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ASSESSMENT OF THE ADSORPTION KINETICS, EQUILIBRIUM AND THERMODYNAMICS FOR THE POTENTIAL REMOVAL OF [NI.sup.2+] FROM AQUEOUS SOLUTION USING WASTE EGGSHELL.

Introduction

Heavy metal pollution of water sources is one of the most: impoetant problems. Various industries--such as mining and smelting of metalliferrous, electroplating, battery manufacture, textile production, refineries, and petrochemical factories etc.--produce wastewater that contains metals (Celekli, Bozkurt 22011) which is discharged to the water bodies after treatment. As heavy metals are non-biodegradable water pollutants, they. tend to accumulate in living organisms (Gupta et al. 2010; Celekli, Bozkurt 2011).

In this experimental study, nickel was selected as an adsorbate, because nickel compounds have widespread application in many industrial processes, such as metal plating, silver refineries, zinc base casting and storage battery industries, and its concentration in industrial wastewaters range from 3.40 to 900 mg/L (Erdogan et al. 2005). Although low concentrations of nickel may be beneficial to organisms as a component in a number of enzymes and stimulate the activation of microorganisms (Aslan, Gurbuz 2011), an exceeded permissible exposure level of nickel causes various health problems such as unintentional weight loss, heart and liver damage, renal edema, lung and pulmonary fibrosis, skin dermatitis, and gastrointestinal discomfort (Bar-Sela et al. 1992; Celekli et al. 2010; Gupta et al. 2010; Kumar et al. 2011; Pahlavanzadeh et al. 2010).

Nickel (II) is one of the toxic pollutants in the industrial effluent wastewaters. Maximum contaminant limits of Ni (II) set by the EU and WHO as 0.02 mg/L and 0.07 mg/L, respectively (EU 2011; WHO 2005). Recommended limits for Ni (II) in reclaimed water for irrigation are 0.2 mg/L and 2.0 mg/L for the short and long-term usage (USEPA 2012).

Due to the accumulation of heavy metals in the food chain and persistence in the ecosystem, it causes the toxicity for living organisms. The wastewaters containing heavy metals are required to be properly treated prior to discharge into the receiving waters (Bhatnagar, Minocha 2010). Such conventional methods as the chemical precipitation, filtration, ion exchange, evaporation, reverse osmosis, solvent extraction, electrochemical treatment, membrane technologies, and adsorption could be applied in order to remove heavy metals from wastewater. Among these methods, adsorption is considered as an efficient and inexpensive method when the low concentration of heavy metal exists in the wastewater (Bermudez et al. 2011; Ghazy et al. 2011; Kumar et al. 2011).

Although the usage of activated carbon for sorption is an expensive method, commercially available activated carbon for the heavy metal removal from wastewater has been studied extensively (Erdogan et al. 2005). Consequently it is important to find new materials for removing by sorption of heavy metals from wastewaters.

In order to decrease the treatment cost of wastewater, researches have been focused on finding cheapest and effective sorbents. Among the numerous natural materials for removing nickel ions, biosorbents such as Spirulina platensis (Celekli, Bozkurt 2011), Gracilaria caudata and Sargassum muticum (Bermudez et al. 2011), Punica granatum peel waste (Bhatnagar, Minocha 2010), cashew nut shell (Kumar et al. 2011), waste tea (Malkoc, Nuhoglu 2009; Shah et al. 2012) (Camella cinencis) (Aikpokpodion et al. 2010), acid-washed barley straw (Thevannan et al. 2011), Thespesia Populnea bark (Prabakaran, Arivoli 2012), activated locust bean husk (Parkia biglobosa) (Oladunni et al. 2012), Sargassum filipendula (Kleinubing et al. 2012), bael tree leaf powder (Kumar, Kirthika 2009), chitosan encapsulated Sargassum sp. (Yang et al. 2011), sugarcane bagasse pith (Krishnan et al. 2011), activated sludge (Liu et al. 2012), treated alga (Oedogonium hatei) (Gupta et al. 2010), chlorella vulgaris (Aksu, Donmez 2006), eggshell (Ghazy et al. 2011) have attracted attention as a low-cost sorbents from wastewater.

The aim of this study was to evaluate the adsorption capacity of the waste eggshell to remove [Ni.sup.2+] ions in the synthetic waters. Effects of the initial pH, [Ni.sup.2+] concentrations, temperature, contact time, and adsorbent dosage were determined in the batch experiments. The equilibrium isotherms; Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich (D - R) were determined by applying various [Ni.sup.2+] concentrations. Adsorption kinetic models were used to analyze the kinetic and mechanisms of [Ni.sup.2+] adsorption.

1. Materials and methods

1.1. Preparation of adsorbent

After washing of the waste eggshell by tap and distilled waters, it was dried at 60[degrees]C for 24 hours in an oven. The dry clean eggshells were crushed and screened through a set of sieves to get the size of 75-106 [micro]m.

1.2. Sorption experimental studies

The synthetic waters were prepared by dissolving known masses of Ni[Cl.sub.2]*6[H.sub.2]O in the distilled water. A known amount of eggshell was used throughout the experiments and final volumes of the solution were 100 mL. Experimental studies were carried in 250 mL glass-stoppered Erlenmeyer flasks.

Experiments were performed at various initial concentrations of [Ni.sup.2+] (5.0-50 mg/L) and waste eggshell amounts (0.1-1.0 g/L). Additionally, temperature and pH were tested for various levels to determine the optimal operational conditions. Kinetic constants were determined at the initial concentrations of 15-25-35 mg [Ni.sup.2+]/L at the constant initial pH value and adsorbent dosage of [congruent to] 7.0 and 0.5 g/L, respectively. Kinetic experiments were also carried out at the temperature of 298-308-318 K. Batch experimental studies were performed in an orbital incubator shaker (Gerhardt) at a constant speed of 150 rpm.

1.3. Analytical methods

In order to get supernatant liquids, the samples were centrifuged at 4000 rpm for 10 min (NF800, NUVE). Concentrations of [Ni.sup.2+] in the solutions were determined with a Merck photometer (PHARO100). A spectraquant analytical kit (Merck, 14785) was used to measure [Ni.sup.2+] concentrations in the initial and final solutions.

1.4. Calculations

The following equation was used to determine the amount of [Ni.sup.2+] adsorbed onto eggshell:

[q.sub.e](mg/g) = ([C.sub.0] - [C.sub.e])(mg / L) x [V/M](mL / g). (1)

Adsorption process was quantified by calculating the sorption percentage (E %) as defined by the Eq. 2:

Sorption(E)(%) = [[C.sub.0] - [C.sub.e]/[C.sub.0]] x 100, (2)

where [q.sub.e] (mg/g) is the maximum amount of [Ni.sup.2+] adsorbed at equilibrium; the initial and equilibrium concentrations of [Ni.sup.2+] in the solutions were shown as [C.sub.0] and [C.sub.e] (mg/L), respectively. M is the amount of eggshell (g), and V (mL) is the total solution volume in the Erlenmeyer flasks.

2. Results and discussion

Sorption experiments were performed in duplicate and the average values of samples were presented in the study. Blank samples (without [Ni.sup.2+]) were used also to compare the results through all batch procedures. Data presented in the figures are mean values of standard deviation ([less than or equal to]7%) from the experiments.

2.1. Effect of contact time

Figure 1 shows the variation of [Ni.sup.2+] uptake with mixing time at pH 7.0 using 0.5 g eggshell. As can be seen from the figure that the equilibrium time for the sorption of [Ni.sup.2+] was about 120 min. At the equilibrium point, the highest [Ni.sup.2+] sorption efficiency of about 50% and the adsorption value of 1.95 mg/g were obtained.

The active sites of sorbents availability and the highest driving force for mass transfer at the beginning of the experiments (zero to 20 min) caused rapid uptake of [Ni.sup.2+] ions from the solution. Due to the occupancy of eggshell active sites and the lower concentrations of [Ni.sup.2+] in the solutions, [Ni.sup.2+] sorption was slower after passing 20 min of agitation times.

2.2. Effects of pH

Since the initial pH of solution not only affects the reactive groups present on the surface of adsorbents (protonation/ deprotonation effects), but also influences solubility of metals and the competition ability of hydrogen ions with metal ions, the initial pH of solution is an important parameter for the evaluation of sorption performances (Bermudez et al. 2011; Celekli, Bozkurt 2011; Chojnacka, 2005). The sorption of [Ni.sup.2+] was investigated as the function of pHs in the range of 3.0 to 7.0 with an increment of 0.5 pH units. Experiments were not extended to pH value of higher than 7.0 because the precipitation of [Ni.sup.2+] ions forming hydroxides. Precipitation of [Ni.sup.2+] may be applied for recovery when the wastewater is not including other pollutants.

Polat and Aslan (2014) determined the temperature and pH effects on the release of [Ca.sup.2+] and HC[O.sup.-.sub.3] from the eggshell. Because the eggshell was composed mainly of calcium carbonate, pH were increased during the experimental study. However, the level of solution pHs were lower than 8.0 at the end of the batch experimental studies.

Sorption of [Ni.sup.2+] on the eggshell sorbents at various pHs are presented in Figure 2. As can be seen in figure that uptake of [Ni.sup.2+] was a function of initial solution pH. The adsorption of [Ni.sup.2+] ions increases with increase in the solution pHs. Significant sorption was not observed at the pH values of 3.0 and 3.5. The lowest [Ni.sup.2+] adsorption efficiency of about 11% was observed at the initial pH value of 3.0. It could be attributed to the higher concentration of hydrogen ions in the solution competing with [Ni.sup.2+] for binding sites on the eggshell. Similar observations were reported in the literature for the sorption of [Ni.sup.2+] ions on the various adsorbents (Bermudez et al. 2011; Celekli, Bozkurt 2011; Kumar et al. 2011). At low pH values, H+ ions occupy most of the adsorption sites of eggshell surface and [Ni.sup.2+] sorption could be limited due to the electric repulsion with H+ ions on the eggshell surface (Kumar et al. 2011). Increasing the pHs values from 3.5 to 6.5, sorption capacities (qe) and the removal efficiencies of [Ni.sup.2+] were increased significantly from 0.67 mg/g to 2.02 mg/g and 17.5% to 50.4% respectively. It was assumed that because the adsorbent surface was more negatively charged at high pHs, the sorption of heavy metal ions by eggshell increased. The [q.sub.e] value and removal efficiency decreases slightly when the initial pH of solution was increased to 7.0.

The sorption capacities and removal efficiencies of [Ni.sup.2+] were increased significantly from 0.43 to 2.02 mg [Ni.sup.2+]/g.eggshell and 11% to 50.5%, respectively by increasing the pH from 3.0 to 6.5.

2.3. Effect of temperature

The effect of temperature on [Ni.sup.2+] uptake capacity of eggshell was studied and results are presented in Figure 3. As can be seen, [Ni.sup.2+] ions uptake capacity of eggshell increased with increasing temperature up to 318 K. An increase in temperature from 298 to 318 K, increases the [q.sub.e] values from 1.96 to 2.2 mg/g. Sorption efficiency achieved about 56% at the temperature of 318 K. The removal efficiencies of [Ni.sup.2+] ions at equilibrium were about 50% and 56% at the temperature of 298 K and 318K, respectively. It was assumed that it was probably related with the increase of [Ca.sup.2+] release from the eggshells at higher temperatures. Polat and Aslan (2014) reported that elevating the temperature from 25 to 50[degrees]C, release of [Ca.sup.2+] ions into the aqueous solution increased about two times. Rising temperature might create new active sites by releasing [Ca.sup.2+] ions from the eggshell (Polat, Aslan 2014) and enlarge the pore size of adsorbent (Demirbas et al. 2009). Additionally, the collision frequency between adsorbent and [Ni.sup.2+] ions is elevated at high temperatures.

Experimental results indicating that the adsorption of [Ni.sup.2+] ions was favored at higher temperature and the sorption of [Ni.sup.2+] is endothermic in nature. As a results the adsorption capacity of eggshell is improved at high temperature.

2.4. Effect of adsorbent amount

The adsorbent dosage is an important parameter in the sorption process. At a given equilibrium concentration of pollutants, the adsorbent takes up more pollutants at lower adsorbent amount than at higher amounts (Al-Homaidan et al. 2014). Effect of eggshell doses on the removal efficiency of [Ni.sup.2+] and [q.sub.e] values are shown in Figure 4. It was observed that the [Ni.sup.2+] removal efficiency of the eggshell was a function of eggshell amounts in the solution. The percent removal of [Ni.sup.2+] declined along with the decrease in eggshell amount.

It can be seen from the figure that initially the removal efficiency increases gradually with the increase in eggshell amount in the aqueous solution while the qe values decreases. The maximum adsorption efficiency of [Ni.sup.2+] ion onto the eggshell was found to be 75.1% at the dose of 10 g/L eggshell. The increase in sorption efficiency of heavy metal could be attributed to the increased number and exchangeable sites of adsorbent available for the adsorption (Kumar et al. 2011).

2.5. Modeling of sorption equilibrium depending on [Ni.sup.2+] concentrations

In order to understand the interaction between a sorbate and an adsorbent, it is important to establish the most appropriate correlation for the equilibrium curves. The experimental data were analyzed by applying the most commonly used equilibrium models namely Langmuir, Freundlich, Temkin, and D-R. The mathematical expressions are given in Table 1. Where [q.sub.m] indicates the monolayer sorption capacity of adsorbate (mg/g). The constants b and E are the mean free energy and sorption per molecule of the sorbate, respectively. Sorption parameters for the isotherms are as follows; [K.sub.L] (L/mg) Langmuir constant related to the energy of sorption, [K.sub.Fi] (L/mg) Freundlich constant related to the sorption capacity of adsorbent, [q.sub.max] (mg/g) is the maximum biosorption capacity of D-R. [b.sub.T] and [A.sub.T] (L/mg) Temkin isotherm parameters, R is the gas constant (8.314 joule.mol/K); T is the absolute temperature (K). The value of [R.sub.L] indicates that the shape of the sorption process is; unfavorable ([R.sub.L] > 1), linear ([R.sub.L] = 1), favorable (0 < [R.sub.L] < 1) or irreversible ([R.sub.L] = 0) (Kilic et al. 2011; Sljivic et al. 2009).

The constants of isotherms equation are presented in Table 2. The best fit was obtained by Langmuir model as compared with the other isotherm models due to determine the highest correlation coefficient value of 0.993. Langmuir model is suggesting that the [Ni.sup.2+] ions were adsorbed onto the eggshell in a monolayer. The maximum monolayer adsorption capacity was found to be 1.845 mg [Ni.sup.2+]/g for the eggshell. The essential characteristic of the Langmuir isotherm can be used to predict the affinity between the sorbent and sorbate using separation factor, "[R.sub.L]". The [R.sub.L] was determined to be 0.01190.107 for the concentrations of 5.0-50 mg [Ni.sup.2+]/L which indicated that the sorption of [Ni.sup.2+] by waste eggshell sample was favorable.

Previous experimental studies indicated that the pretreatment procedure increase the uptake capacity of sorbents (Ahmad et al. 2010; Gupta et al. 2010; Ewecharoen et al. 2009) and most of the organic materials (Gupta et al. 2006; Bhatnagar, Minocka 2010; Celekli, Bozkurt 2011) have higher [q.sub.e] value than an inorganic materials (Otun et al. 2006; Bayat 2002; Rao et al. 2002). In order to justify the validity of eggshell as an adsorbent for [Ni.sup.2+] adsorption, adsorption potential is compared with other adsorbents and summarized in Table 3.

2.6. Kinetics of sorption

Sorption kinetics of [Ni.sup.2+] ions on the eggshell were analyzed using four kinetic models for fitting sorption kinetic data: pseudo-first-order, pseudo-second-order, intraparticle diffusion, and Elovich models. Equations for the kinetic models are presented in Table 1. Experiments were repeated for different initial eggshell amounts (15-25-35 mg/L) and temperatures (298-308-318 K).

Sorption capacities (qe) and the calculated values ([q.sub.e], [k.sub.1], [k.sub.2], [R.sup.2], and h) from the models are presented in Table 4. Comparison the results of kinetic data, it can be concluded that the pseudo-second-order model provided the best correlation coefficient. In addition, the calculated qe values derived from the pseudo-second-order were very close to the experimental ([q.sub.exp]) values.

As can be seen from the Table 4 that the equilibrium adsorption capacity, [q.sub.e], increases as the initial [Ni.sup.2+] concentration, [C.sub.i], increased from 15 to 35 mg/L. However, it was found that the rate constant of pseudo-second-order ([k.sub.2]) seem to have a decreasing trend with increasing the initial [Ni.sup.2+] concentrations. Similar trends were also observed by applying pseudo-second-order model at various temperatures. For example, the values of [q.sub.e] increased from 1.96 mg/g to 2.22 mg/g at the temperature of 298 K and 318 K, respectively. The reason for this situation might be attributed to the less competition for the sorption surfaces sites at lower concentration. At higher concentrations, the competition for the surface active sites is high and consequently lower sorption rates are achieved (Kumar et al. 2011). These results confirmed that the chemisorption mechanisms may play an important role for the sorption of [Ni.sup.2+] on the eggshell.

2.7. Adsorption thermodynamics

In order to determine the thermodynamic parameters such as free energy ([DELTA][G.sup.0], Kj/mol), entalphy ([DELTA][H.sup.0], Kj/mol), and entropy ([DELTA][S.sup.0], j/mol/K)--change of [Ni.sup.2+] adsorption onto the eggshell, the batch experiments were performed at different temperatures of 298, 303, 308, 313, and 318 K. The thermodynamic parameters are calculated using the following equations (Mezenner, Bensmailli 2009):

[DELTA][G.sup.0] = - RT x ln [K.sub.d]; (3)

Ln [K.sub.d] = - ([DELTA][H.sup.0]/RT)+ ([DELTA][S.sup.0]/R), (4)

where [K.sub.d] is the distribution coefficient for the adsorption.

The calculated values of thermodynamic parameters are presented in Table 5. The value of [DELTA][G.sup.0] is small at 298 K and negative with increase in temperature. It indicates that the adsorption process leads to an increase in Gibbs energy. The negative [DELTA][G.sup.0] value means the [Ni.sup.2+] sorption onto the eggshell is feasible and spontaneous in the nature. The value of [DELTA][H.sup.0] (13.66 kj/mol) and [DELTA][S.sup.0] (0.136 Kj/mol/K) were determined from the data. The positive values of [DELTA][H.sup.0] and [DELTA][S.sup.0] suggests the endothermic nature of process and randomness at the eggshell--solution interface during the sorption (Katal et al. 2012).

Conclusions

As can be seen from the experimental results, the waste eggshells might be used for nickel removal from aqueous solution. Following conclusions could be drawn from the study:

1. The maximum sorption capacities were determined at the pH value of 6.5. Adsorption of [Ni.sup.2+] was highly temperature dependent.

2. The [Ni.sup.2+] ions were adsorbed onto the eggshell in a monolayer due to the highest correlation coefficient (0.9995) was determined using the Langmuir model comparing with the other models.

3. The sorption perfectly complies with pseudo-second order reaction than the others (pseudo first order kinetics, intraparticle diffusion, and Elovich models) and the sorption of [Ni.sup.2+] onto the eggshell appeared to be controlled by the chemisorption process.

4. Of the thermodynamic point of view, the sorption mechanisms of [Ni.sup.2+] ions onto the eggshell was endothermic.

http://dx.doi.org/10.3846/16486897.2015.1005015

Acknowledgements

This study was supported by The Research Fund of Cumhuriyet University (CUBAP) under Grant No. M-459, Sivas, Turkey.

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Sukru ASLAN, Dr Lecturer, Department of Environmental Engineering, Cumhuriyet University, Sivas, Turkey. Research interests: adsorption, biological nutrient removal, reuse.

Ayben POLA T, Environmental Engineer, Department of Environmental Engineering, Cumhuriyet University, Sivas, Turkey. Research interests: adsorption, biological nutrient removal.

Ugur Savas TOPCU, Environmental Engineer, Department of Environmental Engineering, Cumhuriyet University, Sivas, Turkey. Research interests: adsorption, biological nutrient removal.

Sukru ASLAN, Ayben POLAT, Ugur Savas TOPCU

Department of Environmental Engineering, Cumhuriyet University, 58140, Sivas, Turkey

Submitted 26 July 201-4; accepted 05 Jan. 2015

Corresponding author: Sukru Aslan

E-mail: saslan@cumhuriyet.edu.tr

Caption: Fig. 1. Contact time effects on the sorption ([C.sub.0] = 20 mg [Ni.sup.2+]/L)

Caption: Fig. 2. Initial pH effects on the sorption of [Ni.sup.2+]

Caption: Fig. 3. Effects of temperature on the sorption of process

Caption: Fig. 4. Effects of eggshell amount on the [Ni.sup.2+] ions sorption
Table 1. Equations of isotherm and kinetic models

                                         Equations

Equilibrium models

Langmuir             [q.sub.e](mg/g) = [q.sub.m][K.sub.L][C.sub.e]/1
                     + [K.sub.L][C.sub.e]]
                     [R.sub.L] = 1/(1 + [K.sub.L] x [C.sub.0])

Freundlich           [q.sub.e](mg/g) = [K.sub.Fi][C.sup.1/n.sub.e]

Temkin               [q.sub.e](mg/g) = B ln [A.sub.T] + B ln[C.sub.e]

Dubinin-             ln[q.sub.e] =ln[q.sub.max] -
Radushkevich         [beta][[epsilon].sup.2]
                     [epsilon] = RT ln (1 + [1/[C.sub.[epsilon]]

Kinetic models

Pseudo               log([q.sub.e] = [q.sub.t]) = log pq.sub.e] -
first-order          [[k.sub.f]/2.303]t

Pseudo               [t/[q.sub.t] = [1/[k.sub.2][q.sup.2.sub.e]]
second-order         + [t/[q.sub.e]]
                     h = [k.sub.2] x [q.sup.2.sub.e]

Intra particle       [q.sub.t] = [k.sub.id][t.sup.1/2] + C
diffusion

Elovich              [q.sub.t] = [1/[beta]]ln[alpha][beta] +
                     [1/[beta]]ln t

                                     Plot

Equilibrium models

Langmuir             [C.sub.e]/[q.sub.e] vs x [C.sub.e]

Freundlich           log [q.sub.e] vs x loq [C.sub.e]

Temkin               [Q.sub.e] vs In[C.sub.e]

Dubinin-             ln [q.sub.e] vs [[epsilon].sup.2]
Radushkevich

Kinetic models

Pseudo               log ([q.sub.e] - [q.sub.t]) vs t
first-order

Pseudo               t/[q.sub.t] vs t
second-order

Intra particle       [q.sub.t] vs [t.sup.1/2]
diffusion

Elovich              [q.sub.t] vs lnt

                                       Parameters

Equilibrium models

Langmuir             [q.sub.m]= 1/slope
                     [k.sub.L] = slope/intercept

Freundlich           [k.sub.F] = exp (intercept)
                     n = 1/(slope)

Temkin               [q.sub.e] = slope
                     [A.sub.t] = exp(intercept)/
                     (slope)

Dubinin-             [q.sub.0] = exp(intercept)
Radushkevich         b = -(slope)

Kinetic models

Pseudo               [q.sub.e] = exp(intercept)
first-order          [k.sub.1] = -(slope)

Pseudo               [q.sub.e] = 1/(slope)
second-order         [k.sub.2] = [(slope).sup.2]/(intercept)

Intra particle       [k.sub.i] = slope
diffusion

Elovich              b = slope
                     a = 1/(slope)
                     exp(intercept/slope)

                           References

Equilibrium models

Langmuir             Kilic et al. (2011);

                     Sljivic et al. (2009)

Freundlich           Tsai et al. (2008)

Temkin               Kilic et al. (2011)

Dubinin-             Baig et al. (2010)
Radushkevich

Kinetic models

Pseudo               Chiou, Li (2002);
first-order          Chairat et al. (2005)

Pseudo               Rao et al. (2002)
second-order

Intra particle       Ghasemi et al. (2012)
diffusion

Elovich              Demirbas et al. (2009)

Table 2. Correlation coefficient and adsorption parameters
for the models

Model                      Sorption Parameters

Freundlich              [R.sup.2]              0.688
                            n                   4.63
                        [k.sub.F]              1.061
Langmuir                [R.sup.2]              0.993
                        [R.sub.L]              0.033
                        [q.sub.m]              1.845
                        [k.sub.L]              1.665
Temkin                  [R.sup.2]              0.690
                        [B.sub.T]              0.282
                     [A.sub.T](L/g)            29.96
R-D                     [R.sup.2]              0.946
                    [q.sub.0] (mg/g)            1.83
             [beta] ([mol.sup.2]/[j.sup.2])    0.519
                       E (kj/mol)               0.98

Table 3. Comparison of maximum monolayer adsorption on Ni (II) ions
onto various adsorbents

Adsorbents                              [q.sub.m] (mg/g)

Pomegranate peel                              69.4
Spirulina platensis                           69.04
Irradiation-grafted activated carbon          55.7
Acid-treated alga                            44.247
Activated carbon                              44.1
Untreated alga                               40.983
Modified activated carbon II                 37.175
Modified activated carbon I                  30.769
Cashew nut shell                             18.868
Calcined phosphate                            15.53
Clarified sludge                              14.3
Red mud                                       13.63
Anode dust                                    8.64
Powdered eggshell                              7.0
Smectite clay                                 6.68
Sawdust                                        4.6
Sepiolite                                     3.44
eggshell                                      2.36
eggshell                                      1.84
Bael tree leaf powder                         1.527
Fly ash (Seyitomer)                           1.160
Fly ash (Afcin-Elbistan)                      0.787
Fly ash                                       0.249
Fly ash                                       0.03
Bagasse                                       0.001

Adsorbents                               [K.sub.L] (ml/g)

Pomegranate peel                          [24.10.sup.3]
Spirulina platensis                           0.0019
Irradiation-grafted activated carbon          0.009
Acid-treated alga                             0.063
Activated carbon                              0.005
Untreated alga                                0.060
Modified activated carbon II                  0.091
Modified activated carbon I                   0.025
Cashew nut shell                              0.071
Calcined phosphate                            0.299
Clarified sludge                              0.222
Red mud                                       0.102
Anode dust                              6.50 x [10.sup.-3]
Powdered eggshell                             0.281
Smectite clay                                 0.586
Sawdust                                       38.14
Sepiolite                                      0.24
eggshell                                      0.478
eggshell                                      1.665
Bael tree leaf powder                         0.0622
Fly ash (Seyitomer)                           1.839
Fly ash (Afcin-Elbistan)                      2.092
Fly ash                                       0.0684
Fly ash                                        0.08
Bagasse                                        0.48

Adsorbents                                     References

Pomegranate peel                        Bhatnagar, Minocka 2010
Spirulina platensis                     Celekli, Bozkurt 2011
Irradiation-grafted activated carbon    Ewecharoen et al. 2009
Acid-treated alga                       Gupta et al. 2010
Activated carbon                        Ewecharoen et al. 2009
Untreated alga                          Gupta et al. 2010
Modified activated carbon II            Hasar 2003
Modified activated carbon I             Hasar 2003
Cashew nut shell                        Kumar et al. 2011
Calcined phosphate                      Hannachi et al. 2010
Clarified sludge                        Hannachi et al. 2010
Red mud                                 Hannachi et al. 2010
Anode dust                              Strkalj et al. 2010
Powdered eggshell                       Otun et al. 2006
Smectite clay                           Mbadcam et al. 2012
Sawdust                                 Bozic et al. 2009
Sepiolite                               Sanchez et al. 1999
eggshell                                Ghazy et al. 2011
eggshell                                This study
Bael tree leaf powder                   Kumar, Kirthika 2009
Fly ash (Seyitomer)                     Bayat 2002
Fly ash (Afcin-Elbistan)                Bayat 2002
Fly ash                                 Agarwal et al. 2013
Fly ash                                 Rao et al. 2002
Bagasse                                 Rao et al. 2002

Table 4. Parameters of adsorption kinetics of [Ni.sup.2+] by eggshell

                                           Pseudo-first-order
[Ni.sup.2+]        [q.sub.e]
(mg/L)            (exp) (mg/g)   [q.sub.e]    [k.sub.1]    [R.sup.2]

15                    1.6          0.035        0.453        0.823
25                    1.94         0.028        0.782        0.795
35                    2.28         0.021        1.183        0.919

Temperature (K)

298                   1.96         0.0138       0.723        0.685
308                   2.39         0.0253       0.991        0.848
318                   2.22         0.035        1.167        0.947

                            Pseudo-second-order
[Ni.sup.2+]
(mg/L)            [q.sub.e]    [k.sub.1]    [R.sup.2]

15                   1.62         0.49        0.996
25                   1.97        0.112        0.997
35                   2.32        0.0613       0.993

Temperature (K)

298                  1.71        0.304        0.999
308                  2.44        0.082        0.993
318                  2.29        0.080        0.997

                        Intraparticle diffusion
[Ni.sup.2+]
(mg/L)              h      [k.sub.p]    [R.sup.2]

15                 1.29      0.055        0.629
25                0.434      0.096        0.904
35                 0.33      0.141        0.918

Temperature (K)

298                0.89       0.09        0.797
308               0.488      0.126        0.678
318               0.419      0.143        0.825

                             Elovich
[Ni.sup.2+]
(mg/L)            [alpha]    [beta]    [alpha]

15                  775       7.813     0.723
25                 15.38      4.74      0.910
35                  2.76      3.14      0.986

Temperature (K)

298                20.07      5.21      0.955
308                 6.32      3.24      0.848
318                 2.45      2.96      0.967

Table 5. Thermodynamic parameters for the adsorption of [Ni.sup.2+]
onto eggshell

             [DELTA][H.sup.0]   [DELTA][S.sup.0]
                (kj/mol)           (kj/mol/K)

[Ni.sup.2+]      13.66               0.136

[DELTA][G.sup.0] (kj/K.mol)

              298 K    303 K    308 K    313 K    318 K

[Ni.sup.2+]   0.013   -0.422   -0.561   -0.610   -0.629


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Date:Sep 1, 2015
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