Research Article Sorption Efficiency of a New Sorbent - downloads

Hindawi Publishing CorporationJournal of ChemistryVolume 2013 Article ID 980825 10 pageshttpdxdoiorg1011552013980825

Research ArticleSorption Efficiency of a New Sorbent towards Cadmium(II)Methylphosphonic Acid Grafted Polystyrene Resin

Nacer Ferrah1 Omar Abderrahim1 Mohamed Amine Didi1 and Didier Villemin2

1 Laborator o Searation and urication echnolog eartment o Chemistr lemcen Universit o 11 lemcen Algeria2 Laboratoire de Chimie Moleacuteculaire et ioorganique UMR CNRS 6507 INC3M FR 3038 ENSICAEN and Universiteacute de Caen14050 Caen France

Correspondence should be addressed to Omar Abderrahim abderrahimomaryahoofr

Received 8 June 2012 Accepted 20 August 2012

Academic Editor Julie Hardouin

Copyright copy 2013 Nacer Ferrah et al is is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

A new chelating polymeric sorbent has been developed using polystyrene resin graedwith phosphonic acid Aer characterizationby FTIR and elementary analysis the new resin has been investigated in liquid-solid extraction of cadmium(II)e results indicatedthat phosphonic resin could adsorb Cd(II) ion effectively from aqueous solution e adsorption was strongly dependent on thepH of the medium and the optimum pH value level for better sorption was between 32 and 52 e inuence of other analyticalparameters including contact time amount of resinmetal ion concentration and the presence of some electrolytes was investigatede maximum uptake capacity of Cd(II) ions was 379mgsdotgminus1 graed resin at ambient temperature at an initial pH value of 50e overall adsorption process was best described by pseudo second-order kinetic When Freundlich and Langmuir isothermswere tested the latter had a better t with the experimental data Furthermore more than 92 of Cd(II) could be eluted by using10molsdotLminus1 HCl in one cycle

1 Introduction

Some heavy metals like Cd Hg As Pb and so forth haveno biological function and are detrimental to the organismseven at a very low concentration [1] ey originate fromnatural sources such as rocks metalliferous minerals andanthropogenic inputs from agriculture metallurgy energyproduction microelectronics mining sewage sludge andwaste disposal [2 3] A concentration higher than theprescribed limit may lead to the formation of nonspeciccomplex compounds in the cell which leads to toxic effectse major sources of cadmium release into the environ-ment are electroplating smelting plastics batteries paintpigments and mining and rening processes [4]

In this industrialized era the presence of cadmium ionsin aqueous water ways has become a serious environmentalproblem and many methods such as ion exchange surfacecomplexation diffusion through the solid reverse osmosismembrane separation chemical oxidation or reduction co-precipitation and control of sample-specic surface area havebeen employed to remove it from wastewater [5ndash8] It reveals

that surface complexation is the most important mechanismwith possibly ion exchange and solid diffusion also contribut-ing to the overall sorption process [9] e use of solid phaseextraction has been proved to be more advantageous in theview of their total insolubility in aqueous phase low rate ofphysical degradation high sorption capacity for metal ionslow organic solvent inventory and good exibility in workingconditions [9]

In the present work we described the synthesis andcharacterization of polystyrene resin graedwith phosphonicacid is resin was applied as a new sorption materialfor cadmium(II) extraction in batch process e effects ofanalytical parameters adsorption kinetic isotherm studiesand desorption process were investigated

2 Experimental

21 Instrumentation Infrared spectra were recorded on aPerkin-Elmer ATR spectrometer A Bruker Advance 400spectrometer was used for 13C and 31P MAS NMR analysis

2 Journal of Chemistry

Elemental analyses were carried out on a ermoquest CHPanalyzer Visible spectra were measured using Perkin-Elmer-Lambda 800 UV-Vis spectrophotometer pH measurementswere taken on a potentiometer Consort C831

22 Reagents Chloromethyl styrene-divinylbenzene copoly-mer (S-3 DVB) was precursor of Amberlite resin giedby Rohm and Haas Company Triethylphosphite hydro-bromic acid acetic acid oxalic acid sodium acetate sodiumsulphate sodium hydroxide (80) dichloromethane sul-phuric acid 95ndash97 acetone and 4-(2-pyridylazo)resorcinol(PAR) were provided from Fluka Cadmium sulphate (99)sodium nitrate sodium acetate ethylenediaminetetraaceticacid (EDTA) ammonium carbonate and sodium chloridewere obtained from Merck Hydrochloride acid (36) andnitric acid (65) were purchased from Reidel-de-Haen

Stock solution (10molsdotLminus1) of cadmium(II) was pre-pared by dissolving her sulphate salt in distilled waterSolutions of lower concentrations were prepared by thedilution of stock solution

23 Synthesis of Polystyrene Resin Anchored with PhosphonicAcid e sorbent phosphonic acid graed polystyrene resinbeads was synthesized using the Arbuzov reaction [10ndash13](Figure 1) In the rst step aer washing the Merrield resinbeads with acetone and dried under vacuumMerrield resin3 (2034 g) was reacted with 35mL of triethylphosphite(excess) e reaction mixture was reuxed for 4 hours (hrs)e phosphonate graed polystyrene resin beads obtainedwere puried from the excess of reactants by washingrepeatedly with water and acetone e resin beads weredried under vacuum (1426 g) In the second step a bromidehydrogen acid (33mL)was added on the phosphonate graedpolystyrene resin beads (1000 g) and vigorously shaken ona vibrating table under reux for 3 hrs In order to removeunreacted reagents the resulting resin beads were lteredwashed repeatedly with distilled water and dichloromethaneand dried in vacuum (862 g)

24 Characterization Studies e structure and purity of thenal complexing agent were identied and characterized byMAS NMR of 31P and 13C spectroscopy FTIR measurementand elemental microanalysiseMASNMR spectra showedthe expected signals due to the polystyrene skeleton andphosphonic units as matched to the proposed structure(Figure 1)

31P MAS NMR is 178 ppm 13C MAS is 364 ppm(CH2ndashP) 12775 1301 1371 and 1385 (CHndashCH) ppmepresence of phosphonic acid was conrmed by the appear-ance of absorption at 3000ndash2850 cmminus1 (OH) 1124 cmminus1

(P=O) 1037 cmminus1 (120584120584as PndashOH) and 941 cmminus1 (120584120584s PndashOH)and by the disappearance of P-OEt band at 1023 cmminus1 [14]e experimental CHP analysis data () of phosphonic acidgraed polystyrene resin is C 8531 H 934 P 235

25 Adsorption Technique Batch technique was applied toinvestigate the different parametric effects on the sorption

process where a certain weight 0030 g (m) of the graedresin was mixed with a certain volume 5mL (V) of Cd(II)aqueous solutions and equilibrated by shaking in a shakerwith speed 250 round perminute (rpm) at room temperaturee ratio of mV (60 gsdotLminus1) was kept constant for all theexperimentse solutionswere separated aer a certain time(t) and the concentrations of Cd(II) in the aqueous phasewere determined before and aer extraction spectropho-tometrically with PAR at pH 55 [15] e absorbance ofPAR-cadmium(II) complex was measured at 520 nm eextraction yield () was determined using the followingequation

Extraction yield () = 100765310076531198621198620 minus 1198621198621198901198901198621198620

10076691007669 100 (1)

where 1198621198620 and 119862119862119890119890 denote the initial and equilibrium concen-trations of Cd(II) in the aqueous phase (molsdotLminus1)

26 Kinetic and Sorption Isotherms In order to quantify theextent of uptake in adsorption kinetics three simple kineticmodels were tested [16]

(1) Lagergrens pseudo rst-order rate equation ex-pressed as follows

log 10076491007649119902119902119890119890 minus 11990211990211990511990510076651007665 = log 119902119902119890119890 minus1198961198961

2303119905119905 (2)

where 1198961198961 (minminus1) is the equilibrium rate constant ofthe pseudo rst-order adsorption 119902119902119905119905 and 119902119902119890119890 are theamount of Cd(II) adsorbed (mgsdotgminus1) at time t andequilibrium time (180min) respectively e valuesof 1198961198961 and 119902119902119890119890 can be obtained from the intercept andslope of the plot of (log(119902119902119890119890 minus 119902119902119905119905)) versus (t2303)

(2) A pseudo second-order adsorption kinetic rate equa-tion is

119905119905119902119902119905119905

=1

11989611989621199021199022119890119890+

119905119905119902119902119890119890 (3)

where 1198961198962 (gsdotmgminus1sdotminminus1) is the rate constant of thepseudo second-order adsorptione values of 1198961198962 and119902119902119890119890 were obtained from the intercept and slope of theplot of (t119902119902119905119905) versus t

(3) A second-order adsorption kinetic rate equation is1

119902119902119890119890 minus 119902119902119905119905=1119902119902119890119890

+ 1198961198963119905119905 (4)

where 1198961198963 (gsdotmgminus1sdotminminus1) is the rate constant of thesecond-order adsorption e values of 1198961198963 and 119902119902119890119890 canbe obtained from the intercept and slope of the plot of(1(119902119902119890119890 minus 119902119902119905119905)) versus t

Sorption isotherms for Cd(II) were determined over theconcentration range of 10minus3 to 10minus2molsdotLminus1 e amount ofions sorbed by phosphonic resin 119902119902119905119905 (mgsdotgminus1) was calculatedby the following relationship

119902119902119905119905 10076531007653mgg10076691007669 = 100764910076491198621198620 minus 11986211986211990511990510076651007665 sdot 119881119881 sdot

119872119872119898119898 (5)

Journal of Chemistry 3

Cl

Merrifield resin

PS-DVB PO

PS-DVB PO

PS-DVB

Phosphonic acid

(OCH2CH3)2CH2+ P(OEt)3

Reflux 4 hrs Reflux 3 hrsCH2 CH2

+ HBr (OH)2

F 1 Scheme for synthesis of methylene phosphonic acid graed polystyrene resin beads

where 119862119862119905119905 is the nal concentrations at certain time t ofthe ions in the liquid phase (molsdotLminus1) V is the volume ofthe aqueous phase (5mL) m is the weight of graed resin(0030 g) and M (112411 gsdotmolminus1) is the atomic weight ofcadmium

3 Results and Discussion

31 Effect of pH Changes in the pH of the medium areone of the most important factors affecting the concen-tration and metal recovery procedure which is related tothe formation of soluble metal complexes and subsequentlytheir stabilities in aqueous solutions It is well known thatsurface charge of adsorbent can be modied by changingthe pH of the solution and the chemical species in thesolution depends on this parameter [17] According to thechemical equilibrium diagram for cadmium in aqueoussolution obtained by the MEDUSA program the speciesCd(OH)2 precipitates at pH higher than 8 and the con-centration of Cd2+ ions in solution decreases (ProgramMEDUSA Make Equilibrium Diagrams Using Sophisti-cated Algorithms httphometelfortnlcheaqs) Under theexperimental conditions of the present paper Cd2+ was themajor species present in solution

In order to optimize the pH for maximum removalexperiments were conducted in the pH range from 177 to515 at ambient temperature 4 hrs equilibration time and10mmolsdotLminus1 metal ion concentration Figure 2 shows theinuence of pH in sorption process of Cd(II) by modiedresin As can be seen from Figure 2 the sorption increasesquickly with increasing pH values from 18 to 32 eprogressive decrease in the retention of metal ions at lowpH is due to [17] the following (i) the competition ofthe hydrogen ion with the metal ions for binding to thephosphonic acid group (PndashOH) (ii) the oxygen atoms (P=O)are more protonated and hence they are less available tocoordinate with the cadmium (iii) the competition betweenthe excess of H+ ions in the medium and positively chargedcationic species present in solution (iv) as pH is increasedthere is a decrease of positive surface charge which results inthe lower coulombic repulsion of the adsorbing metal ionsConsequently the number of moles of Cd(II) removal maydecrease at low pH [18] e observed reduction in the levelof metal ion removal from solution by the sorbent indicatesthat the interaction between the Cd(II) ions and the sorbentis an ion exchange process

e data reveals that the highest extraction yield valueis recorded at the pH range 32ndash52 is is attributed tothe presence of free lone pair of electrons on the oxygen ofphosphoryl (P=O) group and deprotonated oxygen atoms

2 3 4 50

20

40

60

80

Initial pH

Ext

ract

ion

yie

ld (

)

F 2 Effect of the initial pH of the aqueous solution on theretention of Cd(II) by the functionalized resin C 0 = 10mmolsdotLminus1m = 0030 g V = 5mL and contact time = 4 hrs

which are suitable ligands for coordinationwith the cadmiumions [19 20]is cation exchange process can be representedby the following general reaction [6]

ResinndashPndashOH + Cd2+ ⟶ ResinndashPndashOndashCd+ +H+ (6)

In order to make further approaching of the functionalgroup of resin and Cd(II) the spectra of resin before andaer Cd(II) is sorbed are compared It is found that thecharacteristic sorption peak of the bond P=0 (at 1124 cmminus1)disappears on the whole which shows that the formationof the coordination bond between oxygen atom and Cd(II)weakens the stretch vibration and causes the peak to shito the lower frequency e characteristic sorption peak ofPndashOH (941 cmminus1) is weakened and the new characteristicsorption peak of (minusPO3

2minus) is formed [21] which shows thatH+ and Cd2+ has been exchanged All those changes resultfrom the formation of a complex compound

32 Effect of Contact Time e rate of loading of Cd(II) ontothe graed polystyrene resin was determined for two concen-trations of Cd(II) 05 and 10mmolsdotLminus1 by shaking 5mL ofCd(II) with 0030 g of resin in an Erlenmayer ask at ambienttemperature for 2 4 10 15 30 60 120 180 and 200minFigure 3 shows that the initial concentration of Cd(II) has animportant effect on the rate of sorption For all the sorptionexperiments the amount of cadmium ions sorbed onto thegraed resin increased quickly with time and then slowlyreached equilibrium aer 180min e equilibrium times inwhich the polymer attains 50 saturation with Cd(II) (half


0 50 100 150 200

0

20

40

60

80

100

Time (min)

Rem

oval

()

or u

ptak

e (m

gmiddotgminus1

)

F 3 Effect of contact time on the sorption of Cd(II) on thefunctionalized resin from aqueous Cd(II) solutions at two differentconcentrations (1198621198620 and 119862119862

prime0) 1198621198620 = 05mmolsdotLminus1 -percent Cd(II)

removal () -uptake (q) mgsdotgminus1 119862119862prime0 = 10mmolsdotLminus1 -percent

Cd(II) removal () -uptake (q) mgsdotgminus1 V = 5mL m = 0030 ginitial pH = 50

time 11990511990512) are lt24min and lt130min for initial Cd(II) con-centration = 05mmolsdotLminus1 and 10mmolsdotLminus1 respectivelye amounts of cadmium metal ions sorbed at equilibrium(119902119902119890119890) at [Cd(II)] = 05mmolsdotLminus1 and 10mmolsdotLminus1 respec-tively are 902 and 1793mgsdotgminus1

33 Rate of Kinetics Adsorption In this study batch sorptionkinetics of Cd(II) ions at two different concentrations 1198621198620 =05 and 119862119862prime

0 = 10mmolsdotLminus1 with the functionalized polymerhave been studied e different values of constants fromthe slopes and intercepts of linear plots of (2) (gure notshown) (3) (shown in Figure 4) and (4) (gure not showed)are summarized in Table 1 As seen fromTable 1 the obtainedcorrelation coefficient for the pseudo second-order model(gt 099) was better than those of the rst-order and second-order models for the adsorption of Cd(II) at the two con-sidered concentrations suggesting that the pseudo second-order model was more suitable to describe the adsorptionkinetics of phosphonic acid graed on polystyrene resin forCd(II) especially at the lower concentration (05mmolsdotLminus1)is suggests that the rate limiting step may be chemicalsorption or chemisorption involving valency forces throughsharing or exchange of electrons between sorbent (containingO atoms) and sorbate [16] Similar results have been observedin the adsorption of Cd(II) by lignocellulosic sorbent [22]and onto kra and organosolv lignins [23] e values of thesecond-order rate constants (1198961198962) were found to decrease from16442 to 000262 gsdotmgminus1sdotminminus1 as the initial concentrationincreased from 05 to 10mmolsdotLminus1 showing the process tobe highly concentration dependent which is consistent withstudies reported [24]

0 40 80 120 160 2000

4

8

12

16

Time (min)

[Cd(II)]0 = 1 mmolmiddot Lminus 1

[Cd(II)]0 = 05 mmol middot Lminus 1

F 4 Plots for the adsorption of Cd(II)m = 0030 g V = 5mLand initial pH = 50

0 0002 0004 0006 0008 0010

20

40

60

80

100

Yield extraction ()

Yield

extra

ction

()

Uptake (mgmiddot gminus 1)

or up

take

(mgmiddot

gminus1)

[Cd(II)] (mol middot Lminus 1)

F 5 Effect of the initial concentration of Cd(II) on the uptakeand the extraction yieldm = 0030 g V = 5mL equilibrium time =180min and initial pH = 50

34 Sorption Capacity e retention capacity of function-alized resin was determined by equilibrating 0030 g of theresin with 5mL of cadmium(II) ion solutions at differentconcentrations (0110minus2ndash1010minus2molsdotLminus1) under optimumpH e experimental capacity obtained is 379mgsdotgminus1 ofpolymer (Figure 5) At similar conditions this sorbentpossesses very high extraction ability towards Eu(III) andUO2

2+ cations metals the extraction capacities are 1225 and1522mg gminus1 respectively [25 26] is result is attributed tothat phosphonic acid derivatives are more selective towardslanthanides elements [27]


T 1 Models rate constants for Cd(II) sorption kinetics by the functionalized resin

Models Parameters [Cd(II)]0 = 05mmolsdotLminus1 [Cd(II)]0 = 10mmolsdotLminus1

First-order rate

119902119902cal (mgsdotgminus1) 220 1243119902119902exp (mgsdotgminus1) 902 17931198961198961 (minminus1) 0050 0020

119903119903 0800 0880

Pseudo second-order rate

119902119902cal (mgsdotgminus1) 909 200119902119902exp (mgsdotgminus1) 902 1793

1198961198962 (gsdotmgminus1sdotminminus1) 16442 000262119903119903 0999 0991

Second-order rate



35 Adsorption Isotherm e adsorbed amounts of Cd(II)on resin have been determined as a function of the metalconcentration in the supernatant at the equilibrium stateand ambient temperature e Langmuir treatment (7) isbased on the assumption that [28] (i) maximum adsorptioncorresponds to saturated monolayer of adsorbate moleculeson the adsorbent surface (ii) the energy of adsorption isconstant and (iii) there is no transmigration of adsorbate inthe plane of the surface One has

119862119862119890119890119902119902119890119890

=119862119862119890119890119902119902119898119898

+1

119902119902119898119898119870119870119871119871 (7)

where 119902119902119898119898 and 119870119870119871119871 are Langmuir constants related to adsorp-tion capacity and energy of adsorption respectively elinear plot of 119862119862119890119890119902119902119890119890 versus 119862119862119890119890 shows that adsorption obeysLangmuir adsorption model (Figure 6) e correlationcoecient for the linear regression ts of the Langmuir plotwas found to be 0995 119902119902119898119898 and 119870119870119871119871 determined from theLangmuir plot were found to be 382mgsdotgminus1 and 00441Lsdotmolminus1 respectively We note that the capacity of sorptiondeducted aer Langmuir model application is similar to thiscalculated experimentally (379mgsdotgminus1)

e essential characteristics of Langmuir isotherm can beexpressed in terms of a dimensionless constant separationfactor or equilibrium parameter 119877119877119871119871 which is dened by

119877119877119871119871 =1

1 + 1198701198701198711198711198621198620 (8)

e value of 119877119877119871119871 indicates the type of the isotherm to beeither unfavorable (119877119877119871119871 gt 1) linear (119877119877119871119871 = 1) favorable (0 lt119877119877119871119871 lt 1) or irreversible (119877119877119871119871 = 0) As shown in Table 2 thevalues of 119877119877119871119871 are ranged from 09999 to 09995 in the initialCd(II) ions concentrations 001ndash0001molsdotLminus1 ese valuesindicated that the adsorption process is favorable [29 30]

e Freundlich equation was also applied to the adsorp-tion e Freundlich equation is basically empirical but isoen useful as a means of data description It generally agreesquite well compared to Langmuir equation and experimental

2 4 6 8

0

5

10

15

20

25

()lowast10+5

10+3 (molmiddot Lminus1)

F 6 Langmuir plot for the adsorption of Cd(II) m = 0030 gV = 5mL initial pH = 50 and equilibrium time = 180min

data over a moderate range of adsorbate concentrations [28]e linearized Freundlich isotherm is represented by

log 119902119902119890119890 = log119870119870119865119865 +1119899119899log119862119862119890119890 (9)

A plot of log(119902119902119890119890) versus log119862119862119890119890 (gure not shown) is linearat only low concentrations of Cd(II) and the constants 119870119870119865119865and 119899119899 were found to be 15474mgsdotgminus1and 0266 respectivelye correlation coecient for the linear regression ts of theFreundlich plot was found to be 0830

36 Diffusion Study e adsorption of cadmium(II) on thegraed resin from cadmium sulphate solutions at two dif-ferent initial metal concentrations was studied as a functionof time at ambient temperature e adsorption onto ionexchange resin must be considered as a liquid-solid phasereaction which includes several steps [31] (i)e diffusion ofions from the solution to the resin surface (ii) the diffusionof ions within the solid resin and (iii) the chemical reactionbetween ions and functional groups of the resin


T 2 Equilibrium parameter 119877119877119871119871

1198621198620 molsdotLminus1 0001 0002 0004 0005 0006 0008 001119877119877119871119871 099995 099991 099982 099977 099973 099964 099955

T 3 e regression equations (119910119910) regression coefficients (119903119903)and diffusion coefficients (119863119863119903119903)

[Cd(II)] mmolsdotLminus1 Eq (10) Eq (11) Eq (13)

05119884119884 0106119905119905 00119905119905119905119905 00119905119905119905119905119903119903 0925 0932 0900

119863119863119903119903 10minus5 cm119905sdotminminus1 mdash 2485 mdash

10119884119884 006119905119905119905 001199050119905119905 001119905119905119905119903119903 0941 0951 0945


e adsorption of the metal is governed by the slowestof these processes e kinetic models and the rate equationsfor the above three cases have been establishede exchangeof ions can be described by the Nernst-Planck equationswhich apply to counter diffusion of two species in an almosthomogeneous media [17 31]

If the liquid lm diffusion controls the rate of exchangethe following relation can be used

minus ln (1 minus 119865119865) = 119896119896119905119905 (10)

If the cases of the diffusion of ions in the resin phasecontrolling process the equation used is

minus ln 100765010076501 minus 11986511986511990510076661007666 = 119896119896119905119905 (11)

Aer testing both mathematical models proposed forhomogeneous diffusion in the adsorption of Cd(II) onto theresin this is best tted when the metal uptake is the particlediffusion controlled and at time contact le30min (Figure 7)us the values of the adsorption rate constant regressionequations and regression coefficients of the diffusion ofCd(II) in the resin phase calculated from the slope of thestraight lines (Figure 7) are summarized in Table 3

In both (10) and (11) k is the kinetic coefficient or rateconstant k is dened by expression (12)

119896119896 =119863119863119903119903120587120587

119905

1199031199031199050 (12)

where 119863119863119903119903 is the diffusion coefficient in the resin phase and1199031199030 is the average radius of resin particle e values of thediffusion coefficient in the resin phase calculated from (12)are also given in Table 3

When the adsorption of metal ion involves mass trans-fer accompanied by chemical reaction the process can beexplained by the moving boundary model [32] is modelassumes a sharp boundary that separates a completely reactedshell from an unreacted core and that advances from thesurface toward the center of the solid with the progressionof adsorption In this case the rate equation is given by

3 minus 3(1 minus 119865119865)1199053 minus 119905119865119865 = 119896119896119905119905 (13)

0 10 20 30 40 50 60

0

1

2

3

Time (min)

minusln(1minus2 )



F 7 Plot of (11) for Cd(II) adsorption on graed resin m =0030 g V = 5mL and initial pH = 50

0 10 20 30 40 50 60

0

02

04

06

08

Time (min)

3minus3(1minus)23minus2



F 8 Plot of the moving boundary particle diffusion model forthe Cd(II) adsorption on graed resin m = 0030 g V = 5mL andinitial pH = 50

e graphical correlation in Figure 8 of (13) shows thatthe moving boundary particle diffusion model ts only theinitial adsorption on the graed resin e linear regressionanalyses of (13) are also given in Table 3

37 Effect of Electrolytes on Cd(II) Extraction As the sul-phates chlorides and acetate of alkali ions (Na+) frequentlyaccompany cadmium ions in industrial solutions it is worth-while to know if they affect the extraction process efficiency


0 01 02 03 04 05 06 07

20

40

60

80

100

Yiel

d ex

trac

tion

()

Na2SO4

CH3COONa

NaCl

Salt concentration (mol middot Lminus1)

F 9 Effect of Na2SO4 CH3COONa and NaCl salts concen-trations on the extraction of Cd(II) with graed resin m = 0030 g119881119881 119881 119881mL initial pH = 50 C 0 = 10mmolL and equilibriumtime 119881 180min

e inuence on the extraction of Cd(II) was studied at thevarying concentrations of NaCl Na2SO4 and CH3COONain aqueous solution from 01 to 07molsdotLminus1 e inuence ofthe concentration of those salts is shown in Figure 9

At Na2SO4 and NaCl concentrations between 01 and07molsdotLminus1 there is a negative trend on increasing electrolytesconcentrations e decrease in the extraction of Cd(II)may be due to the formation of more stable metal sulphateor chloride complexes which were nonextractable by thegraed resin [33 34]

e presence of CH3COONa does not become annoyinguntil a concentration of 04molsdotLminus1 At high concentrationit was found that the extraction yield drop from 100 to 75when the acetate concentration increases from 04molsdotLminus1 to07molsdotLminus1is effect is attributed to a competition betweenNa+ cations of added salt and Cd(II) in the formation ofbonds with the active sites of the resin [34]

38 Effect of Temperature on Sorption Temperature hastwo major effects on the sorption process Increasing thetemperature is known to increase the rate of the diffusionof the sorbate molecule across the external boundary layerand in the internal pores of the sorbent particle owing to adecrease in the velocity of the solution In addition changingthe temperature will change the equilibrium capacity of thesorbent for the particle sorbate e inuence of temperaturevariation was examined on the sorption of Cd(II) of xedconcentration 10 mmol Lminus1 onto graed resin using 180minof equilibration time and sorbent to aqueous phase ratio of0030 g 5mL from 293K to 333K

Experimental results (yield extraction) concerning theeffect of temperature on the Cd(II) sorption are shown inFigure 10 An increase in temperature results is an increase

290 300 310 320 33080

84

88

92

96

Yie

ld e

xtra

ctio

n (

)

Temperature (K)

F 10 Effect of temperature on the yield extraction of Cd(II) bythe functionalized resin C 0 = 10mmolsdotLminus1m = 0030 g V = 5mLinitial pH = 50 and equilibrium time = 180min

in metal ion sorption ere is about 15 increase in theyield sorption of Cd(II) sorbed on graed resin when thetemperature is raised from 293 to 333K Better sorption athigher temperatures may be either due to acceleration ofsome originally slow sorption steps or due to the enhancedmobility of Cd(II) ions from the solution to the functional-ized resin surface

39 ermodynamic Parameters In environmental engi-neering practice both energy and entropy factors must beconsidered in order to determine which process will occurspontaneously e Gibbs free energy change Δ1198661198660 is thefundamental criterion of spontaneity [35]

e apparent thermodynamic parameters Δ119867119867 and Δ119878119878 forthe sorption process were calculated from the slopes andintercepts of the linear variation of ln119870119870119889119889 versus 1T in Figure11 by

Ln119870119870119889119889 119881Δ119878119878119877119877

minusΔ119867119867119877119877119877119877

(14)

where R is the gas constant 8314 Jsdotmolminus1sdotKminus1 and T is theabsolute temperature in Kelvin e free energy (ΔG) for thesorption was calculated by

Δ119866119866 119881 Δ119867119867 minus 119877119877Δ119878119878119866 (15)

Further the thermodynamic equilibrium constant 119870119870119889119889in mLsdotgminus1 (16) obtained from the distribution constant wasused to compute the apparent thermodynamic parameters

119870119870119889119889 119881100764910076491198621198620 minus 11986211986211989011989010076651007665119881119881

119862119862119890119890119898119898119866 (16)

e calculated apparent thermodynamic parameters forsorption of Cd(II) onto functionalized resin are summarizedin Table 4

In the present work the Gibbs energy decrease in eachcase was responsible for imparting stability to the cadmium


T 4 ermodynamics parameters for sorption process of Cd(II) on functionalized resin

ΔH (kJsdotmolminus1) ΔS (Jsdotmolminus1sdotKminus1) ΔG (kJsdotmolminus1)mdash mdash 293 K 303 K 313 K 323 K 333 K+3553 +13334 minus357 minus490 minus624 minus757 minus890

0003 00031 00032 00033 00034

15

2

25

3

ln

(1 ) (Kminus 1)

F 11 Variation of log119870119870119889119889 with 1T for the sorption ofcadmium(II) onto the graed resin m = 0030 g [Cd(II)]0 =10mmolsdotLminus1 V = 5mL initial pH = 50 and contact time =180min

ions-functionalized resin sorption complexes e negativevalues of ΔG are due to the fact that the sorption processis spontaneous with high affinity of Cd(II) ions to thederivative of phosphonic acids However the negative valuesof ΔG decrease indicating that the spontaneous nature of thesorption of metal ions is inversely proportional to the tem-perature higher temperature favours the sorption processe positive value of ΔH conrms the endothermic natureof the sorption process Hence by increasing temperaturethe degree of sorptionexchange will increase Increasedtemperature will cause a rupturing of the hydration zoneformed around Cd(II) in mother liquid to a great extent anddirect interaction ofmetal ions with functional group of resin(decreasing in hydrated diameter) increasing diffusion forceby supplying partial ion-exchange activation energy increas-ing diffusion into the inner sections of the graed resin andsubsequently an increase in the degree of sorptionexchangee positive value of ΔS reected the affinity of the sorbentfor Cd(II) ions and conrms the increased randomness at thesolid-solution interface during sorption [36]

310 Elution Studies Adsorption and elution processesdepend on the solution pH erefore elution is possible bycontrolling the pHacid concentration of the solution Elu-tion of Cd(II) from loaded graed resin was carried out usingHCl solution at different concentrations (00 to 25molsdotLminus1)e contact time was maintained at 120min e resultsin Figure 12 show that percentage elution increased withincreasing acid concentration and a hydrochloric acidconcentration of 10molsdotLminus1 was found suitable to elute more

0 05 1 15 2 25

0

20

40

60

80

100

Elu

tio

n (

)

[HCl] (mol middot Lminus 1)

F 12 Effect of HCl concentration on the desorption of Cd(II)loaded on graed resin Loaded resin quantity 0030 g acid volume5mL and time contact 120min

than 92 of the Cd(II) from the functionalized resin in onecycle

4 Conclusion

e phosphonic acid graed on polystyrene resin was syn-thesized using the Arbuzov reaction and used as a supportmaterial for Cd(II) sorption in batch process e extractionefficiencywas determined as a function of various parameterssuch as time pH cadmium concentration and electrolyteseffecte experimental capacity obtained is 379mgsdotgminus1ekinetics of Cd(II) adsorption on functionalyzed resin followsthe Pseudo second-order rate e equilibrium isotherm forsorption of the investigated metal ions has been modelledsuccessfully using the Langmuir isotherme Cd(II) uptakeis best explained by a particle diffusion controlled processwhereas the moving boundary model only ts the initialadsorption on the phosphonic resin Various thermodynamicparameters such as ΔG ΔH and ΔS were calculated fromthe data e thermodynamics of Cd(II) ionsfunctionalizedresin system indicate a spontaneous and endothermic natureof the process

More than 92 of loaded Cd(II) on the graed resin canbe eluted with HCl 10molsdotLminus1 aer 120 minutes of shakingin one cycle

e results presented in this work reveal that polystyreneresin functionalized with phosphonic group is feasible for theremoval of cadmium cations from wastewater


Acknowledgments

e authors gratefully acknowledge the Rohm and HaasCompany for their generous gi of chloromethyl polystyreneand the Tassili Program no 10 MDU799 for their nancialsupport

References

[1] B Messner and D Bernhard ldquoCadmium and cardiovasculardiseases cell biology pathophysiology and epidemiologicalrelevancerdquo BioMetals vol 23 no 5 pp 811ndash822 2010

[2] C - Gilmour and G Riedel ldquoBiogeochemistry of trace metalsand metalloidsrdquo in EncyclopEdia of InlandWaters G E LikensEd pp 7ndash15 Elsevier Amsterdam e Netherlands 2009

[3] J Pandey and U Pandey ldquoMicrobial processes at the land-waterinterface and cross-domain causal relationships as inuencedby atmospheric deposition of pollutants in three freshwaterlakes in Indiardquo Lakes and Reservoirs vol 14 no 1 pp 71ndash842009

[4] VM Fthenakis ldquoLife cycle impact analysis of cadmium inCdTePVproductionrdquoRenewable and Sustainable Energy Reviews vol8 no 4 pp 303ndash334 2004

[5] 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

[6] A Corami S Mignardi and V Ferrini ldquoCadmium removalfrom single- and multi-metal (Cd+Pb+Zn+Cu) solutions bysorption on hydroxyapatiterdquo Journal of Colloid and InterfaceScience vol 317 no 2 pp 402ndash408 2008

[7] A Gaikwad ldquoe transport of metal ions through bersupported solid membranes in mixed solventsrdquo Fibers andPolymers vol 12 no 1 pp 21ndash28 2011

[8] O Abderrahim M A Didi B Moreau and D Villemin ldquoAnew sorbent for selective separation of metal polyethylen-imine methylenephosphonic acidrdquo Solvent Extraction and IonExchange vol 24 no 6 pp 943ndash955 2006

[9] K S - Rao M Mohapatra S Anand and P VenkateswarluldquoReview on cadmium removal from aqueous solutionsrdquo Inter-national Journal of Engineering Science and Technology vol 2no 7 pp 81ndash103 2010

[10] D Villemin B Moreau M Kaid and M A Didi ldquoRapidone-pot synthesis of alkane-120572120572120572120572 diylbisphosphonic acids fromdihalogenoalkanes under microwave irradiationrdquo PhosphorusSulfur and Silicon and the Related Elements vol 185 no 8 pp1583ndash1586 2010

[11] D Meziane J Hardouin A Elias E Gueacutenin and M Lecou-vey ldquoMicrowave michaelis-becker synthesis of diethyl phos-phonates tetraethyl diphosphonates and their total or par-tial dealkylationrdquo Heteroatom Chemistry vol 20 no 6 pp369ndash377 2009

[12] A N Pustam and S D Alexandratos ldquoEngineering selectivityinto polymer-supported reagents for transition metal ion com-plex formationrdquo Reactive and Functional Polymers vol 70 no8 pp 545ndash554 2010

[13] A Popa C M Davidescu P Negrea G Ilia A Katsaros andK D Demadis ldquoSynthesis and characterization of phosphonateesterphosphonic acid graed styrenemdashdivinylbenzene copoly-mer microbeads and their utility in adsorption of divalentmetal ions in aqueous solutionsrdquo Industrial and EngineeringChemistry Research vol 47 no 6 pp 2010ndash2017 2008

[14] M C Zenobi C V Luengo M J Avena and E H RuedaldquoAn ATR-FTIR study of different phosphonic acids in aqueoussolutionrdquo Spectrochimica ActamdashPart A vol 70 no 2 pp270ndash276 2008

[15] E Y Hashem ldquoSpectrophotometric studies on the simulta-neous determination of cadmium and mercury with 4-(2-pyridylazo)-resorcinolrdquo Spectrochimica ActamdashPart A vol 58no 7 pp 1401ndash1410 2002

[16] M F Elkady M M Mahmoud and H M Abd-El-RahmanldquoKinetic approach for cadmium sorption using microwavesynthesized nano-hydroxyapatiterdquo Journal of Non-CrystallineSolids vol 357 no 3 pp 1118ndash1129 2011

[17] M S Dzul Erosa T I Saucedo Medina R Navarro MendozaM Avila Rodriguez and E Guibal ldquoCadmium sorption onchitosan sorbents kinetic and equilibrium studiesrdquo Hydromet-allurgy vol 61 no 3 pp 157ndash167 2001

[18] V Araacutembula-Villazana M Solache-Riacuteos and M T OlguiacutenldquoSorption of cadmium from aqueous solutions at differenttemperatures by Mexican HEU-type zeolite rich tuffrdquo Journalof Inclusion Phenomena and Macrocyclic Chemistry vol 55 no3-4 pp 229ndash236 2006

[19] R Corteacutes-Martiacutenez V Martiacutenez-Miranda M Solache-Riacuteosand I Garciacutea-Sosa ldquoEvaluation of natural and surfactant-modied zeolites in the removal of cadmium from aqaeoussolutionsrdquo Separation Science and Technology vol 39 no 11pp 2711ndash2730 2004

[20] J I Daacutevila-Rangel M Solache-Riacuteos and V E Badillo-AlmarazldquoComparison of threeMexican aluminosilicates for the sorptionof cadmiumrdquo Journal of Radioanalytical and Nuclear Chemistryvol 267 no 1 pp 139ndash145 2005

[21] Z N Shu C H Xiong and X Wang ldquoAdsorption behaviorand mechanism of amino methylene phosphonic acid resin forAg(I)rdquo Transactions of Nonferrous Metals Society of China vol16 no 3 pp 700ndash704 2006

[22] W S Eun and R M Rowell ldquoCadmium ion sorption ontolignocellulosic biosorbent modied by sulfonation the originof sorption capacity improvementrdquo Chemosphere vol 60 no 8pp 1054ndash1061 2005

[23] H Harmita K G Karthikeyan and X Pan ldquoCopper and cad-mium sorption onto kra and organosolv ligninsrdquo BioresourceTechnology vol 100 no 24 pp 6183ndash6191 2009

[24] S Izanloo and H Nasseri ldquoCadmium removal from aqueoussolutions by ground pine conerdquo Iranian Journal of Environmen-tal Health Science amp Engineering vol 2 no 1 pp 33ndash42 2005

[25] O Abderrahim N Ferrah M A Didi and D Villemin ldquoAnew sorbent for europium nitrate extraction phosphonic acidgraed on polystyrene resinrdquo Journal of Radioanalytical andNuclear Chemistry vol 209 pp 267ndash275 2011

[26] N Ferrah O Abderrahim M A Didi and D Villemin ldquoSorp-tion efficiency of a new sorbent towards uranyl phosphonicacid graed Merrield resinrdquo Journal of Radioanalytical andNuclear Chemistry vol 289 no 3 pp 721ndash730 2011

[27] J Arichi G Goetz-Grandmont and J P Brunette ldquoSolventextraction of europium(III) from nitrate medium with 4-acyl-isoxazol-5-ones and 4-acyl-5-hydroxy-pyrazoles Effect of saltsand diluentsrdquo Hydrometallurgy vol 82 no 1-2 pp 100ndash1092006

[28] Q Hu Y Meng T Sun et al ldquoKinetics and equilibrium adsorp-tion studies of dimethylamine (DMA)onto ion-exchange resinrdquoJournal of Hazardous Materials vol 185 no 2-3 pp 677ndash6812011


[29] H K Boparai M Joseph and D M OrsquoCarroll ldquoKinetics andthermodynamics of cadmium ion removal by adsorption ontonano zerovalent iron particlesrdquo Journal of Hazardous Materialsvol 186 no 1 pp 458ndash465 2011

[30] S Suganthi and K Srinivasan ldquoPhosphorylated tamarind nutcarbon for the removal of cadmium ions from aqueous solu-tionsrdquo Indian Journal of Engineering andMaterials Sciences vol17 no 5 pp 382ndash388 2010

[31] D C K Ko J F Porter and G McKay ldquoFilm-pore diffusionmodel for the xed-bed sorption of copper and cadmium ionsonto bone charrdquoWater Research vol 35 no 16 pp 3876ndash38862001

[32] W Guan J Pan H Ou et al ldquoRemoval of strontium(II) ions bypotassium tetratitanate whisker and sodium trititanate whiskerfrom aqueous solution equilibrium kinetics and thermody-namicsrdquo Chemical Engineering Journal vol 167 no 1 pp215ndash222 2011

[33] Y Egozy ldquoAdsorption of cadmium and cobalt on montmoril-lonite as a function of solution compositionrdquo Clays and ClayMinerals vol 28 no 4 pp 311ndash318 1980

[34] I Ghodbane L Nouri O Hamdaoui and M Chiha ldquoKineticand equilibrium study for the sorption of cadmium(II) ionsfrom aqueous phase by eucalyptus barkrdquo Journal of HazardousMaterials vol 152 no 1 pp 148ndash158 2008

[35] P Senthil Kumar K Ramakrishnan S Dinesh Kirupha and SSivanesan ldquoermodynamic and kinetic studies of cadmiumadsorption from aqueous solution onto rice huskrdquo BrazilianJournal of Chemical Engineering vol 27 no 2 pp 347ndash3552010

[36] S Mustafa M Waseem A Naeem K H Shah T Ahmad andS Y Hussain ldquoSelective sorption of cadmium by mixed oxidesof iron and siliconrdquo Chemical Engineering Journal vol 157 no1 pp 18ndash24 2010

Submit your manuscripts athttpwwwhindawicom

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2013


Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom


Analytical ChemistryVolume 2013

ISRN Chromatography


Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawi Publishing Corporation httpwwwhindawicom Volume 2013

The Scientific World Journal

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2013


CatalystsJournal of

ISRN Analytical Chemistry


ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2013


Advances in

Physical Chemistry

ISRN Physical Chemistry


SpectroscopyInternational Journal of


ISRN Inorganic Chemistry



Journal of

Chemistry


Inorganic ChemistryInternational Journal of


International Journal ofPhotoenergy


Analytical Methods in Chemistry

Journal of

Volume 2013

ISRN Organic Chemistry



Journal of

Spectroscopy


Elemental analyses were carried out on a ermoquest CHPanalyzer Visible spectra were measured using Perkin-Elmer-Lambda 800 UV-Vis spectrophotometer pH measurementswere taken on a potentiometer Consort C831

22 Reagents Chloromethyl styrene-divinylbenzene copoly-mer (S-3 DVB) was precursor of Amberlite resin giedby Rohm and Haas Company Triethylphosphite hydro-bromic acid acetic acid oxalic acid sodium acetate sodiumsulphate sodium hydroxide (80) dichloromethane sul-phuric acid 95ndash97 acetone and 4-(2-pyridylazo)resorcinol(PAR) were provided from Fluka Cadmium sulphate (99)sodium nitrate sodium acetate ethylenediaminetetraaceticacid (EDTA) ammonium carbonate and sodium chloridewere obtained from Merck Hydrochloride acid (36) andnitric acid (65) were purchased from Reidel-de-Haen

Stock solution (10molsdotLminus1) of cadmium(II) was pre-pared by dissolving her sulphate salt in distilled waterSolutions of lower concentrations were prepared by thedilution of stock solution

23 Synthesis of Polystyrene Resin Anchored with PhosphonicAcid e sorbent phosphonic acid graed polystyrene resinbeads was synthesized using the Arbuzov reaction [10ndash13](Figure 1) In the rst step aer washing the Merrield resinbeads with acetone and dried under vacuumMerrield resin3 (2034 g) was reacted with 35mL of triethylphosphite(excess) e reaction mixture was reuxed for 4 hours (hrs)e phosphonate graed polystyrene resin beads obtainedwere puried from the excess of reactants by washingrepeatedly with water and acetone e resin beads weredried under vacuum (1426 g) In the second step a bromidehydrogen acid (33mL)was added on the phosphonate graedpolystyrene resin beads (1000 g) and vigorously shaken ona vibrating table under reux for 3 hrs In order to removeunreacted reagents the resulting resin beads were lteredwashed repeatedly with distilled water and dichloromethaneand dried in vacuum (862 g)

24 Characterization Studies e structure and purity of thenal complexing agent were identied and characterized byMAS NMR of 31P and 13C spectroscopy FTIR measurementand elemental microanalysiseMASNMR spectra showedthe expected signals due to the polystyrene skeleton andphosphonic units as matched to the proposed structure(Figure 1)

31P MAS NMR is 178 ppm 13C MAS is 364 ppm(CH2ndashP) 12775 1301 1371 and 1385 (CHndashCH) ppmepresence of phosphonic acid was conrmed by the appear-ance of absorption at 3000ndash2850 cmminus1 (OH) 1124 cmminus1

(P=O) 1037 cmminus1 (120584120584as PndashOH) and 941 cmminus1 (120584120584s PndashOH)and by the disappearance of P-OEt band at 1023 cmminus1 [14]e experimental CHP analysis data () of phosphonic acidgraed polystyrene resin is C 8531 H 934 P 235

25 Adsorption Technique Batch technique was applied toinvestigate the different parametric effects on the sorption

process where a certain weight 0030 g (m) of the graedresin was mixed with a certain volume 5mL (V) of Cd(II)aqueous solutions and equilibrated by shaking in a shakerwith speed 250 round perminute (rpm) at room temperaturee ratio of mV (60 gsdotLminus1) was kept constant for all theexperimentse solutionswere separated aer a certain time(t) and the concentrations of Cd(II) in the aqueous phasewere determined before and aer extraction spectropho-tometrically with PAR at pH 55 [15] e absorbance ofPAR-cadmium(II) complex was measured at 520 nm eextraction yield () was determined using the followingequation

Extraction yield () = 100765310076531198621198620 minus 1198621198621198901198901198621198620

10076691007669 100 (1)

where 1198621198620 and 119862119862119890119890 denote the initial and equilibrium concen-trations of Cd(II) in the aqueous phase (molsdotLminus1)

26 Kinetic and Sorption Isotherms In order to quantify theextent of uptake in adsorption kinetics three simple kineticmodels were tested [16]

(1) Lagergrens pseudo rst-order rate equation ex-pressed as follows

log 10076491007649119902119902119890119890 minus 11990211990211990511990510076651007665 = log 119902119902119890119890 minus1198961198961

2303119905119905 (2)

where 1198961198961 (minminus1) is the equilibrium rate constant ofthe pseudo rst-order adsorption 119902119902119905119905 and 119902119902119890119890 are theamount of Cd(II) adsorbed (mgsdotgminus1) at time t andequilibrium time (180min) respectively e valuesof 1198961198961 and 119902119902119890119890 can be obtained from the intercept andslope of the plot of (log(119902119902119890119890 minus 119902119902119905119905)) versus (t2303)

(2) A pseudo second-order adsorption kinetic rate equa-tion is

119905119905119902119902119905119905

=1

11989611989621199021199022119890119890+

119905119905119902119902119890119890 (3)

where 1198961198962 (gsdotmgminus1sdotminminus1) is the rate constant of thepseudo second-order adsorptione values of 1198961198962 and119902119902119890119890 were obtained from the intercept and slope of theplot of (t119902119902119905119905) versus t

(3) A second-order adsorption kinetic rate equation is1

119902119902119890119890 minus 119902119902119905119905=1119902119902119890119890

+ 1198961198963119905119905 (4)

where 1198961198963 (gsdotmgminus1sdotminminus1) is the rate constant of thesecond-order adsorption e values of 1198961198963 and 119902119902119890119890 canbe obtained from the intercept and slope of the plot of(1(119902119902119890119890 minus 119902119902119905119905)) versus t

Sorption isotherms for Cd(II) were determined over theconcentration range of 10minus3 to 10minus2molsdotLminus1 e amount ofions sorbed by phosphonic resin 119902119902119905119905 (mgsdotgminus1) was calculatedby the following relationship

119902119902119905119905 10076531007653mgg10076691007669 = 100764910076491198621198620 minus 11986211986211990511990510076651007665 sdot 119881119881 sdot

119872119872119898119898 (5)


Cl

Merrifield resin

PS-DVB PO

PS-DVB PO

PS-DVB

Phosphonic acid



+ HBr (OH)2







2 3 4 50

20

40

60

80

Initial pH

Ext

ract

ion

yie

ld (

)








0 50 100 150 200

0

20

40

60

80

100

Time (min)

Rem

oval

()

or u

ptak

e (m

gmiddotgminus1

)








0 40 80 120 160 2000

4

8

12

16

Time (min)




0 0002 0004 0006 0008 0010

20

40

60

80

100

Yield extraction ()

Yield

extra

ction

()


or up

take

(mgmiddot

gminus1)








First-order rate


119903119903 0800 0880




Second-order rate




119862119862119890119890119902119902119890119890

=119862119862119890119890119902119902119898119898

+1

119902119902119898119898119870119870119871119871 (7)



119877119877119871119871 =1

1 + 1198701198701198711198711198621198620 (8)



2 4 6 8

0

5

10

15

20

25

()lowast10+5




log 119902119902119890119890 = log119870119870119865119865 +1119899119899log119862119862119890119890 (9)





1198621198620 molsdotLminus1 0001 0002 0004 0005 0006 0008 001119877119877119871119871 099995 099991 099982 099977 099973 099964 099955



05119884119884 0106119905119905 00119905119905119905119905 00119905119905119905119905119903119903 0925 0932 0900


10119884119884 006119905119905119905 001199050119905119905 001119905119905119905119903119903 0941 0951 0945




minus ln (1 minus 119865119865) = 119896119896119905119905 (10)


minus ln 100765010076501 minus 11986511986511990510076661007666 = 119896119896119905119905 (11)



119896119896 =119863119863119903119903120587120587

119905

1199031199031199050 (12)




0 10 20 30 40 50 60

0

1

2

3

Time (min)

minusln(1minus2 )




0 10 20 30 40 50 60

0

02

04

06

08

Time (min)








0 01 02 03 04 05 06 07

20

40

60

80

100

Yiel

d ex

trac

tion

()

Na2SO4

CH3COONa

NaCl








290 300 310 320 33080

84

88

92

96

Yie

ld e

xtra

ctio

n (

)

Temperature (K)





Ln119870119870119889119889 119881Δ119878119878119877119877

minusΔ119867119867119877119877119877119877

(14)


Δ119866119866 119881 Δ119867119867 minus 119877119877Δ119878119878119866 (15)


119870119870119889119889 119881100764910076491198621198620 minus 11986211986211989011989010076651007665119881119881

119862119862119890119890119898119898119866 (16)






0003 00031 00032 00033 00034

15

2

25

3

ln

(1 ) (Kminus 1)




0 05 1 15 2 25

0

20

40

60

80

100

Elu

tio

n (

)




4 Conclusion





Acknowledgments


References















































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy


Cl

Merrifield resin

PS-DVB PO

PS-DVB PO

PS-DVB

Phosphonic acid



+ HBr (OH)2







2 3 4 50

20

40

60

80

Initial pH

Ext

ract

ion

yie

ld (

)








0 50 100 150 200

0

20

40

60

80

100

Time (min)

Rem

oval

()

or u

ptak

e (m

gmiddotgminus1

)








0 40 80 120 160 2000

4

8

12

16

Time (min)




0 0002 0004 0006 0008 0010

20

40

60

80

100

Yield extraction ()

Yield

extra

ction

()


or up

take

(mgmiddot

gminus1)








First-order rate


119903119903 0800 0880




Second-order rate




119862119862119890119890119902119902119890119890

=119862119862119890119890119902119902119898119898

+1

119902119902119898119898119870119870119871119871 (7)



119877119877119871119871 =1

1 + 1198701198701198711198711198621198620 (8)



2 4 6 8

0

5

10

15

20

25

()lowast10+5




log 119902119902119890119890 = log119870119870119865119865 +1119899119899log119862119862119890119890 (9)





1198621198620 molsdotLminus1 0001 0002 0004 0005 0006 0008 001119877119877119871119871 099995 099991 099982 099977 099973 099964 099955



05119884119884 0106119905119905 00119905119905119905119905 00119905119905119905119905119903119903 0925 0932 0900


10119884119884 006119905119905119905 001199050119905119905 001119905119905119905119903119903 0941 0951 0945




minus ln (1 minus 119865119865) = 119896119896119905119905 (10)


minus ln 100765010076501 minus 11986511986511990510076661007666 = 119896119896119905119905 (11)



119896119896 =119863119863119903119903120587120587

119905

1199031199031199050 (12)




0 10 20 30 40 50 60

0

1

2

3

Time (min)

minusln(1minus2 )




0 10 20 30 40 50 60

0

02

04

06

08

Time (min)








0 01 02 03 04 05 06 07

20

40

60

80

100

Yiel

d ex

trac

tion

()

Na2SO4

CH3COONa

NaCl








290 300 310 320 33080

84

88

92

96

Yie

ld e

xtra

ctio

n (

)

Temperature (K)





Ln119870119870119889119889 119881Δ119878119878119877119877

minusΔ119867119867119877119877119877119877

(14)


Δ119866119866 119881 Δ119867119867 minus 119877119877Δ119878119878119866 (15)


119870119870119889119889 119881100764910076491198621198620 minus 11986211986211989011989010076651007665119881119881

119862119862119890119890119898119898119866 (16)






0003 00031 00032 00033 00034

15

2

25

3

ln

(1 ) (Kminus 1)




0 05 1 15 2 25

0

20

40

60

80

100

Elu

tio

n (

)




4 Conclusion





Acknowledgments


References















































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy


0 50 100 150 200

0

20

40

60

80

100

Time (min)

Rem

oval

()

or u

ptak

e (m

gmiddotgminus1

)








0 40 80 120 160 2000

4

8

12

16

Time (min)




0 0002 0004 0006 0008 0010

20

40

60

80

100

Yield extraction ()

Yield

extra

ction

()


or up

take

(mgmiddot

gminus1)








First-order rate


119903119903 0800 0880




Second-order rate




119862119862119890119890119902119902119890119890

=119862119862119890119890119902119902119898119898

+1

119902119902119898119898119870119870119871119871 (7)



119877119877119871119871 =1

1 + 1198701198701198711198711198621198620 (8)



2 4 6 8

0

5

10

15

20

25

()lowast10+5




log 119902119902119890119890 = log119870119870119865119865 +1119899119899log119862119862119890119890 (9)





1198621198620 molsdotLminus1 0001 0002 0004 0005 0006 0008 001119877119877119871119871 099995 099991 099982 099977 099973 099964 099955



05119884119884 0106119905119905 00119905119905119905119905 00119905119905119905119905119903119903 0925 0932 0900


10119884119884 006119905119905119905 001199050119905119905 001119905119905119905119903119903 0941 0951 0945




minus ln (1 minus 119865119865) = 119896119896119905119905 (10)


minus ln 100765010076501 minus 11986511986511990510076661007666 = 119896119896119905119905 (11)



119896119896 =119863119863119903119903120587120587

119905

1199031199031199050 (12)




0 10 20 30 40 50 60

0

1

2

3

Time (min)

minusln(1minus2 )




0 10 20 30 40 50 60

0

02

04

06

08

Time (min)








0 01 02 03 04 05 06 07

20

40

60

80

100

Yiel

d ex

trac

tion

()

Na2SO4

CH3COONa

NaCl








290 300 310 320 33080

84

88

92

96

Yie

ld e

xtra

ctio

n (

)

Temperature (K)





Ln119870119870119889119889 119881Δ119878119878119877119877

minusΔ119867119867119877119877119877119877

(14)


Δ119866119866 119881 Δ119867119867 minus 119877119877Δ119878119878119866 (15)


119870119870119889119889 119881100764910076491198621198620 minus 11986211986211989011989010076651007665119881119881

119862119862119890119890119898119898119866 (16)






0003 00031 00032 00033 00034

15

2

25

3

ln

(1 ) (Kminus 1)




0 05 1 15 2 25

0

20

40

60

80

100

Elu

tio

n (

)




4 Conclusion





Acknowledgments


References















































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy




First-order rate


119903119903 0800 0880




Second-order rate




119862119862119890119890119902119902119890119890

=119862119862119890119890119902119902119898119898

+1

119902119902119898119898119870119870119871119871 (7)



119877119877119871119871 =1

1 + 1198701198701198711198711198621198620 (8)



2 4 6 8

0

5

10

15

20

25

()lowast10+5




log 119902119902119890119890 = log119870119870119865119865 +1119899119899log119862119862119890119890 (9)





1198621198620 molsdotLminus1 0001 0002 0004 0005 0006 0008 001119877119877119871119871 099995 099991 099982 099977 099973 099964 099955



05119884119884 0106119905119905 00119905119905119905119905 00119905119905119905119905119903119903 0925 0932 0900


10119884119884 006119905119905119905 001199050119905119905 001119905119905119905119903119903 0941 0951 0945




minus ln (1 minus 119865119865) = 119896119896119905119905 (10)


minus ln 100765010076501 minus 11986511986511990510076661007666 = 119896119896119905119905 (11)



119896119896 =119863119863119903119903120587120587

119905

1199031199031199050 (12)




0 10 20 30 40 50 60

0

1

2

3

Time (min)

minusln(1minus2 )




0 10 20 30 40 50 60

0

02

04

06

08

Time (min)








0 01 02 03 04 05 06 07

20

40

60

80

100

Yiel

d ex

trac

tion

()

Na2SO4

CH3COONa

NaCl








290 300 310 320 33080

84

88

92

96

Yie

ld e

xtra

ctio

n (

)

Temperature (K)





Ln119870119870119889119889 119881Δ119878119878119877119877

minusΔ119867119867119877119877119877119877

(14)


Δ119866119866 119881 Δ119867119867 minus 119877119877Δ119878119878119866 (15)


119870119870119889119889 119881100764910076491198621198620 minus 11986211986211989011989010076651007665119881119881

119862119862119890119890119898119898119866 (16)






0003 00031 00032 00033 00034

15

2

25

3

ln

(1 ) (Kminus 1)




0 05 1 15 2 25

0

20

40

60

80

100

Elu

tio

n (

)




4 Conclusion





Acknowledgments


References















































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy



1198621198620 molsdotLminus1 0001 0002 0004 0005 0006 0008 001119877119877119871119871 099995 099991 099982 099977 099973 099964 099955



05119884119884 0106119905119905 00119905119905119905119905 00119905119905119905119905119903119903 0925 0932 0900


10119884119884 006119905119905119905 001199050119905119905 001119905119905119905119903119903 0941 0951 0945




minus ln (1 minus 119865119865) = 119896119896119905119905 (10)


minus ln 100765010076501 minus 11986511986511990510076661007666 = 119896119896119905119905 (11)



119896119896 =119863119863119903119903120587120587

119905

1199031199031199050 (12)




0 10 20 30 40 50 60

0

1

2

3

Time (min)

minusln(1minus2 )




0 10 20 30 40 50 60

0

02

04

06

08

Time (min)








0 01 02 03 04 05 06 07

20

40

60

80

100

Yiel

d ex

trac

tion

()

Na2SO4

CH3COONa

NaCl








290 300 310 320 33080

84

88

92

96

Yie

ld e

xtra

ctio

n (

)

Temperature (K)





Ln119870119870119889119889 119881Δ119878119878119877119877

minusΔ119867119867119877119877119877119877

(14)


Δ119866119866 119881 Δ119867119867 minus 119877119877Δ119878119878119866 (15)


119870119870119889119889 119881100764910076491198621198620 minus 11986211986211989011989010076651007665119881119881

119862119862119890119890119898119898119866 (16)






0003 00031 00032 00033 00034

15

2

25

3

ln

(1 ) (Kminus 1)




0 05 1 15 2 25

0

20

40

60

80

100

Elu

tio

n (

)




4 Conclusion





Acknowledgments


References















































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy


0 01 02 03 04 05 06 07

20

40

60

80

100

Yiel

d ex

trac

tion

()

Na2SO4

CH3COONa

NaCl








290 300 310 320 33080

84

88

92

96

Yie

ld e

xtra

ctio

n (

)

Temperature (K)





Ln119870119870119889119889 119881Δ119878119878119877119877

minusΔ119867119867119877119877119877119877

(14)


Δ119866119866 119881 Δ119867119867 minus 119877119877Δ119878119878119866 (15)


119870119870119889119889 119881100764910076491198621198620 minus 11986211986211989011989010076651007665119881119881

119862119862119890119890119898119898119866 (16)






0003 00031 00032 00033 00034

15

2

25

3

ln

(1 ) (Kminus 1)




0 05 1 15 2 25

0

20

40

60

80

100

Elu

tio

n (

)




4 Conclusion





Acknowledgments


References















































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy




0003 00031 00032 00033 00034

15

2

25

3

ln

(1 ) (Kminus 1)




0 05 1 15 2 25

0

20

40

60

80

100

Elu

tio

n (

)




4 Conclusion





Acknowledgments


References















































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy


Acknowledgments


References















































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy



















ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy










ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy

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