Equilibrium, Kinetic, and Thermodynamic Study of Removing Methyl Orange Dye from Aqueous Solution Using Zizphus spina-christi Leaf Powder





Adsorption, Dubinin-Radushkevich isotherm, Methyl orange, Pseudo-second-order, Thermodynamic parameters, Zizphus spina-christi leaf powder


In this study, Zizphus spina-christi leaf powder was applied for the adsorption of methyl orange. The effect of different operating parameters on the Batch Process adsorption was investigated such as solution pH (2-12), effect of contact time (0-60 min.), initial dye concentration (2-20 mg/L), effect of adsorbent dosage (0-4.5 g) and effect of temperature (20-50ᵒC). The results show a maximum removal rate and adsorption capacity (%R= 23.146, qe = 2.778 mg/g) at pH = 2 and equilibrium was reached at 40 min. The pseudo- second-order kinetics were found to be best fit for the removal process (R2 = 0.997). Different isotherm models (Langmuir, Freundlich, Dubini-Radushkevich,Temkin)  were applied in this study and the adsorption process was found to fit Dubinin-Radushkevich  isotherm (R2 = 0.970). The thermodynamic parameters:  ∆Gº, ∆Hº, ∆Sº were also invested, the results indicate the process to be exothermic (∆Hº = -100.933 kJ/mole), non-spontaneous, and more feasible at lower operating temperatures, with a decrease in the randomness at the solid-liquid interface (∆Sº = - 0.370 kJ/mole.K)


Download data is not yet available.


Bulgariu L, Escudero LB, Bello OS, Iqbal M, Nisar J, Adegoke KA, et al. The utilization of leaf-based adsorbents for dyes removal: A review. J Mol Liq . 2019; 276: 728-47 doi:https://doi.org/10.1016/j.molliq.2018.12.001

Kadhom M, Albayati N, Alalwan H, Al-Furaiji M. Removal of dyes by agricultural waste. Sustain Chem Pharm. 2020; 16: 100259 doi:https://doi.org/10.1016/j.scp.2020.100259

Ahmad A, Khan N, Giri BS, Chowdhary P, Chaturvedi P. Removal of methylene blue dye using rice husk, cow dung and sludge biochar: Characterization, application, and kinetic studies. Bioresour Technol. 2020; 306: 123202 doi:https://doi.org/10.1016/j.biortech.2020.123202

Xia L, Zhou S, Zhang C, Fu Z, Wang A, Zhang Q, et al. Environment-friendly Juncus effusus-based adsorbent with a three-dimensional network structure for highly efficient removal of dyes from wastewater. J Clean Prod. 2020; 259: 120812 doi:https://doi.org/10.1016/j.jclepro.2020.120812

Zhang F, Tang X, Huang Y, Keller AA, Lan J. Competitive removal of Pb2+ and malachite green from water by magnetic phosphate nanocomposites. Water Res. 2019; 150: 442-51 doi:https://doi.org/10.1016/j.watres.2018.11.057

Abu Elella MH, ElHafeez EA, Goda ES, Lee S, Yoon KR. Smart bactericidal filter containing biodegradable polymers for crystal violet dye adsorption. Cellulose. 2019; 26(17): 9179-206 doi:https://doi.org/10.1007/s10570-019-02698-1

Khatri J, Nidheesh PV, Anantha Singh TS, Suresh Kumar M. Advanced oxidation processes based on zero-valent aluminium for treating textile wastewater. Chem Eng J. 2018; 348: 67-73 doi:https://doi.org/10.1016/j.cej.2018.04.074

Obiora-Okafo IA, Onukwuli OD. Characterization and optimization of spectrophotometric colour removal from dye containing wastewater by Coagulation-Flocculation. Pol J Chem Technol. 2018; 20(4): 49-59 doi:https://doi.org/10.2478/pjct-2018-0054

Li C, Zhang M, Song C, Tao P, Sun M, Shao M, et al. Enhanced Treatment Ability of Membrane Technology by Integrating an Electric Field for Dye Wastewater Treatment: A Review. J AOAC Int. 2018; 101(5): 1341-52 doi:https://doi.org/10.5740/jaoacint.18-0050

Nwodika C, Onukwuli Do. Adsorption study of kinetics and equilibrium of basic dye on kola nut pod carbon. Gazi Univ J Sci. 2017;30(4):86-102

Abate GY, Alene AN, Habte AT, Getahun DM. Adsorptive removal of malachite green dye from aqueous solution onto activated carbon of Catha edulis stem as a low cost bio-adsorbent. Environ Syst Res. 2020; 9(1): 29 doi:https://doi.org/10.1186/s40068-020-00191-4

Boudechiche N, Fares M, Ouyahia S, Yazid H, Trari M, Sadaoui Z. Comparative study on removal of two basic dyes in aqueous medium by adsorption using activated carbon from Ziziphus lotus stones. Microchem J 2019; 146: 1010-8 doi:https://doi.org/10.1016/j.microc.2019.02.010

Zhang P, O’Connor D, Wang Y, Jiang L, Xia T, Wang L, et al. A green biochar/iron oxide composite for methylene blue removal. J Hazard Mater. 2020; 384: 121286 doi:https://doi.org/10.1016/j.jhazmat.2019.121286

Ragab A, Ahmed I, Bader D. The Removal of Brilliant Green Dye from Aqueous Solution Using Nano Hydroxyapatite/Chitosan Composite as a Sorbent. Molecules. 2019; 24(5) doi:10.3390/molecules24050847

Gouamid M, Ouahrani MR, Bensaci MB. Adsorption Equilibrium, Kinetics and Thermodynamics of Methylene Blue from Aqueous Solutions using Date Palm Leaves. Energy Procedia. 2013; 36: 898-907 doi:https://doi.org/10.1016/j.egypro.2013.07.103

Inyinbor A, Adekola F, Olatunji GA. Kinetics, isotherms and thermodynamic modeling of liquid phase adsorption of Rhodamine B dye onto Raphia hookerie fruit epicarp. Water Resour Ind. 2016; 15: 14-27 doi:https://doi.org/10.1016/j.wri.2016.06.001

Ekrami E, Dadashian F, Arami M. Adsorption of methylene blue by waste cotton activated carbon: equilibrium, kinetics, and thermodynamic studies. Desalination Water Treat. 2016; 57(15): 7098-108 doi:https://doi.org/10.1080/19443994.2015.1015173

Wang L, Chen Z, Wen H, Cai Z, He C, Wang Z, et al. Microwave assisted modification of activated carbons by organic acid ammoniums activation for enhanced adsorption of acid red 18. Powder Technol. 2018; 323: 230-7 doi:https://doi.org/10.1016/j.powtec.2017.10.021

Ragab A, Ahmed I, Bader D. The Removal of Brilliant Green Dye from Aqueous Solution Using Nano Hydroxyapatite/Chitosan Composite as a Sorbent. Molecules. 2019;24(5):847 doi: https://doi.org/10.3390/molecules24050847

Ahmad MA, Ahmad Puad NA, Bello OS. Kinetic, equilibrium and thermodynamic studies of synthetic dye removal using pomegranate peel activated carbon prepared by microwave-induced KOH activation. Water Resour Ind. 2014; 6: 18-35 doi:https://doi.org/10.1016/j.wri.2014.06.002

Aljeboree AM, Alshirifi AN, Alkaim AF. Kinetics and equilibrium study for the adsorption of textile dyes on coconut shell activated carbon. Arab J Chem. 2017; 10: S3381-S93 doi:https://doi.org/10.1016/j.arabjc.2014.01.020

Zhao P, Zhang R, Wang J. Adsorption of methyl orange from aqueous solution using chitosan/diatomite composite. Water Sci Technol. 2017; 75(7): 1633-42 doi:https://doi.org/10.2166/wst.2017.034

Sumanjit, Rani S, Mahajan RK. Equilibrium, kinetics and thermodynamic parameters for adsorptive removal of dye Basic Blue 9 by ground nut shells and Eichhornia. Arab J Chem. 2016; 9: S1464-S77 doi:https://doi.org/10.1016/j.arabjc.2012.03.013

Jawad AH, Ngoh Y, Radzun KA. Utilization of watermelon (Citrullus lanatus) rinds as a natural low-cost biosorbent for adsorption of methylene blue: kinetic, equilibrium and thermodynamic studies. J Taibah Univ Sci J. 2018; 12(4): 371-81 doi:https://doi.org/10.1080/16583655.2018.1476206

Jawad AH, Rashid RA, Ishak MAM, Ismail K. Adsorptive removal of methylene blue by chemically treated cellulosic waste banana (Musa sapientum) peels. J Taibah Univ Sci J. 2018; 12(6): 809-19 doi:https://doi.org/10.1080/16583655.2018.1519893

Saha PD, Chakraborty S, Chowdhury S. Batch and continuous (fixed-bed column) biosorption of crystal violet by Artocarpus heterophyllus (jackfruit) leaf powder. Colloids Surf B. 2012; 92: 262-70 doi:https://doi.org/10.1016/j.colsurfb.2011.11.057

Jain SN, Gogate PR. Adsorptive removal of acid violet 17 dye from wastewater using biosorbent obtained from NaOH and H2SO4 activation of fallen leaves of Ficus racemosa. J Mol Liq. 2017; 243: 132-43 doi:https://doi.org/10.1016/j.molliq.2017.08.009

Wong S, Tumari HH, Ngadi N, Mohamed NB, Hassan O, Mat R, et al. Adsorption of anionic dyes on spent tea leaves modified with polyethyleneimine (PEI-STL). J Clean Prod. 2019; 206: 394-406 doi:https://doi.org/10.1016/j.jclepro.2018.09.201

Ahmaruzzaman M. Removal of Methyl Orange from Aqueous Solution Using Activated Papaya Leaf. Sep Sci Technol. 2012; 47(16): 2381-90

Wong S, Tumari HH, Ngadi N, Mohamed NB, Hassan O, Mat R, et al. Adsorption of anionic dyes on spent tea leaves modified with polyethyleneimine (PEI-STL). J Clean Prod. 2019; 206: 394-406 doi:https://doi.org/10.1016/j.jclepro.2018.09.201

Krika F, Benlahbib OeF. Removal of methyl orange from aqueous solution via adsorption on cork as a natural and low-coast adsorbent: equilibrium, kinetic and thermodynamic study of removal process. Desalination Water Treat. 2015; 53(13): 3711-23 doi:https://doi.org/10.1080/19443994.2014.995136

Bhattacharyya KG, Sharma A. Azadirachta indica leaf powder as an effective biosorbent for dyes: a case study with aqueous Congo Red solutions. J Environ Manage. 2004; 71(3): 217-29 doi:https://doi.org/10.1016/j.jenvman.2004.03.002

Rattanapan S, Srikram J, Kongsune P. Adsorption of Methyl Orange on Coffee grounds Activated Carbon. Energy Procedia. 2017; 138: 949-54 doi:https://doi.org/10.1016/j.egypro.2017.10.064

Mizhir AA, Al-Lami HS, Abdulwahid AA. Kinetic, Isotherm, and Thermodynamic Study of Bismarck Brown Dye Adsorption onto Graphene Oxide and Graphene Oxide-Grafted-Poly (n-butyl methacrylate-co-methacrylic Acid). Baghdad Sci J. 2022; 19(1): 0132 doi:https://doi.org/10.21123/bsj.2022.19.1.0132

Mousa SA, Tareq S, Muhammed EA. Studying the Photodegradation of Congo Red Dye from Aqueous Solutions Using Bimetallic Au–Pd/TiO2 Photocatalyst. Baghdad Sci J. 2021; 18(4): 1261 doi:https://doi.org/10.21123/bsj.2021.18.4.1261