World Journal of Applied Environmental Chemistry All Rights Reserved Euresian Publication 2012 Available online at: www.environmentaljournals.

.org Volume 1, Issue 1: 22-29

Open Access

Research Article

Adsorption of Reactive Dye Using Low Cost Adsorbent: Cocoa (Theobroma Cacao) Shell
Mylsamy Shanker and Theivarasu Chinniagounder Department of Chemistry, PSG College of Technology, Coimbatore 641 004, India. Corresponding author: shankermylsamy@gmail.com

Abstract:
The adsorption behavior of Reactive Yellow 2(RY2) from aqueous solution onto activated carbon prepared from Cocoa (Theobroma cacao) shell was investigated under various experimental conditions. To evaluate the adsorption capacity, initial dye concentration and contact time, effect of solution pH and adsorbent dosage were investigated in a batch mode. Experimental isotherm data was represented with Langmuir, Freundlich, Temkin and Harkins-Jura isotherm models. The adsorption data were found to follow the Langmuir model better than the other models. The data were also fitted to kinetic models such as pseudofirst order, pseudo-second order, Elovich and intraparticle diffusion models. Results indicated that Cocoa shell activated carbon (CSAC) could be a low cost adsorbent for the removal of RY2 from aqueous solution.

Keywords: Effluents, cocoa shell, adsorption, activated carbon, Reactive yellow. Introduction:
Wastewater discharged from dyeing industries causes a serious threat to environment, generally high in both color and organic content (Doralice and Regina, 2001). Color removal from textile effluents has been the target of great attention in the last few years, not only because of its potential toxicity, but mainly due to its visibility problems (Dave et al., 2011). The complex aromatic structures of dyes make them more stable and more difficult to biodegrade (Santhy and Selvapathy, 2006). Conventional methods for removing dyes include adsorption, ozonation, electrocoagulation, ultrafilteration, reverse osmosis, flocculation, oxidation, ion-exchange, etc. (Tim Robinson et al., 2001, Esther Forgacsa et al., 2004). Adsorption has been found to be highly efficient for the removal of color in terms of ease of operation, initial cost and simplicity of design (Garg et al., 2004). The most commonly used adsorbent for color removal is activated carbon, because of its capability for efficiently adsorbing a broad range of different types of adsorbate (Hameed et al., 2007). At present, there is a growing interest in using low-cost and non conventional alternative materials instead of traditional adsorbents (Barka et al., 2011). Several researchers have been studying the use of alternative materials, which, although less efficient, involve lower costs (Joana Dias et al., 2007). Utilization of agricultural solid waste is of great significance for the preparation of activated carbon (Malik, 2004). In this investigation, activated carbon prepared from cocoa shell, an agricultural solid waste was applied for the removal of RY2 dye from aqueous solution.

2.0 Materials and Methods: 2.1 Adsorbent Preparation:

Cocoa (Theobroma cacao) shell collected from local agricultural field was airdried and allowed to chemical activation, by the addition of 50% sulfuric acid with constant stirring (w/v). The resulting product obtained was kept in muffle furnace maintained at 550C for 7 hours. The carbon obtained was washed with double distilled water and soaked in 10% sodium bicarbonate solution and allowed to stand overnight to remove the residual acid from pores of the carbon. The material was washed with distilled water, until the pH of the adsorbent reached 7.0. Then it was dried in a hot air oven at 1005C for 12 hours. The dried material was ground and sieved to get the particle size of 150 m and stored in an airtight container (Namasivayam and Kadirvelu, 1997). The physico-chemical characteristics of CSAC were studied as per the standard testing methods and the physico-chemical properties were reported in our earlier paper (Theivarasu et al., 2011); some important characteristics are given in Table 1.

2.2 Adsorbate Preparation: Reactive yellow

2 (Molecular formula: C25H15Cl3N9Na3O10S3, M.W.: 872.96, C.I. no. 18972, CAS: 50662-99-2) was purchased from Sigma-Aldrich company and used without purification. Stock solution of dye was prepared by dissolving 1 gm of dye in 1000 ml of double distilled water to give the concentration of 1000 mg/L. The stock solutions were diluted with known initial concentrations say 20, 40, 60 and 80 mg/L in accurate proportions.

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Table 1: Characteristics of CSAC Sr. Parameters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 pH Moisture content (%) Ash content (%) Volatile matter (%) Decolourising power(mg/g) Surface area(m/g) Specific gravity Phenol adsorption capacity (%) Iodine number(m /g) Apparent density (g/cm ) Porosity (%) Cation exchange capacity (mmol/g) Conductivity(S/cm) Carbon (%) Nitrogen (%) Sulphur(%) Hydrogen (%) Iron (%) Matter soluble in water (%) Matter soluble in 0.25M HCl (%) Carboxylic acid (meq/g) Basic group (meq/g) Phenolic(meq/g) Lactones(meq/g)
3 2

qe = (Co Ce )
Result

V W

(1)

6.7 15.38 13 18.1 45.8 190.63 0.65 6.8 419 0.34 47.69 2.79 1.89 65.88 0.49 0.54 1.46 1.10 1.63 4.88 0.29 0.03 0.05 0.04

where Co and Ce are the initial and equilibrium adsorbate concentrations (mg/L), respectively, V is the volume of solution (L) and W is the mass of adsorbent (g). The dye removal percentage can be calculated as follows:

% removal =

C0 Ce 100 C0

(2)

where C0 and Ce are the liquid-phase concentrations of dye at initial and equilibrium (mg/L), respectively. Adsorption data obtained from the effect of initial concentration and contact time were employed in testing the applicability of isotherm and kinetic equations, respectively (Kannan and Veemaraj, 2009).

3.0 Results and Discussion: 3.1 Effect of Initial Concentration and Contact Time: For this study, RY2 solution with
initial concentrations 20, 40, 60 and 80 mg/L were agitated with 100 mg of CSAC at 35C. As shown in Figure a, the adsorption at different dye concentrations was rapid at the initial stages and then gradually decreases with the progress of adsorption until the equilibrium was reached. The rapid adsorption at the initial contact time can be attributed to the availability of the positively charged surface of activated carbon (Ahmed El Nemr et al., 2009). The contact time needed for RY2 solution to reach equilibrium was 90 min.

2.3 Adsorption Experiments: Adsorption experiments were carried out in temperature controlled orbital shaker at a constant speed of 125 rpm using 250 mL conical flasks containing 100 mg of CSAC with 50 mL of dye solution at 35C. All the experiments (except the study of pH effect) were carried out at a pH of 60.5. After agitating the flasks for predetermined time intervals, samples were withdrawn from the flasks and the adsorbents were separated from the solution by centrifugation (REMI make) at 2000 rpm for 10 minutes. The absorbance of the supernatant solution was estimated to determine the residual dye concentration, measured at max = 402 nm spectrophotometrically using Elico make UVVisible spectrophotometer. The amount of adsorbate adsorbed at equilibrium condition, qe (mg/g) was calculated using the following equation:

Figure a. Effect of initial concentration and contact time The results indicated that there was no change in the sorption capacity after 90 min; therefore 120 min was fixed as the agitation time for isotherm studies.

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3.2 Effect of Adsorbent Dosage: In order to

investigate the effect of adsorbent mass on the adsorption, a series of adsorption experiments was carried out with different adsorbent dosages at initial concentration of 40 mg/L without changing the volume of dye solution (50 ml) with constant speed of 125 rpm for 2 hours. Similarly the pH (60.5) and temperature (35C) was kept constant. The results follow the expected pattern, in which the percentage sorption increased with increased adsorbent dosage (Figure b). The higher percentage removal with increase in carbon dosage was due to the increase in surface area or due to conglomeration of carbons at higher doses (Kannan and Sundaram, 2001).

Figure c: Effect of initial pH

4.0 Adsorption Isotherms: The analysis of the isotherm data is important to develop an equation, which accurately represents the results and could be used for designing process (Ho et al., 2009). The equilibrium of a solute separated between liquid and solid phase is described by various models of adsorption isotherms such as Langmuir, Freundlich, Temkin and Harkins-Jura isotherm models. The applicability of the isotherm equations was compared by judging the 2 correlation coefficient, r (Demirbas and Nas, 2009). 4.1 Langmuir Isotherm: Langmuir adsorption isotherm model is usually adopted for homogenous adsorption and it is used successfully in monomolecular adsorption processes (Nevine Kamal Amin, 2009). Linear form of Langmuir model is expressed by

Figure b: Effect of adsorbent dosage

3.3 Effect of Initial Solution pH: pH is one of

the most important factors controlling the adsorption of dye onto adsorbent particles, which affects the surface charge of the adsorbents as well as the degree of ionization of different pollutants (Doan et al., 2007). The hydrogen ion and hydroxyl ions are adsorbed quite strongly and therefore the adsorption of other ions is affected by the pH of the solution. If electrostatic interaction was the only mechanism for the dye adsorption, then the removal capacity should be at a maximum within the range pH 6-8. In this pH range the surface of activated carbon is positively charged and dyes are negatively charged (Chun et al., 2004). The effect of solution pH was studied between 1 to 10, initial pH controlled by the addition of 0.1M HCl or 0.1M NaOH and agitated with 100 mg of CSAC for 2 hours at 35C. The effect of initial pH of dye solution on the adsorption of RY2 for initial dye concentration of 40 mg/L was illustrated in Figure c. In view of the above results, higher percentage removal was occurred at pH 6.0 and remaining tests were conducted at pH 60.5.

Ce C 1 = + e qe bQ0 Qo

(3)

The linear plot of Ce/qe versus Ce was shown in Figure d(a). The constants Q0 and b can be calculated from slope and intercept of the plot and the values are tabulated in Table 2. The shape of the Langmuir isotherm was investigated by the dimensionless constant separation term (RL) to determine high affinity adsorption (zacar and engil, 2002). RL was calculated as follows:

RL =

1 1 + bC

(4)
0

RL indicates the type of isotherm to be irreversible (RL= 0), favorable (0 < RL< 1), linear (RL = 1) (or) unfavorable (RL > 1) (Emrah Bulut et al., 2008). In the present investigation, the RL values were less than one which shows the adsorption process was favorable.

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4.2 Freundlich Isotherm: The Freundlich

isotherm model was chosen to estimate the adsorption intensity of the adsorbate on the adsorbent surface (Surya Narayan Dash and Ramachandra Murthy, 2010). Linear form of Freundlich model is expressed by

ln Ce = ln k f +

1 ln Ce n

1/n values indicate the type of isotherm to be irreversible (1/n = 0), favorable (0 < 1/n < 1), unfavorable (1/n > 1) (Chilton et al., 2002). The linear plot of lnqe versus lnCe was shown in figure d(b). The values of 1/n and kf can be calculated from the slope and intercept respectively and the results are given in Table 2. The value of 1/n was less than one indicating the favorable adsorption.

(5)

Figure d. Isotherm plot for the adsorption of RY2 onto CSAC a. Langmuir plot b. Freundlich plot c. Temkin plot d. Harkins-Jura plot

4.3 Temkin Isotherm: Temkin isotherm suggests that the heat of adsorption of all the molecules in the layer would decrease linearly with coverage due to adsorbate/adsorbent interactions (Srisuda Saeung and Virote Boonamnuayvitaya, 2008). The linear form of Temkin isotherm is expressed as qe = ln + ln Ce
(6)

4.4 Harkins - Jura isotherm: Harkins - Jura

isotherm assumes the presence of multilayer adsorption with the existence of heterogeneous pore distribution (Ola Abdelwahab, 2008). The linear form of Harkins-Jura isotherm is expressed as

1 B 1 = log Ce 2 A A qe

(7)

where = (RT)/b, T is the absolute temperature in K, R the universal gas constant, 8.314 J/molK, the Temkin isotherm constant (L/g) and b is related to the heat of adsorption(J/mol). A plot qe versus lnCe gives a linear plot (Figure d(c)) from which the constants for Temkin isotherms was calculated and given in Table 2.

where Ce is the equilibrium concentration of the dye in solution (mg/L), qe is the amount of dye adsorbed onto the adsorbent (mg/g), A and B are the isotherm constants. The constants A and B can 2 be calculated from the plot of 1/qe versus logCe (Figure d(d)) and the values are tabulated in Table 2. Based on the correlation coefficient for all the isotherm models studied, Langmuir model gave 2 the highest r value showing that the adsorption of

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Table 2: Results of isotherm parameters for the adsorption of RY2 onto CSAC Models Langmuir Qm(mg/g) 52.63 Freundlich kf (L/g) 3.8 Temkin (L/g) 0.13 Harkins- Jura A 333.33 RY2 onto CSAC was best described by this model followed by Temkin and Freundlich isotherm models. Harkins-Jura isotherm model presented Isotherm constants b x 10 (L/ mg) 15.2 1/n 0.452 (kJ/mol) 12.14 B 2.33
-3

RL(L/mg) 0.2680-0.5234 n 2.21

0.997 r
2

0.981 r
2

0.995 r
2

0.908

poor fit of the experimental data than the other isotherms.

a. Pseudo-first order

Figure e. Kinetic plot for the adsorption of RY2 onto CSAC b. Pseudo-second order c. Elovich d. Intraparticle diffusion

5.0 Adsorption Kinetics:

Kinetic studies are necessary to optimize different operation condition for the adsorption of dyes. The kinetics of RY2 onto CSAC was analyzed using pseudo- first order kinetic, pseudo- second order kinetic, Elovich and intraparticle diffusion models.

5.1 Pseudo First Order Kinetic Model:

The model was suggested for the adsorption of solid/liquid systems (Mohammad Al-Ghouti et al., 2009). The differential equation is described as follows:

dq t = k1 ( q e q t ) dt

(8)

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The integrated linear form of the model is as follows:

log(q e q t ) = log q e

k1 t 2.303

(9)

where qe is the amount of adsorbate adsorbed per unit mass of adsorbent at equilibrium(mg/g), qt is the amount of adsorbate adsorbed at contact time t (mg/g), k1 is the pseudo-first order rate constant -1 (min ). A plot of log (qe-qt) versus t gives a linear line (Figure e(a)) from which the values of k1 and qe were determined from the slope and intercept respectively and presented in Table 3.

where qt is the sorption capacity at time t (mg/g), is the initial sorption rate (mg/gmin) and is the desorption constant (g/mg) during any one experiment. Integrating this equation by applying the boundary conditions qt= 0 at t= 0 and qt = qt at t= t equation becomes

qt =

ln

ln t

(14)

5.2 Pseudo Second Order Kinetic Model:

The adsorption mechanism over a complete range of the contact time is explained by the pseudo second order kinetic model (Yuh-Shan Ho, 2003). The differential equation is described as follows:

A plot of qt versus lnt yields a linear relationship with a slope of 1/ and an intercept of 1/ln(). The results of Elovich plot for the adsorption of RY2 onto CSAC at various initial concentrations are given in Table 3 (Figure e(c)). The plot was linear with good correlation coefficient (0.973-0.977). The initial adsorption rate, , increases from 1.99 to 6.69 mg/g min with increasing the initial dye concentration from 20 to 80 mg/L. Table 3: Results of kinetics parameters for the adsorption of RY2 onto CSAC Concentration 20 40 60 80 (mg/L) Pseudo-first order kinetics k1 10 (1/min) qeexp(mg/g) qecal(mg/g) r Pseudo-second order kinetics -3 k2 x10 (g/mg min) qecal (mg/g) h r
2 2 -2

dqt = k 2 ( q e qt ) 2 dt

(10)

The linearised form of the above model is

t 1 t = + 2 qt k 2 qe qe

(11)

The initial adsorption rate, h (mg/g min), as t 0 can be defined as

3.68 9.5 7.24 0.98 9

h = k 2 qe

(12)

3.91 18.6 8 15.6 0.98 2

where k2 is the rate constant of pseudo-second order adsorption (g/mg min). A plot of t/qt versus t gives a linear relationship (Figure e(b)), from which qe and k2 were determined from the slope and intercept of the plot respectively and presented in Table 3. For all the systems studied, good 2 correlation coefficients (r ) were obtained by fitting the experimental data to pseudo-second order kinetics than that for the pseudo-first order kinetic model. Therefore, the sorption was more favorably by pseudo-second order kinetic model, which was based on the assumption that the rate limiting step may be chemisorption involving valency forces through sharing or exchange of electrons between sorbent and sorbate (Wang and Li, 2007; Augustine Ofomaja 2008).

3.68 27.7 1 23.3 9 0.97 6

3.45 36.9 7 29.5 8 0.98 0

6.2 10.9 0.73 0.99 7 1.99 0.48 0.97 3

2.9 21.7 1.36 0.99 7 3.50 0.23 0.97 5 1.30 5.99 0.91 5

1.9 32.3 1.96 0.99 7 4.90 0.16 0.97 7 1.96 8.56 0.92 1

1.4 43.5 2.6 0.99 6 6.69 0.1 0.97 7 2.59 11.5 0.92 7

Elovich (mg/ g min) (g/mg) r

2

5.3 Elovich Model: Elovich equation has been

widely used to describe the adsorption of gas onto solid systems and adopted to examine the mechanism of the adsorption process (Senthilkumar et al., 2006). It is generally expressed as follows

Intraparticle Kid(mg/ g min ) C (mg/g) r

2 1/2

0.64 3.27 0.91 3

dqt = exp( qt ) dt

(13)

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5.4 Intraparticle Diffusion Model: It is

suggested to identify the diffusion mechanism and rate controlling steps that affects the adsorption process (Qingye Sun and Linzhang Yang, 2003). According to this theory

qt = k i d t 1 / 2 + C

(15)

where kid is the intraparticle diffusion rate 1/2 constant (mg/g min ), C is the intercept (mg /g). 1/2 A plot of qt versus t gives a linear relationship (Figure e(d)), from which kid values determined from the slope was presented in Table 3.The intercept of the plot reflects the boundary layer effect (Vasanth Kumar and Vadivelan, 2005). If the regression of the plot is linear and passes through the origin, then intraparticle diffusion is the sole rate-limiting step (Hameed et al., 2008). However, the linear plots at each concentration did not pass through the origin. This indicated that the intraparticle diffusion was not a rate controlling step.

6.0 Conclusion:
Adsorbent derived from cocoa shell, an agricultural waste demonstrated outstanding capability in removing RY2 dye from aqueous solution. The selection of activation depends on initial concentration and contact time, adsorbent dose and initial pH of the solution. The optimal pH for favorable adsorption of dye was found to be 60.5. The equilibrium data have been analyzed using Langmuir, Freundlich, Temkin and HarkinsJura isotherms. The Langmuir isotherm was demonstrated to provide the best correlation for the adsorption of RY2 onto CSAC. The kinetics of adsorption was studied by using pseudo- first order, pseudo- second order, Elovich and intraparticle diffusion models. The results demonstrate that adsorption mechanisms in the system follow pseudo-second order kinetics. The pseudo- second order equation was based on the adsorption capacity on the solid phase and is in agreement with a chemisorption mechanism being the rate controlling step. Analysis of the results with the intraparticle diffusion model showed that intraparticle diffusion is not the rate limiting step. From the obtained results, this research had shown promise for the utilization of CSAC for the removal of RY2 from aqueous solution.

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