Research Article Removal of Toxic Metal Ions from Water ...downloads.hindawi.com/archive/2014/873520.pdf · the - ASAUF terpolymer resin was studied by using batch equilibrium method

Research ArticleRemoval of Toxic Metal Ions from Water Using ChelatingTerpolymer Resin as a Function of Different ConcentrationTime and pH

Mangesh S Dhore1 Suraj S Butoliya2 and Anil B Zade1

1 Department of Chemistry Laxminarayan Institute of Technology Rashtrasant Tukdoji Maharaj Nagpur UniversityNagpur 440 010 India

2Department of Chemistry Shri Ramdeobaba College of Engineering amp Management Nagpur 440 013 India

Correspondence should be addressed to Anil B Zade ab zade18yahoocom

Received 22 November 2013 Accepted 28 January 2014 Published 22 May 2014

Academic Editors C-Y Guo B Haidar and M Sanopoulou

Copyright copy 2014 Mangesh S Dhore et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

Terpolymer resin 4-ASAUFwas synthesized by the condensation of 4-aminosalicylic acid (4-ASA) and urea (U) with formaldehyde(F) in the presence of 2N hydrochloric acidThe structure of the resin was characterized by various spectral techniques like infrared(FTIR) and nuclear magnetic resonance (1H and 13C-NMR) spectroscopyThe empirical formula and empirical weight of the resinwere determined by elemental analysis The physiochemical properties of terpolymer resin were determined The morphologicalfeature of the 4-ASAUF terpolymer resin was studied by scanning electronmicroscopy (SEM)The chelating ion-exchange propertyof this copolymer was studied for eight metal ions namely Fe3+ Cu2+ Ni2+ Co2+ Hg2+ Zn2+ Cd2+ and Pb2+ ions by using batchequilibrium method The chelating ion-exchange study was carried out over a wide pH range at different time intervals usingdifferent electrolyte of various ionic strengths

1 Introduction

Ion-exchange process is efficient and eco-friendly extractiontechnique for the separation of metal ions and recovery oftoxic heavy metal ions from the industrial wastes tanneryeffluents and sewages and so forth [1 2] The aromatic com-pound with substituents like ndashOH ndashCOOH and ndashNH

2with

urea and formaldehyde shows selective ion-exchange proper-ties thermal resistance properties and coordinating proper-ties [3ndash6] The chemically modified silica gel N-(1-carboxy-6 hydroxy) benzylidenepropylamine was used as an ion-exchanger for the removal and preconcentration of hazardousmetal ions such as Cr Mn Cd and Pb in natural water sam-ples using batch equilibrium method and atomic absorptionspectroscopy (AAS) technique [7] The metal absorption ofcopolymer gel poly(HPMA-co-IA) and poly(HPMA-co-CA)increases with pH and study proved that poly(HPMA-co-IA)and poly(HPMA-co-CA) could be used as metal absorbents

for Cd2+ and Pb2+ ions [8] Rahangdale et al and Taraseet al investigated the chelation ion-exchange propertiesof resin prepared from 24-dihydroxyacetophenone-biuret-formaldehyde terpolymers and 24-dihydroxybenzaldehydeoxamide and formaldehyde respectively [9 10] The chela-tion ion-exchange properties of copolymer resin derivedfrom 8-hydroxyquinoline 5-sulfonic acid oxamide andformaldehyde indicated that the copolymer had greaterselectivity for Fe2+ Cu2+ and Ni2+ ions than for Co2+ Zn2+Cd2+ and Pb2+ ions [11]Themetal ion-binding properties ofa copolymer resin derived from o-aminophenol melamineand formaldehyde have been reported for the metal ionsFe3+ Zn2+ Cu2+ Pb2+ Cd2+ and Hg2+ [12] Gurnule et al[13] reported that a copolymer prepared from salicylic acidmelamine and formaldehyde was more selective for Fe3+Cu2+ andNi2+ ions than for Co2+ Zn2+ Cd2+ and Pb2+ ionsButoliya et al [14] reported a chelation ion-exchange proper-ties of 24-dihydroxybenzophenone-oxamide-formaldehyde

Hindawi Publishing CorporationISRN Polymer ScienceVolume 2014 Article ID 873520 11 pageshttpdxdoiorg1011552014873520

2 ISRN Polymer Science

HO

HOOC NH2

H2 N NH2

OO

H Hn

n

2n

Δ120∘C5h

OH

HOOC

NH2

HNH

N

O

n

4-Aminosalicylic acidUrea Formaldehyde

4-ASA-U-F-I terpolymer resin

+ +

2N HCl

Figure 1 Chemical reaction of 4-ASAUF terpolymer

terpolymer resins Ahamed et al [15] synthesized a terpoly-mer from anthranilic acid salicylic acid and formaldehydeand evaluated its ion-exchange properties toward toxic metalions Similarly Azarudeen et al synthesized terpolymersfrom 8-hydroxyquinoline anthranilic acid and formalde-hyde and determined their chelating capacity toward specificmetal ions [16]

The present paper explored the newly synthesized ter-polymer resin 4-aminosalicylic acid-urea-formaldehyde (4-ASAUF) in the light of its physiochemical spectral andchelating ion-exchange study

2 Experimental

21 Starting Materials 4-Aminosalicylic acid is of analyticalgrade purity which is purchased from Acros Chemicals Bel-gium Urea formaldehyde (37) metal nitrates indicatorsand disodium salt of ethylenediaminetetraacetic acid (EDTA)were purchased fromSD FineChemicals India All the usedsolvents like N N-dimethylformamide dimethyl sulfoxidetetrahydrofuran acetone and diethyl ether were procuredfromMerck India Double distilled water was used for all theexperiments

22 Synthesis 4-ASAUF terpolymer was prepared by con-densing 4-aminosalicylic acid (153 g 01mol) and urea (06 g01mol) with formaldehyde (75mL 02mol) in presence of2N HCl as a catalyst in the molar proportion of 1 1 2 at120∘C in an oil bath for 5 h The dark reddish brown resinoussolid product was immediately removed filtered repeatedlywashed with cold-distilled water dried in air and powderedwith the help of mortar and pestle The product obtained

was extracted with diethyl ether to remove excess of 4-aminosalicylic acid-formaldehyde copolymer which mightbe present along with 4-ASAUF terpolymer Dried resinsample was dissolved in 8 NaOH regenerated using 1 1HClwater (vv) with constant stirring and filtered Thisprocess was repeated twice Resulting terpolymer samplewas washed with boiling water and dried in a vacuumat room temperature Purified terpolymer resin was finelyground to pass through 300-mesh size sieve and kept ina vacuum over silica gel [17] The purity of newly synthe-sized and purified terpolymer resin sample has been testedand confirmed by thin layer chromatography techniqueDimethyl sulfoxide (DMSO) was used as a solvent fordeveloping chromatogram and was allowed to run for about20 minutes when the chromatogram was exposed to iodinechamber then we get single colour spot for resin sampleThis indicates that the synthesized and purified polymerresin sample has no impurities and is used for furtherstudies only after the confirmation of 100 purity of thesample The chemical reaction of above synthesis is given inFigure 1

23 Physiochemical Studies Terpolymer was subject to ele-mental analysis for carbon hydrogen and nitrogen on PerkinElmer 2400 Elemental Analyzer Physiochemical studies suchas moisture content percentage solids void volume fractiontrue density and sodium exchange capacity were evaluated inaccordance with reported procedures [18]

24 Moisture Content The purified 1 g of terpolymer wastaken in a previously weight Petri dish The Petri dish withterpolymer sample was then dried in a vacuum oven at 105∘C

ISRN Polymer Science 3

for 8 h and reweighed after cooling in a desiccator From theweight of the Petri dish moisture content () was calculated

Moisture content

= ((Weight of the petri dish with terpolymer sample

after drying)

minus (Weight of the petri dish))

times ((Weight of the petri dish with terpolymer sample

before drying)

minus (Weight of the petri dish))minus1 times 100(1)

True density apparent density and void volume fractionwerealso calculated by use of the expressions

True density (119889pol) =119882119901minus119882

(119882119908minus119882119901119908) + (119882

119901minus119882) (2)

where119882 is weight of the specific gravity bottle119882119901is weight

of the specific gravity bottle containing terpolymer 119882119908is

weight of the specific gravity bottle containing water and119882119901119908

is weight of the specific gravity bottle containing bothterpolymer and water

Apparent density (119889col) =Weight of terpolymerVolume of terpolymer

Void volume fraction = 1 minus119889col119889pol

(3)

25 Total Exchange Capacity The total exchange capacityof the terpolymer is the total number of exchanging sitesavailable per unit volume of swollen terpolymer Dry terpoly-mer (10 g accurately weighed H+ form) of uniform particlesize (30ndash60 mesh) was placed in a 250mL Erlenmeyer flaskTo this 200mL standard solution of 01M NaOH in 1MNaCl was added The mixture was equilibrated for 24 h withintermittent shaking After 24 h 50mL of the mixture waswithdrawn and titrated against standard 01M HCl solutionThe total cation- exchange capacity (CEC) was calculatedfrom

CEC =(200 timesmolarity of NaOH)

weight of sample times [solid () 100]

minus(4 times volume of HCl timesmolarity of HCl)weight of sample times [solid () 100]

(4)

where CEC is the cation-exchange capacity of the terpolymer

26 Spectral Studies Infrared spectra were recorded in Fron-tier transform infrared spectrophotometer in the range of4000ndash500 cmminus1 1Hand 13C-NMR studies were performed indimethyl sulfoxide (DMSO-d

6) solvent on Bruker Advance-

II 400MHz and 13C-NMR spectrumwas also recorded usingBruker 100 MHz

27 Ion-Exchange Property The ion-exchange property ofthe 4-ASAUF terpolymer resin was studied by using batchequilibrium method for various metal ions namely Fe3+Cu2+ Ni2+ Co2+ Hg2+ Zn2+ Cd2+ and Pb2+ under threedifferent experimental conditions [4 19]

(i) Determination of Metal Uptake in the Presence of FourDifferent Electrolytes and Their Different Concentrations Ter-polymer sample (25mg) was placed in cleaned glass bottlesand each of the electrolytes (25mL) NaCl NaNO

3 NaClO

4

and Na2SO4at different concentrations namely 001 005

01 05 and 1M was added into the bottles The suspensionswere adjusted to pH 25 for Fe3+ pH 45 for Cu2+ and Hg2+pH 50 for Co2+ Cd2+ Ni2+ and Zn2+ and pH 6 for Pb2+by adding either 01M HCl or 01M NaOH The suspensionswere mechanically stirred for 24 h at room temperatureAfter 24 h 01M of the chosen metal ion solution (2mL)was added to each bottle and these were again vigorouslystirred at room temperature for 24 h The terpolymer wasthen isolated by filtration and washed with distilled waterThe filtrate and the washings were collected and the amountof metal ion was estimated by titrating against standarddisodium EDTA solution using an appropriate indicatorA blank experiment was also performed by following thesame procedure without the terpolymer sample The amountof metal ions taken up by the terpolymer in the presenceof a given electrolyte can be calculated from the differencebetween the actual titration reading and that of the blankreading

(ii) Estimation of Rate of Metal Ion Uptake as a Function ofTime In order to estimate the time required to reach thestate of equilibriumunder the given experimental conditionsa series of experiments of the type described above werecarried out in which the metal ion taken up by the chelatingresinswas determined from time to time at room temperature(in the presence of 25mL of 1M NaNO

3solution) It was

assumed that under the given conditions the state of equilib-rium was established within 24 h The rate of metal uptake isexpressed as percentage of the amount of metal ions taken upafter a certain time related to that at the state of equilibriumand it can be defined by the following relationship Thepercentage amount of metal ions taken up at different timeis defined as

Percentage of metal ion taken up at equilibrium

= (Amount of metal ion adsorbed (after 1 h)

times (Amount of metal ion adsorbed at equilibrium

(after 24 h) )minus1) times 100(5)

Using this expression the amount of metal adsorbed byterpolymer after specific time intervals was calculated andexpressed in terms of percentage metal ion adsorbedThis experiment was performed using 01M metal nitrate


Tran

smitt

ance

()

Wavenumber (cmminus1)

45

60

75

90

105

T

4000 3500 3000 2500 2000 1750 1500 1250 1000 750 500

326163

300124

298581

297038

295109

289130

283536

281414

274856

272927

270806

261547

258263

235509

233965

158742

134824

128652

126916

123251

120744

100491

94899

88398

80045

Figure 2 FT-IR spectra of4-ASAUF terpolymer

solution of Fe3+ Cu2+ Ni2+ Co2+ Hg2+ Zn2+ Cd2+ andPb2+

(iii) Evaluation of the Distribution of Metal Ions at DifferentpH The distribution of each one of the eight metal ionsthat is Fe3+ Cu2+ Ni2+ Co2+ Hg2+ Zn2+ Cd2+ and Pb2+between the polymer phase and the aqueous phase wasdetermined at room temperature and in the presence of1M NaNO

3solution The experiments were carried out as

described above at different pH valuesThe distribution ratio119863 is defined by the following relationship [20]

119863 =Amount of metal ion on resinAmount of metal ion in solution

timesVolume of solution (mL)

Weight of resin (g)

Metal ion adsorbed (uptake) by the resin

= (119885119883

119884)2

0025

(6)

where ldquo119885rdquo is the difference between actual experimentreading and blank reading ldquo119883rdquo gram is the amount of metalion in 2mL 01M metal nitrate solution before uptake andldquo119884rdquo gram of metal ion in 2mL of metal nitrate solution afteruptake

3 Results and Discussion

31 Physicochemical Properties The moisture content of the4-ASAUF terpolymer resin is 34 The moisture content

2 14 036 58 7910 120575ppmChemical shift (ppm)

Figure 3 1H-NMR spectrum of 4-ASAUF terpolymer

of commercial resins (cationic form) is 43ndash53 for IRC-5075 (weak acid active group and COOminus) and 42ndash50 forIRC-84 (weak acid active group and COOminus) Hence theterpolymer had low moisture content The value of truedensity of the resin is 1113 gcm3 The true density of acommercial resin generally lies between 110 and 150 gcm3Hence the result found is in close agreement with the valuesfor commercial resins The void volume fraction of theterpolymerwas 0780Thevoid volume fraction aids diffusionof exchangeable ions on the resin and hence increases therate of exchange of ions The sodium exchange capacity of4-ASAUF terpolymer resin was 326mmol gminus1 dry resinsThis may be because of the high value of void volumefraction and also because of the presence of carboxylic acid(ndashCOOH) amine (ndashNH

2) andhydroxyl (minusOH) groups in the

resin The results from determination of the physicochem-ical properties of 4-ASAUF terpolymer resin are given inTable 1


Table 1 Physiochemical properties and elemental analysis data of 4-ASAUF terpolymer

Terpolymer Monomer empiricalformula

Empirical formulaweight Properties Value Elemental analysis ()

C H N

4-ASAUF C10H11N3O4 23721

Moisture () 34 plusmn 025

5042 448 1713Solids () 966 plusmn 025

True density (dry resin) gcm3 1113 plusmn 005

Void volume fraction 0780 plusmn 0015

Na+ exchange capacity(mmol gminus1 dry resin) 326 plusmn 010

Table 2 IR frequencies of 4-ASAUF terpolymer

Observed bandfrequencies (cmminus1) Vibrational mode Expected band frequencies (cmminus1)

33510 b st minusOH (phenolic) 3200ndash340030012 st w ndashNHndash (amino) gt300028913 m st ndashCH2ndash stretching methylene bridge 2800ndash295014506ndash15404 m gtC=Clt in aromatics 1400ndash160012691 st Carboxylic acid ndashCOOH 1250ndash130015874 st ArndashNH2 (amine) 1560ndash1640120744 sh m CndashO str in phenol 12008004 sh w8488 sh w Pentasubstituted benzene ring 800ndash950

Sh sharp b broad st strong m medium and w weak

32 Elemental Analysis The yield of resin was found to be85 Composition of terpolymer was obtained on the basisof elemental analysis data and was found to be in goodcorrelation to that of calculated values as given in Table 1

4 Spectral Studies of 4-ASAUF Terpolymer

41 FT-IR Spectra The FTIR-spectrum of 4-ASAUF terpoly-mer is represented in Figure 2 and the data is reported inTable 2 Broad band appeared at 328163 cmminus1 which maybe assigned to the stretching vibration of the phenolic ndashOHgroups exhibiting intermolecular hydrogen bonding [21 22]The presence of a weak peak at 30012 cmminus1 describes thendashNHndash in urea moiety which might be present in terpolymerchain [22] The broad band appearing in the spectrum at34104 cmminus1 is assigned to the hydroxyl group of ndashCOOHpresent in the aromatic ring and involves intramolecularhydrogen bonding with the ndashNH of ArndashNH

2[23] This

band seems to be merged with the band arising from ndashNHstretching vibrations of the ArndashNH

2group and this is

further confirmed by the ndashNH bending vibrations appearingat 15874 cmminus1 [24] A sharp and weak peak obtained at28913 cmminus1 indicates the presence of stretching vibrations ofmethylene group (ndashCH

2ndash) in the copolymer chain [22 25]

A medium band displayed between 14506 and15404 cmminus1may be due to stretching vibration of gtC=Clt in aromaticsBroad and strong bands were displayed at 126916 cmminus1for confirming the presence of gtC=O stretching vibrationof carboxylic acid group in the terpolymer chain [22]

gtC=O stretch in phenol is represented at 12074 cmminus1The presence of pentasubstitution of aromatic ring [22] isrecognized from the weak bands appearing in the range80046ndash84888 cmminus1

42 1119867-NMR Spectra 1H-NMR spectral data is given inTable 3 and spectrum is presented in Figure 3 Spectrarevealed different patterns of peaks since each of them pos-sesses a set of protons having different proton environment Asignificant downfield in chemical shift of proton of phenolicndashOH group observed at 120575 = 47 ppm is due to intermediateproton exchange reaction of phenolic ndashOH group [26ndash28] Aweak singlet is observed at 120575 = 75 amp 120575 = 81 ppm and is dueto ortho- and metaprotons of phenol respectively In ureamoiety the singlet observed in the regions 120575 = 71 and 120575 =72 is due to two CH

2ndashNHndashC=O and singlet observed in the

region 120575 = 39 ppm is due to methylene proton of ArndashCH2ndash

NH A broad singlet observed at 120575 = 38 ppmmay be assignedto proton of ArndashNH

2 Singlet observed at 120575 = 270 ppm and

120575 = 82 ppm is due to the proton of ArndashCH2and ArndashCOOH

respectively [22 26]

43 13119862-NMR Spectra The 13C-NMR spectrum of 4-ASAUFterpolymer is shown in Figure 4 and observed chemical shiftis assigned on the basis of the literature [21 26] The C

1

to C6of the aromatic ring shows the peaks at 1134 1378

1401 1162 1146 and 1572 ppm respectively and the peaksthat appeared at 773 ppm are assigned to the methylenecarbon of ArndashCH

2ndashNH linkage [19]The peaks that appeared


Table 3 1H-NMR spectral data of 4-ASAUF terpolymer

Nature of protons assigned Expected chemical shift (120575) ppm Observed chemical shift (120575) ppm of copolymer1H phenolic ndashOH (S) 35ndash9 471H ArndashH (S) 65ndash9 75 and 812H ArndashNH2 (S) 32ndash6 381H ArndashCOOH (S) 10ndash13 821H CH2ndashNHndashC=O (S) 5ndash8 71 and 722H ArndashCH2ndashNH in Urea moiety (S) 25ndash35 392H NHndashCH2 (S) 15ndash35 270S stand for singlet

50 3090 70110130 10150190 170210

Chemical shift (ppm)ppm

Figure 4 13C NMR spectrum of 4-ASAUF terpolymer

Figure 5 SEM image of 4-ASAUF terpolymer

at 1764 ppm are due to the ndashC=O of the ArndashCOOH andpeaks at 1631 amp 384 ppm are assigned to C=O of urea moietyand carbon of NHndashCH

2[29] The results are obtained from

spectral analysis the structure of the terpolymer resin wasclearly elucidated

44 SEM Analysis The typical microphotograph at 2000magnification from SEM of 4-ASAUF is shown in Figure 5The SEM image shows the surface future of the sampleThe image of the 4-ASAUF is clearly indicative of a looselyclose packed structure with high porosity or voids The voidspresented in the terpolymer ligands may be responsible forthe swelling behavior and reactivity of active sites buriedin the polymer matrix and also responsible for exchangeof metal ion The image also showed a transition statebetween the amorphous and crystalline states Howevermore predominantly the terpolymer is amorphous becauseof the polycondensation reaction [29]

45 Ion-Exchange Properties The ion-exchange properties ofthe given terpolymer resin were studied by batch equilibriumtechnique developed by DeGeiso et al [30] and Gregoret al [31] This technique was used to study ion-exchangeproperties of 4-ASAUF terpolymer resin and results arepresented in Tables 4ndash6 Eight metal ions Fe3+ Cu2+ Ni2+Co2+ Hg2+ Zn2+ Cd2+ and Pb2+ in the form of aqueousmetal nitrate solution were usedThe ion-exchange study wascarried out using three experimental variables such as (a)electrolyte and its ionic strength (b) uptake time and (c)pH of the aqueous medium Among these three variablestwo were kept constant and only one was varied at a time toevaluate its effect on metal uptake of the polymer similar tothe earlier coworkers [4 19]

(i) Determination of Metal Uptake in the Presence of FourDifferent Electrolytes and Their Different Concentrations Weexamined the influence of nitrate (NO

3

minus) chloride (Clminus)chlorate (ClO

4

minus) and sulfate (SO4

2minus) at various concen-trations on the equilibrium of metal-resin interaction Theaim of this study is to investigate the effect of the variouselectrolytes with different concentrations on the amountof the metal ions taken up by terpolymer sample whichmight be used in the purification of waste solution Theresults are presented in Table 4 and chelate formation bythe 4-ASAUF terpolymer is shown in Figure 6 This revealsthe fact that the amount of metal ions taken up by agiven amount of terpolymer depends on the nature andconcentration of the electrolyte present in the solutionGenerally as concentration of the electrolyte increases theionization decreases and number of ligands (negative ionsof electrolyte) decreases in the solution which forms thecomplex with less number of metal ions and therefore morenumbers of ions may be available for adsorption on terpoly-mer Hence on increasing concentration uptake of metalions may be increased which is the normal trend But thetrend is different in different electrolytes and their differentconcentrations due to the formation of more or less stablecomplexes of electrolyte ligand or terpolymer withmetal ions(see Figure 7)

If electrolyte ligand-metal ion complex is weaker thanpolymer-metal ion chelates the more numbers of metal ionscan form complexwith polymer hence uptake ofmetal ion ismore But if this complex is stronger than polymer-metal ion


Table 4 Evaluation of the effect of different electrolytes and their concentrations on the uptake of 4-ASAUF terpolymer resins

Metal ion Electrolyte (molL) pH Weight of metal uptake (mmol gminus1) in the presence ofNaNO2 Na2SO4 NaCl NaClO4

Fe3+

001

25

114 211 122 10005 164 153 184 122010 221 133 233 156050 272 111 286 178100 321 042 348 218

Cu2+

001

45

111 277 121 074005 142 222 171 112010 173 176 226 149050 21 121 268 174100 274 083 31 210

Hg2+

001

45

082 171 11 084005 124 121 165 112010 154 10 232 152050 200 069 286 184100 235 025 324 218

Cd2+

001

50

039 182 10 084005 076 141 131 114010 114 100 155 139050 145 076 188 159100 173 043 210 174

Co2+

001

50

117 191 076 072005 142 128 10 11010 177 094 122 142050 210 074 156 184100 234 056 184 21

Zn2+

001

50

034 154 092 074005 081 122 111 094010 126 11 154 141050 154 077 186 177100 220 052 230 194

Ni2+

001

50

121 226 118 121005 143 242 146 146010 186 221 20 176050 226 159 235 223100 263 111 262 241

Pb2+

001

60

042 143 085 050005 077 112 096 076010 117 084 122 11050 152 052 141 127100 178 036 159 153

chelates more numbers of metal ions form strong complexwith electrolyte ligand which make metal uptake capacitylower by polymer

In the presence of nitrate (NO3

minus) chloride (Clminus) andchlorate (ClO

4

minus) the uptake of Fe3+ Cu2+ Ni2+ Co2+Hg2+ Zn2+ Cd2+ and Pb2+ ions increases with increasing

concentration of the electrolyte whereas in the presence ofsulfate (SO

4

2minus) ions the amount of the above-mentionedions taken up by the terpolymer decreases with increasingconcentration of the electrolyte [19]

The ratio of physical core structure of the resin is signif-icant in the uptake of different metal ions by the terpolymer


OH

NH2 NH2

n

OH

HOOC

HN

HN

On

HN

HN

O

COOH

M

H2O

H2O

middot middotmiddot middot

Figure 6 Chelate structure of the 4-ASAUF terpolymer resin

Electrolyte solution + metal ion solution + polymer

Electrolyte ligand-metal ion chelates Polymer-metal ion chelates

Figure 7

The rate ofmetal ion uptake for NO3

minus Clminus ClO4

minus and SO4

2minus

electrolytes at various concentrations follows the order asFe3+ gt Cu2+ asymp Ni2+ gt Co2+ asymp Hg2+ asymp Zn2+ gt Cd2+ asymp Pb2+

The amount of metal ion uptake by the 4-ASAUF terpoly-mer resin is found to be higher when comparing to the othercopolymer resins [2 4 13 20] The uptake of metal ions bythe terpolymer resin was calculated by use of the formula andexpressed in mmol gminus1

Metal ion adsorbed (uptake) by resin

= (119883 minus 119884)119885mmol gminus 1(7)

where ldquo119885rdquo mL is the difference between actual experimentalreading and blank reading ldquo119883rdquo mg is metal ion in the 2mL01M metal nitrate solution before uptake ldquo119884rdquo mg is metalion in the 2mL 01M metal nitrate solution after uptake

By using this equation the uptake of variousmetal ions byresin can be calculated and expressed in terms of millimoleper gram of the terpolymer Thus the metal intake of resinwas analyzed by mass balance calculation

(ii) Estimation of Rate of Metal Ion Uptake as a Function ofTimeTherate ofmetal adsorptionwas determined to find outthe shortest period of time for which equilibrium could beachieved while operating as close to equilibrium conditionsas possible As shaking time increases the terpolymer getsmore time for adsorption hence uptake increases The dataof dependence of the rate of metal ion uptake on the natureof the metal ions is shown in Table 5 The rate refers to thechange in the concentration of the metal ions in the aqueoussolution which is in contact with the given terpolymer Theresults show that the rate of metal uptake may depend uponthe nature of the metal ions and their ionic sizeThus the rateof metal ion uptake follows the order

Metal ion (Ionic size) Fe3+ (055) gt Cu2+ (057) asympNi2+ (069) gtCo2+ (090) asympHg2+ (090) asymp Zn2+ (090)gt Cd2+ (110) asymp Pb2+ (119)

The sequence of rate of metal ion uptake indicates thatthe rate is directly proportional to the size of the metalion For example Fe3+ has more charges and small sizestherefore equilibrium is attained within three hours whileother four transition ions Cu2+ Ni2+ Co2+ Hg2+ and Zn2+have nearly equal cationic size having the same chargestherefore requiring 5 h to attain equilibrium while Cd2+and Pb2+ have large atomic size therefore requiring 6 h toattain equilibriumThe trend is in well agreement with earlierworkers [4 19 32 33]

(iii) Evaluation of the Distribution of Metal Ions at DifferentpH The effect of pH on the metal binding capacity ofthe synthesized terpolymers shows that relative amount ofmetal ion adsorbed by the terpolymer resin increases withincreasing pHof themedium (Table 6)The studywas carriedfrom pH 15 to 65 to prevent absorption or hydrolysis orprecipitation of the metal ions at higher pH The data onthe distribution ratio as a function of pH indicates that thedistribution of each metal between the polymers phase andaqueous phase increases with increasing pH of the mediumThe magnitude of increase however is different for differentmetal cations

The highest working pH is 3 in Fe3+ ions because abovethis pH Fe3+ was found to be absorbed in the resin and ithas lower distribution ratio since Fe3+ forms complex withligand of electrolyte which shows crowding effectThis sterichindrance maybe lowers the distribution ratio of Fe3+ ionCu2+ andNi2+ have higher distribution ratio over pH range of25 to 65 which may be due to the less steric hindrance Thusthe value of distribution ratio for given pH depends uponthe nature and stability of chelatesrsquo formation for particular


Table 5 Comparison of the rates of metal (M) ionsa uptake by 4-ASAUF terpolymer resin

Metal ion pH Percentage of metal ion uptakeb at different times (h)1 2 3 4 5 6 7

Fe3+ 25 46 72 97 mdash mdash mdash mdashCu2+ 45 12 32 465 625 93 mdash mdashHg2+ 45 16 29 44 62 85 mdash mdashCd2+ 5 13 225 355 56 76 95 mdashCo2+ 5 14 325 47 715 87 mdash mdashZn2+ 5 45 27 42 62 71 mdash mdashNi2+ 5 5 195 42 715 88 mdash mdashPb2+ 6 6 185 385 72 775 89 mdasha[M(NO3)2] = 01molL volume = 2mL NaNO3 = 10molL and volume = 25mL room temperaturebMetal ion uptake = (amount of metal ion absorbed times 100)amount of metal ion absorbed at equilibrium

Table 6 Distribution ratio Da of various metal ionsb as function of the pH by 4-ASAUF terpolymer resin

Metal ion pH Distribution ratio of metal ion at different pH15 2 25 3 35 4 5 6 65

Fe3+ 25 6235 9850 18855 3980 mdash mdash mdash mdash mdashCu2+ 45 mdash mdash 4250 4575 5038 8554 14826 62030 102632Hg2+ 45 mdash mdash 2837 7136 8254 29677 35268 38945 54234Cd2+ 5 mdash mdash 14224 15542 21121 26642 33384 44145 61642Co2+ 5 mdash mdash 2222 3132 5433 6979 11645 24223 32288Zn2+ 5 mdash mdash 2230 3882 4780 7374 12270 23663 29275Ni2+ 5 mdash mdash 068 1783 5233 10942 26642 54836 10253Pb2+ 6 mdash mdash 1365 2140 2716 3626 5516 12470 23242aD = weight (in mg) of metal ions taken up by 1 g of terpolymerweight (in mg) of metal ions present in 1mL of solutionb[M(NO3)2] = 01molL volume = 2ml NaNO3 = 10molL and volume = 25mL time 24 h (equilibrium state) at room temperature

metal ion [4 19 33] In the case of Cd2+ and Pb2+ purelyelectrostatic factors are responsible The ion uptake capacityof Cd2+ is lower owing to the large size of its hydrated ionthan that of Cu2+The steric influence of the amine group andhydroxyl group in 4-ASAUF resin is probably responsible fortheir observed low binding capacities for various metal ionsThe higher value of distribution ratio for Cu2+ andNi2+ at pH25 to 65 may be due to the formation of most stable complexwith chelating ligands Therefore the copolymer under studyhas more selectivity of Cu2+ and Ni2+ ions in the range of pH25 to 65 than other ions which form rather weak complexwhile from pH 15 to 3 the polymer has more selectivityof Fe3+ ions The order of distribution ratio of metal ionsmeasured in pH range 15 to 65 is found to be Fe3+ gt Cu2+ gtNi2+ gtHg2+ gt Zn2+ gt Co2+ gt Pb2+ gt Cd2+[4 19 33]

The 4-ASAUF terpolymer resin is a cation-exchangeresin and in cation-exchange resin the equilibrium may beexpressed in terms ofmass action law and the relative amountof metal ions in the resin phase is determined by the relativeconcentrations of these ions in the bulk of the solution

(resin OHminus)H+ + M+ (in solution) rarr (resin OHminus)M+ + H+ (in solution)119870 = [H+] [(resin OHminus) M+][(resin OHminus) H+] [H+]

Equilibrium constant (119870) of this type is useful for comparingthe relative affinities for a resin towards various ions Thecations are arranged in an affinity scale according to thenumerical value of119870 For the metal ions under investigationthe relative affinity is Fe3+ gt Cu2+ asymp Ni2+ gt Cd2+ asymp Hg2+ gtCo2+ asymp Zn2+ asymp Pb2+

The strength of electrolyte and dielectric constant alsoaffects the metal distribution or accumulation of resin

5 Conclusion

The metal complexes taken in the present study are pHdependent and each has a definite pH for optimum chelationa useful property to employ a particularmetal to be separatedfrom a solution using this terpolymer The surface of theterpolymer resin was found to bemore amorphous than crys-talline in nature clearly indicated by void volume fractionand sodium exchange capacity of the synthesized resin forion-exchange applications Synthesis of targeted terpolymer(4-ASAUF) has been achieved and the structure is confirmedby various spectral studies which are supported by the resultsobtained from elemental analysis


Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgments

The authors wish to express their sincere thanks to Dr GM Deshmukh Director In-Charge Laxminarayan Instituteof Technology RTM Nagpur University Nagpur for theconstant encouragement and supportTheywould also like tothank SAIF Punjab University Chandigarh for carrying outspectral analysis and University Grant Commission (UGC)for their financial support

References

[1] D Prabhakaran andM S Subramanian ldquoA new chelating sorb-ent for metal ion extraction under high saline conditionsrdquoTalanta vol 59 no 6 pp 1227ndash1236 2003

[2] S Nabi A Alim A Islam and M Amjad ldquoColumn chromato-graphic separation of metal ions on 1-(2-pyridylazo)-2-naptholmodified Amberlite IR-120 resinrdquo Journal of Separation Sciencevol 28 no 18 pp 2463ndash2467 2005

[3] M M Jadhao L J Paliwal and N S Bhave ldquoIon-exchangeproperties of 221015840-dihydroxybiphenylmdashureamdashformaldehydeterpolymer resinsrdquo Desalination vol 247 no 1ndash3 pp 456ndash4652009

[4] M Karunakaran and C Magesh ldquoThermal and ion-exchangestudies on chelating terpolymer resins derived from o cresolurea formaldehyderdquo Arabian Journal of Chemistry vol 4 no 3pp 339ndash348 2011

[5] C Magesh C T Vijayakumar and M Karunakaran ldquoAnthran-ilic acid-urea-formaldehyde terpolymer resin and their ion-exchange propertiesrdquo International Journal of Chemistry andApplications vol 2 no 1 pp 21ndash32 2010

[6] R N Singru W B Gurnule V A Khati A B Zade and JR Dontulwar ldquoEco-friendly application of p-cresol-melamine-formaldehyde polymer resin as an ion-exchanger and its electri-cal and thermal studyrdquo Desalination vol 263 no 1ndash3 pp 200ndash210 2010

[7] M E Mahmoud I M M Kenawy M A H Hafez and RR Lashein ldquoRemoval preconcentration and determination oftrace heavy metal ions in water samples by AAS via chemi-cally modified silica gel N-(1-carboxy-6-hydroxy) benzylidene-propylamine ion exchangerrdquo Desalination vol 250 no 1 pp62ndash70 2010

[8] M J Orell G D Pizarro O G Marambio and K E GeckelerldquoNovel hydrogels based on itaconic acid and citraconic acidsynthesis metal ion binding and swelling behaviorrdquo Journal ofApplied Polymer Science vol 113 no 1 pp 104ndash111 2009

[9] S S Rahangdale A B Zade and W B Gurnule ldquoChelationion exchange properties of 2 4-dihydroxyacetophenone-biuret-formaldehyde terpolymer resinrdquo E-Journal of Chemistry vol 6no 3 pp 835ndash843 2009

[10] M V Tarase W B Gurnule and A B Zade ldquoIon exchangeproperties of a terpolymer resin derived from 2 4-dihydroxy-benzaldehyde oxamide and formaldehyderdquo E-Journal of Chem-istry vol 6 no 3 pp 639ndash650 2009

[11] R N Singru and W B Gurnule ldquoChelation ion-exchangestudy of copolymer resin derived from 8-hydroxyquinoline 5-sulphonic acid oxamide and formaldehyderdquo Journal of AppliedPolymer Science vol 116 no 6 pp 3356ndash3366 2010

[12] W B Gurnule and D B Patle ldquoMetal ion binding properties ofa copolymer resin synthesis characterization and its applica-tionsrdquo Polymer Bulletin vol 66 no 6 pp 803ndash820 2011

[13] W B Gurnule H D Juneja and L J Paliwal ldquoIon-exchangeproperties of a salicylic acid-melamine-formaldehyde terpoly-mer resinrdquo Reactive and Functional Polymers vol 50 no 2 pp95ndash100 2002

[14] S S Butoliya A B Zade and W B Gurnule ldquoTer-polymer resin viii chelation ion-exchange properties of24-dihydroxybenzophenone-oxamide-formaldehyde terpoly-mer resinsrdquo Journal of Applied Polymer Science vol 113 no 1pp 1ndash9 2009

[15] M A R Ahamed R S Azarudeen M Karunakaran and A RBurkanudeen ldquoSynthesis characterization metal ion bindingcapacities and applications of a terpolymer resin of anthranilicacidsalicylic acidformaldehyderdquo Iranian Polymer Journal vol19 no 8 pp 635ndash646 2010

[16] R S Azarudeen M A R Ahamed and A R BurkanudeenldquoChelating terpolymer resin synthesis characterization and itsion-exchange propertiesrdquoDesalination vol 268 no 1ndash3 pp 90ndash96 2011

[17] R Manavalan and M M Patel ldquoChelation ion-exchangeprop-erties of salicylic acidthioureatrioxane terpolymersrdquoDieMakromolekulare Chemie vol 184 no 4 pp 717ndash723 2003

[18] A Vogel Text Book of Quantitative Chemical Analysis Long-man London UK 5th edition 1989

[19] R S Azarudeen and A R Burkanudeen ldquoSorption investiga-tion on the removal of metal ions from aqueous solutions usingchelating terpolymer resinrdquo Research on Chemical Intermedi-ates vol Volume 38 no 9 pp 1255ndash2173 2012

[20] W B Gurnule P K Rahangdale L J Paliwal and R B KharatldquoSynthesis characterization and ion-exchange properties of4-hydroxyacetophenone biuret and formaldehyde terpolymerresinsrdquoReactive and Functional Polymers vol 55 no 3 pp 255ndash265 2003

[21] K Nakanishi Infrared Absorption Spectroscopy PracticalGolden Day INC and Nankodo Tokyo Japan 1967

[22] A I Vogel Text Book of Practical Organic Chemistry LongmanScientific and Technical London UK 1989

[23] A R Burkanudeen R S Azarudeen M A R Ahamedand W B Gurnule ldquoKinetics of thermal decomposition andantimicrobial screening of terpolymer resinsrdquo Polymer Bulletinvol 67 no 8 pp 1553ndash1568 2011

[24] R M Silverstein and G C Bassler Spectrometric Identificationof Organic CompoundsWiley NewYork NYUSA 2nd edition1967

[25] W Kemp Organic Spectroscopy Macmillan Press Hong Kong1975

[26] R M Silverstein G C Bassler and T C Morrill SpectrometricIdentification of Organic Compounds Wiley Singapore 5thedition 1991

[27] R K Samal B K Senapati and T B Behuray ldquoSynthesis andcharacterization of aniline-doped mixed copolymer resins IIrdquoJournal of Applied Polymer Science vol 62 no 4 pp 655ndash6601996

[28] W B Gurnule P K Rahangadale R B Kharat and L J PaliwalldquoSynthesis and characterization of copolymer derived from 2-hydroxyacetophenone oxamide and formaldehyderdquo Progress in


Crystal Growth and Characterization of Materials vol 45 no1-2 pp 155ndash160 2002

[29] E Pretsch P Buhlmann and C Afflolter Structure Determi-nation of Organic Compounds Springer New York NY USA2000

[30] RCDeGeiso LGDonaruma andEA Tomic ldquoChelation ionexchange properties of a salicylic acid-formaldehyde polymerrdquoAnalytical Chemistry vol 34 no 7 pp 845ndash847 1962

[31] H P Gregor M Tasfer L Cilardl and E I Becker ldquoChelate ionexchange resinsrdquo Industrial and Engineering Chemistry vol 44no 12 pp 2834ndash2839 1952

[32] P E P Michael J M Barbe H D Juneja and L J PaliwalldquoSynthesis characterization and thermal degradation of 8-hydroxyquinoline-guanidine-formaldehyde terpolymerrdquo Euro-pean Polymer Journal vol 43 no 12 pp 4995ndash5000 2007

[33] S S Rahangdale A B Zade and W B Gurnule ldquoTerpolymerresin II synthesis characterization and ion-exchangeproperties of 24-dihydroxyacetophenone-dithiooxamide-formaldehyde terpolymersrdquo Journal of Applied Polymer Sciencevol 108 no 2 pp 747ndash756 2008

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CorrosionInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of



CeramicsJournal of


CompositesJournal of

NanoparticlesJournal of



International Journal of

Biomaterials


NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014


CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research



MetallurgyJournal of


BioMed Research International

MaterialsJournal of


Nano

materials


Journal ofNanomaterials


HO

HOOC NH2

H2 N NH2

OO

H Hn

n

2n

Δ120∘C5h

OH

HOOC

NH2

HNH

N

O

n

4-Aminosalicylic acidUrea Formaldehyde

4-ASA-U-F-I terpolymer resin

+ +

2N HCl

Figure 1 Chemical reaction of 4-ASAUF terpolymer

terpolymer resins Ahamed et al [15] synthesized a terpoly-mer from anthranilic acid salicylic acid and formaldehydeand evaluated its ion-exchange properties toward toxic metalions Similarly Azarudeen et al synthesized terpolymersfrom 8-hydroxyquinoline anthranilic acid and formalde-hyde and determined their chelating capacity toward specificmetal ions [16]

The present paper explored the newly synthesized ter-polymer resin 4-aminosalicylic acid-urea-formaldehyde (4-ASAUF) in the light of its physiochemical spectral andchelating ion-exchange study

2 Experimental

21 Starting Materials 4-Aminosalicylic acid is of analyticalgrade purity which is purchased from Acros Chemicals Bel-gium Urea formaldehyde (37) metal nitrates indicatorsand disodium salt of ethylenediaminetetraacetic acid (EDTA)were purchased fromSD FineChemicals India All the usedsolvents like N N-dimethylformamide dimethyl sulfoxidetetrahydrofuran acetone and diethyl ether were procuredfromMerck India Double distilled water was used for all theexperiments

22 Synthesis 4-ASAUF terpolymer was prepared by con-densing 4-aminosalicylic acid (153 g 01mol) and urea (06 g01mol) with formaldehyde (75mL 02mol) in presence of2N HCl as a catalyst in the molar proportion of 1 1 2 at120∘C in an oil bath for 5 h The dark reddish brown resinoussolid product was immediately removed filtered repeatedlywashed with cold-distilled water dried in air and powderedwith the help of mortar and pestle The product obtained

was extracted with diethyl ether to remove excess of 4-aminosalicylic acid-formaldehyde copolymer which mightbe present along with 4-ASAUF terpolymer Dried resinsample was dissolved in 8 NaOH regenerated using 1 1HClwater (vv) with constant stirring and filtered Thisprocess was repeated twice Resulting terpolymer samplewas washed with boiling water and dried in a vacuumat room temperature Purified terpolymer resin was finelyground to pass through 300-mesh size sieve and kept ina vacuum over silica gel [17] The purity of newly synthe-sized and purified terpolymer resin sample has been testedand confirmed by thin layer chromatography techniqueDimethyl sulfoxide (DMSO) was used as a solvent fordeveloping chromatogram and was allowed to run for about20 minutes when the chromatogram was exposed to iodinechamber then we get single colour spot for resin sampleThis indicates that the synthesized and purified polymerresin sample has no impurities and is used for furtherstudies only after the confirmation of 100 purity of thesample The chemical reaction of above synthesis is given inFigure 1

23 Physiochemical Studies Terpolymer was subject to ele-mental analysis for carbon hydrogen and nitrogen on PerkinElmer 2400 Elemental Analyzer Physiochemical studies suchas moisture content percentage solids void volume fractiontrue density and sodium exchange capacity were evaluated inaccordance with reported procedures [18]

24 Moisture Content The purified 1 g of terpolymer wastaken in a previously weight Petri dish The Petri dish withterpolymer sample was then dried in a vacuum oven at 105∘C



Moisture content


after drying)



before drying)




(119882119908minus119882119901119908) + (119882

119901minus119882) (2)







(3)





(4)







3 NaClO

4




3solution) It was








Tran

smitt

ance

()


45

60

75

90

105

T

4000 3500 3000 2500 2000 1750 1500 1250 1000 750 500

326163

300124

298581

297038

295109

289130

283536

281414

274856

272927

270806

261547

258263

235509

233965

158742

134824

128652

126916

123251

120744

100491

94899

88398

80045








Weight of resin (g)


= (119885119883

119884)2

0025

(6)













C H N

4-ASAUF C10H11N3O4 23721


5042 448 1713Solids () 966 plusmn 025











2[23] This


2group and this is













1







50 3090 70110130 10150190 170210










3


4







Fe3+

001

25

114 211 122 10005 164 153 184 122010 221 133 233 156050 272 111 286 178100 321 042 348 218

Cu2+

001

45

111 277 121 074005 142 222 171 112010 173 176 226 149050 21 121 268 174100 274 083 31 210

Hg2+

001

45

082 171 11 084005 124 121 165 112010 154 10 232 152050 200 069 286 184100 235 025 324 218

Cd2+

001

50

039 182 10 084005 076 141 131 114010 114 100 155 139050 145 076 188 159100 173 043 210 174

Co2+

001

50

117 191 076 072005 142 128 10 11010 177 094 122 142050 210 074 156 184100 234 056 184 21

Zn2+

001

50

034 154 092 074005 081 122 111 094010 126 11 154 141050 154 077 186 177100 220 052 230 194

Ni2+

001

50

121 226 118 121005 143 242 146 146010 186 221 20 176050 226 159 235 223100 263 111 262 241

Pb2+

001

60

042 143 085 050005 077 112 096 076010 117 084 122 11050 152 052 141 127100 178 036 159 153




4



4




OH

NH2 NH2

n

OH

HOOC

HN

HN

On

HN

HN

O

COOH

M

H2O

H2O





Figure 7


minus Clminus ClO4

minus and SO4

2minus
























5 Conclusion





Acknowledgments


References











































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials





Moisture content


after drying)



before drying)




(119882119908minus119882119901119908) + (119882

119901minus119882) (2)







(3)





(4)







3 NaClO

4




3solution) It was








Tran

smitt

ance

()


45

60

75

90

105

T

4000 3500 3000 2500 2000 1750 1500 1250 1000 750 500

326163

300124

298581

297038

295109

289130

283536

281414

274856

272927

270806

261547

258263

235509

233965

158742

134824

128652

126916

123251

120744

100491

94899

88398

80045








Weight of resin (g)


= (119885119883

119884)2

0025

(6)













C H N

4-ASAUF C10H11N3O4 23721


5042 448 1713Solids () 966 plusmn 025











2[23] This


2group and this is













1







50 3090 70110130 10150190 170210










3


4







Fe3+

001

25

114 211 122 10005 164 153 184 122010 221 133 233 156050 272 111 286 178100 321 042 348 218

Cu2+

001

45

111 277 121 074005 142 222 171 112010 173 176 226 149050 21 121 268 174100 274 083 31 210

Hg2+

001

45

082 171 11 084005 124 121 165 112010 154 10 232 152050 200 069 286 184100 235 025 324 218

Cd2+

001

50

039 182 10 084005 076 141 131 114010 114 100 155 139050 145 076 188 159100 173 043 210 174

Co2+

001

50

117 191 076 072005 142 128 10 11010 177 094 122 142050 210 074 156 184100 234 056 184 21

Zn2+

001

50

034 154 092 074005 081 122 111 094010 126 11 154 141050 154 077 186 177100 220 052 230 194

Ni2+

001

50

121 226 118 121005 143 242 146 146010 186 221 20 176050 226 159 235 223100 263 111 262 241

Pb2+

001

60

042 143 085 050005 077 112 096 076010 117 084 122 11050 152 052 141 127100 178 036 159 153




4



4




OH

NH2 NH2

n

OH

HOOC

HN

HN

On

HN

HN

O

COOH

M

H2O

H2O





Figure 7


minus Clminus ClO4

minus and SO4

2minus
























5 Conclusion





Acknowledgments


References











































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




Tran

smitt

ance

()


45

60

75

90

105

T

4000 3500 3000 2500 2000 1750 1500 1250 1000 750 500

326163

300124

298581

297038

295109

289130

283536

281414

274856

272927

270806

261547

258263

235509

233965

158742

134824

128652

126916

123251

120744

100491

94899

88398

80045








Weight of resin (g)


= (119885119883

119884)2

0025

(6)













C H N

4-ASAUF C10H11N3O4 23721


5042 448 1713Solids () 966 plusmn 025











2[23] This


2group and this is













1







50 3090 70110130 10150190 170210










3


4







Fe3+

001

25

114 211 122 10005 164 153 184 122010 221 133 233 156050 272 111 286 178100 321 042 348 218

Cu2+

001

45

111 277 121 074005 142 222 171 112010 173 176 226 149050 21 121 268 174100 274 083 31 210

Hg2+

001

45

082 171 11 084005 124 121 165 112010 154 10 232 152050 200 069 286 184100 235 025 324 218

Cd2+

001

50

039 182 10 084005 076 141 131 114010 114 100 155 139050 145 076 188 159100 173 043 210 174

Co2+

001

50

117 191 076 072005 142 128 10 11010 177 094 122 142050 210 074 156 184100 234 056 184 21

Zn2+

001

50

034 154 092 074005 081 122 111 094010 126 11 154 141050 154 077 186 177100 220 052 230 194

Ni2+

001

50

121 226 118 121005 143 242 146 146010 186 221 20 176050 226 159 235 223100 263 111 262 241

Pb2+

001

60

042 143 085 050005 077 112 096 076010 117 084 122 11050 152 052 141 127100 178 036 159 153




4



4




OH

NH2 NH2

n

OH

HOOC

HN

HN

On

HN

HN

O

COOH

M

H2O

H2O





Figure 7


minus Clminus ClO4

minus and SO4

2minus
























5 Conclusion





Acknowledgments


References











































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials







C H N

4-ASAUF C10H11N3O4 23721


5042 448 1713Solids () 966 plusmn 025











2[23] This


2group and this is













1







50 3090 70110130 10150190 170210










3


4







Fe3+

001

25

114 211 122 10005 164 153 184 122010 221 133 233 156050 272 111 286 178100 321 042 348 218

Cu2+

001

45

111 277 121 074005 142 222 171 112010 173 176 226 149050 21 121 268 174100 274 083 31 210

Hg2+

001

45

082 171 11 084005 124 121 165 112010 154 10 232 152050 200 069 286 184100 235 025 324 218

Cd2+

001

50

039 182 10 084005 076 141 131 114010 114 100 155 139050 145 076 188 159100 173 043 210 174

Co2+

001

50

117 191 076 072005 142 128 10 11010 177 094 122 142050 210 074 156 184100 234 056 184 21

Zn2+

001

50

034 154 092 074005 081 122 111 094010 126 11 154 141050 154 077 186 177100 220 052 230 194

Ni2+

001

50

121 226 118 121005 143 242 146 146010 186 221 20 176050 226 159 235 223100 263 111 262 241

Pb2+

001

60

042 143 085 050005 077 112 096 076010 117 084 122 11050 152 052 141 127100 178 036 159 153




4



4




OH

NH2 NH2

n

OH

HOOC

HN

HN

On

HN

HN

O

COOH

M

H2O

H2O





Figure 7


minus Clminus ClO4

minus and SO4

2minus
























5 Conclusion





Acknowledgments


References











































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials






50 3090 70110130 10150190 170210










3


4







Fe3+

001

25

114 211 122 10005 164 153 184 122010 221 133 233 156050 272 111 286 178100 321 042 348 218

Cu2+

001

45

111 277 121 074005 142 222 171 112010 173 176 226 149050 21 121 268 174100 274 083 31 210

Hg2+

001

45

082 171 11 084005 124 121 165 112010 154 10 232 152050 200 069 286 184100 235 025 324 218

Cd2+

001

50

039 182 10 084005 076 141 131 114010 114 100 155 139050 145 076 188 159100 173 043 210 174

Co2+

001

50

117 191 076 072005 142 128 10 11010 177 094 122 142050 210 074 156 184100 234 056 184 21

Zn2+

001

50

034 154 092 074005 081 122 111 094010 126 11 154 141050 154 077 186 177100 220 052 230 194

Ni2+

001

50

121 226 118 121005 143 242 146 146010 186 221 20 176050 226 159 235 223100 263 111 262 241

Pb2+

001

60

042 143 085 050005 077 112 096 076010 117 084 122 11050 152 052 141 127100 178 036 159 153




4



4




OH

NH2 NH2

n

OH

HOOC

HN

HN

On

HN

HN

O

COOH

M

H2O

H2O





Figure 7


minus Clminus ClO4

minus and SO4

2minus
























5 Conclusion





Acknowledgments


References











































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials






Fe3+

001

25

114 211 122 10005 164 153 184 122010 221 133 233 156050 272 111 286 178100 321 042 348 218

Cu2+

001

45

111 277 121 074005 142 222 171 112010 173 176 226 149050 21 121 268 174100 274 083 31 210

Hg2+

001

45

082 171 11 084005 124 121 165 112010 154 10 232 152050 200 069 286 184100 235 025 324 218

Cd2+

001

50

039 182 10 084005 076 141 131 114010 114 100 155 139050 145 076 188 159100 173 043 210 174

Co2+

001

50

117 191 076 072005 142 128 10 11010 177 094 122 142050 210 074 156 184100 234 056 184 21

Zn2+

001

50

034 154 092 074005 081 122 111 094010 126 11 154 141050 154 077 186 177100 220 052 230 194

Ni2+

001

50

121 226 118 121005 143 242 146 146010 186 221 20 176050 226 159 235 223100 263 111 262 241

Pb2+

001

60

042 143 085 050005 077 112 096 076010 117 084 122 11050 152 052 141 127100 178 036 159 153




4



4




OH

NH2 NH2

n

OH

HOOC

HN

HN

On

HN

HN

O

COOH

M

H2O

H2O





Figure 7


minus Clminus ClO4

minus and SO4

2minus
























5 Conclusion





Acknowledgments


References











































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




OH

NH2 NH2

n

OH

HOOC

HN

HN

On

HN

HN

O

COOH

M

H2O

H2O





Figure 7


minus Clminus ClO4

minus and SO4

2minus
























5 Conclusion





Acknowledgments


References











































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials















5 Conclusion





Acknowledgments


References











































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials






Acknowledgments


References











































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials

















CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials



Documents

Research Article Removal of Toxic Metal Ions from Water ...downloads.hindawi.com/archive/2014/873520.pdf · the - ASAUF terpolymer resin was studied by using batch equilibrium method