South African Journal of Chemical Engineering 41 (2022) 211–222

Contents lists available at ScienceDirect

South African Journal of Chemical Engineering

journal homepage: www.elsevier.com/locate/sajce

Theorithecal and experimental study on the thermodynamic parameters

and adsorption of methylene blue on “Argania shells” in industrial waters
Ousama Ifguis a, *, Younes Ziat b, Fouzia Ammou b, Rachid Bouhdadi a, Mohamed Mbarki a,
Mohamed Benchagra b
a
Engineering Laboratory in Chemistry and Physics of Matter, Faculty of Science and Technics, Sultan Moulay Slimane University, Beni Mellal, Morocco
b
Engineering and Applied Physics Team (EAPT), Sultan Moulay Slimane University, Beni Mellal, Morocco

A R T I C L E I N F O A B S T R A C T

Keywords: The present work consists in studying the kinetic, isothermal and thermodynamic properties related to the
Adsorption adsorption of Methylene Blue in industrial waters. The study proposes an package to study the adsorption on the
Thermodynamic side calculating the parameters: (Langmuir constant KL, Frendlich constant KF, the rate constants for a first order
Graphical user interface
K1, pseudo-second order K2 and second order kinetic K3, and paramètres thermodynamiques) and plotting the
Matlab® Code
trends, through a user-friendly graphical interface. This package aims to save time and avoid errors that may
occur when processing experimental results. The experimental study of methylene blue adsorption on Argan
shells was performed to verify the performance of this package. The experimental study of the adsorption of
methylene blue on the shells of Argan was carried out to verify the performance of this set. It is found that the
amount of adsorption of methylene blue on the shells of Argan is 90.96 mg / g for an estimated equilibrium time
of 240 min. The correlation coefficient showed that the pseudo-second order kinetic equation best describes the
adsorption kinetics. The experimental equilibrium data were analyzed, the Langmuir isotherm provided the best
correlation. In addition, the determination of the thermodynamic parameters shows that the reaction is spon­
taneous and exothermic.

1. Introduction The simulation package of kinetic models, adsorption isotherms and

Water treatment is one of the current issues in order to safeguard the
environment (Osamah and Tawfik, 2020). Industrial effluents are
characterized by the presence of high quantities of organic and inorganic
pollutants, including dyes such as methylene blue (Osamah and Tawfik,
2020; Fadillah et al., 2019).
The adsorption onto low cost adsorbents including waste from
agriculture or industry and natural materials appears as one of the most
interesting process because of its low cost and ease of implementation.
In this context, a lot of studies have been carried out, dealing with for
example, Adsorptive removal of phenol from aqueous solution using
chemically modified Saccharum officinarum biomass (Darla et al.,
2021), Removal of phenol by carbon nanotubes grafted with poly(tri­
mesoyl, m-phenylenediamine) (Saleh et al., 2019), Green materials as
adsorbents for water treatment technologies (Saleh, 2021), Synthesis of
carbon nanotubes grafted with copolymer of acrylic acid and acrylamide
for phenol removal (Saleh et al., 2020).
at the same time thermodynamic study related to adsorption are
necessary in any adsorption study in order to fully understand the
adsorption process between adsorbent and adsorbate, which requires a
complex set of equations to evaluate the efficiency of the adsorbent in
question (Bello et al., 2021; SALEH, 2020). Computer tools can be
exploited to study the different parameters related to adsorption. Using
these computer tools, the user will be able to easily model and simulate
conditions avoiding long and frustrating learning periods (Hernandez
et al., 2014; Golman, 2016).
The main objective of this work is to present an application for the
automation of the operational processes necessary for a study of
adsorption of pollutants, including the plotting of curves and the
calculation of various constants. This automation of kinetic, isothermal,
and thermodynamic models will certainly save field researchers time,
avoid errors that can occur when manually processing their results, and
increase the number of experiments in the learning process (Skorzinski
et al., 2009).

* Corresponding author.
E-mail address: ousama.if@gmail.com (O. Ifguis).

https://doi.org/10.1016/j.sajce.2022.06.010
Received 26 January 2022; Received in revised form 17 April 2022; Accepted 22 June 2022
Available online 25 June 2022
1026-9185/© 2022 Published by Elsevier B.V. on behalf of Institution of Chemical Engineers. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
O. Ifguis et al. South African Journal of Chemical Engineering 41 (2022) 211–222

Fig. 1. Schematic description of the software package for the study

of adsorption.

Fig. 2. The different functions of the application.

The application provides a user-friendly graphical user interface

allowing the formulation of any type of kinetic (First order, Pseudo
second order, Second order), isothermal (Langmuir and Freundlich
models) and paramètres thermodynamiques (ΔG, ΔS, ΔH) model. The
graphical user interface allows to export the results for further analysis
as a spreadsheet in an Excel® file (.xlsx).

2. Simulation of adsorption processes

The package used has a user interface that automates the calculations
necessary for the study of adsorption, whether it is the drawing of
curves, the calculation of rate constants, equilibrium model constants
and thermodynamic parameters. On the other hand, dedicated simula­
tion packages are designed to simulate only specific engineering prob­
lems obtaining results quickly (Kartal and Özveren, 2021), but they are
also usually expensive and the source code is not available, so it is not
possible to modify or upgrade the simulation package easily (Ibrahim,
2011). All the operations necessary for the execution of the task (data
entry, calculations and obtaining results in Excel file) are performed in
this package. Fig. 1 shows a graphic representation of all the parts of the
code, differentiating those that should be defined by the user (INPUT)
and those generated by the software (OUTPUT).
For the conception of this package, the notion of functions is used to
facilitate the understanding and the maintainability of the code. The
different matlab functions are illustrated in Fig. 2, each function pro­ Fig. 3. Operation of Cinetique.m for the calculation of parameters related to
cesses part of the calculation. kinetic models (First order, Pseudo second order, Second order).
Functions contain sequential commands and can accept inputs and
return outputs. Named functions must be defined in a program file and • y1,…,yN are outputs
not at the command line. To define a function, the following syntax is • x1,…,xM are inputs
used: • myfun is the function name
Function [y1,…,yN] = myfun(x1,…,xM)

212
O. Ifguis et al. South African Journal of Chemical Engineering 41 (2022) 211–222

Fig. 5. Operation of thermal.m for the calculation of thermal parameters.

gives, for the first order:

(Qe − Qt ) k1 t
log =− (1)
Qe 2.3
The directing coefficient of the line log (Qe-Qt) as a function of t,
gives access to K1, adsorption rate constant (min− 1).
The kinetic adsorption model of pseudo second order, the rate con­
stant K2 is obtained by the following relation (Ho and Mckay, 1999; Ho
and Mckay, 2000):
t 1 t
= + (2)
Qt 2K2 Qe 2 Qe
Plotting t/Qt as a function of t, leads us to K2 (g.min.mg− 1).
Fig. 4. Operation of Isothermal.m for the calculation of parameters related to
For the second order, the rate constant K3 is given by the following
the Langmuir and Freundlich models.
relation (Ho and Mckay, 1999; Ho and Mckay, 2000):

2.1. Kinetic 1
=
1
+ K3 t (3)
Qe − Qt Qe
From the experimental results, and in order to approach the real The graphical representation of Qe −1 Qt as a function of time, allowing
mechanism of the reaction, the researchers apply different kinetic
us to access K3 (min− 1.g/mg).
models. These mathematical models have been chosen for their
With Qe: quantity adsorbed at equilibrium (mg/g), Qt: quantity
simplicity.
adsorbed at time t (mg/g), t: contact time (min).
The kinetic adsorption model of Lagergreen (Lagergreen, 1898)
The Matlab function Cinetique.m is used to calculate the parameters

213
O. Ifguis et al. South African Journal of Chemical Engineering 41 (2022) 211–222

2.2. Isotherme

The amount of adsorbed substance fixed at time t was estimated from

the following relationship:
(C0 − Cr )
Qt = V (4)
m
With Qt: quantity of the adsorbed substance in mg/g at time t, C0:
initial concentration of the adsorbed substance (mg/L), Ct: residual
concentration at time t (mg/L), m: mass of the adsorbent support (g), V:
volume of the solution (L).
In order to understand the mechanisms related to adsorption, it is
necessary to apply the Langmuir and Freundlich adsorption isotherms
(commonly used models).
The Langmuir model is based on the assumption that the surface is
uniform, without interaction between the adsorbed molecules and has
defined adsorption sites (Langmuir, 1916). In contrast, the Freundlich
model accepts the existence of interactions between the adsorbed mol­
ecules (Freundlich, 1906). The Freundlich equation does not provide an
upper limit on adsorption, which reduces its application to dilute
solutions.
The Langmuir model:
ce 1 1
= ce + (5)
Qe Qmax Qmax kL
Qm: Maximum adsorbed capacity (mg/g); KL: equilibrium charac­
teristic constant of the adsorbent (L/mg); depends on temperature and
experimental conditions; Ce: equilibrium adsorbate concentration (mg/
L).
The Freundlich model:

Qe = kF ce 1/n (6)
Linearization of equation (6) leads to:
1
logqe = logkl + logce (7)
n
Ce: equilibrium adsorbate constant (mg.L − 1), KF: adsorption ca­
pacity constant (mg(n-1)/n.g − 1.L1/n) and n: heterogeneity factor.
The Matlab function Isothermal.m is used to calculate the parame­
ters of the isothermal study for both Langmuir and Freundlich methods.
Fig. 4 shows the Operation of Isothermal.m for the calculation of the
parameters related to the Langmuir and Freundlich models.
The function [Ce,Qe,Langmuir,Qm,KL, Frendlichx,frendlichy,n,KF,
rsqLangmuir,rsqFrendlichy]= isotherme(C0, A, F, K, V, m)

• The Input of the Function : (C0, A, F, K, V, m)

• The output of the Function : [Ce,Qe,Langmuir,Qm,KL, Frendlichx,
frendlichy,n,KF,rsqLangmuir,rsqFrendlichy]
Fig. 6. Operation of Calculate.m for the calculation of R2.

related to the kinetic models (First order, Pseudo second order, Second 2.3. Thermal
order).
Fig. 3 shows the operation of Cinetique.m for the calculation of pa­ The following equations allow us to calculate the thermodynamic
rameters related to kinetic models. parameters:
Function [Ct,Qt,First_order,t1, p1, K1, qe_cal,Pseudo_Second_Order, ΔG∘ = ΔH∘ − TΔS∘ (8)
t2, p2, K2, qe_cal2,Second_Order,t3,p3,K3,qe_cal3,rsqfirstorder,
rsqpseudo2order,rsq2order]=Cinetique (K,F,V,m,T,t,A,i) qe ΔS∘ − ΔH ∘
Log = + (9)
Ce 2.303R 2.303RT
• The Input of the Function : (K,F,V,m,T,t,A)
• The output of the Function : [Ct,Qt,First_order,t1, p1, K1,qe_cal, With:
Pseudo_Second_Order,t2,p2,K2,qe_cal2,Second_Order,t3,p3,K3, ΔG◦ : standard Gibbs free energy (J/mol), ΔH◦ : standard enthalpy (J/
qe_cal3,rsqfirstorder,rsqpseudo2order,rsq2order] mol), ΔS◦ : entropy (J/mol.K), R: universal gas constant (8.314 J/mol.K),
T: absolute temperature (K).

214
O. Ifguis et al. South African Journal of Chemical Engineering 41 (2022) 211–222

Fig. 7. A) Raw Argan shells. B) Argan shells crushed and sieved to 2 mm. C) Thermostatic bath with Erlenmeyer flasks containing methylene blue solutions in contact
with Argan shells.

2.4. Plotting of lines and curves

This Calculate.m function calculates R2 from the operations

explained in the previous steps (Brown., 2009). Fig. 6 shows the oper­
ation of Calculate.m for the calculation of R2. p(1) is the slope and p(2)
is the intercept of the linear predictor. Alternatively, the regression co­
efficients can be obtained using the basic fitting user interface.
The matlab function polyfit is used; therefore, it returns the co­
efficients of a polynomial p(x) of degree n that is the best fit (least
squares method) for the data in y. The coefficients of p are in decreasing
powers and the length of p is n + 1 (Recktenwald., 2000).

2.5. Save the data

The xlswritefig function (hFig,filename,sheetname,xlcell) is used to

save the calculated data as well as the data entered by the user in an
Fig. 8. Methylene blue calibration curve, Solutions with a concentration be­ Excel file. The XLSWRITEFIG function is used to programmatically put a
tween 0.95 and 11.95 mg.L − 1. MATLAB figure inside an Excel spreadsheet (Di Remigio 2021).

The thermal thermique.m calculates the thermal parameters ac­ 2.6. Graphical user interface
cording to the following steps:
Function [Ce,Qe,Thermique_y,Thermique_x,rsqThermique,delta_G, Function varargout = graphic_interface (varargin), This function
delta_S,delta_H,p6]= thermique(T, A, F, K, V, m, R, C0). allows to manage and display the graphical interface that facilitates the
Fig. 5 shows the operation of thermal.m for the calculation of ther­ interaction between the user and the application. Graphical User Inter­
mal parameters. face (GUI) in MATLAB, allows the user to interact with a computer
With: program through various graphical objects (buttons, menus) (Mayor
et al., 2021). These objects are usually controlled with the mouse or
• (T, A, F, K, V, m, R, C0) are input keyboard. Although graphical interfaces seem secondary to the devel­
• Thermique: the Name of the function opment of the content of an application, they must never theless be
• Ce,Qe,Thermique_y,Thermique_x,rsqThermique,delta_G,delta_S,del­ designed and developed with care, rigor and precision. Graphical in­
ta_H,p6 are output terfaces are made up of graphical objects distributed in a parent-child

215
O. Ifguis et al. South African Journal of Chemical Engineering 41 (2022) 211–222

Fig. 9. Variation of the adsorbed quantity of MB as a function of time (sorbent dose = 100 mg, V = 100 ml, T = 25 ◦ C).

plotted calibration line. The equation of the calibration curve is Abs664

Table 1 nm = 0.2214 [MB]. Methylene blue solutions should always be diluted
Absorbance versus contact time at 25 ◦ C (298 with distilled water before proceeding to UV analysis. For a 100 mg.L − 1
K) with 250 rpm stirring. MB solution, the dilution factor is F = 20.
Time (min) Abs The dried shells are crushed using a ring grinder (10 s, 1100 rpm)
0 1.165
and sieved manually to retain only the size range below 2 mm. A volume
5 0.476 of 100 mL of MB solution of concentration 100 mg.L − 1 were introduced
10 0.416 with a mass of 0.1 g of crushed Argan shells in an Erlenmeyer which was
15 0.344 placed in a thermostatic bath at 25 ◦ C under a stirring of 250 rpm. The
20 0.292
absorbance values (Abs) as a function of the contact time at 25 ◦ C (298
30 0.270
45 0.236 K) are presented in Table 1.
60 0.226 The variation in the quantity of MB adsorbed on the Argan shells as a
90 0.201 function of time for 100 mg of biosorbent, 100 ml of MB at 25 ◦ C is given
120 0.196 in Fig. 9. After 240 min, the quantity adsorbed is of the order of 90.96
180 0.175
240 0.158
mg/g.
300 0.158

3.2. Kinetic study

hierarchy (Molina et al., 2019). The automatic generation of code (Al­
gorithm) allows to avoid syntax errors, knowing that the interface 3.2.1. First order
generally hides a large part of the code. The Fig. 10 shows first-order modeling of data corresponding to
experimental values obtained from experiments carried out at 25 ◦ C
3. Experimental data panel (298 K).
The kinetic constant K1, the correlation coefficient R2 and the
3.1. Adsorption isotherms amount of MB adsorbed at equilibrium Qe are reported in Table 2.

The main objective of this part is to calculate the parameters related
to the adsorption in aqueous medium of methylene blue/milled Argan
shells (Fig. 7), via the proposed application.
To determine methylene blue concentrations over time Ct, absor­
bance (Abs) was measured at 664 nm (A664) using a Shimadzu UV visible
2550 spectrophotometer. Solutions prepared with concentrations be­
tween 0.95 and 11.95 mg.L − 1 of MB are presented in Fig. 8.
In order to determine the calibration coefficient K of MB, the
absorbance was plotted against the concentration, Fig. 9 illustrates the
3.2.2. Pseudo second order
The Fig. 11 shows pseudo second order modeling of data corre­
sponding to experimental values obtained from experiments carried out
at 25 ◦ C (298 K).
The kinetic constant K2, the correlation coefficient R2 and the
amount of MB adsorbed at equilibrium Qe are reported in Table 3.
3.2.3. Second order
The Fig. 12 shows second order modeling of data corresponding to

216
O. Ifguis et al. South African Journal of Chemical Engineering 41 (2022) 211–222

Fig. 10. Determination of the rate constant for a first-order kinetic model.

shells according to the Langmuir model.

Table 2 The parameters Qm, KL, R2 (coefficient of determination for the
Shows the first order kinetic parameters for the adsorption of MB on Argan shells Langmuir isotherm), are listed in Table 6.
at 25 ◦ C.
Fig. 14 shows the isotherm modeling of MB adsorption on Argan
Time Abs C(t) Q(t) log10 R^2 K1 Qe shells according to the Freundlich model.
(min) (Qe-Qt First calcule The KF, n, and R2 (coefficient of determination for Freundlich
(i)) order
isotherm) are given in Table 7.
0 1.165 105.239 0 1.958 0.798 0.017 25.756 Figs. 13 and 14 illustrate the MB adsorption models according to
5 0.476 42.999 62.240 1.458 – – –
Langmuir and Freundlich. It can be noted that the Freundlich model is
10 0.416 37.579 67.660 1.367 – – –
15 0.344 31.074 74.164 1.225 – – – not suitable to model the adsorption of MB on the studied crushed argan
20 0.292 26.377 78.861 1.082 – – – shells. On the other hand, the Langmuir model is well applicable to the
30 0.27 24.390 80.849 1.005 – – – experimental results obtained for crushed argan shells. It seems that the
45 0.236 21.318 83.920 0.847 – – – Langmuir model is the most representative of the adsorption mechanism
60 0.226 20.415 84.823 0.788
with correlation coefficients that are equal to R2=0.962.
– – –
90 0.201 18.157 87.082 0.589 – – –
120 0.196 17.705 87.533 0.535 – – –
180 0.175 15.808 89.430 0.186 – – – 3.4. Thermodynamic parameters
240 0.158 14.272 90.966 – – – –
300 0.158 14.272 90.966 – – – –
Table 8 shows the equilibrium absorbance for the solution of con­
centration 100 mg.L − 1. Under different temperatures (293, 308, 318
experimental values obtained from experiments carried out at 25 ◦ C and 328 K).
(298 K). Fig. 15 shows that the plot of ln (Kc) versus T1 . We obtained a good
The kinetic constant K3, the correlation coefficient R2 and the correlation coefficient, which allows us to calculate the ΔH and ΔS of
amount of MB adsorbed at equilibrium Qe are reported in Table 4. MB adsorption by Argan shells.
From Tables 2, 3 and 4 The correlation coefficients show that the best ΔH◦ and ΔS◦ can be accessed by plotting Ln (Kc) as a function of 1 /
fitting model to describe the adsorption of MB on the shells of the T, the results obtained are presented in Table 9. On Argan shells the
studied crushed Argan trees is the pseudo second order model. This negative value of the standard Gibbs free energy change ΔG indicates
model best describes the adsorption process with a correlation coeffi­ that the adsorption process is spontaneous in nature, which indicates
cient of 0.999. The analysis of the kinetic data is in good agreement with that it is favorable at low temperature. For this substrate, the value of the
the literature which indicates that the adsorption of (MB) is of pseudo- standard enthalpy change is negative, which proves that the process is
second order (Lagergren and Svenska, 1898). exothermic.

3.3. Adsorption isotherms and modeling 3.5. Adsorption mechanism

Absorbance values (Abs) at t = 0 and at equilibrium for solutions Fig. 16 illustrates the proposed mechanism of MB adsorption on
with concentrations between 50 and 400 mg.L − 1. At 25 ◦ C with stirring lignocellulosic biomass (argan shells)
250 rpm, are shown in Table 5. Fig. 16 describes the possible adsorption mechanism of MB on
Fig. 13 shows the modeling of MB adsorption isotherm on Argan lignocellulosic biomass (argan shells). The adsorption capacity depends

217
O. Ifguis et al. South African Journal of Chemical Engineering 41 (2022) 211–222

Fig. 11. Determination of the rate constant for a pseudo second order kinetic model.

In this study, a model of adsorption of methylene blue in an aqueous

Table 3 solution by Argan shells (agricultural waste) was studied, in order to
shows the pseudo second order kinetic parameters for the adsorption of MB on determine the kinetic, isothermal and thermodynamic properties. The
Argan shells at 25 ◦ C.
results obtained during this work show that the amount of adsorption of
Time Abs C(t) Q(t) t(i)/ R^2 K2 Qe methylene blue on Argan shells is 90.96 mg/g for an equilibrium time
(min) Qt pseudo calcule estimated at 240 min. The kinetic law of the pseudo second order de­
second
order
scribes correctly the process with a correlation coefficient R2=0.999.
The adsorption follows a Langmuir type law. The thermodynamic
0 1.165 105.239 0 0.999 0.001 91.964
–
analysis highlighted that the adsorption is spontaneous and exothermic
5 0.476 42.999 62.240 0.080 – – –
10 0.416 37.579 67.660 0.147 – – – on the Argan shells.
15 0.344 31.074 74.164 0.202 – – –
20 0.292 26.377 78.861 0.253 – – – Code availability
30 0.27 24.390 80.849 0.371 – – –
45 0.236 21.318 83.920 0.536 – – –
60 0.226 20.415 84.823 0.707 – – –
The code is available as Zip files. Please note that the code runs under
90 0.201 18.157 87.082 1.033 – – – the MATLAB® software environment. Assistance for the application and
120 0.196 17.705 87.533 1.370 – – – implementation of the processes in the application will be provided
180 0.175 15.808 89.430 2.012 – – – upon request. To express your interest, please contact Dr. Ousama
240 0.158 14.272 90.966 2.638 – – –
Ifguis ousama.ifguis@usms.ma at the Faculty of Sciences and Technics,
300 0.158 14.272 90.966 3.297 – – –
Sultan Moulay Slimane University, Béni-Mellal, (Morocco).

on the structural and functional behavior of the sorbent. MB can be
easily adsorbed onto lignocellulosic bioadsorbents by forces such as van
der Waals force and hydrogen bonding interactions (Üner et al., 2016;
Manna et al., 2017).
4. Conclusion
During this study, a user-friendly Matlab application was developed
for the calculation of kinetic, isothermal and thermodynamic model
parameters using a user-friendly graphical interface. The program pro­
vides an easy method for the calculation of various parameters related to
the study of adsorption. This application is a very interesting tool for a
complete study of adsorption (calculation of parameters and plotting of
lines).
CRediT authorship contribution statement
O. Ifguis supervised, proposed the idea and wrote the original draft;
Y. Ziat editing and correction; F. Ammou performed the analysis and
software programation; R. Bouhdadi prepared the samples, interpre­
tation, data accuracy, correction and laboratory validation; M. Mbarki
validated the DATA; M. Benchagra validated the algorithm.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.

218
O. Ifguis et al. South African Journal of Chemical Engineering 41 (2022) 211–222

Fig. 12. Determination of the rate constant for a second order kinetic model.

Table 4
shows the second order kinetic parameters for the adsorption of MB on Argan shells at 25 ◦ C.
Time(min) Abs C(t) Q(t) (1 /(Qe - Qt)) R^2 S Order K3 Qe calcule

0 1.165 105.239 0 0.010 0.949 0.003 830.312

5 0.476 42.999 62.240 0.034 – – –
10 0.416 37.579 67.660 0.042 – – –
15 0.344 31.074 74.164 0.059 – – –
20 0.292 26.377 78.861 0.082 – – –
30 0.27 24.390 80.849 0.098 – – –
45 0.236 21.318 83.920 0.141 – – –
60 0.226 20.415 84.823 0.162 – – –
90 0.201 18.157 87.082 0.257 – – –
120 0.196 17.705 87.533 0.291 – – –
180 0.175 15.808 89.430 0.651 – – –
240 0.158 14.272 90.966 – – – –
300 0.158 14.272 90.966 – – – –

Table 5
− 1
Absorbance at t = 0 and at equilibrium for solutions with concentrations in the range of 50 to 400 mg.L . At 25 ◦ C with 250 rpm stirring.
Solution Abs(t = 0) Abs(t to equilibrium)

Solution 1 0.519 0.078

Solution 2 1.165 0.158
Solution 3 2.94 0.513
Solution 4 4.489 1.403

219
O. Ifguis et al. South African Journal of Chemical Engineering 41 (2022) 211–222

Fig. 13. MB adsorption according to Langmuir.

Table 6
Constants of Langmuir model.
CO Abs F Ce Qe Ce(i)/Qe(i) R^2 Langmuir Qm KL

46.88 0.078 20 7.046 39.833 0.176 0.962 404.107 0.019

105.23 0.158 20 14.272 90.957 0.156 – – –
265.58 0.513 20 46.341 219.238 0.211 – – –
405.51 1.403 20 126.73 278.771 0.454 – – –

Fig. 14. MB adsorption according to Freundlich.

220
O. Ifguis et al. South African Journal of Chemical Engineering 41 (2022) 211–222

Table 7
Constants of Freundlich model.
CO Abs F Ce Qe log(Ce(i)) log(Qe(i)) R^2 Freundlich n KF

46.88 0.078 20 7.046 39.833 1.952 3.684 0.932 1.488 13.097

10,523 0.158 20 14.272 90.957 2.658 4.510
265.58 0.513 20 46.341 219.238 3.836 5.390
405.51 1.403 20 126.738 278.771 4.842 5.630

Table 8
1
Absorbance at equilibrium for solutions of concentrations 100 mg.L −
. Under the
temperatures (293, 308, 318 and 328 K).
Temperature (K) Abs(t to equilibrium)

293 0.158
308 0.169
318 0.205
328 0.210

Fig. 15. Determination of the enthalpy and entropy of adsorption of methylene blue on Argan shells.

Table 9
Thermodynamics associated with adsorption on Argan shells.
Abs Ce Qe log10(Qe/Ce) 1/T delta_G delta_S delta_H R^2 thermal

0.158 14.272 90.957 0.804 0.003 -1982.859 -5.775 -3675.071 0.897

0.169 15.266 89.963 0.770 0.003 -1896.227 – – –
0.205 18.518 86.711 0.670 0.003 -1838.472 – – –
0.21 18.970 86.259 0.657 0.003 -1780.717 – – –

221
O. Ifguis et al.
Fig. 16. Proposed mechanism of MB adsorption on lignocellulosic biomass (argan shells).
Acknowledgments
The authors would like to thank Dr. Béatrice George of Laboratory
of studies and researches on the wood material (LERMAB), faculty of
sciences and techniques, Nancy University, for her support.
References
Bello, M.O., Abdus-Salam, N., Adekola, F.A., Pal, U., 2021. Isotherm and kinetic studies
of adsorption of methylene blue using activated carbon from ackee apple pods.
Chem. Data Collections 31, 100607. https://doi.org/10.1016/j.cdc.2020.100607.
Brown, Scott H. Multiple linear regression analysis: a matrix approach with MATLAB.
Alabama Journal of Mathematics, 2009, vol. 34, p. 1-3.
Darla, Upendra R., Lataye, Dilip H, Zaidi, Zakiullah., 2021. Adsorptive removal of phenol
from aqueous solution using chemically modified Saccharum officinarum biomass:
modelling and process optimisation. Int. J. Environ. Analytical Chem. 1–26.
Di Remigio, G., Rocchi, I., et Zania, V. New method for a SEM-based quantitative
microstructural clay analysis-MiCA. Applied Clay Science, 2021, vol. 214, p. 106248.
Fadillah, Ganjar, Saleh, Tawfik A., et WAHYUNINGSIH, Sayekti, 2019. Enhanced
electrochemical degradation of 4-Nitrophenol molecules using novel Ti/TiO2-NiO
electrodes. J. Mol. Liquids 289, 111108.
Freundlich, H., 1906. Z. Phys. Chem. 57A, 385.
Golman, B., 2016. Transient kinetic analysis of multipath reactions: an educational
module using the ipython software package. Educ. Chem. Eng. 15, 1–18. https://doi.
org/10.1016/j.ece.2015.12.002.
Hernandez, P.R., Bodin, R., Elliott, J.W., Ibrahim, B., Rambo-Hernandez, K.E., Chen, T.
W., de Miranda, M.A., 2014. Connecting the STEM dots: measuring the effect of an
integrated engineering design intervention. Int. J. Technol. design Educ. 24 (1),
107–120. https://doi.org/10.1007/s10798-013-9241-0.
Ho, Y.S., Mckay, G., 1999. Process Biochem 34, 451.
Ho, Y.S., Mckay, G., 2000. Water Res. 34, 735.
Ibrahim, D., 2011. Engineering simulation with MATLAB: improving teaching and
learning effectiveness. Procedia Comput. Sci. 3, 853–858. https://doi.org/10.1016/
j.procs.2010.12.140.
Kartal, F., Özveren, U., 2021. A comparative study for biomass gasification in bubbling
bed gasifier using Aspen HYSYS. Bioresource Technol. Reports 13, 100615. https://
doi.org/10.1016/j.biteb.2020.100615.
222
South African Journal of Chemical Engineering 41 (2022) 211–222
Lagergreen, S., 1898. K Svenska Vetenskapsakad Handl. 24, 1.
Lagergren, S., Svenska, K, 1898. Vetenskapsakad Handl 24, 1.
Langmuir, I., 1916. J. Am. Chem. Soc. 38, 2221.
Manna, S., Roy, D., Saha, P., Gopakumar, D., Thomas, S., 2017. Rapid methylene blue
adsorption using modified lignocellulosic materials. Process Safety and Environ.
Protection 107, 346–356.
Mayor, D., Panday, D., Kandel, H.K., Steffert, T., Banks, D., 2021. CEPS: an open access
MATLAB graphical user interface (GUI) for the analysis of complexity and entropy in
physiological signals. Entropy, 23 (3), 321. https://doi.org/10.3390/e23030321.
Molina, R., Orcajo, G., Martinez, F., 2019. KBR (Kinetics in Batch Reactors): a MATLAB-
based Application With a Friendly Graphical User Interface for Chemical Kinetic
Model Simulation and Parameter estimation. Education for Chemical Engineers, 28,
pp. 80–89.
A. Osamah, B-D, Tawfik, S., 2020. Synthesis of carbon nanotubes grafted with PEG and
its efficiency for the removal of phenol from industrial wastewater Environ.
Nanotechnol. Monitoring & Manag. 13, 100286.
Recktenwald, Gerald W. Numerical methods with MATLAB: implementations and
applications. Upper Saddle River : Prentice Hall, 2000.
Saleh, T.A., 2021. Protocols for synthesis of nanomaterials, polymers, and green
materials as adsorbents for water treatment technologies. Environ. Technol.
Innovation 24, 101821.
Saleh, T.A., SARI, Ahmet, et TUZEN, Mustafa, 2019. Carbon nanotubes grafted with poly
(trimesoyl, m-phenylenediamine) for enhanced removal of phenol. J. Environ.
Manag. 252, 109660.
SALEH, Tawfik A, 2020. Nanomaterials: classification, properties, and environmental
toxicities. Environ. Technol. Innovation 20, 101067.
Saleh, Tawfik A., Elsharif, Asma M., ASIRI, Sarah, et al., 2020. Synthesis of carbon
nanotubes grafted with copolymer of acrylic acid and acrylamide for phenol
removal. Environ. Nanotechnol. Monitoring & Manag. 14, 100302.
Skorzinski, E., Shacham, M., & Brauner, N. (2009). A simulation program for modelling
pollutant dispersion for educational applications. In Computer Aided Chemical
Engineering (Vol. 26, pp. 1233–1238). Elsevier. https://doi.org/10.1016/S1570-
7946(09)70205-6.
Üner, O., Geçgel, Ü., Bayrak, Y., 2016. Adsorption of methylene blue by an efficient
activated carbon prepared from Citrullus lanatus rind: kinetic, isotherm,
thermodynamic, and mechanism analysis. Water, Air, & Soil Pollut. 227 (7), 1–15.