Chemical modification of expanded glass aggregate with N-Benzoyl-N′-(4-methylphenyl) thiourea (TTU) for the adsorptive removal of Cr(III) ion

Tugba Sardohan-Koseoglu; Ulviye Beyza Ogul; Esengul Kır; Fatma Karipcin

doi:10.1016/j.arabjc.2015.11.009

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Original article

12 (

); 772-779

doi:

10.1016/j.arabjc.2015.11.009

Chemical modification of expanded glass aggregate with N-Benzoyl-N′-(4-methylphenyl) thiourea (TTU) for the adsorptive removal of Cr(III) ion

Tugba Sardohan-Koseoglu^{^a,⁎}, Ulviye Beyza Ogul^{^a}, Esengul Kır^{^a}, Fatma Karipcin^{^b}

a Department of Chemistry, Faculty of Arts and Sciences, Suleyman Demirel University, 32260 Isparta, Turkey

b Department of Chemistry, Faculty of Arts and Sciences, Nevsehir Haci Bektas Veli University, 50300 Nevsehir, Turkey

⁎Corresponding author. Tel.: +90 246 2114261; fax: +90 246 2371106. tugbasardohan@sdu.edu.tr (Tugba Sardohan-Koseoglu)

Received: 2015-8-7, Accepted: 2015-11-14, Published: 2015-09-01

Disclaimer:
This article was originally published by Elsevier and was migrated to Scientific Scholar after the change of Publisher.

Peer review under responsibility of King Saud University.

Abstract

In this study, the silylant agent 3-aminopropyl trimethoxysilane (APTES) was anchored on expanded glass aggregate (GA) to prepare a new adsorbent. N-Benzoyl-N′-(4-methylphenyl) thiourea (TTU) bonded to amino-functionalized GA adsorbent with reflux. Developed adsorbent (GA-APTES-TTU) was characterized using thermal analysis (TGA) and scanning electron microscopy (SEM). TGA and SEM studies indicated that modification of the glass aggregate (GA) surfaces was successfully performed. The adsorption studies exhibited that the GA-APTES-TTU could be efficiently used for the removal of Cr(III) from aqueous solutions. The effects of pH, adsorbent dosage, ion concentration, time, and temperature were investigated as adsorption parameters. The maximum removal of Cr(III) was observed at pH 4. The adsorption equilibrium was achieved in 120 min and adsorption of Cr(III) followed the Langmuir isotherm model. The maximum adsorption capacity for Cr(III) was 0.4305 mmol/g with GA-APTES-TTU. Thermodynamic parameters such as the standard free energy (ΔG^o), enthalpy change (ΔH°) and entropy change (ΔS°) were calculated in order to explain the mechanism of adsorption process. The thermodynamic data showed that Cr(III) adsorption was spontaneous, endothermic, and a physisorption reaction. In addition, the adsorption kinetic data fitted to the pseudo-second order model.

Keywords

Adsorption

Cr(III)

Glass aggregate

Modification

Thiourea

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1 Introduction

In recent years, glass beads have been used as support material for surface modification due to their low cost, mechanical strength, similar size and controllability properties. Novel adsorption studies are mainly focused on the adsorption of trace elements on solid supports to separate only an element or a group of similar elements from complex mixtures and quantitative determination.

Recently, many new materials have been developed by the method of immobilization (Espinosa et al., 2007, 2011; Liu et al., 2003 ). Glass beads have large surface area and superior physical properties in comparison with other immobilization materials. Moreover, the modified glass beads have high-metal adsorption efficiency (Shriver-Lake et al., 2002). Metal uptake properties of the glass bead surface can be increased considerably with the binding of organic and inorganic chelating agents.

A number of new adsorbents can be successfully prepared from the glass beads by chemisorption of the active species onto the etched surfaces (Liu et al., 2003; Ozmen et al., 2009; Wang et al., 2013 ). In this study, glass beads were selected as immobilization material because of their superior properties.

Glass beads are modified by the thiourea for the enhancement of adsorption characteristics. Thiourea compounds have been used in agriculture as insecticides, herbicides and plant growth regulators. It is also applied in medical studies due to its antivirus and antitumor properties (Li and Wang, 2003; Maddani and Prabhu, 2010). Thiourea is also known as an efficient chelating agent due to its strong interactions with heavy metal ions (Habtu et al., 2006).

Common methods used to remove heavy metals from waters can be divided into four categories: chemical precipitation (Visvanathan et al., 1989), membrane processes (Kir et al., 2013; Tor et al., 2004), ion-exchange (Pehlivan and Cetin, 2008) and adsorption (Ouadjenia-Marouf et al., 2013; Rajurkar et al., 2011; Schneider et al., 2007; Unlu and Ersoz, 2006 ). Adsorption is widely used in the removal of heavy metals from waters and wastewaters through suitable adsorbents.

Chromium ion is one of the most toxic heavy metals at high concentrations, because of its accumulation tendency in living organisms (Kimbrough et al., 1999). Chromium compounds can be released into groundwater and to the environment from natural rocks as well as from some industrial sources (leather tanning and finishing, pigments electroplating, textile dyeing, wood preservation, etc.) (Gupta et al., 2001; Kimbrough et al., 1999; Kotas and Stasicka, 2000; Tarasevich, 2001 ).

The main goal of this study was to develop a novel adsorbent by the chemical immobilization of N-Benzoyl-N′-(4-methylphenyl) thiourea (TTU) compound on the expanded glass aggregate (GA) and to investigate the adsorption characteristics of this novel adsorbent for the removal of Cr(III) ions from aqueous solutions.

2 Materials and methods

The GA used in this study was supplied from Suleyman Demirel University Pumice Research and Application Center, Isparta, Turkey. The chemical composition of the adsorption material in terms of weight percentage of oxides is listed in Table 1. The main characteristics of the adsorption material are also listed in Table 2.

Table 1 The chemical composition of expanded glass aggregate.

Chemical composition	(wt%)
SiO₂	71.3
Al₂O₃	2.02
Fe₂O₃	0.48
CaO	7.75
MgO	2.07
TiO₂	Trace
Loss	0.78

Table 2 The properties of expanded glass aggregate.

Properties
Particle size (μm)	100–300
Density (g/cm³)	1.92
Unit mass (g/cm³)	0.38
Porosity ratio (%)	74–82
Pore size range (μm)	1–14

APTES, Cr(NO₃)₃·9H₂O, Cd(NO₃)₂·4H₂O, Cu(NO₃)₂·3H₂O, HCl, and NaOH were obtained from Sigma–Aldrich and, Merck. Toluene (Merck) was used after being dried. APTES (3-aminopropyltrimethoxysilane) was used for the bonding of the glass aggregate. The GA was dried at 105 °C. All aqueous solutions were prepared with deionized water. TTU was synthesized according to the method described in the literature (Al-Awadi et al., 1997).

2.1

2.1 Modification of glass aggregate

Dried sample of GA (20.0 g) was activated in 4 mol/L NaOH solution (100 mL). The mixture was refluxed at 100 °C for 15 min. Ultrapure water was added on this mixture and further filtered by a filtration apparatus. Prepared GA was washed with ultra-pure water and dried subsequently in vacuum oven at 120 °C for 24 h.

The activated glass aggregate (10 g) and 6 mL APTES were added to 20 mL dried toluene and the mixture was stirred continuously at 80 °C overnight under nitrogen atmosphere. GA was filtered and washed with toluene, and dried at room temperature for 24 h. The product obtained was named glass aggregate-APTES (GA-APTES) (Fig. 1).

The mechanism steps for the synthesis of GA-APTES and GA-APTES-TTU.

GA-APTES (10 g) and 1.5 g of TTU were added to 20 mL dry toluene and stirred continuously at 25 °C for 4 h. The final product was washed with methanol and dried under vacuum for 24 h named as glass aggregate-APTES-thiourea (GA-APTES-TTU) (Fig. 1).

2.2

2.2 Characterization of GA-APTES-TTU

TGA measurement was performed with Perkin Elmer Diamond thermogravimetric analyzer in a temperature range of 25–900 °C in nitrogen atmosphere. The surface morphology of GA, activated GA, GA-APTES and GA-APTES-TTU samples was assessed with SEM (TESCAN VEGA II LSU). The concentration of the Cr(III) ions was determined by an AAS Perkin Elmer AA800. Mettler Toledo Seven Multi pH/Ion meter was used for pH measurement.

2.3

2.3 Adsorption studies

The adsorption studies of the GA-APTES-TTU were investigated with batch technique in an aqueous solution for Cr(III) ion at 25 °C. The adsorption properties of GA-APTES-TTU for different cations such as Cr (III), Cd (II), Hg (II) and Cu (II) were examined separately. The experimental results showed that adsorption properties of Cr(III) were better than other ions.

GA-APTES-TTU (0.1 g) was mixed with 10 mL of the Cr(III) solution (150 mg/L) over a period of the time in a 50 mL volumetric flasks. Then, the concentration of Cr(III) ions in filtered solution was determined and amount of adsorbed Cr(III) ions was calculated according to Eq. (1):

(1)

q = \frac{C_{o} - C_{e}}{m}

where q is the amount of metal ion adsorbed onto the unit amount of the adsorbent (mmol/g), C_o is initial concentration of metal ion (mmol/L), C_e is concentration of metal ion in solution at equilibrium (mmol/L), and m is the dry weight of the adsorbent (g). Batch study was conducted to determine the optimum conditions. The pH optimization was assessed by varying the pH of the Cr(III) solution from 2 to 6. Eventually, pH 4.0 was used for all experiments. The desired pH values were adjusted by 0.1 mol/L NaOH or 0.1 mol/L HCl. The effects of adsorbent dosage (0.05–1 g), contact time (0.5–72 h), temperature (25–60 °C), and initial Cr(III) concentration (100–600 mg/L) on adsorption were also evaluated.

3 Results and discussion

3.1

3.1 Characterization

The changes on the GA surfaces were investigated by SEM. Fig. 2a–c shows natural, activated, GA-APTES and GA-APTES-TTU material surfaces, respectively. It can be seen that surface modification of glass aggregate was successfully carried out.

SEM micrograph of (a) original expanded glass aggregate, (b) expanded glass aggregate-APTES, and (c) expanded glass aggregate-APTES-TTU.

Fig. 2a shows the homogeneous microparticle morphology of natural GAs prior to modification. The immobilization of TTU into natural GA was confirmed by macroparticle structure (Fig. 2c).

TGA of the adsorbent materials showed the degradation on the anchored surface for the GAs. Thermograms show mass loss of the GA, GA-APTES and GA-APTES-TTU samples which are exposed to the increasing temperature (Fig. 3). The first weight-loss step for all the GAs was due to the physically adsorbed water between 25 °C and 100 °C. The second weight loss of 7% approximately corresponds to the decomposition of the grafted APTES onto the GA surface (b). The third phase of decomposition from 600 °C to 800 °C, with an average weight loss of 13%, corresponds to the decomposition of the organic group immobilized on the surface (c).

TGA curve of GA (a), GA-APTES (b), and GA-APTES-TTU (c).

3.2

3.2 Effect of pH

Fig. 4 shows the Cr(III) adsorption by the GA-APTES-TTU with increasing pH. It was found that the adsorption of Cr(III) was increased with increasing solution pH up to 4. Since the adsorption of chromium was high (>90%) at pH 5 and pH 6, pH 4 where the adsorption amount is 84% was chosen as optimum pH value. Obtained results for Cr(III) adsorption by GA-APTES-TTU are concordant with the previous studies (Lyubchik et al., 2004; Schneider et al., 2007). The higher adsorption of Cr(III) from solution at pH > 4.0 is mainly due to precipitation of Cr(OH)₃ onto the adsorbent surface. Besides, lower adsorption of Cr(III) at pH < 4.0 is mainly due to the stronger competitive adsorption of hydrogen ions (Qiang et al., 2014; Yang et al., 2014). Results generally underline the strong effect of solution pH which is a critical variable that controls the adsorption between the adsorbent and solution interface.

The effect of pH on the adsorption of Cr(III) (Cr(III): 150 mg/L, t: 120 min, adsorbent dosage: 0.3 g, temperature: 298 K).

3.3

3.3 Effect of adsorbent dosage

Adsorbent dosage determines the capacity of an adsorbent. The effect of adsorbent dosage on Cr(III) adsorption at pH 4.0 was studied. Fig. 5 shows the effect of adsorbent dosage on the Cr(III) removal for GA-APTES-TTU. It is observed that up to a certain limit of higher dosages of adsorbent resulted in higher adsorption of Cr(III). This is consistent with the expectation that higher adsorbent dosages will result in lower adsorption capacity values. Optimum adsorbent dosage was 0.3 g of GA-APTES-TTU for 150 mg/L Cr(III) solution. This is an expected result because of higher availability of surface and more adsorbent sites.

The effect of adsorbent dosage (0.05–1.0 g) on the adsorption of Cr(III) (Cr(III): 150 mg/L, t: 120 min., pH 4.0, temperature: 298 K).

3.4

3.4 Effect of contact time and adsorption kinetics

To investigate the effect of contact time on Cr(III) removal efficiency was studied by various contact times. Fig. 6 illustrates the Cr(III) removal capacity of GA-APTES-TTU for different contact times. As contact time was increased, the removal capacity gradually approached an almost constant value as a function of the equilibrium period. The adsorption data obtained were tested in order to understand the mechanism of Cr(III) adsorption on GA-APTES-TTU. Hence, pseudo-first-order and pseudo-second-order kinetic models were used (Ho and Chiang, 2001; Ho and McKay, 2000).

The effect of contact time (30 min-72 h) on the adsorption of Cr(III) (Cr(III): 150 mg/L, adsorbent dosage: 0.3 g, pH: 4.0, temperature: 298 K).

The linearized form of pseudo-first-order kinetic model given below by Lagergren is applied:

(2)

\log (q_{e} - q_{t}) = log q_{e} - \frac{k_{1} \cdot t}{2.303}

where q_e and q_t represent the amount of metal ion that is adsorbed (mg/g) at equilibrium and at time t (min), respectively. k₁ (1/min) is the adsorption rate constant for this model. Pseudo-second-order kinetic model was also applied (Eq. (3)).

(3)

\frac{t}{q_{t}} = \frac{1}{q_{e}} t + \frac{1}{k_{2} q_{e}^{2}}

where k₂ is the pseudo-second-order rate constant for the adsorption (g/(mg min)). q_e and q_t are defined as the same as above (Eq. (3)).

The kinetic parameters (q_e, q_t, k₁ and k₂) were calculated from curves and are listed in Table 3. The results demonstrated that pseudo-second-order model was fitted better than the first-order model. Fig. 7 also shows the pseudo-second-order kinetic model for GA-APTES-TTU adsorbent.

Table 3 The rate constants of adsorption kinetic model for Cr(III) on expanded glass aggregate.

Pseudo-first-order				Pseudo-second-order
q (experimental)	k₁	q_e (calculated)	R²	k₂	q_e (calculated)	R²
1.0685	0.0007	3.1606	0.572	6.0896	1.0698	1.000

q_t = mg/g, k₁ = min⁻¹, q_e = mg/g, k₂ = g/mg min, R² = correlation coefficient.

The fitting of pseudo-second-order model for Cr(III) on expanded glass aggregate (Cr(III): 150 mg/L, pH 4, adsorbent dosage: 0.3 g, temperature: 298 K).

3.5

3.5 The effect of initial concentration and adsorption isotherms

The effect of initial Cr(III) concentration on Cr(III) adsorption by GA-APTES-TTU with different Cr(III) concentration solutions (100–600 mg/L) was also studied. The obtained results are illustrated in Fig. 8. It is understood that the adsorption of Cr(III) was increased with increasing equilibrium concentration in the low concentration range and reaches a plateau value at higher concentration. This result can be explained with an increase in loading capacity of the adsorbent in relation with the concentration of the metal ions.

The effect of initial concentration on the adsorption of Cr(III) (t: 120 min, adsorbent dosage: 0.3 g, pH 4.0, temperature: 298 K).

Experimental data obtained from the effect of initial concentration on adsorption capacity were analyzed by using the Langmuir and Freundlich isotherm models. Parameters of the Langmuir and Freundlich isotherm models for the adsorption of Cr(III) ion are given in Table 4. As illustrated in Table 4, the correlation coefficient (R²), for the Langmuir isotherm model was 0.9838 for GA-APTES-TTU adsorbent. It can be concluded that, the number of adsorption sites on GA-APTES-TTU was limited and metal ion adsorption can be occurred on a homogeneous surface. The Langmuir isotherm model assumes that adsorption takes place on a completely homogenous surface of the chemical adsorbents. In addition, this model is applicable to physical adsorption (monolayer) within a low concentration range (Baran et al., 2007; Li et al., 2015; Yang et al., 2014 ).

Table 4 The parameters of adsorption isotherms.

Model	Parameters
Langmuir	K_b	A_s	R²
	9.8136	0.4305	0.9838

Freundlich	K_f	1/n	R²
	2.1424	0.0203	0.4902

K_f = adsorption capacity (mmol/g adsorbent), n = experimental constant, R² = correlation coefficient, A_s = adsorption capacity (mmol/g), K_b = adsorption energy constant (L/mmol).

3.6

3.6 The effect of temperature and thermodynamic parameters

It is well known that the temperature is one of the important parameters for the adsorption process. Fig. 9 shows the effect of temperature on the Cr(III) adsorption. In order to investigate the effect of temperature on the adsorption of Cr(III) on GA-APTES-TTU, the equilibrium constant (K), was calculated at the temperatures of 298, 308, 323, and 333 K.

The effect of temperature on the adsorption of Cr(III) (Cr(III): 150 mg/L, t: 120 min, adsorbent dosage: 0.3 g, pH 4).

Furthermore, the results reveal that uptake of Cr(III) ions increases with the increasing temperature from 298 to 333 K. This is due to the endothermic adsorption reactions of Cr(III) ion with adsorbent. The obtained results are within the ranges of the physisorption mechanism.

Thermodynamic parameters such as standard free energy (ΔG°), enthalpy change (ΔH°), and entropy change (ΔS°) were calculated from the plotting of log K_eq versus 1/T (Fig. 9).

The Gibbs free energy change of the process was determined by the following equation:

(4)

Δ G^{o} = Δ H^{o} - T Δ S^{o}

(5)

\log K_{eq} = (\frac{Δ S °}{2.303 R}) - (\frac{Δ H °}{2.303 RT})

The values of ΔH° and ΔS° were calculated from the slope and intercept of the plot of log K_eq versus 1/T. Van’t Hoff type Eq. (5) was applied to determine the standard Gibbs free energies (ΔG°). The values obtained are given in Table 5. The negative values of ΔG° indicate that the adsorption process has spontaneous nature and it is thermodynamically favorable (Gubbuk et al., 2013; Debnath and Ghosh, 2008).

Table 5 The thermodynamic parameters for the adsorption of Cr(III) on expanded glass aggregate.

T (K)	1/T	ln K (kJ/mol)	ΔG^o (kJ/mol)	ΔH^o (kJ/mol)	ΔS^o (kJ/mol)
298	0.0033	1.1604	−2.8446
308	0.0032	1.2159	−3.1809	7.1782	0.0336
323	0.0031	1.3944	−3.6854
333	0.0030	1.4445	−4.0217

A positive ΔH° suggests that the adsorption of Cr(III) onto GA-APTES-TTU is endothermic, which is confirmed by the increasing adsorption of Cr(III) with the increasing temperature. The present results are similar to the results obtained by Debnath and Ghosh who studied the adsorption of Cr(III) and Cr(VI) from aqueous solutions by crystalline hydrous titanium oxide (Debnath and Ghosh, 2008). In addition, the positive entropy change (ΔS°) indicates an increase in the degree of freedom of the adsorbed species (Ghrab et al., 2014; Xu et al., 2010).

3.7

3.7 The effect of co-existing ions

In order to study the effect of co-existing ions, metal ions such as Cd and Cu were selected since they have a strong affinity to make complexes with TTU ligand. The adsorption studies were carried out in the presence of 150 mg/L salt solutions of cadmium nitrate, copper nitrate and chromium nitrate at pH 4.0. It can be concluded from the adsorption experiment results that Cd and Cu ions have no significant effect on removal of Cr(III).

The Cr(III) adsorption efficiency of the adsorbent decreased from 82.07% to 55.37% in the presence of 150 mg/L Cd and Cu ions.

3.8

3.8 The performance of GA-APTES-TTU on wastewater

Wastewater collected from leather organized industry-Isparta, Turkey, was studied for Cr(III) removal under same experimental conditions (t: 120 min., adsorbent dosage: 0.1 g, pH 4.0, temperature: 298 K), to check the suitability of the adsorbent for real wastewater treatment. The Cr(III) concentration of tanning wastewater sample was determined and found to be 0.682 mg/L. The final Cr(III) concentration was reduced to 0.411 mg/L for GA-APTES-TTU.

The performance of Cr(III) adsorption in the wastewater has been affected due to the presence of other ions by GA-APTES-TTU.

3.9

3.9 The re-usability of GA-APTES-TTU adsorbent

To determine the GA-APTES-TTU stability, adsorption capacity of the adsorbent for Cr(III) was examined in batch mode. GA-APTES-TTU adsorbent was kept in desiccator after each Cr(III) adsorption experiment. To also clean the adsorbent surface distilled water was used and dried after experiments. The adsorption process was repeated by using the same adsorbent in four runs of 30 day duration. Fig. 10 shows Cr(III) adsorption percentage versus experiment number.

Cr(III) adsorption percentage versus experiment number.

The Cr(III) adsorption capacity of the GA-APTES-TTU adsorbent decreased to almost half of the initial adsorption percentage. These adsorption experiments were carried out at a time of 4 months.

4 Conclusions

In this study, a novel adsorption material GA which is chemically modified by N-Benzoyl-N′-(4-methylphenyl)thiourea was developed and characterized. Cr(III) adsorption properties of this novel adsorbent (GA-APTES-TTU) were investigated by using various parameters. The maximum removal of Cr(III) was observed at an optimum pH of 4.0. Adsorption study indicated that the obtained experimental data fit better with the Langmuir type adsorption isotherm. Moreover, the adsorption kinetic data well fit with the pseudo-second-order model. The adsorption thermodynamic parameters were also calculated and determined for GA-APTES-TTU. The increase in K value with increasing temperature expressed that the adsorption of Cr(III) on the GA-APTES-TTU was an endothermic process.

On the basis of all results, it can be concluded that developed novel GA-APTES-TTU adsorbent has a strong potential for the efficient removal of Cr(III) from aqueous solutions.

Acknowledgment

The authors are grateful for the financial support provided by the Suleyman Demirel University Unit of Scientific Research Project under Project 3753-YL1-13.

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Chemical modification of expanded glass aggregate with N-Benzoyl-N′-(4-methylphenyl) thiourea (TTU) for the adsorptive removal of Cr(III) ion

Abstract

Keywords

Adsorption

Cr(III)

Glass aggregate

Modification

Thiourea

1 Introduction

2 Materials and methods

2.1 Modification of glass aggregate

2.2 Characterization of GA-APTES-TTU

2.3 Adsorption studies

3 Results and discussion

3.1 Characterization

3.2 Effect of pH

3.3 Effect of adsorbent dosage

3.4 Effect of contact time and adsorption kinetics

3.5 The effect of initial concentration and adsorption isotherms

3.6 The effect of temperature and thermodynamic parameters

3.7 The effect of co-existing ions

3.8 The performance of GA-APTES-TTU on wastewater

3.9 The re-usability of GA-APTES-TTU adsorbent

4 Conclusions

Acknowledgment

References

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