Journal of Hazardous Materials 185 (2011) 13321339

Contents lists available at ScienceDirect

Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Adsorption of o-, m- and p-nitrophenols onto organically modied bentonites

Hlya Koyuncu a, , Nuray Yldz b , U gur Salgn c , Fatmanur Kro glu b , Ayla C alml b
a

Forensic Medicine Foundation, Felek Street, No:45, 06300 Kecioren, Ankara, Turkey Ankara University, Faculty of Engineering, Department of Chemical Engineering, 06100, Tando gan, Ankara, Turkey c Cumhuriyet University, Faculty of Engineering, Department of Chemical Engineering, 58140, Sivas, Turkey
b

a r t i c l e

i n f o

a b s t r a c t
Experiments were conducted on the adsorption characteristics of o-, m- and p-nitrophenols by organically modied bentonites at different temperatures. Two organobentonites (HDTMA-B and PEG-B) were synthesized using hexadecyltrimethylammonium bromide (HDTMABr) and poly(ethylene glycol) butyl ether (PEG). Synthesized HDTMA-B and PEG-B were characterized by XRD, FTIR and DTA-TG analyses and their specic surface area, particle size and pore size distributions were determined. BET surface areas and basal spacings (d0 0 1 ) of the HDTMA-B and PEG-B were found to be 38.71 m2 g1 , 69.04 m2 g1 15.17 A, respectively. Increased adsorption with temperature indicates that the process is and 21.96 A, endothermic for o-nitrophenol. On the other hand m- and p-nitrophenols exhibited lower rates of adsorption at higher temperatures suggesting a regular exothermic process taking place. Results were analyzed according to the Langmuir, Freundlich and Dubinin-Redushkevich (D-R) isotherm equations using linearized correlation coefcient at different temperatures. RL separation factors for Langmuir and the n values for Freundlich isotherms showed that m- and p-nitrophenols are favorably adsorbed by HDTMA-B and, p-nitrophenol is favored by PEG-B. Adsorption of o-, m- and p-nitrophenols as single components or from their binary mixtures on HDTMA-B and, p-nitrophenol on PEG-B are all dened to be physical in nature. 2010 Elsevier B.V. All rights reserved.

Article history: Received 26 March 2010 Received in revised form 11 October 2010 Accepted 12 October 2010 Available online 20 October 2010 Keywords: Adsorption HDTMAB PEG Nitrophenols Organobentonites

1. Introduction Phenols and their derivatives are classied to be extremely toxic for human beings and for all aquatic life. As the rate of production of industrial waste waters escalated, the demand for the removal of organic compounds from waste waters including phenols has been increased. Adsorption of phenols on different adsorbents has been heavily investigated by many researchers [13]. The use of activated carbons as adsorbents for the removal of phenolic compounds is a very common practice [4,5]. The major disadvantages of using these carbons are their high price and regeneration cost. Bentonites, on the other hand, posses larger surface area and can be an economic alternative since they are naturally available [6]. In addition, many studies were reported in the literature about the use of bentonites for the removal of phenols [7,8]. Numerous studies have been investigated the use of organobentonites as potential adsorbents for organic contaminants in a wide variety of environmental applications [9,10]. Organobentonites are pro-

Corresponding author. Tel.: +90 312 3407324; fax: +90 312 3406629. E-mail addresses: hkoyuncu@yyu.edu.tr, hulyakoyuncu06@yahoo.com.tr (H. Koyuncu). 0304-3894/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.jhazmat.2010.10.050

duced by the exchange of organic cations (typically a quaternary ammonium cation) with inorganic ones (e.g., Ca2+ , Na+ ) which are naturally present on the internal and external mineral surfaces of bentonite. This process provides a material with modied physical and chemical properties as compared to the original bentonite. Shen [11] also synthesized organobentonite using nonionic organic compounds. Organobentonites are organophillic and have a large sorption capacity for aqueous nonpolar organic compounds [12]. There are many studies for the removal of phenols from aqueous solutions by organobentonites [1318]. Simultaneous sorption of phenols from their solutions by inorganic and organic bentonites was also investigated [19,20]. The authors are aware that there is no investigation reported in the literature about the sorption of nitrophenols by an organobentonite synthesized by non-ionic organic compound (PEG). The main objectives of this study are to characterize HDTMA and PEG-bentonites, to examine their ability to adsorb o-, m- and pnitrophenols from aqueous solution, to determine the effects of various parameters on sorption such as the initial concentration and the process temperature, to investigate the simultaneous sorption of m- and p-nitrophenols by HDTMA-B, and to determine the applicability of various isotherm models (Langmuir, Freundlich, Dubinin-Redushkevich (D-R)) based on the correlation coefcient to nd out the best-t isotherm equation.

H. Koyuncu et al. / Journal of Hazardous Materials 185 (2011) 13321339

1333

Nomenclature Co Ce E K K kf qe V W Qo RL n qm R T Initial liquid phase concentration of the solute (mg L1 ) Equilibrium liquid phase concentration of the solute (mg L1 ) The mean adsorption energy (kJ mol1 ) Langmuir isotherm constant (L mg1 ) The adsorption energy constant (mol2 kJ2 ) Freundlich isotherm constant Amount of solute adsorbed at equilibrium (mg g1 ) Volume of the solution (L) Weight of the HDTMA-B (g) The maximum concentration retained by the adsorbent (mg g1 ) Separation factor (dimensionless constant) Freundlich isotherm constant The theoretical monolayer saturation capacity (mol g1 ) The gas constant (kJ mol1 K1 ) Temperature (K)

in 1 L distilled water and agitated with a magnetic stirrer for 24 h at 600 rpm. After the mixing period, PEG-bentonite suspension was set aside for 24 h at room temperature and then separated from water by centrifugation at 5000 rpm for 15 min. The synthesized organobentonites were freeze-dried, powdered to pass 125 m sieve and preserved in a coloured bottle until use. 2.3. Analyses Specic surface areas (BET) of the original and modied bentonites were determined using a Quantachrome NOVA 2000 series volumetric gas adsorption instrument. The determinations were based on measurements of the corresponding nitrogen adsorption isotherms at 196 C. Before measurements moisture and gases adsorbed on the solid surface or held in the open pores were removed under reduced pressure at 150 C for 5 h. The particle size distributions of the solid samples were determined using a Malvern Mastersizer 2000 (Hydro 2000MU) particle analyzer, which is based on the principle of laser ensemble light scattering. The particles were introduced into the analyzer beam via a sample presentation cell located in the optical unit. XRD patterns of the original and modied bentonites were obtained by X-ray powder diffractometer (Rikagu D-Max 2200). For FTIR analysis (8300 FTIR SHIMADZU) of the samples, KBr pellet method was used. Effect of temperature on the morphology of the original and organobentonites were evaluated by DTA-TG analysis (TA Instrument SDT Q600). 2.4. Adsorption experiments Adsorption studies were performed by the batch technique to obtain equilibrium data. The batch technique was selected because of its simplicity. For the equilibrium studies; batch sorption test of o-, m- and p-nitrophenols on the organobentonites were performed by weighing 0.2 g HDTMA-B or PEG-B samples into 250 mL Erlenmayer asks and adding 50 mL of 501400 mg L1 o-, m- and p-nitrophenols. Flasks were then shaken at 150 rpm for 28 h at constant temperatures (30 C, 35 C and 40 C) to attain equilibrium conditions, and then centrifuged at 5000 rpm for 15 min. The supernatants were ltered and the concentrations of o-, m- and p-nitrophenols in the supernatant solutions were measured spectrophotometrically (Shimazdu, 1600 model UV/VIS spectrophotometer) at wavelengths of 279 nm, 274 nm and 317 nm, respectively. In this study, all experiments were performed at a constant pH of 6.0. The contact time and conditions were selected on the basis of preliminary experiments, which demonstrated that equilibrium was established in 2 h for HDTMA-B and in 8 h for PEG-B. The competitive adsorption of m- and p-nitrophenols (501200 mg L1 ) onto HDTMA-B was also investigated. The experiments were carried out following the procedure described above. The adsorbed amount of o-, m- and p-nitrophenols was determined from the difference. Adsorption isotherms were plotted and the sorption capacities of the organobentonites towards o-, m- and pnitrophenols were evaluated. The amount of solute adsorbed onto HDTMA-B or PEG-B at equilibrium, qe (mg g1 ), was calculated through a mass balance qe = (Co Ce ) V W (1)

2. Materials and methods 2.1. Materials The adsorbent used in this study was provided from Ordu province (Turkey). Its cation exchange capacity (CEC), as determined via methylene blue test according to ANSI/ASTM C837-76 was found to be 65 meq/100 g bentonite [21,22]. The chemical constituent of the white Ordu bentonite was given as 61.15% SiO2 , 14.25% Al2 O3 , 0.98% Fe2 O3 , 0.10% SO3 , 2.21% CaO, 3.36% MgO, 0.77% Na2 O, 0.57% K2 O, and 0.76% others. Ignition loss of the bentonite at 1298 K was found to be 15.85%. For the exchange of inorganic ions with organic cations, hexadecyltrimethylammonium bromide (HDTMABr, Fluka) and poly(ethylene glycol) butyl ether (PEG, Fluka) were used. Organic pollutants studied were o-, m- and pnitrophenols (Fluka) and used without further purication. 2.2. Preparation of HDTMA-B and PEG-B Original bentonite was crushed into small particles and mechanically ground. A decantation process was applied to remove the impurities like quartz as suggested by C elik et al. [23] and Zhu et al. [15]. The bentonite was then dried at 100 C for overnight and ground to pass 125 m sieve to use in the organobentonite synthesis. HDTMA-B was synthesized by ion exchange reaction. The amount of HDTMABr (7 g) equal to the CEC of bentonite (65 meq/100 g) was dissolved in 1 L distilled water and 30 g of bentonite was added and agitated with a magnetic stirrer for 4 h at 600 rpm. Following the mixing period, HDTMA-B was separated from suspension by centrifugation at 5000 rpm for 15 min. The supernatant solution was analyzed for non-adsorbed HDTMABr using a total organic carbon analyzer, TOC 5310B. Variations of HDTMABr concentration in solutions were given in Table 1. To synthesize PEG-bentonite; the known amount (2 g) of poly(ethylene glycol) butyl ether and 50 g bentonite were mixed
Table 1 Variations of HDTMABr concentration in the solutions. Organic cation HDTMABr Initial solution (mg L1 ) 7106 Supernatant solution after third washing (mg L1 ) 206.50

Ammonium cation uptake on bentonite (mg L1 ) 6899.50

Specic uptake (mg g1 ) 229.98

CEC (%) 97

1334

H. Koyuncu et al. / Journal of Hazardous Materials 185 (2011) 13321339

Table 2 Properties of original bentonite and synthesized organobentonites. Sample Original bentonite HDTMA-B PEG-B Total organic carbon (%) 0.29 18.75 Surface area (m2 g1 ) 80.67 38.71 69.04 d0 0 1 (A)

8
Original bentonite HDTMA-B PEG-B

100

80

Insize (%)

60 4 40 2

where Co and Ce are the initial and equilibrium liquid phase concentration of the solute (mg L1 ), respectively, V is the volume of the solution (L) and W is the mass of the organobentonite used (g). 3. Results and discussion 3.1. Characterization of adsorbents Variations of the solution concentration of unadsorbed HDTMABr cations during adsorption were shown in Table 1. The found uptake amounts of HDTMABr cations were calculated from the mass balance, being equivalent to about 97% CEC on average. Total organic carbon content, BET surface areas and basal spacings (d0 0 1 ) of the original bentonite and the organobentonites are presented in Table 2. The organic carbon content of the original sample was lower than the HDTMA-B. The organic carbon in the HDTMA-B was almost entirely derived from the exchanged organic cations. The specic surface areas of the samples were calculated from nitrogen adsorption isotherms by the BET method mainly for comparative purposes. The organobentonites had lower surface area (HDTMA-B, 38.71 m2 g1 and PEG-B, 69.04 m2 g1 ) than the original sample (80.67 m2 g1 ). The relatively low surface area of the organobentonites indicates that only the external surface was accessible to nitrogen gas [24]. For a textural characterization of any porous solid, the concept of surface area does not provide a visual picture. Pore size and pore size distributions are necessary if the material is to be fully characterized. The pore size distribution (Fig. 1) in the mesopore region was obtained by BJH method and similar changes were observed for the original and modied bentonites [25]. Particle size analyses of the original bentonite and organobentonite samples were also performed and illustrated in Fig. 2. The distributions are presented in terms of undersize (cumulative particle size distribution) and insize (size distribution in the range). Analysis of the original bentonite and the organobentonite sam0,0030 0.0030

20

0 0.1 1 10 100

0 1000

Particle size (mm)

Fig. 2. Particle size distributions of original bentonite and synthesized organobentonite expressed in terms of undersize and insize.

ples showed that the latter contained coarser particles relative to the former. It is obvious from Fig. 2 that the whole size range of the original bentonite was ner than the organobentonites. As can be seen from Fig. 2, 90% of the original bentonite was less than 35 m insize, whereas 90% of HDTMA-B and 90% of PEG-B were less than 152 m and 63 m insize, respectively. When inorganic cations are exchanged by an organic cation, the sample is held more rmly in the layer resulting in aggregation and higher particle size (Fig. 2).

Differantial pore volume (cm3 g-1)

0.0025 0,0020 0.0020 0.0015 0.0010 0,0005 0.0005 0.0

Original bentonite HDTMA-B PEG-B

200

400

600

800

1000

Pore diameter ()
Fig. 1. Pore size distributions of the original bentonite and synthesized organobentonites. Fig. 3. FTIR spectras of the original bentonite (a), HDTMA-B (b), PEG-B (c).

Undersize (%)

14.97 21.96 15.17

H. Koyuncu et al. / Journal of Hazardous Materials 185 (2011) 13321339

1335

Fig. 4. XRD patterns of the original bentonite (a), HDTMA-B (b), PEG-B (c).

FTIR spectrums of the original bentonite and organobentonite samples are shown in Fig. 3. Both the original bentonite and the organobentonites show characteristic peaks of bentonite. The absorption band at 3650 cm1 is due to stretching vibrations of structural OH groups of montmorillonite. A complex band at 1050 cm1 is related to stretching vibrations of SiO groups. The H2 O-stretching vibration was observed as a broad band at 3450 cm1 . The spectrum of HDTMA-B (Fig. 3b) also showed the absorption band at 30002850 cm1 related to stretching vibrations of CH groups. However, no more distinct change on the absorption band at 935450 cm1 in the spectrum of original bentonite, HDTMA-B and PEG-B (Fig. 3) was observed. XRD patterns of the original bentonite and organobentonite samples were shown in Fig. 4. The XRD results show that organic cation modication has caused structural changes in the bentonite sample. The X-Ray diffraction basal spacing (d0 0 1 ) of the origi The interlayer spacing of the bentonite nal bentonite was 14.97 A. increased with the nonionic and cationic surfactants and reached and 21.96 A for PEG-B and HDTMA-B, respectively. Interto 15.17 A layer spacing of the samples were presented in Table 2. Jaynes and Vance [24] reported that the interlayer spacings of organoben On the basis of the XRD results obtained by tonites as 1034 A. earlier studies of montmorillonite modied with alkylamonium salts Jaynes and Boyd [26] and Lagaly [27] have shown that alkyl bilayers (17.7 A), pseuchains might form monolayer (13.7 A), and parafn structure (>22 A). In dotrimolecular layers (21.7 A) this study, the organobentonite derived from cationic surfactant showed larger interlayer spacing than the organobentonite derived from nonionic surfactant. This may be attributed to formation of bilayers and parafn complexes in which HDTMA ions are in direct contact with each other, leading to the formation of partition phases derived from the C16 and C18 hydrocarbon groups. The DTA-TG patterns of the original bentonite and organobentonite samples were shown in Fig. 5. These patterns demonstrate that the inorganic cation in bentonite was replaced by an organic cation. The DTA patterns of HDTMA-B exhibit exothermic peaks at about 250400 C due to combustion of the organic carbon.

Fig. 5. Thermograms of the original bentonite (a), HDTMA-B (b), PEG-B (c).

3.2. Effect of initial concentration on adsorption Effect of initial concentration on adsorption was investigated at concentrations ranging from 50 mg L1 to 1400 mg L1 in case of single compound sorption of o-, m- and p-nitrophenols, and from 50 mg L1 to 1200 mg L1 in case of binary sorption of m- and p-nitrophenols at different temperatures (30 C, 35 C and 40 C). Adsorption efciency was calculated from Eq. (2). Adsorption efciency (%) = (Co Ce ) 100 Co (2)

where Co and Ce (mg L1 ) are initial and equilibrium concentrations, respectively. Fig. 6 illustrates the effect of initial concentration on the adsorption in case of the single compound at different temperatures. The uptakes were 53%, 56% and 77% at low o-, m- and p-nitrophenols concentrations at 30 C, respectively. An increased adsorption was observed with temperature, indicating an endothermic process for o-nitrophenol, however, for mand p-nitrophenols at low concentrations the process was truly exothermic. Although the effect of temperature was also signicant for the adsorption of m- and p-nitrophenol in case of the binary system, no regular change by temperature was observed. This may depend on solutesolute or soluteadsorbent interactions in binary systems. Fig. 7 illustrates the effect of initial concentration of p-nitrophenol on adsorption by PEG-B at different temperatures. The uptake is 72% at low p-nitrophenol concentration at 30 C, while it is 77% for the HDTMA-B system.

1336

H. Koyuncu et al. / Journal of Hazardous Materials 185 (2011) 13321339

Fig. 7. Effect of initial solution concentration on the adsorption of p-nitrophenol onto PEG-B at different temperatures (equilibrium time 8 h).

single compound and m- and p-nitrophenol in case of the binary system were shown in Figs. 8 and 9. The isotherms for adsorption of p-nitrophenol onto PEG-B at different temperatures are shown in Fig. 10. The Langmuir adsorption isotherm [28] has been successfully applied to many real sorption processes. It predicts the maximum monolayer adsorption capacity of the adsorbent and also determines whether the adsorption is favorable. The linearized Langmuir isotherm is represented by Eq. (3). Ce 1 Ce = + qe Qo (Qo K ) (3)

Fig. 6. Effect of initial solution concentration on the adsorption in case of the single compound, o-nitrophenol (a), m-nitrophenol (b), p-nitrophenol (c) onto HDTMA-B at different temperatures (equilibrium time 2 h).

3.3. Adsorption isotherms In order to determine the adsorption mechanisms of o-, m- and p-nitrophenol in case of single compound and m- and p-nitrophenol in case of binary systems onto the HDTMA-B and PEG-B and to evaluate the relation to temperatures, Langmuir, Freundlich and D-R isotherm equations were applied to the experimental data. The constant parameters of the isotherm equations for these processes were calculated by regression using linear form of isotherm equations. The constant parameters and correlation coefcients (R2 ) are summarized in Tables 3 and 4. Since the adsorption equilibrium time of o- and m-nitrophenol onto PEG-B could not been determined, the parameters were calculated for only adsorption of p-nitrophenol onto PEG-B (Table 5). It was found that the adsorption equilibrium time of o-, mand p-nitrophenol onto HDTMA-B was 2 h, while it was 8 h for p-nitrophenol adsorption onto PEG-B. The isotherms for the adsorption of o-, m- and p-nitrophenol onto HDTMA-B in case of

where Ce is the solute concentration at equilibrium (mg L1 ), qe is the adsorption capacity in equilibrium (mg g1 ), K is Langmuir adsorption constant (L mg1 ), and Qo is the maximum concentration retained by the adsorbent (mg g1 ). The Langmuir (Ce /qe vs Ce ) plots of m- and p-nitrophenol were found to be linear for the entire concentration range studied and the correlation coefcients were extremely high (Tables 3 and 4). However, the correlation coefcient was found to be low for o-nitrophenol. Thus, it can be deduced that the Langmuir isotherm equation is not suitable for the adsorption of o-nitrophenol onto HDTMA-B. The maximum adsorption capacities were determined as 208.33 mg g1 for m-nitrophenol and 133.33 mg g1 for pnitrophenol onto HDTMA-B in case of single compound, and 10.29 mg g1 for m-nitrophenol and 42.92 mg g1 for p-nitrophenol onto HDTMA-B in case of the binary system at 40 C. Senturk et al. [29] reported the Langmuir adsorption capacity for phenol from aqueous solution onto cetyltrimethylammoniumbromide (CTAB) bentonite to be 333 mg g1 . For the adsorption of p-nitrophenol onto PEG-B, the maximum adsorption capacity was determined as 344.83 mg g1 at 40 C (Table 5). To determine whether the adsorption process is favorable for the Langmuir type adsorption process, isotherm can be classied by a term of RL , a dimensionless constant separation factor, which is dened as below [30]: RL = 1 (1 + KCo ) (4)

The RL values are found in the range of 0.920.25 and 0.780.06 for m- and p-nitrophenol onto HDTMA-B in case of single compound, 0.840.03 and 0.340.01 for m- and p-nitrophenol onto HDTMA-B in case of the binary system, and 0.880.11 for p-nitrophenol onto PEG-B at 3040 C, showing favorable adsorption and a relatively high nitrophenol uptake is achievable at low concentrations in the solution [31,32].

H. Koyuncu et al. / Journal of Hazardous Materials 185 (2011) 13321339 Table 3 Constant parameters and correlation coefcients calculated for various adsorption models at different temperatures for o-, m- and p-nitrophenol onto HDTMA-B. o-Nitrophenol Temperature ( C) Langmuir equation Qo (mg g1 ) K (L mg1 ) 103 R2 RL Freundlich equation kf (L g1 ) n R2 D-R equation qm (mol g1 ) 103 K (mol2 k1 J2 ) E (kJ mol1 ) R2 0.005 0.507 0.936 189.042 0.024 4.564 0.964 0.079 0.719 0.992 88.460 0.015 5.774 0.990 0.209 0.761 0.998 53.939 0.012 6.455 0.999

1337

m-Nitrophenol 40 30 120.482 2.785 0.929 0.870.26 0.913 1.429 0.968 2.481 0.008 7.906 0.983 35 172.414 1.669 0.996 0.920.37 0.504 1.188 0.972 4.053 0.009 7.454 0.983 40 208.333 2.927 0.892 0.870.25 0.324 1.008 0.897 10.028 0.011 6.742 0.919

p-Nitrophenol 30 107.527 14.314 0.997 0.580.06 1.056 1.125 0.986 3.914 0.007 8.452 0.919 35 212.766 5.438 0.988 0.780.15 2.422 1.541 0.997 3.628 0.006 9.129 0.984 40 133.333 7.369 0.951 0.730.12 2.502 1.458 0.967 3.721 0.006 9.129 0.972

30

35

Table 4 Constant parameters and correlation coefcients calculated for various adsorption models at different temperatures for simultaneous sorption of m- and p-nitrophenol onto HDTMA-B. m-Nitrophenol Temperature ( C) Langmuir equation Qo (mg g1 ) K (L mg1 ) R2 RL Freundlich equation kf (L g1 ) n R2 D-R equation qm (mol g1 ) 103 K (mol2 k1 J2 ) E (kJ mol1 ) R2 30 54.054 0.004 0.803 0.840.21 0.257 1.138 0.983 1.854 0.009 7.454 0.991 35 37.736 0.010 0.809 0.660.08 0.577 1.284 0.914 1.838 0.007 8.452 0.935 40 10.288 0.032 0.885 0.30.03 0.616 1.773 0.689 0.414 0.005 10.000 0.728 p-Nitrophenol 30 41.322 0.093 0.986 0.180.01 3.657 1.965 0.970 1.261 0.005 10.000 0.997 35 47.619 0.063 0.987 0.240.01 6.577 2.695 0.841 0.669 0.003 12.910 0.981 40 42.919 0.038 0.994 0.340.02 7.463 3.378 0.989 0.617 0.003 12.910 0.996

The Freundlich adsorption isotherm model is based on multilayer adsorption. In this model, the mechanism and the rate of adsorption are functions of the constants n and kf . The Freundlich adsorption isotherm can be expressed [33] as below: ln qe = ln kf + 1 n ln Ce (5)

Table 5 Constant parameters and correlation coefcients calculated for various adsorption models at different temperatures for p-nitrophenol onto PEG-B. p-Nitrophenol Temperature ( C) Langmuir equation Qo (mg g1 ) K (L mg1 ) R2 RL Freundlich equation kf (L g1 ) n R2 D-R equation qm (mol g1 ) 103 K (mol2 k1 J2 ) E (kJ mol1 ) R2 30 243.902 0.006 0.996 0.760.11 1.313 1.191 0.997 7.098 0.008 7.906 0.987 35 270.270 0.004 0.991 0.820.14 2.157 1.341 0.989 8.468 0.009 7.454 0.913 40 344.828 0.003 0.992 0.880.21 3.617 1.495 0.866 40.563 0.012 6.455 0.934

where kf (L g1 ) and n are isotherm constant which indicate the capacity and intensity of the adsorption, respectively. The linear plot of ln qe versus ln Ce at each temperature indicates that adsorption of o-, m- and p-nitrophenol follows Freundlich isotherm. The Freundlich adsorption isotherm constants and correlation coefcients were given in Table 3 and Table 4. The values of kf and n determined from the Freundlich model changed with temperature. The value of n for Freundlich isotherm was found to be greater than 1, indicating that m- and p-nitrophenol onto HDTMA-B are favorably adsorbed at all the temperatures studied for single and the binary systems [34,35]. However, n values less than 1, indicates that o-nitrophenol is unfavorably adsorbed at all temperatures studied. For the adsorption of p-nitrophenol onto PEG-B, the value of n was found to be greater than 1 (Table 5), indicating that p-nitrophenol is favorably adsorbed by PEG-B at all the temperatures studied [34,35]. Also, a higher value of n indicates better adsorption and formation of relatively strong bond between the adsorbate and adsorbent [32]. The Dubinin-Radushkevich adsorption isotherm model is temperature independent and more general than the Freundlich and Langmuir models. It predicts the energy of adsorption per unit mass of adsorbate and a maximum adsorption capacity. The linear form of the D-R isotherm [36] is, ln qe = ln qm K 2 (6)

where (Polanyi potential) is equal to RT ln(1 + 1/Ce ), qe is the amount of the solute adsorbed per unit mass (mol g1 ), qm is

1338

H. Koyuncu et al. / Journal of Hazardous Materials 185 (2011) 13321339

Fig. 9. Isotherms for simultaneous sorption of m-nitrophenol (a) and p-nitrophenol (b) onto HDTMA-B at different temperatures (equilibrium time 2 h).

3.4. Competition between m- and p-nitrophenol The adsorption efciencies of m- and p-nitrophenol onto HDTMA-B were 56% and 77% in case of single compound (Fig. 6) and 21% and 37% in case of the binary system, respectively (200 mg L1 , 30 C). The higher adsorption efciency was reached in case of the single compound for m- and p- nitrophenol and the adsorption efciency of p-nitrophenol was higher than m-nitrophenol in the binary system. Therefore, it can be concluded that there was a competition for the adsorption between m- and p-nitrophenol which may be due to the similar sorption sites of m- and p-nitrophenol.

Fig. 8. Isotherms for the adsorption of o-nitrophenol (a), m-nitrophenol (b) and p-nitrophenol (c) onto HDTMA-B at different temperatures (equilibrium time 2 h).

the theoretical monolayer saturation capacity (mol g1 ), Ce is the equilibrium concentration of the solute (mol L1 ), K is the constant of the adsorption energy (mol2 kJ2 ), R is the gas constant (kJ mol1 K1 ) and T is the temperature (K). K is related to mean adsorption energy (E, kJ mol1 ) by, E= 1 (2K )1/2 (7)

The constant obtained from the plot of ln qe versus 2 at temperatures of 30 C, 35 C and 40 C are shown in Tables 35. The mean adsorption energy (E) gives information about chemical and physical adsorption [37]. It was found to be in the range of 4.5612.70 kJ mol1 , which is lower than the range of adsorption reaction 816 kJ mol1 . Thus the type of adsorption of o-, m- and p-nitrophenol for single or the binary system on the HDTMA-B and p-nitrophenol on the PEG-B were dened as physical adsorption.

Fig. 10. Isotherms for adsorption of p-nitrophenol onto PEG-B at different temperatures (equilibrium time 8 h).

H. Koyuncu et al. / Journal of Hazardous Materials 185 (2011) 13321339

1339

4. Conclusions To the best of our knowledge there is no any report comparing adsorption properties and characterization of ionic and non-ionic organobentonites. In this study, it was found that the BET surface areas and basal spacings (d0 0 1 ) of the HDTMA-B and PEG-B were 15.17 A, respecfound as 38.71 m2 g1 , 69.04 m2 g1 and 21.96 A, tively. The adsorption was endothermic for o-nitrophenol, while it was exothermic for m- and p-nitrophenols at low concentrations. Also, it was found that m- and p-nitrophenol are favorably adsorbed by HDTMA-B and p-nitrophenol is favorably adsorbed by PGE-B. The type of adsorption of o-, m- and p-nitrophenol for single or the binary systems on the HDTMA-B and p-nitrophenol on the PGE-B was dened as physical adsorption. Acknowledgment The authors gratefully acknowledge the funding for this work by Ankara University Scientic Research Projects (Project no: BAP.2002.0745011). References
[1] C.-T. Hsieh, H. Teng, Liquid-phase adsorption of phenol onto activated carbons prepared with different activation levels, J. Colloid Interface Sci. 230 (1) (2000) 171175. [2] L.R. Radovic, C. Moreno-Castilla, J. Rivera-Utrilla, Carbon materials as adsorbents in aqueous solutions, Chem. Phys. Carbon 27 (4) (2000) 227406. [3] N. Roostaei, F.H. Tezel, Removal of phenol from aqueous solutions by adsorption, J. Environ. Manage. 70 (2004) 157164. [4] M.S.E. Abdo, S.A. Nosier, Y.A. Tawil, S.M. Fadl, Removal of phenol from aqueous solution by mixed adsorbents maghara coal and activated carbon, J. Environ. Sci. A-32 (1997) 11591169. [5] E.G. Furuya, H.T. Chang, Y. Miura, K.E. Noll, A fundamental analysis of the isotherm for the adsorption of phenolic compounds on activated carbon, Sep. Purif. Technol. 11 (1997) 6978. [6] M. Hermosin, P. Martin, J. Cornej, Adsorption mechanisms of monobutyltin in clay minerals, Environ. Sci. Technol. 27 (1993) 26062611. [7] S. Al-Asheh, F. Banat, L. Abu-Aitah, Adsorption of phenol using different types of activated bentonites, Sep. Purif. Technol. 33 (2003) 110. [8] F. Banat, B. Al-Bashir, S. Al-Asheh, O. Hayajneh, Adsorption of phenol by bentonite, Environ. Pollut. 107 (2000) 391398. [9] D.C. Rodrquez-Sarmiento, J.A. Pinzn-Bello, Adsorption of sodium dodecylbenzene sulfonate on organophilic bentonites, Appl. Clay Sci. 18 (2001) 173181. [10] Y.-H. Shen, Removal of phenol from water by adsorptionocculation using organobentonite, Water Res. 36 (2002) 11071114. [11] Y.H. Shen, Preparations of organobentonite using nonionic surfactants, Chemosphere 44 (2001) 989995. [12] S.L. Bartelt-Hunt, S.E. Burns, J.A. Smith, Nonionic organic solute sorption onto two organobentonites as a function of organic-carbon content, J. Colloid Interface Sci. 266 (2003) 251258. [13] J. Ma, L. Zhu, Removal of phenols from water accompanied with synthesis of organobentonite in one-step process, Chemosphere 68 (10) (2007) 18831888. [14] Z. Rawajh, N. Nsour, Characteristics of phenol and chlorinated phenols sorption onto surfactant-modied bentonite, J. Colloid Interface Sci. 298 (1) (2006) 3949.

[15] R. Zhu, L. Zhu, L. Xu, Sorption characteristics of CTMAbentonite complexes as controlled by surfactant packing density, Colloid Surf. A 294 (13) (2007) 221227. [16] Q. Zhou, H.P. He, J.X. Zhu, W. Shen, R.L. Frost, P. Yuan, Mechanism of p-nitrophenol adsorption from aqueous solution by HDTMA+-pillared montmorillonite-implications for water purication, J. Hazard. Mater. 15 (13) (2008) 10251032. [17] U.F. Alkaram, A.A. Mukhlis, A.H. Al-Dujaili, The removal of phenol from aqueous solutions by adsorption using surfactant-modied bentonite and kaolinite, J. Hazard. Mater. 169 (13) (2009) 324332. [18] A. Marsal, E. Bautista, I. Ribosa, R. Pons, M.T. Garca, Adsorption of polyphenols in wastewater by organo-bentonites, Appl. Clay Sci. 44 (12) (2009) 151155. [19] M. Borisover, E.R. Graber, F. Bercovich, Z. Gerstl, Suitability of dyeclay complexes for removal of non-ionic organic compounds from aqueous solutions, Chemosphere 44 (5) (2001) 10331040. [20] L. Zhu, R. Zhu, Simultaneous sorption of organic compounds and phosphate to inorganicorganic bentonites from water, Sep. Purif. Technol. 54 (115) (2007) 7176. [21] Y. Yukselen, A. Kaya, Suitability of the methylene blue test for surface area, cation exchange capacity and swell potential determination of clayey soils, Eng. Geol. 102 (12) (2008) 3845. [22] G. Kahr, F.T. Madsen, Determination of the cation exchange capacity and surface area of bentonite, illite and kaolinite by methylene blue adsorption, Appl. Clay Sci. 9 (5) (1995) 327336. [23] A. C elik, N. Yldz, A. C alml, Sorption characteristic of organic compounds on three hexadecyl-trimethylammonium-semectits having different cation exchange capacities, Rev. Chem. Eng. 15 (4) (1999) 349362. [24] W.F. Jaynes, G.F. Vance, Btex sorption by organo-clays: cosorptive enhancement and equivalence of interlayer coplexes, Soil Sci. Soc. Am. J. 60 (8) (1996) 17421749. [25] E.P. Barrett, L.G. Joyner, P.H. Halenda, The determination of pore volume and area distributions in porous substance. I. Computations from nitrogen isotherms, J. Am. Chem. Soc. 73 (1951) 373380. [26] W.F. Jaynes, S.A. Boyd, Clay mineral type and organic compound sorption by hexadecyl ammonium-exchanged clays, Soil Sci. Soc. Am. J. 55 (1991) 43. [27] G. Lagaly, Interaction of alkylamines with different types of layered compounds, Solid State Ionics 22 (1986) 4351. [28] I. Langmuir, The adsorption of gases on plane surfaces of glass, mica and Platinum, J. Am. Chem. Soc. 40 (1918) 13611403. [29] H.B. Senturk, D. Ozdes, A. Gundogdu, C. Duran, M. Soylak, Removal of phenol from aqueous solutions by adsorption onto organomodied Tirebolu bentonite: equilibrium, kinetic and thermodynamic study, J. Hazard. Mater. 172 (1,15) (2009) 353362. [30] T.W. Weber, R.K. Chakravorti, Pore and solid diffusion models for xed-bed adsorbers, Am. Inst. Chem. Eng. 20 (1974) 228238. [31] C.A. Bas ar, Applicability of the various adsorption models of three dyes adsorption onto activated carbon prepared waste apricot, J. Hazard. Mater. B135 (2006) 232241. [32] J.U. Kenedy Oubagaranadin, Z.V.P. Murthy, Adsorption of divalent lead on a montmorillonite-illite type of clay, Ind. Eng. Chem. Res. 48 (2009) 1062710636. [33] H. Freundlich, Colloid and Capillary Chemistry, Methuen, London, 1926. [34] S.D. Faust, O.M. Aly, Adsorption Processes for Water Treatment, Butterworths, 1987. [35] P.K. Malik, Use of activated carbons prepared from sawdust and rice-husk for adsorption of acid dyes: a case study of acid yellow 36, Dyes Pigments 56 (3) (2003) 239249. [36] A. Kilislio glu, B. Bilgin, Thermodynamic and kinetic investigations of uranium adsorption on amberlite IR-118H resin, Appl. Radiat. Isotopes 58 (2003) 155160. [37] W. Riemam, H. Walton, Ion exchange in analytical chemistry International Series of Monographsin Analytical Chemistry, vol. 38, Pergamon Press, Oxford, 1970.