Research ArticleAdsorption Studies of Textile Dye (Chrysoidine) from AqueousSolutions Using Activated Sawdust
Muhammad Waqar Ashraf 1 Nidal Abulibdeh1 and Abdus Salam2
1Department of Mathematics amp Natural Sciences Prince Mohammad Bin Fahd University PO Box 1661AlKhobar 31952 Saudi Arabia2Department of Chemistry King Abdulaziz University Rabigh Campus Jeddah Saudi Arabia
Correspondence should be addressed to Muhammad Waqar Ashraf mashrafpmuedusa
Received 8 November 2018 Revised 9 January 2019 Accepted 4 February 2019 Published 13 March 2019
Academic Editor Jose C Merchuk
Copyright copy 2019 Muhammad Waqar Ashraf et al +is is an open access article distributed under the Creative CommonsAttribution License which permits unrestricted use distribution and reproduction in anymedium provided the original work isproperly cited
Chrysoidine is a type of industrial azo dye and a well-known toxicant Due to its good dyeing characteristics it is widely used fordyeing leather paper feather grass wood bamboo etc Hence it is very important to remove or reduce its concentration belowthe contamination level in the waste line by using low-cost technologies Sawdust is a plentiful material available very cheaply fromsawmills and woodworks+erefore the present work was conducted to study sorption ability of both raw sawdust and chemicallyactivated sawdust carbon on the removal of chrysoidine from the aqueous solutions Adsorption isotherms of the dye on sawdustwere determined and correlated with usual isotherm equations like Freundlich and Langmuir Experimental results have shownthat sawdust has a high adsorption efficiency and the adsorption of chrysoidine followed Freundlichrsquos isotherm Although rawsawdust proved to be slightly less efficient in comparison to chemically treated sawdust but in economic terms raw sawdust ismore cost-effective as the difference in the percent dye removal is less than the difference in the manufacturing costs+e influenceof several parameters such as effect of temperature adsorbent dose adsorption time etc on the adsorption process was studiedalong with thermodynamic parameters such as enthalpy (ΔHdeg) and entropy (ΔSdeg)
1 Introduction
Wastewaters from textile industries are colored which ismainly due to dyes used in textile industry Chemical speciespresent in textile effluents are of diverse nature henceposing a challenge to conventional physicochemical andbiological treatment methods Dyes are almost invariablytoxic and additionally a visible pollutant so their removalfrom the effluent stream is ecologically essential Recentestimates indicate that approximately 12 of synthetic dyesused each year are lost during manufacture and processingoperations and that 20ndash35 of these input dyes enter theenvironment through effluents from the treatment of re-sidual industrial water Dyes are easily visible even in ex-tremely diluted forms posing aesthetic problems and aretoxic to human and aquatic life [1ndash5]
Numerous procedures such as chemical coagulationusing alum lime ferric chloride and ferric sulphate
biosorption oxidation methods using chloride and ozonemembrane separation biological treatment magnetic par-ticles and adsorption have been employed to remove dyesfrom industrial effluents [1 3ndash7] Adsorption requires lessland area least effect to toxic chemicals greater flexibility inthe design and operation and superior removal of organiccontaminants +erefore significant attention has been di-rected to adsorption as a process for color removal fromwastewaters since it offers the most economical and effectivetreatment methods Recently various research groups haveused different low-cost waste natural materials as an ad-sorbent for the separation of basic dyes Nurchi et al [2]investigated the sorption of chrysoidine on row cork andcork entrapped in calcium alginate and the amountsadsorbed were about 027 and 029mmolg of chrysoidine inaqueous solutions at a pH of 7 Jain et al [8] removedhazardous dye naphthol yellow S from wastewater usingactivated carbon and activated deoiled mustard Mittal et al
HindawiInternational Journal of Chemical EngineeringVolume 2019 Article ID 9728156 8 pageshttpsdoiorg10115520199728156
[9] investigated the adsorption of chrysoidine Y on bottomash and deoiled soya +e dye sorption capacities of bottomash (BET surface area 8705 cm2middotgminus1) and deoiled soya(BET surface area 7286 cm2middotgminus1) were determined as361times 10minus5molmiddotgminus1 and 192times10minus5molmiddotgminus1 at 30degC re-spectively Younes et al [10] and Pal et al [11] have reviewedand studied biomass-derived activated carbons for ad-sorptive heat pump applications Gupta et al [12] studied theremoval of indigo carmine dye from industrial effluents bydeoiled mustard and charcoal +e adsorption experimentswere carried out at 30degC pH 30 for charcoal and pH 80 fordeoiled mustard and adsorbate concentration 2times10minus4molmiddotLminus1 Amounts of adsorbates were found as approxi-mately 033times10minus4molmiddotLminus1 for 040 gmiddotLminus1 for charcoal and025times10minus4molmiddotLminus1 for 75 gmiddotLminus1 of deoiled mustard Larousand Meniai [13] studied the use of carbonized sawdust as anadsorbent for phenol Raghuvanshi et al [14] have usedchemically treated sawdust as a bioadsorbent for the removalof methylene blue dye
Chrysoidine is a type of industrial azoic dye Due to itsgood dyeing fastness it is widely used for dyeing leatherpaper feather grass wood bamboo etc Chrysoidine cancause acute and chronic toxicity to mammals when takenorally or inhaled and its median lethal concentration (LC5024 h) for fish was 05mgL According to American DyeManufacturing Institute (ADMI) the basic dyes are gen-erally more toxic than acidic or direct dyes [15]
+e objective of this paper was to explore the removal ofchrysoidine basic dye in an aqueous solution by adsorptionon the sawdust Chrysoidine removal has never been triedbefore by using chemically treated and raw sawdust +einfluence of several parameters on adsorption such ascontact time dye concentration temperature etc on theadsorption process was also studied
2 Materials and Methods
Sawdust was grabbed from a nearby wood working factoryand divided into two portions by weight One part waschemically treated while the second was kept for use in itsraw form+e first partwas treated with sulphuric acid in theratio of 4 3 parts by weight +e material was kept in avacuum oven for 24 hours at 150degC +e carbonized materialwas washed thrice with distilled water to remove anyunreacted acid and dried at 100degC for 24 hours +e materialwas finely grounded and passed through sieve ISS 600 andstored +is material was used in adsorption experiments aschemically activated sawdust+e second part of the sawdustwas saturated with the distilled water and washed repeatedlyto remove the typical yellow color of the sawdust caused bylignin Subsequently it was treated with formaldehyde for6 hours to remove the lignin +e material was dried in avacuum oven at 60degC for 24 hours and this dried materialwas grounded to fine powder and sieved through ISS 600+is material was used throughout as untreated sawdustadsorbent [14]
+e dye chrysoidine is a basic dye with CAS number532-82-1 molecular weight 24871 color index number
11270 λmax 449 nm and empirical formula (Hill Notation)C12H12N4middotHCl +e structural formula is shown in Figure 1
All reagents used in the present study were of analyticalreagent (AR) grade and supplied by Sigma-Aldrich
21 Adsorption Studies In order to explore the adsorptionefficiency of both versions of sawdust a series of experimentswas conducted During the experiments 10times10minus4 kg to10times10minus3 kg of both adsorbents were taken separately in250mL conical flasks sealed with parafilm on an electricrotary shaking machine in 100mL aqueous solution of thedye (variable concentrations) at different temperatures andtime intervals After predetermined time intervals the so-lution was analyzed for the residual concentration of dye byusing a Shimadzu UV-VIS spectrophotometer at 449 nm Asimilar procedure was followed for another set of flaskscontaining same dye concentration but without sawdust tobe used as blank All the experiments were conducted intriplicate at neutral pH +e adsorption of the dye can bedescribed in terms of dye removal
dye removal() c0 minus cf
c0times 100 (1)
where c0 is the initial and cf is the final concentrations of thedye in the solution
22 Adsorption 1ermodynamics +e spontaneity of theadsorption process is normally described by changes in thestandard enthalpy (ΔHdeg) Gibbrsquos free energy (ΔGdeg) andentropy (ΔSdeg) Decrease in ΔGdeg normally indicates aspontaneous process and the opposite is true for a non-spontaneous reaction +e relations for the thermodynamicparameters are given as follows
ΔGdeg minusRT ln Ka (2)
where Ka is the thermodynamic equilibrium constant
Kd ca
ceasymp Ka (3)
where Kd is the adsorption equilibrium constant and ca is theadsorbed concentration
ΔGdeg ΔHdeg minusTΔSdeg (4)
ln Ka minusΔHdeg
RT+ΔSdegR
(5)
A linear relation between ln Ka and inverse temperatureis used to evaluate ΔHdeg and ΔSdeg
23 Adsorption Isotherms Adsorption analysis is normallyperformed using adsorption isotherms Freundlich isothermis the earliest known relationship describing the adsorptionequation and is often expressed as
qe KFc1ne (6)
2 International Journal of Chemical Engineering
where qe is the adsorption density (mg of adsorbate per gmof adsorbent) ce is the equilibrium concentration (mgL)KF is the Freundlich constant and n is an exponent [16]
+e equation can be converted in a linear form by takingthe log on both sides as
log qe log KF +1nlog ce (7)
A plot of log qe against log ce yields a straight lineindicating the conformation of Freundlichrsquos isotherm foradsorption +e constants can be determined from thecorresponding slope and intercept
Langmuir isotherm is another most frequently usedadsorption isotherm [17] It is described by the followingrelation
qe qmax middotbce
1 + bce (8)
where qmax is the maximum adsorption capacity and b is theLangmuir constant (Lmg)
+is equation can also be converted into a straight line asce
qe
1qmaxb
+1
qmaxce (9)
A plot of ceqe vs ce gives a straight line +e slope andintercept gives the values of Langmuir constants
Equations (2) and (4) can be straightforward but maylead to errors as mentioned elsewhere [13] ISOT-Calc andother statistical and mathematical packages [18 19] havebeen used to fit the nonlinear isotherm data In this studyiterative LevenbergndashMarquardt and nonlinear least squareswas used to find the parameters Nonlinear optimization wasbased on minimizing the objective function defined as
OF 1113944 wi qeexp minus qecalc1113874 11138752 (10)
where qeexp is the experimental adsorption density qecalc is themodeled adsorption density and wi is the data weighingcoefficient for every point (ce qe)
+e compatibility of an adsorbent-adsorbate pair can beindicated by a nondimensional parameter RL RL is called theseparation parameter and it is derived from Langmuirconstant
RL 1
1 + bc0 (11)
where RL gt 1 indicates nonfavorable combination 0ltRL lt 1favors adsorption and RL 1 is for nonlinear adsorptionwhereas RL 0 shows irreversible adsorption
3 Results and Discussion
Figures 2(a) and 2(b) describe the effect of initial dyeconcentration on the rate of adsorption on sawdust bothtreated and untreated It can be deduced that for any par-ticular experiment the rate of adsorption decreased withtime until it gradually approached a plateau owing to thecontinuous decrease in the driving force (concentration) andalso indicating that the adsorbent is saturated at this point+e saturation point was reached within 40 to 50minutes Inthe beginning the adsorption process was found to be veryfast and a large amount of the total concentration of dye wasremoved in the first half an hour Activated sawdust reachedequilibrium slightly earlier than the raw sawdust Moreoverthe initial adsorption rate was high for initial dye concen-tration as resistance to dye uptake decreases when the masstransfer driving force increases +is observation indicatedthat the removal of dye is dependent upon the initialconcentration of the solution
+e effect of various concentrations of treated andnontreated sawdust on adsorption is shown in Figures 3(a)and 3(b) Graphs show a decline in the dye concentration at arapid pace as the sawdust quantity is increased Chemicallytreated sawdust gave the greater removal at all levels of theadsorbent dose In the beginning the rate of dye removalwas faster which slowed down as the dose increased +iscan be attributed to the fact that at a lower adsorbent dosethe dye molecules are easily reachable and therefore re-moval per unit mass of adsorbent is higher A larger surfacearea of the adsorbent particles and smaller size of adsorbatemolecules favor adsorption
+e rate of adsorption is higher at the initial stage as sitesare vacant for adsorption Adsorption and desorption occursimultaneously and an adsorption equilibrium is reachedwhen isotherms are applied With a rise in adsorbentquantity there is a less corresponding increase in adsorptionresulting from lower adsorptive capacity utilization of ad-sorbent +e results obtained from above experiment in-dicate that chemically treated sawdust has a large potential asan adsorbent for dye removal as compared to raw sawdust
It has been reported that if the solubility of the adsorbateincreases with an increase in temperature then the chemicalpotential decreases and both these effects working in thesame direction cause a decrease in adsorption Converselyif the temperature has the reverse effect on the solubilitythen both the said effects will act in the opposite directionand adsorption may increase or decrease depending on thepredominant factor [14]+e adsorption rates of chrysoidineat three different temperatures (30degC 40degC and 50degC) werestudied as shown in Figure 4(a) and 4(b) In case of rawsawdust the rate of dye adsorption decreased with an in-crease in temperature from 30degC to 50degC with a 4 gL dose in5minutes time from a 100 gL dye solution +is behaviorindicated that the process is exothermic in nature +is canbe attributed to the predisposition of the dye molecules toescape from the solid phase to bulk phase with a rise intemperature of the solution However in the case of treatedsawdust the rate of dye uptake increases rapidly
N=N
H2N
NH2
HCl
Figure 1 +e structural formula of chrysoidine
International Journal of Chemical Engineering 3
e thermodynamic parameters (ΔHdeg and ΔSdeg) wereobtained from the slope and intercept of the linear re-gression line tted on the lnK vs 1T data e plot for rawand activated sawdust is shown in Figure 5 and the ther-modynamic parameters values are given in Table 1
From Table 1 it can be seen that ΔGdeg is negative in-dicating that the adsorption is spontaneousWith the increasein temperature ΔGdeg become less negative or the spontaneitydecreases by increasing temperature Compared to rawsawdust activated sawdust showed more negative value forΔGdeg indicating more feasibility of adsorption ΔHdeg is alsonegative showing the process is exothermic And the processis physisorption as chemisorption proceeds with the enthalpy
changes in the range of minus80 to minus200 kJmol e negativevalue of ΔSdeg reveals the adsorption is ordered Similarly morenegative value of ΔSdeg indicates decreasing randomness onactivated surface than raw sawdust Overall it can be con-cluded from the obtained thermodynamic parameters that theactivated sawdust betters in terms of feasibility exothermicityand ordered layering than raw sawdust
For adsorption of chrysoidine on sawdust there may be apossibility of intraparticle diusion In order to investigatethis possibility experiments were conducted and aredepicted in Figures 6(a) and 6(b)
e plots (Figures 6(a) and 6(b)) with log (dye re-moval) () versus log time (min) for adsorption at three
20 40 60Time (min)
80 100 1200
q (m
gg)
0
10
20
30
40
50
50 mgL100 mgL150 mgL
200 mgL250 mgL300 mgL
(a)
20 40 60Time (min)
80 100 1200
q (m
gg)
0
10
20
30
40
50
50 mgL100 mgL150 mgL
200 mgL250 mgL300 mgL
(b)
Figure 2 Eect of contact time on dye (dose 4 gL) adsorption on (a) raw sawdust and (b) chemically treated sawdust
Time (min)20 40 60 80 100 1200
q (m
gg)
0
200
400
600
800
01 g02 g04 g
06 g08 g1 g
(a)
Time (min)20 40 60 80 100 1200
q (m
gg)
0
200
400
600
800
01 g02 g04 g
06 g08 g1 g
(b)
Figure 3 Eect of (a) raw sawdust dose (100mgL) and (b) chemically treated sawdust dose on dye adsorption
4 International Journal of Chemical Engineering
dierent temperatures ranging between 30 and 50degCresulted in straight lines which specify the existence ofintraparticle diusion ese plots are used to describewhether adsorption is controlled by diusion in the ad-sorbent particles or the consecutive diusion in the bulk ofthe solution [20ndash22]
31 Adsorption Isotherms e two most frequently usedadsorption isotherms are employed in Figure 7 for theadsorption of chrysoidine on raw and activated sawdust Itcan be seen that the coecient of determination (R2) is lower
in Freundlich isotherm erefore it can be presumed thatthe adsorption of chrysoidine on raw and activated sawdustfollows Langmuir adsorption model
e parameters of the Freundlich and Langmuir linearisotherms are given in Table 2 and the same were used tocompare the experimental curves Lower values of ob-jective function (OF) were obtained in case of Langmuirisotherm
Similarly Figure 8 shows the nonlinear curve t-tings of Freundlich and Langmuir isotherms Lowervalues of OF render Langmuir better model for the
q (m
gg)
0
5
10
15
20
25
30
Time (min)10 20 30 40 50 60 700
30degC40degC50degC
(a)
q (m
gg)
0
5
10
15
20
25
30
Time (min)10 20 30 40 50 60 700
30degC40degC50degC
(b)
Figure 4 Eect of temperature on dye removal with (a) raw sawdust (conc 100mgL dose 4 gL) and (b) chemically treated sawdust (conc100mgL dose 4 gL)
00030
05
1
15
2
25
000305 00031 000315
lnK
(ndash)
00032 000325 000331T (Kndash1)
Raw sawdusty = 47191822 lowast xndash 144839
Activated sawdusty = 5657569 lowast xndash 162594
Figure 5 LnK vs 1T curves for raw and activated saw dust
Table 1 ermodynamic parameters at dierent temperatures
Temperature (degC)Raw sawdust Chemically treated sawdust
Ka (minus) ΔGdeg(kJmol) ΔHdeg (kJmol) ΔSdeg (Jmol-K) Ka (minus) ΔGdeg (kJmol) ΔHdeg (kJmol) ΔSdeg (Jmol-K)
adsorption of chrysoidine on raw and activated sawdustthan Freundlich
e parameters of Freundlich and Langmuir obtainedfrom nonlinear tting are reported in Table 3 e
comparison of linear and nonlinear methods clearly revealsthat the OF values are lower in case of nonlinear method
Langmuir constant ldquobrdquo estimated from the nonlinearmethod was then used to calculate RL Evolution of RL with
Log(
dye r
emov
al) (
)
05 1 15Log(time) (min)
215
16
17
18
19
2
50degC
30degC40degC
R2 (0976)R2 (0992)R2 (0839)
(a)
05 1 15Log(time) (min)
2
Log(
dye r
emov
al) (
)
15
16
17
18
19
2
50degC
30degC40degC
R2 (0989)R2 (0984)R2 (0879)
(b)
Figure 6 Log (dye removal) () versus log time (min) for (a) raw sawdust and (b) chemically treated sawdust
Log ce (mgL)
Logq
e (m
gg)
0501
12
14
16
18
1 15 252
Freundlich (R2 = 0749)
Experimentalraw sawdust
Freundlich (R2 = 0780)
Experimentalactivated sawdust
(a)
c eq
e (m
gg)
0
1
2
3
4
6
5
ce (mgL)500 100 150 200
Langmuir (R2 = 0996)
Experimentalraw sawdust
Langmuir (R2 = 0997)
Experimentalactivated sawdust
(b)
Figure 7 Freundlich (a) and Langmuir (b) linear isotherms of raw and chemically treated sawdust for chrysoidine removal
Table 2 Comparison of the optimized Freundlich and Langmuir isotherms parameters for the adsorption of chrysoidine on raw andchemically treated sawdust
SawdustFreundlich Langmuir
KF (mg(1minus1n) gminus1middotL1n) n OF (mg2g2) qmax (mgg) b (Lmg) b (Lmol) OF (mg2g2)
an initial dye concentration of raw and activated sawdust isshown in Figure 9 RL of activated sawdust is lower (0019 to0104) compared to raw sawdust (0026 to 0136) indicatingbetter suitability of activated sawdust over raw sawdust forthis adsorbent-adsorbate combination
Recovery of the spent adsorbent is an important eco-nomic factor in determining the practicability of an ad-sorption system However sawdust is a wood by-productwhich is a waste material available in plenty and bears nocost erefore the recovery of adsorbent was not furtherpursued
4 Conclusion
Sawdust in both forms proved to be an ecient adsorbent forchrysoidine dye from aqueous solutionis work has provedthe potentiality of sawdust to be an eective adsorbent eadsorption of chrysoidine followed Langmuirrsquos isotherm Assawdust is a cheap material and easily available the process isexpected to be economical Although untreated sawdustproved to be less eective in comparison to treated sawdusteconomically speaking the percentage of dye removal is lessthan the dierence in the commercial costs
1005000
10
q e (m
gg)
20
30
40
150 200
ExperimentalFreundlichLangmuir
ce (mgL)
(a)
q e (m
gg)
ExperimentalFreundlichLangmuir
1005000
10
20
30
40
150 200ce (mgL)
(b)
Figure 8 Freundlich and Langmuir nonlinear isotherms of (a) raw sawdust and (b) chemically treated sawdust for chrysoidine removal
Table 3 Comparison of the optimized Freundlich and Langmuir isotherms parameters for the adsorption of chrysoidine on raw andactivated sawdust
SawdustFreundlich Langmuir
KF (mg(1minus1n) gminus1middotL1n) n OF (mg2g2) qmax (mgg) b (Lmg) b (Lmol) OF (mg2g2)
Figure 9 Eect of initial concentration on the Langmuir adsorption factor of raw and activated saw dust
International Journal of Chemical Engineering 7
Data Availability
+e adsorption data used to support the findings of thisstudy are included within the article in the form of graphsData tables are not included just to avoid duplication
Conflicts of Interest
+e authors declare that there are no conflicts of interestregarding the publication of this paper
Acknowledgments
+e authors are thankful to Prince Mohammad Bin FahdUniversity for supporting the present work +anks are alsodue to King Abdulaziz University Rabigh campus forproviding some raw materials
References
[1] M W Ashraf ldquoRemoval of methylene blue dye fromwastewater by using supported liquid memberane technol-ogyrdquo Polish Journal of Chemical Technology vol 18 no 2pp 26ndash30 2016
[2] V M Nurchi M Crespo-Alonso R Biesuz et al ldquoSorption ofchrysoidine by row cork and cork entrapped in calcium al-ginate beadsrdquo Arabian Journal of Chemistry vol 7 no 1pp 133ndash138 2014
[3] K-L Chang C-C Chen J-H Lin et al ldquoRice straw-derivedactivated carbons for the removal of carbofuran from anaqueous solutionrdquo New Carbon Materials vol 29 no 1pp 47ndash54 2014
[4] T A Arica E Ayas and M Y Arica ldquoMagnetic MCM-41silica particles grafted with poly(glycidylmethacrylate) brushmodification and application for removal of direct dyesrdquoMicroporous and Mesoporous Materials vol 243 no 1pp 164ndash175 2017
[5] T A Arica M Kuman O Gercel and E Ayas ldquoPoly(dop-amine) grafted bio-silica composite with tetraethylenepent-amine ligands for enhanced adsorption of pollutantsrdquoChemical Engineering Research and Design vol 141pp 317ndash327 2019
[6] G Bayramoglu and M Yilmaz ldquoAzo dye removal using freeand immobilized fungal biomasses isotherms kinetics andthermodynamic studiesrdquo Fibers and Polymers vol 19 no 4pp 877ndash886 2018
[7] G Bayramoglu B Altintas and M Y Arica ldquoSynthesis andcharacterization of magnetic beads containing aminated fi-brous surfaces for removal of Reactive Green 19 dye kineticsand thermodynamic parametersrdquo Journal of Chemical Tech-nology amp Biotechnology vol 87 no 5 pp 705ndash713 2012
[8] R Jain V K Gupta and S Sikarwar ldquoAdsorption and de-sorption studies on hazardous dye Napthol Yellow Srdquo Journalof Hazardous Materials vol 182 no 1-3 pp 749ndash756 2010
[9] A Mittal J Mittal A Malviya and V K Gupta ldquoRemovaland recovery of Chrysoidine Y from aqueous solutions bywaste materialsrdquo Journal of Colloid and Interface Sciencevol 344 no 2 pp 497ndash507 2010
[10] M M Younes I I El-Sharkawy A E Kabeel and B B SahaldquoA review on adsorbent-adsorbate pairs for cooling appli-cationsrdquo Applied 1ermal Engineering vol 114 no 5pp 394ndash414 2017
[11] A Pal K +u S Mitra et al ldquoStudy on biomass derivedactivated carbons for adsorptive heat pump applicationrdquoInternational Journal of Heat and Mass Transfer vol 110pp 7ndash19 2017
[12] V K Gupta R Jain S Malathi and A Nayak ldquoAdsorption-desorption studies of indigocarmine from industrial effluentsby using deoiled mustard and its comparison with charcoalrdquoJournal of Colloid and Interface Science vol 348 no 2pp 628ndash633 2010
[13] S Larous and A-HMeniai ldquo+e use of sawdust as by productadsorbent of organic pollutant fromwastewater adsorption ofphenolrdquo Energy Procedia vol 18 pp 905ndash914 2012
[14] S P Raghuvanshi R Singh C P Kaushik and A K RaghavldquoRemoval of textile basic dye from aqueous solutions usingsawdust as bio-adsorbentrdquo International Journal of Envi-ronmental Studies vol 62 no 3 pp 329ndash339 2005
[15] American Dye Manufacturing Institute Inc Dyes and theEnvironment Reports on Selected Dyes and 1eir EffectsAmerican Dye Manufacturing Institute Inc Springfield VAUSA 1974
[16] H Freundlich ldquoUber dye adsorption in Lusungenrdquo Zeitschriftfur Physikalische Chemie vol 57 no 1 pp 385ndash470 1906
[17] I Langmuir ldquo+e adsorption of gases on plane surfaces ofglass mica and platinumrdquo Journal of the American ChemicalSociety vol 40 no 9 pp 1361ndash1384 1918
[18] J L Beltran J J Pignatello and M Teixido ldquoISOT_Calc aversatile tool for parameter estimation in sorption isothermsrdquoComputers amp Geosciences vol 94 pp 11ndash17 2016
[19] R Li B Wen S Zhang Z Pei and X Shan ldquoInfluence oforganic amendments on the sorption of pentachlorophenolon soilsrdquo Journal of Environmental Sciences vol 21 no 4pp 474ndash480 2009
[20] G Mckay M El Geundi and M M Nassar ldquoExternal masstransport processes during the adsorption of dyes onto ba-gasse pithrdquo Water Research vol 22 no 12 pp 1527ndash15331988
[21] Y-S Ho W-T Chiu and C-C Wang ldquoRegression analysisfor the sorption isotherms of basic dyes on sugarcane dustrdquoBioresource Technology vol 96 no 11 pp 1285ndash1291 2005
[22] A Purai and V K Rattan ldquoAcid blue 92 (leather dye) removalfrom wastewater by adsorption using biomass ash and acti-vated carbonrdquo Carbon Letters vol 11 no 1 pp 1ndash8 2010
Chemical EngineeringInternational Journal of Antennas and
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International Journal of
Hindawiwwwhindawicom Volume 2018
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Navigation and Observation
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Hindawi
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Advances in
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Submit your manuscripts atwwwhindawicom
[9] investigated the adsorption of chrysoidine Y on bottomash and deoiled soya +e dye sorption capacities of bottomash (BET surface area 8705 cm2middotgminus1) and deoiled soya(BET surface area 7286 cm2middotgminus1) were determined as361times 10minus5molmiddotgminus1 and 192times10minus5molmiddotgminus1 at 30degC re-spectively Younes et al [10] and Pal et al [11] have reviewedand studied biomass-derived activated carbons for ad-sorptive heat pump applications Gupta et al [12] studied theremoval of indigo carmine dye from industrial effluents bydeoiled mustard and charcoal +e adsorption experimentswere carried out at 30degC pH 30 for charcoal and pH 80 fordeoiled mustard and adsorbate concentration 2times10minus4molmiddotLminus1 Amounts of adsorbates were found as approxi-mately 033times10minus4molmiddotLminus1 for 040 gmiddotLminus1 for charcoal and025times10minus4molmiddotLminus1 for 75 gmiddotLminus1 of deoiled mustard Larousand Meniai [13] studied the use of carbonized sawdust as anadsorbent for phenol Raghuvanshi et al [14] have usedchemically treated sawdust as a bioadsorbent for the removalof methylene blue dye
Chrysoidine is a type of industrial azoic dye Due to itsgood dyeing fastness it is widely used for dyeing leatherpaper feather grass wood bamboo etc Chrysoidine cancause acute and chronic toxicity to mammals when takenorally or inhaled and its median lethal concentration (LC5024 h) for fish was 05mgL According to American DyeManufacturing Institute (ADMI) the basic dyes are gen-erally more toxic than acidic or direct dyes [15]
+e objective of this paper was to explore the removal ofchrysoidine basic dye in an aqueous solution by adsorptionon the sawdust Chrysoidine removal has never been triedbefore by using chemically treated and raw sawdust +einfluence of several parameters on adsorption such ascontact time dye concentration temperature etc on theadsorption process was also studied
2 Materials and Methods
Sawdust was grabbed from a nearby wood working factoryand divided into two portions by weight One part waschemically treated while the second was kept for use in itsraw form+e first partwas treated with sulphuric acid in theratio of 4 3 parts by weight +e material was kept in avacuum oven for 24 hours at 150degC +e carbonized materialwas washed thrice with distilled water to remove anyunreacted acid and dried at 100degC for 24 hours +e materialwas finely grounded and passed through sieve ISS 600 andstored +is material was used in adsorption experiments aschemically activated sawdust+e second part of the sawdustwas saturated with the distilled water and washed repeatedlyto remove the typical yellow color of the sawdust caused bylignin Subsequently it was treated with formaldehyde for6 hours to remove the lignin +e material was dried in avacuum oven at 60degC for 24 hours and this dried materialwas grounded to fine powder and sieved through ISS 600+is material was used throughout as untreated sawdustadsorbent [14]
+e dye chrysoidine is a basic dye with CAS number532-82-1 molecular weight 24871 color index number
11270 λmax 449 nm and empirical formula (Hill Notation)C12H12N4middotHCl +e structural formula is shown in Figure 1
All reagents used in the present study were of analyticalreagent (AR) grade and supplied by Sigma-Aldrich
21 Adsorption Studies In order to explore the adsorptionefficiency of both versions of sawdust a series of experimentswas conducted During the experiments 10times10minus4 kg to10times10minus3 kg of both adsorbents were taken separately in250mL conical flasks sealed with parafilm on an electricrotary shaking machine in 100mL aqueous solution of thedye (variable concentrations) at different temperatures andtime intervals After predetermined time intervals the so-lution was analyzed for the residual concentration of dye byusing a Shimadzu UV-VIS spectrophotometer at 449 nm Asimilar procedure was followed for another set of flaskscontaining same dye concentration but without sawdust tobe used as blank All the experiments were conducted intriplicate at neutral pH +e adsorption of the dye can bedescribed in terms of dye removal
dye removal() c0 minus cf
c0times 100 (1)
where c0 is the initial and cf is the final concentrations of thedye in the solution
22 Adsorption 1ermodynamics +e spontaneity of theadsorption process is normally described by changes in thestandard enthalpy (ΔHdeg) Gibbrsquos free energy (ΔGdeg) andentropy (ΔSdeg) Decrease in ΔGdeg normally indicates aspontaneous process and the opposite is true for a non-spontaneous reaction +e relations for the thermodynamicparameters are given as follows
ΔGdeg minusRT ln Ka (2)
where Ka is the thermodynamic equilibrium constant
Kd ca
ceasymp Ka (3)
where Kd is the adsorption equilibrium constant and ca is theadsorbed concentration
ΔGdeg ΔHdeg minusTΔSdeg (4)
ln Ka minusΔHdeg
RT+ΔSdegR
(5)
A linear relation between ln Ka and inverse temperatureis used to evaluate ΔHdeg and ΔSdeg
23 Adsorption Isotherms Adsorption analysis is normallyperformed using adsorption isotherms Freundlich isothermis the earliest known relationship describing the adsorptionequation and is often expressed as
qe KFc1ne (6)
2 International Journal of Chemical Engineering
where qe is the adsorption density (mg of adsorbate per gmof adsorbent) ce is the equilibrium concentration (mgL)KF is the Freundlich constant and n is an exponent [16]
+e equation can be converted in a linear form by takingthe log on both sides as
log qe log KF +1nlog ce (7)
A plot of log qe against log ce yields a straight lineindicating the conformation of Freundlichrsquos isotherm foradsorption +e constants can be determined from thecorresponding slope and intercept
Langmuir isotherm is another most frequently usedadsorption isotherm [17] It is described by the followingrelation
qe qmax middotbce
1 + bce (8)
where qmax is the maximum adsorption capacity and b is theLangmuir constant (Lmg)
+is equation can also be converted into a straight line asce
qe
1qmaxb
+1
qmaxce (9)
A plot of ceqe vs ce gives a straight line +e slope andintercept gives the values of Langmuir constants
Equations (2) and (4) can be straightforward but maylead to errors as mentioned elsewhere [13] ISOT-Calc andother statistical and mathematical packages [18 19] havebeen used to fit the nonlinear isotherm data In this studyiterative LevenbergndashMarquardt and nonlinear least squareswas used to find the parameters Nonlinear optimization wasbased on minimizing the objective function defined as
OF 1113944 wi qeexp minus qecalc1113874 11138752 (10)
where qeexp is the experimental adsorption density qecalc is themodeled adsorption density and wi is the data weighingcoefficient for every point (ce qe)
+e compatibility of an adsorbent-adsorbate pair can beindicated by a nondimensional parameter RL RL is called theseparation parameter and it is derived from Langmuirconstant
RL 1
1 + bc0 (11)
where RL gt 1 indicates nonfavorable combination 0ltRL lt 1favors adsorption and RL 1 is for nonlinear adsorptionwhereas RL 0 shows irreversible adsorption
3 Results and Discussion
Figures 2(a) and 2(b) describe the effect of initial dyeconcentration on the rate of adsorption on sawdust bothtreated and untreated It can be deduced that for any par-ticular experiment the rate of adsorption decreased withtime until it gradually approached a plateau owing to thecontinuous decrease in the driving force (concentration) andalso indicating that the adsorbent is saturated at this point+e saturation point was reached within 40 to 50minutes Inthe beginning the adsorption process was found to be veryfast and a large amount of the total concentration of dye wasremoved in the first half an hour Activated sawdust reachedequilibrium slightly earlier than the raw sawdust Moreoverthe initial adsorption rate was high for initial dye concen-tration as resistance to dye uptake decreases when the masstransfer driving force increases +is observation indicatedthat the removal of dye is dependent upon the initialconcentration of the solution
+e effect of various concentrations of treated andnontreated sawdust on adsorption is shown in Figures 3(a)and 3(b) Graphs show a decline in the dye concentration at arapid pace as the sawdust quantity is increased Chemicallytreated sawdust gave the greater removal at all levels of theadsorbent dose In the beginning the rate of dye removalwas faster which slowed down as the dose increased +iscan be attributed to the fact that at a lower adsorbent dosethe dye molecules are easily reachable and therefore re-moval per unit mass of adsorbent is higher A larger surfacearea of the adsorbent particles and smaller size of adsorbatemolecules favor adsorption
+e rate of adsorption is higher at the initial stage as sitesare vacant for adsorption Adsorption and desorption occursimultaneously and an adsorption equilibrium is reachedwhen isotherms are applied With a rise in adsorbentquantity there is a less corresponding increase in adsorptionresulting from lower adsorptive capacity utilization of ad-sorbent +e results obtained from above experiment in-dicate that chemically treated sawdust has a large potential asan adsorbent for dye removal as compared to raw sawdust
It has been reported that if the solubility of the adsorbateincreases with an increase in temperature then the chemicalpotential decreases and both these effects working in thesame direction cause a decrease in adsorption Converselyif the temperature has the reverse effect on the solubilitythen both the said effects will act in the opposite directionand adsorption may increase or decrease depending on thepredominant factor [14]+e adsorption rates of chrysoidineat three different temperatures (30degC 40degC and 50degC) werestudied as shown in Figure 4(a) and 4(b) In case of rawsawdust the rate of dye adsorption decreased with an in-crease in temperature from 30degC to 50degC with a 4 gL dose in5minutes time from a 100 gL dye solution +is behaviorindicated that the process is exothermic in nature +is canbe attributed to the predisposition of the dye molecules toescape from the solid phase to bulk phase with a rise intemperature of the solution However in the case of treatedsawdust the rate of dye uptake increases rapidly
N=N
H2N
NH2
HCl
Figure 1 +e structural formula of chrysoidine
International Journal of Chemical Engineering 3
e thermodynamic parameters (ΔHdeg and ΔSdeg) wereobtained from the slope and intercept of the linear re-gression line tted on the lnK vs 1T data e plot for rawand activated sawdust is shown in Figure 5 and the ther-modynamic parameters values are given in Table 1
From Table 1 it can be seen that ΔGdeg is negative in-dicating that the adsorption is spontaneousWith the increasein temperature ΔGdeg become less negative or the spontaneitydecreases by increasing temperature Compared to rawsawdust activated sawdust showed more negative value forΔGdeg indicating more feasibility of adsorption ΔHdeg is alsonegative showing the process is exothermic And the processis physisorption as chemisorption proceeds with the enthalpy
changes in the range of minus80 to minus200 kJmol e negativevalue of ΔSdeg reveals the adsorption is ordered Similarly morenegative value of ΔSdeg indicates decreasing randomness onactivated surface than raw sawdust Overall it can be con-cluded from the obtained thermodynamic parameters that theactivated sawdust betters in terms of feasibility exothermicityand ordered layering than raw sawdust
For adsorption of chrysoidine on sawdust there may be apossibility of intraparticle diusion In order to investigatethis possibility experiments were conducted and aredepicted in Figures 6(a) and 6(b)
e plots (Figures 6(a) and 6(b)) with log (dye re-moval) () versus log time (min) for adsorption at three
20 40 60Time (min)
80 100 1200
q (m
gg)
0
10
20
30
40
50
50 mgL100 mgL150 mgL
200 mgL250 mgL300 mgL
(a)
20 40 60Time (min)
80 100 1200
q (m
gg)
0
10
20
30
40
50
50 mgL100 mgL150 mgL
200 mgL250 mgL300 mgL
(b)
Figure 2 Eect of contact time on dye (dose 4 gL) adsorption on (a) raw sawdust and (b) chemically treated sawdust
Time (min)20 40 60 80 100 1200
q (m
gg)
0
200
400
600
800
01 g02 g04 g
06 g08 g1 g
(a)
Time (min)20 40 60 80 100 1200
q (m
gg)
0
200
400
600
800
01 g02 g04 g
06 g08 g1 g
(b)
Figure 3 Eect of (a) raw sawdust dose (100mgL) and (b) chemically treated sawdust dose on dye adsorption
4 International Journal of Chemical Engineering
dierent temperatures ranging between 30 and 50degCresulted in straight lines which specify the existence ofintraparticle diusion ese plots are used to describewhether adsorption is controlled by diusion in the ad-sorbent particles or the consecutive diusion in the bulk ofthe solution [20ndash22]
31 Adsorption Isotherms e two most frequently usedadsorption isotherms are employed in Figure 7 for theadsorption of chrysoidine on raw and activated sawdust Itcan be seen that the coecient of determination (R2) is lower
in Freundlich isotherm erefore it can be presumed thatthe adsorption of chrysoidine on raw and activated sawdustfollows Langmuir adsorption model
e parameters of the Freundlich and Langmuir linearisotherms are given in Table 2 and the same were used tocompare the experimental curves Lower values of ob-jective function (OF) were obtained in case of Langmuirisotherm
Similarly Figure 8 shows the nonlinear curve t-tings of Freundlich and Langmuir isotherms Lowervalues of OF render Langmuir better model for the
q (m
gg)
0
5
10
15
20
25
30
Time (min)10 20 30 40 50 60 700
30degC40degC50degC
(a)
q (m
gg)
0
5
10
15
20
25
30
Time (min)10 20 30 40 50 60 700
30degC40degC50degC
(b)
Figure 4 Eect of temperature on dye removal with (a) raw sawdust (conc 100mgL dose 4 gL) and (b) chemically treated sawdust (conc100mgL dose 4 gL)
00030
05
1
15
2
25
000305 00031 000315
lnK
(ndash)
00032 000325 000331T (Kndash1)
Raw sawdusty = 47191822 lowast xndash 144839
Activated sawdusty = 5657569 lowast xndash 162594
Figure 5 LnK vs 1T curves for raw and activated saw dust
Table 1 ermodynamic parameters at dierent temperatures
Temperature (degC)Raw sawdust Chemically treated sawdust
Ka (minus) ΔGdeg(kJmol) ΔHdeg (kJmol) ΔSdeg (Jmol-K) Ka (minus) ΔGdeg (kJmol) ΔHdeg (kJmol) ΔSdeg (Jmol-K)
adsorption of chrysoidine on raw and activated sawdustthan Freundlich
e parameters of Freundlich and Langmuir obtainedfrom nonlinear tting are reported in Table 3 e
comparison of linear and nonlinear methods clearly revealsthat the OF values are lower in case of nonlinear method
Langmuir constant ldquobrdquo estimated from the nonlinearmethod was then used to calculate RL Evolution of RL with
Log(
dye r
emov
al) (
)
05 1 15Log(time) (min)
215
16
17
18
19
2
50degC
30degC40degC
R2 (0976)R2 (0992)R2 (0839)
(a)
05 1 15Log(time) (min)
2
Log(
dye r
emov
al) (
)
15
16
17
18
19
2
50degC
30degC40degC
R2 (0989)R2 (0984)R2 (0879)
(b)
Figure 6 Log (dye removal) () versus log time (min) for (a) raw sawdust and (b) chemically treated sawdust
Log ce (mgL)
Logq
e (m
gg)
0501
12
14
16
18
1 15 252
Freundlich (R2 = 0749)
Experimentalraw sawdust
Freundlich (R2 = 0780)
Experimentalactivated sawdust
(a)
c eq
e (m
gg)
0
1
2
3
4
6
5
ce (mgL)500 100 150 200
Langmuir (R2 = 0996)
Experimentalraw sawdust
Langmuir (R2 = 0997)
Experimentalactivated sawdust
(b)
Figure 7 Freundlich (a) and Langmuir (b) linear isotherms of raw and chemically treated sawdust for chrysoidine removal
Table 2 Comparison of the optimized Freundlich and Langmuir isotherms parameters for the adsorption of chrysoidine on raw andchemically treated sawdust
SawdustFreundlich Langmuir
KF (mg(1minus1n) gminus1middotL1n) n OF (mg2g2) qmax (mgg) b (Lmg) b (Lmol) OF (mg2g2)
an initial dye concentration of raw and activated sawdust isshown in Figure 9 RL of activated sawdust is lower (0019 to0104) compared to raw sawdust (0026 to 0136) indicatingbetter suitability of activated sawdust over raw sawdust forthis adsorbent-adsorbate combination
Recovery of the spent adsorbent is an important eco-nomic factor in determining the practicability of an ad-sorption system However sawdust is a wood by-productwhich is a waste material available in plenty and bears nocost erefore the recovery of adsorbent was not furtherpursued
4 Conclusion
Sawdust in both forms proved to be an ecient adsorbent forchrysoidine dye from aqueous solutionis work has provedthe potentiality of sawdust to be an eective adsorbent eadsorption of chrysoidine followed Langmuirrsquos isotherm Assawdust is a cheap material and easily available the process isexpected to be economical Although untreated sawdustproved to be less eective in comparison to treated sawdusteconomically speaking the percentage of dye removal is lessthan the dierence in the commercial costs
1005000
10
q e (m
gg)
20
30
40
150 200
ExperimentalFreundlichLangmuir
ce (mgL)
(a)
q e (m
gg)
ExperimentalFreundlichLangmuir
1005000
10
20
30
40
150 200ce (mgL)
(b)
Figure 8 Freundlich and Langmuir nonlinear isotherms of (a) raw sawdust and (b) chemically treated sawdust for chrysoidine removal
Table 3 Comparison of the optimized Freundlich and Langmuir isotherms parameters for the adsorption of chrysoidine on raw andactivated sawdust
SawdustFreundlich Langmuir
KF (mg(1minus1n) gminus1middotL1n) n OF (mg2g2) qmax (mgg) b (Lmg) b (Lmol) OF (mg2g2)
Figure 9 Eect of initial concentration on the Langmuir adsorption factor of raw and activated saw dust
International Journal of Chemical Engineering 7
Data Availability
+e adsorption data used to support the findings of thisstudy are included within the article in the form of graphsData tables are not included just to avoid duplication
Conflicts of Interest
+e authors declare that there are no conflicts of interestregarding the publication of this paper
Acknowledgments
+e authors are thankful to Prince Mohammad Bin FahdUniversity for supporting the present work +anks are alsodue to King Abdulaziz University Rabigh campus forproviding some raw materials
References
[1] M W Ashraf ldquoRemoval of methylene blue dye fromwastewater by using supported liquid memberane technol-ogyrdquo Polish Journal of Chemical Technology vol 18 no 2pp 26ndash30 2016
[2] V M Nurchi M Crespo-Alonso R Biesuz et al ldquoSorption ofchrysoidine by row cork and cork entrapped in calcium al-ginate beadsrdquo Arabian Journal of Chemistry vol 7 no 1pp 133ndash138 2014
[3] K-L Chang C-C Chen J-H Lin et al ldquoRice straw-derivedactivated carbons for the removal of carbofuran from anaqueous solutionrdquo New Carbon Materials vol 29 no 1pp 47ndash54 2014
[4] T A Arica E Ayas and M Y Arica ldquoMagnetic MCM-41silica particles grafted with poly(glycidylmethacrylate) brushmodification and application for removal of direct dyesrdquoMicroporous and Mesoporous Materials vol 243 no 1pp 164ndash175 2017
[5] T A Arica M Kuman O Gercel and E Ayas ldquoPoly(dop-amine) grafted bio-silica composite with tetraethylenepent-amine ligands for enhanced adsorption of pollutantsrdquoChemical Engineering Research and Design vol 141pp 317ndash327 2019
[6] G Bayramoglu and M Yilmaz ldquoAzo dye removal using freeand immobilized fungal biomasses isotherms kinetics andthermodynamic studiesrdquo Fibers and Polymers vol 19 no 4pp 877ndash886 2018
[7] G Bayramoglu B Altintas and M Y Arica ldquoSynthesis andcharacterization of magnetic beads containing aminated fi-brous surfaces for removal of Reactive Green 19 dye kineticsand thermodynamic parametersrdquo Journal of Chemical Tech-nology amp Biotechnology vol 87 no 5 pp 705ndash713 2012
[8] R Jain V K Gupta and S Sikarwar ldquoAdsorption and de-sorption studies on hazardous dye Napthol Yellow Srdquo Journalof Hazardous Materials vol 182 no 1-3 pp 749ndash756 2010
[9] A Mittal J Mittal A Malviya and V K Gupta ldquoRemovaland recovery of Chrysoidine Y from aqueous solutions bywaste materialsrdquo Journal of Colloid and Interface Sciencevol 344 no 2 pp 497ndash507 2010
[10] M M Younes I I El-Sharkawy A E Kabeel and B B SahaldquoA review on adsorbent-adsorbate pairs for cooling appli-cationsrdquo Applied 1ermal Engineering vol 114 no 5pp 394ndash414 2017
[11] A Pal K +u S Mitra et al ldquoStudy on biomass derivedactivated carbons for adsorptive heat pump applicationrdquoInternational Journal of Heat and Mass Transfer vol 110pp 7ndash19 2017
[12] V K Gupta R Jain S Malathi and A Nayak ldquoAdsorption-desorption studies of indigocarmine from industrial effluentsby using deoiled mustard and its comparison with charcoalrdquoJournal of Colloid and Interface Science vol 348 no 2pp 628ndash633 2010
[13] S Larous and A-HMeniai ldquo+e use of sawdust as by productadsorbent of organic pollutant fromwastewater adsorption ofphenolrdquo Energy Procedia vol 18 pp 905ndash914 2012
[14] S P Raghuvanshi R Singh C P Kaushik and A K RaghavldquoRemoval of textile basic dye from aqueous solutions usingsawdust as bio-adsorbentrdquo International Journal of Envi-ronmental Studies vol 62 no 3 pp 329ndash339 2005
[15] American Dye Manufacturing Institute Inc Dyes and theEnvironment Reports on Selected Dyes and 1eir EffectsAmerican Dye Manufacturing Institute Inc Springfield VAUSA 1974
[16] H Freundlich ldquoUber dye adsorption in Lusungenrdquo Zeitschriftfur Physikalische Chemie vol 57 no 1 pp 385ndash470 1906
[17] I Langmuir ldquo+e adsorption of gases on plane surfaces ofglass mica and platinumrdquo Journal of the American ChemicalSociety vol 40 no 9 pp 1361ndash1384 1918
[18] J L Beltran J J Pignatello and M Teixido ldquoISOT_Calc aversatile tool for parameter estimation in sorption isothermsrdquoComputers amp Geosciences vol 94 pp 11ndash17 2016
[19] R Li B Wen S Zhang Z Pei and X Shan ldquoInfluence oforganic amendments on the sorption of pentachlorophenolon soilsrdquo Journal of Environmental Sciences vol 21 no 4pp 474ndash480 2009
[20] G Mckay M El Geundi and M M Nassar ldquoExternal masstransport processes during the adsorption of dyes onto ba-gasse pithrdquo Water Research vol 22 no 12 pp 1527ndash15331988
[21] Y-S Ho W-T Chiu and C-C Wang ldquoRegression analysisfor the sorption isotherms of basic dyes on sugarcane dustrdquoBioresource Technology vol 96 no 11 pp 1285ndash1291 2005
[22] A Purai and V K Rattan ldquoAcid blue 92 (leather dye) removalfrom wastewater by adsorption using biomass ash and acti-vated carbonrdquo Carbon Letters vol 11 no 1 pp 1ndash8 2010
Chemical EngineeringInternational Journal of Antennas and
Propagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Navigation and Observation
International Journal of
Hindawi
wwwhindawicom Volume 2018
Advances in
Multimedia
Submit your manuscripts atwwwhindawicom
where qe is the adsorption density (mg of adsorbate per gmof adsorbent) ce is the equilibrium concentration (mgL)KF is the Freundlich constant and n is an exponent [16]
+e equation can be converted in a linear form by takingthe log on both sides as
log qe log KF +1nlog ce (7)
A plot of log qe against log ce yields a straight lineindicating the conformation of Freundlichrsquos isotherm foradsorption +e constants can be determined from thecorresponding slope and intercept
Langmuir isotherm is another most frequently usedadsorption isotherm [17] It is described by the followingrelation
qe qmax middotbce
1 + bce (8)
where qmax is the maximum adsorption capacity and b is theLangmuir constant (Lmg)
+is equation can also be converted into a straight line asce
qe
1qmaxb
+1
qmaxce (9)
A plot of ceqe vs ce gives a straight line +e slope andintercept gives the values of Langmuir constants
Equations (2) and (4) can be straightforward but maylead to errors as mentioned elsewhere [13] ISOT-Calc andother statistical and mathematical packages [18 19] havebeen used to fit the nonlinear isotherm data In this studyiterative LevenbergndashMarquardt and nonlinear least squareswas used to find the parameters Nonlinear optimization wasbased on minimizing the objective function defined as
OF 1113944 wi qeexp minus qecalc1113874 11138752 (10)
where qeexp is the experimental adsorption density qecalc is themodeled adsorption density and wi is the data weighingcoefficient for every point (ce qe)
+e compatibility of an adsorbent-adsorbate pair can beindicated by a nondimensional parameter RL RL is called theseparation parameter and it is derived from Langmuirconstant
RL 1
1 + bc0 (11)
where RL gt 1 indicates nonfavorable combination 0ltRL lt 1favors adsorption and RL 1 is for nonlinear adsorptionwhereas RL 0 shows irreversible adsorption
3 Results and Discussion
Figures 2(a) and 2(b) describe the effect of initial dyeconcentration on the rate of adsorption on sawdust bothtreated and untreated It can be deduced that for any par-ticular experiment the rate of adsorption decreased withtime until it gradually approached a plateau owing to thecontinuous decrease in the driving force (concentration) andalso indicating that the adsorbent is saturated at this point+e saturation point was reached within 40 to 50minutes Inthe beginning the adsorption process was found to be veryfast and a large amount of the total concentration of dye wasremoved in the first half an hour Activated sawdust reachedequilibrium slightly earlier than the raw sawdust Moreoverthe initial adsorption rate was high for initial dye concen-tration as resistance to dye uptake decreases when the masstransfer driving force increases +is observation indicatedthat the removal of dye is dependent upon the initialconcentration of the solution
+e effect of various concentrations of treated andnontreated sawdust on adsorption is shown in Figures 3(a)and 3(b) Graphs show a decline in the dye concentration at arapid pace as the sawdust quantity is increased Chemicallytreated sawdust gave the greater removal at all levels of theadsorbent dose In the beginning the rate of dye removalwas faster which slowed down as the dose increased +iscan be attributed to the fact that at a lower adsorbent dosethe dye molecules are easily reachable and therefore re-moval per unit mass of adsorbent is higher A larger surfacearea of the adsorbent particles and smaller size of adsorbatemolecules favor adsorption
+e rate of adsorption is higher at the initial stage as sitesare vacant for adsorption Adsorption and desorption occursimultaneously and an adsorption equilibrium is reachedwhen isotherms are applied With a rise in adsorbentquantity there is a less corresponding increase in adsorptionresulting from lower adsorptive capacity utilization of ad-sorbent +e results obtained from above experiment in-dicate that chemically treated sawdust has a large potential asan adsorbent for dye removal as compared to raw sawdust
It has been reported that if the solubility of the adsorbateincreases with an increase in temperature then the chemicalpotential decreases and both these effects working in thesame direction cause a decrease in adsorption Converselyif the temperature has the reverse effect on the solubilitythen both the said effects will act in the opposite directionand adsorption may increase or decrease depending on thepredominant factor [14]+e adsorption rates of chrysoidineat three different temperatures (30degC 40degC and 50degC) werestudied as shown in Figure 4(a) and 4(b) In case of rawsawdust the rate of dye adsorption decreased with an in-crease in temperature from 30degC to 50degC with a 4 gL dose in5minutes time from a 100 gL dye solution +is behaviorindicated that the process is exothermic in nature +is canbe attributed to the predisposition of the dye molecules toescape from the solid phase to bulk phase with a rise intemperature of the solution However in the case of treatedsawdust the rate of dye uptake increases rapidly
N=N
H2N
NH2
HCl
Figure 1 +e structural formula of chrysoidine
International Journal of Chemical Engineering 3
e thermodynamic parameters (ΔHdeg and ΔSdeg) wereobtained from the slope and intercept of the linear re-gression line tted on the lnK vs 1T data e plot for rawand activated sawdust is shown in Figure 5 and the ther-modynamic parameters values are given in Table 1
From Table 1 it can be seen that ΔGdeg is negative in-dicating that the adsorption is spontaneousWith the increasein temperature ΔGdeg become less negative or the spontaneitydecreases by increasing temperature Compared to rawsawdust activated sawdust showed more negative value forΔGdeg indicating more feasibility of adsorption ΔHdeg is alsonegative showing the process is exothermic And the processis physisorption as chemisorption proceeds with the enthalpy
changes in the range of minus80 to minus200 kJmol e negativevalue of ΔSdeg reveals the adsorption is ordered Similarly morenegative value of ΔSdeg indicates decreasing randomness onactivated surface than raw sawdust Overall it can be con-cluded from the obtained thermodynamic parameters that theactivated sawdust betters in terms of feasibility exothermicityand ordered layering than raw sawdust
For adsorption of chrysoidine on sawdust there may be apossibility of intraparticle diusion In order to investigatethis possibility experiments were conducted and aredepicted in Figures 6(a) and 6(b)
e plots (Figures 6(a) and 6(b)) with log (dye re-moval) () versus log time (min) for adsorption at three
20 40 60Time (min)
80 100 1200
q (m
gg)
0
10
20
30
40
50
50 mgL100 mgL150 mgL
200 mgL250 mgL300 mgL
(a)
20 40 60Time (min)
80 100 1200
q (m
gg)
0
10
20
30
40
50
50 mgL100 mgL150 mgL
200 mgL250 mgL300 mgL
(b)
Figure 2 Eect of contact time on dye (dose 4 gL) adsorption on (a) raw sawdust and (b) chemically treated sawdust
Time (min)20 40 60 80 100 1200
q (m
gg)
0
200
400
600
800
01 g02 g04 g
06 g08 g1 g
(a)
Time (min)20 40 60 80 100 1200
q (m
gg)
0
200
400
600
800
01 g02 g04 g
06 g08 g1 g
(b)
Figure 3 Eect of (a) raw sawdust dose (100mgL) and (b) chemically treated sawdust dose on dye adsorption
4 International Journal of Chemical Engineering
dierent temperatures ranging between 30 and 50degCresulted in straight lines which specify the existence ofintraparticle diusion ese plots are used to describewhether adsorption is controlled by diusion in the ad-sorbent particles or the consecutive diusion in the bulk ofthe solution [20ndash22]
31 Adsorption Isotherms e two most frequently usedadsorption isotherms are employed in Figure 7 for theadsorption of chrysoidine on raw and activated sawdust Itcan be seen that the coecient of determination (R2) is lower
in Freundlich isotherm erefore it can be presumed thatthe adsorption of chrysoidine on raw and activated sawdustfollows Langmuir adsorption model
e parameters of the Freundlich and Langmuir linearisotherms are given in Table 2 and the same were used tocompare the experimental curves Lower values of ob-jective function (OF) were obtained in case of Langmuirisotherm
Similarly Figure 8 shows the nonlinear curve t-tings of Freundlich and Langmuir isotherms Lowervalues of OF render Langmuir better model for the
q (m
gg)
0
5
10
15
20
25
30
Time (min)10 20 30 40 50 60 700
30degC40degC50degC
(a)
q (m
gg)
0
5
10
15
20
25
30
Time (min)10 20 30 40 50 60 700
30degC40degC50degC
(b)
Figure 4 Eect of temperature on dye removal with (a) raw sawdust (conc 100mgL dose 4 gL) and (b) chemically treated sawdust (conc100mgL dose 4 gL)
00030
05
1
15
2
25
000305 00031 000315
lnK
(ndash)
00032 000325 000331T (Kndash1)
Raw sawdusty = 47191822 lowast xndash 144839
Activated sawdusty = 5657569 lowast xndash 162594
Figure 5 LnK vs 1T curves for raw and activated saw dust
Table 1 ermodynamic parameters at dierent temperatures
Temperature (degC)Raw sawdust Chemically treated sawdust
Ka (minus) ΔGdeg(kJmol) ΔHdeg (kJmol) ΔSdeg (Jmol-K) Ka (minus) ΔGdeg (kJmol) ΔHdeg (kJmol) ΔSdeg (Jmol-K)
adsorption of chrysoidine on raw and activated sawdustthan Freundlich
e parameters of Freundlich and Langmuir obtainedfrom nonlinear tting are reported in Table 3 e
comparison of linear and nonlinear methods clearly revealsthat the OF values are lower in case of nonlinear method
Langmuir constant ldquobrdquo estimated from the nonlinearmethod was then used to calculate RL Evolution of RL with
Log(
dye r
emov
al) (
)
05 1 15Log(time) (min)
215
16
17
18
19
2
50degC
30degC40degC
R2 (0976)R2 (0992)R2 (0839)
(a)
05 1 15Log(time) (min)
2
Log(
dye r
emov
al) (
)
15
16
17
18
19
2
50degC
30degC40degC
R2 (0989)R2 (0984)R2 (0879)
(b)
Figure 6 Log (dye removal) () versus log time (min) for (a) raw sawdust and (b) chemically treated sawdust
Log ce (mgL)
Logq
e (m
gg)
0501
12
14
16
18
1 15 252
Freundlich (R2 = 0749)
Experimentalraw sawdust
Freundlich (R2 = 0780)
Experimentalactivated sawdust
(a)
c eq
e (m
gg)
0
1
2
3
4
6
5
ce (mgL)500 100 150 200
Langmuir (R2 = 0996)
Experimentalraw sawdust
Langmuir (R2 = 0997)
Experimentalactivated sawdust
(b)
Figure 7 Freundlich (a) and Langmuir (b) linear isotherms of raw and chemically treated sawdust for chrysoidine removal
Table 2 Comparison of the optimized Freundlich and Langmuir isotherms parameters for the adsorption of chrysoidine on raw andchemically treated sawdust
SawdustFreundlich Langmuir
KF (mg(1minus1n) gminus1middotL1n) n OF (mg2g2) qmax (mgg) b (Lmg) b (Lmol) OF (mg2g2)
an initial dye concentration of raw and activated sawdust isshown in Figure 9 RL of activated sawdust is lower (0019 to0104) compared to raw sawdust (0026 to 0136) indicatingbetter suitability of activated sawdust over raw sawdust forthis adsorbent-adsorbate combination
Recovery of the spent adsorbent is an important eco-nomic factor in determining the practicability of an ad-sorption system However sawdust is a wood by-productwhich is a waste material available in plenty and bears nocost erefore the recovery of adsorbent was not furtherpursued
4 Conclusion
Sawdust in both forms proved to be an ecient adsorbent forchrysoidine dye from aqueous solutionis work has provedthe potentiality of sawdust to be an eective adsorbent eadsorption of chrysoidine followed Langmuirrsquos isotherm Assawdust is a cheap material and easily available the process isexpected to be economical Although untreated sawdustproved to be less eective in comparison to treated sawdusteconomically speaking the percentage of dye removal is lessthan the dierence in the commercial costs
1005000
10
q e (m
gg)
20
30
40
150 200
ExperimentalFreundlichLangmuir
ce (mgL)
(a)
q e (m
gg)
ExperimentalFreundlichLangmuir
1005000
10
20
30
40
150 200ce (mgL)
(b)
Figure 8 Freundlich and Langmuir nonlinear isotherms of (a) raw sawdust and (b) chemically treated sawdust for chrysoidine removal
Table 3 Comparison of the optimized Freundlich and Langmuir isotherms parameters for the adsorption of chrysoidine on raw andactivated sawdust
SawdustFreundlich Langmuir
KF (mg(1minus1n) gminus1middotL1n) n OF (mg2g2) qmax (mgg) b (Lmg) b (Lmol) OF (mg2g2)
Figure 9 Eect of initial concentration on the Langmuir adsorption factor of raw and activated saw dust
International Journal of Chemical Engineering 7
Data Availability
+e adsorption data used to support the findings of thisstudy are included within the article in the form of graphsData tables are not included just to avoid duplication
Conflicts of Interest
+e authors declare that there are no conflicts of interestregarding the publication of this paper
Acknowledgments
+e authors are thankful to Prince Mohammad Bin FahdUniversity for supporting the present work +anks are alsodue to King Abdulaziz University Rabigh campus forproviding some raw materials
References
[1] M W Ashraf ldquoRemoval of methylene blue dye fromwastewater by using supported liquid memberane technol-ogyrdquo Polish Journal of Chemical Technology vol 18 no 2pp 26ndash30 2016
[2] V M Nurchi M Crespo-Alonso R Biesuz et al ldquoSorption ofchrysoidine by row cork and cork entrapped in calcium al-ginate beadsrdquo Arabian Journal of Chemistry vol 7 no 1pp 133ndash138 2014
[3] K-L Chang C-C Chen J-H Lin et al ldquoRice straw-derivedactivated carbons for the removal of carbofuran from anaqueous solutionrdquo New Carbon Materials vol 29 no 1pp 47ndash54 2014
[4] T A Arica E Ayas and M Y Arica ldquoMagnetic MCM-41silica particles grafted with poly(glycidylmethacrylate) brushmodification and application for removal of direct dyesrdquoMicroporous and Mesoporous Materials vol 243 no 1pp 164ndash175 2017
[5] T A Arica M Kuman O Gercel and E Ayas ldquoPoly(dop-amine) grafted bio-silica composite with tetraethylenepent-amine ligands for enhanced adsorption of pollutantsrdquoChemical Engineering Research and Design vol 141pp 317ndash327 2019
[6] G Bayramoglu and M Yilmaz ldquoAzo dye removal using freeand immobilized fungal biomasses isotherms kinetics andthermodynamic studiesrdquo Fibers and Polymers vol 19 no 4pp 877ndash886 2018
[7] G Bayramoglu B Altintas and M Y Arica ldquoSynthesis andcharacterization of magnetic beads containing aminated fi-brous surfaces for removal of Reactive Green 19 dye kineticsand thermodynamic parametersrdquo Journal of Chemical Tech-nology amp Biotechnology vol 87 no 5 pp 705ndash713 2012
[8] R Jain V K Gupta and S Sikarwar ldquoAdsorption and de-sorption studies on hazardous dye Napthol Yellow Srdquo Journalof Hazardous Materials vol 182 no 1-3 pp 749ndash756 2010
[9] A Mittal J Mittal A Malviya and V K Gupta ldquoRemovaland recovery of Chrysoidine Y from aqueous solutions bywaste materialsrdquo Journal of Colloid and Interface Sciencevol 344 no 2 pp 497ndash507 2010
[10] M M Younes I I El-Sharkawy A E Kabeel and B B SahaldquoA review on adsorbent-adsorbate pairs for cooling appli-cationsrdquo Applied 1ermal Engineering vol 114 no 5pp 394ndash414 2017
[11] A Pal K +u S Mitra et al ldquoStudy on biomass derivedactivated carbons for adsorptive heat pump applicationrdquoInternational Journal of Heat and Mass Transfer vol 110pp 7ndash19 2017
[12] V K Gupta R Jain S Malathi and A Nayak ldquoAdsorption-desorption studies of indigocarmine from industrial effluentsby using deoiled mustard and its comparison with charcoalrdquoJournal of Colloid and Interface Science vol 348 no 2pp 628ndash633 2010
[13] S Larous and A-HMeniai ldquo+e use of sawdust as by productadsorbent of organic pollutant fromwastewater adsorption ofphenolrdquo Energy Procedia vol 18 pp 905ndash914 2012
[14] S P Raghuvanshi R Singh C P Kaushik and A K RaghavldquoRemoval of textile basic dye from aqueous solutions usingsawdust as bio-adsorbentrdquo International Journal of Envi-ronmental Studies vol 62 no 3 pp 329ndash339 2005
[15] American Dye Manufacturing Institute Inc Dyes and theEnvironment Reports on Selected Dyes and 1eir EffectsAmerican Dye Manufacturing Institute Inc Springfield VAUSA 1974
[16] H Freundlich ldquoUber dye adsorption in Lusungenrdquo Zeitschriftfur Physikalische Chemie vol 57 no 1 pp 385ndash470 1906
[17] I Langmuir ldquo+e adsorption of gases on plane surfaces ofglass mica and platinumrdquo Journal of the American ChemicalSociety vol 40 no 9 pp 1361ndash1384 1918
[18] J L Beltran J J Pignatello and M Teixido ldquoISOT_Calc aversatile tool for parameter estimation in sorption isothermsrdquoComputers amp Geosciences vol 94 pp 11ndash17 2016
[19] R Li B Wen S Zhang Z Pei and X Shan ldquoInfluence oforganic amendments on the sorption of pentachlorophenolon soilsrdquo Journal of Environmental Sciences vol 21 no 4pp 474ndash480 2009
[20] G Mckay M El Geundi and M M Nassar ldquoExternal masstransport processes during the adsorption of dyes onto ba-gasse pithrdquo Water Research vol 22 no 12 pp 1527ndash15331988
[21] Y-S Ho W-T Chiu and C-C Wang ldquoRegression analysisfor the sorption isotherms of basic dyes on sugarcane dustrdquoBioresource Technology vol 96 no 11 pp 1285ndash1291 2005
[22] A Purai and V K Rattan ldquoAcid blue 92 (leather dye) removalfrom wastewater by adsorption using biomass ash and acti-vated carbonrdquo Carbon Letters vol 11 no 1 pp 1ndash8 2010
Chemical EngineeringInternational Journal of Antennas and
Propagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Navigation and Observation
International Journal of
Hindawi
wwwhindawicom Volume 2018
Advances in
Multimedia
Submit your manuscripts atwwwhindawicom
e thermodynamic parameters (ΔHdeg and ΔSdeg) wereobtained from the slope and intercept of the linear re-gression line tted on the lnK vs 1T data e plot for rawand activated sawdust is shown in Figure 5 and the ther-modynamic parameters values are given in Table 1
From Table 1 it can be seen that ΔGdeg is negative in-dicating that the adsorption is spontaneousWith the increasein temperature ΔGdeg become less negative or the spontaneitydecreases by increasing temperature Compared to rawsawdust activated sawdust showed more negative value forΔGdeg indicating more feasibility of adsorption ΔHdeg is alsonegative showing the process is exothermic And the processis physisorption as chemisorption proceeds with the enthalpy
changes in the range of minus80 to minus200 kJmol e negativevalue of ΔSdeg reveals the adsorption is ordered Similarly morenegative value of ΔSdeg indicates decreasing randomness onactivated surface than raw sawdust Overall it can be con-cluded from the obtained thermodynamic parameters that theactivated sawdust betters in terms of feasibility exothermicityand ordered layering than raw sawdust
For adsorption of chrysoidine on sawdust there may be apossibility of intraparticle diusion In order to investigatethis possibility experiments were conducted and aredepicted in Figures 6(a) and 6(b)
e plots (Figures 6(a) and 6(b)) with log (dye re-moval) () versus log time (min) for adsorption at three
20 40 60Time (min)
80 100 1200
q (m
gg)
0
10
20
30
40
50
50 mgL100 mgL150 mgL
200 mgL250 mgL300 mgL
(a)
20 40 60Time (min)
80 100 1200
q (m
gg)
0
10
20
30
40
50
50 mgL100 mgL150 mgL
200 mgL250 mgL300 mgL
(b)
Figure 2 Eect of contact time on dye (dose 4 gL) adsorption on (a) raw sawdust and (b) chemically treated sawdust
Time (min)20 40 60 80 100 1200
q (m
gg)
0
200
400
600
800
01 g02 g04 g
06 g08 g1 g
(a)
Time (min)20 40 60 80 100 1200
q (m
gg)
0
200
400
600
800
01 g02 g04 g
06 g08 g1 g
(b)
Figure 3 Eect of (a) raw sawdust dose (100mgL) and (b) chemically treated sawdust dose on dye adsorption
4 International Journal of Chemical Engineering
dierent temperatures ranging between 30 and 50degCresulted in straight lines which specify the existence ofintraparticle diusion ese plots are used to describewhether adsorption is controlled by diusion in the ad-sorbent particles or the consecutive diusion in the bulk ofthe solution [20ndash22]
31 Adsorption Isotherms e two most frequently usedadsorption isotherms are employed in Figure 7 for theadsorption of chrysoidine on raw and activated sawdust Itcan be seen that the coecient of determination (R2) is lower
in Freundlich isotherm erefore it can be presumed thatthe adsorption of chrysoidine on raw and activated sawdustfollows Langmuir adsorption model
e parameters of the Freundlich and Langmuir linearisotherms are given in Table 2 and the same were used tocompare the experimental curves Lower values of ob-jective function (OF) were obtained in case of Langmuirisotherm
Similarly Figure 8 shows the nonlinear curve t-tings of Freundlich and Langmuir isotherms Lowervalues of OF render Langmuir better model for the
q (m
gg)
0
5
10
15
20
25
30
Time (min)10 20 30 40 50 60 700
30degC40degC50degC
(a)
q (m
gg)
0
5
10
15
20
25
30
Time (min)10 20 30 40 50 60 700
30degC40degC50degC
(b)
Figure 4 Eect of temperature on dye removal with (a) raw sawdust (conc 100mgL dose 4 gL) and (b) chemically treated sawdust (conc100mgL dose 4 gL)
00030
05
1
15
2
25
000305 00031 000315
lnK
(ndash)
00032 000325 000331T (Kndash1)
Raw sawdusty = 47191822 lowast xndash 144839
Activated sawdusty = 5657569 lowast xndash 162594
Figure 5 LnK vs 1T curves for raw and activated saw dust
Table 1 ermodynamic parameters at dierent temperatures
Temperature (degC)Raw sawdust Chemically treated sawdust
Ka (minus) ΔGdeg(kJmol) ΔHdeg (kJmol) ΔSdeg (Jmol-K) Ka (minus) ΔGdeg (kJmol) ΔHdeg (kJmol) ΔSdeg (Jmol-K)
adsorption of chrysoidine on raw and activated sawdustthan Freundlich
e parameters of Freundlich and Langmuir obtainedfrom nonlinear tting are reported in Table 3 e
comparison of linear and nonlinear methods clearly revealsthat the OF values are lower in case of nonlinear method
Langmuir constant ldquobrdquo estimated from the nonlinearmethod was then used to calculate RL Evolution of RL with
Log(
dye r
emov
al) (
)
05 1 15Log(time) (min)
215
16
17
18
19
2
50degC
30degC40degC
R2 (0976)R2 (0992)R2 (0839)
(a)
05 1 15Log(time) (min)
2
Log(
dye r
emov
al) (
)
15
16
17
18
19
2
50degC
30degC40degC
R2 (0989)R2 (0984)R2 (0879)
(b)
Figure 6 Log (dye removal) () versus log time (min) for (a) raw sawdust and (b) chemically treated sawdust
Log ce (mgL)
Logq
e (m
gg)
0501
12
14
16
18
1 15 252
Freundlich (R2 = 0749)
Experimentalraw sawdust
Freundlich (R2 = 0780)
Experimentalactivated sawdust
(a)
c eq
e (m
gg)
0
1
2
3
4
6
5
ce (mgL)500 100 150 200
Langmuir (R2 = 0996)
Experimentalraw sawdust
Langmuir (R2 = 0997)
Experimentalactivated sawdust
(b)
Figure 7 Freundlich (a) and Langmuir (b) linear isotherms of raw and chemically treated sawdust for chrysoidine removal
Table 2 Comparison of the optimized Freundlich and Langmuir isotherms parameters for the adsorption of chrysoidine on raw andchemically treated sawdust
SawdustFreundlich Langmuir
KF (mg(1minus1n) gminus1middotL1n) n OF (mg2g2) qmax (mgg) b (Lmg) b (Lmol) OF (mg2g2)
an initial dye concentration of raw and activated sawdust isshown in Figure 9 RL of activated sawdust is lower (0019 to0104) compared to raw sawdust (0026 to 0136) indicatingbetter suitability of activated sawdust over raw sawdust forthis adsorbent-adsorbate combination
Recovery of the spent adsorbent is an important eco-nomic factor in determining the practicability of an ad-sorption system However sawdust is a wood by-productwhich is a waste material available in plenty and bears nocost erefore the recovery of adsorbent was not furtherpursued
4 Conclusion
Sawdust in both forms proved to be an ecient adsorbent forchrysoidine dye from aqueous solutionis work has provedthe potentiality of sawdust to be an eective adsorbent eadsorption of chrysoidine followed Langmuirrsquos isotherm Assawdust is a cheap material and easily available the process isexpected to be economical Although untreated sawdustproved to be less eective in comparison to treated sawdusteconomically speaking the percentage of dye removal is lessthan the dierence in the commercial costs
1005000
10
q e (m
gg)
20
30
40
150 200
ExperimentalFreundlichLangmuir
ce (mgL)
(a)
q e (m
gg)
ExperimentalFreundlichLangmuir
1005000
10
20
30
40
150 200ce (mgL)
(b)
Figure 8 Freundlich and Langmuir nonlinear isotherms of (a) raw sawdust and (b) chemically treated sawdust for chrysoidine removal
Table 3 Comparison of the optimized Freundlich and Langmuir isotherms parameters for the adsorption of chrysoidine on raw andactivated sawdust
SawdustFreundlich Langmuir
KF (mg(1minus1n) gminus1middotL1n) n OF (mg2g2) qmax (mgg) b (Lmg) b (Lmol) OF (mg2g2)
Figure 9 Eect of initial concentration on the Langmuir adsorption factor of raw and activated saw dust
International Journal of Chemical Engineering 7
Data Availability
+e adsorption data used to support the findings of thisstudy are included within the article in the form of graphsData tables are not included just to avoid duplication
Conflicts of Interest
+e authors declare that there are no conflicts of interestregarding the publication of this paper
Acknowledgments
+e authors are thankful to Prince Mohammad Bin FahdUniversity for supporting the present work +anks are alsodue to King Abdulaziz University Rabigh campus forproviding some raw materials
References
[1] M W Ashraf ldquoRemoval of methylene blue dye fromwastewater by using supported liquid memberane technol-ogyrdquo Polish Journal of Chemical Technology vol 18 no 2pp 26ndash30 2016
[2] V M Nurchi M Crespo-Alonso R Biesuz et al ldquoSorption ofchrysoidine by row cork and cork entrapped in calcium al-ginate beadsrdquo Arabian Journal of Chemistry vol 7 no 1pp 133ndash138 2014
[3] K-L Chang C-C Chen J-H Lin et al ldquoRice straw-derivedactivated carbons for the removal of carbofuran from anaqueous solutionrdquo New Carbon Materials vol 29 no 1pp 47ndash54 2014
[4] T A Arica E Ayas and M Y Arica ldquoMagnetic MCM-41silica particles grafted with poly(glycidylmethacrylate) brushmodification and application for removal of direct dyesrdquoMicroporous and Mesoporous Materials vol 243 no 1pp 164ndash175 2017
[5] T A Arica M Kuman O Gercel and E Ayas ldquoPoly(dop-amine) grafted bio-silica composite with tetraethylenepent-amine ligands for enhanced adsorption of pollutantsrdquoChemical Engineering Research and Design vol 141pp 317ndash327 2019
[6] G Bayramoglu and M Yilmaz ldquoAzo dye removal using freeand immobilized fungal biomasses isotherms kinetics andthermodynamic studiesrdquo Fibers and Polymers vol 19 no 4pp 877ndash886 2018
[7] G Bayramoglu B Altintas and M Y Arica ldquoSynthesis andcharacterization of magnetic beads containing aminated fi-brous surfaces for removal of Reactive Green 19 dye kineticsand thermodynamic parametersrdquo Journal of Chemical Tech-nology amp Biotechnology vol 87 no 5 pp 705ndash713 2012
[8] R Jain V K Gupta and S Sikarwar ldquoAdsorption and de-sorption studies on hazardous dye Napthol Yellow Srdquo Journalof Hazardous Materials vol 182 no 1-3 pp 749ndash756 2010
[9] A Mittal J Mittal A Malviya and V K Gupta ldquoRemovaland recovery of Chrysoidine Y from aqueous solutions bywaste materialsrdquo Journal of Colloid and Interface Sciencevol 344 no 2 pp 497ndash507 2010
[10] M M Younes I I El-Sharkawy A E Kabeel and B B SahaldquoA review on adsorbent-adsorbate pairs for cooling appli-cationsrdquo Applied 1ermal Engineering vol 114 no 5pp 394ndash414 2017
[11] A Pal K +u S Mitra et al ldquoStudy on biomass derivedactivated carbons for adsorptive heat pump applicationrdquoInternational Journal of Heat and Mass Transfer vol 110pp 7ndash19 2017
[12] V K Gupta R Jain S Malathi and A Nayak ldquoAdsorption-desorption studies of indigocarmine from industrial effluentsby using deoiled mustard and its comparison with charcoalrdquoJournal of Colloid and Interface Science vol 348 no 2pp 628ndash633 2010
[13] S Larous and A-HMeniai ldquo+e use of sawdust as by productadsorbent of organic pollutant fromwastewater adsorption ofphenolrdquo Energy Procedia vol 18 pp 905ndash914 2012
[14] S P Raghuvanshi R Singh C P Kaushik and A K RaghavldquoRemoval of textile basic dye from aqueous solutions usingsawdust as bio-adsorbentrdquo International Journal of Envi-ronmental Studies vol 62 no 3 pp 329ndash339 2005
[15] American Dye Manufacturing Institute Inc Dyes and theEnvironment Reports on Selected Dyes and 1eir EffectsAmerican Dye Manufacturing Institute Inc Springfield VAUSA 1974
[16] H Freundlich ldquoUber dye adsorption in Lusungenrdquo Zeitschriftfur Physikalische Chemie vol 57 no 1 pp 385ndash470 1906
[17] I Langmuir ldquo+e adsorption of gases on plane surfaces ofglass mica and platinumrdquo Journal of the American ChemicalSociety vol 40 no 9 pp 1361ndash1384 1918
[18] J L Beltran J J Pignatello and M Teixido ldquoISOT_Calc aversatile tool for parameter estimation in sorption isothermsrdquoComputers amp Geosciences vol 94 pp 11ndash17 2016
[19] R Li B Wen S Zhang Z Pei and X Shan ldquoInfluence oforganic amendments on the sorption of pentachlorophenolon soilsrdquo Journal of Environmental Sciences vol 21 no 4pp 474ndash480 2009
[20] G Mckay M El Geundi and M M Nassar ldquoExternal masstransport processes during the adsorption of dyes onto ba-gasse pithrdquo Water Research vol 22 no 12 pp 1527ndash15331988
[21] Y-S Ho W-T Chiu and C-C Wang ldquoRegression analysisfor the sorption isotherms of basic dyes on sugarcane dustrdquoBioresource Technology vol 96 no 11 pp 1285ndash1291 2005
[22] A Purai and V K Rattan ldquoAcid blue 92 (leather dye) removalfrom wastewater by adsorption using biomass ash and acti-vated carbonrdquo Carbon Letters vol 11 no 1 pp 1ndash8 2010
Chemical EngineeringInternational Journal of Antennas and
Propagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Navigation and Observation
International Journal of
Hindawi
wwwhindawicom Volume 2018
Advances in
Multimedia
Submit your manuscripts atwwwhindawicom
dierent temperatures ranging between 30 and 50degCresulted in straight lines which specify the existence ofintraparticle diusion ese plots are used to describewhether adsorption is controlled by diusion in the ad-sorbent particles or the consecutive diusion in the bulk ofthe solution [20ndash22]
31 Adsorption Isotherms e two most frequently usedadsorption isotherms are employed in Figure 7 for theadsorption of chrysoidine on raw and activated sawdust Itcan be seen that the coecient of determination (R2) is lower
in Freundlich isotherm erefore it can be presumed thatthe adsorption of chrysoidine on raw and activated sawdustfollows Langmuir adsorption model
e parameters of the Freundlich and Langmuir linearisotherms are given in Table 2 and the same were used tocompare the experimental curves Lower values of ob-jective function (OF) were obtained in case of Langmuirisotherm
Similarly Figure 8 shows the nonlinear curve t-tings of Freundlich and Langmuir isotherms Lowervalues of OF render Langmuir better model for the
q (m
gg)
0
5
10
15
20
25
30
Time (min)10 20 30 40 50 60 700
30degC40degC50degC
(a)
q (m
gg)
0
5
10
15
20
25
30
Time (min)10 20 30 40 50 60 700
30degC40degC50degC
(b)
Figure 4 Eect of temperature on dye removal with (a) raw sawdust (conc 100mgL dose 4 gL) and (b) chemically treated sawdust (conc100mgL dose 4 gL)
00030
05
1
15
2
25
000305 00031 000315
lnK
(ndash)
00032 000325 000331T (Kndash1)
Raw sawdusty = 47191822 lowast xndash 144839
Activated sawdusty = 5657569 lowast xndash 162594
Figure 5 LnK vs 1T curves for raw and activated saw dust
Table 1 ermodynamic parameters at dierent temperatures
Temperature (degC)Raw sawdust Chemically treated sawdust
Ka (minus) ΔGdeg(kJmol) ΔHdeg (kJmol) ΔSdeg (Jmol-K) Ka (minus) ΔGdeg (kJmol) ΔHdeg (kJmol) ΔSdeg (Jmol-K)
adsorption of chrysoidine on raw and activated sawdustthan Freundlich
e parameters of Freundlich and Langmuir obtainedfrom nonlinear tting are reported in Table 3 e
comparison of linear and nonlinear methods clearly revealsthat the OF values are lower in case of nonlinear method
Langmuir constant ldquobrdquo estimated from the nonlinearmethod was then used to calculate RL Evolution of RL with
Log(
dye r
emov
al) (
)
05 1 15Log(time) (min)
215
16
17
18
19
2
50degC
30degC40degC
R2 (0976)R2 (0992)R2 (0839)
(a)
05 1 15Log(time) (min)
2
Log(
dye r
emov
al) (
)
15
16
17
18
19
2
50degC
30degC40degC
R2 (0989)R2 (0984)R2 (0879)
(b)
Figure 6 Log (dye removal) () versus log time (min) for (a) raw sawdust and (b) chemically treated sawdust
Log ce (mgL)
Logq
e (m
gg)
0501
12
14
16
18
1 15 252
Freundlich (R2 = 0749)
Experimentalraw sawdust
Freundlich (R2 = 0780)
Experimentalactivated sawdust
(a)
c eq
e (m
gg)
0
1
2
3
4
6
5
ce (mgL)500 100 150 200
Langmuir (R2 = 0996)
Experimentalraw sawdust
Langmuir (R2 = 0997)
Experimentalactivated sawdust
(b)
Figure 7 Freundlich (a) and Langmuir (b) linear isotherms of raw and chemically treated sawdust for chrysoidine removal
Table 2 Comparison of the optimized Freundlich and Langmuir isotherms parameters for the adsorption of chrysoidine on raw andchemically treated sawdust
SawdustFreundlich Langmuir
KF (mg(1minus1n) gminus1middotL1n) n OF (mg2g2) qmax (mgg) b (Lmg) b (Lmol) OF (mg2g2)
an initial dye concentration of raw and activated sawdust isshown in Figure 9 RL of activated sawdust is lower (0019 to0104) compared to raw sawdust (0026 to 0136) indicatingbetter suitability of activated sawdust over raw sawdust forthis adsorbent-adsorbate combination
Recovery of the spent adsorbent is an important eco-nomic factor in determining the practicability of an ad-sorption system However sawdust is a wood by-productwhich is a waste material available in plenty and bears nocost erefore the recovery of adsorbent was not furtherpursued
4 Conclusion
Sawdust in both forms proved to be an ecient adsorbent forchrysoidine dye from aqueous solutionis work has provedthe potentiality of sawdust to be an eective adsorbent eadsorption of chrysoidine followed Langmuirrsquos isotherm Assawdust is a cheap material and easily available the process isexpected to be economical Although untreated sawdustproved to be less eective in comparison to treated sawdusteconomically speaking the percentage of dye removal is lessthan the dierence in the commercial costs
1005000
10
q e (m
gg)
20
30
40
150 200
ExperimentalFreundlichLangmuir
ce (mgL)
(a)
q e (m
gg)
ExperimentalFreundlichLangmuir
1005000
10
20
30
40
150 200ce (mgL)
(b)
Figure 8 Freundlich and Langmuir nonlinear isotherms of (a) raw sawdust and (b) chemically treated sawdust for chrysoidine removal
Table 3 Comparison of the optimized Freundlich and Langmuir isotherms parameters for the adsorption of chrysoidine on raw andactivated sawdust
SawdustFreundlich Langmuir
KF (mg(1minus1n) gminus1middotL1n) n OF (mg2g2) qmax (mgg) b (Lmg) b (Lmol) OF (mg2g2)
Figure 9 Eect of initial concentration on the Langmuir adsorption factor of raw and activated saw dust
International Journal of Chemical Engineering 7
Data Availability
+e adsorption data used to support the findings of thisstudy are included within the article in the form of graphsData tables are not included just to avoid duplication
Conflicts of Interest
+e authors declare that there are no conflicts of interestregarding the publication of this paper
Acknowledgments
+e authors are thankful to Prince Mohammad Bin FahdUniversity for supporting the present work +anks are alsodue to King Abdulaziz University Rabigh campus forproviding some raw materials
References
[1] M W Ashraf ldquoRemoval of methylene blue dye fromwastewater by using supported liquid memberane technol-ogyrdquo Polish Journal of Chemical Technology vol 18 no 2pp 26ndash30 2016
[2] V M Nurchi M Crespo-Alonso R Biesuz et al ldquoSorption ofchrysoidine by row cork and cork entrapped in calcium al-ginate beadsrdquo Arabian Journal of Chemistry vol 7 no 1pp 133ndash138 2014
[3] K-L Chang C-C Chen J-H Lin et al ldquoRice straw-derivedactivated carbons for the removal of carbofuran from anaqueous solutionrdquo New Carbon Materials vol 29 no 1pp 47ndash54 2014
[4] T A Arica E Ayas and M Y Arica ldquoMagnetic MCM-41silica particles grafted with poly(glycidylmethacrylate) brushmodification and application for removal of direct dyesrdquoMicroporous and Mesoporous Materials vol 243 no 1pp 164ndash175 2017
[5] T A Arica M Kuman O Gercel and E Ayas ldquoPoly(dop-amine) grafted bio-silica composite with tetraethylenepent-amine ligands for enhanced adsorption of pollutantsrdquoChemical Engineering Research and Design vol 141pp 317ndash327 2019
[6] G Bayramoglu and M Yilmaz ldquoAzo dye removal using freeand immobilized fungal biomasses isotherms kinetics andthermodynamic studiesrdquo Fibers and Polymers vol 19 no 4pp 877ndash886 2018
[7] G Bayramoglu B Altintas and M Y Arica ldquoSynthesis andcharacterization of magnetic beads containing aminated fi-brous surfaces for removal of Reactive Green 19 dye kineticsand thermodynamic parametersrdquo Journal of Chemical Tech-nology amp Biotechnology vol 87 no 5 pp 705ndash713 2012
[8] R Jain V K Gupta and S Sikarwar ldquoAdsorption and de-sorption studies on hazardous dye Napthol Yellow Srdquo Journalof Hazardous Materials vol 182 no 1-3 pp 749ndash756 2010
[9] A Mittal J Mittal A Malviya and V K Gupta ldquoRemovaland recovery of Chrysoidine Y from aqueous solutions bywaste materialsrdquo Journal of Colloid and Interface Sciencevol 344 no 2 pp 497ndash507 2010
[10] M M Younes I I El-Sharkawy A E Kabeel and B B SahaldquoA review on adsorbent-adsorbate pairs for cooling appli-cationsrdquo Applied 1ermal Engineering vol 114 no 5pp 394ndash414 2017
[11] A Pal K +u S Mitra et al ldquoStudy on biomass derivedactivated carbons for adsorptive heat pump applicationrdquoInternational Journal of Heat and Mass Transfer vol 110pp 7ndash19 2017
[12] V K Gupta R Jain S Malathi and A Nayak ldquoAdsorption-desorption studies of indigocarmine from industrial effluentsby using deoiled mustard and its comparison with charcoalrdquoJournal of Colloid and Interface Science vol 348 no 2pp 628ndash633 2010
[13] S Larous and A-HMeniai ldquo+e use of sawdust as by productadsorbent of organic pollutant fromwastewater adsorption ofphenolrdquo Energy Procedia vol 18 pp 905ndash914 2012
[14] S P Raghuvanshi R Singh C P Kaushik and A K RaghavldquoRemoval of textile basic dye from aqueous solutions usingsawdust as bio-adsorbentrdquo International Journal of Envi-ronmental Studies vol 62 no 3 pp 329ndash339 2005
[15] American Dye Manufacturing Institute Inc Dyes and theEnvironment Reports on Selected Dyes and 1eir EffectsAmerican Dye Manufacturing Institute Inc Springfield VAUSA 1974
[16] H Freundlich ldquoUber dye adsorption in Lusungenrdquo Zeitschriftfur Physikalische Chemie vol 57 no 1 pp 385ndash470 1906
[17] I Langmuir ldquo+e adsorption of gases on plane surfaces ofglass mica and platinumrdquo Journal of the American ChemicalSociety vol 40 no 9 pp 1361ndash1384 1918
[18] J L Beltran J J Pignatello and M Teixido ldquoISOT_Calc aversatile tool for parameter estimation in sorption isothermsrdquoComputers amp Geosciences vol 94 pp 11ndash17 2016
[19] R Li B Wen S Zhang Z Pei and X Shan ldquoInfluence oforganic amendments on the sorption of pentachlorophenolon soilsrdquo Journal of Environmental Sciences vol 21 no 4pp 474ndash480 2009
[20] G Mckay M El Geundi and M M Nassar ldquoExternal masstransport processes during the adsorption of dyes onto ba-gasse pithrdquo Water Research vol 22 no 12 pp 1527ndash15331988
[21] Y-S Ho W-T Chiu and C-C Wang ldquoRegression analysisfor the sorption isotherms of basic dyes on sugarcane dustrdquoBioresource Technology vol 96 no 11 pp 1285ndash1291 2005
[22] A Purai and V K Rattan ldquoAcid blue 92 (leather dye) removalfrom wastewater by adsorption using biomass ash and acti-vated carbonrdquo Carbon Letters vol 11 no 1 pp 1ndash8 2010
Chemical EngineeringInternational Journal of Antennas and
Propagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Navigation and Observation
International Journal of
Hindawi
wwwhindawicom Volume 2018
Advances in
Multimedia
Submit your manuscripts atwwwhindawicom
adsorption of chrysoidine on raw and activated sawdustthan Freundlich
e parameters of Freundlich and Langmuir obtainedfrom nonlinear tting are reported in Table 3 e
comparison of linear and nonlinear methods clearly revealsthat the OF values are lower in case of nonlinear method
Langmuir constant ldquobrdquo estimated from the nonlinearmethod was then used to calculate RL Evolution of RL with
Log(
dye r
emov
al) (
)
05 1 15Log(time) (min)
215
16
17
18
19
2
50degC
30degC40degC
R2 (0976)R2 (0992)R2 (0839)
(a)
05 1 15Log(time) (min)
2
Log(
dye r
emov
al) (
)
15
16
17
18
19
2
50degC
30degC40degC
R2 (0989)R2 (0984)R2 (0879)
(b)
Figure 6 Log (dye removal) () versus log time (min) for (a) raw sawdust and (b) chemically treated sawdust
Log ce (mgL)
Logq
e (m
gg)
0501
12
14
16
18
1 15 252
Freundlich (R2 = 0749)
Experimentalraw sawdust
Freundlich (R2 = 0780)
Experimentalactivated sawdust
(a)
c eq
e (m
gg)
0
1
2
3
4
6
5
ce (mgL)500 100 150 200
Langmuir (R2 = 0996)
Experimentalraw sawdust
Langmuir (R2 = 0997)
Experimentalactivated sawdust
(b)
Figure 7 Freundlich (a) and Langmuir (b) linear isotherms of raw and chemically treated sawdust for chrysoidine removal
Table 2 Comparison of the optimized Freundlich and Langmuir isotherms parameters for the adsorption of chrysoidine on raw andchemically treated sawdust
SawdustFreundlich Langmuir
KF (mg(1minus1n) gminus1middotL1n) n OF (mg2g2) qmax (mgg) b (Lmg) b (Lmol) OF (mg2g2)
an initial dye concentration of raw and activated sawdust isshown in Figure 9 RL of activated sawdust is lower (0019 to0104) compared to raw sawdust (0026 to 0136) indicatingbetter suitability of activated sawdust over raw sawdust forthis adsorbent-adsorbate combination
Recovery of the spent adsorbent is an important eco-nomic factor in determining the practicability of an ad-sorption system However sawdust is a wood by-productwhich is a waste material available in plenty and bears nocost erefore the recovery of adsorbent was not furtherpursued
4 Conclusion
Sawdust in both forms proved to be an ecient adsorbent forchrysoidine dye from aqueous solutionis work has provedthe potentiality of sawdust to be an eective adsorbent eadsorption of chrysoidine followed Langmuirrsquos isotherm Assawdust is a cheap material and easily available the process isexpected to be economical Although untreated sawdustproved to be less eective in comparison to treated sawdusteconomically speaking the percentage of dye removal is lessthan the dierence in the commercial costs
1005000
10
q e (m
gg)
20
30
40
150 200
ExperimentalFreundlichLangmuir
ce (mgL)
(a)
q e (m
gg)
ExperimentalFreundlichLangmuir
1005000
10
20
30
40
150 200ce (mgL)
(b)
Figure 8 Freundlich and Langmuir nonlinear isotherms of (a) raw sawdust and (b) chemically treated sawdust for chrysoidine removal
Table 3 Comparison of the optimized Freundlich and Langmuir isotherms parameters for the adsorption of chrysoidine on raw andactivated sawdust
SawdustFreundlich Langmuir
KF (mg(1minus1n) gminus1middotL1n) n OF (mg2g2) qmax (mgg) b (Lmg) b (Lmol) OF (mg2g2)
Figure 9 Eect of initial concentration on the Langmuir adsorption factor of raw and activated saw dust
International Journal of Chemical Engineering 7
Data Availability
+e adsorption data used to support the findings of thisstudy are included within the article in the form of graphsData tables are not included just to avoid duplication
Conflicts of Interest
+e authors declare that there are no conflicts of interestregarding the publication of this paper
Acknowledgments
+e authors are thankful to Prince Mohammad Bin FahdUniversity for supporting the present work +anks are alsodue to King Abdulaziz University Rabigh campus forproviding some raw materials
References
[1] M W Ashraf ldquoRemoval of methylene blue dye fromwastewater by using supported liquid memberane technol-ogyrdquo Polish Journal of Chemical Technology vol 18 no 2pp 26ndash30 2016
[2] V M Nurchi M Crespo-Alonso R Biesuz et al ldquoSorption ofchrysoidine by row cork and cork entrapped in calcium al-ginate beadsrdquo Arabian Journal of Chemistry vol 7 no 1pp 133ndash138 2014
[3] K-L Chang C-C Chen J-H Lin et al ldquoRice straw-derivedactivated carbons for the removal of carbofuran from anaqueous solutionrdquo New Carbon Materials vol 29 no 1pp 47ndash54 2014
[4] T A Arica E Ayas and M Y Arica ldquoMagnetic MCM-41silica particles grafted with poly(glycidylmethacrylate) brushmodification and application for removal of direct dyesrdquoMicroporous and Mesoporous Materials vol 243 no 1pp 164ndash175 2017
[5] T A Arica M Kuman O Gercel and E Ayas ldquoPoly(dop-amine) grafted bio-silica composite with tetraethylenepent-amine ligands for enhanced adsorption of pollutantsrdquoChemical Engineering Research and Design vol 141pp 317ndash327 2019
[6] G Bayramoglu and M Yilmaz ldquoAzo dye removal using freeand immobilized fungal biomasses isotherms kinetics andthermodynamic studiesrdquo Fibers and Polymers vol 19 no 4pp 877ndash886 2018
[7] G Bayramoglu B Altintas and M Y Arica ldquoSynthesis andcharacterization of magnetic beads containing aminated fi-brous surfaces for removal of Reactive Green 19 dye kineticsand thermodynamic parametersrdquo Journal of Chemical Tech-nology amp Biotechnology vol 87 no 5 pp 705ndash713 2012
[8] R Jain V K Gupta and S Sikarwar ldquoAdsorption and de-sorption studies on hazardous dye Napthol Yellow Srdquo Journalof Hazardous Materials vol 182 no 1-3 pp 749ndash756 2010
[9] A Mittal J Mittal A Malviya and V K Gupta ldquoRemovaland recovery of Chrysoidine Y from aqueous solutions bywaste materialsrdquo Journal of Colloid and Interface Sciencevol 344 no 2 pp 497ndash507 2010
[10] M M Younes I I El-Sharkawy A E Kabeel and B B SahaldquoA review on adsorbent-adsorbate pairs for cooling appli-cationsrdquo Applied 1ermal Engineering vol 114 no 5pp 394ndash414 2017
[11] A Pal K +u S Mitra et al ldquoStudy on biomass derivedactivated carbons for adsorptive heat pump applicationrdquoInternational Journal of Heat and Mass Transfer vol 110pp 7ndash19 2017
[12] V K Gupta R Jain S Malathi and A Nayak ldquoAdsorption-desorption studies of indigocarmine from industrial effluentsby using deoiled mustard and its comparison with charcoalrdquoJournal of Colloid and Interface Science vol 348 no 2pp 628ndash633 2010
[13] S Larous and A-HMeniai ldquo+e use of sawdust as by productadsorbent of organic pollutant fromwastewater adsorption ofphenolrdquo Energy Procedia vol 18 pp 905ndash914 2012
[14] S P Raghuvanshi R Singh C P Kaushik and A K RaghavldquoRemoval of textile basic dye from aqueous solutions usingsawdust as bio-adsorbentrdquo International Journal of Envi-ronmental Studies vol 62 no 3 pp 329ndash339 2005
[15] American Dye Manufacturing Institute Inc Dyes and theEnvironment Reports on Selected Dyes and 1eir EffectsAmerican Dye Manufacturing Institute Inc Springfield VAUSA 1974
[16] H Freundlich ldquoUber dye adsorption in Lusungenrdquo Zeitschriftfur Physikalische Chemie vol 57 no 1 pp 385ndash470 1906
[17] I Langmuir ldquo+e adsorption of gases on plane surfaces ofglass mica and platinumrdquo Journal of the American ChemicalSociety vol 40 no 9 pp 1361ndash1384 1918
[18] J L Beltran J J Pignatello and M Teixido ldquoISOT_Calc aversatile tool for parameter estimation in sorption isothermsrdquoComputers amp Geosciences vol 94 pp 11ndash17 2016
[19] R Li B Wen S Zhang Z Pei and X Shan ldquoInfluence oforganic amendments on the sorption of pentachlorophenolon soilsrdquo Journal of Environmental Sciences vol 21 no 4pp 474ndash480 2009
[20] G Mckay M El Geundi and M M Nassar ldquoExternal masstransport processes during the adsorption of dyes onto ba-gasse pithrdquo Water Research vol 22 no 12 pp 1527ndash15331988
[21] Y-S Ho W-T Chiu and C-C Wang ldquoRegression analysisfor the sorption isotherms of basic dyes on sugarcane dustrdquoBioresource Technology vol 96 no 11 pp 1285ndash1291 2005
[22] A Purai and V K Rattan ldquoAcid blue 92 (leather dye) removalfrom wastewater by adsorption using biomass ash and acti-vated carbonrdquo Carbon Letters vol 11 no 1 pp 1ndash8 2010
Chemical EngineeringInternational Journal of Antennas and
Propagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Navigation and Observation
International Journal of
Hindawi
wwwhindawicom Volume 2018
Advances in
Multimedia
Submit your manuscripts atwwwhindawicom
an initial dye concentration of raw and activated sawdust isshown in Figure 9 RL of activated sawdust is lower (0019 to0104) compared to raw sawdust (0026 to 0136) indicatingbetter suitability of activated sawdust over raw sawdust forthis adsorbent-adsorbate combination
Recovery of the spent adsorbent is an important eco-nomic factor in determining the practicability of an ad-sorption system However sawdust is a wood by-productwhich is a waste material available in plenty and bears nocost erefore the recovery of adsorbent was not furtherpursued
4 Conclusion
Sawdust in both forms proved to be an ecient adsorbent forchrysoidine dye from aqueous solutionis work has provedthe potentiality of sawdust to be an eective adsorbent eadsorption of chrysoidine followed Langmuirrsquos isotherm Assawdust is a cheap material and easily available the process isexpected to be economical Although untreated sawdustproved to be less eective in comparison to treated sawdusteconomically speaking the percentage of dye removal is lessthan the dierence in the commercial costs
1005000
10
q e (m
gg)
20
30
40
150 200
ExperimentalFreundlichLangmuir
ce (mgL)
(a)
q e (m
gg)
ExperimentalFreundlichLangmuir
1005000
10
20
30
40
150 200ce (mgL)
(b)
Figure 8 Freundlich and Langmuir nonlinear isotherms of (a) raw sawdust and (b) chemically treated sawdust for chrysoidine removal
Table 3 Comparison of the optimized Freundlich and Langmuir isotherms parameters for the adsorption of chrysoidine on raw andactivated sawdust
SawdustFreundlich Langmuir
KF (mg(1minus1n) gminus1middotL1n) n OF (mg2g2) qmax (mgg) b (Lmg) b (Lmol) OF (mg2g2)
Figure 9 Eect of initial concentration on the Langmuir adsorption factor of raw and activated saw dust
International Journal of Chemical Engineering 7
Data Availability
+e adsorption data used to support the findings of thisstudy are included within the article in the form of graphsData tables are not included just to avoid duplication
Conflicts of Interest
+e authors declare that there are no conflicts of interestregarding the publication of this paper
Acknowledgments
+e authors are thankful to Prince Mohammad Bin FahdUniversity for supporting the present work +anks are alsodue to King Abdulaziz University Rabigh campus forproviding some raw materials
References
[1] M W Ashraf ldquoRemoval of methylene blue dye fromwastewater by using supported liquid memberane technol-ogyrdquo Polish Journal of Chemical Technology vol 18 no 2pp 26ndash30 2016
[2] V M Nurchi M Crespo-Alonso R Biesuz et al ldquoSorption ofchrysoidine by row cork and cork entrapped in calcium al-ginate beadsrdquo Arabian Journal of Chemistry vol 7 no 1pp 133ndash138 2014
[3] K-L Chang C-C Chen J-H Lin et al ldquoRice straw-derivedactivated carbons for the removal of carbofuran from anaqueous solutionrdquo New Carbon Materials vol 29 no 1pp 47ndash54 2014
[4] T A Arica E Ayas and M Y Arica ldquoMagnetic MCM-41silica particles grafted with poly(glycidylmethacrylate) brushmodification and application for removal of direct dyesrdquoMicroporous and Mesoporous Materials vol 243 no 1pp 164ndash175 2017
[5] T A Arica M Kuman O Gercel and E Ayas ldquoPoly(dop-amine) grafted bio-silica composite with tetraethylenepent-amine ligands for enhanced adsorption of pollutantsrdquoChemical Engineering Research and Design vol 141pp 317ndash327 2019
[6] G Bayramoglu and M Yilmaz ldquoAzo dye removal using freeand immobilized fungal biomasses isotherms kinetics andthermodynamic studiesrdquo Fibers and Polymers vol 19 no 4pp 877ndash886 2018
[7] G Bayramoglu B Altintas and M Y Arica ldquoSynthesis andcharacterization of magnetic beads containing aminated fi-brous surfaces for removal of Reactive Green 19 dye kineticsand thermodynamic parametersrdquo Journal of Chemical Tech-nology amp Biotechnology vol 87 no 5 pp 705ndash713 2012
[8] R Jain V K Gupta and S Sikarwar ldquoAdsorption and de-sorption studies on hazardous dye Napthol Yellow Srdquo Journalof Hazardous Materials vol 182 no 1-3 pp 749ndash756 2010
[9] A Mittal J Mittal A Malviya and V K Gupta ldquoRemovaland recovery of Chrysoidine Y from aqueous solutions bywaste materialsrdquo Journal of Colloid and Interface Sciencevol 344 no 2 pp 497ndash507 2010
[10] M M Younes I I El-Sharkawy A E Kabeel and B B SahaldquoA review on adsorbent-adsorbate pairs for cooling appli-cationsrdquo Applied 1ermal Engineering vol 114 no 5pp 394ndash414 2017
[11] A Pal K +u S Mitra et al ldquoStudy on biomass derivedactivated carbons for adsorptive heat pump applicationrdquoInternational Journal of Heat and Mass Transfer vol 110pp 7ndash19 2017
[12] V K Gupta R Jain S Malathi and A Nayak ldquoAdsorption-desorption studies of indigocarmine from industrial effluentsby using deoiled mustard and its comparison with charcoalrdquoJournal of Colloid and Interface Science vol 348 no 2pp 628ndash633 2010
[13] S Larous and A-HMeniai ldquo+e use of sawdust as by productadsorbent of organic pollutant fromwastewater adsorption ofphenolrdquo Energy Procedia vol 18 pp 905ndash914 2012
[14] S P Raghuvanshi R Singh C P Kaushik and A K RaghavldquoRemoval of textile basic dye from aqueous solutions usingsawdust as bio-adsorbentrdquo International Journal of Envi-ronmental Studies vol 62 no 3 pp 329ndash339 2005
[15] American Dye Manufacturing Institute Inc Dyes and theEnvironment Reports on Selected Dyes and 1eir EffectsAmerican Dye Manufacturing Institute Inc Springfield VAUSA 1974
[16] H Freundlich ldquoUber dye adsorption in Lusungenrdquo Zeitschriftfur Physikalische Chemie vol 57 no 1 pp 385ndash470 1906
[17] I Langmuir ldquo+e adsorption of gases on plane surfaces ofglass mica and platinumrdquo Journal of the American ChemicalSociety vol 40 no 9 pp 1361ndash1384 1918
[18] J L Beltran J J Pignatello and M Teixido ldquoISOT_Calc aversatile tool for parameter estimation in sorption isothermsrdquoComputers amp Geosciences vol 94 pp 11ndash17 2016
[19] R Li B Wen S Zhang Z Pei and X Shan ldquoInfluence oforganic amendments on the sorption of pentachlorophenolon soilsrdquo Journal of Environmental Sciences vol 21 no 4pp 474ndash480 2009
[20] G Mckay M El Geundi and M M Nassar ldquoExternal masstransport processes during the adsorption of dyes onto ba-gasse pithrdquo Water Research vol 22 no 12 pp 1527ndash15331988
[21] Y-S Ho W-T Chiu and C-C Wang ldquoRegression analysisfor the sorption isotherms of basic dyes on sugarcane dustrdquoBioresource Technology vol 96 no 11 pp 1285ndash1291 2005
[22] A Purai and V K Rattan ldquoAcid blue 92 (leather dye) removalfrom wastewater by adsorption using biomass ash and acti-vated carbonrdquo Carbon Letters vol 11 no 1 pp 1ndash8 2010
Chemical EngineeringInternational Journal of Antennas and
Propagation
International Journal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
Navigation and Observation
International Journal of
Hindawi
wwwhindawicom Volume 2018
Advances in
Multimedia
Submit your manuscripts atwwwhindawicom
Data Availability
+e adsorption data used to support the findings of thisstudy are included within the article in the form of graphsData tables are not included just to avoid duplication
Conflicts of Interest
+e authors declare that there are no conflicts of interestregarding the publication of this paper
Acknowledgments
+e authors are thankful to Prince Mohammad Bin FahdUniversity for supporting the present work +anks are alsodue to King Abdulaziz University Rabigh campus forproviding some raw materials
References
[1] M W Ashraf ldquoRemoval of methylene blue dye fromwastewater by using supported liquid memberane technol-ogyrdquo Polish Journal of Chemical Technology vol 18 no 2pp 26ndash30 2016
[2] V M Nurchi M Crespo-Alonso R Biesuz et al ldquoSorption ofchrysoidine by row cork and cork entrapped in calcium al-ginate beadsrdquo Arabian Journal of Chemistry vol 7 no 1pp 133ndash138 2014
[3] K-L Chang C-C Chen J-H Lin et al ldquoRice straw-derivedactivated carbons for the removal of carbofuran from anaqueous solutionrdquo New Carbon Materials vol 29 no 1pp 47ndash54 2014
[4] T A Arica E Ayas and M Y Arica ldquoMagnetic MCM-41silica particles grafted with poly(glycidylmethacrylate) brushmodification and application for removal of direct dyesrdquoMicroporous and Mesoporous Materials vol 243 no 1pp 164ndash175 2017
[5] T A Arica M Kuman O Gercel and E Ayas ldquoPoly(dop-amine) grafted bio-silica composite with tetraethylenepent-amine ligands for enhanced adsorption of pollutantsrdquoChemical Engineering Research and Design vol 141pp 317ndash327 2019
[6] G Bayramoglu and M Yilmaz ldquoAzo dye removal using freeand immobilized fungal biomasses isotherms kinetics andthermodynamic studiesrdquo Fibers and Polymers vol 19 no 4pp 877ndash886 2018
[7] G Bayramoglu B Altintas and M Y Arica ldquoSynthesis andcharacterization of magnetic beads containing aminated fi-brous surfaces for removal of Reactive Green 19 dye kineticsand thermodynamic parametersrdquo Journal of Chemical Tech-nology amp Biotechnology vol 87 no 5 pp 705ndash713 2012
[8] R Jain V K Gupta and S Sikarwar ldquoAdsorption and de-sorption studies on hazardous dye Napthol Yellow Srdquo Journalof Hazardous Materials vol 182 no 1-3 pp 749ndash756 2010
[9] A Mittal J Mittal A Malviya and V K Gupta ldquoRemovaland recovery of Chrysoidine Y from aqueous solutions bywaste materialsrdquo Journal of Colloid and Interface Sciencevol 344 no 2 pp 497ndash507 2010
[10] M M Younes I I El-Sharkawy A E Kabeel and B B SahaldquoA review on adsorbent-adsorbate pairs for cooling appli-cationsrdquo Applied 1ermal Engineering vol 114 no 5pp 394ndash414 2017
[11] A Pal K +u S Mitra et al ldquoStudy on biomass derivedactivated carbons for adsorptive heat pump applicationrdquoInternational Journal of Heat and Mass Transfer vol 110pp 7ndash19 2017
[12] V K Gupta R Jain S Malathi and A Nayak ldquoAdsorption-desorption studies of indigocarmine from industrial effluentsby using deoiled mustard and its comparison with charcoalrdquoJournal of Colloid and Interface Science vol 348 no 2pp 628ndash633 2010
[13] S Larous and A-HMeniai ldquo+e use of sawdust as by productadsorbent of organic pollutant fromwastewater adsorption ofphenolrdquo Energy Procedia vol 18 pp 905ndash914 2012
[14] S P Raghuvanshi R Singh C P Kaushik and A K RaghavldquoRemoval of textile basic dye from aqueous solutions usingsawdust as bio-adsorbentrdquo International Journal of Envi-ronmental Studies vol 62 no 3 pp 329ndash339 2005
[15] American Dye Manufacturing Institute Inc Dyes and theEnvironment Reports on Selected Dyes and 1eir EffectsAmerican Dye Manufacturing Institute Inc Springfield VAUSA 1974
[16] H Freundlich ldquoUber dye adsorption in Lusungenrdquo Zeitschriftfur Physikalische Chemie vol 57 no 1 pp 385ndash470 1906
[17] I Langmuir ldquo+e adsorption of gases on plane surfaces ofglass mica and platinumrdquo Journal of the American ChemicalSociety vol 40 no 9 pp 1361ndash1384 1918
[18] J L Beltran J J Pignatello and M Teixido ldquoISOT_Calc aversatile tool for parameter estimation in sorption isothermsrdquoComputers amp Geosciences vol 94 pp 11ndash17 2016
[19] R Li B Wen S Zhang Z Pei and X Shan ldquoInfluence oforganic amendments on the sorption of pentachlorophenolon soilsrdquo Journal of Environmental Sciences vol 21 no 4pp 474ndash480 2009
[20] G Mckay M El Geundi and M M Nassar ldquoExternal masstransport processes during the adsorption of dyes onto ba-gasse pithrdquo Water Research vol 22 no 12 pp 1527ndash15331988
[21] Y-S Ho W-T Chiu and C-C Wang ldquoRegression analysisfor the sorption isotherms of basic dyes on sugarcane dustrdquoBioresource Technology vol 96 no 11 pp 1285ndash1291 2005
[22] A Purai and V K Rattan ldquoAcid blue 92 (leather dye) removalfrom wastewater by adsorption using biomass ash and acti-vated carbonrdquo Carbon Letters vol 11 no 1 pp 1ndash8 2010
![DiestersBiolubricantBaseOil:Synthesis,Optimization ...downloads.hindawi.com/journals/ijce/2012/896598.pdfbiolubricants [2]. Synthetic biolubricant based on renewable resources are](https://static.documents.pub/doc/80x56/5fb2937c9caf334bb4463247/diestersbiolubricantbaseoilsynthesisoptimization-biolubricants-2-synthetic.jpg)
