Equilibrium and Kinetics Studies of the Adsorption of Basic Dyes onto PVOH Facilely Intercalated Kaolinite - A Comparative Study of Adsorption Efficiency


  • Chigbundu C. Emmanuel Bells University of Technology, Ota, Ogun State, Nigeria
  • Adebowale O. Kayode Faculty of Sciences, University of Ibadan, Oyo State, Nigeria.


Intercalation, polyvinyl alcohol, kaolinite, Basic dyes, adsorption equilibrium


Communication in Physical Sciences, 2021, 7(4): 331-347

Authors: Chigbundu C. Emmanuel* and Adebowale O. Kayode

Received:29 September 2021/Accepted 23 November 2021

Most basic dyes are known for their toxic impact on the environment, especially in the aquatic ecosystem. . Unfortunately, consistent discharge of dye containing wastes into most water bodies has generated serious challenges, which can only be solved through consistent research approaches. his study is designed to compare the adsorption capacities of purified (PRK) and polyvinyl alcohol (PVOH) intercalated raw kaolinite (PIK) for the adsorption of some basic dyes from an aqueous solution. Scanning electron microscope (SEM) with energy dispersive X-ray (EDX), Fourier-transform infrared (FTIR) Spectroscopy and X-ray diffractometer (XRD) were used to verify changes in morphology, surface functional groups and crystal lattice sequence adjustment in PIK adsorbent. Cation Exchange Capacity (CEC) and Point of Zero Charge (PZC) of both adsorbents were determined by methylene blue adsorption and salt addition technique, respectively. The adsorption characteristics of both adsorbents were investigated under various conditions such as varying adsorbent dosages, period of contact, temperature and pH. Thermodynamic parameters were used to evaluate the effect of temperature on the adsorption process, while non-linear regressions were used to fit the experimental data to various adsorption and kinetic models. UV-visible spectrometer was used to determine the absorbance of dyes left in the solution un-adsorbed throughout the experimental study.  The morphology of PIK revealed a compacted structure with pores, while the crystal lattice adjustment of PIK showed basal plane contraction to 4.06Å when compared with PRK respectively. Surface functionality study revealed several peaks such as CH3 and CH2 assigned to 2893 and 2990 cm-1 respectively on PIK but absent on the FTIR graph of PRK.  The adsorption isotherm model showed that PIK was twice efficient for the uptake of BR2 and BG5 compared to PRK. The Elovich model equation suitably described the adsorption kinetics while the thermodynamic parameters revealed that the adsorption was spontaneous and endothermic. In comparison to other desorption agents, acetic acid was found to be a good desorption agent.


Download data is not yet available.

Author Biographies

Chigbundu C. Emmanuel, Bells University of Technology, Ota, Ogun State, Nigeria

Chemical and Food Sciences Department

Adebowale O. Kayode, Faculty of Sciences, University of Ibadan, Oyo State, Nigeria.

Department of Chemistry


Abdullahi T., Harun Z. and Othman M. H. D. (2017). A review on sustainable synthesis of zeolite from kaolinite resources via hydrothermal process. Advanced Powder Technology, 28, 8, pp 1827-1840, https://doi.org/10.1016/j.apt.2017.04.028.

Abella, S. R. and Zimmer, B. W. (2007). Estimating organic carbon from loss-on-ignition in northern Arizona forest soils. Soil Science Society of America Journal. 71, pp. 545–550.

Adebowale, K. O., Olu-Owolabi, B. I., Chigbundu, E. C. (2014). Removal of Safranin-O from aqueous solution by adsorption onto kaolinite clay. Journal of Encapsulation and Adsorption Sciences. 4, pp. 89-104. http://dx.doi.org/10.4236-/jeas.2014.43010

Adejumoke A. I., Folahan A. A. and Gabriel A. (2015). Adsorption of Rhodamine B Dye from Aqueous Solution on Irvin giagabonensis Biomass: Kinetics and Thermodynamics Studies. South African Journal of Chemistry. 68, pp. 115–125

Ahmad, R. and Kumar, R. (2010). Adsorptive removal of Congo red dye from aqueous solution using bael shell carbon. Applied Surface Science. 257, pp. 1628–1633.

Tabak A., Afsin B., Caglar B. and Caglar S. 2016. dimethyl Sulfoxide Species Entrapped by Raw and Acid-Activated Sepiolite Framework. Sinop University Journal of Natural Sciences. 1, 1, pp. 76 – 82.

AL Da,amy M.A. AL Rubaeey, E.T. AL Khaleeli, A.B. Abdul Majeed, M.N. and AL Njar Z.A. (2013) Adsorption of cationic dyes from synthetic textile effluent by Iraqi porcelanite rocks, Journal of Asian Scientific Research, 3, 10. pp. 1011-1021.

Alkan, M., Benlikaya, R., (2009). Poly (vinyl alcohol) Nanocomposites with sepiolite and heat-treated Sepiolites. Journal of Applied Polymer Science. 112, pp. 3764–3774. DOI 10.1002/app.29830

Bahareh A. E., Banafsheh A. E., Mina S. K, and Seyyedeh Z.G. (2014). Industrial wastewater treatment by membrane systems. Indian Journal of Fundamental and Applied Life Sciences. 4, pp. 1168-1177

Balázs Z., Erzsébet H., Éva M., Róbert K, and János. (2015). Preparation and characterization of kaolinite nanostructures: reaction pathways, morphology and structural order. Clay Minerals. 50, pp. 329–340

Balsamo, M., Budinova, T., Erto, A.; Lancia, A., Petrova, B., Petrov, N., Tsyntsarski, B. (2013). CO2 adsorption onto synthetic activated carbon: Kinetic, thermodynamic and regeneration studies. Separation and Purification Technology. 116, pp. 214–221.

Bello O. S., Adeogun I. A., Ajaelu J. C. and Fehintola E. O. (2008). Adsorption of methylene blue onto activated carbon derived from periwinkle shells: kinetics and equilibrium studies. Journal of Chemical Ecology. 24, 4, pp. 285–295

Saikia B. J. and Parthasarathy G. K. (2010). Fourier Transform Infrared Spectroscopic Characterization of Kaolinite from Assam and Meghalaya. Northeastern India. Journal of Modern Physics. 1, pp. 206-210. Doi:10.4236/jmp.2010.14031

Bhattacharyya K. G, Sen G. S., and Sarma G. K. (2014). Interactions of the dye, Rhodamine B with kaolinite and montmorillonite in water. Applied Clay Science 99, pp. 7–17.

Bulut, E., Ozacar, M., and Sengil, I. A. (2008). Adsorption of Malachite Green Onto Bentonite: Equilibrium and Kinetic Studies and Process Design. Microporous and Mesoporous Materials. 115, pp. 234–246.

Carretero, M. I. and Pozo, M. (2010). Clay and non-clay minerals in the pharmaceutical and cosmetic industries part II. Active ingredients. Applied Clay Science. 47, (3–4), pp. 171–181.

Dewi, R. Agusnar, H. Alfian, Z. Tamrin (2018). Characterization of technical kaolin using XRF, SEM, XRD, FTIR and its potentials as industrial raw materials Journal of Physics: Conference Series 1116 pp. 042010 IOP Publishing doi:10.1088/1742-6596/1116/4/042010

Dhaif-Allah M. A. H., Taqui S. N., Syed U. T., and Syed A. A. (2019). Development of sustainable acid blue 113 dye adsorption system using nutraceutical industrial Tribulusterrestris spent. SN Applied Sciences. 1, (4), pp. 330

Dias, M., Valério, A., de Oliveira, D., de Souza, A. A. and de Souza, S. M. U. (2020). Adsorption of natural annatto dye by kaolin: kinetic and equilibrium, Environmental Technology, 41, 20, pp. 2648-2656.

Donat R., Akdogan A., Erdem E. Cetisli H. 2005. Thermodynamics of Pb2+ and Ni2+ adsorption onto natural bentonite from aqueous solutions. Journal of Colloid and Interface Science. 286, 1, pp. 43-52.

Eddy, N. O., Udoh, C. O. and Ukpong, I. J. (2004). Heavy metals in the sediment of the Cross River Estuary at Oron, South Eastern Nigeria. African Journal of Environmental Pollution and Health, 3, 1, pp. 6-10

El Bakouri, H., Usero, J., Morillo, J., and Ouassini, A., (2009). Adsorptive features of acid-treated olive stones for drin pesticides: equilibrium, kinetic and thermodynamic modeling studies. Bioresoures Technology. 100, pp. 4147–4155.

Unuabonah E. I., Ugwuja C. G., Omorogie M. O., Adewuyi A. and Oladoja N. A. (2018). Clays for Efficient Disinfection of Bacteria in Water. Applied Clay Science. 151, pp. 211- 223. http://dx.doi.org/10.1016/j.clay.2017.10.005

Feng-Chin W., Ru-Ling T. and Ruey-Shin J. (2009). Characteristics of Elovich Equation Used for the Analysis of Adsorption Kinetics in Dye–Chitosan Systems. Chemical Engineering Journal 150, (2-3), pp. 366-373, DOI: 10.1016/j.cej.2009.01.014

Freundlich, H.M.F. 1906. Journal of Physical Chemistry. Pp. 385–370.

Nwosu F. O., Ajala O. J., Owoyemi R. M. and Raheem B. G. (2018). Preparation and characterization of adsorbents derived from bentonite and kaolin clays. Applied Water Science. 8, pp. 195 – 205, httpspp.//doi.org/10.1007/s13201-018-0827-2

Fritz W., Schluender E. U. (1974). Chemical Engineering Science, 29, 5, pp. 1279 – 1282.

Gamze V., Ahmet D., Kaan Y., Selin T., Elif S. and Sinan B. M. 2012. Removal of 4-nitrophenol from aqueous solution by natural low cost adsorbents (using Zeolite and Bentonite). Indian Journal of Chemical Technology. 19, pp. 7-25.

Gardolinski J. E, Peralta-Zamora P, and Wypych F. (1999). Preparation and Characterization of a Kaolinite-1-methyl-2-Pyrrolidone Intercalation Compound.Journal of Colloid and Interface Science. 211, (1), pp. 137 - 141. doi: 10.1006/jcis.1998.5982.PMID: 9929445

Havelcova, T. H. M., Mizera, J., Sykorovˇıa, I., Pekar, M., (2009).Sorption of metal ions on lignite and the derived humic substances.Journal of Hazardous Materials. 161, pp. 559–564.

Herney-Ramirez, J., Vicente, M. A., and Madeira, L. M., (2010). Heterogeneous photo-Fenton oxidation with pillared clay based catalysts for wastewater treatment: a review. Applied Catalysis B: Environmental. 98, pp. 10–26.

Ho, Y., McKay, G. A. (1998). Comparison of chemisorption kinetic models applied to pollutant removal on various sorbents. Process Safety and Environmental Protection. 76, pp. 332-340.

IFRA Analytical Method (2019). Determination of peroxide value ‘ISO-Standard 3960’ modified 3rded 2001 AOCS CD 8b-90 European Pharmacopeia Leatherhead Food R. A. Geneva, Switzerland.

Inyinbor A. A, Adekola F. A. and Olatunji G. A. (2017). Liquid phase adsorptions of Rhodamine B dye onto raw and chitosan supported mesoporous adsorbents: isotherms and kinetics studies. Applied Water Science. 7, pp. 2297–2307 DOI 10.1007/s13201-016-0405-4

Jia, Z., Li, Z., Ni, T., and Li, S. (2017). Adsorption of low-cost absorption materials based on biomass (Cortaderiaselloana flower spikes) for dye removal: Kinetics, isotherms and thermodynamic studies. Journal of Molecular Liquids. 229, pp. 285–292.

Jin, L. Liu, Q. Sun, Z. Ni, X. and Wei, M. (2010). Preparation of 5-fluorouracil/β-cyclodextrin complex intercalated in layered double hydroxide and the controlled drug release properties, Industrial and Engineering Chemistry Research. 49, pp. 11176 –11181.

Lagergren, S., (1898). About the theory of so called adsorption of soluble substances, (translated)- The Royal Swedish Academy of Sciences' Documents. 24, pp.1-39.

Langmuir, I. (1918). Journal of the American Chemical Society. 40, 9, pp. 1361–1403.

Letaief S. and Detellier C. (2008). Interlayer grafting of glycidol (2, 3-epoxy-1-propanol) on kaolinite. Canadian Journal of Chemistry, 86, pp. 1-6

Low, M. J. D. (1960). Kinetics of chemosorption of gases on solids. Chemical Reviews. 60, pp. 267 – 312.

Ma, X., Zhou, W., Fu, Z., Cheng, Y., Min, M., Liu, Y., Zhang, Y., Chen, P., Ruan, R., (2014).Effect of wastewater-borne bacteria on algal growth and nutrients removal in wastewater-based algae cultivation system. Bioresource Technology. 167, pp. 8–13.

Makó, E.; Kovács, A.; Kristóf, T. (2019). Influencing parameters of direct homogenization intercalation of kaolinite with urea, dimethyl sulfoxide, formamide, and N-methylformamide. Applied Clay Science. 182, pp. 105- 287

Makó, E., Kristóf, J., Horváth, E. and Vágvölgyi, V. (2013). Mechanochemical intercalation of low reactivity kaolinite. Applied Clay Science. 83–84, pp. 24–31.

Mbaye, A., Diop, C. A. K., Miehe B. J., Senocq F. and Maury F., 2014. Characterization of natural and chemically modified kaolinite from Mako (Senegal) to remove lead from aqueous solutions. Clay Minerals. 49, (n° 4), pp. 527-539. ISSN 0009-8558.

Mbey, J. A., Thomas, F., Ngally S. C. J., Liboum; N. D. (2013). An insight on the weakening of the interlayer bonds in a Cameroonian kaolinite through DMSO intercalation. Applied Clay Science. 83–84, pp. 327–335.

Meziane O., Bensedira A., Guessoum M. and Haddaoui N. 2017. Preparation and Characterization of Intercalated kaolinite with urea, dimethyl formamide and an Alkylammonium Salt Using Guest Displacement Reaction. Journal of Materials and Environmental Sciences. JMES. 8 .10, pp. 3625-3635

El-Latif M. M. A., Elkady M. F., Ibrahim A. M., and Mona O. (2010). Alginate/ Polyvinyl Alcohol - Kaolin Composite for Removal of Methylene Blue from Aqueous Solution in a Batch Stirred Tank Reactor. Journal of American Science. 6, 5, pp. 12- 34

Nandi, B. K., Goswami, A. and Purkait, M. K. (2009).Adsorption characteristics of brilliant green dye on kaolin. Journal of Hazardous Materials, 161, 1, pp. 387-395. https://doi.org/10.1016/j.jhazmat.2008.03.110

Caponi N., Collazzo G. C., Jahn S. L., Dotto G. L., Mazutti M. A., and Foletto E. L. (2017). Use of Brazilian Kaolin as a Potential Low-cost Adsorbent for the Removal of Malachite Green from Colored Effluents. Materials Research. 20, (2), pp. 1 -13 http://dx.doi.org/10.1590/1980-5373-mr-2016-0673¬

Odoemelam, S. A., Emeh, N. U. and Eddy, N. O. (2018). Experimental and computational Chemistry studies on the removal of methylene blue and malachite green dyes from aqueous solution by neem (Azadiracthaindica) leaves. Journal of Taibah University of Science, 12, 3, pp. 255–265doi.org/10.1080/16583655.2018.-1465725.

Ogbodu, R. O., Omorogie, M. O., Unuabonah, E. I., and Babalola, J. O. (2015). Biosorption of heavy metals from aqueous solutions Parkiabiglobosa biomass: equilibrium, kinetics, and thermodynamic studies. Environmental Progress and Sustainable Energy. 34, 6, pp. 1694–1704.

Omorogie, M. O., Babalola, J. O., Unuabonah, E. I., Gong, J. R. (2014). Hybrid materials from agro-waste and nanoparticles: implications on the kinetics of the adsorption of inorganic pollutants. Environmental Technology. 35, 5, pp. 611–619.

Djomgoue P. and Njopwouo D. (2013). FT-IR Spectroscopy Applied for Surface Clays Characterization. Journal of Surface Engineered Materials and Advanced Technology. 3, pp. 275-282 http://dx.doi.org/10.4236/jsemat.2013.34037

Rashid, A., Bhatti, H. N., Iqbal, M., and Noreen, S. (2016). Fungal biomass composite with bentonite efficiency for Nickel and Zinc adsorption: a mechanistic study. Journal of Ecological Engineering. 91, pp. 459–471,

Redlich, O. Peterson, D. L. 1959. The Journal of Physical Chemistry 63, 6, pp. 1024–1024.

Salwa D. A. and Essam H. (2011). Characterization of Egyptian Smectitic Clay Deposits by Methylene Blue Adsorption.American Journal of Applied Sciences. 8, 12, pp. 1282-1286, ISSN 1546-9239

Sarma, G.¬ K., Sen ¬G. S. and Bhattacharyya K.¬G. (2019). Removal of ¬hazardous basic dyes from -aqueous solution by ¬adsorption onto ¬kaolinite and ¬acid-treated kaolinite: kinetics, isotherm and¬ mechanistic study. SN Applied Sciences 1, pp. 211 |https://doi.org/10.1007/s42452-019-0216-y

Shaban, M. Sayed, M. I. Shahien, M. G. Abukhadra, M. R. Ahmed, Z. M. (2018). Adsorption behavior of inorganic and organic modified kaolinite for Congo red dye from water; kinetic modeling and equilibrium studies. Journal of Sol-Gel Science and Technology. 87, pp. 427–441.

Shieu, A., Hu, S. C., Chang, S. M., Ko, T. Y., Hsieh, A., Chan, A. 2017. Adsorption kinetics and breakthrough of carbon dioxide for the chemical modified activated carbon filter used in the building.Sustanability. 9, pp. 1533.

Sips R. (1948). Combined form of Langmuir and Freundlich equations. The Journal of Chemical Physics. 16, pp. 490–495.

Slobodan, K. Milonjic, (2007). A consideration of the correct calculation of thermodynamic parameters of adsorption. I. 72, (12), pp. 1363–1367

Sousa J. P., Splendor D., Gonçalves I. M. B., Costa P., and Sousa L. J. M. (2013). Note on the Measurement of Bulk Density and Tapped Density of Powders According to the European Pharmacopeia. 143, pp. 1098–1100. doi: 10.1208/s12249-013-9994-5

Sumanjit K., Rani S., and Mahajan R. K, (2013). Adsorption Kinetics for the Removal of Hazardous Dye Congo Red by Biowaste Materials as Adsorbents. Journal of Chemistry, Article ID 628582, 12pp. https://doi.org/10.1155/2013/628582

Tahir, M. A., Bhatti, H. N., and Iqbal, M. (2016). Solar red and brittle blue direct dyes adsorption onto Eucalyptus angophoroides bark: equilibrium, kinetics and thermodynamic studies. Journal of Environmental Chemical Engineering. 4, pp. 2431–2439.

Tan, D. Yuan, P. Annabi-Bergaya, F. Dong, F. Liu, D. and He, H. (2015).A comparative study of tubular halloysite and platy kaolinite as carriers for the loading and release of the herbicide amitrole. Applied Clay Science. 114, pp. 190–196.

Unuabonah, E. I., Olu-Owolabi, B. I., Adebowale, K. O., Yang, L. Z. (2008). Removal of Lead and Cadmium from Aqueous Solution by Polyvinyl Alcohol-Modified Kaolinite Clay: A Novel Nano-Clay Adsorbent. Adsorption Science and Technology, 26, pp. 383-405. http://dx.doi.org/10.1260/02636174.26.6.383

Vučurović V. M., Razmovski R. N., Tekić and M. N., (2012). Methylene blue (cationic dye) adsorption onto sugar beet pulp: equilibrium isotherm and kinetic studies. Journal of the Taiwan Institute of Chemical Engineers. 43, (1), pp. 108–111.

Wang, T. H., Li, M. H., and Teng, S. P. (2009). Bridging the gap between batch and column experiments: a case study of Cs adsorption on granite. Journal of Hazardous Materials. 161, pp. 409–415.

Xue, M. Q., Li, J., and Xu, Z. M., (2012). Environmental friendly crush-magnetic separation technology for recycling metal-plated plastics from end-of-life vehicles. Environmental Science and Technology.46, pp. 2661–2667.

Kuang Y., Zhang X. and Zhou S. (2020). Adsorption of Methylene Blue in Water onto Activated Carbon by Surfactant Modification. Water. 12, pp. 587; doi:10.3390/w12020587

Zhang S. H, Zhou Y. C, Ou X. M, Qiang Y. H, Xia H. Guang P. X., Yu G. and Pu F. X. (2013). Study on the occurrence status of formamide in kaolinite-formamide intercalation system and the microstructure of its compounds by FTIR and XRD. Spectroscopy and Spectral Analysis. 33, 11, pp. 2978-2982.