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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry

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Adsorption Kinetics and Thermodynamics of Acid Blue 25

and Methylene Blue dye Solutions on Natural Sepiolite
a b c a a a b
Zhao-Xiang Han , Zhen Zhu , Dan-Dan Wu , Jue Wu & Yu-Rong Liu
a
School of Chemical Engineering, Huaihai Institute of Technology , Lianyungang City , Jiangsu , China
b
Chongqing Key Laboratory of Micro/Nano Materials Engineering and Technology , Chongqing City , China
c
Jiangsu Provincial Key Laboratory of Coastal Wetland Bioresources and Environmental Protection , Yancheng City , Jiangsu , China
Accepted author version posted online: 13 May 2013.

To cite this article: Zhao-Xiang Han , Zhen Zhu , Dan-Dan Wu , Jue Wu & Yu-Rong Liu (2013): Adsorption Kinetics and Thermodynamics of Acid
Blue 25 and Methylene Blue dye Solutions on Natural Sepiolite, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry,
DOI:10.1080/15533174.2013.770755

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Adsorption Kinetics and Thermodynamics of Acid Blue 25 and Methylene Blue dye Solutions on Natural Sepiolite

Zhao-Xiang Han1,2,3, Zhen Zhu1, Dan-Dan Wu1, Jue Wu1, Yu-Rong Liu2
1
School of Chemical Engineering, Huaihai Institute of Technology, Lianyungang City, Jiangsu,China
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2
Chongqing Key Laboratory of Micro/Nano Materials Engineering and Technology, Chongqing City, China
3
Jiangsu Provincial Key Laboratory of Coastal Wetland Bioresources and Environmental Protection, Yancheng City, Jiangsu,

China

Abstract: Natural sepiolite was used as an adsorbent for the investigation of the adsorption kinetics, isotherms,

thermodynamic parameters of an acid blue 25 (AB25), methylene blue (MB) from aqueous solution at various pHs,

temperatures, the kinetics and thermodynamics for the removal of the two dyes onto natural sepiolite have also been

investigated. The adsorbed amounts of AB25 increased with decreasing pH and the optimum pH value for the AB25 and MB

were found to be 3.0 and 9.0 respectively. The adsorption capacity of AB25 onto natural sepiolite increased with the

increasing temperature, indicating that AB25 and MB dye adsorption on the natural sepiolite was an endothermic process, the

second order model is found to be more suitable to describe the adsorption kinetic data than the first order model for natural

sepiolite on the AB25 and MB and the adsorption process of AB25 and MB are showing pseudo-second order kinetic behavior,


Address correspondence to Zhao-Xiang Han, School of Chemical Engineering, Huaihai Institute of Technology, 59# Cangwu
Road, Lianyungang city, Jiangsu 222005, China.

Tel.: +86-518-85895409; E-mail: hjyyzx@sina.com

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respectively. The adsorption of AB25 and MB on natural sepiolite may be followed by an intraparticle diffusion up to 60 an 90

min respectively, and the Langmuir equation represents the adsorption process better. The fit of the data for AB25 and MB

adsorption onto natural sepiolite suggests that the D-R model gave slightly closer fittings than those of Langmuir and
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Freundlich models. The adsorption of AB25 on natural sepiolite has a low potential barrier, which is also indicates a physical

adsorption. The negative values ofΔG0 and positiveΔH0 which has been obtained indicates that the MB adsorption process is a

spontaneous and endothermic.

Keywords: kinetics; thermodynamics; acid blue 25; methylene blue; sepiolite

INTRODUCTION

Dyes are extensively used for textile dyeing, paper printing, leather dyeing, color photography and as additives in petroleum

products[1]. Contamination of water resources with dyes is not desirable since it damages the aesthetic nature of water and

reduces the light penetration through the water’s surface. Furthermore, the colored effluents may contain chemicals that are

toxic, carcinogenic, mutagenic or teratogenic for microbes and fish species.[2] Sepiolite, which is a zeolite like clay mineral,

provides a high specific surface area. It is a magnesium hydrosilicate with amicro-fibrous structure and has a theoretical high

surface area and high chemical and mechanical stability[3,4]. These characteristics of sepiolite are related to its powerful

adsorbent properties and its ability to absorb organic or inorganic ions. Sepiolite (Mg4Si6O15(OH)2·6H2O) is a natural clay

mineral with formula of magnesium hydro-silicate[5]. The unique fibrous structure allows penetration of organic and inorganic

ions into the structure of sepiolite. Naturally occurring low cost sepiolite as an ion exchanger offers great potential for

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removing dyes from industrial wastewater. In the present study, natural sepilite adsorbent has been attempted for the removal

of acid blue 25 (AB25) and methylene blue (MB) from the aqueous media. This study of adsorption equilibrium, isotherms and

kinetics is essential in supplying the basic information required for the design and operation of adsorption equipments for
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different dyes wastewater treatment. Different adsorption isotherms such as Freundlich, Langmuir and Dubinin-Radushkevich

models have been applied to the adsorption data. The kinetics and thermodynamics for the removal of the two dyes onto

natural sepilite have also been investigated.

MATERIALS AND METHODS

Materials

Sepiolite was obtained from Hebei Jiali Trade Co.,Ltd., China. The chemical characteristics of the sepiolite (white), the

cation exchange capacity (25.00 meq 100/g), density (2.55 g/cm3) and specific surface area (342 m2/g), particle size (75µm)[6].

A commercial textile dye Acid Blue 25 (AB25) and methylene blue (MB) dyes were obtained from Jinan Pengdao Chemical

CO.,LTD and Zibo Pulisi Trading Co., Ltd, China, and were used without further purification. Concentrations of dyes were

determined by finding out the absorbance at the characteristic wavelength using a double beam Uv-vis spectrophotometer.

Calibration curves were plotted between absorbance and concentration of the dye solution.

Kinetic and Equilibrium Studies

Batch experiments for the removal of AB25 and MB were carried out in a thermostatic shaker at 200 rpm to study the effect

of parameters, initial dye concentration (C0=250 mg/L), pH (3–9), adsorbent dosage (1–5 g/L) and temperature (293–323 K)

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for a contact time of 180 min . Before mixing with the adsorbent, pH of the adsorbate solution was adjusted by adding 0.1N

HCl or 0.1N NaOH. AB25 and MB samples were prepared by dissolving a known quantity of the dye in double-distilled water

and used as a stock solution and diluted to the required initial concentration. Kinetics of adsorption was determined by
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analyzing adsorptive uptake of AB25 and MB dye from aqueous solution at different time intervals[4, 7]. 250 mL of AB25 and

MB dye solution of known concentration and initial pH was taken in a 250 ml screw-cap conical flask with are quired amount

of adsorbent and was agitated in the thermostat rotary shaker at 293 K for a specified period of contact time. For each set of

experiments, a blank test was always carried out. The flasks were successively removed at various time intervals. For

adsorption isotherms, AB25 and MB dye solutions were agitated with known amount of adsorbent and fixed pH till the

equilibrium was reached 180 min. Each experiment was replicated three times, and the mean values were used in these

analyses.

RESULTS AND DISCUSSION

Effect of pH

The pH of the solutions plays an important role in the whole adsorption process and change of pH affects the adsorptive

process through dissociation of functional groups on the adsorbent surface active sites, and then this subsequently leads to a

shift in reaction kinetics and equilibrium characteristics of adsorption process. Natural sepiolite has proved to be an effective

adsorbent for the removal of acid blue dye 25 (AB25) via adsorption from aqueous solution ( Fig.1). It was observed that the

adsorption is highly dependent on pH of the solution which affects the surface charge of the adsorbent and the degree of

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ionization of adsorbate. The absorbtion amounts of AB25 increased with decreasing pH, and the optimum pH value for the

AB25 was found to be 3.0. The amount of AB25 absorbed increased from 18.5 to 36.6 mg/g for natural sepiolite, respectively

as the pH decreased from 9 to 3. The variation in adsorption capacity in this pH range was largely due to the structural changes
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being effected in the dye molecules and the surface adsorption characteristics of sepiolite indicating that the adsorption

capacities of the adsorbents were pH dependent. At low pH, natural sepiolite surface is closely associated with the hydronium

(H3O+) ions. The surface of natural sepiolite becomes positively charged, thereby increasing electrostatic attractions between

negatively charged dye anions and positively charged adsorption sites and causing an increase in the dye adsorption. With the

gradual increase in the pH of the solution, a decrease in the positive charge on the oxide or solution interface has been

observed and the adsorbent surface appears negatively charged due to deprotonation of the adsorbent surface. As the pH of the

solution increases, the number of negatively charged sites increases. A negatively charged surface site on the adsorbent does

not favour the adsorption of dye anions due to the electrostatic repulsion. Therefore, the removal of dye decreases at higher pH

values may be due to the abundance of OH− ions and because of electrostatic repulsion between the negatively charged surface

of adsorbent and the anionic acid dye molecules. There are also no exchangeable anions on the outer surface of the adsorbent

at higher pH values due to the presence of excess OH− ions competing with dye anions for adsorption sites and a result of the

adsorption decreases [4,8]. Similar observations were reported by other studies for adsorption of dyes indicating that the

adsorbent had a net positive charge on its surface [9,10,11,12].

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The pH of the solution affects the surface charge of the adsorbents as well as the degree of ionization of different pollutants.

The adsorption of methylene blue dye (MB) on natural sepiolite was studied in a pH range of 3-9 at 20 C and the studies were

carried out for 180 min and the optimum pH value for the MB was found to be 9.0. Initial dye concentration was 250 mg/L
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according to previous study[13]. The percentage removal of MB by natural sepiolite was increased with increase in pH ( Fig.1).

Alkan et al. [14] found that sepiolite had pHiep at pH 6.6. In this case, natural sepiolite has negative zeta potential above the

value of pHiep, and positive zeta potential below that of pHiep. It can be said with certainty that the adsorption rate of MB on

natural sepiolite increases with increase in solution pH. Higher removal of MB in the alkaline pH range has been reported by

other workers as well [15,16,17,18].

Effect of Temperature

The removal of AB25 on natural sepilite as a function of temperature was studied by varying the temperature from 293 to

323 K, while keeping all other parameters constant. The results are shown in Fig.2A. It was observed from the figure that the

maximum adsorption capacity of the dye increased for natural sepiolite. The adsorption capacity of AB25 onto natural sepiolite

increased with the increasing temperature, indicating that the dye adsorption on the natural sepiolite was favored at higher

temperatures and the adsorption was an endothermic process, increasing from 39.3 mg/g at 293 K to 87.5 mg/g at 323 K, the

adsorption of the AB25 dye onto the natural sepiolite sample increases at higher temperatures, which indicates that the amount

of the adsorbed AB25 dye is an endothermic process. The fact that the adsorption rate of AB193 onto natural sepiolite at

various temperatures increases may be due to an increase in the mobility of AB193 ions with an increase in the temperature in

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the solution [4]. This effect suggests that an explanation of the adsorption mechanism associated with the removal of AB25 on

natural sepiolite involves a physical process. The result may be explained with increase in the mobility of the large AB25 dye

molecules depending on increase in temperature and a number of these molecules to interact adsorption cites. Moreover, the
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alteration of temperature from 293 to 328 K may induce a swelling effect within the internal structure of the natural sepiolite

enabling the same molecules to penetrate further. Similar trends were also observed by other researchers for aqueous phase

adsorptions [4,7,13].

The effect of temperature on the adsorption rate of MB on natural sepiolite was investigated at 293 to 323 K. Fig.2B shows

the results of experiments carried out at different temperatures for MB adsorption on natural sepiolite and that of MB from

34.1 mg/g to 93.2 mg/g, indicating the process to be endothermic as AB25 adsorption. This kind of temperature dependence of

the adsorbed amount of the dyes may reflect the increase in the case with which the dye penetrates into the natural sepiolite

because of its larger diffusion coefficient. In fact, a possible mechanism of interaction is the reaction between the hydroxyl end

groups of the natural sepiolite and the cationic group in the dye molecules, such a reaction could be favoured at higher

temperatures [4,7,13]. Increasing the temperature is known to increase the rate of diffusion of the adsorbate molecules across the

external boundary layer and in the internal pores of the natural sepiolite particle. In addition, changing temperature will change

the equilibrium capacity of the adsorbent for a particular adsorbate [7, 19].

Adsorption Kinetics

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The adsorption data has also been applied to three different kinetic models, namely, pseudo-first, pseudo-second order and

intraparticle diffusion models. In both pseudo-first and pseudo-second order models, all the steps of adsorption including

external diffusion, internal diffusion and adsorption are lumped together. Linear forms of pseudo-first order and pseudo-second
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order equations are given in Eqs. (1) and (2) as well intraparticle diffusion equation (3), respectively [20, 21].

Ln(qe-qt)=lnqt-k1t (1) ; t/qt=1/k2qe2+t/qe (2) ; qt=kit1/2+C (3), where qe and qt are the amount of dye adsorbed (mg/g) on the

adsorbents at the equilibrium and at time t, respectively, and k1 is the rate constant of adsorption (1/h), k2 is the rate constant of

pseudo-secondorder adsorption (g/mg h), ki (1/h) is the rate constant for intraparticle diffusion and C is the intercept. The linear

plots of ln(qe-qt)versus t for the first-order reaction and t/qt against t for the pseudo-second-order reaction for the adsorption of

AB25 onto natural sepiolite have also been tested to obtain the rate parameters, the kinetic parameters of AB25 under different

conditions were calculated from these plots and are given in Fig.3 and Table 1. Fig.3A and Fig.3B show the plots for the

pseudo-first and second order kinetic models, respectively and the values of different parameters calculated from the intercepts

and slopes of these plots are given in Tables 1. According to correlation coefficient values, the second order model is found to

be more suitable to describe the adsorption kinetic data than the first order model for natural sepiolite on the AB25 and MB.

The calculated adsorption amount at equilibrium qe is in good agreement with the experimental values for the second order

model. On the basis of both of these evidences, it has been confirmed that the adsorption process of AB25 and MB are

showing pseudo-second order kinetic behavior, respectively. Similar behavior has also been reported in literature[22,23], and in

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the adsorption of acid dyes by acid-activated bentonite[14], surfactant-modified bentonite [24,25], Acid Red 57, Acid Blue 294

and Acid Blue 193 onto sepiolite [4, 26] and Acid Red 57 onto surfactant modified sepiolite [27].

The pseudo first-order and pseudo-second-order models can’t identify the diffusion mechanism and the kinetic results were
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then subjected to analyze by the intraparticle diffusion model [28] for diffusion mechanism. The plot of uptake qt versus t1/2

should be linear and if it passes through the origin then intraparticle diffusion will be the sole rate-limiting process [4,26,27, 29].

The intraparticle diffusion plots for the effect of temperature on the adsorption of AB25 and MB onto natural sepiolite are

shown in Fig.3. It was observed that there are two linear portions and the plots of qt versus t1/2 exhibited an initial linear portion

followed by a plateau which occurred after 60 and 90 min for AB25 and MB for natural sepiolite in our study, the initial linear

portion of the plots seems to be due to boundary layer adsorption and the linear portion to intraparticle diffusion, with the

plateau corresponding to equilibrium. It indicates that the adsorption although intraparticle diffusion was involved in the

adsorption process, it was not the rate-controlling step. The values of the intraparticle diffusion constant ki were obtained from

the slopes of the linear portions of the plots and are listed in Table 1. The coefficient of determination (r2i) of AB25 and MB

for the intraparticle diffusion model were 0.700 and 0.990. These values indicate that the adsorption of AB25 and MB on

natural sepiolite may be followed by an intraparticle diffusion up to 60 an 90 min, respectively.

Adsorption Isotherms

The adsorption isotherms for AB25 and MB were studied at 293 K and 323 K. The analysis of the isotherm data by fitting

them to different isotherm models is an important step to find the suitable model that can be used for design of adsorption

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systems. Three adsorption isotherm models, Langmuir, Freundlich and Dubinin-Radushkevich were used in the study. The

Langmuir equation can be expressed in a mathematical form as shown in Eq.(4): Ce/qe=1/Q0b+Ce/Q0 (4); The essential

characteristics of the Langmuir isotherm can be expressed in terms of a dimensionless constant, separation factor or
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equilibrium parameter RL, which is calculated using the following equation: RL=1/(1+bC0) (5); The Freundlich isotherm

describes equilibrium on heterogeneous surfaces and hence does not assume monolayer capacity. The linearized form of the

equation can be written as follows: logqe=logkF+nlogCe (6); The Dubinin-Radushkevich (D-R) equation can be written as:

lnqe=lnXm-kε2 (7). The most probable energy of adsorption, E (kJ/mol), was chosen to be E=(2K)−1/2.

Where Ce is the equilibrium concentration (mg/L), qe is the amount adsorbed at equilibrium (mg/g), Q0 is the adsorption

capacity (mg/g) and b is the Langmuir constant (l/mg). RL values lie between 0 and 1, indicating the on-going adsorption

process is favorable for the dye using

natural sepiolite; kF and n are Freundlich constants and were calculated from the slope and intercept of the Freundlich plots; ε

is the Polanyi potential that can be found as E=RTIn(1+1/Ce), Xm is the ultimate capacity per unit area in adsorbent micropores;

k is a constant related to the adsorption energy (mol2/kJ2); R is the gas constant (J/Kmol)[13, 30].Three adsorption isotherm

models parameters are shown in Table2. Adsorption isotherms were obtained by experimental data using Eqs. (4), (6) and (7).

The coefficient of determination (r2) obtained from the Langmuir isotherm model (r2>0.989) were higher than for the

Freundlich (r2>0.913) and D-R isotherm model (r2>0.896) for AB25 on natural sepiolite. Therefore, the Langmuir equation

better represents the adsorption process. The separation parameter values of RL,were calculated using Eq.(5) and given in

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Table2.The RL values for the present adsorption process were found in the range of 0.038-0.598 indicating that the adsorption

process was favorable.

The Freundlich constant KF is associated with the degree of adsorption. The larger value of KF for MB on natural sepiolite at
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323 K than that of at 293 K showed the process to be favorable at higher temperature and the equilibrium data fitted well with

Freundlich isotherm model (r2 >0.992) which gave closer fittings than the Langmuir model (r2>0.934) and D-R isotherm

model (r2 >0.928) for MB on natural sepiolite. Fig.6 indicates the D-R isotherm for AB25 and MB adsorption on natural

sepiolite. The fit of the data for AB25 and MB adsorption onto natural sepiolite suggests that the D-R model gave slightly

closer fittings than those of Langmuir and Freundlich models.

Thermodynamic Analyses

Thermodynamic parameters provide in depth information of inherent energetic changes associated with adsorption, the

thermodynamic parameters including change in the Gibbs free energy (ΔG0), enthalpy (ΔH0) and entropy (ΔS0) were

determined to elucidate the process of adsorption by using following equations and represented in Table3. The thermodynamic

parameters including the Arrhenius activation energy (Ea), activation free energy change (ΔG0), activation enthalpy change

(ΔH0), and activation entropy change (ΔS0) can be calculated by using the following equations[31,32]: Lnk2=lnA-Ea/RT (8);

kc=CA/CS (9); ΔG0=-RTlnkc (10); lnkc=ΔS0/R-ΔH0/RT (10), where Ea is the Arrhenius activation energy (kJ/mol). A is the

Arrhenius factor, R the gas constant (8.314 J/mol K) and T is the solution temperature; KC is the equilibrium constant, CA is

the amount of dye adsorbed on the natural sepiolite from the solution at equilibrium (mg/L), and CS is the equilibrium

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concentration of dye solutions (mg/L). ΔH0 andΔS0 were calculated from the slope and intercept of van’t Hoff plots of ln KC

against 1/T.

A linear plot of lnk2 versus 1/T for the adsorption of AB25 onto natural sepiolite is constructed to generate the Ea value from
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the slope (Fig.5A), a straight line with slope −Ea/R is obtained. The magnitude of activation energy gives an idea about the

type of adsorption which is mainly physical or chemical. The value of activation energy (Ea=28.89 kJ/mol) given in Table 3

confirm the nature of physisorption processes of AB25 onto natural sepiolite. Low activation energies (5-40 kJ/mol) are

characteristics for physisorption, while higher activation energies (40-800 kJ/mol) suggest chemisorption [4, 33]. The result

obtained is 28.89 kJ/mol with the coefficient of determination (r2) of 0.995 for the adsorption of AB25 on natural sepiolite,

indicating that the adsorption has a low potential barrier, which also indicates a physical adsorption. Similar result was

reported for adsorption of acid red 57 and acid blue 294 onto acid activated bentonite, and acid blue 193 onto natural sepiolite

in which the activation energies obtained were 29.3, 14.6 and 32.41 kJ/mol, respectively [4,34]. By plotting a graph of lnkc

versus 1/T (Table3), the valuesΔH0 andΔS0 can be estimated from the slopes and intercepts, the results obtained for natural

sepiolite are -0.792 kJ/mol and -0.894 kJ/mol at 293 K, respectively, therefore,ΔH0 andΔS0 were calculated for natural sepiolite

and found -15.231 and -16.758 kJ/mol, the negative value ofΔH0 showed that the AB25 adsorption on natural sepiolite was a

exothermic.

ΔH0 andΔS0 were calculated the slope and intercept of van’t Hoff plot of ln KC versus 1/T (Fig.5B). The lowΔH0 values for

MB give a clear evidence that the interactions between MB and the surface hydroxyl groups of natural sepiolite may be weak.

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Table3 shows the negative values ofΔG0 and positiveΔH0 obtained indicated that the MB adsorption process is a spontaneous

and an endothermic. The positive value of ΔS0 suggests increased randomness at the solid-solution interface occur in the

internal structure of the adsorption of MB onto natural sepiolite. The positive values of Ea, andΔH0 indicate the presence of an
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energy barrier in the adsorption process and endothermic process [34].Similar result removal of acid blue 62 anionic dye by

sepiolite at 25, 35, 45 and 55C. The results obtained that the enthalpy change (ΔH) the adsorption process of acid blue 62 on

sepiolite adsorbent was endothermic[35].

CONCLUSIONS

This study investigated the kinetics and thermodynamics of the adsorption of AB25 and MB onto natural sepiolite. The

adsorbed amounts of AB25 increased with decreasing pH and the optimum pH value for the AB25 and MB were found to be

3.0 and 9.0 respectively. The adsorption capacity of AB25 onto natural sepiolite increased with the increasing temperature,

indicating that AB25 and MB dye adsorption on the natural sepiolite was favored at higher temperatures and the adsorption

was an endothermic process. According to correlation coefficient values, the second order model is found to be more suitable

to describe the adsorption kinetic data than the first order model for natural sepiolite on the AB25 and MB and the adsorption

process of AB25 and MB are showing pseudo-second order kinetic behavior, respectively. The adsorption of AB25 and MB on

natural sepiolite may be followed by intraparticle diffusion up to 60 an 90 min, respectively. The coefficient of determination

(r2) obtained from the Langmuir isotherm model were higher than for the Freundlich and D-R isotherm model for AB25 on

natural sepiolite. Therefore, the Langmuir equation better represents the adsorption process. The larger value of KF for MB on

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natural sepiolite at 323 K than that of at 293 K showed the process to be favorable at higher temperature and the equilibrium

data fitted well with Freundlich isotherm model (r2 >0.992) which gave closer fittings than the Langmuir model (r2>0.934) and

D-R isotherm model (r2 >0.928) for MB on natural sepiolite. The fit of the data for AB25 and MB adsorption onto natural
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sepiolite suggests that the D-R model gave slightly closer fittings than those of Langmuir and Freundlich models.The

adsorption of AB25 on natural sepiolite has a low potential barrier, which also indicates a physical adsorption. The negative

values ofΔG0 and positiveΔH0 obtained indicates that the MB adsorption process is a spontaneous and endothermic.

ACKNOWLEDGEMENTS

This research was supported by Chongqing Key Laboratory of Micro/Nano Materials Engineering and Technology

(No.KFJJ1106), Jiangsu Provincial Key Laboratory of Coastal Wetland Bioresources and Environmental Protection

(No.JLCBE11004), and Jiangsu Marine Resources Development Research Institute (No.JSIMR10E04).We thank Jiahong

Wang and Wenzhou Lv for exemplary technical assistance.

REFERENCES

1. K.R. Ramakrishna and T. Viraraghavan. Dye removal using low cost adsorbents. Water Sci. Technol., 1997, 36, 189–196.

2. H. Zollinger, Colour Chemistry-Synthesis, Properties and Application of Organic Dyes and Pigments.

VCH, NewYork, 1987, 92–102.

3. Nihal Bekta, Burcu Akman Agım. Kinetic and equilibrium studies in removing lead ions from aqueous solutions by natural

sepiolite. Journal of Hazardous Materials, 2004, B112, 115–122.

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4. Adnan Özcan, E. MineÖncu, A. SafaÖzcan. Kinetics, isotherm and thermodynamic studies of adsorption

of Acid Blue 193 from aqueous solutions onto natural sepiolite, Colloids and Surfaces A: Physicochem. Eng. Aspects, 2006,

277, 90–97.
Downloaded by [Universitaets und Landesbibliothek] at 04:45 10 June 2013

5. A. García-Sánchez, A. Alastuey, X. Ouerol, Heavy metal adsorption by different minerals: application to the remediation of

polluted soils. Sci. Total Environ., 1999, 242, 179–188.

6. Mahir Alkan, Özkan Demirbas, Mehmet Dogan. Adsorption kinetics and thermodynamics of an anionic

dye onto sepiolite. Microporous and Mesoporous Materials, 2007, 101, 388–396.

7. Mehmet Dogan, Yasemin Özdemir, Mahir Alkan. Adsorption kinetics and mechanism of cationic methyl violet and

methylene blue dyes onto sepiolite. Dyes and Pigments, 2007, 75, 701–713.

8. Z. Wu, I.-S. Ahn, C.-H. Lee, J.-H. Kim, Y.G. Shul, K. Lee, Enhancing the organic dye adsorption on porous xerogels,

Colloids Surf. A: Physicochem. Eng. Aspect., 2004, 240, 157–164.

9. A. Bousher, X. Shen and R.G.J. Edyvean, Removal of coloured organic matter by adsorption onto low cost waste materials.

Water Res., 1997, 31, 2084–2092.

10. S. Chiou and H.Y. Li, Equilibrium and kinetic modeling of adsorption of reactive dye on crosslinked

chitosan beads. J. Hazard. Mater., 2002, B93, 233–248.

11. P.K. Malik, Dye removal from wastewater using activated carbon developed from sawdust: adsorption

equilibrium and kinetics. J. Hazard. Mater., 2004, 113, 81–88.

15
ACCEPTED MANUSCRIPT
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12.G. Akkaya and A. Ozer, Biosorption of Acid Red 274 (AR 274) on Dicranella varia: Determination of

equilibrium and kinetic model parameters. Process Biochem., 2005, 40, 3559–3568.

13. E. Demirbas, M.Z. Nas. Batch kinetic and equilibrium studies of adsorption of Reactive Blue 21 by fly ash and sepiolite.
Downloaded by [Universitaets und Landesbibliothek] at 04:45 10 June 2013

Desalination, 2009, 243, 8–21.

14. Alkan M, Demirbasx Ö, Dogan M. Electrokinetic properties of sepiolite suspensions in different electrolyte media. J

Colloid Interface Sci., 2005b, 281(1), 240–248.

15. Dogan M, Alkan M. Adsorption kinetics of methyl violet onto perlite. Chemosphere, 2003, 50, 517–528.

16. Dogan M, Alkan M, Türkyılmaz A, Özdemir Y. Kinetics and mechanism of removal of methylene blue by adsorption onto

perlite. J Hazard Mater., 2004, B109, 141–148.

17. Mall ID, Upadhyay SN. Treatment of methyl violet bearing wastewater from paper mill effluent using low cost adsorbents.

J Indian Pulp Paper Technol Assoc., 1995, 7(1), 51–57.

18. Mall ID, Srivastava VC, Agarwal NK. Removal of Orange-G and Methyl Violet dyes by adsorption onto bagasse fly

ashdkinetic study and equilibrium isotherm analyses. Dyes Pigments, 2006, 69, 210–223.

19. V.K. Gupta, I. Ali, Suhas, D. Mohan, Equilibrium uptake and sorption dynamics for the removal of a basic dye (basic red)

using low-cost adsorbents. J. Colloid Interface Sci., 2003, 265, 257–264.

20. Y.S. Ho and G. McKay, Sorption of dye from aqueous solution by peat. Chem. Eng. J., 1998, 70,

115–124.

16
ACCEPTED MANUSCRIPT
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21. M. Ozacar and A.I. Sengil, Adsorption of metal complex dyes from aqueous solutions by pine sawdust,

Biores. Technol., 2005, 96, 791–795.

22. McKay G, Poots VJP. Kinetics and diffusion processes in colour removal from effluent using wood as an adsorbent. J
Downloaded by [Universitaets und Landesbibliothek] at 04:45 10 June 2013

Chem Technol Biotechnol., 1980, 30, 279–292.

23. McKay G, Blair HS, Gardner JR. Rate studies for the adsorption of dyestuffs on chitin. J Colloid Interface Sci., 1983, 95,

108.

24. Daza L, Mendioroz S, Pajares JA. Mercury adsorption by sulfurized fibrous silicates. Clays Clay Miner., 1991, 39(1), 14–

21.

25. Dogan M, Alkan M, Onganer Y. Adsorption of methylene blue on perlite from aqueous solutions. Water Air Soil Pollut.,

2000, 120, 229–248.

26. Balci S, Dincel Y. Ammonium ion adsorption with sepiolite: use of transient uptake method. Chem Eng Process, 2002, 41,

79–85.

27. Batabyal D, Sahu A, Chaudhuri SK. Kinetics and mechanism of removal of 2,4-dimethyl phenol from aqueous solutions

with coal fly ash. Sep Sci Technol., 1995, 5(4), 179–186.

28. Ho YS, McKay G. Kinetic models for the sorption of dye from aqueous solution by wood. Proc Saf Environ Protect.,

1998c, 76(B2), 183–191.

29. Ho YS, McKay G. Sorption of dyes and copper ions onto biosorbents. Process Biochem., 2003, 38(7), 1047–1061.

17
ACCEPTED MANUSCRIPT
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30. Rushdi I. Yousef, Bassam El-Eswed. Adsorption characteristics of natural zeolites as solid adsorbents for phenol removal

from aqueous solutions: Kinetics, mechanism, and thermodynamics studies.Chemical Engineering Journal, 2011, 171, 1143–

1149.
Downloaded by [Universitaets und Landesbibliothek] at 04:45 10 June 2013

31. Muhammad Aslam Malana, Sana Ijaz, Muhammad Naeem Ashiq. Removal of various dyes from aqueous media onto

polymeric gels by adsorption process: Their kinetics and thermodynamics. Desalination, 2010, 263, 249–257.

32. Chao Yin Kuo, Chung Hsin Wu. Adsorption of direct dyes from aqueous solutions by carbon nanotubes:

Determination of equilibrium, kinetics and thermodynamics parameters. Journal of Colloid and Interface Science, 2008, 327,

308–315.

33. H. Nollet, M. Roels, P. Lutgen, P. Van der Meeren, W. Verstraete, Removal of PCBs from wastewater using fly ash.

Chemosphere, 2003, 53, 655–665.

34. A.S. Ozcan, A. Ozcan, Adsorption of acid dyes from aqueous solutions onto acid-activated bentonite. J. Colloid Interf.

Sci., 2004, 27, 639–646.

35. M. Alkan, S.C elikc capa, O. Demirbas, M. Dogan, Removal of reactive blue 221 and acid blue 62 anionic dyes from

aqueous solutions by sepiolite. Dyes Pigments, 2005, 65, 251–259.

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270
A
240
210 B

210
180
180
150
150
qt (mol/g)

120

qt (mol/g)
120
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pH3.0
pH9.0 90 pH5.0
90
pH7.0 pH7.0
60 pH5.0 60 pH9.0
pH3.0
30 30

0
0

0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120 140 160 180
Time (min) Time (min)

FIG.1. The effect of pH on the adsorption rate of (A) AB25 and (B) MB dyes on sepiolite (C0:250 mg/L, T:293K).

100
B
90
90
A 323K
80 313K
80
323K 303K
313K 70
70 293K
303K
293K 60
60
qt (mg/g)

50
qt(mg/g)

50

40
40

30
30

20
20

10
10

30 60 90 120 150 180

30 60 90 120 150 180
Time (min) Time (min)

FIG.2. The effect of temperature on the adsorption rate of (A) AB25 (C0=250 mg/L, pH3.0)and (B) MB (C0=250 mg/L, pH

9.0) dyes on natural sepiolite.

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A
0.5 C
240
180 B
210
160
0.0
180
30 60 90 120 150 180
140

qt (mg/g)
Time(min) 150
Log(qe-qt)

t/qt(min g/mg)
120
-0.5 AB25
120
100 MB
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90
AB25 80
-1.0 MB AB25
60
60 MB
30
40
-1.5
1.6 1.8 2.0 2.2 2.4
30 60 90 120 150 180
1/2 1/2
Time (min) t (min )

FIG.3. Pseudo-first order kinetics plot (A), Pseudo-second order kinetics plot (B) and Intraparticle diffusion (C) for the

adsorption of AB25 (C0=250 mg/L, pH3.0) and MB (C0=250 mg/L, pH 9.0) dyes on natural sepiolite (T=323K).

0 200 400 600 800 1000 1200

1.0 B
4.5

A -2
0.5 2 2 2
4.0
-4
E (kJ /mol )

0.0 -6
3.5
1.2 1.4 1.6 1.8 2.0 2.2 2.4 C AB25
MB
Ce/q e (g/L)

-8
logCe
logqe

-0.5 lnqe
3.0

-10

2.5 -1.0 AB25

AB25 -12
MB MB

2.0 -1.5 -14

50 100 150 200 250

-16
Ce (mg/L) -2.0

FIG.4. Langmuir isotherms (A), Freundlich isotherms (B) and D-R isotherm (C) for the adsorption of AB25 and MB on natural

sepiolite at 293 K, respectively.

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0.00312 0.00318 0.00324 0.00330 0.00336 0.00342
3.6 A
-0.25
B
3.3 -1
1/T (K )
-0.30 AB25
3.0 MB
AB25
MB -0.35
2.7
lnk2

-0.40

lnkc
2.4
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-0.45
2.1

-0.50
1.8

0.00312 0.00318 0.00324 0.00330 0.00336 0.00342 -0.55

-1
1/T (K )

FIG.5. Arrhenius plot (A) and Plot of ln KC vs. 1/T for estimation of thermodynamic parameters (B) for AB25 (C0=250 mg/L,

pH3.0) and MB (C0=250 mg/L, pH 9.0) on natural sepiolite, respectively.

Table1 Kinetics data for adsorption of AB25 (C0=250 mg/L, pH3.0)and MB (C0=250 mg/L, pH 9.0) on sepiolite

Dye T(K) First-order Second-order Intraparticle diffusion

k1(1/h) qe. calc(mg/g) r21(1/h) k2(1/h) qe,exp(mg/g) qe,calc(mg/g) h (h) r22 ki(1/h) C r2p

293 1.236 18.263 0.798 2.875 15.662 15.73 86.52 0.987 8.42 32.68 0.972

AB25 303 1.185 19.787 0.981 2.566 17.853 17.96 67.34 0.963 6.31 27.54 0.965

313 1.332 21.386 0.886 2.387 16.725 17.00 58.86 0.988 5.87 21.65 0.974

323 1.254 23.458 0.673 2.651 19.876 20.12 83.21 0.975 6.19 10.89 0.912

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293 0.663 27.841 0.964 1.138 21.869 22.35 47.45 0.969 4.56 12.36 0.935

MB 303 0.782 29.569 0.973 1.386 23.563 23.19 53.68 0.995 3.89 17.98 0.942

313 0.584 30.673 0.955 1.259 25.674 25.89 66.74 0.997 6.78 22.87 0.965
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323 0.618 32.834 0.896 1.094 27.432 27.92 50.98 0.994 5.95 31.64 0.928

Table2 Langmuir, Freundlich and Tempkin parameters for the adsorption of AB25 and MB onto sepiolite at different

temperatures

Dye T(K) Langmuir isotherm Freundlich isotherm D-R isotherm

Q0 b K Xm E
RL r2 kF(mg/g) n r2 r2
2 2
(mg/g) (1/mg) (mol /kJ ) (mg/g) (kJ/mol)

0.042-
293 53.78 0.032 0.989 5.3 0.48 0.913 6.423 36.78 0.281 0.896
0.598
AB25
0.038-
323 56.53 0.038 0.997 6.8 0.49 0.928 4.825 40.54 0.362 0.898
0.502

0.032-
MB 293 78.42 0.056 0.934 2.6 1.32 0.992 3.679 36.63 0.435 0.928
0.456

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0.025-
323 89.16 0.059 0.958 3.9 1.36 0.995 1.966 40.92 0.496 0.935
0.408
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Table 3 Thermodynamic parameters of AB25 and MB onto natural sepiolite at different temperatures

Dye T(K) Ea(kJ/mol) kc ΔG0(kJ/mol) ΔH0(kJ/mol) ΔS0(J/mol K)

293 0.685 -0.817

AB25 303 28.89 0.539 -0.652 -15.231 -16.758

313 0.427 -0.473

323 0.312 -.0328

293 0.545 -0.642

MB 303 20.35 0.438 -0.526 6.541 10.396

313 0.382 -0.365

323 0.201 -0.206

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