EQUILIBRIUM MODELING OF MONO AND BINARY SORPTION

Transcription

1 Chmical ad Procss Egirig 016, 37 (4), DOI: /cp EQUILIBRIUM MODELING OF MONO AND BINARY SORPTION OF CU(II) AND ZN(II) ONTO CHITOSAN GEL BEADS Józf Nastaj *, Małgorzata Tuligłowicz, orad Witkiwicz Wst Pomraia Uivrsity of Tchology, Dpartmt of Chmical Egirig ad Eviromtal Protctio Procsss, Szczci, al. Piastów 4, Szczci, Polad Th objctiv of th work ar i-dpth xprimtal studis of Cu(II) ad Z(II) io rmoval o chitosa gl bads from both o- ad two-compot watr solutios at th tmpratur of 303. Th optimal procss coditios such as: ph valu, dos of sorbt ad cotact tim wr dtrmid. Basd o th optimal procss coditios, uilibrium ad kitic studis wr carrid out. Th maximum sorptio capacitis uald: mg/g ad mg/g for Cu(II) ad Z(II) ios rspctivly, wh th sorbt dos was 10 g/l ad th ph of a solutio was 5.0 for both havy mtal ios. O-compot sorptio uilibrium data wr succssfully prstd for six of th most usful thr-paramtr uilibrium modls: Lagmuir-Frudlich, Rdlich-Ptrso, Sips, obl-corriga, Hill ad Toth. Extdd forms of Lagmuir-Frudlich, obl-corriga ad Sips modls wr also wll fittd to th two-compot uilibrium data obtaid for diffrt ratios of coctratios of Cu(II) ad Z(II) ios (1:1, 1:, :1). Exprimtal sorptio data wr dscribd by two kitic modls of th psudo-first ad psudo-scod ordr. Furthrmor, a attmpt to xplai th mchaisms of th divalt mtal io sorptio procss o chitosa gl bads was udrtak. ywords: chitosa, havy mtals, uilibrium modlig, biary solutios 1. INTRODUCTION I th last dcad, th prsc of havy mtal ios i th viromt has attractd atttio of rsarchs. Th amout of havy mtal rlas ito th viromt is icrasig as a rsult of dvlopmt of idustrial procsss ad tchological xpasio. Th pottial sourcs of havy mtal ios ar idustrial wastwatrs which iclud: frtilizrs, pigmts, mtal fiishig tc. (Arh-Hwag t al., 008; Tomczak, 013). Wast strams cotaiig Cu(II) origiatd from a varity of idustris amog othrs: mishig ad coppr lctroplatig, which caus a sigificat thrat to auatic lif ad mak atural watr usuitabl for public us (Alimohamadi t al., 005; Hasa t al., 008). Z(II) ca b foud i wastwatr drivd from various lctroplatig pollutats.g.: acid mi draiag (AMD), lctroplatig ad from muicipal wastwatr. Z(II) is ot biodgradabl ad ca accumulat throughout th food chai, bcomig a srious dagr (Norto t al., 004). Thrfor Cu(II) ad Z(II) ios ar amog th most commo havy mtals i idustris wastwatrs. Th accumulatio of Cu(II) ios i huma body causs brai, ski ad pacras damag ad hart disass. Z(II) ios ar o th list of priority pollutats givig ris to srious poisoig cass. Th havy mtals, which ar dtrimtal to o's halth, ca b rmovd from wastwatr usig various covtioal mthods such as: prcipitatio, rvrs osmosis, chmical rductio, io xchag *Corrspodig author, -mail: joas@zut.du.pl cp.czasopisma.pa.pl; dgruytr.com/viw/j/cp Uauthticatd Dowload Dat 3/14/18 4:36 AM 485

2 J. Nastaj, M. Tuligłowicz,. Witkiwicz, Chm. Procss Eg., 016, 37 (4), ad physical sorptio (Vli ad Alyuz, 007). Howvr, th abov procsss procd slowly ad thir ffctivss dpds o may factors such as: th ph of a solutio, th typ of a havy mtal ios (oxidatio stat, typ of complxs) ad th coctratio or th prsc of othr substacs dissolvd i watr. Th biosorptio procss is a altrativ to traditioal mthods of havy mtal rmoval from auous solutios. It is a biological purificatio mthod of wastwatrs, basd o th bidig of mtal ios o th biosorbt surfac. Chitosa is a low cost atural matrial, usd for biosorptio of havy mtal ios (Alimohamadi t al., 005; Ch t al., 008; Hasa t al., 008; Norto t al., 004; Svil ad Alyuz, 007). Chitosa is a drivativ of chiti, which ca b xtractd from fugi, ad i larg uatitis, from th xosklto of crustacas such as crabs, shrimps, krill ad crawfish. I compariso with chiti, chitosa is mor fficit i trms of sorptio capacity. It is du to th prsc of a larg umbr of fr amio groups o chitosa chai which ar rsposibl for th high sorptio capacity (Sakararamakrisha t al., 007). Howvr, ulik chiti, chitosa is solubl i dilut orgaic acids, such as actic or formic acids. Th most itrstig fact, compard to othr sorbts, is that chitosa ca b procssd ito: flaks (Jha t al., 1987), bads (Bara t al., 006) ad mmbras (Osifo t al., 008). Chitosa ca b physically ad chmically modifid to improv th sorptio capacity ad th chmical stability of chitosa i acid mdia (yzas ad Bikiaris, 015). Chitosa without modificatio has alrady high chmical stability i acid mdia. It is rsistat to biochmical ad microbiological dgradatio ad most of all has high affiity for sorptio of havy mtal ios. Most of th studis ddicatd to mtal io biosorptio o various modifid chitosa cocr o compot mtal io watr solutios, although th ral auatic solutios grally cosist of toxic havy mtal mixturs (Wa Ngah ad Fatiatha, 008). Thrfor th mai objctiv of this study was to ivstigat th sorptio procss of coppr (Cu(II)) ad zic (Z(II)) ios from o- ad two-compot watr solutios o umodifid chitosa gl bads.. SORPTION MECHANISMS Chitosa is a strogly complxig polymr i rlatio to havy mtal ios. Amio groups of chitosa chais i which itrog is th door of lctro pairs ar rsposibl for th formatio of such complxs (Ji ad Bai, 00; Ososy ad Skaugrud, 1990; Riaudo, 006). Both itrog ad oxyg atoms hav lo pairs of lctros which ca bid a proto of mtal io to form a complx (Osoy ad Skaugrud, 1990). Howvr, itrog atoms hav strogr tdcy to doat th lo pair of lctros with havy mtal ios to form a complx tha th oxyg atom. Basd o th abov cosidratio, th procss ca procd accordig to th followig ractio (Ji ad Bai, 00): R NH + H + R NH 3 + This ractio idicats th protoatio ad dprotoatio procsss of amio groups i chitosa. Th bidig mchaism of th group with havy mtal ios is vry spcific ad ca dpd o othr factors, such as: ph valu or typ of mtal io. For xampl, at a lowr ph of a solutio mor amio groups ar protoatd. Whras at highr ph valus, OH - ios ca b adsorbd to th surfac of chitosa gl bads through a hydrog bod (Ji ad Bai, 00; Riaudo, 006): R NH +OH - R NH OH - () (1) Uauthticatd 486 cp.czasopisma.pa.pl; dgruytr.com/viw/j/cp Dowload Dat 3/14/18 4:36 AM

3 Euilibrium modlig of moo ad biary sorptio of Cu(II) ad Z(II) oto chitosa gl bads Wh havy mtal ios wr addd ito th solutio, th ractio procdd du to sharig of th lo pair of th lctros from th itrog atom with havy mtal io, i th similar mar as ractio (Sakararamakrisha t al., 007): R NH + M + R NH M + (3) Howvr, th lctrical attractio forc btw lo pair lctros from th itrog atom ad th bivalt havy mtal io ca b strogr tha that btw th lo pair of lctros from th itrog atom ad th moovalt proto (H + ) (Ji ad Bai, 00; Osoy ad Skaugrud, 1990; Riaudo, 006; Wag t al., 004). From ths diffrcs i th forc of th bidig w ca writ aothr ractio dscribd as follows: R NH M + R NH M + + H + (4) I this ractio a comptitiv adsorptio of M + ovr H + to th itrog atom occurs, which ca b cosidrd as io xchag mchaism (Ji ad Bai, 00; Ososy ad Skaugrud, 1990). I compariso to ractio (3), ractio (4) ca ru slowly, du to smallr forc attractio btw th N i R-NH 3 ad M + (Oyrto t al., 1999). For th complx of R NH M + it is gratr bidig forc of M + with th OH - group from watr: R NH M + + H O MOH + + R-NH 3 + (5) This ractio togthr with ractios () ad (4) mak havy mtal ios b prst i th complx of R NH M + rathr tha b distributd i th solutio. Havy mtal sorptio o chitosa gl bads ca also b cotrolld by th trasport of havy mtal ios from th solutio bulk to th chitosa bad surfac. Th trasport of havy mtal catio M + to th surfac sits R NH 3 + could b ihibitd at vry low ph of solutio. 3. EXPERIMENTAL METHODS 3.1. Matrials Th chitosa flaks usd i xprimts wr dactylatd approximatly 85% ad thir dyamic viscosity (0 C) was 300 mpa s. Th chitosa was purchasd from Biolog Biotchologi ud Logistic GmbH. Coppr(II) sulfat (CuSO 4 ) ad zic sulfat hptahydrat (ZSO 4 7H O) usd i th sorptio xprimts wr purchasd from Chmpur ad wr of aalytical grad Prparatio of chitosa gl bads Prparatio of chitosa gl bads ivolvs dissolvig 17.5 g of chitosa flaks i 1L of % auous solutio of actic acid ad lavig th solutio for 4 h. Th th dissolvd chitosa is subjctd to filtratio i ordr to rmov ay kid of cotamiatio. Th formatio of drops ivolvs th us of th prssur mthod, which cosists of comprssd air big brought to a cotair with a solutio of chitosa. Th chitosa solutio was prssd through a capillary with a diamtr of mm fiishd with th blad to facilitat th formatio of droplts. Th diamtr of chitosa gl bads was about.5 mm. Dischargd drops fll frly ito th cylidr with a solutio of 10% sodium hydroxid. Th procss was coductd by applyig cotiuous mixig. I th fial stp bads wr washd with distilld watr to rmov ay rsidus of sodium hydroxid. Bfor th sorptio procss chitosa gl bads wr kpt i distilld watr at last sv days. Uauthticatd cp.czasopisma.pa.pl; dgruytr.com/viw/j/cp 487 Dowload Dat 3/14/18 4:36 AM

4 J. Nastaj, M. Tuligłowicz,. Witkiwicz, Chm. Procss Eg., 016, 37 (4), Sorptio studis ph ffcts Th ffct of th ph of solutios o Cu(II) ad Z(II) sorptio wr xamid by addig 10 g of wt chitosa bads (dry mass was rlatd to wt o ad was at a costat ratio i xprimts) ito 00 ml solutios cotaiig Cu(II) ad/or Z(II) to 50 ml dark flasks. I o-compot systms th io iitial coctratio was costat ad uald 60 mg/l. I two-compot solutios th Cu(II)-Z(II) mixtur of coctratio ratio 1:1 was usd i which ach io iitial coctratio was also costat ad uald 64 mg/l. Ths solutios wr adjustd to ph 4.0, 5.0, 6.0 ad 6.5 with 0.1 M hydrochloric acid or 0.1 M sodium hydroxid solutio. Coctratios of solutios wr masurd with Iductivly Coupld Plasma Spctromtr ICP-AES (Jobi Yvo, Frac). Th sorptio capacity was calculatd usig th rlatio: C C 0 V (6) m 3... Effct of sorbt dos Th dpdc of mtal io sorptio o th dos of chitosa gl bads was xamid usig various amouts of sorbt, ragig from 5 to 15 g wt chitosa bads ito 00 ml solutios cotaiig Cu(II) or Z(II) i th coctratio of 60 mg/l. Thus, th sorbt dos ragd from 5 to 75 g/l. Coctratios wr also masurd with Iductivly Coupld Plasma Spctromtr ICP-AES Effct of cotact tim Exprimts of cotact tim ffct wr carrid out by placig 10 g of wt chitosa bads ito 00 ml solutio cotaiig Cu(II) or Z(II) ios, with a sorbt dos of 50 g/l. Sampls wr stirrd i a icubator shakr at a costat valu of ph at 30 C. Sampls wr agitatd at 175 rpm for various priods of tim. Th 30 ml of ths solutios at som itrvals of tim wr filtrd ad thir coctratios wr masurd with ICP-AES. Th sorptio capacitis wr calculatd from E. (6) Sorptio isothrms Euilibrium batch sorptio studis wr carrid out by placig 10 g of wt chitosa bads ito 00 ml solutios cotaiig Cu(II) ad/or Z(II) ios at various iitial coctratios, with a sorbt dos of 50 g/l. Th iitial coctratio of Cu(II) ad Z(II) ios i th o-compot solutios ragd from 0 mg/l to 100 mg/l. Th iitial coctratio of Cu(II) ad Z(II) ios i two-compot solutios ragd from 0 mg/l to 800 mg/l. Th sorptio uilibrium i two-compot systms was studid i solutios cotaiig Cu(II) ad Z(II) at diffrt ratios of coctratio 1:1, 1:, :1. Th flasks wr placd i a icubator shakr at 30 C ad wr agitatd at 175 rpm for various priods of tim. Th coctratio of Cu(II) ad Z(II) ios i th solutio was aalyzd with ICP-AES. 4. RESULTS AND DISCUSSION 4.1. FTIR study of th chitosa gl bads Our studis of Fourir trasform ifrard spctroscopy (FTIR) of chitosa gl bads wr prformd to dtrmi th molcular structur of itrmolcular itractios btw th compots i chitosa Uauthticatd 488 cp.czasopisma.pa.pl; dgruytr.com/viw/j/cp Dowload Dat 3/14/18 4:36 AM

5 Euilibrium modlig of moo ad biary sorptio of Cu(II) ad Z(II) oto chitosa gl bads gl bads. FTIR absorptio spctra show th absorbac dpdc o th wav umbr. Th rsults of FTIR spctra ar show i Fig. 1. Th major paks of th chitosa gl bads ar locatd aroud 360 cm -1 for OH strtchig vibratio polysaccharid chai ad 1651 cm -1 for -NH strtchig vibratio. Aothr pak at cm -1 ca b attributd to CH strtchig vibratios. Th carboyl bod (CO) drivd from chiti ca b obsrvd i th spctrum of 1651 cm -1. Th polysaccharid strtchig vibratio (CH) is locatd aroud 1100 cm -1. Th hydrog bods btw th polysaccharid chais ar brok at th xps of itractio with mtal catios. Thus chitosa matrial bcoms mor amorphous. Th pak at 100 cm - 1 ca b attributd to strtchig vibratio of th bod C-O i polysaccharid chais (Wu t al., 008). Fig. 1. FTIR spctrum of chitosa gl bads Fig.. ph ffct o th sorptio capacity of Cu(II) or Z(II) ios o chitosa gl bads from o-compot auous solutios Fig. 3. ph ffct o th sorptio capacity of Cu(II) ad Z(II) ios o chitosa gl bads from two-compot auous solutio Uauthticatd cp.czasopisma.pa.pl; dgruytr.com/viw/j/cp 489 Dowload Dat 3/14/18 4:36 AM

6 J. Nastaj, M. Tuligłowicz,. Witkiwicz, Chm. Procss Eg., 016, 37 (4), Sorptio ffcts ph ffcts Th ph of a solutio affcts th adsorptio capacity of chitosa. Th ffct of th ph of a solutio o th sorptio of Cu(II) ad Z(II) ios o chitosa gl bads was ivstigatd i th rag of ph from 4.0 to 6.5 ad from 4.0 to 6.0 for o- ad two-compot systms, rspctivly. Highr valus of solutio ph wr ot tstd du to th fact that i ph highr tha 7 prcipitatio of Cu(II) or Z(II) may occur. Rsults ar show i Figs ad 3. It ca b s from ths figurs that thr is a slight icras i sorptio capacity with a icras i solutio ph. For both o- ad two-compot solutios it is vidt that thr ar small diffrcs i th sorptio capacity for ph ragig btw 5.0 ad 6.0. Th maximum sorptio capacity of Cu(II) ad Z(II) ios occurs at ph 5 for both mtal ios. This is bcaus i acidic solutios, mor protos will b availabl to protoat ami groups to form groups NH 3, rducig th umbr of bidig sits for th adsorptio of Cu(II) ad/or Z(II). Whras, at highr solutio ph adsorptio icrass du to th dcrasd ihibitory ffct of H + (Wa Ngah t al., 005). Thrfor havy mtal ios wr bttr sorbd by chitosa at highr solutio ph. Th optimum ph valus wr dtrmid for Cu(II) ad Z(II) as ph 5.0 for o- ad two- compot solutios. Th optimum ph valus wr usd i furthr o-compot xprimtal studis, such as th dos of chitosa gl bads or th cotact tim Effct of sorbt dos Th dpdc of mtal io sorptio o th dos of wt chitosa gl bads was studid usig various amouts of sorbt i th rag of 5-75 g/l. Rsults i Fig. 4 show that th sorptio capacitis of mtal ios i sorbt sampl slightly icras with th icras of th sorbt dos. Th sorptio capacity of Cu(II) was cosidrably gratr tha that of Z(II) i th dos rag of 5-75 g/l Effct of cotact tim Th ffct of cotact tim o th sorptio of Cu(II) ad Z(II) ios o chitosa gl bads was ivstigatd ad xprimtal rsults ar prstd i Figs 5 ad 6. Th ffct of cotact tim is a importat paramtr bcaus it rflcts sorptio kitics. Th coctratio of mtal ios i th sorbt icrass rapidly at th iitial sorptio stag, ad th rmais costat. Sorptio uilibrium was rachd withi about 1000 mi for Cu(II) ad 40 mi for Z(II). Th maximum valu of mtal io coctratio i rlatioship of t vrsus tim t (cotact tim) at a costat io coctratio C 0 is a sparat poit i sorptio isothrm. Simultaously, th rlatio of cotact tim is usd i modlig of procss kitics (rlatioship of t vrsus t at th giv ). I ordr to ivstigat th sorptio mchaism, rat costats of sorptio kitics hav to b dtrmid. Th psudo-first ordr kitic modl ca b prstd i a liar form (Rpo t al., 010): k1 log( t ) log t (7).303 Th psudo-scod ordr kitic modl ca b prstd i aothr liar form (Rpo t al., 010): t t (8) k t Costats of psudo-first ad psudo-scod ordr kitic modls wr dtrmid by last suars mthod usig th liar rgrssio. Uauthticatd 490 cp.czasopisma.pa.pl; dgruytr.com/viw/j/cp Dowload Dat 3/14/18 4:36 AM

7 Euilibrium modlig of moo ad biary sorptio of Cu(II) ad Z(II) oto chitosa gl bads Fig. 4. Dos ffct of chitosa gl bads o sorptio capacity of Cu(II) ios ad Z(II) from o-compot solutios Fig. 5. Effct of cotact tim of chitosa gl bads i auous solutio of Cu(II) ios o sorptio capacity Fig. 6. Effct of cotact tim of chitosa gl bads i auous solutio of Z(II) ios o sorptio capacity Th avrag rlativ rrors δ [%], which ar th masur of fit accuracy of rat costats to xprimtal data, wr calculatd from th followig uatio: δ (9) N 1 xpi calci N i 1 xp i Th obtaid valus of psudo-first ordr (k 1 ) ad psudo-scod ordr (k ) rat costats, th avrag rlativ rrors (δ) ad dtrmiatio cofficit (R ) ar show i Tabl 1. It is vidt that th psudofirst ordr kitic modl gav a vry poor approximatio of th xprimtal data. Th corrlatd rsults of th psudo-scod ordr kitic modl for Cu(II) ad Z(II) ios, accordig to E. (8), ar prstd i Figs. 5 ad 6, rspctivly. Uauthticatd cp.czasopisma.pa.pl; dgruytr.com/viw/j/cp 491 Dowload Dat 3/14/18 4:36 AM

8 J. Nastaj, M. Tuligłowicz,. Witkiwicz, Chm. Procss Eg., 016, 37 (4), Tabl 1. Approximatd psudo-first ordr ad psudo-scod ordr kitic rat costats for Cu(II) ad Z(II) ios o chitosa gl bads. T 303, ph 5, dos 50 g/l Havy mtal Cu xp Psudo-first ordr modl calc k 1 [mi -1 ] δ [%] R [-] xp Psudo-scod ordr modl calc k [g/(mg mi)] δ [%] R [-] Havy mtal Z xp Psudo-first ordr modl calc k 1 [mi -1 ] δ [%] R [-] xp Psudo-scod ordr modl calc k [g/(mg mi)] δ [%] R [-] For th scod-ordr kitic modl th avrag rlativ rror (δ) was 4.74% for Cu(II) ios ad 5.48% for Z(II) ios. Thrfor th psudo-scod ordr kitic modl is bttr for dscribig th sorptio kitics of th aalyzd havy mtals. Our data wr also cosistt with othr litratur data (Corriga ad obl, 195; Ho ad Mcay, 1999; ousalya t al., 010; Rpo t al., 010; Rupig t al., 006). Furthrmor, it is kow that wh th psudo-scod ordr kitic modl shows th bst fittig to th xprimtal data, th sorptio mchaism ivolvs chmisorptio (Wag t al., 01) Sorptio isothrm dtrmiatio for o-compot systms Th aalysis of sorptio procss uilibrium ruirs dtrmiatio of th isothrm. Sorptio isothrm is th most sigificat factor for aalyzig th atur of adsorbat-adsorbt itractio. Th sorptio uilibrium studis of Cu(II) ad Z(II) ios o chitosa gl bads wr dscribd by six of th most commo thr-paramtr uilibrium modls: Lagmuir-Frudlich, Rdlich- Ptrso, Sips ad obl-corriga, Hill ad Toth. Lagmuir-Frudlich isothrm uatio is a modificatio of th Lagmuir ad Frudlich uilibrium modls providig a commo isothrm uatio calld Lagmuir-Frudlich (Ch, 013; Wag t al., 01; Hamdaoui ad Naffrchoux, 007; ousalya t al., 010; Ososy ad Skaugrud 1990; Oyrto t al., 1999; Rpo t al., 010; Riaudo, 006; Wag t al., 004): LF mlf LFC (10) 1 LF + LFC Th thr-paramtr Rdlich-Ptrso uilibrium modl is aothr combiatio of Frudlich ad Lagmuir uilibrium modls ad is itdd to dscrib th htrogity of th sorbt surfac. Th Rdlich-Ptrso isothrm uatio is giv by (Rpo t al., 010): C RP (11) 1 + B RP RPC obl-corriga uilibrium modl is also a thr-paramtr mpirical modl which is also aothr combiatio of th Lagmuir ad Frudlich isothrm uatios. obl-corriga uilibrium modl is giv by (Ha t al., 005): Uauthticatd 49 cp.czasopisma.pa.pl; dgruytr.com/viw/j/cp Dowload Dat 3/14/18 4:36 AM

9 Euilibrium modlig of moo ad biary sorptio of Cu(II) ad Z(II) oto chitosa gl bads C CC C BCC (1) 1 + Sips proposd o mor uatio similar i form to th Lagmuir-Frudlich isothrm uatio (Ch, 013; Rpo t al, 010): S ( SC ) ( C ) S ms (13) 1 + S Hill isothrm uatio dscribs th bidig of diffrt spcis o homogous sorbt surfac. This modl assums that sorptio is a phomo cocrd with th bidig abilitis of ligads at o sit o th macromolcul. It may ifluc diffrt bidig sits of th sam macromolcul (Ch, 013): H mhc (14) H H + C Toth proposd a uilibrium modl which is xprssd i th followig form (Lodiro t al., 005): C (15) mt T T 1/ ( 1 + ( T TC) ) Tabl. Approximatd paramtrs ad avrag rlativ rrors of various uilibrium modls for Cu(II) ad Z(II) ios o th chitosa gl bads Lagmuir-Frudlich isothrm costats Rdlich-Ptrso isothrm costats mlf LF [L/mg] LF [-] δ [%] RP [L/g] B RP [L/mg] RP [-] δ [%] Cu Cu Z Z obl-corriga isothrm costats Sips isothrm costats C [L/g] B C [L/mg] C [-] δ [%] ms S [L/mg] S [-] δ [%] Cu Cu Z Z Hill isothrm costats Toth isothrm costats mh H [mg/l] H [-] δ [%] mt T [L/mg] T [-] δ [%] Cu Cu Z Z Th costats of th Lagmuir-Frudlich (E. (10)), Rdlich-Ptrso (E. (11)) obl-corriga (E. (1)), Sips (E. (13)), Hill (E. (14)) ad Toth (E. (15)) uilibrium modls wr fittd to th xprimtal data of Cu(II) ad Z(II) ios ad rsults ar show i Tabl. Ths fittd costats wr dtrmid usig th uasi-nwto oliar stimatio mthod with Statistica softwar. Th uilibrium modls fittd to th o-compot sorptio xprimtal data of Cu(II) ad Z(II) ios o chitosa gl bads ar show i Figs. 7 ad 8. Th obtaid maximum sorptio capacitis ( m ) uald mg/g for Cu(II) ios (Fig. 7) ad mg/g for Z(II) ios (Fig. 8). Uauthticatd cp.czasopisma.pa.pl; dgruytr.com/viw/j/cp 493 Dowload Dat 3/14/18 4:36 AM

10 J. Nastaj, M. Tuligłowicz,. Witkiwicz, Chm. Procss Eg., 016, 37 (4), Fig. 7. Exprimtal ad fittd sorptio isothrms of Cu(II) ios o chitosa gl bads usig various uilibrium modls Fig. 8. Exprimtal ad fittd sorptio isothrms of Z(II) ios o chitosa gl bads usig various uilibrium modls From aalysis of Tabl it ca b cocludd that th Lagmuir-Frudlich, Hill ad Sips uilibrium modls approximat wll th sorptio bhavior. Ths isothrm fuctios ovrlap i Figs. 7 ad 8. Thir avrag rlativ rror (δ) for Cu(II) is about 3%. For Z(II) th rrors ar similar ad vary i th rag from 5.61% to 6.36%. Also obl-corriga uilibrium modl uit wll dscribs th xprimtal data. Its avrag rlativ rror for Cu(II) has th sam low valu as th bst modls ( δ3.06%). Howvr, th rror for Z(II) ios is gratr (δ 1.36%). Rdlich-Ptrso ad Toth modl gav th worst fittig rsults with high rrors, spcially for Z(II) ios. Basd o th avrag rlativ rrors (δ) for both mtal ios, th uilibrium modls fit accuracy to th xprimtal data of Cu(II) ad Z(II) ios is i th followig ordr: Lagmuir- Frudlich > Hill > Sips > obl-corriga > Rdlich-Ptrso > Toth Sorptio isothrm dtrmiatio for two-compot systms I th last dcad thr wr svral xampls of mpirical isothrm modls, which provid paramtrs drivd from a o-compot systm. Ufortuatly, som modls fail wh itractios btw mtals i th mixtur occur. Th maximum sorptio capacity ( m ) ad htrogity factor () dpd o th coctratios of othr compots i th mixtur. Thrfor, th most dsirabl approach to two-compot systm modlig is a stimatio of two-compot isothrm o th basis of th associatio costat drivd from o-compot isothrms: LF, RP, C, S, H, T for Lagmuir- Frudlich, Rdlich-Ptrso, obl-corriga, Sips, Hill ad Toth, rspctivly. I our study, th uilibrium data of two-compot systms was modld usig th xtdd forms of th thrparamtr isothrm uatios such as: Lagmuir-Frudlich, obl-corriga, Sips, Rdlich-Ptrso, Hill ad Toth. Thy ar prstd i Tabl 3. Ths modlig calculatios wr carrid out usig Mapl softwar (Maplsoft) by mas of oliar programmig basd o th modifid Nwto mthod. Ukow paramtrs wr stimatd by miimizig th objctiv fuctio (Qi, 003) for combid data of all coctratio ratios: xp ) i j calci j ( (16) i whr i ad j ar th first ad scod compot i th particular two-compot mixtur. j Uauthticatd 494 cp.czasopisma.pa.pl; dgruytr.com/viw/j/cp Dowload Dat 3/14/18 4:36 AM

11 Euilibrium modlig of moo ad biary sorptio of Cu(II) ad Z(II) oto chitosa gl bads Tabl 3. Extdd forms of th thr-paramtr isothrm uatios for two mtal ios Two-compot isothrm Lagmuir- Frudlich Rdlich-Ptrso obl-corriga Sips Hill Toth Euatio systm 1LF mlf 1 1LFC LF LF 1LFC1 + LFC LF mlflfc 1 1LF LF 1LFC1 LFC Litratur + + (Viira t al., 007) C 1RP 1 1 1RP RP 1 + B1 RPC1 + BRPC (Sulaymo t al., RPC 011) 1 + 1RP B RP 1RPC1 + BRPC 1C 1CC C B C 1CC1 + BCC (Nastaj, 013) C CC 1 + 1C B C 1CC1 + BCC 1 1 ( 1 1 ) S ms SC ( ) S ( ) S SC + SC ( ) S m S SC 1 + ( ) S ( ) S SC + SC 1H mh 1 C1 1 1H H 1H + C1 + H + C (Al-Ashh t al., H mhc 003) 1H H 1H + C1 + H + C 1T mt 1 1TC / 1 1/ (1 ( 1 1 ) T ) T (1 ( ) T + ) T TC + + TC T mttc 1 1/ 1 1/ (1 ( 1 1 ) T ) T (1 ( ) T + ) T TC + + TC (Al-Ashh t al., 000; Rpo t al., 010) (All t al., 004) Two-compot sorptio studis wr coductd i thr iitial coctratio ratios (Cu(II)-Z(II) 1:1, 1:, :1) at a costat ph, costat sorbt dos ad costat tmpratur. Th iitial coctratios wr i th rag of mg/l for Cu(II) ios ad mg/l for Z(II) ios. Rsults ar prstd i Tabl 4 ad Figs. 9 through 11. Vry high valus of th avrag rlativ rrors δ % wr obtaid for xtdd modls of Rdlich- Ptrso ad Toth. Thus, rsults of ths two-compot modls ar usuitabl for dscriptio of Cu(II) ad Z(II) io sorptio ad thrfor ar ot prstd hr. Hill modl was also omittd du to similarity of obtaid rsults to thos for Sips isothrm. For th o-compot systms it was vidt that sorptio capacity of Cu(II) was isigificatly highr tha that for Z(II) ios (Figs 7 ad 8). For two-compot sorptio studis, th maximum sorptio capacity of Cu(II) ios was sv to twlv tims highr tha that of Z(II) ios, for all th studid systms (Figs. 9 through 11). Uauthticatd cp.czasopisma.pa.pl; dgruytr.com/viw/j/cp 495 Dowload Dat 3/14/18 4:36 AM

12 J. Nastaj, M. Tuligłowicz,. Witkiwicz, Chm. Procss Eg., 016, 37 (4), Fig. 9. Rlatioship of adsorptio capacitis of Cu(II) ad Z(II) o chitosa gl bads vrsus mtal io coctratio i two-compot uilibrium-iitial coctratio ratio 1:1. Exprimtal ad various isothrm modlig data Tabl 4. Approximatd paramtrs ad avrag rlativ rrors of various xtdd uilibrium modls for sorptio of Cu(II) ad Z(II) io mixtur o chitosa gl bads m 1 LF LF Extdd Lagmuir-Frudlich modl 1 [L/mg] 1 LF [-] m LF LF [L/mg] LF [-] δ 1,1:1 (%) δ 1,:1 (%) δ 1.1: (%) δ,1:1 (%) δ,:1 (%) δ,1: (%) Extdd obl-corriga modl B 1 C [L/mg] 1 C [L/g] 1 C [-] B C [L/mg] C [L/g] C [-] δ 1,1:1 (%) δ 1,:1 (%) δ 1,1: (%) δ,1:1 (%) δ,:1 (%) δ,1: (%) m 1 S S Extdd Sips modl 1 [L/mg] 1 S [-] m S S [L/mg] S [-] δ 1,1:1 (%) δ 1,:1 (%) δ 1,1: (%) δ,1:1 (%) δ,:1 (%) δ,1: (%) Uauthticatd 496 cp.czasopisma.pa.pl; dgruytr.com/viw/j/cp Dowload Dat 3/14/18 4:36 AM

13 Euilibrium modlig of moo ad biary sorptio of Cu(II) ad Z(II) oto chitosa gl bads Fig. 10. Rlatioship of adsorptio capacitis of Cu(II) ad Z(II) o chitosa gl bads vrsus mtal io coctratio i two-compot uilibrium-iitial coctratio ratio 1:. Exprimtal ad various isothrm modlig data Fig. 11. Rlatioship of adsorptio capacitis of Cu(II) ad Z(II) o chitosa gl bads vrsus mtal io coctratio i two-compot uilibrium-iitial coctratio ratio :1. Exprimtal ad various isothrm modlig data From aalysis of Figs. 9 through 11 o ca coclud that th xtdd Lagmuir-Frudlich modl dscribs grally fairly wll th sorptio bhavior i th two-compot systms, xcpt Z(II) i th prsc of Cu(II) for th coctratio ratio of 1: (δ 75.75%). I othr systms ad coctratio ratios, th rror valus vary from 1.56% to.09%. Th xtdd Sips modl gav th bst fittig to th xprimtal data for th coctratio ratio of 1:1 (Fig. 9) for Cu(II) i th prsc of Z(II). Th avrag rlativ rror (δ 1 ) uals 19.10%, Howvr, for Z(II) ios i th prsc of Cu(II) ios th avrag rlativ rror (δ ) is highr ad uals 3.59%. Takig ito accout both coctratio ratios, rlativ rrors for th xtdd Lagmuir-Frudlich modl (δ %, δ.09%) ar mor uiformly distributd. For th coctratio ratio of 1:, th most uiformly distributd avrag rlativ rrors ar obtaid for obl-corriga modl (δ %, δ 34.54%). Lagmuir-Frudlich ad Sips modls gav lowr valus of th avrag rlativ rrors oly for Cu(II) i th prsc of Z(II) ios (δ % ad δ %, rspctivly) ad dfiitly highr valus for Z(II) ios i th prsc of Cu(II) ios (δ 75.75%, δ %, rspctivly). Whras, for th coctratio ratio of :1 (Figur 11), for Cu(II) i th prsc of Z(II), th bst fittig is providd by th xtdd Lagmuir-Frudlich modl. Th avrag rlativ rror (δ 1 ) for Cu(II) ios i th prsc of Z(II) ios uals 18.33% ad for Z(II) ios i th prsc of Cu(II) ios (δ ) uals 1.56%. A slightly wors, but fairly good approximatio is xhibitd by th Sips modl (δ 1 1.8%, δ 11.70%). 5. CONCLUSIONS I th study, sorptiv rmoval of Cu(II) ad Z(II) ios from o- ad two-compot solutios o chitosa gl bads was ivstigatd at 303. Th sorptio of mtal ios was ot strogly dpdd o th ph of a solutio ad th dos of sorbt. Maximum havy mtal rmoval capacitis from watr solutios wr obtaid at ph5.0 for Cu(II) ad Z(II) ios both i th o- ad two-compot Uauthticatd cp.czasopisma.pa.pl; dgruytr.com/viw/j/cp 497 Dowload Dat 3/14/18 4:36 AM

14 J. Nastaj, M. Tuligłowicz,. Witkiwicz, Chm. Procss Eg., 016, 37 (4), systms. Th optimum dos of sorbt was dtrmid as 50 g/l for all studid havy mtals. Euilibrium cotact tims wr rachd: for Cu(II) withi about 1000 mi, whras for Z(II) ios withi 40 mi. It was provd that th psudo-scod ordr kitic modl is aduat to dscrib th sorptio kitics of th mtiod havy mtals oto chitosa gl bads, which is cosistt with othr rports. A attmpt was mad to xplai sorptio mchaism of th ivstigatd havy mtals o chitosa gl bads. Amio groups of chitosa chai i which itrog is door of th lctro pairs ar maily rsposibl for th formatio of complxs with havy mtal catios (Ji ad Bai, 00). Additioally, this mchaism dpds o othr factors such as: th ph of a solutio, dacylatio procss ad chitosa form. Th maximum sorptio capacitis ( m ) i o-compot solutios uald mg/g for Cu(II) ios ad mg/g for Z(II) ios. Six, most commo thr-paramtr uilibrium modls: Lagmuir- Frudlich, Rdlich-Ptrso, Sips, obl-corriga, Hill ad Toth, wr fittd to o-compot xprimtal uilibrium sorptio data. Th accuracy of uilibrium modl fittigs for Cu(II) ad Z(II) ios wr i th followig ordr: Lagmuir-Frudlich > Hill > Sips > obl-corriga > Rdlich-Ptrso > Toth. Fially, two-compot uilibrium data wr dscribd by th xtdd Lagmuir-Frudlich, obl-corriga ad Sips modls, which wr basd o th prvious modlig rsults obtaid for th o-compot systms. Th ovrall bst fittig accuracy was obtaid for th Lagmuir-Frudlich modl. As a rsult of th study, o ca draw a coclusio that chitosa gl bads ca b succssfully usd for rmoval of havy mtals both from o-compot ad two-compot solutios. It ca b attributd to strog affiity of chitosa gl bads to havy mtals. Additioally, chitosa gl bads ar rlativly asily maufacturd ad ar thrfor abudat sorbts. For this raso thy ca b rcommdd for us i th rmoval of havy mtals from wastwatr. This study was fudd by dvlopmt ad rsarch projct for youg scitist /17. SYMBOLS B C B RP B 1C B 1RP B C B RP C C 0 C 1 C o-compot obl-corriga costat, L/mg o-compot Rdlich-Ptrso costat, L/mg obl-corriga costat for Cu(II) i two-compot mixtur, L/mg Rdlich-Ptrso costat for Cu(II) i two-compot mixtur, L/mg obl-corriga costat for Z(II) i two-compot mixtur, L/mg Rdlich-Ptrso costat for Z(II) i two-compot mixtur, L/mg uilibrium liuid phas coctratio of mtal io, mg/l iitial coctratio of mtal io, mg/l uilibrium liuid phas coctratio of Cu(II) io i two-compot mixtur, mg/l uilibrium liuid phas coctratio of Z(II) io i two-compot mixtur, mg/l k 1 rat costat of psudo-first ordr kitic modl, mi -1 k rat costat of psudo-scod ordr kitic modl, g/(mg mi) H o-compot Hill isothrm costat, mg/l C o-compot obl-corriga isothrm costat, L/g LF o-compot Lagmuir-Frudlich isothrm costat, L/mg RP o-compot Rdlich-Ptrso isothrm costat, L/g S o-compot Sips isothrm costat, L/mg o-compot Toth modl costat, L/mg T Uauthticatd 498 cp.czasopisma.pa.pl; dgruytr.com/viw/j/cp Dowload Dat 3/14/18 4:36 AM

15 Euilibrium modlig of moo ad biary sorptio of Cu(II) ad Z(II) oto chitosa gl bads 1H 1C 1LF 1RP 1S 1T H C LF RP S T m N H C LF RP S T 1H 1C 1LF 1RP 1S 1T H C LF RP S T 1 m mh mlf ms mt m1h m1lf Hill isothrm costat for Cu(II) i two-compot mixtur, mg/l obl-corriga isothrm costat for Cu(II) i two-compot mixtur, L/g Lagmuir-Frudlich isothrm costat for Cu(II) i two-compot mixtur, L/mg Rdlich-Ptrso isothrm costat for Cu(II) i two-compot mixtur, L/g Sips isothrm costat for Cu(II) i two-compot mixtur, L/mg Toth modl costat for Cu(II) i two-compot mixtur, L/mg Hill isothrm costat for Z(II) i two-compot mixtur, mg/l obl-corriga isothrm costat for Z(II) i two-compot mixtur, L/g Lagmuir-Frudlich isothrm costat for Z(II) i two-compot mixtur, L/mg Rdlich-Ptrso isothrm costat for Z(II) i two-compot mixtur, L/g Sips isothrm costat for Z(II) i two-compot mixtur, L/mg Toth modl costat for Z(II) i two-compot mixtur, L/mg wight of th dry chitosa bads, g umbr of data poits o-compot sorbt htrogity costat of Hill isothrm o-compot sorbt htrogity costat of obl-corriga isothrm o-compot sorbt htrogity costat of Lagmuir-Frudlich isothrm o-compot sorbt htrogity costat of th Rdlich-Ptrso isothrm o-compot sorbt htrogity costat of Sips isothrm o-compot sorbt htrogity costat of Toth isothrm sorbt htrogity costat of Hill isothrm for Cu(II) i two-compot mixtur sorbt htrogity costat of obl-corriga isothrm for Cu(II) i two-compot mixtur sorbt htrogity costat of Lagmuir-Frudlich isothrm for Cu(II) i twocompot mixtur sorbt htrogity costat of th Rdlich-Ptrso isothrm for Cu(II) i twocompot mixtur sorbt htrogity costat of Sips isothrm for Cu(II) i two-compot mixtur sorbt htrogity costat of Toth isothrm for Cu(II) i two-compot mixtur sorbt htrogity costat of Hill isothrm for Z(II) i two-compot mixtur sorbt htrogity costat of obl-corriga isothrm for Z(II) i two-compot mixtur sorbt htrogity costat of Lagmuir-Frudlich isothrm forz(ii) i twocompot mixtur sorbt htrogity costat of th Rdlich-Ptrso isothrm for Z(II) i twocompot mixtur sorbt htrogity costat of Sips isothrm for Z(II) i two-compot mixtur sorbt htrogity costat of Toth isothrm for Z(II) i two-compot mixtur xprimtal sorptio capacity o chitosa gl bads, mg/g o-compot uilibrium sorptio capacity o chitosa gl bads, mg/g Cu(II) ios uilibrium sorptio capacity o chitosa gl bads i two-compot mixtur, mg/g Z(II) ios uilibrium sorptio capacity o chitosa gl bads i two-compot mixtur, mg/g compot maximum adsorptio capacity, mg/g o-compot Hill maximum adsorptio capacity, mg/g o-compot Lagmuir-Frudlich maximum adsorptio capacity, mg/g o-compot Sips maximum adsorptio capacity, mg/g o-compot Toth maximum adsorptio capacity, mg/g Hill maximum adsorptio capacity of Cu(II) i two-compot mixtur, mg/g Lagmuir-Frudlich maximum adsorptio capacity of Cu(II) i two-compot mixtur, mg/g Uauthticatd cp.czasopisma.pa.pl; dgruytr.com/viw/j/cp 499 Dowload Dat 3/14/18 4:36 AM

16 J. Nastaj, M. Tuligłowicz,. Witkiwicz, Chm. Procss Eg., 016, 37 (4), m1s m1t mh mlf ms mt t t t cot V Subscripts xp calc i j Sips maximum adsorptio capacity of Cu(II) i two-compot mixtur, mg/g Toth maximum adsorptio capacity of Cu(II) i two-compot mixtur, mg/g Hill maximum adsorptio capacity of Z(II) i two-compot mixtur, mg/g Lagmuir-Frudlich maximum adsorptio capacity of Z(II) i two-compot mixtur, mg/g Sips maximum adsorptio capacity of Z (II) i two-compot mixtur, mg/g Toth maximum adsorptio capacity of Z (II) i two-compot mixtur, mg/g amouts of mtal ios sorbd o chitosa gl bads at tim t, mg/g tim, mi cotact tim, h volum of solutio of mtal ios, L xprimtal calculatd first compot i th particular two-compot mixtur scod compot i th particular two-compot mixtur REFERENCES Al-Ashh S., Baat F., Al-Omari R., Duvjak Z., 000. Prdictios of biary sorptio isothrms for th sorptio of havy mtals by pi bark usig sigl isothrm data. Chmosphr, 41, DOI: /S (99)00497-X. Alimohamadi M., Abolhamd G., shtkar A., 005. Pb(II) ad Cu(II) biosorptio o Rhizopus arrhizus modlig moo- ad multi-compot systms. Mir. Eg., 18, DOI: /j.mig All S.J., Mckay G., Portr J.F., 004. Adsorptio isothrm modls for basic dy adsorptio by pat i sigl ad biary compot systms. J. Colloid Itrf. Sci., 80, DOI: /j.jcis Bara A., Biçak E., Baysal S.H., Öal S., 006. Comparativ studis o th adsorptio of Cr(VI) ios o to various sorbts. Biorsourc Tchol., 98, DOI: / j.biortch Ch A.H., Liu S.C., Ch C.Y., Ch C.Y., 008. Comparativ adsorptio of Cu(II), Z(II) ad Pb(II) ios i auous solutio o th crosslikd chitosa with pichlorohydri. J. Hazard. Matr., 154, DOI: /j.jhazmat Ch C., 013. Evaluatio of uilibrium sorptio isothrm uatios. Th Op Chm. Eg. J., 7, DOI: / Corriga T.E, obl R.A., 195. Adsorptio isothrm for pur hydrocarbos. Id. Eg. Chm., 44, DOI: /i50506a049. Hamdaoui O., Naffrchoux E., 007. Modlig of adsorptio isothrms of phol ad chlorophols oto graular activatd carbo Part II. Modls with mor tha two paramtrs. J. Hazard. Matr., 147, DOI: /j.jhazmat Ha R., Zhag J., Zou W., Shi H., Liu H., 005. Eulibrium biosorptio isothrm for lad io o chaff. J. Hazard Matr., B15, DOI: /j.jhazmat Hasa S., Ghosh T.., Viswaath D. S, Boddu V. M., 008. Disprsio of chitosa o prlit for hacmt of coppr(ii) adsorptio capacity. J. Hazard. Matr., 15, DOI: /j.jhazmat Ho Y. S., Mcay G., Psudo-scod ordr modl for sorptio procss. Procss Biochm., 34, DOI: /S (98) Jha I.N., Iygar L., Prabhakara-Rao A.V.S., Rmoval of cadmium usig chitosa. J. Eviro. Eg., 114, DOI: /(ASCE) (1988)114:4(96). Ji L., Bai R., 00. Mchaisms of lad adsorptio o chitosa/pva hydrog bads. Lagmuir, 18, DOI: /la05917l. ousalya G.N., Gadhi M. R., Makshi S., 010. Sorptio of chromium(vi) usig modifid forms of chitosa bads. It. J. Biol. Macromol., 47, DOI: / j.ijbiomac Uauthticatd 500 cp.czasopisma.pa.pl; dgruytr.com/viw/j/cp Dowload Dat 3/14/18 4:36 AM

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