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International Journal of Chemical & Physical Sciences, 05 Oct 2021 | https://doi.org/10.30731/ijcps.10.4.2021.1-7
Year : 2021 | Volume: 10 | Issue: 4 | Pages : 01-07

Adsorptive removal of Malachite Green from aqueous solution using low cost adsorbent

  • 1, Department of Chemistry, Vinayakrao Patil Mahavidyalaya,
  • 2, ,
  • 3, Department of Chemistry, Vinayakrao Patil Mahavidyalaya, Vaijapur, 423701, IN
  • 4, Vinaykrao Patil College, Vaijapur,
  • 5, Vinayakrao Patil mahavidyalaya vaijapur,
  • 6, Vinayakrao patil collage vaijapur,
  • 7, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad, Maharashtra, India,

Adsorption capacity of Malachite Green on low cost adsorbent prepared from Hyptissuaveolens (vilaytitulsi) is studied in the present work. Malachite Green adsorption increases with increase in dye concentration and temperature. The optimum ph is 9.0 for dye adsorption. The adsorption data was analysed and it was found that pseudo-second order kinetic is most suited for the present study. The spontaneous nature of adsorption is observed from negative value of ΔG and the endothermic nature from positive value of ΔH

Introduction

Synthetic dyes become a part of modern life due to their application in textile and printing industries. Discharging of untreated waste water containing dyes can seriously damage the environment. One of the significant reason is that dye, even in low concentration, affect the penetration of sunlight [1]. Different technologies are used to remove dye from waste water such as photo catalysis, bio degradation [2], ozonation [3] membrane filtration [4] etc. among these techniques adsorption is most widely used due to operational ease and cost effectiveness [5]. Activated carbon is effective adsorbent for removal of hazardous material by adsorption but its use is not cost effective and regeneration method is costly [6]. Several low cost adsorbent and bioadsobent such as neem saw dust [7], wood apple [8], sand paper waste [9], ginger waste [10], almond gum [11], coffee husk [12] were reported for removal of malachite green. The bio adsorbent, with higher adsorption efficiency, ease of availability and low cost, is still need of present research.

Malachite Green belongs to triphenyl methane class, it is used in leather, paper, textile and rubber industries [13]. Malachite green was report to have serious adverse effect on human and due its complicated structure, it is very difficult to remove it from aqueous solution using biological treatment and chemical coagulation [14]. As a continuation of our work to find the adsorptive capacity of bio adsorbent prepared from Hyptis suaveolens [15, 16] in the present study adsorption capacity of the bio adsorbent was determined for Malachite green. To determine the adsorption efficiency various adsorption parameter such as dye concentration, contact time, pH and temperature was investigated in the present study.

Materials and Methods

2.1Preparation of Adsorbent

The steams and braches of fully grown plants of Hyptissuaveolens (VilaytiTulsi) were collected and cut into small pieces, washed with distilled water, dried under shed. The adsorbent was prepared as per the procedure mentioned in our earlier publication [15].

2.2 Preparation of sorbet

Malachite Green (MG), a cationic dye was purchased from Sigma Aldrich India with molecular formula C23H25ClN2 was used for present study. A stock solution of 1000 mg L-1 was prepared by dissolving accurately weigh dye quantity in double distilled water. Dilution with double distilled was carried out to get desired experimental concentration.

2.3 Adsorption Studies

For adsorption studies, 0.1 g bio adsorbent was added to 250 mL stoppered glass bottle containing 50 mL dye solution of desired concentration and pH, the solution was stirred by mechanical shaker. After predetermined time interval small fraction were withdrawn and centrifugation at 2,000 rpm to sepaterate the dye solution from adsorbent. The initial pH was achieved using 0. M NaOH and 0.1 M HCl. The solid phase dye concentration was determined using equation 1.

                                                                                      (1)

Where Co is initial dye concentration and Ct is dye concentration at time t in mg L-1, V is volume of solution in L qt is adsorption amount at time t, and W is weight of adsorbent in g. The Langmuir and Freundlich isotherm used to determine adsorption capacity of adsorbent.

The dye concentration remain unadsorbed was determined by measuring the absorption of supernatant solution at 618nmusing Elico double beam spectrophotometer SL-210. Effect of adsorbent dose was deliberate by varying the dosage (0.05 to 0.3 g). To study the effect of temperature on adsorption, 0.1 g adsorbent was added to 50 mL of dye solution of desired concentration at various temperature.

Results

3 Results and Discussion

3.1 Effect of pH

The ionization of dyes and surface of adsorbent was affected by pH of the dye solution [17]. The adsorbent capacity mainly affected by initial pH [31]. 0.1 g adsorbent was shaken for 30 min with 50 mL solution of 50mg L-1 dye concentration. The adsorption of Malachite Green increases with increase in pH and reaches a maximum value 19.15 mg g-1at pH 9 further increase in pH does not affect the adsorption.

Fig 1. Effect of pH on dye removal

 

3.2 Effect of Adsorbent dose

At optimum pH varying adsorbent amount (0.05 to 0.3 g) was stirred with 50 mg L-1 dye concentration for 30 min. It has been observed that due to increase in adsorption site the % removal of dye increases from 73.84 % to 81.31% but unit adsorption was decreased from 36.9 mg g-1 to 6.9 mg g-1 as amount of adsorbent was increased from 0.05 g to 0.3 g.

Fig. 2 Effect of Adsorbent dose

3.3 Effect of dye concentration

0.1 g adsorbent was stirred with  50mL dye solution with varying concentration from 50 mg L-1 to 125 mg L-1) at optimum pH. From the results as shown in Fig.3, the percentage removal of dye decreases as the initial dye concentration increases, but the unit adsorption increases from 20.05 mg g-1 to 54.68 mg g-1. 

Fig. 3 Effect of initial dye concentration on adsorption

3.4 Adsorption dynamics

3.4.1 The pseudo first order kinetic model

The pseudo first order kinetic model expression is given by Lagergren [18] as follows

                                                                           (2)

Where qt and qe are amount of dye adsorbed at time t and equilibrium, respectively k1 is the rate constant. Poor correlation coefficient (R2) for the Lagergren pseudo first order plot shows inapplicability to present study.

3.4.2 The pseudo second order kinetic model

The pseudo second order Lagergren equation is expressed as [18]

                                                               (3)

The Fig.4 shows Plot of t/qtversus t. Values of equilibrium adsorption capacity (qe) and second order rate constant (k2) were determined from the slopes and intercepts and represented in table 1.The present system follows pseudo second order Lagergren model. The adsorption process was affected by adsorbent and adsorbate concentration.

Fig. 4The pseudo second order kinetic

Table 1 Rate constants for pseudo first-order and pseudo second-order adsorption

Conc.

C0 (mg L-1)

pseudo first-order

pseudo second-order

qe (mg g-1)

K1 (min-1)

R2

qe (mg g-1)

K2 (min-1)

R2

50

15.30

0.1061

0.9094

22.72

0.007073

0.9788

75

30.63

0.1381

0.9767

34.24

0.007250

0.9961

100

44.03

0.1229

0.9897

47.39

0.004339

0.9969

125

83.71

0.1473

0.9525

61.72

0.002591

0.9928

 

3.5 Adsorption equilibrium study

Two isotherm, Langmuir isotherm and Freundlich isotherm was used for present study.

3.5.1 Langmuir isotherm

Langmuir isotherm is represented by following equation [19]

                                                               (4)

Where Ce is the equilibrium dye solution concentration (mg L-1),qm is Langmuir constant (related to adsorption capacity) (mg g-1), b is Langmuir constant (related to energy of adsorption) (L mg-1)and qe is the amount adsorbed at equilibrium (mg g-1).

3.5.2 Freundlich isotherm

Freundlich isotherm is represented by following equation [19, 20]

                                                   (5)

Where n is adsorption intensity, kf is adsorption capacity, qe is equilibrium dye concentration in solid and Ce is equilibrium dye concentration in solution. The isotherm parameters are given in table 2.

 

Table 2 Langmuir and Freundlich isotherm parameter

 

Temp (0 K)

Langmuir isotherm parameter

Freundlich isotherm parameter

qm (mg g-1)

b (L mg-1)

R2

n

kf (mg g-1)

R2

313

151.515

0.01093

0.9487

0.3512

0.0293

0.9980

323

161.29

0.01099

0.9468

0.3420

0.0291

0.9957

333

163.934

0.01094

0.9439

0.3359

0.027

0.9986

 

3.6 Effect of temperature

From the present study it has been observed that the percentage removal increases with increase in the temperature. The equation 7 was used to determine thermodynamic parameter.

                                                                   (7)

Where K0 is equilibrium constant, Cliquid is equilibrium liquid phase concentration (mg L-1) and Csolid is equilibrium solid phase concentration (mg L-1).

Gibb’s free energy (ΔG) is represented by following equation [21]

                                                            (8)

Where R is gas constant, T is temperature in Kelvin and K0 is equilibrium constant.

The Van’t Hoff equation is represented by following equation.

                                                           (9)

From the Van’t Hoff plot the values of ΔH and ΔS were determined and represented in table 3.

Table 3 Thermodynamic parameter of adsorption

Temp (0 K)

ΔG

(kJ mole-1)

ΔH

(kJ mole-1)

ΔS

(J K-1 mole-1)

313

-35.54

9.74

57.48

323

-38.91

333

-40.49

Conclusion

Adsorptive removal of Malachite Green was studied on Bio adsorbent prepared from Hyptissuaveolens (VilaytiTulsi). The kinetic process follows the pseudo second order kinetic model. The Freundlich isothermmodel was best suited for the adsorption equilibrium data. The presents study shows that the maximum adsorption capacity is 61.72 mg g-1. Negative value of ΔG and positive values of ΔH and ΔS represent aendothermic and spontaneous adsorption. The bio adsorbent prepared from Hyptissuaveolens (VilaytiTulsi) can be used as a low cost adsorbent for the removal of Malachite Green.

Conflict of Interest Statement

The authors declare that they have no conflict of interest

References

1.       M. R. R. Kooh, L. B.L. Lim, L. H. Lim and J.M.R.S. Bandara “Batch adsorption studies on the removal of malachite green from water by chemically modified Azollapinnata”Desalination and Water Treatment, 2016, Volume 57, Issue 31, pages 14632-14646. https://doi.org/10.1080/19443994.2015.1065450

2.       P. Arabkhani and A. Asfaram “Development of a novel three-dimensional magnetic polymer aerogel as an efficient adsorbent for malachite green removal” Journal of Hazardous Materials (2019), https://doi.org/10.1016/j.jhazmat.2019.121394

3.       M. K. Dahri, M. R. R. Kooh and L. B.L. Lim “ Water remediation using low cost adsorbent walnut shell for removalof malachite green: Equilibrium, kinetics, thermodynamic andregeneration studies” Journal of Environmental Chemical Engineering 2 (2014) 1434–1444http://dx.doi.org/10.1016/j.jece.2014.07.008

4.       Y. Song, S. Ding, S. Chen, H. Xu, Y. Mei, and J. Ren “Removal of malachite green in aqueous solution by adsorption on sawdust” Korean J. Chem. Eng., 32(12), 2443-2448 (2015).

http://dx.doi.org/10.1007/s11814-015-0103-1

5.       T.P. Krishna Murthya, B.S. Gowrishankarc, M.N. Chandra Prabhaa, M. Kruthia and R. Hari Krishnad “Studies on batch adsorptive removal of malachite green from synthetic wastewater using acid treated coffee husk: Equilibrium, kinetics andthermodynamic studies” Microchemical Journal, 146, 192–201, (2019). https://doi.org/10.1016/j.microc.2018.12.067

6.       R. Han, Y. Wang, Q. Sun, L. Wang, J. Song, X. He and C. Dou, “Malachite green adsorption onto natural zeolite and reuse by microwaveirradiation” Journal of Hazardous Materials 175, 1056–1061, (2010). https://doi.org/10.1016/j.jhazmat.2009.10.118

7.       S.D. Khattria and M.K. Singh, “Removal of malachite green from dye wastewater using neem sawdustby adsorption” Journal of Hazardous Materials, 167, 1089–1094,(2009). https://doi.org/10.1016/j.jhazmat.2009.01.101

8.       A. S. Sartape , A. M. Mandhare , V. V. Jadhav,P. D. Raut , M. A. Anuse and S. S. Kolekar, “Removal of malachite green dye from aqueous solution with adsorption technique using Limoniaacidissima(wood apple) shell as low cost adsorbent. Arabian Journal of Chemistry, (2014).http://dx.doi.org/10.1016/j.arabjc.2013.12.019

9.       Y. ?. Co?kun, N.Aksuner and JaleYanik, “Sandpaper Wastes as Adsorbent for the Removalof Brilliant Green and Malachite Green Dye” ActaChim. Slov. 66, 402–413, (2019).

https://doi.org/10.17344/acsi.2018.4881

10.   R. Ahmad and R. Kumar, “Adsorption studies of hazardous malachite green onto treated ginger waste” Journal of Environmental Management, 91, 1032–1038, (2010). https://doi.org/10.1016/j.jenvman.2009.12.016

11.   F. Bouaziza, M. Koubaab,F. Kallela, R. E. Ghorbela and S. E. Chaabounia, “Adsorptive removal of malachite green from aqueous solutions byalmond gum: Kinetic study and equilibrium isotherms” International Journal of Biological Macromolecules, 105, 56–65, (2017). http://dx.doi.org/10.1016/j.ijbiomac.2017.06.106

12.   T.P. Krishna Murthya,, B.S. Gowrishankarc, M.N. Chandra Prabhaa, M. Kruthia, and R. Hari Krishnad, “Studies on batch adsorptive removal of malachite green from synthetic wastewater using acid treated coffee husk: Equilibrium, kinetics andthermodynamic studies” Microchemical Journal, 146, 192–201, (2019). https://doi.org/10.1016/j.microc.2018.12.067

13.   A. A. Adeyi, S. N. A. M. Jamil , L. C. Abdullah  and T. S. Y. Choong, “Adsorption of Malachite Green Dye from Liquid Phase UsingHydrophilic Thiourea-Modified Poly(acrylonitrile-co-acrylic acid):Kinetic and Isotherm Studies” Journal of Chemistry, 2019, Article ID 4321475. https://doi.org/10.1155/2019/4321475

14.   M. Baek, C. O. Ijagbemi, Se-Jin O and D. Kim, “Removal of Malachite Green from aqueous solution usingdegreased coffee bean” Journal of Hazardous Materials, 176, 820–828, (2010). https://doi.org/10.1016/j.jhazmat.2009.11.110

15.   S. D. Pardeshi,J. P.Sonar, A. M. Zine and S. N. Thore, “Kinetic and thermodynamic study of adsorption of methylene blue and rhodamine B on adsorbent prepared from Hyptissuaveolens (VilaytiTulsi)”. Journal of the Iranian Chemical Society, 10, 1159–1166, (2013). https://doi.org/10.1007/s13738-013-0256-y

16.   N. N. Gund , B. M. Marmat , A. S. Salunke , J. P. Sonar , S. A. Dokhe, A. M. ZIne, S. N. Thore and S. D. Pardeshi, “Removal of Rhodamine 6G from Aqueous Solution by Adsorption on Bio Adsorbent Prepared from HyptisSuaveolens (VilaytiTulsi): Kinetic,Equilibrium and Thermodynamic Study”, International Journal of Chemical and Physical Sciences, 10,2, (2021).

17.   S. Chowdhury, R. Mishra, P. Saha and P. Kushwaha, “Adsorption thermodynamics, kinetics and isosteric heat of adsorption of malachite green onto chemically modified rice husk” Desalination, 265, 159–168,(2011). https://doi.org/10.1016/j.desal.2010.07.047

18.   M. K. Dahri, M. R. R. Kooh and L. B.L. Lim, “Application of Casuarina equisetifolia needle for the removal of methylene blue and malachite green dyes from aqueous solution” Alexandria Engineering Journal, 54, 1253–1263, (2015). http://dx.doi.org/10.1016/j.aej.2015.07.005

19.   H. N. Tran, S.J. You, B.A. Hosseini and H.P. Chao, “Mistakes and inconsistencies regarding adsorption of contaminants from aqueous solutions: A critical review”, Water Research, (2017) https://doi.org/10.1016/j.watres.2017.04.014

20.   A. M. Zine, S. N. Thore , R. P. Pawar ,S. D.  Pardeshi, N. M. Ligde and J. P. Sonar,  “Adsorption studies of Acid Red 73 on Partheniumhysterophorous L.”  International Journal of Chemical and Physical Sciences 7, 4: 13-22, (2018). https://doi.org/10.30731/ijcps.7.4.2018.13-22

H. Tang, W. Zhou and L. Zhang, “Adsorption isotherms and kinetics studies of malachite green on chitin hydrogels” Journal of Hazardous Materials, 209– 210, 218– 225, (2012). https://doi.org/10.1016/j.jhazmat.2012.01.010


Keywords: basicgreen,adsorbent,bioadsorbent,vilayatitulsi,kinetic

Citation: Dr.Sandeep Pardeshi*,Jayant Sonar,zine.ashok,Ms.Arti Salunke,Ms.Bhagyashri Marmat,Ms.Nikita Gund,Mr.SHRIKANT DOKHE,Dr.Sandeep Pardeshi,Jayant Sonar,zine.ashok,Ms.Arti Salunke,Ms.Bhagyashri Marmat,Ms.Nikita Gund,Mr.SHRIKANT DOKHE ( 2021), Adsorptive removal of Malachite Green from aqueous solution using low cost adsorbent. International Journal of Chemical & Physical Sciences, 10(4): 01-07

Received: 15/06/2021; Accepted: 02/07/2021;
Published: 05/10/2021

Edited by:

Dr.Sandeep Pardeshi, , Department of Chemistry, Vinayakrao Patil Mahavidyalaya,

Reviewed by:

mazahar_64@rediffmail.com, , Principal, Maulana Azad College, Aurangabad, IN

, , ,

Copyright: YES.

*Correspondence: Dr.Sandeep Pardeshi, sandeeppardeshi007@gmail.com