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Research ArticlePotential Biosorbent Derived from Calligonum polygonoides forRemoval of Methylene Blue Dye from Aqueous Solution

Asma Nasrullah1 Hizbullah Khan1 Amir Sada Khan12 Zakaria Man2

Nawshad Muhammad3 Muhammad Irfan Khan4 and Naser M Abd El-Salam5

1Department of Chemistry University of Science and Technology Bannu Khyber Pakhtunkhwa 28100 Pakistan2PETRONAS Ionic Liquid Centre Department of Chemical Engineering Universiti Teknologi PETRONAS (UTP)31750 Tronoh Perak Malaysia3Interdisciplinary Research Centre in Biomedical Materials (IRCBM) COMSATS Institute of Information TechnologyLahore Pakistan4Department of Chemical Engineering Universiti Teknologi PETRONAS (UTP) 31750 Tronoh Perak Malaysia5Riyadh Community College King Saud University Riyadh 11437 Saudi Arabia

Correspondence should be addressed to Asma Nasrullah advent chemistyahoocom

Received 23 July 2014 Revised 10 September 2014 Accepted 17 September 2014

Academic Editor Guangliang Liu

Copyright copy 2015 Asma Nasrullah et alThis is an open access article distributed under theCreative CommonsAttribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

The ash of C polygonoides (locally called balanza) was collected from Lakki Marwat Khyber Pakhtunkhwa Pakistan and wasutilized as biosorbent for methylene blue (MB) removal from aqueous solution The ash was used as biosorbent without anyphysical or chemical treatment The biosorbent was characterized by using various techniques such as Fourier transform infraredspectroscopy (FTIR) thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) The particle size and surfacearea were measured using particle size analyzer and Brunauer-Emmett-Teller equation (BET) respectively The SEM and BETresults expressed that the adsorbent has porous nature Effects of various conditions such as initial concentration of methyleneblue (MB) initial pH contact time dosage of biosorbent and stirring rate were also investigated for the adsorption process Therate of the adsorption of MB on biomass sample was fast and equilibrium has been achieved within 1 hour The kinetics of MBadsorption on biosorbent was studied by pseudo-first- and pseudo-second-order kinetic models and the pseudo-second-order hasbetter mathematical fit with correlation coefficient value (1198772) of 0999 The study revealed that C polygonoides ash proved to be aneffective alternative inexpensive and environmentally benign biosorbent for MB removal from aqueous solution

1 Introduction

Environmental pollution is a serious and challenging prob-lem all over the world because of the rapid progress in societyscience technology and industries The industrial effluentcontaining both inorganic and organic toxic material whichdischarging into surface water that seriously affect biodiver-sity ecosystem functioning and natural activities of aquaticsystem Among these pollutants one such pollutant is thesynthetic dyes which are considered to be the most commonand toxic water pollutants [1ndash5] The dye compounds havebeen extensively used in various industries to colorize theproducts such as in papers and pulp textiles plastics wool

paints rubber manufacturing printing cottons cosmeticproducts foods and pharmaceuticals The extensive use ofdyes and dyes containing compounds disturb the aquaticsystem by inhibiting the sunlight from reaching water andthus reducing photosynthesis and increasing the biologicaloxygen demand (BOD) and chemical oxygen demand (COD)values [1ndash3 5] Among these dyes some cause depletion of thedissolved oxygen content of water thus affecting aquatic lifebadly In addition certain textile dyes are carcinogenic andtoxic to living organisms and have adverse effect on humanhealth domestic animals and wildlife [6]

Among the dyeing agents methylene blue (MB) which isa heterocyclic aromatic chemical compound is widely used in

Hindawi Publishing Corporatione Scientific World JournalVolume 2015 Article ID 562693 11 pageshttpdxdoiorg1011552015562693

2 The Scientific World Journal

Table 1 Resonance structure and some important physical properties of MB (3 7-bis(dimethyl amino)phenothiazine-5-ium chloride) [30]

N

N

S

CH3

CH3

CH3+

NH3C NH3C

N

CH3

CH3

CH3

S N+

Mw (gmol) Size (nm) 119878 (gL) log119870ow 119879119898(∘C)

31985 169 times 074 times 038 4360 558 100ndash110Mw molecular weight119878 water solubility at 25∘C119870ow octanol water partition coefficient119879119898 melting point

the textile industries [6ndash9]MB andMB like other textile dyescan cause eye burns in humans and animals skin irritationdyspnea convulsions cyanosis tachycardia and dyspneaand if ingested can cause gastrointestinal tract irritation nau-sea vomiting also diarrhea and so forth [10ndash12]Due to thesetoxicological and hazardous effects of dyes on environmentand subsequently on living organism the removal of thesedyes fromwastewater is a key challenging task for researchersand an important area of research directed towards a betterlife [10 13ndash15]

There are various physical and chemicalmethods used forremoval of textile dyes from aqueous media These includeion exchange membrane filtration electrochemical destruc-tion ozonation flotation chemical coagulation biologicaland chemical oxidation precipitation and electrokinetic andadsorptionmethods [16ndash19] Howevermost of thesemethodshave some major drawbacks such as the applicability atrelative high concentration of dye insufficient dye removalhigh cost and production of extra waste [20] Similarlythe biological methods often demand a very strict controlof experimental conditions and especially the pH and thedecontamination process is usually very slow Alike inchemical oxidation methods the biodegradation productsare often carcinogenic and toxic in nature which affects theaquatic life

Activated carbon has been extensively used as an adsor-bent for the removal of dyes because of the acidic natureand showed pores nature of its surface [21ndash23] However theactivated carbon is costly and challenging in regenerationwhich raises the cost of waste water treatment [24 25]Thus there is a great demand for such type of adsorbentwhich is cheaper and still has high adsorption capabilitytowards pollutants and dyes without any additional expensivepretreatment Presently cellulose and lignocellulosic biomasshave got considerable attraction because of the abundanceeffectiveness low cost and environmentally friendly natureof these biopolymers Thus biosorption has been proved tobe the most effective technique for the removal of MB fromthe aqueous solution [16 26ndash29]

In this research work C polygonoides (locally calledbalanza which is used as fuel for domestic cooking purposesand in bricks kiln industry)was collected fromLakkiMarwatKhyber Pakhtunkhwa Pakistan and utilized as biosorbent

for MB removal from aqueous solution without any physicalor chemical treatment The utilization of this alternativeabundant low cost and environment friendly bioadsorbentwill effectively reduce both the waste disposal problem andthe cost of waste decontamination

2 Materials and Methods

21 Methylene Blue All the chemicals used in the presentresearch work were of analytical grade and purchased fromSigma-Aldrich BDH andMerck MB with chemical formulaC16H18ClN3S3H2O (Table 1) was used as model adsorbent

to study the adsorption capacity of biosorbent The stocksolution of 1000 ppm of MB was prepared and subsequentlytheir solutions of desired concentration were prepared byapplying the dilution formula (119872

11198811= 11987221198812)

22 Preparation of Biosorbent The Calligonum polygonoidesash was washed with double distilled water to remove solubleimpurities and then dried in oven at 110∘C for 5 hours Thepowdered material thus obtained was sieved through 45120583msieve using Retsch AS 200 basic and was stored in air tightglass bottle for further experimental study (Figure 1)

23 Characterization of Biosorbent

231 Scanning Electronic Microscopic (SEM) Analysis Thesurface structure of biosorbent was analyzed using scanningelectron microscopy (JMT-300 JEOL)

232 Surface Area Analysis The surface area of C poly-gonoides ash sample was determined using Brunauer-Emmett-Teller (BET) method and the pore size diameter wasobtained by BJH method from the adsorptiondesorptionisotherm of nitrogen gas at 770 K employing MicromeriticsASAP 2010 apparatus

233 Fourier Transform Infrared Spectroscopy The chemicalstructure and nature of functional groups C polygonoidesash were studied using FTIR transmission spectra on aPerkin Elmer SpectrumOne For FTIR spectrameasurementsample was mixed with KBr in the ratio of 11000 and pressed

The Scientific World Journal 3

(a) C polygonoides (b) C polygonoides ash

Figure 1 Digital photographs of C polygonoides and its ash

into the pellet using a Perkin Elmer hydraulic pump FTIRspectrum was recorded in the wave number range from 4000to 450 cmminus1 with resolution of 5 cmminus1

234 TGAAnalysis To investigate the thermal characteristicor weight-loss profiles of C polygonoides ash a thermogravi-metric analyzer (Pyris-1 Perkin Elmer Shelton CT) was usedover the temperature range from50∘C to 800∘Cat heating rate10∘CminThe analysis was conducted underN

2gas with flow

rate of 50mLmin and weight of samples taken was around5ndash7mg

235 Particle Size Analysis The particle size distributionswere measured using Mastersizer 2000 ver 554 serialnumber Mal 18486 (Malvern Ltd UK) For particles sizedistribution measurement 05 g of C polygonoides ash wasloaded into the tray and dispersed by compress air to bringsample into laser beam for measurement of the particle sizedistributions

24 Experiments for Dye Adsorption The biosorption exper-iment of MB was conducted by adding 100mg of biosorbentto 25mL of aqueous solution of MB dye (4ndash10mgL) in50mL of conical flask and shaken at 300 rpm in orbitalshaker at 298K After specific interval of time samplealiquots were withdrawn and centrifuged to separate thedye loaded from dye solution The remaining concentration

of MB was measured spectrophotometrically by measuringthe absorbance of the supernatant (dye solution) left aftercentrifugation To find the optimum experimental condi-tions for MB removal for MB removal the effect of time(10ndash120min) initial dye concentration (2mgLndash10mgL)biosorbent loading (20ndash100mg) and shaking velocity (100ndash600 rpm) were thoroughly studied

The color removal efficiency (119877) and adsorption capacityof C polygonoides ash were measured by applying the follow-ing equations

(119877) = (1198620minus 119862119905

1198620

) 100 (1)

119902119905=(1198620minus 119862119905) 119881

119898

(2)

119902119890=(1198620minus 119862119890) 119881

119898 (3)

where 119902119890and 119902

119905(mgg) are the amount of MB adsorbed at

time 119905 and equilibrium respectively 1198620 119862119905 and 119862

119890(mgL)

are concentration of MB at initial time 119905 and equilibriumrespectively 119881 is the solution volume and 119898 (g) is the massof biosorbent

25 Kinetic Study and Model Fitting To study the adsorptionmechanism of MB on biosorbent pseudo-first- and pseudo-second-order kinetic models were used


251 The Pseudo-First-Order Equation The pseudo-first-order kineticmodel or Lagergren kinetic equation is generallyexpressed as follows

log (119902119890minus 119902119905) = log 119902

1minus 1198961sdot119905

2303 (4)

where 119902119890is the amounts adsorbed (mgg) at equilibrium 119902

119905

is the amounts adsorbed (mgg) at any time and 1198961is the

adsorption rate constant for pseudo-first-order (sminus1)

252 The Pseudo-Second-Order Model If the rate of sorp-tion is a second-order mechanism the pseudo-second-orderkinetic rate equation is used and it is expressed as

119889119902119905

119889119905= 1198962(1199022minus 119902119905)2

119889119902119905

(1199022minus 119902119905)2= 1198962119889119905

(5)

By integration of (3) for the boundary conditions when 119905 = 0and 119902119905= 119902119894

1

1199022minus 119902119905

=1

1199022

+ 1198962119889119905 (6)

where 1198962(gmgsdotmin) is the rate constant of pseudo-second-

order

119905

119902119905

=1

11989621199022

2

+1

1199022

119905 (7)

If 119905119902119905is plotted against 119905 it gives a straight line which means

that the adsorption follows pseudo-second-order kineticsThis model is based upon the assumption if the rate limitingstep may be chemisorption which involve valence forces dueto the electron sharing or exchange of electron between theadsorbent and adsorbate

3 Results and Discussion

31 Particle Size Distributions After thermal treatment theparticle size of adsorbent decreases Decrease in particles sizeof adsorbent usually results in enhanced adsorption of dyebecause the adsorption capacity of the adsorbent is directlyproportional to the exposed surface area and inversely relatedto the particle diameter of nonporous material [42] Byincreasing the particle size the number of particles per givenmass decreases which results in decrease in specific surfacearea and hence the adsorption capacity The particle sizedistribution of pure C polygonoides powder changed from(01) 1239 120583m (05) 12079120583m and (09) 480309 120583m to (01)236 120583m (05) 2790120583m and (09) 38284 120583m respectivelyafter burning The C polygonoides ash sample becomes blackin color with some gray particles resulting from differentstages of carbon combustion during burning process ofthe biomass The amount of black particles decreases withincreasing the calcination time and temperature

Table 2 Surface properties of C polygonoides ash

Surface properties ValuesBET surface area 43810m2

sdotgminus1

Average pores volume 0016691 cm3sdotgminus1

Average pore diameter 15256 A

32 Surface Area (BET) The process of adsorption is amultistep complex phenomenon and therefore many factorsaffect the phenomenon Among these factors the pore sizeof adsorbent significantly affects the adsorption processPores size is generally classified into various groups suchas micropores (lt2 nm diameter) mesopores (2ndash50 nm) andmacropores (gt50 nm) The surface chemistry of adsorbentand its pores structure considerably affect the adsorption ofbig molecules like MB into its structure MB has molecularcross-sectional diameter of about 08 nm and cannot easilypenetrate material with pores smaller than 13 nm Thesurface area ofC polygonoides ash depends on the amorphouscarbon content During the dye adsorption process thediffusion of dye molecules to the active sites takes place firstwhich is followed by attachment of these dyemolecules to theactive sites The pore size and total pore volume thus play adecisive role in the adsorption process

C polygonoides ash has significant surface area and widepore size distributionTheBET surface area ofC polygonoidesash is 43810m2g whereas BJH adsorptiondesorption sur-face area of pores of C polygonoides ash is 411947108m2gFor C polygonoides ash the single point total pore volume ofpores (119889

119862 119901119900119897119910119892119900119899119900119894119889119890119904lt 3166 A) is found to be 0016691 cm3g

The cumulative adsorptiondesorption pore volume of thepores (17 A lt 119889 lt 3000 A) of C polygonoides ash is0019823019556 cm3g (Table 2) The C polygonoides ashthus is found to consist of mesopores predominantly Thisis what is desirable for the liquid phase adsorptive removal ofmetal ions and dyes

33 Fourier Transform Infrared Spectroscopy It is importantto know the exact chemical structure of the adsorbent inorder to understand the adsorption process FTIR spec-troscopy was thus employed to characterize the chemicalstructure of C polygonoides before and after thermal treat-ment (Figure 2) The broad band around 3400 cmminus1 can beassigned to the stretching vibration of OndashH andNndashH groupsThis peak is broad because of the complex vibrational modesdue to participation of ndashOH group in hydrogen bondingThis peak represents the presence of hydroxyl group andchemisorbed water in the adsorbent [43 44] Beside thisthe vibrational modes in this area also correspond to inter-and intramolecular hydrogen bonding The presence of apeak at 2910 cmminus1 shows the symmetric and asymmetric CndashH stretching due to the existence of methyl andor methylenegroups [45] The peak located at 1380 cmminus1 is indicative of ndashCH3group The sharp intense peak at about 1637 cmminus1 cor-

responds to OndashH bending vibration of secondary adsorbedwater molecules The bands at 1528 and 1445 cmminus1 confirmthe presence of C=C bond of alkene and aromatic ring [46]


Wavenumber (cmminus1)4000 3500 3000 2500 2000 1500 1000 500

20

30

40

50

60

70

80

90

34122928

1637

15291445

13721240

11063700

34352927

2516

14601419 1119

874

713

a

b

T(

)

Figure 2 FTIR spectra of (a)C polygonoides and (b)C polygonoidesash

The FTIR spectra showed the presence of another peak at1100 cmminus1 which may tentatively be assigned to SindashOndashSi andndashCndashOndashH stretching and ndashOH deformation The absorptionpeaks in region from 1000 to 1200 cmminus1 represented themain skeleton of cellulose The presence of peak at 1035 cmminus1represents stretching vibration of cellulosehemicellulose andary-OH group in lignin The presence of polar groups onthe surface is likely to give considerable cation exchangecapacity to the adsorbents The occurrence of peaks at about793 shows the existence of SindashH [35] The presence ofadsorption band in region from 1300 to 900 cmminus1 representsthe carbonyl component (ie alcohols esters carboxylicacid or ethers) [16 47] The presence of absorbance peaksin region from 900 cmminus1 shows OndashH stretching vibrationswhich represented aromatic groups In C polygonoides ashthe peak (900 cmminus1) of secondary adsorbed water is notpresent because of thermal treatmentThe appearance of peakat 3700 cmminus1 in C polygonoides ash is related to stretching offree OndashH functional group [35]The presence of polar groupson the surface is likely to give considerable cation exchangecapacity to the adsorbents

34 Morphology of Adsorbent Scanning electronic micros-copy (SEM) study is one the most popular primary andwidely used characterization techniques applied for the studyof surface properties andmorphology of biosorbent materialMoreover SEM study also tells about porosity and textureof biosorbent material [25 44 48 49] Figure 3 shows thatC polygonoides ash has small cavities on surface and hasa porous texture that may provide large surface for theadsorption of the dye molecules

35 Thermogravimetric Analysis Thermogravimetric anal-ysis (TGA) is an important analytical technique used tostudy the thermal characteristics of carbonaceous materialsThe TGA provide information on the degradation processof material occurring at different temperatures and underdifferent atmosphere

Figure 3 SEM analysis of C polygonoides ash

The C polygonoides ash was subjected to TGA underargon atmosphere Figures 4(a) and 4(b) show the TGA anddifferential thermal analysis (DTA) curves forC polygonoidesash respectively TGA result of C polygonoides ash shows atypical three-stage mass loss

(i) The first mass decomposition occurred below 100∘Cwhich could attribute to water eliminationdesorp-tion which are physically absorbed in C polygonoidesash The DTA graph also shows an endothermic peakat 100∘C In this region the loss of very small amountof volatile compounds may also be contributed to theweight loss

(ii) The secondmass loss which appeared around 300∘C isdue to the thermal decomposition of cellulosehemi-celluloselignin degradation

(iii) The third mass decomposition occurred between 350and 550∘C corresponding to the burning of carbona-ceous residues [50]

4 Optimizations of Parameters

41 Effect of Contact Time and Initial Concentration of DyeThe time of contact between the dye and adsorbent and alsothe concentration of dye can affect the adsorption processFigures 5(a) and 5(b) show adsorption with respect to contacttime and initial concentration of MB on the surface ofC polygonoides ash respectively The removal efficiencyand adsorption capacity of MB increased with increase ofcontact time and reached equilibrium after 60min Increasein contact time after 60min cannot enhance the adsorptionof MB on C polygonoides ash [50] In the beginning the removal of dye is very rapid due to the adsorption ofmore molecules of dye on the unsaturated external surfaceof adsorbent After 60min the surface pores of adsorbentare covered and it becomes difficult for dyes molecule toenter into the interior of adsorbent The initial rapid removal of dye may be due presence of more binding sites foradsorption of dye molecules and the slow removal of dye inthe last stages may be due to occupationsaturation of thesebinding sites with dyes molecules [51] The equilibrium timerequired for the adsorption of different dye concentration isindependent of their initial concentration The result showsthat for all of the initial concentration the equilibrium wasreached in the same time Khattri and Sing also obtained


100 200 300 400 500 600 700 800

40

50

60

70

80

90

100W

eigh

t cha

nge (

)

Temperature (∘C)

(a)

100 200 300 400 500 600 700 800

Der

ivat

ive w

eigh

t

minus30

minus25

minus20

minus15

minus10

minus05

00

05

Temperature (∘C)

(b)

Figure 4 (a) TGA curve of C polygonoides ash (b) DTA curve of C polygonoides ash

0 10 20 30 40 50 60 70 80 90 100 110 120 130767880828486889092949698

100

Adso

rptio

n (

)

Time (min)

10mgL8mgL

6mgL4mgL

(a)

0 20 40 60 80 100 120 140

6

9

12

15

18

21

24

27

30Ad

sorp

tion

capa

city

(mg

g)

Time (min)

10mgL8mgL

6mgL4mgL

(b)

Figure 5 (a) Effect of contact time on adsorption of MB on C polygonoides ash (b) Adsorption capacity plot for adsorption of variousconcentration of MB on C polygonoides ash

the same observation during adsorption of MG on neemsawdust [35 44 50] It was found that with increase of theconcentration of dye from 4 to 10mgL the rate of adsorptionand thus removal and adsorption capacity increase It isvery common practice in the adsorption of dyes moleculesthat with increase of initial concentration of dyes the capacityof adsorption increases because of strong driving force andtransfers of more dye molecules from aqueous phase to solidphase increase [15]

Tables 3(a) and 3(b) show a comparison of removal andadsorption capacity of C polygonoides ash with that of otheradsorbents reported in the literature It becomes clear that theadsorption capacity of the C polygonoides ash is higher thanmany of the reported adsorbents

42 Effect of Shaking Speed To investigate the effect of stir-ring speed on the adsorption of MB on C polygonoides ashthe experiments were carried using different stirring speedfrom 100 to 600 using dye concentration of 10mgL contacttime was 60min and the temperature was 298K Figure 6shows the effect of shaking speed on theMB adsorptionWithincreasing of the shaking speed the adsorption or removalof dye from aqueous solution was increased This increasein adsorption reached a maximum at 300 rpm and after thisthere is no such considerable increase in the adsorption ofdyes This increase in adsorption reached a maximum at300 rpm and further increase in speed had no significanteffect on the adsorption of the dyeThe increase in adsorptionof MBmay be to the decrease in the thickness of diffuse layer


Table 3 (a) Comparison of contact time for dye adsorption (b)Comparison of adsorption capacity of C polygonoides with otherreported adsorbents

(a)

Adsorbent Shaking timemin ReferencesC polygonoides 60min This workTea waste 720 [31]Jackfruit leaf 300 [32]Pomelo skin 315 [33]Jackfruit peel 180 [34]Coconut bunch waste 300 [35]

(b)

AdsorbentAdsorption capacity References

(mgg)

C polygonoides 2472 This workNaOH treated rawkaolin

1634 [36]

NaOH treated purekaolin

2049 [36]

Beech sawdustpretreated with CaCl2

1302 [37]

Calotropisprocera leaf 417 [38]Orange peel 143 [39]Jute fiber carbon 2799 [40]Sawdust 3783 [41]

around the surface of adsorbent with increasing the stirringspeed [13]

43 Effect of Adsorbent Dose The amount of adsorbentgreatly affects the removal of dye from aqueous solutionThe effect of C polygonoides ash amount on MB adsorptionwas investigated in the range from 20mg to 100mg Figure 7shows that with increase of C polygonoides ash amount the adsorption capacity of MB is increased [52] This increasein adsorption of MB with the increase of C polygonoides ashamount is due to the increase in the availability of more andmore surface area and active sites Similarly by increasing thesurface area more and more adsorption pores are availablefor MB adsorption [53] Further increase in concentration ofboth C polygonoides ash beyond 100mg the adsorption ofMB cannot increase this may be due to saturation of vacantspaces or the aggregationagglomeration of biosorbent parti-cles with each other In the present study therefore 100mg ofC polygonoides ash was optimized Similar results have beenreported by other researchers for other dye adsorptions [54]

44 Kinetics of Adsorption and Model Fittings The adsorp-tion mechanism process of MB on C polygonoides ash wasevaluated by using pseudo-first-order and pseudo-second-order kinetic models [55] (Table 4) From Figure 8 andTables 5 and 6 it is clear that the adsorption of MB onC polygonoides can be fitted in the pseudo-second-orderkinetics with regression coefficient (1198772) 0999

0 100 200 300 400 500 600 700

87

90

93

96

99

102

Adso

rptio

n (

)

Shaking speed (rpm)

Figure 6 Effect of shaking speed on adsorption of MB on Cpolygonoides ash

20 40 60 80 100 120 14068

72

76

80

84

88

92

96

100

Rem

oval

()

Adsorbent amount (mg)

Figure 7 Effect of adsorption dose on MB adsorption on Cpolygonoides ash

Table 4 Pseudo-first-order kinetics data for adsorption of MB onC polygonoides ash

Conc mgL Intercept Slope 1198772

4 minus0711 minus00220 0999536 minus06242 minus00272 098398 minus05695 minus00298 0952210 minus04653 minus00361 08851

Table 5 Pseudo-second-order kinetics data for adsorption of MBC polygonoides ash


4 168 107 099986 175 105 099998 173 103 0999810 167 101 0999

45 Intraparticle and Liquid Film Diffusion Model The dif-fusivity of the solute molecules plays an important role inthe determination of overall rate of an adsorption process


Table 6 Pseudo-second-order kinetic parameters of various kinet-ics parameters for the adsorption of MB onto C polygonoides atdifferent initial dye concentrations

Conc 1199022

1198962

ℎ1198772

mgL (mg gminus1) (gmgminus1minminus1) (mg gminus1minminus1)4 093 046 0402 099996 095 051 0467 099998 096 054 0507 0999810 098 058 0567 09999

Although the pseudo-second-order equation was found tothe best fitted order for present experimental data the resultsobtained from this model are not sufficient to predict thediffusion mechanism During a solidliquid adsorption pro-cess adsorbate transfer was usually governed by liquid phasemass transport (boundary-layer diffusion) or intraparticlemass diffusion or both The slowest step which might beeither film diffusion or pore diffusion would obviously be theoverall rate-controlling step of the adsorption process Theintraparticle and liquid film diffusionmodels are representedby

119902119905= 119870119894sdot 11988911990505 (8)

Figure 9 shows the interparticle diffusionmodel fitting for theadsorption of various concentration of MB The result showsthat the plot of 119902 versus 11990505 is not very linear for whole timeand can be divided into two regionsThemultilinearity of theplot for MB adsorption shows the multistage adsorption ofMB on the C polygonoides Normally if the plot of 119902

119905versus

11990505 passed through origin this indicates the interparticlediffusion is only the rate limiting step However in this studyit is clear that the plot of 119902 versus 11990505 is not passing throughthe origin which shows that the intraparticle diffusion is notinvolved in the adsorption process therefore it is not a solerate-controlling stepThis result confirms that the adsorptionprocess is followed by two or more than two phases [4 56]

In the first region the plot is linear due to mass transferwhich allows the MB molecules to be transported to theexternal surface of biomass through film diffusion In thisportion the adsorption is very first because of the stronginteraction between the MB molecules and the externalsurface of the adsorbent

After boundary-layer diffusion the MB moleculesentered through pores to the interior of the biomass byintraparticle diffusion as reflected by the second linearportion of the plot The stage of gradual adsorption whoserate was controlled by intraparticle diffusion was followedby a final equilibrium stage during which the intraparticlediffusion started to slow and become stagnant as theadsorbate molecules occupied all of the active sites of theadsorbent and the maximum adsorption was attainedAlthough all of the intraparticle diffusion plots for differentinitial dye concentrations provided a linear relationshipnone of the line segments passed through the origin Thenonzero intercepts of the plots indicate that intraparticlediffusion is involved in the adsorption process but is not

10mgL8mgL

6mgL4mgL

tqt

0 20 40 60 80 100 1200

20

40

60

80

100

120

140

Time (min)

(min

gm

g)

Figure 8 Pseudo-second-order kinetics plot for adsorption of MBon C polygonoides ash

10mgL8mgL

6mgL4mgL

t05 (min)2 3 4 5 6 7 8 9 10 11 12 13

6

9

12

15

18

21

24

27Ad

sorp

tion

capa

city

(mg

g)

Figure 9 Plot of intraparticle diffusion model for MB adsorptionby C polygonoides ash at different initial dye concentrations

the sole rate-controlling step for the adsorption of MB Theincrement of 119896

119894119889with increasing initial MB concentration

simplifies that the increased driving force at high initialconcentrations promotes intraparticle diffusion of theadsorbate onto the adsorbent

46 Adsorption Mechanism of Dye The adsorption mecha-nism depends on the structure of dye molecule and also thesurface of adsorbent The MB is cationic dye having aminegroup in its structure formula and while dissolving in waterits molecule dissociated into MB+ and Clminus1 The FTIR resultshows that the C polygonoides ash has ndashOH group which ismore exposed and has strong chemical interaction betweendye ions and adsorbent and interacts mechanically becauseof easy penetration of dye ions to the microstructure ofadsorbent


N

CH3

S+

CH3

CH3

CH3

N

N

Clminus

N+CH3N

Clminus

S

N

CH3 CH3

CH3

HOOH OH OH

OHOHOH

O1 4

CH2OH CH2OH CH2OH

O O

O O OC polygonoidesH-bonding

Figure 10 Mechanism of adsorption of MB molecules on biosorbent

The mechanism for adsorption of MB on adsorbent maybe involving the following major steps

(a) Migration of DyeMolecules In this step the passage of MBmolecules from bulk of the solution occurred to the surfaceof the adsorbent

(b) Diffusion of DyeMolecules In this step the diffusion of dyemolecules can take place through the boundary layer to thesurface of the adsorbent

(c) Adsorption of DyeMolecules In this step there is formationof surface hydrogen bonding between the nitrogen atom ofMB and hydroxyl group of C polygonoides ash Figure 10shows the proposed possible mechanism for adsorption ofMB molecules on the surface of C polygonoides ash

CPndashOH 997888rarr CPndashOminus +H+

CPndashOminus +MBplusmn 997888rarr CPndashOndashMB +H+(9)

(d) Intraparticle Diffusion of Dye In this final step the dyemolecules get approached inside the pores of adsorbent

5 Conclusions

From this present research work the following main conclu-sions are investigated

C polygonoides ash is proved to be the promising biosor-bent for removal of MB from aqueous solution The per-centage of removal of dye on these biosorbents is fast and

adsorption equilibrium is achieved in about 60min Morethan 97 removal of MBwas approached in first 60min afterthat no increase in adsorption was taking place Dye adsorp-tion increased with the increase in the amount of adsorbateThe adsorption of MB on C polygonoides ash adsorbentfollowed the pseudo-second-order kinetics models which areindicated by correlation coefficient values A comparison ofadsorption capacity of C polygonoides ash with many otherbiosorbents reported in the literature indicates far betterperformance of C polygonoides Due to its low cost highadsorption capacity and environmentally friendly nature Cpolygonoides ash could be used as a promising adsorbent infuture for effective large scale removal of MB from aqueoussolution on a large scale

Conflict of Interests

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

Acknowledgments

The authors acknowledge the Department of ChemistryUniversity of Science and Technology Bannu 28100 KhyberPakhtunkhwa Pakistan for supporting this research workand also thankful to theDeanship of Scientific Research KingSaud University Riyadh for funding the work through thecollaborative research work with research group Project noRGP-210


References

[1] M A Martın-Gonzalez O Gonzalez-Dıaz P Susial et alldquoReuse of phoenix canariensis palm frond mulch as biosorbentand as precursor of activated carbons for the adsorption ofImazalil in aqueous phaserdquo Chemical Engineering Journal vol245 pp 348ndash358 2014

[2] R RMohammed andM F Chong ldquoTreatment and decoloriza-tion of biologically treated PalmOilMill Effluent (POME) usingbanana peel as novel biosorbentrdquo Journal of EnvironmentalManagement vol 132 pp 237ndash249 2014

[3] M T Yagub T K Sen S Afroze and H M Ang ldquoDye andits removal from aqueous solution by adsorption a reviewrdquoAdvances in Colloid and Interface Science vol 209 pp 172ndash1842014

[4] A Roy B Adhikari and S B Majumder ldquoEquilibrium kineticand thermodynamic studies of azo dye adsorption from aque-ous solution by chemically modified lignocellulosic jute fiberrdquoIndustrial and Engineering Chemistry Research vol 52 no 19pp 6502ndash6512 2013

[5] R Christie Environmental Aspects of Textile Dyeing ElsevierNew York NY USA 2007

[6] M Rafatullah O Sulaiman R Hashim and A AhmadldquoAdsorption of methylene blue on low-cost adsorbents areviewrdquo Journal of HazardousMaterials vol 177 no 1ndash3 pp 70ndash80 2010

[7] S Chatterjee A Kumar S Basu and S Dutta ldquoApplication ofresponse surface methodology for methylene blue dye removalfrom aqueous solution using low cost adsorbentrdquo ChemicalEngineering Journal vol 181-182 pp 289ndash299 2012

[8] C Kannan K Muthuraja and M R Devi ldquoHazardous dyesremoval fromaqueous solution overmesoporous aluminophos-phate with textural porosity by adsorptionrdquo Journal of Haz-ardous Materials vol 244-245 pp 10ndash20 2013

[9] Z Chen J Zhang J Fu et al ldquoAdsorption of methyleneblue onto poly(cyclotriphosphazene-co-441015840-sulfonyldiphenol)nanotubes kinetics isotherm and thermodynamics analysisrdquoJournal of Hazardous Materials vol 273 pp 263ndash271 2014

[10] M Gouamid M R Ouahrani and M B Bensaci ldquoAdsorptionequilibrium kinetics and thermodynamics of methylene bluefrom aqueous solutions using date palm leavesrdquo Energy Proce-dia vol 36 pp 898ndash907 2013

[11] X Luo S Zhang and X Lin ldquoNew insights on degradationof methylene blue using thermocatalytic reactions catalyzed bylow-temperature excitationrdquo Journal of Hazardous Materialsvol 260 pp 112ndash121 2013

[12] C Zhou S Lee K Dooley and Q Wu ldquoA facile approachto fabricate porous nanocomposite gels based on partiallyhydrolyzed polyacrylamide and cellulose nanocrystals foradsorbing methylene blue at low concentrationsrdquo Journal ofHazardous Materials vol 263 part 2 pp 334ndash341 2013

[13] F A Pavan E C Lima S L P Dias and A C MazzocatoldquoMethylene blue biosorption from aqueous solutions by yellowpassion fruit wasterdquo Journal ofHazardousMaterials vol 150 no3 pp 703ndash712 2008

[14] S M de Oliveira Brito H M C Andrade L F Soares and RP de Azevedo ldquoBrazil nut shells as a new biosorbent to removemethylene blue and indigo carmine from aqueous solutionsrdquoJournal ofHazardousMaterials vol 174 no 1ndash3 pp 84ndash92 2010

[15] X Han W Wang and X Ma ldquoAdsorption characteristics ofmethylene blue onto low cost biomass material lotus leafrdquoChemical Engineering Journal vol 171 no 1 pp 1ndash8 2011

[16] Y-Z Zhang Y-Q Jin Q-F Lu and X-S Cheng ldquoRemoval ofcopper ions and methylene blue from aqueous solution usingchemicallymodifiedmixed hardwoods powder as a biosorbentrdquoIndustrial and Engineering Chemistry Research vol 53 no 11pp 4247ndash4253 2014

[17] A Mittal V K Gupta A Malviya and J Mittal ldquoProcess devel-opment for the batch and bulk removal and recovery of a haz-ardous water-soluble azo dye (Metanil Yellow) by adsorptionover waste materials (BottomAsh and De-Oiled Soya)rdquo Journalof Hazardous Materials vol 151 no 2-3 pp 821ndash832 2008

[18] LMNieto S B D Alami G Hodaifa et al ldquoAdsorption of ironon crude olive stonesrdquo Industrial Crops and Products vol 32 no3 pp 467ndash471 2010

[19] S Karthikeyan V K Gupta R Boopathy A Titus and GSekaran ldquoA new approach for the degradation of high concen-tration of aromatic amine by heterocatalytic Fenton oxidationKinetic and spectroscopic studiesrdquo Journal ofMolecular Liquidsvol 173 pp 153ndash163 2012

[20] S S Ahluwalia and D Goyal ldquoMicrobial and plant derivedbiomass for removal of heavy metals from wastewaterrdquo Biore-source Technology vol 98 no 12 pp 2243ndash2257 2007

[21] L Ai C Zhang F Liao et al ldquoRemoval of methylene blue fromaqueous solution with magnetite loaded multi-wall carbonnanotube kinetic isotherm and mechanism analysisrdquo Journalof Hazardous Materials vol 198 pp 282ndash290 2011

[22] A Kurniawan and S Ismadji ldquoPotential utilization of Jatrophacurcas L press-cake residue as new precursor for activated car-bon preparation application in methylene blue removal fromaqueous solutionrdquo Journal of the Taiwan Institute of ChemicalEngineers vol 42 no 5 pp 826ndash836 2011

[23] L Ai and J Jiang ldquoRemoval of methylene blue from aqueoussolution with self-assembled cylindrical graphene-carbon nan-otube hybridrdquo Chemical Engineering Journal vol 192 pp 156ndash163 2012

[24] V KGupta S Agarwal andTA Saleh ldquoChromium removal bycombining the magnetic properties of iron oxide with adsorp-tion properties of carbon nanotubesrdquo Water Research vol 45no 6 pp 2207ndash2212 2011

[25] J P Chen S Wu and K H Chong ldquoSurface modification ofa granular activated carbon by citric acid for enhancement ofcopper adsorptionrdquo Carbon vol 41 no 10 pp 1979ndash1986 2003

[26] V K Gupta A Mittal L Kurup and J Mittal ldquoAdsorptionof a hazardous dye erythrosine over hen feathersrdquo Journal ofColloid and Interface Science vol 304 no 1 pp 52ndash57 2006

[27] Y Wang X J Wang M Liu et al ldquoCr(VI) removal from waterusing cobalt-coated bamboo charcoal prepared withmicrowaveheatingrdquo Industrial Crops and Products vol 39 no 1 pp 81ndash882012

[28] M T Yagub T K Sen and M Ang ldquoRemoval of cationic dyemethylene blue (MB) from aqueous solution by ground raw andbasemodified pine cone powderrdquoEnvironmental Earth Sciencesvol 71 no 4 pp 1507ndash1519 2014

[29] A E Ofomaja A Pholosi and E B Naidoo ldquoKinetics andcompetitive modeling of cesium biosortion onto chemicallymodified pine cone powderrdquo Journal of the Taiwan Institute ofChemical Engineers vol 44 no 6 pp 943ndash951 2013

[30] Z-Y Zhang and X-C Xu ldquoWrapping carbon nanotubes withpoly (sodium 4-styrenesulfonate) for enhanced adsorption ofmethylene blue and its mechanismrdquo Chemical EngineeringJournal vol 256 pp 85ndash92 2014


[31] N Nasuha and B H Hameed ldquoAdsorption of methylene bluefrom aqueous solution onto NaOH-modified rejected teardquoChemical Engineering Journal vol 166 no 2 pp 783ndash786 2011

[32] M T Uddin M Rukanuzzaman M M R Khan and A IslamldquoJackfruit (Artocarpus heterophyllus) leaf powder an effectiveadsorbent for removal of methylene blue from aqueous solu-tionsrdquo Indian Journal of Chemical Technology vol 16 no 2 pp142ndash149 2009

[33] B H Hameed D K Mahmoud and A L Ahmad ldquoSorptionof basic dye from aqueous solution by pomelo (Citrus grandis)peel in a batch systemrdquoColloids and Surfaces A Physicochemicaland Engineering Aspects vol 316 no 1ndash3 pp 78ndash84 2008

[34] B Hameed ldquoRemoval of cationic dye from aqueous solutionusing jackfruit peel as non-conventional low-cost adsorbentrdquoJournal of Hazardous Materials vol 162 no 1 pp 344ndash3502009

[35] S Khattri and M Singh ldquoRemoval of malachite green fromdye wastewater using neem sawdust by adsorptionrdquo Journal ofHazardous Materials vol 167 no 1ndash3 pp 1089ndash1094 2009

[36] D Ghosh and K G Bhattacharyya ldquoAdsorption of methyleneblue on kaoliniterdquo Applied Clay Science vol 20 no 6 pp 295ndash300 2002

[37] F A Batzias and D K Sidiras ldquoDye adsorption by calciumchloride treated beech sawdust in batch and fixed-bed systemsrdquoJournal of Hazardous Materials vol 114 no 1ndash3 pp 167ndash1742004

[38] H Ali and S KMuhammad ldquoBiosorption of crystal violet fromwater on leaf biomass of Calotropis procerardquo Journal of Environ-mental Science and Technology vol 1 pp 143ndash150 2008

[39] G Annadurai R S Juang and D J Lee ldquoUse of cellulose-basedwastes for adsorption of dyes from aqueous solutionsrdquo Journalof Hazardous Materials vol 92 no 3 pp 263ndash274 2002

[40] K Porkodi and K V Kumar ldquoEquilibrium kinetics and mech-anismmodeling and simulation of basic and acid dyes sorptiononto jute fiber carbon Eosin yellow malachite green andcrystal violet single component systemsrdquo Journal of HazardousMaterials vol 143 no 1-2 pp 311ndash327 2007

[41] H Parab M Sudersanan N Shenoy T Pathare and B VazeldquoUse of agro-industrial wastes for removal of basic dyes fromaqueous solutionsrdquo CleanmdashSoil Air Water vol 37 no 12 pp963ndash969 2009

[42] A Said M Abd El-Wahab S A Soliman and A Aly ldquoPotentialapplication of propionic acid modified sugarcane bagasse forremoval of basic and acid dyes from industrial wastewaterrdquo inProceedings of the International Conference on EnvironmentalEngineering and Applications (ICEEA rsquo10) pp 154ndash156 Septem-ber 2010

[43] A A M Daifullah B S Girgis and H M H Gad ldquoUtilizationof agro-residues (rice husk) in small waste water treatmentplansrdquoMaterials Letters vol 57 no 11 pp 1723ndash1731 2003

[44] L B L Lim N Priyantha D T B Tennakoon H I Chieng MK Dahri and M Suklueng ldquoBreadnut peel as a highly effectivelow-cost biosorbent for methylene blue equilibrium thermo-dynamic and kinetic studiesrdquo Arabian Journal of Chemistry2014

[45] Q-F Lu Z-K Huang B Liu and X Cheng ldquoPreparation andheavy metal ions biosorption of graft copolymers from enzy-matic hydrolysis lignin and amino acidsrdquo Bioresource Technol-ogy vol 104 pp 111ndash118 2012

[46] E Natarajan and E G Sundaram ldquoPyrolysis of rice husk in afixed bed reactorrdquo World Academy of Science Engineering andTechnology vol 56 no 32 pp 504ndash508 2009

[47] R Gong Y Jin F Chen J Chen and Z Liu ldquoEnhanced mala-chite green removal from aqueous solution by citric acidmodified rice strawrdquo Journal of Hazardous Materials vol 137no 2 pp 865ndash870 2006

[48] K G Bhattacharyya and A Sharma ldquoAzadirachta indica leafpowder as an effective biosorbent for dyes a case study withaqueous Congo Red solutionsrdquo Journal of Environmental Man-agement vol 71 no 3 pp 217ndash229 2004

[49] G Akkaya and F Guzel ldquoBioremoval and recovery of Cu(II)and Pb(II) from aqueous solution by a novel biosorbent water-melon (Citrullus lanatus) seed hulls kinetic study equilibriumisotherm SEM and FTIR analysisrdquo Desalination and WaterTreatment vol 51 no 37ndash39 pp 7311ndash7322 2013

[50] Z A AlOthman M A Habila R Ali A Abdel Ghafar andM S El-din Hassouna ldquoValorization of two waste streamsinto activated carbon and studying its adsorption kineticsequilibrium isotherms and thermodynamics formethylene blueremovalrdquo Arabian Journal of Chemistry 2013

[51] A P Vieira S A A Santana C W B Bezerra et al ldquoKineticsand thermodynamics of textile dye adsorption from aqueoussolutions using babassu coconut mesocarprdquo Journal of Haz-ardous Materials vol 166 no 2-3 pp 1272ndash1278 2009

[52] E I Unuabonah G U Adie L O Onah and O G AdeyemildquoMultistage optimization of the adsorption of methylene bluedye onto defatted Carica papaya seedsrdquo Chemical EngineeringJournal vol 155 no 3 pp 567ndash579 2009

[53] V Nair A Panigrahy and R Vinu ldquoDevelopment of novelchitosan-lignin composites for adsorption of dyes and metalions from wastewaterrdquo Chemical Engineering Journal vol 254pp 491ndash502 2014

[54] J-Z Guo B Li L Liu and K Lv ldquoRemoval of methylene bluefrom aqueous solutions by chemically modified bamboordquoChemosphere vol 111 pp 225ndash231 2014

[55] Y S Ho J C Y Ng and G McKay ldquoKinetics of pollutantsorption by biosorbents reviewrdquo Separation and PurificationMethods vol 29 no 2 pp 189ndash232 2000

[56] V K Gupta D Pathania N C Kothiyal and G SharmaldquoPolyaniline zirconium (IV) silicophosphate nanocomposite forremediation ofmethylene blue dye fromwaste waterrdquo Journal ofMolecular Liquids vol 190 pp 139ndash145 2014

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


Table 1 Resonance structure and some important physical properties of MB (3 7-bis(dimethyl amino)phenothiazine-5-ium chloride) [30]

N

N

S

CH3

CH3

CH3+

NH3C NH3C

N

CH3

CH3

CH3

S N+

Mw (gmol) Size (nm) 119878 (gL) log119870ow 119879119898(∘C)

31985 169 times 074 times 038 4360 558 100ndash110Mw molecular weight119878 water solubility at 25∘C119870ow octanol water partition coefficient119879119898 melting point

the textile industries [6ndash9]MB andMB like other textile dyescan cause eye burns in humans and animals skin irritationdyspnea convulsions cyanosis tachycardia and dyspneaand if ingested can cause gastrointestinal tract irritation nau-sea vomiting also diarrhea and so forth [10ndash12]Due to thesetoxicological and hazardous effects of dyes on environmentand subsequently on living organism the removal of thesedyes fromwastewater is a key challenging task for researchersand an important area of research directed towards a betterlife [10 13ndash15]

There are various physical and chemicalmethods used forremoval of textile dyes from aqueous media These includeion exchange membrane filtration electrochemical destruc-tion ozonation flotation chemical coagulation biologicaland chemical oxidation precipitation and electrokinetic andadsorptionmethods [16ndash19] Howevermost of thesemethodshave some major drawbacks such as the applicability atrelative high concentration of dye insufficient dye removalhigh cost and production of extra waste [20] Similarlythe biological methods often demand a very strict controlof experimental conditions and especially the pH and thedecontamination process is usually very slow Alike inchemical oxidation methods the biodegradation productsare often carcinogenic and toxic in nature which affects theaquatic life

Activated carbon has been extensively used as an adsor-bent for the removal of dyes because of the acidic natureand showed pores nature of its surface [21ndash23] However theactivated carbon is costly and challenging in regenerationwhich raises the cost of waste water treatment [24 25]Thus there is a great demand for such type of adsorbentwhich is cheaper and still has high adsorption capabilitytowards pollutants and dyes without any additional expensivepretreatment Presently cellulose and lignocellulosic biomasshave got considerable attraction because of the abundanceeffectiveness low cost and environmentally friendly natureof these biopolymers Thus biosorption has been proved tobe the most effective technique for the removal of MB fromthe aqueous solution [16 26ndash29]

In this research work C polygonoides (locally calledbalanza which is used as fuel for domestic cooking purposesand in bricks kiln industry)was collected fromLakkiMarwatKhyber Pakhtunkhwa Pakistan and utilized as biosorbent

for MB removal from aqueous solution without any physicalor chemical treatment The utilization of this alternativeabundant low cost and environment friendly bioadsorbentwill effectively reduce both the waste disposal problem andthe cost of waste decontamination

2 Materials and Methods

21 Methylene Blue All the chemicals used in the presentresearch work were of analytical grade and purchased fromSigma-Aldrich BDH andMerck MB with chemical formulaC16H18ClN3S3H2O (Table 1) was used as model adsorbent

to study the adsorption capacity of biosorbent The stocksolution of 1000 ppm of MB was prepared and subsequentlytheir solutions of desired concentration were prepared byapplying the dilution formula (119872

11198811= 11987221198812)

22 Preparation of Biosorbent The Calligonum polygonoidesash was washed with double distilled water to remove solubleimpurities and then dried in oven at 110∘C for 5 hours Thepowdered material thus obtained was sieved through 45120583msieve using Retsch AS 200 basic and was stored in air tightglass bottle for further experimental study (Figure 1)

23 Characterization of Biosorbent

231 Scanning Electronic Microscopic (SEM) Analysis Thesurface structure of biosorbent was analyzed using scanningelectron microscopy (JMT-300 JEOL)

232 Surface Area Analysis The surface area of C poly-gonoides ash sample was determined using Brunauer-Emmett-Teller (BET) method and the pore size diameter wasobtained by BJH method from the adsorptiondesorptionisotherm of nitrogen gas at 770 K employing MicromeriticsASAP 2010 apparatus

233 Fourier Transform Infrared Spectroscopy The chemicalstructure and nature of functional groups C polygonoidesash were studied using FTIR transmission spectra on aPerkin Elmer SpectrumOne For FTIR spectrameasurementsample was mixed with KBr in the ratio of 11000 and pressed






2gas with flow






(119877) = (1198620minus 119862119905

1198620

) 100 (1)

119902119905=(1198620minus 119862119905) 119881

119898

(2)

119902119890=(1198620minus 119862119890) 119881

119898 (3)

where 119902119890and 119902



119890(mgL)





log (119902119890minus 119902119905) = log 119902

1minus 1198961sdot119905

2303 (4)


119905




119889119902119905

119889119905= 1198962(1199022minus 119902119905)2

119889119902119905

(1199022minus 119902119905)2= 1198962119889119905

(5)


1

1199022minus 119902119905

=1

1199022

+ 1198962119889119905 (6)


order

119905

119902119905

=1

11989621199022

2

+1

1199022

119905 (7)







sdotgminus1











20

30

40

50

60

70

80

90

34122928

1637

15291445

13721240

11063700

34352927

2516

14601419 1119

874

713

a

b

T(

)













100 200 300 400 500 600 700 800

40

50

60

70

80

90

100W

eigh

t cha

nge (

)

Temperature (∘C)

(a)

100 200 300 400 500 600 700 800

Der

ivat

ive w

eigh

t

minus30

minus25

minus20

minus15

minus10

minus05

00

05

Temperature (∘C)

(b)


0 10 20 30 40 50 60 70 80 90 100 110 120 130767880828486889092949698

100

Adso

rptio

n (

)

Time (min)

10mgL8mgL

6mgL4mgL

(a)

0 20 40 60 80 100 120 140

6

9

12

15

18

21

24

27

30Ad

sorp

tion

capa

city

(mg

g)

Time (min)

10mgL8mgL

6mgL4mgL

(b)







(a)


(b)


(mgg)


1634 [36]


2049 [36]


1302 [37]





0 100 200 300 400 500 600 700

87

90

93

96

99

102

Adso

rptio

n (

)

Shaking speed (rpm)


20 40 60 80 100 120 14068

72

76

80

84

88

92

96

100

Rem

oval

()








4 168 107 099986 175 105 099998 173 103 0999810 167 101 0999




Conc 1199022

1198962

ℎ1198772



119902119905= 119870119894sdot 11988911990505 (8)


119905versus




10mgL8mgL

6mgL4mgL

tqt

0 20 40 60 80 100 1200

20

40

60

80

100

120

140

Time (min)

(min

gm

g)


10mgL8mgL

6mgL4mgL

t05 (min)2 3 4 5 6 7 8 9 10 11 12 13

6

9

12

15

18

21

24

27Ad

sorp

tion

capa

city

(mg

g)







N

CH3

S+

CH3

CH3

CH3

N

N

Clminus

N+CH3N

Clminus

S

N

CH3 CH3

CH3

HOOH OH OH

OHOHOH

O1 4

CH2OH CH2OH CH2OH

O O










5 Conclusions






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of






2gas with flow






(119877) = (1198620minus 119862119905

1198620

) 100 (1)

119902119905=(1198620minus 119862119905) 119881

119898

(2)

119902119890=(1198620minus 119862119890) 119881

119898 (3)

where 119902119890and 119902



119890(mgL)





log (119902119890minus 119902119905) = log 119902

1minus 1198961sdot119905

2303 (4)


119905




119889119902119905

119889119905= 1198962(1199022minus 119902119905)2

119889119902119905

(1199022minus 119902119905)2= 1198962119889119905

(5)


1

1199022minus 119902119905

=1

1199022

+ 1198962119889119905 (6)


order

119905

119902119905

=1

11989621199022

2

+1

1199022

119905 (7)







sdotgminus1











20

30

40

50

60

70

80

90

34122928

1637

15291445

13721240

11063700

34352927

2516

14601419 1119

874

713

a

b

T(

)













100 200 300 400 500 600 700 800

40

50

60

70

80

90

100W

eigh

t cha

nge (

)

Temperature (∘C)

(a)

100 200 300 400 500 600 700 800

Der

ivat

ive w

eigh

t

minus30

minus25

minus20

minus15

minus10

minus05

00

05

Temperature (∘C)

(b)


0 10 20 30 40 50 60 70 80 90 100 110 120 130767880828486889092949698

100

Adso

rptio

n (

)

Time (min)

10mgL8mgL

6mgL4mgL

(a)

0 20 40 60 80 100 120 140

6

9

12

15

18

21

24

27

30Ad

sorp

tion

capa

city

(mg

g)

Time (min)

10mgL8mgL

6mgL4mgL

(b)







(a)


(b)


(mgg)


1634 [36]


2049 [36]


1302 [37]





0 100 200 300 400 500 600 700

87

90

93

96

99

102

Adso

rptio

n (

)

Shaking speed (rpm)


20 40 60 80 100 120 14068

72

76

80

84

88

92

96

100

Rem

oval

()








4 168 107 099986 175 105 099998 173 103 0999810 167 101 0999




Conc 1199022

1198962

ℎ1198772



119902119905= 119870119894sdot 11988911990505 (8)


119905versus




10mgL8mgL

6mgL4mgL

tqt

0 20 40 60 80 100 1200

20

40

60

80

100

120

140

Time (min)

(min

gm

g)


10mgL8mgL

6mgL4mgL

t05 (min)2 3 4 5 6 7 8 9 10 11 12 13

6

9

12

15

18

21

24

27Ad

sorp

tion

capa

city

(mg

g)







N

CH3

S+

CH3

CH3

CH3

N

N

Clminus

N+CH3N

Clminus

S

N

CH3 CH3

CH3

HOOH OH OH

OHOHOH

O1 4

CH2OH CH2OH CH2OH

O O










5 Conclusions






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



log (119902119890minus 119902119905) = log 119902

1minus 1198961sdot119905

2303 (4)


119905




119889119902119905

119889119905= 1198962(1199022minus 119902119905)2

119889119902119905

(1199022minus 119902119905)2= 1198962119889119905

(5)


1

1199022minus 119902119905

=1

1199022

+ 1198962119889119905 (6)


order

119905

119902119905

=1

11989621199022

2

+1

1199022

119905 (7)







sdotgminus1











20

30

40

50

60

70

80

90

34122928

1637

15291445

13721240

11063700

34352927

2516

14601419 1119

874

713

a

b

T(

)













100 200 300 400 500 600 700 800

40

50

60

70

80

90

100W

eigh

t cha

nge (

)

Temperature (∘C)

(a)

100 200 300 400 500 600 700 800

Der

ivat

ive w

eigh

t

minus30

minus25

minus20

minus15

minus10

minus05

00

05

Temperature (∘C)

(b)


0 10 20 30 40 50 60 70 80 90 100 110 120 130767880828486889092949698

100

Adso

rptio

n (

)

Time (min)

10mgL8mgL

6mgL4mgL

(a)

0 20 40 60 80 100 120 140

6

9

12

15

18

21

24

27

30Ad

sorp

tion

capa

city

(mg

g)

Time (min)

10mgL8mgL

6mgL4mgL

(b)







(a)


(b)


(mgg)


1634 [36]


2049 [36]


1302 [37]





0 100 200 300 400 500 600 700

87

90

93

96

99

102

Adso

rptio

n (

)

Shaking speed (rpm)


20 40 60 80 100 120 14068

72

76

80

84

88

92

96

100

Rem

oval

()








4 168 107 099986 175 105 099998 173 103 0999810 167 101 0999




Conc 1199022

1198962

ℎ1198772



119902119905= 119870119894sdot 11988911990505 (8)


119905versus




10mgL8mgL

6mgL4mgL

tqt

0 20 40 60 80 100 1200

20

40

60

80

100

120

140

Time (min)

(min

gm

g)


10mgL8mgL

6mgL4mgL

t05 (min)2 3 4 5 6 7 8 9 10 11 12 13

6

9

12

15

18

21

24

27Ad

sorp

tion

capa

city

(mg

g)







N

CH3

S+

CH3

CH3

CH3

N

N

Clminus

N+CH3N

Clminus

S

N

CH3 CH3

CH3

HOOH OH OH

OHOHOH

O1 4

CH2OH CH2OH CH2OH

O O










5 Conclusions






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



20

30

40

50

60

70

80

90

34122928

1637

15291445

13721240

11063700

34352927

2516

14601419 1119

874

713

a

b

T(

)













100 200 300 400 500 600 700 800

40

50

60

70

80

90

100W

eigh

t cha

nge (

)

Temperature (∘C)

(a)

100 200 300 400 500 600 700 800

Der

ivat

ive w

eigh

t

minus30

minus25

minus20

minus15

minus10

minus05

00

05

Temperature (∘C)

(b)


0 10 20 30 40 50 60 70 80 90 100 110 120 130767880828486889092949698

100

Adso

rptio

n (

)

Time (min)

10mgL8mgL

6mgL4mgL

(a)

0 20 40 60 80 100 120 140

6

9

12

15

18

21

24

27

30Ad

sorp

tion

capa

city

(mg

g)

Time (min)

10mgL8mgL

6mgL4mgL

(b)







(a)


(b)


(mgg)


1634 [36]


2049 [36]


1302 [37]





0 100 200 300 400 500 600 700

87

90

93

96

99

102

Adso

rptio

n (

)

Shaking speed (rpm)


20 40 60 80 100 120 14068

72

76

80

84

88

92

96

100

Rem

oval

()








4 168 107 099986 175 105 099998 173 103 0999810 167 101 0999




Conc 1199022

1198962

ℎ1198772



119902119905= 119870119894sdot 11988911990505 (8)


119905versus




10mgL8mgL

6mgL4mgL

tqt

0 20 40 60 80 100 1200

20

40

60

80

100

120

140

Time (min)

(min

gm

g)


10mgL8mgL

6mgL4mgL

t05 (min)2 3 4 5 6 7 8 9 10 11 12 13

6

9

12

15

18

21

24

27Ad

sorp

tion

capa

city

(mg

g)







N

CH3

S+

CH3

CH3

CH3

N

N

Clminus

N+CH3N

Clminus

S

N

CH3 CH3

CH3

HOOH OH OH

OHOHOH

O1 4

CH2OH CH2OH CH2OH

O O










5 Conclusions






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


100 200 300 400 500 600 700 800

40

50

60

70

80

90

100W

eigh

t cha

nge (

)

Temperature (∘C)

(a)

100 200 300 400 500 600 700 800

Der

ivat

ive w

eigh

t

minus30

minus25

minus20

minus15

minus10

minus05

00

05

Temperature (∘C)

(b)


0 10 20 30 40 50 60 70 80 90 100 110 120 130767880828486889092949698

100

Adso

rptio

n (

)

Time (min)

10mgL8mgL

6mgL4mgL

(a)

0 20 40 60 80 100 120 140

6

9

12

15

18

21

24

27

30Ad

sorp

tion

capa

city

(mg

g)

Time (min)

10mgL8mgL

6mgL4mgL

(b)







(a)


(b)


(mgg)


1634 [36]


2049 [36]


1302 [37]





0 100 200 300 400 500 600 700

87

90

93

96

99

102

Adso

rptio

n (

)

Shaking speed (rpm)


20 40 60 80 100 120 14068

72

76

80

84

88

92

96

100

Rem

oval

()








4 168 107 099986 175 105 099998 173 103 0999810 167 101 0999




Conc 1199022

1198962

ℎ1198772



119902119905= 119870119894sdot 11988911990505 (8)


119905versus




10mgL8mgL

6mgL4mgL

tqt

0 20 40 60 80 100 1200

20

40

60

80

100

120

140

Time (min)

(min

gm

g)


10mgL8mgL

6mgL4mgL

t05 (min)2 3 4 5 6 7 8 9 10 11 12 13

6

9

12

15

18

21

24

27Ad

sorp

tion

capa

city

(mg

g)







N

CH3

S+

CH3

CH3

CH3

N

N

Clminus

N+CH3N

Clminus

S

N

CH3 CH3

CH3

HOOH OH OH

OHOHOH

O1 4

CH2OH CH2OH CH2OH

O O










5 Conclusions






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



(a)


(b)


(mgg)


1634 [36]


2049 [36]


1302 [37]





0 100 200 300 400 500 600 700

87

90

93

96

99

102

Adso

rptio

n (

)

Shaking speed (rpm)


20 40 60 80 100 120 14068

72

76

80

84

88

92

96

100

Rem

oval

()








4 168 107 099986 175 105 099998 173 103 0999810 167 101 0999




Conc 1199022

1198962

ℎ1198772



119902119905= 119870119894sdot 11988911990505 (8)


119905versus




10mgL8mgL

6mgL4mgL

tqt

0 20 40 60 80 100 1200

20

40

60

80

100

120

140

Time (min)

(min

gm

g)


10mgL8mgL

6mgL4mgL

t05 (min)2 3 4 5 6 7 8 9 10 11 12 13

6

9

12

15

18

21

24

27Ad

sorp

tion

capa

city

(mg

g)







N

CH3

S+

CH3

CH3

CH3

N

N

Clminus

N+CH3N

Clminus

S

N

CH3 CH3

CH3

HOOH OH OH

OHOHOH

O1 4

CH2OH CH2OH CH2OH

O O










5 Conclusions






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



Conc 1199022

1198962

ℎ1198772



119902119905= 119870119894sdot 11988911990505 (8)


119905versus




10mgL8mgL

6mgL4mgL

tqt

0 20 40 60 80 100 1200

20

40

60

80

100

120

140

Time (min)

(min

gm

g)


10mgL8mgL

6mgL4mgL

t05 (min)2 3 4 5 6 7 8 9 10 11 12 13

6

9

12

15

18

21

24

27Ad

sorp

tion

capa

city

(mg

g)







N

CH3

S+

CH3

CH3

CH3

N

N

Clminus

N+CH3N

Clminus

S

N

CH3 CH3

CH3

HOOH OH OH

OHOHOH

O1 4

CH2OH CH2OH CH2OH

O O










5 Conclusions






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


N

CH3

S+

CH3

CH3

CH3

N

N

Clminus

N+CH3N

Clminus

S

N

CH3 CH3

CH3

HOOH OH OH

OHOHOH

O1 4

CH2OH CH2OH CH2OH

O O










5 Conclusions






Acknowledgments



References



































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


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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