Thermodynamic and Kinetic Behaviors of Copper (II) and Methyl Orange (MO) Adsorption on Unmodified and Modified Kaolinite Clay

*Aicha Kourim, Moulay Abderrahmane Malouki and Aicha Ziouche*

## **Abstract**

In this study, the adsorption of Copper Cu (II) and methyl Orange (MO) from aqueous solution, on Tamanrasset's unmodified and modified Kaolinite clay which as low cost adsorbents, was studied using batch experiments. The adsorption study includes both equilibrium adsorption isotherms, kinetics and thermodynamics study. For the characterization of the adsorbent several properties are determined such as pH, the Specific Surface Area, the Point of Zero Charge and the Cation Exchange Capacity. Indeed, various parameters were investigated such as contact time, initial metal and dye concentration, mass of solid, pH of the solution and temperature. The adsorption process as batch study was investigated under the previews experimental parameters.

**Keywords:** Adsorption, Kaolinite, Copper, Methyl Orange, Kinetic, Isotherms

## **1. Introduction**

The extensive use of chemicals in developing and developed countries over the last century increased the amount of dyes and heavy metals which is released into surface and underground water through discharges of wastewater produced from metallurgical, mining, chemical, research laboratories, printing paper and battery manufacturing industries [1, 2]. Copper (Cu (II)) is extremely toxic, not biodegradable and it accumulated in living organisms, and may thus pose a threat to human beings. In addition, Copper ions is considered as vital transition metal ion because of its necessity in biological activities of living organism, whereas at certain concentration, it causes serious damages to human health and environment [3–5].

Methyl orange (MO) is an azo soluble dye, shows low biodegradability and is soluble in water hence it is difficult to remove from aqueous solutions by common water purification methods. As other dyes MO is toxic and carcinogenic, posing serious hazards to humans and the environment [6].

Purification of water can be achieved by physicochemical and biological methods. The physicochemical methods include precipitation [7], membrane filtration [8], liquid–liquid extraction [9] reverse osmosis [10], electrolysis or ultrasonic electrolysis [11], electrodialysis [12], electrodeposition [13], ion exchange resins [14], incineration and electrokinetic method [15], flotation [16], flocculation [17], coagulation [18], photocatalysis [19], adsorption and biosorption [20]. Biological process includes biodegradation or bioremediation [21], phycoremediation [22]. Adsorption method is more effective, economic with high potential and low energy consumption specially it has the advantage of the utilization of abundant with low cost adsorbents.

Clay minerals in the soil play the role of a natural scavenger by removing and accumulating pollutants through ion exchange and adsorption process. Generally, these minerals are categorized into Montmorillonite, smectites, Illite and kaolinite [23]. Kaolinite is a harmful charge clay mineral with a soft consistency. It made up of a silicon tetrahedral (T) sheet and an aluminum octahedral (O) sheet which called 1:1layer clay (2 sheets). Kaolinite has considered as an excellent adsorbent clay because of its high specific surface area, high exchange capacity, large potential for ion exchange, surface charges, charge density, chemical and mechanical stability, a variety of surface and structural properties, hydroxyl groups on the edge, silanol groups of crystalline defects or broken surfaces, and Lewis and Brönsted acidity [24–27]. Kaolinite clay also has been widely accepted as low cost abundant adsorbent for the removal of copper and methyl orange from wastewater due to the surface structure and edges. Recently many studies used natural kaolinite [28], other scientists used purified kaolinite in other wise other researchers used organo kaolinite as adsorbents [29]. However, kaolinite in its different geological origins may have variable chemical compositions and structural deformation. Elements such as Fe, Ti, Mn, Mg, and Cr, and impure phases, such as quartz, and Illite, are normally contained in natural kaolinite. Even, a small amount of these impurities may significantly affect the chemical properties of kaolinite. Those researches were carried out with physical or chemical modification of kaolinite in order to enhance the properties of kaolinite and to increase the adsorption capacity.

The aim of this paper is to access the ability of Tamanrasset's kaolinite clay and its derivatives (purified, activated, pillared and modified) to adsorb Cu(II) and MO from aqueous solution. The effect of the contact time, temperature, mass of solid, solution pH and concentration of the adsorbate was studied. The kinetics and factors controlling the adsorption were also studied. Therefore, the physicochemical characteristics of materials were considered such as pH, the specific surface area, the point of zero charge and the cation exchange capacity.

## **2. Material and methods**

#### **2.1 The adsorbate and solution**

The adsorbates in this study were copper and methyl orange prepared by dissolving CuCl2, 2H2O and MO into 1000 mL of deionized water to stock solution concentration of 1000 mg/L, the adjustment of pH in the solution was achieved by adding NaOH and HCl 0,1 M are from Sigma-Aldrich. The desirable experimental concentrations of solutions were prepared by diluting the stock solution with distilled water when necessary.

*Thermodynamic and Kinetic Behaviors of Copper (II) and Methyl Orange (MO) Adsorption on… DOI: http://dx.doi.org/10.5772/intechopen.98625*

## **2.2 The adsorbents**

## *2.2.1 Raw clay*

The natural clay sample was obtained from Tamanrasset south of Algeria. It was prepared before use by sun drying, then ground into fin particles and sieved to a particle size of 300 μm after that, it was stored in a desiccator for late experimental use.

### *2.2.2 Purified clay*

The clay was purified with the purpose of removing all crystalline phases and organic matter according to the procedure described by Robert and Tessier in order to obtain 2 micrometers clay fractions intercalated with sodium ions (Clay-Na) [30].

## *2.2.3 Activated clay*

The chemical activated clay was carried out by adding 50 g of raw clay to 500 ml of sulfuric acid 1.5 M and refluxing at 110°C for 4 h. The resulting clay suspension was then rapidly quenched by adding 500 ml of ice water. After cooling the sample was washed several times with distilled water until neutral pH, then filtered, dried in oven and calcined at 500°C for 4 hours [31, 32].

#### *2.2.4 Pillared clay*

The pillaring solution was prepared by the slow addition of NaOH 0.225 M to a 0.5 M solution of AlCl3 at room temperature, until a molar ratio of OH/Al = 1.8 was reached. The pillaring of Clay-Na by polycation of aluminum is carried out according to the conventional procedure (cationic exchange with a heat treatment) [33].

#### *2.2.5 Clay-CTAB*

In 500 ml Buchner, 10 g of purified clay was added to 250 ml of CTAB solution 0.02 M, the mixture was stirring at room temperature for 24 h. Then, the suspension was filtered and washed several times until the negative test of Br-. The CTAB-Clay was dried at 105°C for one hour, ground and stored in sterile glass box [34, 35].

#### **2.3 Physicochemical characteristics of adsorbents**

#### *2.3.1 The pH of adsorbent*

Ten grams of crushed kaolinite was stirred in 75 ml of deionized water in a beaker over the night then it filtered. The pH was measured by a glass electrode (pH METER HI2210) [36].

#### *2.3.2 The specific surface area*

Sear's method was chosen to estimate the surface areas of clay adsorbents [37]. 0.5 g of each clay was acidified with 0.1 M HCl to a pH 3–3,5. The volume was made up to 50 ml with distilled water after addition of 10 g of NaCl. The titration was carried out with standard 0.1 M NaOH buffer solution from pH 4 to pH 9. The volume, V, required to raise the pH from 4 to 9 was noted and the surface area was computed from the following equation:

$$\mathbf{S(m^2/g)} = \mathbf{32V} - \mathbf{25} \tag{1}$$

## *2.3.3 The point of zero charge*

The point of zero chare or pHPzc is point where the net charge of the material equal to 0. The PZC war determined by the pH drift method [38, 39].

#### *2.3.4 The cation exchange capacity*

The CEC of materials was calculated by methylene blue method [40].

#### **2.4 Bath equilibrium studies**

Bath experiments were performed in asset of 250 mL Erlenmeyer flasks that contain a volume of 100 mL in each flask of fixed initial concentrations of metal and dye solutions. The flasks were kept in a thermostated water bath (Wise bath® eed Back Control Digital Timer Function, Laboratory Instruments) shaker at a constant speed of 150 rpm for 360 min (6 h). The sample solutions were filtered at equilibrium to determine the residual concentrations. The amount of adsorbate adsorbed at the equilibrium condition, qe (mg/g), was calculated by the following Equations [41]:

$$q\_{\epsilon} = \frac{(\mathbf{C}\_0 - \mathbf{C}\_{\epsilon})V}{W} \tag{2}$$

Were C0 and Ce are the initial and equilibrium metal and dye concentrations (mg/L), respectively. V is the volume of solution (L) and W is the mass of adsorbent used (g).

The concentration of Cu(II) before and after adsorption was determined by a flam atomic absorption spectrometry (Analyst 700 Perkin Elmer Atomic Absorption Spectrometer) and the concentration of MO was determined by UV–Visible spectrometry (M209T Spectronic Camspec).

#### **2.5 Kinetics studies**

The kinetic experiments, adsorption capacity of Cu (II) and MO at time t, qt (mg/g), was calculated as follows:

$$q\_t = \frac{(C\_0 - C\_t)V}{W} \tag{3}$$

Were Ct (mg/L) is the concentration of copper/Methyl orange at any time t (min).

## **3. Results and discussion**

#### **3.1 Characterization of adsorbents**

#### *3.1.1 pH and the point of zero charge*

The surface of kaolinite has a net positive surface charge at pH < PZC, whereas at pH > PZC, it has a negative surface charge. The PZC value or natural kaolinite was8.9 this value indicates that the adsorption of copper and methyl orange by untreated kaolinite will occur at pH ≥ 8.9.

*Thermodynamic and Kinetic Behaviors of Copper (II) and Methyl Orange (MO) Adsorption on… DOI: http://dx.doi.org/10.5772/intechopen.98625*

#### *3.1.2 Surface area*

The specific surface area of 5 to 25 m<sup>2</sup> /g for the untreated kaolinite clay. The specific surface area of natural, purified, activated, pillared, and CTAB kaolinite are measured as 25.4, 36.7, 30.14, 42.1 and 43.15 m<sup>2</sup> /g, respectively. The specific surface area increased up to 30.1 for activated clay. Such the high value of specific area is not achieved in the present work by treatment with 1.5 M H2SO4 acid. The chemical modification opens up the edge of the platelets and as consequence, the surface area and the pore diameter increase too.

## *3.1.3 Cation exchange capacity*

The kaolinite used in the present work had CEC of 5.92 meq/100 g as measured by methylene blue method. Kaolinite as other clay minerals contain both Brönsted and Lewis acid cites associated respectively with the interlamellar region and the edge sites.

The ions exchange capacity of kaolinite is attributed to the structural defects, broken bonds and structural hydroxyl transfers. Chemical modifications increase the total number of exchange sites. The results obtained are summarized in **Table 1**.

## **3.2 Bath studies**

## *3.2.1 Effect of adsorbent dose*

The adsorbent dose is an important parameter too because it determines the capacity of adsorbent for a given initial concentration of metal solution.

**Figure 1a** and **b** showed that the amount adsorbed qe decrease with the increase of adsorbent dosage. This is due to the increase in surface area and hence more available adsorption sites competing for the same number of initial ion concentration [42].

#### *3.2.2 Effect of time contact and initial concentration*

Equilibrium time is an important parameter in the studies of wastewater treatment. The adsorption of Cu2+ onto clay (0,08 g of raw, purified and pillared clay, 0.1 g of activated clay and 0.06 of modified CTAB clay) at various initial concentrations (5, 25, 50, and 100mg/L), and in the case of methyl orange the dosage of modified and unmodified clay was 0.1 g at various initial concentrations (5, 20, and 35 mg/L) was studied as a function of contact time in order to determine the necessary adsorption equilibrium time.

**Figure 2a** and **b** shows the effects of contact time and initial concentration on the adsorption of copper and methyl orange into raw clay. We notice that the adsorption is rapid at the initial stages during 10–50 minutes. This is due to the fast


#### **Table 1.** *Physicochemical properties of adsorbents.*

**Figure 1***. Effect of adsorbent dose on the amount adsorbed onto copper and methyl orange.*

that there were a large number of vacant sites for metal on the external surface of clay particles. Then it's gradually decreases with the progress of adsorption until the equilibrium is reached because of the active sites saturation of the adsorbent [43, 44]. As shown in **Figure 2**, the contact time for the Cu(II) and MO to reach equilibrium was 50 min and 60 min, respectively.

The **Table 2** below shows the adsorption capacity of adsorbed at the equilibrium (qe) increased with an increase in the initial concentrations.

#### *3.2.3 Effect of pH on the amount adsorbed*

pH is the most important environmental factors influencing not only site dissociation, but also the solution chemistry and in the efficiency of adsorption [45], it effects both the dye structure and the surface on the adsorbent. As seen in **Figure 3** the sorption capacity of copper increased whenever pH of the solution increases. While, the adsorption amount of methyl orange onto the clay increases as pH is lowered from 11 to 2, confirmed that the initial solution pH is a key adsorption parameter that strongly affects metal and dye adsorption because of the decreased positive charges on the adsorbent surface with an increased pH. The pH of the solution also affects the solubility and species of adsorbate, the adsorbents, and the degree of ionization of the adsorbate [46–48].

**Figure 2.** *Effect of initial concentration and contact time.*

*Thermodynamic and Kinetic Behaviors of Copper (II) and Methyl Orange (MO) Adsorption on… DOI: http://dx.doi.org/10.5772/intechopen.98625*


**Table 2.**

*The amount adsorbed.*

**Figure 3.** *Effect of pH.*

### *3.2.4 Effect of temperature on the amount of adsorption*

Because temperature is an important parameter for adsorption process and bath adsorption studies were carried out at different temperatures and concentrations of Cu(II) ions and MO dye. The amount of sorption increasing with increasing temperature witch indicates that the nature of this adsorption is a chemical sorption [42]. Whereas, the adsorption capacity of MO onto raw and activated kaolinite decrease whenever temperature increase, as shown if **Figure 4**, indicating possibilities of reversible adsorption process [49].

#### **3.3 Kinetic studies**

Two kinetic models fitted this adsorption process very well as explained below [50, 51].

#### *3.3.1 Pseudo-first order kinetic model*

The pseudo first-order kinetic model is expressed as:

$$\log\left(q\_{\varepsilon} - q\_{t}\right) = \log q\_{\varepsilon} - \left(\frac{k\_{1}}{2.303}\right)t \tag{4}$$

Where **qt** is the amount adsorbed (mg/g) at time t (sec) and **k1** is the pseudo-first order constant (s�<sup>1</sup> ) and calculated by linear regression of log(qe-qt) versus t plot.

#### *3.3.2 Pseudo-second order kinetic model*

The pseudo second-order kinetic model is given as:

$$
\left(\frac{t}{q\_t}\right) = \left(\frac{t}{q\_\epsilon}\right) + \left(\frac{1}{k\_2 q\_\epsilon^2}\right) \tag{5}
$$

**Figure 4.** *Effect of varying temperatures on the amount adsorbed.*

Where, **k2** is the pseudo second order rate constant (g.mg�<sup>1</sup> .s�<sup>1</sup> ) and can be calculated by linear regression of *<sup>t</sup> qt* versus **t** plot. The adsorption kinetics constants and the correlation coefficient values R2 are summarized in **Tables 3** and **4**: The values of the correlation coefficient R2 of the pseudo-second order model are significantly higher than those of the pseudo-first model.

## **3.4 Adsorption isotherms**

The adsorption isotherm of Cu2+ and MO was checked whether it fits the Langmuir and Freundlich isotherms (**Table 5**).


*Thermodynamic and Kinetic Behaviors of Copper (II) and Methyl Orange (MO) Adsorption on… DOI: http://dx.doi.org/10.5772/intechopen.98625*


**Table 3.**

*Kinetic parameters for the adsorption of Cu(II) onto adsorbents at different initial concentrations.*


#### **Table 4.**

*Kinetic parameters for the adsorption of MO onto adsorbents at different initial concentrations.*

The Langmuir isotherm theory assumes that the adsorption is single-layer and takes place at homogenous sites specific to the adsorbent. The equation of Langmuir isotherm model is given as:

$$\frac{C\_{\epsilon}}{q\_{\epsilon}} = \frac{1}{K\_{L}} \frac{C\_{\epsilon}}{q\_{\max}} + \frac{C\_{\epsilon}}{q\_{\max}} \tag{6}$$

and the Freundlich isotherm assumes that the adsorption is multi-layer and that the surface of the adsorbent heterogeneous [52]:

$$
\ln q\_{\epsilon} = \ln K\_F + \frac{1}{n} \ln \mathcal{C}\_{\epsilon} \tag{7}
$$

Where KL Langmuir isotherm constant (L/mg), n is the degree of non-linearity and KF is Freundlich isotherm constant (mg1–1/n L1/ng).


#### **Table 5.**

*Adsorption isotherms of copper onto kaolinite clay.*

The data show that Langmuir model is more suitable to describe the adsorption reaction of copper and methyl orange on modified kaolinite and it is better fitted to Freundlich isotherm model onto natural clay with experimental data with higher R2 values. So it's surface mono-layer adsorption and the adsorption sites are homogeneous.

*Thermodynamic and Kinetic Behaviors of Copper (II) and Methyl Orange (MO) Adsorption on… DOI: http://dx.doi.org/10.5772/intechopen.98625*


#### **Table 6.**

*Thermodynamics parameters at different temperatures.*

#### **3.5 The thermodynamic studies**

The thermodynamic parameters **ΔG°, ΔH°** and **ΔS°** are computed from the plots on ln KL vs. 1/T, and are better described by following Equations [53]:

$$
\ln K\_L = \frac{\Delta S}{R} - \frac{\Delta H}{RT} \tag{8}
$$

$$
\Delta G = \Delta H - T\Delta S \tag{9}
$$

Where, **R** is The gas constant 8.314\*10<sup>3</sup> (KJ/mol. K), **T** is temperature (K) and **KL** known as the distribution coefficient of the adsorbate, is equal to Ce/qe(L/g) (**Table 6**).

### **4. Conclusion**

The thermodynamics and kinetic study of the removal of copper (II) and methyl orange from aqueous solution using natural clay and its composites has been investigated in this work. The adsorption process showed that purified and CTAB clays were effective in the uptake of copper and methyl orange from aqueous solutions until 34.12 mg/g and 15.78 mg/g, respectively. Whereas, activated and pillared kaolinite are not efficient adsorbent for the removal of Cu(II) and methyl orange, respectively; with amount of adsorption less than 2 mg/g. The amounts of Cu2+ and MO were found to vary with pH and the dose of adsorbent. The adsorption data conformed to Langmuir model, and its fitted to pseudo first order and pseudo second order. However, pseudo second order best described for the adsorption process. The determined negative free energy changes ΔG° and positive entropy ΔS ° indicated the feasibility and spontaneous nature of the adsorption process. The negative value of enthalpy change ΔH° suggests that the adsorption process is exothermic, while, the interactions are entotermic accompanied by increase in entropy and Gibbs energy.

*Clay and Clay Minerals*

## **Author details**

Aicha Kourim<sup>1</sup> \*, Moulay Abderrahmane Malouki<sup>2</sup> and Aicha Ziouche<sup>3</sup>

1 Department of Material Sciences, University of Tamanrasset, Algeria

2 Sciences and Environment Research Laboratory, University of Tamanrasset, Algeria

3 Research Center in Industrial Technologies CRTI, Algiers, Algeria

\*Address all correspondence to: aichakourim@gmail.com

© 2021 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

*Thermodynamic and Kinetic Behaviors of Copper (II) and Methyl Orange (MO) Adsorption on… DOI: http://dx.doi.org/10.5772/intechopen.98625*

## **References**

[1] A. Bogusz, P. Oleszczuk and R. Dobrowlski, "Application of laboratory prepared and commercially available biochars to adsorption of cadmium, copper and zinc ions frow water," Bioresource Technology*,* pp. 196, 540-549 doi: 10.1016/j. biortech.2015.08.006, 2015.

[2] X. Yan, Y. Wan, Y. Zheng, F. He, Z. Yu, J. Huang, H. Wang, Y. S. Ok, Y. Jiang and B. Gao, "Surface functional groups of carbon-based adsorbents and their roles in the removal of heavy metals from aqueous solutions: A critical review," Chemical Engineering Journal*,* vol. 366, pp. 608-621, 2019.

[3] Taty-Costodess, H. Fauduet, C. Porte and A. Delacroixs, "Removal of Cd(II) and P(II) ions from aqueous solutions by adsorption onto sawdust of pinus sylvestris," J Hazard Master*,* pp. 105 (1-3): 121-142, 2003.

[4] Wang, Y. Pan, P. Cai, T. Guo and H. Xiao, "Single and binary adsorption of heavy metal ions from aqueous solutions using sugarcane cellulose-based adsorbent," Bioresource Technology*,* pp. 241, 482-490 doi: 10.1016/j. biortech.2017.05.162, 2017.

[5] Y. Zhou, Y. He, Y. Xiang, S. Meng, X. Lui, J. Yu, J. Yang, J. Zhang, P. Qin and L. Luo, "Single and simultaneous adsorption of pefloxacin and Cu(II) ions from aqueous solutions by oxidized multiwalled carbon nanotube," Science of the Total Environment*,* vol. 646, pp. 29-36, 2019.

[6] Y. Tang, J. Tian, T. Malkoske, W. Le and B. Chen, "Facile ultrasonic synthesis of novel zinc sulfide/carbon nanotubecoaxial nanocables for enhanced photodegradation of methyl orange," J. Mater Sci., no. 52, pp. 1581-1589, 2017.

[7] G. M. Worrall, J. T. Buswell, C. A. English, M. G. Hetherington and

G. D. W. Smith, "A study of the precipitation of copper particles in a ferrite matrix," Journal of Nuclear Materials, vol. 148, pp. 107-114, 1987.

[8] R. S. Juang and M. N. Chen, "Removal of Copper (II) Chelates of EDTA and NTA from Dilute Aqueous Solutions by Membrane Filtration," Ind. Eng. Chem. Res, vol. 36, no. 1, pp. 179-186, 1997.

[9] G. T. Wei, J. C. Chen and Z. Yang, "Studies on Liquid/Liquid Extraction of Copper Ion with Room Temperature Ionic Liquid," Journal of the Chinese Chemical Society, vol. 50, pp. 1123-1130, 2003.

[10] T. Bakalár, M. Búgel and L. Gajdošová, "Heavy metal removal using reverse osmosis," Acta Montanistica Slovaca, vol. 3, pp. 250-253, 2009.

[11] R. Farooq, Y. Wang, F. Lin, S. F. Shaukat, J. Donalson and A. J. Chouhdary, "Effect of ultrasound on the removal of copper from the model solutions for copper electrolysis process," Water Research, vol. 36, no. 12, pp. 3165-3169, 2002.

[12] F. S. Eberhard and I. Hamawand, "Selective Electrodialysis for Copper Removal from Brackish Water and Coal Seam Gas Water," International Journal of Environmental Research, vol. 11, pp. 1-11, 2017.

[13] A. Kuleyin and H. Erikli-Uysal, "Recovery of Copper Ions from Industrial Wastewater by Electrodeposition," International Journal of ELECTROCHEMICAL SCIENCE, vol. 15, pp. 1474-1485, 2020.

[14] R. K. Misra, S. K. Jain and P. K. Khatri, "Iminodiacetic acid functionalized cation exchange resin for adsorptive removal of Cr(VI), Cd(II), Ni(II) and Pb(II) from their aqueous

solutions," Journal of Hazardous Materials, vol. 185, pp. 1508-1512, 2011.

[15] T. Huang, L. Liu, S. Wu and S. Zhang, "Research on a closed-loop method that enhances the electrokinetic removal of heavy metals from municipal solid waste incineration fly ashes," Chem. Pap., vol. 73, pp. 3053-3065, 2019.

[16] E. A. Deliyanni, G. Z. Kyzas and K. A. Matis, "Various flotation techniques for metal ions removal," Journal of Molecular Liquids, vol. 225, pp. 260-264, 2017.

[17] G. K. G. C. Barros, R. P. F. Mel and E. L. B. Neto, "Removal of copper ions using sodium hexadecanoate by ionic flocculation," Separation and Purification Technology, vol. 200, pp. 294-299, 2018.

[18] X. Tang, H. Zheng, H. Teng, Y. Sun, J. Guo, W. Xie, Q. Yang and W. Chen, "Chemical coagulation process for the removal of heavy metals from water: a review," Desalination and Water Treatment, vol. 57, no. 4, pp. 1733-1748, 2016.

[19] L. Clarizia, M. RaceLuca, L. Onotri, I. Somma, N. Fiorentino, R. Andreozzi and R. Marotta, "Removal of Copper, Iron and Zinc from Soil Washing Effluents Containing Ethylenediaminedisuccinic Acid as Chelating Agent Through Sunlight Driven Nano-TiO2-Based Photocatalytic Processes," Nanotechnologies for Environmental Remediation, pp. 239-253, 2017.

[20] J. B. Dulla, M. R. Tamana, S. Boddu, K. Pulipati and K. Srirama, "Biosorption of copper(II) onto spent biomass of Gelidiella acerosa (brown marine algae): optimization and kinetic studies," Appl. Water Sci., vol. 56, no. 10, 2020.

[21] F. Akhtar, K. M. Archana, V. G. Krishnaswamy and R. Rajagopal, "Remediation of heavy metals (Cr, Zn) using physical, chemical," SN Applied Sciences, vol. 267, no. 2, 2020.

[22] S. Ahmad, A. Pandey, V. Pathak, V. Tyagi and R. Kothari, "Phycoremediation: Algae as Ecofriendly Tools for the Removal of Heavy Metals from Wastewaters," in Bioremediation of Industrial Waste for Environmental Safety, 2020, pp. 53-76.

[23] S. E. Bailey, T. J. Olin, M. R. Bricka and D. D. Adrian, "A review of potentially low- cost sorbents for heavy metals," Water Research, vol. 33, no. 11, pp. 2469-2479, 1999.

[24] H. H. Murray, "Applied clay mineralogy today and tomorrow," Clay Minerals, no. 34, pp. 39-49, 1999.

[25] T. J. Rong and J. Xiao, "The catalytic cracking activity of the Kaolin group minerals," Materials Letters, no. 57, pp. 297-301, 2002.

[26] V. Vimonses, S. Lei, B. Jin, W. K. Chow and C. Saint, "Adsorption of congo red by three Australian kaolins," Applied Clay Science, vol. 43, no. 3-4, pp. 465-472, 2009.

[27] X. Lui, X. Lu, M. Sprik, J. Cheng, E. J. Meijer and R. Wang, "Acidity of edge surface sites of montmorillonite and kaolinite," Geohimica et Cosmochimica Acta, vol. 117, pp. 180-190, 2013.

[28] J. Won, X. Wirth and S. E. Bums, "An experimental study of cotransport of heavy metals with kaolinite colloids," Journal of Hazardous Materials, no. 373, pp. 476-482, 2019.

[29] M. O. Omorogie, F. O. Arunbiade, M. O. Alfred, O. T. Olaniyi, T. A. Adewumi, A. A. Bayode, A. E. Ofomaja, E. B. Naidoo, C. P. A. T. A. Okoli and E. I. Unuabonah, "The sequestral capture of fluoride, itrate and phosphate by metal-doped and sulfactant-modified hybrid clay materials," Chem. Pap., vol. 72, no. 2, pp. 409-417, 2018.

*Thermodynamic and Kinetic Behaviors of Copper (II) and Methyl Orange (MO) Adsorption on… DOI: http://dx.doi.org/10.5772/intechopen.98625*

[30] M. Robert and D. Tessier, "Méthode de préparation des argiles des sols pour études minéralogiques," Ann. Agrom*,* pp. 25, 859-882, 1974.

[31] V. Sori, T. Roy, S. Dhara, G. Choudhary, P. Sharma and R. K. Sharma, "On the ivestigation of acid and sulfactant modification of natural clay for photocatalytic water remediation," J Master Sci*,* pp. 53, 10095-10110, 2018.

[32] A. K. Panda, B. G. Mishra, D. K. Mishra and R. K. Singh, "Effect of sulphuric acid treatment on the physicchemical characteristics of kaolin clay," *Colloids and Surfaces A : Physicochem.* Eng. Aspects*,* pp. 363, 98-104, 2010.

[33] D. Nistor, N. D. Miron and I. Siminiceanu, "PREPARATION DES ARGILES PNTEES D'ORIGINE ROUMAINE AVEC DES POLYCATIONS D'ALUMINIUM ET DE FER," *Quatrième Colloque Franco-Roumain de Chimie Appliquée,* pp. VII(3), 1582-540X, 2006.

[34] M. A. Akl, A. M. Youssef and M. M. Al-Awadhi, "Adsorption of Acid Dyes onto Bentonite and Sulfactant-modified Bentonite," J. Anal. Bioanal. Tech.*,* p. 4: 174, 2013.

[35] L.-G. Yan, L.-L. Qin, H.-Q. Yu, S. Li, R.-R. Shan and B. Du, "Adsorption of acid dyes from aqueous solution by CTMAB modified bentonite: Kinetic and isotherm modeling," Journal of Molecular Liquids*,* pp. 211, 1074-1081, 2015.

[36] W. Keller and K. Matlack, "The pH of clay suspensions in the field and laboratory, and methods of meausurment of their pH," Applied Clay Science*,* pp. 5, 123-133, 1990.

[37] K. G. Bhattacharyya and S. S. Gupta, "kaolinite, montmorillonite, and thier modified derivatives as adsorbent for removal of Cu (II) from aqueous solution," Separation and Purification Technology*,* pp. 50,388-397, 2006.

[38] M. V. Lopez-Raman, F. Stoeckli, C. Morino-Castilla and F. Carrasco-Marin, "On the characterization of acidic and basic surface sites on carbons techniques," Carbon*,* pp. 37: 1215-1221, 1999.

[39] K. M. A. Kifuani, V. P. Noki, D. P. J. Ndelo, W. M. D. Mukana, B. G. Ekoko, L. B. Ilinga and M. J. Mukinayi, "Adsorption de la quinine bichlorohydrate sur un charbon actif peu couteux à base de Bagasse de canne à sucre imprégnée de l'acide phosphorique," *Int. J. Biol. Chem. Sci.,* pp. 6(3): 1337-1359, 2012.

[40] J. Cenens and R. A. Schoonheydt, "VISIBLE SPECTROSCOPY OF METHYLENE BLUE ON HECTORITE, LAPONITEB, AND BARASYMIN AQUEOUS SUSPENSION," *Clays and Clay Minerals,* vol. 36, no. 3, pp. 214-224, 1988.

[41] R. Torres-Caban, C. V. Vega-Olivencia, L. Alamo-Nole, D. Morales-Irizarry, F. Romman-Velazquez and N. Mina-Camilde, "Removal of Copper from Water by Adsorption with Calcium-Algate/Spent-coffe-Grounds Composite Beads," Materials*,* pp. 12, 395, 2019.

[42] Y. H. Li, B. Xia, Q. S. Zhao, F. Q. Lui and P. Zhang, "Removal of copper ions from aqueous solution by calcium alginate immobilized kaolin," J. Environ. Sci*,* pp. 23, 404-411, 2011.

[43] S. V. Badmaeva, S. T. Khankhasaeva and E. T. Dashinamzhilova, "Experimental Simulation of Sorption Processes of Heavy Metals on Natural Clay Minerals," in *IOP Conference Serie: Earth and Environmental Science*, 2019.

[44] F. Hamadache, A. Chergui, F. Halet, A. R. Yeddou and B. Nadjemi, "Copper, Zinc and Nickel's removal by bentonite clay: case study in mono and multicomponent systems," *Algerian* Journal of Environmental Science and Technology*,* pp. 2437-1114, 2019.

[45] R. Msaadi, G. Yilmaz, A. Allushi, S. Hamadi, S. Ammar, M. M. Chehimi and Y. Yagci, "Highly Selective Copper Ion Imprited Clay/Polymer Nanocomposites Prepared by Visible Light Initiated Radical Photopolymerization," Polymers*,* pp. 11, 286, 2019.

[46] J. T. Nwabanne and P. K. Igbokwe, "The thermodynamic and kinetic behaviors of lead (II) adsorption on Activaed Carbon derived from Palmyra Plam Nut," *International Journal of Applied ,* pp. Vol,2 No.3, 2012.

[47] K. Huang, Y. Xia and H. Zhu, "Removal of heavy metal ions from aquous solution by chemically modified mangosteen pericarp," Desalin. Water Treat.*,* pp. 52, 7108-7116, 2014.

[48] P. Pavasant, R. Apiratikul, V. Sungkhum, P. Suthiparinyanont, S. Wattanachira and T. F. Marhaba, "Biosorption of Cu2+, Cd2+, Pb2+, and Zn2+ uzing dried marine green macroalga Caulerpa Lentillifera," Bioresour Technol*,* pp. 97, 2321-2329, 2006.

[49] A. T. Sdiri, T. Higashi and F. Jamoussi, "Adsorption of copper and zinc onto natural clay in single and binary systems," Int. J. Environ. Sci. Technol*,* pp. 11, 1081-1092, 2014.

[50] S. Lagergren, "About the theory of so-called adsorption of soluble substances, Kungliga Svenska Vetenskapsakademiens," handlingar, pp. 24: 1-39, 1898.

[51] Y. S. Ho and G. McKay, "Pseudo-second order model for sorption processes," Process Biochemistry, pp. 34: 451-465, 1999.

[52] D. Saha, N. Mirando and A. Levchenko, "Liquid and vapor phase adsorption of BTX in lignin derived activated carbon: Equilibrium and kinetics study," Journal of Cleaner Production, pp. 182, 372-378, 2018.

[53] A. Ozer, F. Tumen and M. Bildik, "Cr (III) Removal from Aqueous Solutions by Depectinated Sugar Beet Pulp," Environment Technology, pp. 18: 9, 893-901, 1997.

## **Chapter 4**
