Malaysian Journal of Analytical Sciences, Vol. 7, No.

2 (2001) 453-456
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Preliminary Study on Application of Sago Starch Based Poly(Hydroxamic Acid) Resin for Extraction of Lanthanide Group Elements from Aqueous Media
Mohamad Zaki Ab Rahman, Md Lutfor Rahman, Md Jelas Haron, Sidik Silong, Wan Md Zin Wan Yunus and Mansor B. Ahmad
Department of Chemistry, Faculty of Science and Environmental Studies, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor (Received 6 September 2000) Abstract: Sago starch was used as a backbone polymer for synthesizing poly(hydroxamic acid) chelating resin. The hydroxamic acid functional group was identified by visual color test and infrared spectroscopy. The chelating behaviors of the hydroxamic acid ligand with a series of lanthanide elements were studied by using batch technique. The binding capacity of lanthanum was about 2.30 mmol g-1 at pH 6, higher than other metal ions tested namely dysprosium, praseodymium and cerium which were found to have significant binding capacity at pH 7. The rate of exchange (t) of copper ion was found to be < 5 min, which was fast. It was also observed that the metal ions binding capacity were pH dependent and its selectivity towards these metal ions is in the following order: La3+ > Dy3+ > Pr3+ > Ce3+ > Nd3+ > Gd3+ > Eu3+ > Tb3+. This chelating ligand has the advantage of significant binding capacity and a fast rate of equilibrium. It could be considered as an efficient resin for extraction of heavier lanthanide elements from the environment or other sources. Abstrak: Kanji sagu telah digunakan sebagai tulang belakang polimer untuk menyedia resin pengkelat poli(asid hidroksamik). Kumpulan berfungsi asid hidroksamik pada resin telah dikenalpasti melalui ujian warna dan spektroskopi infra merah. Keupayaan ligan asid hidroksamik mengkelat unsur-unsur kumpulan lantanida telah dikaji dengan kaedah kelompok. Muatan ion logam lantanum yang terikat pada resin tersebut adalah tinggi iaitu kira-kira 2.30 mmolg-1 pada pH 6 sementara unsurunsur disprosium, praseodimium dan serium didapati mempunyai muatan yang bermakna pada pH 7. Kadar penukaran (t) ion kuprum adalah cepat iaitu kurang daripada 5 min. Mautan ion logam juga didapati bergantung kepada pH dan kepilihan resin terhadap ion logam yang dikaji adalah seperti berikut: La3+ > Dy3+ > Pr3+ > Ce3+ > Nd3+ > Gd3+ > Eu3+ > Tb3+. Kelebihan ligan pengkelat ini ialah ia mempunyai muatan ion logam yang agak tinggi dan juga kadar keseimbangan yang cepat. Ia berkemungkinan besar dapat digunakan sebagai resin untuk mengekstrak unsur lantanida berat daripada persekitaran dan punca-punca lain.

___________________________________________________________________________________________ Introduction Ion exchange resins bearing chelating functional groups have long been of interest for removing metals from water. The design of chelating ligands depends on the stability of the basic macromolecular network and its ability to add on the desired chelating functional groups [1, 2]. Because the alkali and alkaline earth metals occur in relatively high concentrations in natural waters, a desirable property of metal chelating ligands having useful environmental or commercial application is their ability to bind heavier elements selectively. They should be able to bind the heavier transition, rare earth, and main group metal ions in the presence of high concentration of calcium, magnesium, sodium and potassium. The chelating resins containing hydroxamic groups can also play a vital role in environmental monitoring of toxic trace metals. Highly promising is the use of this resin for extraction of toxic metals in the environment and sewage water [3]. There is also a possibility of using poly(hydroxamic acid) resin to extract rare earth from seawater. The commercial importance of poly(hydroxamic acid) resin seems to have potential, together with the knowledge that hydroxamic groups can form complexes with a wide range of metals [46]. The chelating polymer materials are mainly used in analytical, industrial and radiochemical laboratories, but only a limited extent in solving environmental problems. Metal pollution of the environment possesses a unique problem, since metals are not subjected to biodegradation. Among the newer chelating ion exchange resin, the preparation of this chelating poly(hydroxamic acid) resin from poly(methyl acrylate) (PMA) grafted sago starch is a new starting polymer to obtain this resin. The starting material for the resin preparation especially sago starches are available and also it is a renewable source. In this report, the poly(hydroxamic acid) chelating resin was prepared using modified method [7] by cheapest starting material and the chelating behavior was investigated.

MOHAMAD ZAKI AB RAHMAN et al.: PRELIMINARY STUDY ON APPLICATION OF SAGO STARCH Experimental The PMA grafted sago starch was prepared by free radical initiating process. The reaction mechanism and procedure were described elsewhere [8]. The concentrations of ceric ammonium nitrate, methyl acrylate, sulfuric acid, sago starch (AGU, anhydro glucose units) used for preparation of the grafted copolymer product were 8.77 x 10-3, 0.803, 0.175 and 0.135 mol L-1, respectively. The reaction temperature and period were 50C and 60 min, respectively. The preparation of chelating resin was carried out by the reaction between PMA grafted sago starch and hydroxylamine. The preparation of NH2OH solution as follows: About 42.10 g of hydroxylamine hydrochloride (NH2OH.HCl) was dissolved in 300 ml aqueous methanol solution (methanol : water; 5:1). The HCl was neutralized by NaOH solution and the precipitate of NaCl was removed by filtration. The pH of the reaction solution was adjusted to pH 13 by NaOH solution. Then, 20.00 g of PMA grafted sago starch was placed into the flask and hydroxylamine solution was added to the flask, equipped with a mechanical stirrer, condenser and water bath. The reaction was carried out at 72C for 2h. The resin was separated by filtration and washed several times with aqueous methanol solution. Then the resin was treated with 200 ml of aqueous methanol 0.2M HCl solution at least for 5 min. Finally the resin was filtered and washed several times with aqueous methanol solution and dried at 50C to constant weight. Reaction of poly(acrylate ester) with hydroxylamine is shown in Scheme 1, based on Domb et al [7]. Infrared spectra of PMA grafted sago starch and resin samples were obtained from FT-IR Spectrometer (Perkin- Elmer 1725). Metal ions binding capacity of the resin was measured by batch equilibration technique with solution of varying pH (pH 3-7). Exactly 0.2000 g of dry resin was placed into a series of 100 ml polyethylene bottle and resins were allowed to equilibrate with 25 ml distill water. Then 20 ml of 0.1M sodium acetate buffer solution at various pH and 20 ml of 0.1M metal ion solution were added to each bottle. The mixture was shaken for 24h. Then 5ml supernatant solution was collected and analyzed for metal ions by ICP (Perkin 1000). Sorption capacity was calculated as the amount of metal ions (mmol) sorb per gram of dried resin.
O P C OCH3 NH2OH OH P O C NHOH + CH3OH

where P is the backbone polymer

Scheme 1 Results and Discussion Infrared spectra of PMA grafted sago starch and resin samples are shown in Fig. 1. Result of IR spectra of sago starch was described elsewhere [8]. IR spectra of poly(methyl acrylate) grafted sago starch shows a new absorption band of PMA at 1741 cm-1 of C=O due to stretching mode in addition to the same absorption bands of sago starch (Fig. 1.a). The C=O band of 1741 cm-1 disappeared and formed a new band of hydroxamic acid of C=O at 1646 cm-1, and amide II band of N-H at 1568 cm-1 (Fig. 1.b). Therefore, poly(hydroxamic acid) functional group was successfully prepared from the grafted copolymer.

(a)

(b)
4000 3500 3000 2500 2000 1500 1000 500 0

cm

-1

Fig 1. Absorption spectra of (a) poly(methyl acrylate) grafted sago starch and (b) poly(hydoxamic acid) resin at the IR region.

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Transmittance

MOHAMAD ZAKI AB RAHMAN et al.: PRELIMINARY STUDY ON APPLICATION OF SAGO STARCH Conductivity measurement Several microemulsion samples in the MA/Tween 80:Brij 30(80:20)/H2O system were prepared at 60:40, 50:50, 35:65 and 20:80 weight ratios of MA:(Tween 80:Brij 30). Conductivity property of the samples was measured by using a conductivity meter (Jenway Model 4020 and conductivity cell Model PCM 141) with a cell constant of 1.01 at 25.0 0.5oC. The sorption behavior of poly(hydroxamic acid) resin toward some metal ions investigated are shown in Fig 2 and Fig 3. From the results one can infer that the relative amount of metal ions taken up by the resin were pH dependent and increases steadily with the increase of the pH of the medium. This resin exhibits high affinity for lanthanum at pH 6 with binding capacity about 2.30 mmol g-1. The binding capacity of dysprosium, praseodymium, cerium, neodymium, gadolinium, europium and terbium at pH 7 were found to be 2.08, 1.88, 1.86, 1.64, 1.50, 0.71 and 0.54 mmol g-1, respectively. The selectivity of the resin towards these metal ions is in the following order: La3+ > Dy3+ > Pr3+ > Ce3+ > Nd3+ > Gd3+ > Eu3+ > Tb3+.

Metal ion Capacity / mmol g

-1

2.5 2 1.5 1 0.5 0 2 3 4 5 6 7 8

La(III) Dy(III) Ce(III) Nd(III)

pH
Fig 2. Metal ions sorption capacity as a function of pHusing by poly(hydroxamic acid) resin.

Metal ion Capacity / mmol g

-1

2 1.5 1 0.5 0 2 3 4 5 6 7 8

Eu(III) Pr(III) Gd(III) Tb(III)

pH
Fig. 3. Metal ion sorption capacity as a function of pH using by poly(hydroxamic acid) resin.

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MOHAMAD ZAKI AB RAHMAN et al.: PRELIMINARY STUDY ON APPLICATION OF SAGO STARCH The rate of exchange of Cu2+ ion was determined by contacting of resin beads with Cu2+ solution for various time intervals. The time required for 50% exchange (t1/2) was calculated from the Cu2+ ion exchange by the resin according to method described by Lee et al. [9]. It was found that the sorption rate of Cu2+ ion very fast i.e. t1/2 <5 min. Most of hydroxamic acids complexes with transition metal salts are highly colored. It has been observed that complex formation requires the hydroxylamine oxygen to be unsubstituted, although the nitrogen may bear a substituent [10]. Much evidence is now accumulated that the hydroxamate anion is a bidentate ligand and forms a complex in which the metal ion is bound to both oxygen by chelation [4, 5, 10]. Conclusion A new chelating resin containing hydroxamic acid functional group was prepared from poly(methyl acrylate) grafted sago starch. The chelating behavior of the resin towards some metal ions was studied out and the binding capacities of lanthanum, dysprosium, praseodymium and cerium were found to be excellent. The preparation of this resin from the PMA grafted copolymer is efficient, cost effective and simple work up. It can be considered as potential resin for the extraction of lanthanum group elements from environment or other source. References 1. A. Winston and D. Kirchner, J. Am. Chem. Soc. 11 (1978) 597. 2. F. Vernon, Pure. Appl. Chem. 54 (1982) 2151. 3. P. N. Sophiamma and K. Sreekumar, J. Appl. Polym. Sci. 62 (1996) 1753. 4. W. Kern and R.C. Schulz, Angew Chem. Int. Ed. Engl. 69 (1957) 153. 5. F. Vernon and H. Eccles, Anal Chim Acta 77 (1975) 145. 6. F. Vernon and Wan Yunus, Anal Chim Acta 123 (1981) 309. 7. A. J. Domb, E. G. Cravalho, and R. Langer, J. Polym. Sci., Part A 26 (1988) 2623. 8. Lutfor Rahman, S. Sidik, Wan Md Zin, M Z Ab Rahman, A. Mansor and H. Jelas, J. Appl. Polym. Sci. 76 (2000) 516. 9. C. H. Lee, J. S. Kim, M. Y. Suh, and W. Lee, Anal Chim Acta 339 (1997) 303. 10. P. A. S. Smith, in The Chemistry of OpenChain Organic Nitrogen Compounds Chapman & Hall, London, 1962, p. 68.

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