Removal of Crystal Violet Dye from Aqueous Solutions onto Date Palm Fiber by Adsorption Technique

Abstract

The adsorption of crystal violet (CV) onto date palm fibers (DPFs) was examined in aqueous solution at 25°C. The experimental maximum adsorption capacity value was 0.66×10⁻⁶. Langmuir, Freundlich, Elovich and Temkin models were applied to describe the equilibrium isotherms. The influence of pH and temperature on dye removal was evaluated. The percentage removal of CV dye by adsorption onto DPF at different pH and temperatures showed that these factors play a role in the adsorption process. Thermodynamic analysis was performed, and the Gibbs free energy Δ𝐺^o, enthalpy change Δ𝐻^o, and entropy Δ𝑆^o were calculated. The negative values of Δ𝐺^o indicate spontaneous adsorption. The negative value of Δ𝐻^o indicates that the interaction between CV and DPF is exothermic, and the positive value of Δ𝑆^o indicates good affinity between DPF and CV. The kinetic data were fitted to a pseudo-second-order model.

1. Introduction

Adsorption using different adsorbents is superior to the other separation techniques because of its efficacy, economy, ability to separate a wide range of chemical compounds, and simple procedure. Research in the past few years has focused on utilizing waste materials from agricultural products because they are inexpensive, ecofriendly, and renewable. Several materials have been studied as potential adsorbents, such as orange peels [1], mango seed husks [2], pineapple stems [3], coconut bunch waste [4], pumpkin seeds [5], and cotton plant waste [6]. Wastewater from dyeing and finishing operations in the textile industry is generally high in both color and organic content. Effluents discharged from dyeing industries are highly colored and can be toxic to aquatic life in the receiving waters [7, 8]. Color removal from textile effluents has received attention due to its visibility even more than its potential toxicity [9, 10]. Saudi Arabia is among the developing countries with a need to establish new industries based on utilizing natural resources in various sectors. Date palm is an important fruit crop of Saudi Arabia and occupies a large percentage of the cultivated land. Thus, using date palm waste to develop new adsorbents for the wastewater treatment by adsorption is quite attractive.

This work studies the removal of CV dye by adsorption using date palm fiber (DPF). The effect of pH and temperature and the thermodynamic parameters are also evaluated. Finally, the adsorption kinetics are investigated.

2. Materials and Methods

The date palm fiber (DPF) used for the preparation of the adsorbent was obtained locally from a farm in the southern region of Riyadh City in Saudi Arabia. The material was sorted, cut, crushed, grinded, and sieved to obtain fine particles. Crystal violet (CV) was supplied by Techno PharmChem, Bahadurgarh (India). The dye content is at least 88%. Distilled water was used to prepare solutions at the desired concentrations by diluting the stock solution. For each individual test, 0.25 g samples of the adsorbent were placed into screw-capped Erlenmeyer flasks containing 25 mL of CV solution at different concentrations, from 0.9 × 10⁻⁵ to 7 × 10⁻⁵mol/L. The flasks were shaken for a sufficient period to achieve equilibrium using an orbital shaker (J. P. Selecta, Spain) at 100 rpm and 25°C. The mixture solution was filtered using Whatman filter paper (125 mm Ø, Cat. no. 1001 125). The dye uptake was monitored spectrophotometrically by measuring the absorbance at 𝜆_max 584 nm. The amount of adsorption at equilibrium, 𝑞_𝑒 (mol/g), was calculated by 𝑞_𝑒=𝐶₀−𝐶_𝑒𝑉𝑚, (1) where 𝐶₀ and 𝐶_𝑒 (mol/L) are the liquid-phase dye concentrations initially and at equilibrium, respectively, 𝑉 is the volume of the solution (L), and 𝑚 is the mass of dry adsorbent (g). The equilibrium data were then fitted using four different isotherm models, namely, the Langmuir, Freundlich, Elovich, and Temkin models.

The percentage removal was studied as a function of pH. The effect of pH on the adsorption process was studied by preparing adsorbent-adsorbate solutions with fixed adsorbent dose (0.25 gm) and dye concentration (3 × 10⁻⁵) but different pH by adding NaOH (1 M) or HCl (1 M) solutions and shaking until equilibrium.

The temperature dependence of CV sorption onto DPF was studied with a constant initial concentration at 100 rpm. The percentage removal at 25, 35, 45, and 55°C was recorded. The thermodynamic parameters Δ𝐺^∘, Δ𝐻^∘, and Δ𝑆^∘ were calculated.

The kinetic study was also performed with a flask shaken only for the desired time period.

3. Results and Discussion

3.1. Adsorption Isotherms

The adsorption isotherm indicates how the adsorption molecules are distributed between the liquid phase and the solid phase when the adsorption process is at equilibrium [11]. The adsorption isotherm of CV onto DPF is illustrated in Figure 1. This isotherm is classified as type S according to the Giles et al. classification, indicating that adsorption becomes easier for increasing concentration. The S curve of the adsorption isotherm generally reflects strong competition between the solvent and the adsorbed species for the adsorbent surface sites [12]. From Figure 1, the experimental maximum adsorption capacity for the dye onto DPF is approximately 0.66 × 10⁻⁶mol g⁻¹.

Figure 1 

Adsorption isotherm of CV onto DPF (experimental conditions: 25°C, 100 rpm, 𝜆max of absorbance =584 nm, and adsorbent mass =0.25 gm per 25 mL of CV solution at different concentrations: 0.9 × 10−5–7 × 10−5).

The fitting of the isotherm data to different models is an important step for finding a suitable model that can be used for design purposes [13]. Linear forms of the Langmuir, Freundlich, Elovich, and Temkin adsorption isotherm models ((2), (3), (4), and (5), resp.) were used to verify the sorption data: 1𝑞_𝑒=1𝒬₀+1𝑏𝒬₀1𝐶_𝑒,log𝑞_𝑒=log𝐾_𝑓+1𝑛log𝐶_𝑒,𝑞ln^𝑒𝐶_𝑒=ln𝐾_𝐸𝒬₀−𝑞_𝑒𝒬₀,𝑞_𝑒=𝐵ln𝐴+𝐵ln𝐶_𝑒, (2)(3)(4)(5) where 𝐶_𝑒 is the equilibrium concentration, 𝑞_𝑒 is the amount of adsorbate adsorbed per unit mass of adsorbent, 𝒬₀ is the maximum adsorption capacity, 𝑏 is the Langmuir constant related to the adsorption rate, 𝐾_𝑓 is the Freundlich isotherm constant related to adsorption capacity (indicating the quantity of dye adsorbed onto the adsorbent), 𝑛 is the Freundlich isotherm constant related to adsorption intensity (indicating the favorability of the adsorption process), 𝐾_𝐸 is the Elovich equilibrium constant, and 𝐵 and 𝐴 are constants related to the heat of adsorption and the equilibrium binding constant, respectively, 𝐵=𝑅𝑇/𝑏, where 𝑅 is the constant gas, 𝑇(K) is the absolute temperature, and 𝑏 is the Temkin isotherm constant.

The Langmuir [14] model assumes uniform energies of adsorption onto the surface and no transmigration of the adsorbate along the plane of the surface. A linear fit to the Langmuir equation yields Langmuir constant (𝑏) and the maximum adsorption capacity (𝒬₀) from the slopes and the intercepts, respectively.

The Freundlich model assumes that as the adsorbate concentration increases, the concentration of adsorbate on the adsorbent surface also increases. The linear form of the Freundlich isotherm model yields a straight line. The slope and intercept of the obtained fit are used to calculate the Freundlich constants 𝑛 and 𝐾_𝑓 [15]. The Elovich model [16] is based on a kinetic principle assuming that the adsorption sites increase exponentially with adsorption, which implies a multilayer adsorption. The Elovich maximum adsorption capacity and Elovich constant can be calculated from the slopes and the intercepts of the plot of ln (𝑞_𝑒/𝐶_𝑒) versus 𝑞_𝑒. The Temkin [17] isotherm equation assumes that the heat of adsorption of all the molecules in the layer decreases linearly with coverage due to adsorbent-adsorbate interactions and that the adsorption is characterized by a uniform distribution of the binding energies up to some maximum binding energy. The Temkin equilibrium constants can be calculated from the slope and intercept of the plot of 𝑞_𝑒 versus ln 𝐶_𝑒. However, all the constants of these models are given in Table 1.

Table 1 

Isotherm model constants for the adsorption of CV onto DPF.

The applicability of the isotherm equations to describe the adsorption process was judged based on the maximum value of adsorption and correlation coefficients (𝑅²), which are a measure of goodness of fit.

For Langmuir, the maximum value of adsorption (𝒬₀) is negative and this observation reflects the inadequacy of this model for explaining the adsorption process, although it shows a good linearity compared to other models (see Figure 2 and Table 1).

Figure 2 

Langmuir plot of CV onto DPF (experimental conditions: 25°C, 100 rpm, 𝜆max of absorbance =584 nm, and adsorbent mass =0.25 gm per 25 mL of CV solution at different concentrations: 0.9 × 10−5–7 × 10−5).

For Freundlich model, the maximum adsorption capacity obtained using the equation is higher than the experimental value, indicating that the experimental adsorption data does not fit this model, although the high 𝑅² value it takes (see Figure 3 and Table 1).

Figure 3 

Freundlich plot of CV onto DPF (experimental conditions: 25°C, 100 rpm, 𝜆max of absorbance =584 nm, and adsorbent mass = 0.25 gm per 25 mL of CV solution at different concentrations: 0.9 × 10−5–7 × 10−5).

The adsorption capacity determined using the linear transformation of the Elovich equation (=0.579 × 10⁻⁶) is approximately equal to the experimental measurements at equilibrium, corresponding to the plateau of the adsorption isotherms (=0.66 × 10⁻⁶). Thus, the assumption of exponential covering of adsorption sites, which implies multilayer adsorption, is in agreement with the experimental results in the studied concentration range. Regarding the 𝑅² value, this model also shows good linearity, with 𝑅² is close to unity, see Figure 4 and Table 1.

Figure 4 

Elovich plot of CV onto DPF (experimental conditions: 25°C, 100 rpm, 𝜆max of absorbance =584 nm, and adsorbent mass =0.25 gm per 25 mL of CV solution at different concentrations: 0.9 × 10−5–7 × 10−5).

For the Temkin isotherm, The value of 𝑅² is the lowest of all studied models. Thus, this model describes the adsorption isotherm of CV onto DPF poorly, see Figure 5 and Table 1.

Figure 5 

Temkin plot of CV onto DPF (experimental conditions: 25°C, 100 rpm, 𝜆max of absorbance =584 nm, and adsorbent mass =0.25 gm per 25 mL of CV solution at different concentrations: 0.9 × 10−5–7 × 10−5).

Thus, it can be said that the experimental adsorption data fit the Elovich model was fairly well compared to the other models based on the maximum value of adsorption and correlation coefficients (𝑅²).

3.2. Effect of pH

Acidity is very important in the adsorption process, especially for dye adsorption. The pH of a medium will control the magnitude of the electrostatic charges imparted by the ionized dye molecules. Both the adsorbent and adsorbate may have functional groups that can be protonated or deprotonated to produce different surface charges in solutions at different pH, resulting in electrostatic attraction or repulsion between the charged adsorbates and adsorbents [18]. Therefore, the effect of pH on the adsorption behavior of the dye on the adsorbent was studied by observing the percentage of dye removal over a wide pH range of 2–11. The variation in the removal of CV with pH is shown in Figure 6. As presented in the figure, the obtained results show that the percentage removal of dye decreases slightly with increasing basicity up to pH 7.0, after which it remains almost constant. This behavior may be due to the increase in negative charge density of surface at acidic pH, resulting in a attraction between the positively charged dye molecule and adsorbent. As the pH increases, the surface charge density on the adsorbent decreases, resulting in electrostatic repulsion from the positive charge of the dye molecule.

Figure 6 

Percentage removal of CV dye onto DPF at different pH values (experimental conditions: 25°C, 100 rpm, 𝜆max of absorbance =584 nm, and adsorbent mass =0.25 gm, and dye concentration =3 × 10−5).

3.3. Effect of Temperature

The effect of temperature on the sorption of CV by DPF is shown in Figure 7. The percentage of dye removal decreases from 94% to 89% for dye as the solution temperature increases from 25 to 55°C. Because the adsorption decreased as the temperature increased, the system is considered to be exothermic. A similar trend was reported by Chandra et al. [19] for the adsorption of MB on activated carbon prepared from durian shell, who explained that as the temperature increased, the physical bonding between the organic compound (including the dye) and the active sites of the adsorbent weakened. In addition, the dye solubility also increased, which caused the interaction between the solute and solvent to become stronger than that between the solute and adsorbent. Therefore, the solute was more difficult to adsorb.

Figure 7 

Percentage removal of CV dye onto DPF at different temperatures (experimental conditions: 25, 35, 45, and 55°C, 100 rpm, 𝜆max of absorbance =584 nm, and adsorbent mass =0.25 gm).

3.4. Thermodynamic Parameters

The thermodynamic parameters for the adsorption of CV on DPF were calculated using the following equations, and the values are given in Table 2 (Figure 8 represents (7)); Δ𝐺^∘=−𝑅𝑇ln𝐾_ads,ln𝐾_ads=Δ𝑆^∘𝑅−Δ𝐻^∘.𝑅𝑇 (6)(7) The equilibrium constants (𝐾_ads) were calculated according to the following equation [20]: 𝐾_ads=dyeconcentrationonthesolidatequilibrium,dyeconcentratiinsolutionatequilibrium (8) where Δ𝐺^∘, Δ𝐻^∘ and Δ𝑆^∘ are the changes in Gibb’s free energy, enthalpy, and entropy, respectively. The negative free energy value at 25°C indicates the feasibility of the process and its spontaneous nature. The exothermic nature of process was confirmed by the negative value of enthalpy change Δ𝐻^∘. The positive entropy change Δ𝑆^∘ indicates the good affinity of DPF for CV and the increasing disorder at the solid-solution interface during the adsorption process.

Table 2 

Thermodynamic parameters for the adsorption of CV onto DPF.

Figure 8 

ln𝐾ads versus 1/𝑇 according to the van’t Hoff equation (7) (experimental conditions: 25, 35, 45, and 55°C, 100 rpm, 𝜆max of absorbance =584 nm, and adsorbent mass =0.25 gm).

3.5. Kinetic Study

The study of adsorption kinetics describes the solute uptake rate, which controls the residence time of the adsorbate at the solid/solution interface. The kinetics of CV adsorption onto DPF were analyzed using pseudo-first-order and pseudo-second-order kinetic models. The linear pseudo-first-order equation [21] is given as follows: ln𝑞_𝑒−𝑞_𝑡=ln𝑞_𝑒−𝐾₁𝑡, (9) where 𝑞_𝑒 and 𝑞_𝑡 are the amount adsorbed at equilibrium and at time 𝑡, respectively, and (𝐾₁) is the rate constant of the pseudo-first-order adsorption. A plot of ln(𝑞_𝑒−𝑞_𝑡) versus 𝑡 (see Figure 9) should be linear, and rate constant (𝐾₁) and adsorption capacity at equilibrium (𝑞_𝑒) can be determined from the slope and intercept of the plot, respectively. The value of 𝑅² (=0.067) indicates that the first-order Lagergren equation did not fit the complete range of the adsorption process well.

Figure 9 

ln(𝑞𝑒−𝑞𝑡) versus time (min) for the adsorption of CV onto DPF (experimental conditions: 25°C, 100 rpm, 𝜆max of absorbance =584 nm, and adsorbent mass =0.25 gm, period time: 15, 30, 45, 60, 75, 90, 106, 120, 135, and 150 min).

The linear pseudo-second-order equation [22] is given as follows: 𝑡𝑞_𝑡=1𝐾₂𝑞²_𝑒+1𝑞_𝑒𝑡, (10) where (𝐾₂) is the pseudo-second-order rate constant. The slope of the plot of 𝑡/𝑞_𝑡 versus 𝑡 gives the value of 𝑞_𝑒, and the intercept can be used to calculate (𝐾₂). The plot of 𝑡/𝑞_𝑡 versus 𝑡 (see Figure 10) yields a very straight line. The correlation coefficient (𝑅²) for this model is 0.992, indicating a better fit for the former. The calculated and experimental 𝑞_𝑒 values agreed satisfactorily. However, the calculated, 𝑞_𝑒, and the rate constant, (𝐾₂), are given in Table 3.

Table 3 

Rate constant and adsorption capacity at equilibrium for the adsorption of CV onto DPF.

Figure 10 

𝑡/𝑞𝑡 versus time (min) for the adsorption of CV onto DPF (experimental conditions: 25°C, 100 rpm, 𝜆max of absorbance =584 nm, and adsorbent mass =0.25 gm, period of time: 15, 30, 45, 60, 75, 90, 106, 120, 135, and 150 min).

4. Conclusions

This study indicates that date palm fiber (DPF) is a promising adsorbent for the removal of crystal violet dye (CV) from aqueous solutions over a range of concentrations. Equilibrium data were analyzed according to Langmuir, Freundlich, Elovich, and Temkin isotherms. Despite the much higher correlation coefficient for the Langmuir and Freundlich models, the Elovich model was best able to describe the adsorption isotherm of CV onto DPF because the maximum adsorption capacity obtained from this model was equal to the experimental value. The temperature and pH play a role in the adsorption process. Greater adsorption occurred at low temperature and pH. The thermodynamic calculations indicated that the process was spontaneous and exothermic. The kinetics analysis revealed that the pseudo-second-order model was a better fit of the experimental data than the first-order kinetic expressions.

Acknowledgment

The authors would like to thank the Deanship of Scientific Research at Princess Nora University for providing the funding for this work under project number 016-ك-31.