Removal of Basic Violet 14 from aqueous solution using sulphuric acid activated materials
© The Author(s). 2016
Received: 25 December 2015
Accepted: 5 May 2016
Published: 17 May 2016
In this study the adsorption of Basic Violet, 14 from aqueous solution onto sulphuric acid activated materials prepared from Calophyllum inophyllum (CS) and Theobroma cacao (TS) shells were investigated. The experimental data were analysed by Langmuir, Freundlich and Temkin isotherm models. The results showed that CS has a superior adsorption capacity compared to the TS. The adsorption capacity was found to be 1416.43 mg/g for CS and 980.39 mg/g for TS. The kinetic data results at different concentrations were analysed using pseudo first-order and pseudo-second order model. Boyd plot indicates that the dye adsorption onto CS and TS is controlled by film diffusion. The adsorbents were characterised by scanning electron microscopy. The materials used in this study were economical waste products and hence can be an attractive alternative to costlier adsorbents for dye removal in industrial wastewater treatment processes.
KeywordsSulphuric acid activated materials Adsorption Dye removal Equilibrium Kinetics
Colour is an important characteristic of effluent and it leads to serious environmental threat. The highly coloured dyes affect the water bodies by inhibiting sunlight penetration and hence affecting the photosynthetic activity. These highly coloured dyes are extensively used for colouring in industries like textile, paper, leather and cosmetic industries. Dyes and pigments are highly toxic, carcinogenic and mutagenic (Dutta 1994; Yagub et al. 2014). The worldwide dye consumption in textile industry is more than 107 kg/year that is mainly used in fabrics (Ahamed et al. 2007).
As dyes have a complex structure and synthetic origin, it is difficult to decolourise and various treatment methods have different efficiency in treating dye waste water. There are different treatment methods to decolourise dye waste water like coagulation (Orfao et al. 2006), Photocatalytic degradation (Sun et al. 2008), electrochemical, degradation (Fan et al. 2008), chemical oxidation, ozonation and coagulation (Arslan 2001; Kim et al. 2005). However, these processes are costly and cannot be effectively used for a wide range of dye wastewater.
Adsorption using low cost adsorbents is widely used, since it is one of the most effective methods for dye removal from wastewaters because of their unique properties in adsorption of both cationic and anionic dyes. The advantages of adsorption process are simplicity in operation, inexpensive compared to other separation methods, insensitivity to toxic substances and no sludge formation (Waranusantigul et al. 2003).
In treatment of colored effluents different low-cost adsorbents have been investigated at the laboratory scale for effective treatment with different degrees of success (Bhattacharyya and Sharma 2005). Some of the low cost adsorbents are, waste pea shells (Khan et al. 2014), water chestnut peel (Khan et al. 2013), bamboo sawdust (Khan and Nazir 2015), Curcuma angustifolia scales (Maiyalagan et al. 2014), Curry tree seed (Suresh et al. 2011a) Curry tree stem (Suresh et al. 2011b), etc. Still there is a need for effective adsorbents in dye wastewater treatment.
In this study the paper compares the ability of two sulphuric acid activated materials for removing Basic Violet 14 from aqueous solution using the shells of Calophyllum inophyllum (CS) and Theobroma cacao (TS) shells.
Preparation of adsorbent
The raw material Calophyllum inophyllum (CS) shell and Theobroma cacao (TS) shells were collected and it is washed with water to remove the dirt, dust and other surface impurities. The washed shells were dried for 24 h. The dried shells were then soaked in 18N∙H2SO4 (1:2, w/v) and kept in oven at 120 °C for 12 h. This is done to activate the carbonaceous material by chemical activation. The product is washed several times with distilled water and soaked in 1 % sodium bicarbonate solution for 12 h to remove any residual acid and kept in oven at 110 °C for 12 h. The acid treated biomass adsorbent, thus obtained is crushed and sieved to uniform particle size using ASTM standard sieve (Mesh No. 100). The adsorbents thus obtained were labeled as CS and TS.
Batch adsorption experiments
Results and discussion
Characterization of adsorbent
The surface morphologies of the sulphuric acid activated adsorbents CS and TS were analyzed by scanning electron microscroscope (SEM). The surface of the adsorbents CS and TS prior to adsorption process and after the adsorption was shown in Fig. 1a–d. It is clear, that the adsorbents have a rough morphology with considerable porous nature where suitable conditions exist for the dye to be trapped and adsorbed into the adsorbent. The SEM image of CS shows a good morphology compared to TS for adsorption. It is evident from Fig. 1b, that the surface of CS is covered by a layer of Basic Violet 14 and significant changes were observed due to dye adsorption. In TS as a result of entrapment of the dye into the adsorbent a homogeneously dye adhered surface can be observed in Fig. 1d.
Effect of adsorbent dosage
To find the effect of adsorbent dosage on to the adsorbate, a fixed adsorbate concentration of 260 mg/L and a constant volume (50 mL) is taken, keeping all other experimental conditions constant. It is observed that the amount of Basic Violet 14 adsorbed decreases as the concentration of the adsorbent increases. Thus, it can be observed that maximum dye removal occurs at 10 mg to 30 mg in both CS and TS and then decreased with increase in adsorbent mass.
Langmuir, Freundlich and Temkin constants for CS and TS
Q m (mg/g)
K L (L/mg)
K F (mg/g)
K T (L/mg)
From Table 1, Q m, the maximum monolayer adsorption capacity of CS is found to be 1416.43 mg/g and for TS is found to be 980.39 mg/g. The applicability of the linear form of the Langmuir model to CS and TS, proved by the high correlation coefficients R 2 > 0.998 suggests that the Langmuir isotherm provides a good model of the sorption system.
The Freundlich constants KF and n can be calculated from the slope and intercept of the linear plot with log qe versus logCe. The magnitude of the component ‘n’ gives an indication of the favourability of adsorption process and KF is the constant related to the adsorption capacity.
According to Treybal (1980), it has been shown that n > 1, represents favorable adsorption. The n value was found to be 1.85 for CS and 3.51 for TS which indicates favourable adsorption. 1/n indicates the adsorption intensity of dye onto the adsorbent or surface heterogeneity, becoming more heterogeneous as its value gets closer to 0. The isotherm constants Kf and n were calculated from the linear form of the model and the value of Kf, n, and the Correlation Coefficients are given in the Table 1.
The linear form of the Temkin equation is used to analyze the adsorption data and it is observed that the Temkin isotherm fitted well for CS and TS. The Temkin isotherm constants were calculated from the plot of qe versus ln Ce (Fig. 4b) and are given in the Table 1. In CS and TS the Temkin isotherm fitted well with a high correlation coefficient. The isotherm data’s were well represented by the Langmuir, and Temkin isotherm with R2 values fitting in the following series, Langmuir > Temkin > Freundlich. In CS and TS the R2 values were found to be high (>0.99) for all the three isotherms studied, hence, it can be concluded that both monolayer and heterogenous surface conditions exists in the present study. Since CS and TS is observed to have good adsorption capacity and hence it can be used as an effective, low cost adsorbent as an alternative material to commercial activated carbon in the removal of dyes from aqueous solution.
Kinetic model values for the adsorption of Basic Violet 14 on to CS and TS
Pseudo first order values
Pseudo second order values
qe(Calc) (mg g−1)
k2 (g mg−1 min−1)
h (mg g−1min−1)
7.83 × 10−2
7.96 × 10−4
7.18 × 10−2
8.27 × 10−4
6.52 × 10−2
8.42 × 10−4
6.70 × 10−2
5.74 × 10−4
10.13 × 10−2
2.14 × 10−3
9.70 × 10−2
1.69 × 10−3
9.44 × 10−2
1.38 × 10−3
9.05 × 10−2
2.00 × 10−3
A Plot of log(qe − qt) versus time for CS and TS enables to calculate the rate constant k1 and from the slope and intercept of the plot qe(pred) can be calculated. The adsorption kinetics of Basic Violet 14 from aqueous solution by CS and TS is studied and the influence of various operating parameters on the adsorption process is evaluated. It is observed that the dye uptake was very rapid and the saturation time was found to be 60 min in CS and 40 min in TS.
Adsorption capacities of different low cost adsorbents for dye removal from aqueous solution
Adsorption capacity (mg/g)
Basic Violet 10
Khattri and Singh (2000)
Basic Violet 10
Ho et al. (2005)
Basic Violet 10
Namasivayam et al. (2001)
Activated sludge biomass
Basic Violet 3
Chu and Chen (2002)
Basic Violet 3
Khattri and Singh (1999)
Basic Violet 14
Gupta et al. (2008)
Basic Violet 14
Gupta et al. (2008)
Curcuma angustifolia Scales
Basic Violet 14
Maiyalagan et al. (2014)
Calophyllum inophyllum Shells
Basic Violet 14
Theobroma cacao Shells
Basic Violet 14
Intraparticle diffusion coefficient and diffusion coefficient (Di) for CS and TS
Kip (mg/g min0.5)
9.16 × 10−11
8.41 × 10−11
7.64 × 10−11
7.85 × 10−11
1.18 × 10−10
1.13 × 10−10
1.11 × 10−10
1.06 × 10−10
Basic Violet 14 adsorbs effectively in the surface of the two sulphuric acid activated adsorbents CS and TS and equilibrium is attained in 60 min for CS and 40 min for TS. The isotherm data prove monolayer adsorption for CS and TS and the adsorption capacity was found to be 1416.43 mg/g for CS and 980.39 mg/g for TS. The kinetic study proves that the pseudo second order model provides the best fit for both the adsorbents. Film diffusion process is involved in the adsorption of Basic Violet 14 onto CS and TS. The comparative studies on the adsorption of prepared activated carbons CS and TS onto Basic Violet 14 showed a higher percentage of dye removal for CS. This study shows that the sulphuric acid activated adsorbent CS and TS can be used as an effective material in the adsorption of Basic Violet 14 from aqueous solution.
The Author is thankful to Centre for Nanoscience and Technology, Anna University, for SEM analysis and SAIF, IIT Madras for FT-IR analysis.
The author declare that he has no competing interests.
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