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J. Surface Sci. Technol., Vol 24, No. 3-4, pp. 179-193, 2008 2008 Indian Society for Surface Science and Technology, India.

Removal of Rhodamine-B by Adsorption on Walnut Shell Charcoal

of Applied Chemistry, Guru Nanak Dev University, Amritsar-143 005, India. of Chemistry, Guru Nanak Dev University, Amritsar-143 005, India.

Abstract Dyes are among the priority water pollutants. In this study we report the removal of Rhodamine-B from its aqueous solutions by adsorption on walnut shell charcoal using batch technique. The effects of various experimental parameters on adsorption such as contact time, temperature, initial pH, initial dye concentration, sorbent dosage and ionic strength were examined and the optimal experimental conditions were evaluated. At initial pH of 9, the dye studied could be removed effectively in a period of 5 hours. The adsorption data were fitted to Freundlich and Langmuir adsorption isotherms for the calculation of various adsorption parameters. The adsorption results indicated that the dye, Rhodamine-B can be effectively removed from its aqueous solutions by using walnut shell charcoal as an adsorbent. Keywords : Langmuir and Freundlich isotherms, equilibrium time, sorbent dosage, ionic strength.

INTRODUCTION

The presence of waste products in the environment is a world wide problem and it has been highlighted by various environmentalist groups. The organic effluents, produced in industries such as textiles, paper, plastic, cosmetics, rubber, etc., impart intense colour to the water bodies in which it is discharged. Discharging of dyes into water resources even in a small amount can affect the aquatic life and the food web. Dyes can also cause allergic dermatitis and skin irritation and may lead to carcinogenic and other disorders. Today there are more than 10,000 dyes available commercially [1], most of which are not easy to biodegrade because of their stability toward light and oxidation; also these dyes are resistant to aerobic digestion [2] due to their complex aromatic molecular structure and synthetic origin [3]. The use of dyes at
*Author for correspondence. Tel. : +91-183-2256818; Fax : 91-183-2258820

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such a large scale often poses pollution problems in the form of coloured wastewater discharged into environmental water bodies, which cut transmission of sunlight into streams and thereby reduces photosynthetic activity [4]. Some dyes are known to be toxic or mutagenic and carcinogenic [5]. Use of variety of dyes and chemicals in the dyeing processes causes considerable variation in the wastewater characteristics like pH, colour and chemical oxygen demand (COD). The conventional methods of sewage treatment, such as primary and secondary treatment systems are not suitable for the treatment of effluents containing dye molecules because these molecules are very complex in nature and are stable to heat and light. The adsorption process provides an attractive and alternative treatment, especially if the adsorbent is inexpensive and readily available. Granular activated carbon is the most popular adsorbent and has been used with great success [6], but is expensive. Consequently, many investigators have studied the feasibility of using low cost substances, such as plum kernels [7], chitin [8], peat [9], natural clay [10], boiler bottom ash [11], bagasse pith [12], orange peel [13], banana pith [14], tea leaves [15], pea shells charcoal [16], saw dust [17,18], rice husk ash [19,20], perlite [21], chitosan [22], eichhornia ash [23], bagasse fly ash [24], lemon peel [25], bottom ash [26], etc as adsorbents for the removal of dyes from wastewaters. Critical reviews of low cost adsorbents for wastewater treatment are available [27-29]. The present study investigates the adsorption of Rhodamine-B (RB) on a naturally occurring cheaper source of adsorbent, namely, walnut shell charcoal (WSC), which is available in plenty in India. Various parameters affecting the adsorption have been studied. Data have been fitted to Freundlich and Langmuir adsorption isotherms. Isotherm constants are calculated and discussed.
EXPERIMENTAL

Materials : The commercial grade Rhodamine-B (RB) dye obtained from Qualigens Fine Chemicals, Mumbai, was used as such without further purification. The characteristics of RB are given in Table 1 and its structure is given in Fig. 1. All the other chemicals used, were of AR grade. Water used was deionised and doubly distilled. Method : Preparation of adsorbent The walnut shells were extensively washed with tap water to remove soil and dust, sprayed with distilled water and then dried in an oven at 100C. Then the adsorbent materials were burnt in the absence of free access of air to get its charcoal. The charcoal of walnut shells (WSC) was sieved to different particles sizes and then the particles in the size ranges between 200250 microns were preserved in the desiccator for subsequent use.

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45170 C28H31N2O3Cl 479.02 554 60000.0

mol1

cm1)

II

III Fig. 1. Structure of Rhodamine-B in acidic (I), neutral (II) and alkaline (III) aqueous media.

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Preparation of dye solutions The dye stock solution was prepared by dissolving accurately weighed dye in known volume of distilled water. The serial dilutions were made by diluting the dye stock solution in accurate proportions to the desired initial concentrations. The pH of each dye solution was adjusted with 0.1M HCl or NaOH using a pH meter Adsorption experiments were carried out in a rotary shaker (150 rpm) using 250 ml shaking flasks containing 100 ml of dye solutions of different concentrations at various initial pH values. Various fixed amounts of adsorbent were added to each flask and then the flasks were sealed to prevent any change in volume of the solution during experiments. After shaking the flasks for predetermined time intervals at a given temperature, the samples were taken out from the flasks and the dye solutions were separated from the sorbent by filtration with whatman filter paper 42 after the filter paper is completely soaked with the dye solution. Dye concentrations in the filtrate were estimated by measuring absorbance at the max of the dye with 160-A UV-VIS Spectrophotometer (Shimadzu, Japan) and computing from a calibration curve. The percent dye sorbed by the adsorbent at a given temperature, initial dye concentration, initial pH, adsorbent dose, ionic strength (when salts are added) and contact time, was calculated in each case using the following equation : q = (Co - Ce) /Co X 100 where C o and C e are the initial and equilibrium concentrations of the dye, respectively. The experiments were conducted in duplicate and the negative controls (with no sorbent) were simultaneously carried out to ensure that sorption was by the adsorbent material and not by the container.
RESULTS AND DISCUSSION

Effect of Contact Time %Dye sorbed were estimated at different times keeping the other parameters fixed and the results are shown in Fig. 2. It was observed that the rate of removal of Rhodamine B increases with increase in contact time. 5 h was taken as the equilibrium time for subsequent experiments as shown by the figure.
Effect of pH

Because the initial pH of solution can significantly influence adsorption of dyes, the effects of pH on dye adsorption on the WSC was studied. The value of pH used ranged from 3 to 11. As elucidated in Fig. 3, the removal was appreciable when

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% Dye sorbed

Time / h
Fig. 2. Effect of contact time on adsorption of Rhodamine-B. (Walnut shell charcoal = 1 g, pH = 9, temperature = 40 C and initial dye concentration = 2.92 105 mol dm3.)

% Dye sorbed

pH

Fig. 3. Effect of pH on adsorption of Rhodamine-B. (Walnut shell charcoal = 1 g, equilibrium time = 5 h, initial dye concentration = 2.92 105 mol dm3 and temperature = 40 C.

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the initial pH medium was kept basic. The dye removal was maximum at pH 9 and then there was a decreasing trend. Dye removal kept constant at pH less than 5. The possible reason for such type of behaviour is due to the fact that basic dyes are positively charged. As initial pH of the test solution increased, the number of negatively charged adsorbent sites increased and positively charged adsorbent sites decreased which favours the adsorption of positively charged dye cation due to electrostatic attraction. Thus at higher pH, adsorption will be more and at lower pH, adsorption will be lesser. Also lower adsorption of basic dyes at acidic pH is due to the presence of excess H+ ions competing with the dye cations for the adsorption sites. For this reason pH 9, where maximum removal was observed, was selected for subsequent experimental work.
Effect of Dye Concentration and Temperature

The influence of dye concentration on % dye adsorbed was studied at three temperatures. The effect of dye concentration was studied by keeping the adsorbent dose constant at 1g. The concentration of dye was in the range of 1.85 2.92 105 mol dm3. As shown in Fig. 4, there was regular decrease in percentage of colour removal when the concentrations of the dye were increased. Similar results have been observed by some other workers [30]. A decrease in colour removal upto 7% was observed when the concentration of RB was increased from 1.85 to 2.92

% Dye sorbed

[Dye] 104 / mol dm3 Fig. 4. Effect of concentration of Rhodamine-B on %Dye sorbed at various temperatures. ( 40C, 50C, 60C) (Walnut shell charcoal = 1g; pH = 9 and equilibrium time = 5 h.)

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105 mol dm3. However, it had been seen that the decrease in percentage colour removal was more pronounced at higher temperatures.
Effect of sorbent dose

The effect of sorbent dose on the removal of the dye is shown in Fig. 5. The percentage of the dye sorbed increased as the sorbent dose was increased over the range, 1 - 7 g. The adsorption of the dye increased from 40 to 75% with the increase in sorbent dose. This observation is consistent with Langmuir hypothesis of an increasing competition among adsorbent particles for organic substances with increasing number of adsorbent particles per unit volume [31].

% Dye sorbed

Adsorbent dosage / g
Fig. 5. Effect of variation of amount of walnut shell charcoal on adsorption of the dye, Rhodamine-B. ( pH = 9, equilibrium time = 5 h, temperature = 40 C and initial dye concentration = 2.92 105 mol dm3.)

Effect of ionic strength

The effect of ionic strength on adsorption of the dye was studied by the addition of sodium chloride and potassium chloride to the solution. The concentration of both the salts were kept in the range of 0 to 0.5 M. As shown in Fig. 6, increasing the ionic strength of the solution caused decrease in adsorption percentages of the dye. This could be attributed to the competition phenomenon between the dye molecules

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% Dye sorbed

[Salt] / M Fig. 6. Effect of ion strength on the adsorption of Rhodamine-B (A-with NaCl; B-with KCl) (Walnut shell charcoal = 1 g, pH = 9, equilibrium time = 5 h, temperature = 40 C and initial dye concentration = 2.92 105 mol dm3.)

and the ions for the same sites of the adsorbent. From the results in Fig. 6, it can be seen that in the presence of NaCl, the % dye sorbed decrease upto 60% and in presence of KCl at the same concentration, decrease is upto 40%. So it can be concluded that an effluent containing Rhodamine-B have to be cleared off from the ions before their removal by adsorption, otherwise the presence of these ions in the solution can hinder the adsorption of dye on WSC.
Freundlich Adsorption Isotherm

The data so obtained were fitted to Freundlich and Langmuir adsorption isotherms. The Freundlich isotherm is represented as :
log x 1 log k log C e m n

where x/m is the amount of dye adsorbed per unit weight of the adsorbent, Ce, is the equilibrium concentration, k and n are empirical constants and their values were obtained from the intercepts (log k) and slopes (1/n) of the linear plots of log x/m versus log Ce (Fig 7). Values of n and k are shown in Table 2. The quantity 1/n is less than unity; it indicates favourable adsorption [32]. Chopra et al. [33] have

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40

log (x/m)

log Ce 50

log (x/m)

log Ce 60

log Ce Fig. 7. Plot of log (x/m) vs log Ce at 40C, 50C and 60C.

log (x/m)

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TABLE 2.
n and k values for Rhodamine-B on Walnut shells charcoal (WSC) at different temperatures Temp. (C) 40 50 60 Slope 0.5874 0.5638 0.5432 Intercept 0.160 0.236 0.590 n 1.70 1.77 1.84 k 0.69 0.58 0.26

WSC = 1 g, pH = 9 and equilibrium time = 5 h.

concluded that values of n greater than unity indicates that relative adsorption decreases with increase in the concentration of the dye, as is also evident from Fig. 4.
Langmuir Adsorption Isotherm

The Langmuir isotherm is represented as follows :

where Ce is the concentration of the dye solution at equilibrium, q is the mass of the dye adsorbed per gram of the adsorbent. Cm is the mass of the dye that 1 gm of adsorbent can adsorb when the monolayer is complete and b is the isotherm constant for particular adsorbate-adsorbent combination. The Cm and b values were calculated from the intercept (1/Cm) and slope (1/bCm) of linear plots of 1/q versus 1/Ce. The values are given in Table 3 and plots are shown in Fig. 8. The plots are linear and the correlation coefficients are in between 0.930.98 hence the dye
TABLE 3.
Cm and b values for adsorption of Rhodamine-B on Walnut shell charcoal (WSC) at various temperatures. Temp. (C) 40 50 60 Slope 0.2036 0.2694 0.5505 Intercept 25543 27180 41421 Cm (mol dm3) 3.91 10 3.68 10 2.41
5 5

b (1 mol1) 125616 100868 75374

Cm (mg/g) 18.7 17.6 11.5

105

WSC = 1 g, pH = 9 and equilibrium time = 5 h.

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40
(1/q) 104

(1/Ce) 105 50
(1/q) 104

(1/Ce) 105

60
(1/q) 104

(1/Ce) 105 Fig. 8. Plots of 1/q vs 1/Ce at different temperatures, 40C, 50C and 60C, respectively.

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followed the Langmuir model at the chosen concentration range. The adsorption capacities are found to be different at different temperatures. The maximum sorption capacity (Cm) was found to be 18.7 mg/gm of absorbent for RB at 40C, whereas it decreases to 17.6 and 11.5 mg/g at 50C and 60C, respectively. Hall et al. (34) have suggested a dimensionless equilibrium parameter, namely, R, in order to reveal the essential characteristics of Langmuir isotherm relating R with the Langmuir constant b and the initial concentration of the adsorbate solution, Co, i.e., R = 1/ (1+bCo). R> 1 and R in the range, 0 1 imply unfavaurable and favourable adsorption, respectively. The values of R were determined at three different temperatures and are given in Table 4. It has been found that in all the cases and at all temperatures, the values of R were in between zero and one which indicate highly favourable adsorption and the applicability of Langmuir isotherm. The half-adsorption time of the dye, t, is the time required for the WSC to take up half as much dye as it would otherwise take at equilibrium [21]. This time is often used as a measure of the rate of adsorption and is given by t = 0.693 / k
TABLE 4.
Values of R of dye Rhodamine-B adsorption on WSC at different temperatures. Initial dye concentration Co 105 (mol dm3) 1.85 1.99 2.12 2.25 2.38 2.52 2.65 2.78 2.92
b in dm3 mol1

Values of R 40C b=125616 0.300 0.286 0.273 0.261 0.251 0.240 0.231 0.223 0.214 50C b=100868 0.349 0.333 0.319 0.306 0.294 0.282 0.272 0.263 0.253 60C b=75374 0.418 0.400 0.385 0.370 0.358 0.345 0.334 0.323 0.312

Ce x 105 Ce x 105

mole L-1

K x 105

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Rate constant values of all the t systems were also calculated by using the equation, C = Coekt, along with t values (Table 5). The results agree with the values previously reported for such systems [35]. The surface residence times are large indicating strong bonding to the surface active sites and the adsorbate-adsorbent interactions are likely to be specific ones.
TABLE 5.
Rate constant k and t1/2 values for the adsorption of Rhodamine-B at various concentrations and at different temperatures on walnut shell charcoal.
40C Co105 (M) 1.85 1.99 2.12 2.25 2.38 2.52 2.65 2.78 2.92 Ce105 (M) 0.44 0.50 0.55 0.60 0.65 0.70 0.75 0.81 0.86 k105 s1 7.98 7.67 7.50 7.34 7.21 7.12 7.01 6.85 6.79 t1/2 103 s 8.69 9.03 9.25 9.44 9.61 9.64 9.78 10.11 10.20 Ce105 (M) 0.54 0.60 0.66 0.72 0.78 0.84 0.90 0.96 1.02 50C k105 s1 6.84 6.66 6.48 6.33 6.20 6.10 5.99 5.91 5.84 t1/2103 s 10.13 10.40 10.69 10.94 11.17 11.36 11.57 11.73 11.87 Ce105 (M) 0.89 0.96 1.05 1.14 1.23 1.32 1.41 1.50 1.60 60C k105 s1 4.06 4.05 3.90 3.78 3.67 3.59 3.50 3.43 3.34 t1/2103 s 17.07 17.11 17.76 18.33 18.88 19.30 19.80 20.20 20.75

Co = Initial concentration and Ce = Equilibrium concentration

CONCLUSION

The present study showed that the WSC is a promising adsorbent for the removal of Rhodamine-B from aqueous solutions, since it is easily available in large quantity and its treatment method is very economical. At initial basic pH, the dye could be removed effectively. The isothermal data of adsorption followed both Langmuir and Freundlich isotherms.

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