Environmental Science and Pollution Research

, Volume 25, Issue 31, pp 31579–31592 | Cite as

Role of sorption energy and chemisorption in batch methylene blue and Cu2+ adsorption by novel thuja cone carbon in binary component system: linear and nonlinear modeling

  • Saeed Rehman
  • Adnan Adil
  • Ahsan Jabbar Shaikh
  • Jehanzeb Ali Shah
  • Muhammad Arshad
  • Muhammad Arif Ali
  • Muhammad BilalEmail author
Research Article


Functionalized thuja cone carbon (FTCC) was synthesized thermochemically. It was carried out by carbonization (250 °C) and activation (320 °C), followed by surface functionalization in 0.5 M HAN (HNO and HCl3) mixture and subsequent heating in H2SO4 (95%) at 90 °C. This was used for methylene blue (MB) adsorption in single component system (SCS) and binary component system (BCS) with Cu2+. Maximum adsorption capacity of MB (83.4 mg/g) was achieved at pH 10 at 100 mg/L of adsorbate solution. MB and Cu2+ adsorption onto FTCC obeyed pseudo-second-order model kinetics. Spontaneous and endothermic MB adsorption was noticed with negative Gibbs free energy change (− 6.34, − 9.20, and − 13.78 kJ/mol) and positive enthalpy change (133.91 kJ/mol). At low concentrations, Cu2+ adsorption increased by 14 mg/g with least reduction of MB adsorption (< 4 mg/g) in BCS. Isotherm models (Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich) support the increase in Cu2+ adsorption in BCS. The sorption heat of MB shifted from 165.16 kJ/mol (SCS) to 150.85 kJ/mol in BCS (Temkin) and from 57.74 kJ/mol (SCS) to 50.50 kJ/mol in BCS (D-R), which supports the lower MB uptake in BCS due to decrease in sorption energy. The sorption heat of Cu2+ is increased (148.43 kJ/mol) in the BCS than SCS (155.36 kJ/mol), which makes the equal distribution of increased bonding energies; therefore, FTCC surface sites increased the Cu2+ uptake in the BCS. Desorption studies concluded the reusability of FTCC by 75% and 79% for MB and Cu2+ adsorption respectively. This study recommends to determine the best fit of isotherm and kinetic models to adsorption data by linear as well as nonlinear regression fit.


Sorption energy Chemisorption Thuja cone carbon Methylene blue Copper Binary component system 



Author is also thankful to Dr. Tayyab Ashfaq for his valuable contribution in nonlinear and linear modeling of adsorption kinetics and improvement of manuscript.

Funding information

This work was financially supported by the Higher Education Commission, Pakistan [Project number 20-1915].

Compliance with ethical standards

Competing interest

The authors declare that have no competing interests.


  1. Açıkyıldız M, Gürses A, Güneş K, Yalvaç D (2015) A comparative examination of the adsorption mechanism of an anionic textile dye (RBY 3GL) onto the powdered activated carbon (PAC) using various the isotherm models and kinetics equations with linear and non-linear methods. Appl Surf Sci 354:279–284. CrossRefGoogle Scholar
  2. Agarwal S, Tyagi I, Gupta VK, Ghasemi N, Shahivand M, Ghasemi M (2016) Kinetics, equilibrium studies and thermodynamics of methylene blue adsorption on Ephedra strobilacea saw dust and modified using phosphoric acid and zinc chloride. J Mol Liq 218:208–218. CrossRefGoogle Scholar
  3. Akar T, Ozcan AS, Tunali S, Ozcan A (2008) Biosorption of a textile dye (acid blue 40) by cone biomass of Thuja orientalis: estimation of equilibrium, thermodynamic and kinetic parameters. Bioresour Technol 99:3057–3065. CrossRefGoogle Scholar
  4. Akar ST et al (2009) Removal of copper (II) ions from synthetic solution and real wastewater by the combined action of dried Trametes versicolor cells and montmorillonite. Hydrometallurgy 97:98–104. CrossRefGoogle Scholar
  5. Allen SJ, Gan Q, Matthews R, Johnson PA (2005) Kinetic modeling of the adsorption of basic dyes by kudzu. J Colloid Interface Sci 286:101–109. CrossRefGoogle Scholar
  6. Belayachi A, Bestani B, Bendraoua A, Benderdouche N, Duclaux L (2016) The influence of surface functionalization of activated carbon on dyes and metal ion removal from aqueous media. Desalin Water Treat 57:17557–17569. CrossRefGoogle Scholar
  7. Cadaval TRS, Dotto GL, Pinto LAA (2015) Equilibrium isotherms, thermodynamics, and kinetic studies for the adsorption of food azo dyes onto chitosan films. Chem Eng Commun 202:1316–1323. CrossRefGoogle Scholar
  8. Calvete T, Lima EC, Cardoso NF, Vaghetti JC, Dias SL, Pavan FA (2010) Application of carbon adsorbents prepared from Brazilian-pine fruit shell for the removal of reactive orange 16 from aqueous solution: kinetic, equilibrium, and thermodynamic studies. J Environ Manag 91:1695–1706. CrossRefGoogle Scholar
  9. Chemteam (2017) Dilutions, definition, and calculations. Accessed 22 April 2017 2017Google Scholar
  10. Dural MU, Cavas L, Papageorgiou SK, Katsaros FK (2011) Methylene blue adsorption on activated carbon prepared from Posidonia oceanica (L.) dead leaves: kinetics and equilibrium studies. Chem Eng J 168:77–85. CrossRefGoogle Scholar
  11. Foo K, Hameed B (2010) Insights into the modeling of adsorption isotherm systems. Chem Eng J 156:2–10. CrossRefGoogle Scholar
  12. Frantz TS, Silveira N, Quadro MS, Andreazza R, Barcelos AA, Cadaval TR, Pinto LA (2017) Cu (II) adsorption from copper mine water by chitosan films and the matrix effects. Environ Sci Pollut Res 24:5908–5917. CrossRefGoogle Scholar
  13. Freundlich H (1906) Over the adsorption in solution. J Phys Chem 57:e470Google Scholar
  14. Gardazi SMH, Ali M, Rehman S, Ashfaq T, Bilal M (2016) Process optimization of hazardous malachite green (MG) adsorption onto white cedar waste: isotherms, kinetics and thermodynamic studies. Curr Anal Chem 12:1–12. CrossRefGoogle Scholar
  15. Ghaedi M, Hajati S, Karimi F, Barazesh B, Ghezelbash G (2013) Equilibrium, kinetic and isotherm of some metal ion biosorption. J Ind Eng Chem 19:987–992. CrossRefGoogle Scholar
  16. Gupta VK, Suhas (2009) Application of low-cost adsorbents for dye removal- a review. J Environ Manag 90:2313–2342. CrossRefGoogle Scholar
  17. Han F, Xu C, Sun W-Z, Yu S-T, Xian M (2017) Effective removal of salicylic and gallic acids from single component and impurity-containing systems using an isatin-modified adsorption resin. RSC Adv 7:23164–23175. CrossRefGoogle Scholar
  18. Haroon H, Ashfaq T, Gardazi SMH, Sherazi TA, Ali M, Rashid N, Bilal M (2016) Equilibrium kinetic and thermodynamic studies of Cr (VI) adsorption onto a novel adsorbent of Eucalyptus camaldulensis waste: Batch and column reactors. Korean J Chem Eng 33:2898–2907. CrossRefGoogle Scholar
  19. Hilal NM, Emam A, El-Bayaa A, Zidan A (2013) Adsorption of barium and iron ions from aqueous solutions by the activated carbon produced from masot ash. Life Sci J 3:10 296Google Scholar
  20. Ho Y-S, McKay G (1998) Kinetic models for the sorption of dye from aqueous solution by wood. Process Saf Environ Prot 76:183–191. CrossRefGoogle Scholar
  21. Kalavathy MH, Miranda LR (2010) Comparison of copper adsorption from aqueous solution using modified and unmodified Hevea brasiliensis saw dust. Desalination 255:165–174. CrossRefGoogle Scholar
  22. Kim Y, Kim C, Choi I, Rengaraj S, Yi J (2004) Arsenic removal using mesoporous alumina prepared via a templating method. Environ Sci Technol 38:924–931. CrossRefGoogle Scholar
  23. Langmuir I (1918) The adsorption of gases on plane surfaces of glass, mica and platinum. J Am Chem Soc 40:1361–1403. CrossRefGoogle Scholar
  24. Lin J, Wang L (2009) Comparison between linear and non-linear forms of pseudo-first-order and pseudo-second-order adsorption kinetic models for the removal of methylene blue by activated carbon. Front Environ Sci Eng China 3:320–324. CrossRefGoogle Scholar
  25. Liu Y (2009) Is the free energy change of adsorption correctly calculated? J Chem Eng Data 54:1981–1985. CrossRefGoogle Scholar
  26. Malkoc E (2006) Ni (II) removal from aqueous solutions using cone biomass of Thuja orientalis. J Hazard Mater 137:899–908. CrossRefGoogle Scholar
  27. McNaught AD, Wilkinson A (1997) Compendium of chemical terminology: IUPAC. In: The Royal Society of Chemistry. Blackwell Science Cambridge, CambridgeGoogle Scholar
  28. Moura JM, Gründmann DDR, Cadaval TRS, Dotto GL, Pinto LAA (2016) Comparison of chitosan with different physical forms to remove reactive black 5 from aqueous solutions. J Environ Chem Eng 4:2259–2267. CrossRefGoogle Scholar
  29. Moussout H, Ahlafi H, Aazza M, Maghat H (2018) Critical of linear and nonlinear equations of pseudo-first order and pseudo-second order kinetic models. Karbala Int J Mod Sci 4:244–254. CrossRefGoogle Scholar
  30. Parimal S, Prasad M, Bhaskar U (2010) Prediction of equillibrium sorption isotherm: comparison of linear and nonlinear methods. Ind Eng Chem Res 49:2882–2888. CrossRefGoogle Scholar
  31. Politi D, Sidiras D (2012) Wastewater treatment for dyes and heavy metals using modified pine sawdust as adsorbent. Process Eng 42:1969–1982. CrossRefGoogle Scholar
  32. Puziy AM, Poddubnaya OI, Martínez-Alonso A, Suárez-García F, Tascón JM (2005) Surface chemistry of phosphorus-containing carbons of lignocellulosic origin. Carbon 43:2857–2868. CrossRefGoogle Scholar
  33. Ragupathy S, Raghu K, Prabu P (2015) Synthesis and characterization of TiO2 loaded cashew nut shell activated carbon and photocatalytic activity on BG and MB dyes under sunlight radiation. Spectrochim Acta A 138:314–320. CrossRefGoogle Scholar
  34. Rehman S et al (2017) Simultaneous physisorption and chemisorption of reactive Orange 16 onto hemp stalks activated carbon: proof from isotherm modeling. Biointerf Res APP Chem 7:2021–2029Google Scholar
  35. Rosas JM, Berenguer R, Valero-Romero MJ, Rodríguez-Mirasol J, Cordero T (2014) Preparation of different carbon materials by thermochemical conversion of lignin. Front Mater 1:29. CrossRefGoogle Scholar
  36. Santana Cadaval TR, Camara AS, Dotto GL, Pinto LAA (2013) Adsorption of Cr (VI) by chitosan with different deacetylation degrees. Desalin Water Treat 51:7690–7699. CrossRefGoogle Scholar
  37. Visa M, Bogatu C, Duta A (2010) Simultaneous adsorption of dyes and heavy metals from multicomponent solutions using fly ash. Appl Surf Sci 256:5486–5491. CrossRefGoogle Scholar
  38. Vutskits L, Briner A, Klauser P, Gascon E, Dayer AG, Kiss JZ, Muller D, Licker MJ, Morel DR (2008) Adverse effects of methylene blue on the central nervous system. J Am Soc Anesthesiol 108:684–692. CrossRefGoogle Scholar
  39. Wong Y, Szeto Y, Cheung W, McKay G (2004) Adsorption of acid dyes on chitosan - equilibrium isotherm analyses. Process Biochem 39:695–704. CrossRefGoogle Scholar
  40. Wu Y, Fan Y, Zhang M, Ming Z, Yang S, Arkin A, Fang P (2016) Functionalized agricultural biomass as a low-cost adsorbent: Utilization of rice straw incorporated with amine groups for the adsorption of Cr (VI) and Ni (II) from single and binary systems. Biochem Eng J 105:27–35. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Saeed Rehman
    • 1
  • Adnan Adil
    • 1
  • Ahsan Jabbar Shaikh
    • 2
  • Jehanzeb Ali Shah
    • 1
  • Muhammad Arshad
    • 3
  • Muhammad Arif Ali
    • 4
  • Muhammad Bilal
    • 1
    Email author
  1. 1.Department of Environmental SciencesCOMSATS University IslamabadAbbottabadPakistan
  2. 2.Department of ChemistryCOMSATS University IslamabadAbbottabadPakistan
  3. 3.IESENational University of Sciences and Technology (NUST)IslamabadPakistan
  4. 4.Department of Soil ScienceBahauddin Zakariya UniversityMultanPakistan

Personalised recommendations