ADSORPTION PROPERTIES OF ANTHRANILIC ACID CONTAINING
POLYMERIC RESINS FOR SEPARATION OF METAL IONS
Pathik Shah*, Pradeep Upadhyaya.
Central Institute of Plastics Engineering & Technology (CIPET), Ahmedabad pathikas@gmail.com SYNTHESIS OF RESIN BY MICROWAVE
IRRADIATION
In the first step, Anthranilic acid (0.1 mol) was taken in a 250 mL threenecked round bottom fitted with a stirrer, a thermometer and a condenser and was dissolved in DMF solvent (20 mL). To that formaldehyde (0.3 mol as 37%) and a solution of resorcinol/ M-Cresol (0.1 mol) in 10 mL DMF were added simultaneously drop wise giving a clear solution and was stirred for 1 h. The mixture was refluxed in microwave oven using irradiation of 2.46
GHz at 80±2ºC for 50s until a viscous solution was obtained with the formation of a hard mass of resin. The colour of resultant resin is red-brown. Then sealed and cured at 70-75ºC for 12 h stored in polyethylene bottle. As carboxylic acid groups normally are decomposed above
100ºC, the resin was cured below 90ºC.
The dry resin sample free from impurities was directly examined for FTIR, SEM, and elemental analysis..To convert the FAR and FAM resin samples in H+ form, the resulting hard mass was crushed to 20+30 or -60 +100 BSS mesh size as needed. The resin was conditioned by 0.1
N HCl solutions. The resins were washed with distilled water until free from acid.
The resin was air dried to remove surface moisture. Where Y= -OH for resorcinol (FAR) and –
CH3 for M cresol (FAM).

Physico-chemical properties:
FAR
Properties
Moisture content (%)
14.02
True density (dres) g/cm3
1.06
Apparent density (dcol) g/ml 0.71
Void volume fraction
0.36
Sodium ion-exchange 6.50 capacity mmol/g dry resin
Concentration
of fixed 6.21 ionogenic group mmol/cm3
Volume capacity
3.85

FAM
12.11
1.11
0.69
0.40
6.75
6.62
3.76

Elemental Analysis and FTIR spectra:
Analysis %, Calculated (Found)
Resin
C
H
N
FAR
70.7(71.0)
4.9(5.0) 5.5(5.9)
FAM
70.6(70.4)
5.1(5.4) 5.5(5.5)

Optical photographs :
FAR resin

Ni

1

Cu

0.9

Zn

0.8

Cd

0.7

Pb

0.6
0.5

Phenolic
(-OH)
stretching
(N-H) stretching of amino group
(C-N) stretching of
(Ar- NH2)
Methylene(-CH2)
stretching
>C=O
stretching
(carboxylic ketone)
(N-H) bending of RNH2
Stretching due to tetra substituted benzene ring
(C-H) bending of
1450Ar-CH3
1330

-

1380

Scanning Electron Micrograph (SEM):

FAR resin exchange order:

capacity

Zn(II) > Cu(II) >
Pb (II)> Ni(II) > Cd(II)

0.3
0.2
0.1
3

Vibrational mode

FAM resin

0.4

0

Frequency (cm-1)
Observed
Reported
FAR FAM
3500 - 3429 3400
3200
3500 - 3429 3400
3200
13351261 1279
1250
3000 - 2921 2924
2850
1690 - 1655 1718
1650
16501614 1615
1580
860-800 868 854

CONCLUSION

Chelating properties of synthesized polymeric resins:
Exchange capacity mmol/g dry resin

Polymeric chelating resins, FAR and FAM were synthesized by condensation polymerization of
Formaldehyde,
Anthranilic acid, and Resorcinol/M-cresol in 1:3:1 molar ratio in DMF media by the microwave method. The physicochemical properties of the synthesized resins were determined. The Polymeric chelating resins were characterized by FTIR and elemental analysis. The morphologies of the resins were examined by Optical
Photographs and SEM. The metal ion uptake capacities of the synthesized resins were determined for Ni(II), Cu(II),
Zn(II), Cd(II) and Pb(II) with respect to pH of the media and metal ion concentration.
The multiple functional groups present in chelating resins and difference in the methods of synthesis demonstrate a significant influence on the extent of metal uptake. The clean separation of metal ions from Pb(II)- Cd(II) and Pb(II) –Zn(II) mixture on polymeric chelating resin was achieved up to 85% at optimized Kd values of metal ions.
Keywords: Metal Ions, Polymeric
Chelating Resin, Morphology, Analytical
Separation.

RESULT AND DISCUSSION

RESULT AND DISCUSSION

Exchange capacity mmol/g dry resin

ABSTRACT

3.5

4

4.5

5

pH

5.5

6

6.5

7

Ni

1.5
1.4
1.3
1.2
1.1
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

Cu
Zn
Cd
Pb

FAM Resin exchange capacity order :
Ni(II) > Cu(II) >
Cd(II) > Zn(II) >Pb(II)

3

3.5

4

4.5

5

pH

5.5

6

6.5

The separation of binary mixtures by FAR and FAM resin at different conditions and
Distribution Coefficient value Kd

Pb(II)
Cd(II)
Pb(II)
Zn(II)

Eluent (Tartaric acid)
FAR
FAM
Conc.(M) pH Conc.(M)
0.5
3
1
0.2
3
0.3
0.3
3
0.1
0.1
3.5
0.3

pH
3.5
3
5
3

The optimized condition of concentration and pH of eluting agent (Tartaric acid) for FAR and
FAM resins ( Distribution Coefficient value Kd)

Separation of
Pb(II)
and
Cd(II).
Surface analysis has found to be of great use in understanding the surface features of the material. The morphology of resins exhibits growth of crystals from polymer solutions corresponding to the most prominent organization in polymers on a large scale such
Size of original
Size it will be on the Poster as in size of few millimeters of spherulites.
Ideally, spherulites are the aggregates of submicroscopic size particles. Spherulites are characterized by secondary structural features, such as faint corrugations. The higher magnification shows coexistence of an appreciable amorphous fraction with few shallow pits. The optical photographs of synthesized resins appear to be reddish brown to black in colour

REFERENCES

7

Analytical Applications:

Metal
Eluted

The present resin syntheses are time saver and simple. This is clearly seen from fact that where other commercial resins needs hours of refluxing, these resins can be synthesized in few minutes. Chelating resins are stable and can be used for the removal of metal ions at room temperature. The presence of heavy metal ion viz. Pb(II) and Cd(II) in aquatic system pose heavy risk to human health.
Therefore removal of such metal ions from water bodied may be considered an interesting and important research activity.
Separation of heavy metal ions from binary mixture and ternary mixture have been successfully carried out. Metal industries effluent contains Ni(II) and Cu(II). Removal of these toxic metal ions has prime importance.
Use of chelating resin is the method of choice due to its high separation efficiency and good reproducibility; therefore, these resins can be used in enrichment of metals from various sources by adopting preconcentration and separation from various matrices.

Separation of
Pb(II)
and
Zn(II).

The recovery of metal ions has been up to 85
% in all cases. Synthesized resins were very useful for separation of metal ions particularly for heavy metal ions.

1. Mustafa Soylaka and Zeynep Topalak.
Arabian Journal of Chemistry (2012). DOI:
10.1016/j.arabjc.2012.04.043
2. Naguaa Badawy, Mahmoud A. International
Journal of Hazardous Materials Research
(2013), 1(1), 01- 15
3. Aminul Islam, Mohammad Asaduddin Laskar and Akil Ahmad. Talanta, (2010), 81(4–5),
1772–1780.
4. Chunnuan Ji, , Shuhui Song, Chunrong
Wang,
Changmei Sun,
Rongjun
Qu,
Chunhua Wang, and Hou Chen.
Chemical Engineering Journal, (2010),
165(2), 573–580.
5. Chuh-Yean Chen, Chen-Li Chiang, and
Chuh-Rou Chen, Separation and Purification
Technology (2007), 54(3), 396–403.
6. Yiyong Chen and Yan Zhao. Reactive and
Functional Polymers (2003) 55, 89–98.
7. Pratik E.P. Michael,
J.M. Barbe, H.D.
Juneja, and L.J. Paliwal Synthesis, European
Polymer Journal. (2007), 43(12), 4995-5000.
8. M. V. Tarase, A. B. Zade, W. B. Gurnule.
Journal of Applied Polymer Science. (2008)
108(2), 738–746.
9. R. N. Singru, A. B. Zade, and W. B. Gurnule,
Journal of Applied Polymer Science. (2008)
109(2), 859–868.
10. D. Feng , C. Aldrich and H. Tan , Minerals
Engineering, (2000), 13(6), 623-642.
11. Vogel AI, A Text Book of Quantitative
Inorganic Analysis, Longman, London, 4th ed., (a) 318, 886 (b) 125, 1978.
12. Kunin R, Kreiger RE, Elements of Ion
Exchange, (Ed.), Huntington, Huntington,
New York, 163, 1971.
13. Kunin R, Ion Exchange Resins, 2nd ed.,
Wiley, New York, 325, 337, 345, 1958. 25.
Helfferich F, Ion Exchange, McGraw-Hill, New
York, 75, 76, 86, 233, 1962.
14. Silverstein RM, Bassler GC, Morril TC,
Spectrometric Identification of Organic
Compounds, 2nd ed., Wiley, New York, 1969.

Template provided by: “posters4research.com