Equilibrium Model and Adsorption Kinetics of Methylene Blue with

Kluwak Shell Carbon

H. R. Yuliani

, A. Musfirah A., Isma Ayu N. P. Z., Ida Adriani I. and Haera Setiawati

Chemical Engineering Department, Politeknik Negeri Ujung Pandang, Perintis Kemerdekaan KM 10 Tamalanrea

Makaassar, Indonesia

Keywords: Dsorption, Methylene Blue, Kinetics, Langmuir, Pseudo Second Order.

Abstract: This study aims to determine the equilibrium model and adsorption kinetics of methylene blue (MB) solution

using kluwak shell carbon (KTK) both activated and without activation. Equilibrium adsorption was carried

out on a volume of 50 ml of methylene blue at 9 concentrations of MB 80, 90, 100, 110, 120, 125, 130, 140

and 150 ppm, 0.15 g KTK, 90 min with a shaker speed of 300 rpm. Process kinetics, volume 400 ml

concentration of 100 ppm, 1.2 g KTK, MB for 105 minutes, sampling interval 15 min, stirrer speed 300 rpm.

The adsorption equilibrium model are Freundlich and Langmuir, while the kinetic model are Pseudo First

Order and Pseudo Second Order. Determination of both the equilibrium and kinetic models are determined

by the larger correlation coefficient (R

). The calculation of these two models are based on the equilibrium

concentration (Ce) and a certain time concentration (Ct) measured using UV-VIS at a wavelength of 662 nm,

the absorbance is converted to Ce or Ct with the standard curve equation MB. The results showed that the

equilibrium adsorption and kinetics of MB using KTK and KTK 3M KOH followed the Langmuir equilibrium

and Pseudo Second Order kinetics. MB adsorption equilibrium 𝑞





.∗. 



..

, R

0.8020 and kinetics









.∗ .²





.

𝑡, R

0.9853 at unactivated KTK. KTK 3M KOH 𝑞





.∗. 



..

), R

0.9932 and









.∗ .²





.

𝑡, R

0.993.

1 INTRODUCTION

Methylene blue is a dye that is often used in the textile

industry for dyeing and the craft industry. Disposal of

methylene blue solution waste has a negative impact

when exposed to contact with humans and the

environment so that a technique is needed to remove

the content or concentration of industrial waste

(Yuliani, et al., 2019). Adsorption is one method that

is often used in waste treatment aimed at reducing or

eliminating contaminants. This method is quite easy

to apply in wastewater purification by using an

adsorbent that functions to absorb dye compounds

(adsorbates) contained in industrial waste. The

adsorbents that are often used are activated carbon,

silica, alumni, but they are expensive, so it is

necessary to study alternative adsorbents that are

relatively inexpensive and environmentally friendly

(Rohaizar, 2013). Kluwak shell is a sheath of kluwak

https://orcid.org/0000-0002-5420-3175

meat which after being taken as rawon seasoning then

this shell will become for the environment. Based on

the composition of kluwak shell contains cellulose,

hemicellulose, and XRD results contain Ca so that it

can be used as an adsorbent. The performance of the

adsorbent is enhanced through carbonization which is

then activated. Activated carbon has a large surface

area due to the presence of pores formed during

carbonization by evaporating volatiles in the material.

This increase in carbon can be further increased

through physical and chemical activation. In this

study, it was carried out by activating kluwak shell

carbon with KOH which aims to bind dirt and

dissolve volatile substances during carbonization,

both of which dissolve and are wasted during

washing. The variables studied were how the effect of

3M KOH activation on kluwak shell carbon on

performance with adsorbents in the form of the

maximum adsorption capacity (qm), the amount of

adsorbent adsorbed at equilibrium conditions in

800

Yuliani, H., A., A., Z., I., I., I. and Setiawati, H.

Equilibrium Model and Adsorption Kinetics of Methylene Blue with Kluwak Shell Carbon.

DOI: 10.5220/0010953900003260

In Proceedings of the 4th International Conference on Applied Science and Technology on Engineering Science (iCAST-ES 2021), pages 800-805

ISBN: 978-989-758-615-6; ISSN: 2975-8246

 2023 by SCITEPRESS – Science and Technology Publications, Lda. Under CC license (CC BY-NC-ND 4.0)

determining the equilibrium model and the adsorption

kinetics of methylene blue. The adsorption

equilibrium model that will be studied is the

Freundlich and Langmuir equations. The Freundlich

equation describes heterogeneous adsorption which

shows multilayer with a constant value of 'n' while the

Langmuir equation describes monolayer adsorption

and the value of adsorption capacity (qm). Adsorption

equilibrium equations (Do, 1998) and (Mohit, Sunil,

Shraddha, & Pradeep, 2019).

Freundlich Equilibrium

qe = kf. Ce1/n (1)

qe is the amount of adsorbate adsorbed (mg/g), kf is

the Freundlich constant (l/mg), and n describes the

adsorption intensity parameter in the Freundlich

model.

Langmuir Equilibrium

(2)

qm is the maximum adsorption capacity (mg/g), b is

the Langmuir constant (l/mg).

The adsorption speed of the adsorbate by the

adsorbent is determined by two models, namely

Pseudo First Order (PFO) and Pseudo Second Order

(PSO).

Pseudo First Order Kinetics

This model was first proposed by Lagergen

(Lagergren, 1989) which is shown in Equation (1).

Pseudo-first order drawing adsorption occurs

physically through the pores of the adsorbent.

𝑑𝑞𝑡

𝑑𝑡

𝑘1



𝑞𝑒 𝑞𝑡



(3)

k1(1/min) rate constants are all order one and qt is the

amount of adsorbate adsorbed per gram of adsorbent

at the time of sampling interval (mg/g).

Second Order Pseudo Kinetics

Pseudo-second-order (quasi-second order) shows the

adsorption capacity proportional to the number of

active sites of the adsorbent. The pseudo equation is

shown in Equation (4).

𝑑𝑞𝑡

𝑑𝑡

𝑘2



𝑞𝑒  𝑞𝑡





(4)

k2(g.mg-1min-1) pseudo second order adsorption

rate constant. qt is obtained using Equation (5)

𝑞𝑡  

𝐶𝑜  𝐶𝑡

𝑚

𝑥 𝑉𝑎

(5)

Va (L) is the volume of the adsorbent and m is the

mass of the adsorbent (g).

The selection of the appropriate equilibrium

equation model and adsorption kinetics is based on

the correlation coefficient value that is greater than or

close to the value 1.

2 METHODOLOGY

The research was carried out in the department of

chemical engineering and batch and continuous

processes. Analysis in the Laboratory of Chemical

Engineering Instruments at the State Polytechnic of

Ujung Pandang.

A. Materials

The kluwak shell comes from Soppeng Regency.

Methylene Blue (Merck), 98% KOH (Merck),

filter paper, and Aquadest.

B. Equipment

Erlenmeyer, Beaker, Measuring flask, Measuring

flask, Funnel, Sample Tube, sample vial, Shaker,

Three-neck flask, Centrifuge tube, Magnetic

hotplate, Motor, Stative, Stirrer, Rotary

Centrifuge, Oven, and UV-VIS Spectrometer.

C. Procedures

1. Activation

Kluwak shell carbon was immersed in 3M KOH

(KTKA-3M) in a 1000 ml Erlenmeyer according to

the concentration at a ratio of 1: 4, stirred using a

magnetic stirrer at 80oC for 4 hours and allowed to

stand for 24 hours. The activated kluwak shell

carbon was separated by filtering and the cake was

washed using distilled water until the filtrate was

neutral in pH. The wet KTKA -3M was dried in an

oven at 105

2. Adsorption

50 mL of MB solution with concentrations of 80, 90,

100, 110, 120, 125, 130, 140, and 150 ppm were

added to a 100 mL Erlenmeyer and labeled 1-9. Add

each Erlenmeyer as much as 0.15 grams of kluwak

shell carbon (KTK), then placed and arranged in a

shaker. Turn on the shaker, set the time to 90

minutes and the shaker speed to 300 rpm. The

sample was put in a centrifuge tube and placed into

a rotary centrifuge, speed of 500 rpm for 10 minutes.

Filter samples 1-9 using a funnel and filter paper, the

filtrate obtained is then put in a bottle and labeled.

*) Same treatment for KTKA-3M.

3. Kinetics

• Methylene Blue Concentration: 100 ppm

• 400 ml of 100 ppm methylene blue solution was

put into a neck flask 3 then added 1.2 grams of

kluwak flour then while stirring with a stirrer

Equilibrium Model and Adsorption Kinetics of Methylene Blue with Kluwak Shell Carbon

801

speed of 300 rpm for 105 minutes and every 15

minutes a sample was taken. The MB solution

and adsorbent were centrifuged at 500 rpm for

10 minutes and then filtered. The filtrate was

then tested using UV-VIS Spectrophotometer.

4. Analaysis

The filtrate from UV-VIS test results will get

absorbance converted to concentration. The

adsorption shows the concentration (Ce) for 90

minutes and the concentration kinetics every time

according to the duration (Ct) MB, namely

various taking times every 15 minutes for 105

minutes, wavelength 662 nm.

The test results in the form of initial concentration

(Co), equilibrium concentration (Ce) and

concentration at time t (Ct) were then processed

to determine the equilibrium model and

adsorption kinetics of methylene blue solution

using KTK and KTKA-3M.

3 RESULTS AND DISCUSSION

A. Standard Curve Determination

The standard curve is made from a series of

standard solutions which are still within the

linearity limits so that they can be linearly

regressed. The purpose of making a standard

curve is to determine Co, Ce and Ct in the test

solution with the "x" axis is the concentration and

the "y" axis is the absorbance. The equation y =

mx + c. Methylene blue has a wavelength of 662

nm with MB 0, 1, 2, 3, 4, and 5 ppm

concentrations tested. The test results obtained the

equation Abs = 0.1993*Ce + 0.004 with R_Square

0.9971 close to 1 which indicates that the equation

is accurate as shown in Figure 1. Ce is at

adsorption equilibrium and Ce is replaced by Ct

when calculating the adsorption kinetics.

Figure 1: Standard Curve.

B. Adsorption Equilibrium Model

Equilibrium model testing is carried out to

determine the appropriate equilibrium model to be

used in a study. The determination of the

equilibrium model depends on the value of the

correlation coefficient (R

). The appropriate

equilibrium model is an equilibrium model with a

value of R2 that is higher or closer to 1 (Tan &

Ahmad, 2007).

1. Freundlich's Equilibrium Model

Equation (1) is linearized so that the equation is

obtained:

Log qe = log kf – 1/n* log Ce (6)

The values of kf and n are obtained by graphing

the relationship between log qe (y) and log Ce (x).

Slope = 1/n and Intercept (log kf), shown in Figure

Figure 2: Log qe Vs Log Ce.

The correlation coefficient is 0.441 for the

Freundlich equation on CEC so that it is

concluded that it does not meet.

2. Langmuir Equilibrium Model

The Langmuir equation shows the maximum

amount that can be absorbed by the adsorbent

(qm), the calculation is carried out linearly in

Equation (2).

(7)

The relationship of Ce/qe (y) to Ce (x) is obtained

with a slope of 1/qm and an intercept (1/(qm*b)

so that the values of b and qm are obtained. The

illustration is shown in Figure 3.

iCAST-ES 2021 - International Conference on Applied Science and Technology on Engineering Science

802

Figure 3: Ce/qe VS Ce of KTK.

The linearization of Equation (7) and Figure 3

shows that the value of R

at the Langmuir

equilibrium is higher than the Freundlich

equilibrium. The KTKA-3M and CEC are shown

in Table 1. The balance of methylene blue

adsorption using CEC and 3M KTKA following

the Langmuir equation is shown by a correlation

coefficient that is greater than the Freundlich

equation according to Table 1.

Activation increases the adsorption capacity of the

adsorbent with the value of qm increasing three

times (3x) than kluwak shell carbon without

activation. This indicates that the activation

increases the performance of the adsorbent with

an increased surface area which indicates the

formation of more pores and active groups on the

surface of the adsorbent. According to Lanjar, et

al (Lanjar et al., 2018) Adsorption of Methyl

Violet Dye by Activated Carbon Based on

Pineapple Leaf Waste follows the Langmuir

equilibrium with the equation y= 4.854* x +

0.2407 where y = ce/qe and x is Ce at R

0.9

Table 1: Adsoprsi Equilibrium Freundlich dan Langmuir.

C. Adsorption Kinetic Model

The value of the adsorption reaction rate (K1 and

K2) and the value of qe obtained through

linearization of Equation (3) for pseudo-order 1

adsorption kinetics model (PFO) and linearization

of Equation (4) on pseudo-order (PSO).

1 .Pseudo First Order Kinetics

(8)

ln (qe-qt) and t data are plotted as in Figure 4

Figure 4: KTKA-3M . Pseudo First Order Kinetic Curve.

In Figure 4, the equation ln (qe-qt) = 2.4989 –

0.00437 with a k1 value of 0.0437 min-1 and a

magnitude of qe in the form of 10 intercepts

12.1690 mg/g. The pseudo-first-order equation

0.6903 indicates that it is not significant and

the suitability of the

value is not close to 1.

2.Second Order Pseudo Kinetics

The values of k2 and qe for pseudo-second order are

determined using Equation (9).

(9)

The relationship of t/qt to t is shown in Figure 5,

where the value of qe is obtained from 1/slope and

k2 (slope/(intercept*qe).

Figure 5: KTKA-3M . Pseudo Second Order Kinetic Curve.

The equation t/qt = 0.0271*t + 0.0486 which

shows that 0.0271 is the slope value referring to 1/qe

so that the qe value is 1/slope which is 36.9080 mg/g.

The pseudo-second order adsorption rate (k2) is

obtained from intercept 1/(k2.qe2), k2 is obtained

from (Slope/(Intercept*qe)) which is 0.02709 g,gm-

1min-1 and the correlation coefficient is 0.9993 close

to 1. The calculation results are good pseudo-first-

order and second-order are all summed up in Table 2.

Table 2: Pseudo First Order and Pseudo Second Order

Adsorption Kinetics.

t/qt = 0,0271*t + 0,0486

R² = 0,9993

050100150

t/qt

t (minute))

Equilibrium Model and Adsorption Kinetics of Methylene Blue with Kluwak Shell Carbon

803

The adsorption kinetics equation of KTK and KTKA

3M KOH follows the appropriate Pseudo Second-

order kinetic model as shown in Table 2 by

comparing the correlation coefficient (R

). The value

of the pseudo-second-order correlation coefficient is

greater than the pseudo-first-order and close to one.

This indicates that the adsorption of methylene blue

uses KTK and 3M KTKA chemically. If the price of

R2 in the pseudo-first-order is greater and closer to

the value of 1 than the price of R

in the pseudo-

second-order then the adsorption is physically and

vice versa if the R

in the pseudo-second-order is

greater and approaches the value 1 of the value of R

in the pseudo-first-order then the adsorption involves

a chemical reaction. The kinetic model is based on the

adsorption rate data in Table 2, which in this study

shows that following the pseudo-second-order

kinetics model presents a more presentative

adsorption rate model. The pseudo-second-order

modeling is based on the assumption that adsorption

involves a chemical process between the adsorbent

and the adsorbate . The same thing also happened in

a study conducted by Eko Ariyanto, et al (Ariyanto,

Juniar, Sari, & Marindah, 2014) on the adsorption of

methylene blue and methylene red using activated

carbon from agricultural waste following the pseudo-

second-order kinetic equation with a qe of 27.7 mg/g

for methylene blue and 23.3 mg/g adsorbate

methylene red at a dye concentration of 20 ppm in 100

ml. The adsorption of methylene blue removal using

activated carbon from coconut shell shows a kinetic

equation following the pseudo-second-order model

with a correlation coefficient of about 0.9, both

physical activation of coconut shell in the form of

heating 700

C, chemical activation using H

(Khuluk, Rahmat, Buhani, & Suharso, 2019). The

adsorption rate data on the adsorption study of

methylene blue dye with activated carbon from durian

peel using KOH and NaOH as activators stated that

the pseudo-second-order modeling showed a more

presentative adsorption rate model based on the

assumption that adsorption involves a chemical

reaction between the adsorbent and the adsorbate

(Hanum, Gultom, & Simanjuntak, 2017). Methyl blue

adsorption kinetics using activated carbon of banana

peel waste with a value of qe 0.0033 mg/g and k2

1.8172 gmol

-1

min

-1

(Kurniati, Prastuti, & Septiani,

2019). In the research conducted by Evi Susanti and

Nofrianto (Susanti & Nofdianto, 2014), the kinetics

model of Cr6+ ion absorption from water media to

periphyton biomass is pseudo-second-order, the

equation t/qe = 0.550*t+3.554 with a correlation

coefficient of 0.947. Methyl orange adsorption using

synthetic alum on cotton and cotton fiber, both of

which followed a pseudo-second-order kinetic model

with R2 0.98 (Ikhsan, Widjayanti LFX , & Sunarto,

2013).

4 CONCLUSIONS

1. Equilibrium adsorption of methylene blue using

kluwak shell carbon (KTK) and 3M KOH

activation (KTKA 3M) follows the Langmuir

equation.

2. The adsorption kinetics of methylene blue with 3M

CEC and KTKA, namely Pseudo Second Order.

3. Equilibrium and kinetic equations.

KTK

qe=(15.2732*0.0382 C_e)/( 1+0.0382.Ce),

0.8020 and t/qt=1/(0.0326* 30.6020²)+

1/30.7020 t, R2 0.9853

KTK 3M KOH

qe=(45.0341*1.8722 C_e)/( 1+1.8722.Ce),

0.9932 and t/qt=1/(0.0271* 36.9080²)+

1/36.9080 t,R2 0.9932.

ACKNOWLEDGEMENTS

We would like to say thank you to the chemical

engineering community for the cooperation and

facilities and infrastructure, the kluwak team is

amazing.

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