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Hindawi Publishing CorporationJournal of ChemistryVolume 2013 Article ID 842435 8 pageshttpdxdoiorg1011552013842435

Research ArticleChemical Recycling of Expanded PolystyreneWasteSynthesis of Novel Functional Polystyrene-Hydrazone Surface forPhenol Removal

Ali N Siyal1 2 Saima Q Memon2 Sajida Parveen2 Asma Soomro2

Mazhar I Khaskheli2 andM Y Khuhawar2

1MA Kazi Institute of Chemistry University of Sindh Jamshoro 76080 Pakistan2 Institute of Advance Research Studies in Chemical Science University of Sindh Jamshoro 76080 Pakistan

Correspondence should be addressed to Saima Q Memon msaima77gmailcom

Received 28 June 2012 Revised 2 September 2012 Accepted 16 September 2012

Academic Editor Dimitris P Makris

Copyright copy 2013 Ali N Siyal 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

Expanded polystyrene (EPS) waste was chemically recycled to a novel functional polystyrene-hydrazone (PSH) surface byacetylation of polystyrene (PS) and then condensation with phenyl hydrazine e synthesized surface was characterized by theFT-IR and elemental analysis Synthesized novel functional PSH surface was successfully applied for the treatment of phenol-contaminated industrial wastewater by solid-phase extraction Multivariant sorption optimization was achieved by factorial designapproach 9993 of phenol was removed from aqueous solution FT-IR study showed the involvement of nitrogen of hydrazonemoiety of synthesized surface for the uptake of phenol through the hydrogen bonding

1 Introduction

Phenolic pollutants are found in wastewater as a result ofvarious industrial processes such as wood preservation coalconversion petroleum rening metal casting and manu-facturing of plastics textiles iron steel paper and pulp[1ndash3] e concentration of phenol in these wastewatersusually ranges from 100ndash1000mgLminus1 Removal of phenoliccontaminants from wastewater is important before dischargeinto natural water because of their toxicity for human andaquatic bodies Several methods have been reported for theremoval of phenol from wastewater such as incinerationmicrobial degradation bacterial and chemical oxidationsolvent extraction electrochemical techniques irradiationand so forth [4] ese methods have serious shortcomingssuch as lack of purication high costs hazardous byprod-uct formation and low efficiency erefore attention hasbeen paid to the development of attractive sorbents forremoval of phenolic pollutants from wastewater [5] Dif-ferent polystyrene based materials such as benzoyl-PS-DVB[6] 24-dicarboxybenzoyl-PS-DVB [7] o-carboxybenzoyl-PS-DVB [8] acetyl-PS-DVB [9 10] toluene-PS-DVB [11]

diethylenetriamine-PS-DVB [12] sulfonated PS-DVB [1314] Amberlite XAD-4 and Amberlite IRA96C [15ndash17] havebeen reported for the removal of phenols and phenoliccompounds In this study we focus on the novel routefor chemical recycling of EPS waste to the new functionalpolystyrene-hydrazone (PSH) surface for the treatment ofphenol contaminated industrial wastewater Factorial designapproach is applied for multivariant sorption optimization

2 Materials andMethods

21 Adsorbent Synthesis of Polystyrene-Hydrazone (PSH)Surface Figure 1 shows the chemical route for conversionof EPS waste into functional polystyrene-hydrazone (PSH)surface 30 g of EPS was dissolved into 100mL of carbontetrachloride (CCl4) Solution was ltered to remove anyinsoluble impurities by simple ltration e ltrate waspoured into round bottom ask contained 335 g of anhy-drous aluminum chloride (AlCl3) and 198mL of acetylchloride (CH3COCl) was added drop wise with stirring andreuxed for 50min at 60∘Ce reaction mixture was settled

2 Journal of Chemistry

lowast lowastH2C H2C H2CCH2 CH2 CH2

lowast lowast lowast lowast

C CO CH3

CH3

NndashNHndashPh

CH3COCl AlCl3H2NndashNHndashPh

(a) Polystyrene (PS) (b) Acetyl-PS (c) PS-Hydrazone (PSH) surface

Dil acid45C

F 1 Reaction scheme for conversion of EPS into PS-Hydrazone (PSH) surface

T 1 Levels of factors used in experimental design for theremoval of phenol on PSH surface

Factors Coded levelsminus1 0 +1

Amount (mg) A (1198831198831) 10 55 100Concentration (mgLminus1) 119861119861 (1198831198832) 5 30 55pH 119862119862 (1198831198833) 2 55 9Time (min)119863119863 (1198831198834) 10 95 180

at room temperature andworked upwith 005NHCl Acetyl-PS (b) was ltered off washed with 10N sodium bicarbonate(NaHCO3) solution to remove excess of acid washed withdeionized water to remove base and air-dried 30 g acetyl-PS was taken into round bottom ask contained 50mLof acidied distilled water and heated for 30min at 50∘C202mL of phenyl hydrazine was added into the reactionmixture and reuxed for 60min at 50∘C e nal productPSH (c) was ltered off washed with deionized water andair-dried

22 Sorbate Phenol Solution A stock solution of phenol wasprepared (1000mgLminus1) by dissolving appropriate amount ofphenol (Merck) in 30 methanol e stock solution wasdiluted with de-ionized water to obtained series of workingsolutions (5ndash55mgLminus1) pH of solutions was maintainedat 90 55 and 20 with 05N NaOH acetate buffer and10N HCl respectively CH3COONa CH3COOH HCl andNaOH were purchased fromMerck (Germany)

23 Batch Experiments All batch sorption experiments wereperformed in thermostated shaker at constant temperatureof 25∘C for a period of 10ndash180min with shaking speedof 100 rpm using 250mL stoppered conical asks con-tained 10mL of phenol solution of different concentrations(5ndash55mgLminus1) and pH (2ndash9) e adsorption of phenol ontoPSH surface was conducted by shaking different weightedamounts (10ndash100mg) of PSH surface with 10mL phenolsolutions (5ndash55mgLminus1) e concentration of phenol in thesolution was analyzed via reverse phase HPLC (Hitachimodel-655A-11) using Zorbax XDB-C18 column of dimen-sions 150 times 46mm 5 120583120583m Phenol was eluted with methanoland water (5 25) at ow rate of 10mLminminus1 and wasdetected by UV-Visible detector (Hitachi 655A) at 254 nm

Equation (1) was used to calculate the percent of phenoladsorption

adsorption =119862119862119894119894 minus 119862119862119890119890119862119862119894119894

times 100 (1)

where 119862119862119890119890 and 119862119862119894119894 are the equilibrium and initial concentra-tions (mgLminus1) phenol solutions respectively

24 Factorial Design Classical sorption optimizationrequires large number of experiments to nd optimumresponse of independent variables Major drawback ofthis method is that it is based on variation of only oneindependent parameter at a time keeping constant the otherparameters so the combined effect of all the independentparameters cannot be studied simultaneously which couldlead to unreliable results [18] In factorial design approachinteractions of two or more variables can be studied at a timehence comparatively more reliable results with less numberof experiments andminimum treatment time and cost can beobtained [19] Factorial design approach is an experimentaltechnique designed to predict optimal response of variablesCentral Composite Design (CCD) was chosen to study theeffect of adsorbent amount (A mg) pH of phenol solution(B) initial phenol concentration (C mgLminus1) and contacttime (D min) on the uptake of phenol Each independentvariable was studied at three different levels (high mediumand low coded as +1 0 and minus1 resp) as shown in Table 1e CCDmodel consists of eighteen batch experiments eachexperiment was performed twice to predict mean values forCCD analysis under Response Surface Methodology (RSM)Design of experiments was analyzed statistically by StatGraphics plus for Windows 51 (Stat Point Technologies Inc2009) [20]

3 Results and Discussions

31 Characterization Figure 2 represents the spectra forEPS Acetyl-PS and PS-Hydrazone surface the characteristicpeak for C=O stretching at 161101 cmminus1 in spectrum-Asupports the conversion of PS into acetyl-PS e disap-pearance of peak for C=O at 161101 cmminus1 in spectrum-B and appearance of additional peak for C=N and NndashHstretching at 1411 cmminus1 and 32925 cmminus1 respectively inspectrum-C supports the conversion of acetyl-PS into PS-hydrazone (PSH) surface

e formation of acetyl-PS and PSH surface was con-rmed by elemental analysis (CNHS Analyser FLASH

Journal of Chemistry 3

T 2 Experimental design and results for adsorption of phenol on PSH surface

Trail Coded values AdsorptionA B C D Observed Predicted

1 minus1 minus1 +1 minus1 8234 82392 minus1 minus1 minus1 minus1 2033 20283 0 +1 0 0 8187 81874 +1 +1 minus1 minus1 2176 21725 +1 +1 +1 minus1 6798 68036 0 0 0 minus1 7498 74977 minus1 +1 +1 +1 7698 77038 +1 0 0 0 7865 78639 0 0 +1 0 7934 791310 +1 minus1 +1 +1 8498 850311 0 0 minus1 0 1867 188412 +1 minus1 minus1 +1 2045 204013 minus1 +1 minus1 +1 0898 089314 0 minus1 0 0 9798 979715 minus1 0 0 0 8723 872216 0 0 0 +1 7690 768917 0 0 0 0 8322 832618 0 0 0 0 8322 8326

100

95

90

85

80

75

70

65

4000 3500 3000 2500 2000 1500 1000 500

A

B

C

Wavenumber (cmminus 1)

32925 cmminus 1 161101 cmminus 1

1411 cmminus 11021 cmminus 1

T(

)

BBBB

C


1411 cmminus 11021 cmminus 11111111111

F 2 FT-IR Spectra PS (A) Acetyl-PS (B) and PS-Hydrazonesurface (C)

EA1112) Acetyl-PS resulted as C 8243 H 75764 O1001 and theoretically calculated values for C11H12O areC 8246 H 755 O 999 Elemental analysis conrmedthe successful introduction of acetyl group on PS Elementalanalysis of PSH surface resulted as C 7769 H 651 N 1007O 573 and theoretically calculated values for C17H18N2are C 7767 H 652 N 1006 O 575 conrming thesuccessful conversion of acetyl-PS into PSH surface

32 Statistical Analysis e tting and accuracy of CCDmodel were estimated by analysis of variance (ANOVA) asgiven in Table 3 e ANOVA result indicated that lack oft is not signicant as 119875119875 119875 119875119875119875119875 (0043 119875 005) so the nullhypothesis could not be rejected as the CCD model wouldgive poor or misleading results if it was an inadeuate t[23] Residual and three-dimensional (3D) surface plots wereexamined to estimate the CCD model competency [18]

321 Interpretation of Residual Graphs Figure 3(a) plotsthe residuals versus predicted values e residual is thedifference between the observed and the predicted values Allthe residuals are scattered randomly about zero and all pointswere found in the range of +15 to minus15 showing that theerrors have a constant variance and conrmed the tting ofthe model

Figure 3(b) shows the plot for observed versus predictedvalues of percent removal of phenol on PSH surface Actualvalues measure the percent removal data for a particularrun and the predicted values were evaluated from the CCDmodel Values of 1198771198772 and 1198771198772adj119875 were found to be 9997 and9987 respectively indicating a close agreement betweenthe predicted and observed values as shown in Table 2

Figure 3(c) plot shows the normal probability versusresiduals for the removal of phenol by PSH surface Resid-uals show how well the model satises the assumptions ofANOVA whereas the residuals measure the number of stan-dard deviations separating the actual and predicted valuesPlot indicates that neither the response transformation wasneeded nor there was any apparent problem with normality

Figure 3(d) shows the residual of each experimental runplot shows the residual of each experiment are scatteredrandomly around the zero and all points are found in therange of +15 to minus15 showing that lack of t is not signicantfor model

322 Interpretation of 3D Response Surface Plots e 3Dresponse surface graph shows the combined effect of anytwo independent variables on the adsorption of phenolkeeping other parameters at their optimized conditionsFigure 4(a) shows combined effect of pH and agitationtime on the removal of phenol by PSH surface at optimum


Predicted

Residuals

0 20 40 60 80 100

009

019

029

minus021

minus011

minus001

(a)

Predicted

Observed

0 20 40 60 80 100

0

20

40

60

80

100

(b)

Residuals

002 012 022

01

1

5

20

50

80

95

99

999

minus018 minus008

()

(c)

Run order

Resid

uals

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

009

019

029

minus021

minus011

minus001

(d)

F 3 Plots for validation of model for the uptake of phenol (a) residuals versus predicted values (b) observed versus predicted values(c) Normal Probability versus Residuals (d) residuals versus run order

T 3 ANOVA and estimated regression coefficients for adsorption of phenol on PSH surface

Source Sum of Squares Df Mean Square 119865119865-Ratio 119875119875-Value Regression coefficientConstant mdash mdash mdash mdash mdash minus47503A amount 3680 1 3680 114095 00001 0077B con 129766 1 129766 402240 0 minus0779C pH 90860 1 90860 28164155 0 39792D time 18432 1 18432 5713 00048 0279AA 0279577 1 0279577 867 00603 minus0001AB 189225 1 189225 5865 00046 0001AC 463685 1 463685 143730 0 minus0015AD 25664 1 25664 79552 00001 minus0001BB 11682 1 111682 346184 0 0013BC 189728 1 189728 58811 00002 minus0019BD 417385 1 417385 129378 0 minus0003CC 296367 1 296367 9186574 0 minus2797CD 738113 1 738113 228795 0 0011DD 135706 1 135706 420653 0 minus0001Total error 00967826 3 00322609 mdash mdash mdashTotal (corr) 151180 17 mdash mdash mdash mdash

initial concentration of phenol (5mgLminus1) and adsorbent dose(51mg) e adsorption of phenol increases with increaseof agitation time and pH of phenol solution and becomesmaximumat pH7 with further increase of pH there is a slightdecrease in adsorption which may be explained on thebasis of decreasing the chances of hydrogen boding because ofpossible interaction of hydroxyl group of base with the acidichydrogen of phenol and hydrazone moiety of surface

Figure 4(b) shows combined effect of phenol concentra-tions and agitation time on the removal of phenol by PSHsurface at optimum adsorbent dose (51mg) and pH (7) eplot show themaximum adsorption at initial concentrationof 5mgLminus1 and agitation time of 67ndash80min e furtherincrease in agitation time decreases the adsorption whichmay be due to desorption of phenol from surface Figure4(c) shows combined effect of pH and adsorbent dose on


100

80

60

40

20

0

Rem

ova

l (

)

2 3 4 5 6 7 8 910

67124

181

pHTime (m

in)

(a)

100

80

60

40

20

0

Rem

ova

l (

)

10 67124

181

Time (min)

5 15 25 35 45 55Conc (mgLminus1)

(b)

100

80

60

40

20

0

Rem

ova

l (

)

2 3 4 56 7 8

9

pH10 30 50 70 90 110Amount (mg)

(c)

F 4 3D Plots for combined effects of variables (a) pH and agitation time (b) initial adsorbate concentration and agitation time (c) pHand adsorbent dose on adsorption of phenol on PSH surface

0 100 200 300 400 500 600

Standardized eect

AAD time

ABBCAD

A amountBDACCDBB

B conDDCC

C pH

+minus

F 5 Pareto chart for adsorption of phenol on PSH surface

removal of phenol by PSH surface at optimum concentrationof phenol (5mgLminus1) and agitation time (50min) e phenoluptake increases with increase in pH and becomesmaximumat pH 7 a slight increase is registered with increasingadsorbent dose Optimum values obtained by CCD modelare adsorbent dosage 51mg pH 7 phenol concentration5mgLminus1 agitation time 50min Maximum adsorption ofphenol on PSH surface was 9993 achieved at optimumconditions

Amount Con pH Time

0

20

40

60

80

100

Rem

ova

l (

)

F 6 Main effects plot for adsorption of phenol on PSHsurface

323 Pareto Chart Figure 5 shows the Pareto chart of theestimated effects in decreasing order of magnitude elength of each bar is proportional to the standardized effectwhich is the estimated effect divided by its standard erroris is equivalent to computing a t-statistic for each effectIt was observed that for a 95 condence level and eightdegrees of freedom the 119905119905 value is equal to 319 e verticalline can be used to judge which effects are statistically signif-icant Any bars which extend beyond the line correspond toeffects which are statistically signicant at 950 condencelevel

324 Main Effects Plot Figure 6 shows the estimated adsorption as a function of each experimental factor In each


T 4 Langmuir and D-R isotherm parameters

Langmuir D-RCapacity (mmolgminus1) 119877119877119871119871 1198771198772 Capacity (mmolgminus1) Energy (kJmolminus1) 1198771198772

1873 00057ndash01 0982 1962 1093 0973

T 5 Comparative adsorption capacities of PS based materials for the removal of phenol

Adsorbent Capacity (mmolgminus1) ReferencesAmberlite XAD-4 0259 [10]Acetyl-Amberlite XAD-4 0420 [10]Amberlite XAD-7 0795 [12]Amberlite IRA96C 0636 [17]Methylamino-Hypercrosslinked styrene-DVB (PS) 0820 [21]Phenol hydroxyl-PS 0636 [22]N-0 1153 [23]N-1 1358 [23]N-2 1013 [23]PSH 1873 and 1962 is workNJ-0 Hypercrosslinked PS-DVB resin with 549 residual chloromethyl groupsNJ-1 NJ-0 with dimethylamine groupNJ-2 NJ-0 with timethylamine group

plot the factor of interest is varied from its low level to its highlevel while all other factors are held constant at their centralvalues e adsorption slightly decreases with an increasein adsorbent amount slightly decreases and then becomeconstant with increase of phenol concentration potentiallyincreases with increase in pH (7ndash9) and reaches maximumat pH 7 and decreases with further increase of pH due tointeraction of acidic hydrogen of phenol and PSH surfacewith basic group increases with increasing shaking timeand decreases with further increase in shaking time due todesorption

33 Isotherm Studies Isotherm study describes sorptionequilibrium In this study isotherm study was performed bychanging adsorbent concentration ranging 5ndash55mgLminus1 andkeeping optimum other independent parameters (adsorbentdose 51mg agitation time 50min pH 7) at 25∘C Langmuirand Dubinin-Radushkevich (D-R) models were evaluatedusing (2) and (3) respectively

119862119862119890119890119862119862ads

=1119876119876119876119876

+119862119862119890119890119876119876 (2)

ln 119862119862ads = ln119870119870DminusR minus 1205731205731205731205732 (3)

where119862119862ads is the adsorbed amount of phenol on PSH surface(mggminus1) and 119862119862119890119890 is the equilibrium concentration of phenol(mgLminus1) while 119876119876 and 119876119876 are the Langmuir constants relatedto the monolayer sorption capacity (mggminus1) and affinity ofthe binding sites (L gminus1) respectively 120573120573 is related to themean sorption free energy per mole of the sorbent whenit is transferred from innite distance in the solution tothe surface of the solid and 120573120573 is Polanyi potential and isequal to RT ln(1 + 1119862119862119890119890) where T is temperature and R isgeneral gas constant (Jmolminus1Kminus1) e isotherm constants Q

and b were calculate from the slope and intercept of plotbetween119862119862119890119890119862119862ads and119862119862119890119890e isotherm showed good t to theexperimental data with good correlation coefficient (0982)e characteristic separation factor of Langmuir isotherm119877119877119871119871 can be calculated by using (4)

119877119877119871119871 =1

1 + 1007649100764911987611987611986211986211989411989410076651007665 (4)

where 119862119862119894119894 is the initial phenol concentration and b is theLangmuir constant e numerical value of 119877119877119871119871 can beinterpreted as 119877119877119871119871 = 0 irreversible 119877119877119871119871 gt 1 unfavorable119877119877119871119871 = 1 linear and 0 lt 119877119877119871119871 lt 1 favorable [24] e calculatedvalues of 119877119877119871119871 were found in the range of 00057ndash01 indicatedfavorable nature of sorption

D-R isotherm assumes no homogeneous surface of thesorbent material and a good linear relationship betweenln 119862119862ads and 1205731205732 with correlation coefficient 0973 e esti-mated value of mean sorption energy (E) was calculated793 k Jmolminus1 from the slope of plot (120573120573) e magnitude of Eindicates the nature of sorption process 119864119864 gt 119864ndash16 k Jmolminus1

(chemisorption) and119864119864 lt 119864 k Jmolminus1 (physisorption) [25] Onthe basis of this observation it can be anticipated that sorptionof phenol on PSH surface predominantly followed physisorp-tion e Langmuir and D-R parameters are summarized inTable 4

34 Comparative Capacities for Phenol Adsorption Differentsorbents have been reported in literature for the removal phe-nol having different capacities Table 5 shows the comparativecapacities of PS based adsorbent for the adsorption of phenolfrom aqueous solutions e capacity of PSH surface for theremoval of phenol is comparable or better which enable thesynthesized surface to be more effective for the removal ofphenol


T 6 Model validation for the removal of phenol by PSH surface

Adsorbent Dose (mg) pH Conc (mgLminus1) Time (min) Adsorption of phenolPredicted Experimental

51 70 5 50 100 9993

T 7 Removal of phenol by PSH surface from industrial wastewater

Sample Conc (mgLminus1) of phenol Removal of phenol RSD ()S1 458 8809 18S2 374 7621 27S3 510 8733 11S4 270 8465 21S1 Wastewater sample collected from Korangi site area Karachi PakistanS2 Wastewater sample collected from Kotri site area PakistanS3 Wastewater sample collected from Hyderabad site area PakistanS4 Wastewater sample collected from Faisalabad site area Pakistan

100

95

90

85

80

75

70

65

60

A

B

T(

)

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cmminus1)

32925 cmminus1

1411 cmminus11021 cmminus1

AAA

B

32925 cmminus1

1411 cmminus11021 c 1

F 7 FT-IR spectra (A) plain PSH surface (B) phenol loadedPSH surface

N

N

C

H O

H

PhN

N

C

H

H

O Ph

+

PSH surface Phenol Hydrogen bonding

F 8 e possible sorption mechanisms for the uptake ofphenol by PSH surface

35 Possible Sorption Mechanism Figure 7 shows the FT-IR spectrum for PSH surface plain (A) and phenol-loadedPSH surface (B) and the characteristic decrease in inten-sities of peaks at 32925 cmminus1 and 1411 cmminus1 indicated theinvolvement of nitrogen and hydrogen of PSH surface forthe adsorption of phenol e hydrazone moiety of PSHsurface has participated for the uptake of phenol via hydrogenbonding as shown in Figure 8

36 Method Validation e optimum sorption conditionsdetermined from mathematical model were validated byconducting sorption experiments at optimum conditionspredicted by CCD model e experimental and predictedremoval values were found in good agreement as shown inTable 6

37 Application of Method e proposed method was suc-cefuly applied for the treatment of industrial wastewatercollected fromVarious industrial site areas in Pakistaneremoval of phenol by PSH surface from each sample is givenin Table 7

4 Conclusion

e EPS waste was successfully chemically recycled tonovel functional PSH surface e synthesized PSH sur-face was applied for the treatment of phenol industrialwastewater e multi-variant sorption optimization wasachieved by factorial design approach is study givesthe solution of waste management problems caused byEPS waste along with phenol-contaminated water treatmenttechnology Adsorption capacities from Langmuir isothermand D-R isotherm were calculated as 1873mmolgminus1 and1962mmolgminus1 respectively

Conic of neress

Authors do not have any conict of interests with parties

References

[1] N Caza J K Bewtra N Biswas and K E Taylor ldquoRemoval ofphenolic compounds from synthetic wastewater using soybeanperoxidaserdquo Water Research vol 33 no 13 pp 3012ndash30181999

[2] K Ikehata I D Buchanan and D W Smith ldquoTreatment of oilrenery wastewater using crude Coprinus cinereus peroxidase


and hydrogen peroxiderdquo Journal of Environmental Engineeringand Science vol 2 no 6 pp 463ndash472 2003

[3] S Rengaraj S H Moon R Sivabalan B Arabindoo andV Murugesan ldquoAgricultural solid waste for the removal oforganics adsorption of phenol from water and wastewater bypalm seed coat activated carbonrdquo Waste Management vol 22no 5 pp 543ndash548 2002

[4] E Miland M R Smyth and O C Fagain ldquoPhenol removalby modied peroxidasesrdquo Journal of Chemical Technology andBiotechnology vol 67 pp 227ndash236 1996

[5] M Pletsch B S De Araujo and B V Charlwood ldquoNovelbiotechnological approaches in environmental remediationresearchrdquo Biotechnology Advances vol 17 no 8 pp 679ndash6871999

[6] N Masque M Galia R M Marce and F Borrull ldquoSolid-phaseextraction of phenols and pesticides in water with a modiedpolymeric resinrdquo Analyst vol 122 pp 425ndash428 1997

[7] N Masque M Galia R M Marce and F Borrull ldquoInuence ofchemical modication of polymeric resin on retention of polarcompounds in solid-phase extractionrdquo Chromatographia vol50 pp 21ndash26 1999

[8] N Masque M Galia R M Marce and F Borrull ldquoChemicalremoval of humic substances interfering with the on-line solid-phase extractionmdashliquid chromatographic determination ofpolar water pollutantsrdquo Chromatographia vol 48 pp 231ndash2361998

[9] L Schmidt J J Sun and J S Fritz ldquoSolid-phase extractionof phenols using membranes loaded with modied polymericresinsrdquo Journal of Chromatography vol 641 pp 57ndash61 1993

[10] A Li Q Zhang J Chen Z Fei C Long andW Li ldquoAdsorptionof phenolic compounds on Amberlite XAD-4 and its acetylatedderivativeMX-4rdquo Reactive and Functional Polymers vol 49 no3 pp 225ndash233 2001

[11] J Huang R Deng and K Huang ldquoEquilibria and kinetics ofphenol adsorption on a toluene-modied hyper-cross-linkedpoly(styrene-co-divinylbenzene) resinrdquo Chemical EngineeringJournal vol 171 no 3 pp 951ndash957 2011

[12] H Jianhan Z Hongwei J Xiaoying and D Shuguang ldquoEffi-cient adsorptive removal of phenol by a diethylenetriamine-modied hypercrosslinked styrenemdashdivinylbenzene (PS) resinfrom aqueous solutionrdquoChemical Engineering Journal vol 195-196 pp 40ndash48 2012

[13] D L Ambrose J S Fritz M R Buchmeiser N Atzl and GK Bonn ldquoNew high-capacity carboxylic acid functionalizedresins for solid-phase extraction of a broad range of organiccompoundsrdquo Journal of Chromatography A vol 786 no 2 pp259ndash268 1997

[14] I Rodriacuteguez M I Turnes M H Bollaiacuten M C Mejuto andR Cela ldquoDetermination of phenolic pollutants in drinkingwater by capillary electrophoresis in the sample stackingmoderdquoJournal of Chromatography A vol 778 pp 279ndash288 1997

[15] Y Ku andK C Lee ldquoRemoval of phenols from aqueous solutionby XAD-4 resinrdquo Journal of Hazardous Materials vol 80 no1ndash3 pp 59ndash68 2000

[16] M Sinan Bilgili ldquoAdsorption of 4-chlorophenol from aqueoussolutions by xad-4 resin isotherm kinetic and thermodynamicanalysisrdquo Journal of Hazardous Materials vol 137 no 1 pp157ndash164 2006

[17] W M Zhang J L Chen B C Pan Q X Zhang and B ZhangldquoSynergistic adsorption of phenol from aqueous solution ontopolymeric adsorbentsrdquo Journal of HazardousMaterials vol 128pp 123ndash129 2006

[18] M J Sanchez H J Beltran and M C Carmona IndustrialCrops and Products vol 33 pp 409ndash417 2011

[19] J Zolgharnein A Shahmoradi andM R Sangi ldquoOptimizationof Pb(II) biosorption by Robinia tree leaves using statisticaldesign of experimentsrdquo Talanta vol 76 no 3 pp 528ndash5322008

[20] K J Cronje K Chetty M Carsky J N Sahu and B CMeikap ldquoOptimization of chromium(VI) sorption potentialusing developed activated carbon from sugarcane bagasse withchemical activation by zinc chloriderdquoDesalination vol 275 no1ndash3 pp 276ndash284 2011

[21] C He J Huang J Liu L Deng and K Huang ldquoMethylamino-group-modied hypercrosslinked polystyrene resin for theremoval of phenol from aqueous solutionrdquo Journal of AppliedPolymer Science vol 119 no 3 pp 1435ndash1442 2011

[22] A Li C Long Y Sun Q Zhang F Liu and J ChenldquoA new phenolic hydroxyl modied polystyrene adsorbentfor the removal of phenolic compounds from their aqueoussolutionsrdquo Separation Science and Technology vol 37 no 14pp 3211ndash3226 2002

[23] J Kumar C Balomajumder and P Mondal ldquoApplication ofagro-based biomasses for zinc removal from wastewatermdashareviewrdquo Clean Soil Air Water vol 39 no 7 pp 641ndash652 2011

[24] H K Kim J G Kim J D Cho and J W Hong ldquoOptimiza-tion and characterization of UV-curable adhesives for opticalcommunications by response surface methodologyrdquo PolymerTesting vol 22 no 8 pp 899ndash906 2003

[25] A N Siyal S Q Memon and M I Khaskheli ldquoOptimizationand equilibrium studies of Pb(II) removal by Grewia Asiaticaseed a factorial design approachrdquo Polish Journal of ChemicalTechnology vol 14 pp 71ndash77 2012

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CatalystsJournal of


lowast lowastH2C H2C H2CCH2 CH2 CH2

lowast lowast lowast lowast

C CO CH3

CH3

NndashNHndashPh

CH3COCl AlCl3H2NndashNHndashPh

(a) Polystyrene (PS) (b) Acetyl-PS (c) PS-Hydrazone (PSH) surface

Dil acid45C

F 1 Reaction scheme for conversion of EPS into PS-Hydrazone (PSH) surface

T 1 Levels of factors used in experimental design for theremoval of phenol on PSH surface

Factors Coded levelsminus1 0 +1

Amount (mg) A (1198831198831) 10 55 100Concentration (mgLminus1) 119861119861 (1198831198832) 5 30 55pH 119862119862 (1198831198833) 2 55 9Time (min)119863119863 (1198831198834) 10 95 180

at room temperature andworked upwith 005NHCl Acetyl-PS (b) was ltered off washed with 10N sodium bicarbonate(NaHCO3) solution to remove excess of acid washed withdeionized water to remove base and air-dried 30 g acetyl-PS was taken into round bottom ask contained 50mLof acidied distilled water and heated for 30min at 50∘C202mL of phenyl hydrazine was added into the reactionmixture and reuxed for 60min at 50∘C e nal productPSH (c) was ltered off washed with deionized water andair-dried

22 Sorbate Phenol Solution A stock solution of phenol wasprepared (1000mgLminus1) by dissolving appropriate amount ofphenol (Merck) in 30 methanol e stock solution wasdiluted with de-ionized water to obtained series of workingsolutions (5ndash55mgLminus1) pH of solutions was maintainedat 90 55 and 20 with 05N NaOH acetate buffer and10N HCl respectively CH3COONa CH3COOH HCl andNaOH were purchased fromMerck (Germany)

23 Batch Experiments All batch sorption experiments wereperformed in thermostated shaker at constant temperatureof 25∘C for a period of 10ndash180min with shaking speedof 100 rpm using 250mL stoppered conical asks con-tained 10mL of phenol solution of different concentrations(5ndash55mgLminus1) and pH (2ndash9) e adsorption of phenol ontoPSH surface was conducted by shaking different weightedamounts (10ndash100mg) of PSH surface with 10mL phenolsolutions (5ndash55mgLminus1) e concentration of phenol in thesolution was analyzed via reverse phase HPLC (Hitachimodel-655A-11) using Zorbax XDB-C18 column of dimen-sions 150 times 46mm 5 120583120583m Phenol was eluted with methanoland water (5 25) at ow rate of 10mLminminus1 and wasdetected by UV-Visible detector (Hitachi 655A) at 254 nm

Equation (1) was used to calculate the percent of phenoladsorption

adsorption =119862119862119894119894 minus 119862119862119890119890119862119862119894119894

times 100 (1)

where 119862119862119890119890 and 119862119862119894119894 are the equilibrium and initial concentra-tions (mgLminus1) phenol solutions respectively

24 Factorial Design Classical sorption optimizationrequires large number of experiments to nd optimumresponse of independent variables Major drawback ofthis method is that it is based on variation of only oneindependent parameter at a time keeping constant the otherparameters so the combined effect of all the independentparameters cannot be studied simultaneously which couldlead to unreliable results [18] In factorial design approachinteractions of two or more variables can be studied at a timehence comparatively more reliable results with less numberof experiments andminimum treatment time and cost can beobtained [19] Factorial design approach is an experimentaltechnique designed to predict optimal response of variablesCentral Composite Design (CCD) was chosen to study theeffect of adsorbent amount (A mg) pH of phenol solution(B) initial phenol concentration (C mgLminus1) and contacttime (D min) on the uptake of phenol Each independentvariable was studied at three different levels (high mediumand low coded as +1 0 and minus1 resp) as shown in Table 1e CCDmodel consists of eighteen batch experiments eachexperiment was performed twice to predict mean values forCCD analysis under Response Surface Methodology (RSM)Design of experiments was analyzed statistically by StatGraphics plus for Windows 51 (Stat Point Technologies Inc2009) [20]

3 Results and Discussions

31 Characterization Figure 2 represents the spectra forEPS Acetyl-PS and PS-Hydrazone surface the characteristicpeak for C=O stretching at 161101 cmminus1 in spectrum-Asupports the conversion of PS into acetyl-PS e disap-pearance of peak for C=O at 161101 cmminus1 in spectrum-B and appearance of additional peak for C=N and NndashHstretching at 1411 cmminus1 and 32925 cmminus1 respectively inspectrum-C supports the conversion of acetyl-PS into PS-hydrazone (PSH) surface

e formation of acetyl-PS and PSH surface was con-rmed by elemental analysis (CNHS Analyser FLASH





100

95

90

85

80

75

70

65

4000 3500 3000 2500 2000 1500 1000 500

A

B

C




T(

)

BBBB

C


1411 cmminus 11021 cmminus 11111111111










Predicted

Residuals

0 20 40 60 80 100

009

019

029

minus021

minus011

minus001

(a)

Predicted

Observed

0 20 40 60 80 100

0

20

40

60

80

100

(b)

Residuals

002 012 022

01

1

5

20

50

80

95

99

999

minus018 minus008

()

(c)

Run order

Resid

uals

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

009

019

029

minus021

minus011

minus001

(d)







100

80

60

40

20

0

Rem

ova

l (

)

2 3 4 5 6 7 8 910

67124

181

pHTime (m

in)

(a)

100

80

60

40

20

0

Rem

ova

l (

)

10 67124

181

Time (min)

5 15 25 35 45 55Conc (mgLminus1)

(b)

100

80

60

40

20

0

Rem

ova

l (

)

2 3 4 56 7 8

9

pH10 30 50 70 90 110Amount (mg)

(c)


0 100 200 300 400 500 600

Standardized eect

AAD time

ABBCAD

A amountBDACCDBB

B conDDCC

C pH

+minus



Amount Con pH Time

0

20

40

60

80

100

Rem

ova

l (

)







1873 00057ndash01 0982 1962 1093 0973





119862119862119890119890119862119862ads

=1119876119876119876119876

+119862119862119890119890119876119876 (2)




119877119877119871119871 =1

1 + 1007649100764911987611987611986211986211989411989410076651007665 (4)








51 70 5 50 100 9993



100

95

90

85

80

75

70

65

60

A

B

T(

)

4000 3500 3000 2500 2000 1500 1000 500


32925 cmminus1


AAA

B

32925 cmminus1

1411 cmminus11021 c 1


N

N

C

H O

H

PhN

N

C

H

H

O Ph

+






4 Conclusion


Conic of neress


References





































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





100

95

90

85

80

75

70

65

4000 3500 3000 2500 2000 1500 1000 500

A

B

C




T(

)

BBBB

C


1411 cmminus 11021 cmminus 11111111111










Predicted

Residuals

0 20 40 60 80 100

009

019

029

minus021

minus011

minus001

(a)

Predicted

Observed

0 20 40 60 80 100

0

20

40

60

80

100

(b)

Residuals

002 012 022

01

1

5

20

50

80

95

99

999

minus018 minus008

()

(c)

Run order

Resid

uals

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

009

019

029

minus021

minus011

minus001

(d)







100

80

60

40

20

0

Rem

ova

l (

)

2 3 4 5 6 7 8 910

67124

181

pHTime (m

in)

(a)

100

80

60

40

20

0

Rem

ova

l (

)

10 67124

181

Time (min)

5 15 25 35 45 55Conc (mgLminus1)

(b)

100

80

60

40

20

0

Rem

ova

l (

)

2 3 4 56 7 8

9

pH10 30 50 70 90 110Amount (mg)

(c)


0 100 200 300 400 500 600

Standardized eect

AAD time

ABBCAD

A amountBDACCDBB

B conDDCC

C pH

+minus



Amount Con pH Time

0

20

40

60

80

100

Rem

ova

l (

)







1873 00057ndash01 0982 1962 1093 0973





119862119862119890119890119862119862ads

=1119876119876119876119876

+119862119862119890119890119876119876 (2)




119877119877119871119871 =1

1 + 1007649100764911987611987611986211986211989411989410076651007665 (4)








51 70 5 50 100 9993



100

95

90

85

80

75

70

65

60

A

B

T(

)

4000 3500 3000 2500 2000 1500 1000 500


32925 cmminus1


AAA

B

32925 cmminus1

1411 cmminus11021 c 1


N

N

C

H O

H

PhN

N

C

H

H

O Ph

+






4 Conclusion


Conic of neress


References





































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Predicted

Residuals

0 20 40 60 80 100

009

019

029

minus021

minus011

minus001

(a)

Predicted

Observed

0 20 40 60 80 100

0

20

40

60

80

100

(b)

Residuals

002 012 022

01

1

5

20

50

80

95

99

999

minus018 minus008

()

(c)

Run order

Resid

uals

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

009

019

029

minus021

minus011

minus001

(d)







100

80

60

40

20

0

Rem

ova

l (

)

2 3 4 5 6 7 8 910

67124

181

pHTime (m

in)

(a)

100

80

60

40

20

0

Rem

ova

l (

)

10 67124

181

Time (min)

5 15 25 35 45 55Conc (mgLminus1)

(b)

100

80

60

40

20

0

Rem

ova

l (

)

2 3 4 56 7 8

9

pH10 30 50 70 90 110Amount (mg)

(c)


0 100 200 300 400 500 600

Standardized eect

AAD time

ABBCAD

A amountBDACCDBB

B conDDCC

C pH

+minus



Amount Con pH Time

0

20

40

60

80

100

Rem

ova

l (

)







1873 00057ndash01 0982 1962 1093 0973





119862119862119890119890119862119862ads

=1119876119876119876119876

+119862119862119890119890119876119876 (2)




119877119877119871119871 =1

1 + 1007649100764911987611987611986211986211989411989410076651007665 (4)








51 70 5 50 100 9993



100

95

90

85

80

75

70

65

60

A

B

T(

)

4000 3500 3000 2500 2000 1500 1000 500


32925 cmminus1


AAA

B

32925 cmminus1

1411 cmminus11021 c 1


N

N

C

H O

H

PhN

N

C

H

H

O Ph

+






4 Conclusion


Conic of neress


References





































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


100

80

60

40

20

0

Rem

ova

l (

)

2 3 4 5 6 7 8 910

67124

181

pHTime (m

in)

(a)

100

80

60

40

20

0

Rem

ova

l (

)

10 67124

181

Time (min)

5 15 25 35 45 55Conc (mgLminus1)

(b)

100

80

60

40

20

0

Rem

ova

l (

)

2 3 4 56 7 8

9

pH10 30 50 70 90 110Amount (mg)

(c)


0 100 200 300 400 500 600

Standardized eect

AAD time

ABBCAD

A amountBDACCDBB

B conDDCC

C pH

+minus



Amount Con pH Time

0

20

40

60

80

100

Rem

ova

l (

)







1873 00057ndash01 0982 1962 1093 0973





119862119862119890119890119862119862ads

=1119876119876119876119876

+119862119862119890119890119876119876 (2)




119877119877119871119871 =1

1 + 1007649100764911987611987611986211986211989411989410076651007665 (4)








51 70 5 50 100 9993



100

95

90

85

80

75

70

65

60

A

B

T(

)

4000 3500 3000 2500 2000 1500 1000 500


32925 cmminus1


AAA

B

32925 cmminus1

1411 cmminus11021 c 1


N

N

C

H O

H

PhN

N

C

H

H

O Ph

+






4 Conclusion


Conic of neress


References





































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




1873 00057ndash01 0982 1962 1093 0973





119862119862119890119890119862119862ads

=1119876119876119876119876

+119862119862119890119890119876119876 (2)




119877119877119871119871 =1

1 + 1007649100764911987611987611986211986211989411989410076651007665 (4)








51 70 5 50 100 9993



100

95

90

85

80

75

70

65

60

A

B

T(

)

4000 3500 3000 2500 2000 1500 1000 500


32925 cmminus1


AAA

B

32925 cmminus1

1411 cmminus11021 c 1


N

N

C

H O

H

PhN

N

C

H

H

O Ph

+






4 Conclusion


Conic of neress


References





































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




51 70 5 50 100 9993



100

95

90

85

80

75

70

65

60

A

B

T(

)

4000 3500 3000 2500 2000 1500 1000 500


32925 cmminus1


AAA

B

32925 cmminus1

1411 cmminus11021 c 1


N

N

C

H O

H

PhN

N

C

H

H

O Ph

+






4 Conclusion


Conic of neress


References





































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

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