 10.0 g; initial pH, 6.0; agitation time, 2h)
Fig. S 6(c) Plot of ln kc vs.1/T for Zn 2+ adsorption
(AD, 10.0 g; initial pH, 6.0; agitation time, 2h)
Fig. S7 (a) Intraparticle diffusion plot for Cr 3+ adsorption
(AD, 10.0 g; initial pH, 3.0; agitation time, 1h)
Fig.S7 (b) Intraparticle diffusion plot for Ni2+ adsorption
(AD, 10.0 g; initial pH, 6.0; agitation time, 2h)
6
Fig.S7 (c) Intraparticle diffusion plot for Zn 2+ adsorption
(AD, 10.0 g; initial pH, 6.0; agitation time, 2h)
7