Environmental Surfaces and Interfaces 3 (2025) 103–111

Contents lists available at ScienceDirect

Environmental Surfaces and Interfaces

journal homepage: www.keaipublishing.com/ESI

Towards a deeper understanding of the adsorption of methyl orange on a

commercial activated carbon: Study of impact factors, isotherm and ]]
]]]]]]
]]

mechanism
Younes Dehmania,b,c, , Dison S.P. Francod, Jordana Georgind, Redouane Mghaiouinie,
⁎

Bouchra Ba Mohammedf, Rachid Kacimig, Taibi Lamhasnih, Eder C. Limai,

Noureddine El Messaoudij, Abouarnadasse Sadikc
a
Interfaces, Confinement, Matériaux et Nanostructures (ICMN), CNRS-Université d′Orléans, UMR 7374, 1B Rue de la Férollerie, C.S., 45071 Orléans Cedex 2, 40059,
France
b
Institut de Chimie des Milieux et des Matériaux de Poitiers, IC2MP UMR 7285 CNRS, Université de Poitiers, France
c
Laboratory of Chemistry/Biology Applied to the Environment, Faculty of Sciences, MoulayIsmaïl University, BP 11201-Zitoune, Meknes 50070, Morocco
d
Department of Civil and Environmental. Universidad de la Costa, CUC, Calle 58 # 55–66, Barranquilla, Atlántico, Colombia
e
Laboratoire d′Ingénierie des Systèmes Avancés, Ecole Nationale des Sciences Appliquées, Université Ibn Tofail, Kénitra, Morocco
f
Laboratoire des Matériaux, Membranes et Nanotechnologie, Département de Chimie, Faculté des Sciences, Université Moulay Ismail, PB 11201, Zitoune, Kénitra, Morocco
g
IM2NP, UMR CNRS 7334, Aix-Marseille Université, Marseille 13013, France
h
Institut National des Sciences de l’Archéologie et du Patrimoine (INSAP), Angle rues 5 et 7, Avenue Allal El-Fassi, BP 6828, Madinat Al Irfane, Rabat-Instituts, Morocco
i
Institute of Chemistry, Federal University of Rio Grande do Sul (UFRGS), Bento Gonçalves 9500, Porto Alegre, RS 91501-970, Brazil
j
Laboratory of Applied Chemistry and Environment, Faculty of Sciences, Ibn Zohr University, Agadir 80000, Morocco

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

Keywords: This study investigates the use of commercially available activated carbon for the removal of methyl orange from
Methyl orange aqueous solutions. The main characteristics of the activated carbon are as follows: BET specific surface area:
Activated carbon 641 m²/g; Pore volume: 0.28 cm³ /g; Microporous nature: More than 70 % of the total pore volume are micro­
Adsorption modelling pores. A systematic approach was adopted to analyze how factors such as contact time, initial pH of the solution,
Adsorption mechanism
and temperature influence carbon adsorption capacity. A maximum removal capacity value of 100 mg/g with an
elimination rate exceeding 98 %. The adsorption behavior of methyl orange was modeled with the statistical
physical modeling of the adsorption process using the single trainer model, which provided a better under­
standing of the adsorption mechanism of methyl orange on activated carbon. This suggests that activated carbon
can be an effective adsorbent for the removal of colored compounds from water. The experimental isothermal
results encourage the use of this material in the treatment of industrial tannery effluents.

1. Introduction solved [3–5]. In addition, methyl orange is a bis-azo dye that changes
color at low pH due to the protonation of its amino groups. Helianthine,
As the population continues to grow and industrialization accel­ also called methyl orange (MO), orange III or methyl orange, is a co­
erates, water pollution is becoming more and more severe. Many new lored indicator used in chemistry to mark the presence of an acidic
pollutants, such as persistent organic pollutants, plastics, solvents, dyes, medium (it turns pink-red) or a basic medium (it turns yellow-orange).
paints, etc., have been identified in aquatic environments [1,2]. Dye It is therefore used for acid-base assays.
pollutants are one of the most serious environmental problems at pre­ Activated carbon is recognised as an effective adsorbent for water
sent. How to effectively remove dyes from the water system and reduce treatment, particularly for eliminating organic contaminants such as
their threat to human health is an urgent problem that needs to be dyes, thanks to its large specific surface area and high adsorption

⁎
Corresponding author at: Interfaces, Confinement, Matériaux et Nanostructures (ICMN), CNRS-Université d′Orléans, UMR 7374, 1B Rue de la Férollerie, C.S.,
45071 Orléans Cedex 2, 40059, France.
E-mail address: dehmaniy@gmail.com (Y. Dehmani).

https://doi.org/10.1016/j.esi.2025.02.002
Received 22 November 2024; Received in revised form 22 February 2025; Accepted 25 February 2025
Available online 26 February 2025
2949-8643/© 2025 The Authors. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open access article under the CC BY
license (http://creativecommons.org/licenses/by/4.0/).
Y. Dehmani, D.S.P. Franco, J. Georgin et al. Environmental Surfaces and Interfaces 3 (2025) 103–111

capacity [6]. To maximize its effectiveness, a thorough understanding 10 mL of the solution using a syringe and immediately filter the solution
of the adsorption mechanisms is required. Conventional models, such as through a filter of more than 0.45 μm. microporous membrane; 5) The
the Freundlich and Langmuir models, offer insight into adsorption ca­ solution was analyzed with a UV/Visible spectrophotometer
pacities but fail to accurately account for the interactions between The adsorption capacity (at any time and at equilibrium) for the 2-
adsorbed molecules and activated carbon active sites [7–10]. To ad­ nitrophenol was calculated according to the mass balance equation
dress these limitations, statistical physics-based models are gaining
C0 Ct
popularity. These advanced models offer a more detailed molecular- Qt = *V
(1)
m
level understanding of adsorption, better capturing the intricate inter­
actions between solutes and adsorbent surfaces [6–8]. Methods for C0 Ce
Qe = *V
eliminating methyl orange include advanced oxidation processes based m (2)
on hydroxyl radicals (HO-). Although these methods are effective, they
where C0 is the initial dye concentration (mg/L), Ct its concentration
can generate toxic by-products, limiting their application in certain
(mg/L) at time t (min), V the solution volume (L) and m the amount of
circumstances. Other traditional techniques such as coagulation,
samples used (g).
membrane filtration or biological degradation also offer viable solu­
tions [11–21]. However, adsorption remains the preferred method due
to its effectiveness, ease of implementation and limited environmental 2.4. Physical statistical modeling
impact [22].
Activated carbon, especially from natural sources, effectively ad­ The Supplementary Material provides a description of the models
sorbs compounds like methyl orange. For example, it can remove up to used.
98.94 % of methyl orange within three hours of contact time [11].
These results highlight the importance of activated carbon's porous 2.5. Parameter estimation and model evaluation
structure, functional groups and high adsorption capacity.The aim of
this project is to study the adsorption mechanisms of methyl orange on Matlab programming was used to estimate the model parameters.
commercial activated carbon[23–25]. This will include analysis of ad­ The Supplementary Material contains the statistical formulas used for
sorption kinetics and the influence of pH, as well as physico-chemical the assessment.
characterisation of the activated carbon. Classical isothermal models, as
well as approaches based on statistical physics, will be applied to better 3. Results and discussion
understand the mechanisms governing the adsorption of the dye. The
novelty of this work lies in the use of a physico-statistical model to 3.1. Characterization of activated carbon
elucidate the adsorption mechanism of methyl orange on activated
carbon and to determine the experimental adsorption conditions. The crystalline structure of commercial activated carbon has been
characterised by XRD (X ray diffraction) analysis. The diffractogram is
2. Material and methods shown in the Fig. 1(c) in the range 5° < 2θ < 70°. Broad lines were
observed at 2θ = 24.3°, indicating a typical amorphous crystalline
2.1. Chemicals and reagents structure in carbon materials [26,27].
Analysis of the FT-IR spectrum reveals several characteristic bands,
Sigma-Aldrich supplied the commercial activated carbon that was indicative of specific functional groups. These bands were interpreted
utilized as the adsorbent. Methyl orange dye was dissolved in distilled by comparing them to reference spectra [5,17,18]. A broad band at
water to create stock solutions, which were acquired from Organic 3472 cm-¹ and 3844 cm-¹ corresponds to the elongation of hydroxyl
Acro.Aesor Alpha was the supplier of additional reagents, such as po­ groups (OH) in water Fig. 1(b).
tassium chloride (KCl), sodium hydroxide (NaOH), sodium chloride
(NaCl), and hydrochloric acid (HCl). To guarantee the precision and • Another broad band at 2920 cm-¹ and 2945 cm-¹ is associated with
dependability of the experimental findings, all of the substances utilized the elongation of C-H groups.
in this investigation were of analytical quality. • A band at 1645 cm-¹ and 1750 cm-¹ can be attributed to the elon­
gation of C]C double bonds, present in olefins (alkenes) and aro­
2.2. Characterization methods matic compounds.
• Very weak bands, between 1392 cm-¹ and 1506 cm-¹ , are linked to
Prior to the adsorption tests, the materials were characterized by C-H deformations in aliphatic chains.
various methods. Curves of adsorption and desorption of N2 at 77 K • A broad band between 1000 cm-¹ and 1120 cm-¹ corresponds to in-
were used to calculate the surface area and total pore volume of the plane deformation of C-O bonds in aliphatic compounds [82–84].
carbon-based materials. A volumetric analyzer supplied by • Finally, bands located at 400 cm-¹ and 605 cm-¹ are attributed to the
Micromeritics (ASAP 2010) was used for these measurements. Fourier elongation of C-X bonds, resulting from carbon activation.
transform infrared spectroscopy (FTIR) was measured using a JASCO
4100 spectrometer from 4000–400 cm-1. Scanning electron microscopy The N₂ adsorption/desorption isotherm (Fig. 1(a)) exhibits a type IV
(SEM) with energy dispersive X-ray (EDX) analysis was carried out profile, indicating a mesoporous structure. This suggests pore sizes
using a Joel JSM-IT500HR instrument. ranging from 2 to 50 nm, making the activated carbon suitable for
adsorbing larger organic molecules and various pollutants [28–30].
2.3. Adsorption assays Mesoporous materials are particularly advantageous in adsorption ap­
plications due to their high surface area and pore volume, which fa­
To study the kinetics of the adsorption reaction, we measured the cilitate enhanced interactions between the adsorbent and the adsorbate.
residual concentration of the standard range solutions after introduc­ The textural properties of the activated carbon are summarized in. The
tion of activated carbon at regular time intervals. The protocol was as specific surface area, measured using the Brunauer–Emmett–Teller
follows: 1) Pour 200 mL of the chosen solution into a beaker while (BET) method, is 641 m² g⁻¹ , which is relatively low compared to
stirring magnetically; 2) Weigh accurately and add 50 mg of activated standard activated carbons, which often exceed 1000 m² g⁻¹ . This re­
carbon to each beaker; 3) Start a timer; 4) At each programmed time duced surface area may suggest a limited adsorption capacity, poten­
(0 min, 10 min, 20 min, 30 min, 60 min, 90 min and 120 min), withdraw tially due to the preparation or activation process affecting the

104
Y. Dehmani, D.S.P. Franco, J. Georgin et al. Environmental Surfaces and Interfaces 3 (2025) 103–111

Fig. 1. (a) BET; (b) FTIR; (c) XRD; and SEM of the activated carbon.

development of micropores and mesopores. The pore diameter (Dₚ) of

46 Å and pore volume (Vₚ) of 0.28 cm³ g⁻¹ , as estimated by the Bar­
rett–Joyner–Halenda (BJH) method, indicate a significant proportion of
mesopores within the structure. This mesoporosity enhances the ma­
terial's capacity to adsorb large organic molecules, aligning with its
intended application in removing pollutants such as nitrophenols.The
BET method determines the total surface area of the material by mea­
suring the amount of gas adsorbed onto its surface. The T-plot method,
on the other hand, provides information about the distribution of pore
sizes, specifically micropores and mesopores. The difference in surface
area values obtained from these techniques reflects the material's in­
ternal structure (Fig. 1(d)), including the relative abundance of mi­
cropores and mesopores, which can significantly impact the adsorption
efficiency for specific compounds [19–21].

3.2. Adsorption of methyl orange

pH is a parameter that plays an important role in the adsorption

phenomena of organic or inorganic compounds. pH is one of the
parameters that control the appearance of charges on the surface of the Fig. 2. pH effect onto the methyl orange adsorption (t = 120 min; m=20 mg;
adsorbent and on the adsorbed molecule, this charge is dependent on T = 298 K; Ci=150 mg/L).
pH from zero charge point. From Fig. 2 it is possible to observe that the
adsorption of methyl orange by activated carbon is strongly influenced optimum pH value for maximum adsorption of methyl orange on the
by the pH of the solution. A maximum elimination rate value corre­ carbons under the conditions studied is pH = 2.
sponds to the acidic pH (2), which decreases beyond this value up to Adsorption kinetics were studied to determine the equilibrium time,
pH = 10 [31,32]. These results [31,32] are supported by those ob­ a crucial factor for economic water treatment. The results show that the
tained by on the elimination of dyes from aqueous solutions on removal rate of methyl orange increases with the stirring time. It is
activated carbon prepared from biomass. According to these authors, found that four hours is sufficient to reach equilibrium and this is true
activated carbon has a positively charged surface. Consequently, at acid for all manipulations. It is also noted that adsorption is rapid in the first
pH, the number of positively charged sites increases, which favours the 30 minutes after reaching the saturation plateau of the activated carbon
adsorption of anions by electrostatic attraction. This may be the case for [33–35]. Fig. 3
the anionic dye methyl orange. The rate of adsorption in alkaline media Fig. 4 shows the evolution of the quantity of methyl orange ad­
decreases with increasing pH, which can be explained by the excess of sorbed by activated carbon as a function of initial concentrations be­
OH- ions in the medium leading to competition with this anionic dye for tween 50 mg/L and 300 mg/L.It can be seen that the amount of ad­
the active carbon adsorption sites. The high concentration and high sorbent fixed on the activated carbon increases as a function of the
mobility of OH- ions will favour their adsorption over the dyes. The concentration. In fact, an increase in the initial concentration

105
Y. Dehmani, D.S.P. Franco, J. Georgin et al. Environmental Surfaces and Interfaces 3 (2025) 103–111

Fig. 3. Contact time effect on the methyl orange adsorption (pH=2; Fig. 5. Temperature effect on the methyl orange adsorption and fitted kinetic
m=20 mg; T = 298 K; Ci=150 mg/L). models (pH=2; m=20 mg; Ci=150 mg/L).

Table 1
Estimated kinetical parameters for the pseudo-first order and pseudo-second
order.

Models Parameters Temperature (ºC)

30 40 50

Pseudo first order qe (mg g−1) 79.05 123.17 147.96

k1 (min−1) 0.0306 0.0201 0.0274
R2 0.9828 0.9697 0.9724
ARE (%) 5.511 8.147 7.141
MSE (mg g−1)2 15.34 63.60 86.52
BIC 23.54 34.92 37.38
Pseudo second order qe (mg g−1) 93.93 156.19 178.72
k2 (g 3.793 1.279 1.714
mg−1.min−1)x104
R2 0.9927 0.9782 0.9849
ARE (%) 3.099 6.235 4.536
MSE (mg g−1)2 6.482 45.73 47.25
BIC 16.65 32.28 32.54
qexp(mg g−1) 80 120 150

Fig. 4. Initial methyl orange concentration effect onto the adsorption capacity For the PSO it was found an R2 of 0.9927, an ARE low of 3.099, an MSE
(pH=2; m=20 mg; T = 298 K; t = 120 min). low of 6.482 (mg g−1)2, and a BIC low of 16.65. This indicates that the
PSO is the best model for describing the methyl orange/activated
strengthens the concentration gradient and thus increases the driving carbon system.
force for the transfer of particles in solution to the surface of the ad­ Table 2 compares the adsorption capacity of different types of ad­
sorbent. The results demonstrate the efficiency of activated carbon in sorbent for methyl orange reported in the literature. It can be assumed
the removal of methyl orange, with efficiencies greater than 99 %. that differences in properties and operating conditions may lead to
These performances highlight the potential of this material to treat different results. These differences are evident in the results reported in
tannery effluent, even at high concentrations. [21,36–38]. Table 2, indicating that the characteristics of the adsorbent have a
The adsorption process is subject to two significant influences ex­ significant impact on its efficiency. The activated carbon employed in
erted by temperature. First, a rise in temperature promotes molecular this investigation demonstrated a high adsorption capacity and notable
diffusion across the adsorbent particles' interior pores and external efficiency, with a pollutant removal efficiency exceeding 99 %. Ad­
boundary layer. This is likely to occur alongside a decrease in solution ditionally, it was observed that the initial concentration utilized in our
viscosity. Additionally, temperature influences adsorption capacity adsorption experiments was lower than that reported in previous stu­
(Fig. 5). The findings demonstrate that the removal rate of methyl or­ dies, with a contact time not exceeding 180 minutes. Our findings in­
ange rises with temperature, reaching a maximum value at 30 °C. Be­ dicate that the adsorbent under examination was particularly effective
yond this temperature, the rate declines [11,12,14,15]. in eliminating this deleterious pollutant from aquatic environments.
One of the main topics in adsorption is the prediction of the ad­
sorption capacity concerning time. In this case, the pseudo-first order 3.3. Physics-statistics modeling
(PFO) and pseudo-second order (PSO) were employed to describe the
methyl orange/activated carbon at different temperatures. The statis­ The adsorption capacity at the equilibrium for the system methyl
tical indicators and parameters obtained for the chosen models are orange/activated carbon is given in Fig. 6. According to the Giles
shown in Table 1. The PFO presented a minimum R2 of 0.9697, an ARE classification [47] the isotherm data follows the S-group pattern, also
low of 5.511 %, an MSE low of 15.34 (mg g−1)2, and a BIC low of 23.54. known as the cooperative adsorption group. This is likely due to

106
Y. Dehmani, D.S.P. Franco, J. Georgin et al. Environmental Surfaces and Interfaces 3 (2025) 103–111

Table 2
Comparison of the amount adsorbed by various adsorbents in literature works and this adsorbent.

Author Adsorbent Adsorbed quantity (mg/g) Rendement] (%) Ref

Tapan Kumar Saha Chitosan 30 mg/g [39]

Jimin Fan SMNPS 53.19 [40]
H.Y. Zhu α-Fe2O3 28.90 [41]
Masoud Shariati-Rad N–TiO2 14.1 [42]
A.A.A. Darwish CuO 121.95 [43]
Fortunate Phenyo Sejie Clay 4 mg/g [16]
Ting Jiang carbon/NiFe2O4 136.61 [17]
Balram Singh Yadav MgAl LDH 139.20 [18]
Layaly Obeid Chitosan/maghemite 1 mg/g [44]
S. Asuha TiO 2 80 [45]
El Hadj Mekatel zeolite NaA/CuO 90 [46]
this work 100 mg/g 98 %

Table 3
Fitting results according to the physical statistical model and temperature.

Model T Statistical indicators

(K) Radj2 ARE (%) MSE (mg g−1)2 BIC

Monolayer 298.15 0.9653 321.8 45.37 54.91

with one 308.15 0.9565 360.5 45.91 49.58
energy 318.15 0.9781 212.9 18.11 51.19
site 328.15 0.9580 389.4 18.46 56.62
(MO) BIC 53.08
Monolayer 298.15 0.9604 330.7 43.64 55.90
with two 308.15 0.9465 369.1 41.91 49.84
energy 318.15 0.9793 181.1 20.35 50.48
sites 328.15 0.9599 334.4 22.77 56.00
(MT) BIC 53.05
Double layer 298.15 0.9826 161.6 17.97 48.71
with one 308.15 0.9784 179.1 29.27 43.98
energy 318.15 0.9768 225.4 23.74 51.71
site (DO) 328.15 0.9838 149.9 8.35 48.03
BIC 48.11
Double layer 298.15 0.8609 1239 17.970 67.60
with two 308.15 0.3709 4883 29.272 70.72
Fig. 6. Methyl orange adsorption capacity at equilibrium onto activated carbon energy 318.15 0.9367 592 23.736 60.94
at different system temperatures. sites 328.15 0.7211 2481 8.350 73.85
(DT) BIC 68.28
interactions between the adsorbate and solvent or adsorbate molecules. Triple layer 298.15 0.9943 52.96 22.18 38.67
with one 308.15 0.9092 707.5 39.44 61.99
Adsorbate/solvent interactions are common in hydrocarbon dilution
energy 318.15 0.9856 139.7 18.88 47.40
with organic liquids like hexane.On the other hand, possible interac­ site (TO) 328.15 0.9830 157.9 9.760 48.50
tions can occur between the adsorbate and adsorbate, through inter­ BIC 49.14
locking of the adsorbed molecules, such as the dimer formation. In the
case of methyl orange, it is known that the molecules will be found in
dimer form at negative pH in special on the presence of hydrochloric or
sulfuric acid [48]. Regarding the temperature effects, it was found that data. Taking this rule into consideration and employing the average
the adsorption capacity (Qe, mg g−1) tends to increase with the rise of value, it was found the following order DO < MT < MO < DO <
the system temperature. This behavior can be attributed to i) the TO < DT Because the double layer with two energy sites has the highest
temperature increases the methyl orange dilution, thus facilitating the BIC of 68.3 and the monolayer model with two energy sites has the
movement and the adsorption; ii) the material is thermal dependent, lowest BIC of 34.1, the MT was chosen to represent the experimental
meaning that the n is affected by temperature. This effect can be further data and interpret the steric parameters that were found.
specified through the application of physical statistical modeling. Fig. 7 shows the DO predicted parameters based on the system
The fitted physical-statistical models are given in Table 3. To eval­ temperature. The observed and predicted adsorption capacities are
uate the fitting of each model, different statistical indicators were em­ displayed in Fig. 7 (a). It was found that the DO can predict the exact
ployed, i) the R2adj which compensates the different number of para­ experimental values; 293.1, 297.3, 300.0, and 302.9 mg g−1 according
meters per model, ii) the ARE and the MSE which relates the model to temperature. The number of adsorbed molecules (n) and the receptor
prediction to the experimental data and iii) the BIC which indicate what densities changed according to the temperature are given in Fig. 7 (b).
model is the most suitable for describing the experimental data. Most It was estimated that the number of molecules decreases from 1.19 to
models have an R2adj value above 0.90, with the double layer with two 0.57 when the system temperature increases from 298.15 to 328.15 K.
energy sites showing one of the highest values, like 0.9838, indicating The n values are an important aspect of the physics-statistics modeling,
that the model is not appropriate for explaining the experimental re­ which enables the interpretation of the adsorption phenomena. Mole­
sults. ARE and MSE varied with temperature and model, indicating that cular orientation is indicated by the n value's magnitude. Values above
most models can adequately describe the experimental data. Last, the or equal to unity suggest non-parallel adsorption [10]. When the n
BIC is based on a logarithmic function, meaning that the small and values are between the range of 0.5 and 1, the adsorbate molecules are
negative values indicate that the model represents the experimental adsorbed in a hybrid manner (parallel and non-parallel); Furthermore,

107
Y. Dehmani, D.S.P. Franco, J. Georgin et al. Environmental Surfaces and Interfaces 3 (2025) 103–111

Fig. 7. Experimental and predicted adsorption capacity (a), number of molecules, anchorage number, and density of the receptor (b), concentration at half-
saturation and adsorption energy (c), according to the system temperature.

molecules are adsorbed parallel to the surface when values are less than is less than 40 kJ mol−1. Sonawane and collaborators [50] have in­
0.5. The methyl orange molecules are adsorbed in this instance in a vestigated the adsorption of methyl orange onto the AlMnTiO nano­
non-parallel manner (at lower temperatures). These theoretical results composite and they report that the DL describes the experiment with
are in agreement with the isotherm classification and the dimer for­ equivalent energy of adsorption.
mation, which alter how the molecules are adsorbed at the surface.
Besides that, it is possible to obtain the anchorage number (Fig. 7 (b)), 3.4. Thermodynamic state simulation
the inverse value of the number of molecules. The anchorage number
tends to increase with the temperature, going from 0.83 to 1.73; at Using the grand partition function from statistical physics, we can
lower temperatures, the methyl orange will be adsorbed in less than on predict the system's thermodynamic states, as detailed in the supple­
the activate site, nonetheless, the increase of the temperature leads to mentary material. Fig. 9 (a) shows the simulations obtained for the
the methyl orange occupying more than one site; once again this can be configurational entropy according to the methyl orange equilibrium
related with the dimer formation or molecular agglomeration [49] concentration and the temperature. The configurational entropy de­
From the adsorption capacity and the number of molecules is pos­ pends on the initial concentration, which leads to two separate regions:
sible to estimate the receptor density (ρ, mg g−1) as depicted in Fig. 7 i) when Ce < C1/2 and ii) when Ce > C1/2. The first region is related
(b). It was estimated that the density of the receptor sites tends to in­ there is a lower concentration of methyl orange molecules and a high
crease nonlinearly with the system temperature, going from 246.1 to number of available receptor sites. This behavior occurs until the con­
526.1 mg g−1. This behavior indicates that the molecules change from a centration reaches its maximum value, at the entropic peaks, which
scattering state to an agglomeration state, which correlates to the me­ corresponds to the C1/2 values. After that, the number of receptors starts
thyl orange dimer formation proprieties. Thus, it is possible to sum­ to decrease and the adsorbed molecules are organized.Higher tem­
marize the temperature effect on the adsorption of methyl orange, as peratures increase configurational entropy, leading to greater mole­
depicted in Fig. 8. At lower temperatures, methyl orange occupies cular movement. The DO model assumes identical adsorption sites,
available sites, forming bilayers and dimers. As the temperature rises suggesting a similar mechanism for first and second layers.The Gibbs
the dimer formation effects increase as well, thus, increasing the density free energy results according to the methyl orange concentrations and
of the receptor sites. Last, the concentration at half-saturation (C1/2, mg temperature are given in Fig. 9 (b). The adsorption is spontaneous in all
g−1) and the estimated adsorption energy are depicted in Fig. 7 (c). The feasible states, as may be seen by first noting that the Gibbs energy is
C1/2 tends to diminish, from 15.81 to 8.46 mg L−1, with the system negative at all concentrations and temperatures. Second, the increase of
temperature, these results directly reflect the temperature affinity and the methyl orange concentration tends to diminish the Gibbs free en­
effect on the system; meaning that half of the concentration is more ergy, presenting the highest rate of change until the C1/2. This behavior,
easily removed from the aqueous phase. Furthermore, the adsorption once again, is related to the ratio between the number of methyl orange
energy is calculated using the C1/2 algorithm. It was discovered that molecules and the density of the receptor sites [7]. After that, the Gibbs
the energy in this instance increased from 14.26 to 17.40 kJ mol−1; this free energy continues to slowly diminish until reaching a plateau after
behavior is associated with the system's endothermic character. Ad­ the 60 mg L−1. As for the temperature, it was found that the Gibbs
ditionally, the system's type has a direct bearing on the adsorption energy tends to increase as well, similar to the results obtained from the
energy's magnitude. Hydrogen, electrostatic, and π-π interactions are configurational entropy. However, in this case, the temperature tends
examples of physical interactions that cause adsorption when the value to affect only the early stages of the Gibbs free energy, eg at 20 mg L−1,

108
Y. Dehmani, D.S.P. Franco, J. Georgin et al. Environmental Surfaces and Interfaces 3 (2025) 103–111

Fig. 8. Adsorption mechanism according to the theoretical interpretation of the dual layer model.

Fig. 9. Thermodynamic state simulations: configurational entropy (Sa) (a), Gibbs free energy (Ga) (b), and internal energy (Eint).

the Gaβ changes from −72.7 to −79.3, slightly more spontaneous. The surface. It was demonstrated that there was hardly any aggregation
simulated internal energy is shown in Fig. 9 (c). Similar to Gibbs en­ caused by electrostatic interactions. Physical interactions were found to
ergy, the internal energy exhibits a decreasing trend with concentration be the cause of both dyes' endothermic adsorption on these activated
and an increasing trend with temperature at equilibrium. Overall, the carbons, according to calculations of adsorption energies. Overall, the
behavior of the internal energy mirrors that of Gibbs free energy, sug­ dye adsorption mechanism was better understood because to these
gesting an endothermic nature of the system. theoretical and experimental findings. In addition, the parameters of
the medium affected the adsorption capacity such as temperature, pH
4. Conclusion and contact time, a capacity of 100 mg/g and an elimination rate ex­
ceeding 98 % were noted for this study.
This work describes the theoretical analysis of methyl orange ad­
sorption on activated carbons using the statistical physics model, which CRediT authorship contribution statement
is based on the creation of double adsorbate layers with varying ad­
sorption energies. The findings demonstrated that, depending on the Franco Dison S. P.: Writing – review & editing, Writing – original
adsorbent characteristics, two distinct phenol molecule adsorption po­ draft, Validation, Methodology, Investigation. Dehmani Younes:
sitions on activated carbons could be seen for the two series. Utilizing a Writing – review & editing, Writing – original draft, Methodology.
two-layer physical model demonstrated that the adsorption tempera­ Sadik Abouarnadasse: Writing – review & editing, Writing – original
ture affected the adsorption positions of both dyes on the adsorbent draft, Validation, Supervision. El Messaoudi Noureddine: Writing –

109
Y. Dehmani, D.S.P. Franco, J. Georgin et al. Environmental Surfaces and Interfaces 3 (2025) 103–111

review & editing, Writing – original draft. Lima Eder C: Writing – re­ [15] Y. Zhu, L. Ma, X. Hai, Z. Yang, X. Li, M. Chen, M. Yuan, H. Xiong, Y. Gao, L. Wang,
view & editing, Writing – original draft, Supervision. Lamhasni Taibi: F. Shi, Adsorption of methyl orange by porous membranes prepared from deep
eutectic supramolecular polymer-modified chitosan, Environ. Res. 236 (2023)
Writing – review & editing, Writing – original draft. Kacimi Rachid: 116778, https://doi.org/10.1016/j.envres.2023.116778.
Writing – review & editing, Writing – original draft. Ba Mohammed [16] M. Silas Nadiye-Tabbiruka, P. Sejie, S. Nadiye-Tabbiruka, Removal of Methyl
Bouchra: Writing – original draft, Methodology. Mghaiouini Orange (MO) from water by adsorption onto modified local clay (Kaolinite), Phys.
Chem. 6 (2016) 39–48, https://doi.org/10.5923/j.pc.20160602.02.
Redouane: Writing – original draft. Georgin Jordana: Writing – re­ [17] T. Jiang, Y.D. Liang, Y.J. He, Q. Wang, Activated carbon/NiFe2O4 magnetic com­
view & editing, Writing – original draft, Visualization, Validation, posite: a magnetic adsorbent for the adsorption of methyl orange, J. Environ. Chem.
Methodology. Eng. 3 (2015) 1740–1751, https://doi.org/10.1016/j.jece.2015.06.020.
[18] B.S. Yadav, S. Dasgupta, Effect of time, pH, and temperature on kinetics for ad­
sorption of methyl orange dye into the modified nitrate intercalated MgAl LDH
Declaration of Competing Interest adsorbent, Inorg. Chem. Commun. 137 (2022) 109203, https://doi.org/10.1016/j.
inoche.2022.109203.
The authors declare that they have no known competing financial [19] E.A. Mohamed, A.Q. Selim, S.A. Ahmed, L. Sellaoui, A. Bonilla-Petriciolet, A. Erto,
Z. Li, Y. Li, M.K. Seliem, H2O2-activated anthracite impregnated with chitosan as a
interests or personal relationships that could have appeared to influ­ novel composite for Cr(VI) and methyl orange adsorption in single-compound and
ence the work reported in this paper. binary systems: Modeling and mechanism interpretation, Chem. Eng. J. 380 (2020),
https://doi.org/10.1016/j.cej.2019.122445.
[20] M. Kashif, U. Baig, Synthesis of Co 3 O 4 nanoparticles and their performance to­
Appendix A. Supporting information
wards methyl orange dye removal: characterisation, adsorption and response sur­
face methodology, J. Clean. Prod. 211 (2019) 1141–1153, https://doi.org/10.
Supplementary data associated with this article can be found in the 1016/j.jclepro.2018.11.232.
[21] C. Jaramillo-páez, J.A. Navío, M.C. Hidalgo, A. Bouziani, M. El, 2017, Degradation
online version at doi:10.1016/j.esi.2025.02.002.
of Methyl Orange and Phenol, 332 (2017) 521–533..
[22] A.M. Shehap, R.A. Nasr, M.A. Mahfouz, A.M. Ismail, Journal of Environmental
Chemical Engineering Preparation and characterizations of high doping chitosan /
References MMT nanocomposites films for removing iron from ground water, J. Environ.
Chem. Eng. 9 (2021) 104700, https://doi.org/10.1016/j.jece.2020.104700.
[1] A. Djelloul, N. Boutaleb, A.O. Ezzat, L. Sabantina, O.H. Abd-Elkader, B.D. Alkoudsi, [23] A. Bonilla-petriciolet, I.T. De Aguascalientes, Adsorption in Water Treatment,
M. Hamadouche, A. Benyoucef, Polyaniline–modified metal oxides adsorbents for Elsevier Inc, 2019, https://doi.org/10.1016/B978-0-12-409547-2.14390-2.
the application in the Congo red dye adsorption, Colloids Surf. A: Physicochem. [24] O. Baytar, Ö. Şahin, C. Saka, S. Ağrak, Characterization of microwave and con­
Eng. Asp. 703 (2024) 135266. ventional heating on the pyrolysis of pistachio shells for the adsorption of methy­
[2] H. Lee, S. Fiore, F. Berruti, Adsorption of methyl orange and methylene blue on lene blue and iodine, Anal. Lett. 0 (2018) 1–16, https://doi.org/10.1080/
activated biocarbon derived from birchwood pellets, Biomass-.-. Bioenergy 191 00032719.2017.1415920.
(2024) 107446, https://doi.org/10.1016/j.biombioe.2024.107446. [25] D. Richard, M. de L. Delgado Núñez, D. Schweich, Adsorption of complex phenolic
[3] T. Sheela, Y.A. Nayaka, Kinetics and thermodynamics of cadmium and lead ions compounds on active charcoal: adsorption capacity and isotherms, Chem. Eng. J.
adsorption on NiO nanoparticles, Chem. Eng. J. 191 (2012) 123–131, https://doi. 148 (2009) 1–7, https://doi.org/10.1016/j.cej.2008.07.023.
org/10.1016/j.cej.2012.02.080. [26] M. Jabri, Y. Dehmani, I. Loulidi, A. Kali, A. Amar, H. Lgaz, C. Hadey, F. Boukhlifi,
[4] A. Amari, M. Chlendi, A. Gannouni, A. Bellagi, Applied Clay Science Optimised Valorization of lignocellulosic wastes material for efficient adsorption of a cationic
activation of bentonite for toluene adsorption, Appl. Clay Sci. 47 (2010) 457–461, azo dye and sludge recycling as a reinforcement of thermoplastic composite, Fluids
https://doi.org/10.1016/j.clay.2009.11.035. 8 (2023) 37, https://doi.org/10.3390/fluids8020037.
[5] M. Jeguirim, M. Belhachemi, L. Limousy, S. Bennici, Adsorption/reduction of nitrogen [27] F.L. Article, Y. Dehmani, H. Moussout, H. Moussout, I. Daou, D. Franco, Y. Dehmani, J.
dioxide on activated carbons: Textural properties versus surface chemistry – a review, Georgin, H. Ahlafi, A. Shaim, M. Belfaquir, M. Taky, T. Lamhasni, E. Lima, O. Zegaoui,
Chem. Eng. J. 347 (2018) 493–504, https://doi.org/10.1016/j.cej.2018.04.063. S. Abouarnadasse, M. Badawi, S. Valange, Applied Surface Science Towards an un­
[6] J. Georgin, D.S.P. Franco, Y. Dehmani, P. Nguyen-Tri, N. El Messaoudi, Current derstanding of the interaction of the surface and the interface between methyl orange
status of advancement in remediation technologies for the toxic metal mercury in and raw walnut shell: theoretical and experimental study, (n.d.).
the environment: a critical review, Sci. Total Environ. 947 (2024) 174501, https:// [28] M.Ben Yahia, L. Sellaoui, Adsorptive removal of sunset yellow dye by biopolymers
doi.org/10.1016/j.scitotenv.2024.174501. functionalized with (3–aminopropyltriethoxysilane): Analytical investigation via
[7] I. Daou, Y. Dehmani, H. Moussout, D.S.P. Franco, J. Georgin, M. El, B. Mustapha, advanced model, J. Mol. Liq. 312 (2020), https://doi.org/10.1016/j.molliq.2020.
T. Abdelillah, S. Omar, Z. Sadik, Adsorption of methyl orange and methylene blue 113395.
from aqueous solutions on pure bentonite: statistical physical modeling provides an [29] H.A. Kiwaan, F.S. Mohamed, N.A. El-Ghamaz, N.M. Beshry, A.A. El-Bindary,
analytical interpretation, Environ. Monit. Assess. (2024), https://doi.org/10.1007/ Experimental and electrical studies of Na-X zeolite for the adsorption of different dyes,
s10661-024-13239-0. J. Mol. Liq. 332 (2021) 115877, https://doi.org/10.1016/j.molliq.2021.115877.
[8] H. Moussout, I. Daou, D.S.P. Franco, Y. Dehmani, J. Georgin, H. Ahlafi, A. Shaim, [30] M. Belhachemi, F. Addoun, Comparative adsorption isotherms and modeling of
M. Belfaquir, M. Taky, T. Lamhasni, E.C. Lima, O. Zegaoui, S. Abouarnadasse, methylene blue onto activated carbons, Appl. Water Sci. 1 (2011) 111–117, https://
Towards a profound understanding of methyl orange removal from industrial doi.org/10.1007/s13201-011-0014-1.
wastewater using a raw walnut shell: kinetics, equilibrium, thermodynamics, and [31] M. Ghaedi, S. Hajjati, Z. Mahmudi, I. Tyagi, S. Agarwal, A. Maity, V.K. Gupta,
statistical physics calculations, J. Mol. Liq. 410 (2024) 125606, https://doi.org/10. Modeling of competitive ultrasonic assisted removal of the dyes - Methylene blue
1016/j.molliq.2024.125606. and Safranin-O using Fe3O4 nanoparticles, Chem. Eng. J. 268 (2015) 28–37,
[9] H. Moussout, Y. Dehmani, D.S.P. Franco, J. Georgin, I. Daou, T. Lamhasni, C. Ilyas, https://doi.org/10.1016/j.cej.2014.12.090.
H. Ahlafi, M. Taky, A. Shaim, A. Sadik, Towards an in-depth experimental and [32] M.F. Chong, K.P. Lee, H.J. Chieng, I.I. Syazwani Binti Ramli, Removal of boron from
theoretical understanding of the cadmium uptake mechanism on a synthesized ceramic industry wastewater by adsorption-flocculation mechanism using palm oil
chitin biopolymer, J. Mol. Liq. 383 (2023) 122106, https://doi.org/10.1016/j. mill boiler (POMB) bottom ash and polymer, Water Res. 43 (2009) 3326–3334,
molliq.2023.122106. https://doi.org/10.1016/j.watres.2009.04.044.
[10] Y. Dehmani, S. Arif, D.S.P. Franco, J. Georgin, T. Lamhasni, H. Hajjaj, A. Dehbi, [33] H. Cheng, Y. Liu, X. Li, Adsorption performance and mechanism of iron-loaded
S. Abouarnadasse, H. Gallard, E.C. Lima, Copper and nickel composite carbon biochar to methyl orange in the presence of Cr6+ from dye wastewater, J. Hazard.
catalysts prepared from olive husks on the adsorption process of phenol and p- Mater. 415 (2021) 125749, https://doi.org/10.1016/j.jhazmat.2021.125749.
nitrophenol: comparative theoretical study via an analytical model, J. Mol. Liq. 409 [34] X. Cheng, D. Jiang, H. Chen, B. Barati, C. Yuan, H. Li, S. Wang, Multi-stage ad­
(2024), https://doi.org/10.1016/j.molliq.2024.125346. sorption of methyl orange on the nitrogen-rich biomass-derived carbon adsorbent:
[11] U. Habiba, T.A. Siddique, S. Talebian, J.J.L. Lee, A. Salleh, B.C. Ang, A.M. Afifi, DFT and MD evaluation, Chemosphere 338 (2023) 139218, https://doi.org/10.
Effect of deacetylation on property of electrospun chitosan/PVA nanofibrous 1016/j.chemosphere.2023.139218.
membrane and removal of methyl orange, Fe(III) and Cr(VI) ions, Carbohydr. [35] E.M. El-Sayed, T.M. Tamer, A.M. Omer, M.S. Mohy Eldin, Development of novel
Polym. 177 (2017) 32–39, https://doi.org/10.1016/j.carbpol.2017.08.115. chitosan schiff base derivatives for cationic dye removal: methyl orange model,
[12] R. Lafi, L. Abdellaoui, I. Montasser, A. Hafiane, Removal of methyl orange from Desalin. Water Treat. 57 (2016) 22632–22645, https://doi.org/10.1080/
aqueous solution onto modified extracted cellulose from Stipa Tenacissima L, Int. J. 19443994.2015.1136694.
Environ. Anal. Chem. 102 (2022) 8124–8140, https://doi.org/10.1080/03067319. [36] R. Salah Hassan Boushara, K. Johari, N. Musfirah Mustafa, Adsorption of anionic
2020.1845663. methyl orange dye on hybrid spherical silica in fixed-bed column, Mater. Today.:
[13] M.K. Uddin, U. Baig, Synthesis of Co3O4 nanoparticles and their performance to­ Proc. (2023), https://doi.org/10.1016/j.matpr.2023.08.250.
wards methyl orange dye removal: characterisation, adsorption and response sur­ [37] A.S. Asranudin, D. Purnomo, H. Prasetyoko, H. Bahruji, Single-step synthesis and
face methodology, J. Clean. Prod. 211 (2019) 1141–1153, https://doi.org/10. modification of CTAB-hectorite for efficient adsorption of methyl orange dye,
1016/j.jclepro.2018.11.232. Mater. Chem. Phys. 291 (2022) 126749, https://doi.org/10.1016/j.matchemphys.
[14] K. Wei, T. Lv, T. Wang, H. Zhou, Y. Jiang, X. Qin, Z. Liu, High adsorption of methyl 2022.126749.
orange by nitrogen-doped activated carbon derived from kraft lignin via self-acti­ [38] T.-S. Guo, S.-D. Yang, H.-M. Cui, Q.-F. Yu, M.-F. Li, Synthesis of lignin nanoparti­
vation, Surf. Interfaces 42 (2023) 103484, https://doi.org/10.1016/j.surfin.2023. cle‑manganese dioxide complex and its adsorption of methyl orange, Int. J. Biol.
103484. Macromol. 253 (2023) 127012, https://doi.org/10.1016/j.ijbiomac.2023.127012.

110
Y. Dehmani, D.S.P. Franco, J. Georgin et al. Environmental Surfaces and Interfaces 3 (2025) 103–111

[39] T.K. Saha, N.C. Bhoumik, S. Karmaker, M.G. Ahmed, H. Ichikawa, Y. Fukumori, [45] S. Asuha, X.G. Zhou, S. Zhao, Adsorption of methyl orange and Cr(VI) on meso­
Adsorption of methyl orange onto chitosan from aqueous solution, J. Water Resour. porous TiO2 prepared by hydrothermal method, J. Hazard. Mater. 181 (2010)
Prot. 02 (2010) 898–906, https://doi.org/10.4236/jwarp.2010.210107. 204–210, https://doi.org/10.1016/j.jhazmat.2010.04.117.
[40] J. Fan, Z. Zhao, W. Liu, Y. Xue, S. Yin, Solvothermal synthesis of different phase N- [46] E.H. Mekatel, S. Amokrane, A. Aid, D. Nibou, M. Trari, Adsorption of methyl orange
TiO2 and their kinetics, isotherm and thermodynamic studies on the adsorption of on nanoparticles of a synthetic zeolite NaA/CuO, Comptes Rendus Chim. 18 (2015)
methyl orange, J. Colloid Interface Sci. 470 (2016) 229–236, https://doi.org/10. 336–344, https://doi.org/10.1016/j.crci.2014.09.009.
1016/j.jcis.2016.02.045. [47] C.H. Giles, D. Smith, A.P. D’Silva, I.A. Easton, D. Smith, A general treatment and
[41] H.Y. Zhu, R. Jiang, Y.Q. Fu, J.H. Jiang, L. Xiao, G.M. Zeng, Preparation, character­ classification of the solute adsorption isotherm part I, Theor., J. Colloid Interface
ization and dye adsorption properties of γ-Fe 2 O 3 /SiO 2 /chitosan composite, Appl. Sci. 47 (1974) 766–778, https://doi.org/10.1016/0021-9797(74)90253-7.
Surf. Sci. 258 (2011) 1337–1344, https://doi.org/10.1016/j.apsusc.2011.09.045. [48] Y.A. Mikheev, Y.A. Ershov, Proof of the absence of trans–cis photoisomerization of
[42] M. Shariati-Rad, M. Irandoust, S. Amri, M. Feyzi, F. Ja’fari, Magnetic solid phase methyl orange rydimers in an aqueous medium and inclusion complexes, Russ. J.
adsorption, preconcentration and determination of methyl orange in water samples Phys. Chem. A 93 (2019) 2314–2322, https://doi.org/10.1134/
using silica coated magnetic nanoparticles and central composite design, Int. Nano S0036024419090140.
Lett. 4 (2014) 91–101, https://doi.org/10.1007/s40089-014-0124-5. [49] I. Ben Khemis, M. Bouzid, N. Mechi, A. Ben Lamine, Statistical physics modeling
[43] A.A.A. Darwish, M. Rashad, H.A. AL-Aoh, Methyl orange adsorption comparison on and interpretation of the adsorption of enantiomeric terpenes onto the human ol­
nanoparticles: Isotherm, kinetics, and thermodynamic studies, Dyes Pigments 160 factory receptor OR1A1, Int. J. Biol. Macromol. 171 (2021) 428–434, https://doi.
(2019) 563–571, https://doi.org/10.1016/j.dyepig.2018.08.045. org/10.1016/j.ijbiomac.2020.12.209.
[44] L. Obeid, A. Bée, D. Talbot, S.Ben Jaafar, V. Dupuis, S. Abramson, V. Cabuil, [50] K.E.S.U.F.I.M.N.Mahesh R. Sonawane, Tarulata N. Chhowala, C. Bathula, Statistical
M. Welschbillig, Chitosan/maghemite composite: a magsorbent for the adsorption physics double-layer models for the experimental study and theoretical modeling of
of methyl orange, J. Colloid Interface Sci. 410 (2013) 52–58, https://doi.org/10. methyl orange dye adsorption on AlMnTiO nanocomposite, J. Environ. Sci. Health,
1016/j.jcis.2013.07.057. Part A 58 (2023) 447–458, https://doi.org/10.1080/10934529.2023.2190710.

111