Journal of Molecular Structure 1240 (2021) 130611

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Journal of Molecular Structure

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

Ceratonia Siliqua L seeds extract as eco-friendly corrosion inhibitor for

carbon steel in 1 M HCl: Characterization, electrochemical, surface
analysis, and theoretical studies
Said Abbout, Ph.D a,b,∗, Driss Chebabe b, Meryem Zouarhi a, Malak Rehioui a,
Zouhair Lakbaibi b, Najat Hajjaji a
a
Team of Materials, Electrochemistry and Environment (LCOCE). Department of Chemistry, Faculty of Sciences, Ibn Tofail University, BP 133, 14000 Kenitra,
Morocco
b
Laboratory of Materials Engineering for the Environment and Natural Resources, Faculty of Sciences and Techniques, University Moulay Ismail of Meknes,
BP 509 Boutalamine 52000 Errachidia, Morocco

a r t i c l e i n f o a b s t r a c t

Article history: Electrochemical and theoretical behaviors of the carbon steel was investigated in 1 M HCl solution using
Received 18 March 2021 the Ceratonia Siliqua L seeds (CFE) extract. This extract was analyzed using GC–MS technique; it was
Revised 29 April 2021
found that the extract contains 18 compounds on which the main constituents represent 27.78 wt.%
Accepted 30 April 2021
vanillin (VN), 25.69 wt.% α -tumerone (AT), 11.68 wt.% 2-heptanal (HP), 9.49 wt.% mome-inositol (MI),
Available online 9 May 2021
4.94 wt.% 1-dotiacontanol(DT), and 2.92 wt.% linoleic acid (LA). The corrosion inhibition and adsorption
Keywords: (CIA) behavior were investigated using the electrochemical measurements (open circuit potential (OCP),
Corrosion inhibition polarization curves (PC) and impedance spectroscopy (IS)), and both thermodynamic and kinetic param-
Electrochemical methods eters (Ha , Sa and Ea). The outcomes show that CFE extract exhibits a worthy anti-corrosion action
Ceratonia Siliqua L seeds with an inhibition efficiency (η%) of 95% at 100 mg/l at 298 °K. This result could be attributed probably
HCl 1 M to the adsorption of CFE extract matrix on carbon steel surface, and this was confirmed by surface visu-
Density functional theory
alization using SEM-EDS technique. The adsorption of CFE extract onto carbon steel surface is controlled
Natural bond orbital
Metropolis Monte Carlo method
by a Langmuir adsorption isotherm, which suggests that there are no interactions between molecules of
the CFE during adsorption. The computational chemistry calculations by density functional theory (DFT),
natural bond orbital (NBO), molecular electrostatic potential surface (MESP) and Metropolis Monte Carlo
(MC) methods were performed to better understand the inhibition and adsorption behavior of the main
constituents of CFE extract on the Fe (110) surface.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction Recently, the researcher’s community has interested in plant ex-

Acid solutions are widely used in industrial fields, the main
field application being pickling or cleaning, stimulation of the oil
wells and elimination of localized deposits (unevenly distributed
tartar, rust, bacterial deposits) [1]. On the other hand, acids are
widely used in many processes of industrial synthesis [2]. Due to
the aggressiveness of these acid solutions, the use of corrosion in-
hibitors has become essential to limit the attack on metal mate-
rials. However, many synthesis inhibitors are expensive and toxic
against human and environment.
∗
Corresponding author.
E-mail address: Said.abbout@uit.ac.ma (S. Abbout).
tracts, due to their non-toxicity and biodegradability, so they form
new ecological corrosion inhibitors [3–4].
Ceratonia Siliqua L seeds extract has widely used for their bio-
logical and pharmaceutical proprieties [5,6]. In addition, this sub-
stance contains heteroatoms (O, N, S and P) such as tannins,
polyphenol and flavonoids [7], which can be considered as a good
inhibitor with high efficiency. Furthermore, the Ceratonia Siliqua L
seed extract was reported for their good antioxidant activities [8],
which can be used in the corrosion inhibition field [9].
It should be noted that the majority of current research on the
significant inhibition of the innovative corrosion inhibitors (sus-
tainable and green) derive from the plant-based was focused on
corrosion control of metals or alloys in acidic (sulfuric or hy-
drochloric) media. Therefore, specific inhibitors of neutral saline
mediums are needed which go beyond what has so far been es-
tablished to face threats from corrosion of metals. This leads us

https://doi.org/10.1016/j.molstruc.2021.130611
0022-2860/© 2021 Elsevier B.V. All rights reserved.
S. Abbout, D. Chebabe, M. Zouarhi et al.
to look differently when choosing a green inhibitor for the appro-
priate application, several factors such as sustained availability of
sources, extraction process (solvent), cost, best inhibition efficiency,
and especially the environmental effects should be taken into ac-
count [10].
Over the past few years, researchers around the world reported
most bioactive extracts derived from medicinal plants as promising
green anticorrosive agents [11–13]. However, a number of plants
have been investigated in relation to their anticorrosive activity,
but a great majority of plants has not been satisfactorily studied as
anticorrosive agents. Therefore, there are considerable opportuni-
ties to discover out innovative, economical, novel, and eco-friendly
corrosion inhibitors from this outstanding source of natural prod-
ucts.
The novelty of this study is to use the Ceratonia Siliqua L seeds
extract as corrosion inhibitor to improve the carbon steel resis-
tance against 1 M HCl solution. The protective effect of this ex-
tract has done by electrochemical experiments and morphological
characterization measurements. Further to these details, we found
that theoretical approaches have also widely used to a deep under-
standing of adsorption mechanism between the metal surface and
inhibitor, elucidating the chemical and physical properties of struc-
tures and sometimes proving the adsorption behavior of inhibitor
compound towards the metal surface [14,15].
In this manuscript, our investigations will be displayed in three
structured parts; first, i) a determination of the chemical compo-
sition of studied CFE extract using GC–MS techniques, then ii) an
investigation the inhibitory action of CFE extract using the elec-
trochemical tests (OCP, PC and IS) and both thermodynamic and
kinetic parameters (Ha , Sa and Ea ). Finally, iii) the theoretical
approaches such as DFT, NBO, MESP and MC were used to evalu-
ate the corrosion inhibition (CIA) behavior of the six major com-
pounds of CFE extract on the surface of iron metal Fe (110) (the
main constituent of carbon steel) in 1 M HCl. This study provide
supportive highlights about the inhibition and adsorption behavior
of the main constituents of CFE against carbon steel corrosion in
1 M HCl. The corrosion inhibition process was carried in acidic so-
lution and consequently, the protonation of more nucleophilic cen-
ters of inhibitors will be probably possible; for this reason, the data
obtained for the neutral forms will be discussed, and then com-
pared to those of the protonated forms.
2. Experimental
2.1. Extraction protocol
The extraction process was performed by a Soxhlet extraction
technique for 6 h with chloroform as solvent (sigma Aldrich). Then,
the solvent was evaporated using a rotary evaporator. Finally, the
oil extract was kept at 4 °C to prevent degradation of the com-
pounds for further analysis.
2.2. GC–MS analysis of CFE extract
The GC–MS analysis of the CFE extract was accomplished using
a GC–MS type Bruker 456-GC coupled with mass spectrometer op-
erating in electronic impact mode. The capillary column used is an
Rxi-5 Sil MS (30 × 0.25 mm ID × 0.25 μm). The temperature of
the column is initially maintained at 333°K C for 5 min, with a rise
of 10 °C / min to 573°K where it remains 70 min.
The identification of the structures of the CFE extract was con-
firmed by comparing the obtained mass spectra with those of the
pure compounds with references in the library of mass spectra of
the apparatus [16].
2
Journal of Molecular Structure 1240 (2021) 130611
2.3. Corrosion study
The material is carbon steel with the following chemical com-
position: 0.2% of Si, 0.519% of Mn, 0.157% of C, 0.007% of P, 0.009%
of S and the rest is iron. The inhibitor is the chloroform extract
form Ceratonia Siliqua L seeds (CFE). The corrosive solution is 1 M
HCl solution prepared from concentrate 37% HCl (Sigma Aldrich)
and distillated water.
2.4. Electrochemical experiment
The electrochemical experiments were carried out using a Po-
tentiostat type Bio Logic SP-200 device controlled by a computer
equipped by means of EC-Lab software with an electrochemical
cell composed of three electrodes: saturated calomel as reference
electrode, the counter electrode is platinum and an iron disc with
surface equal 1 cm2 as working electrode. The working electrode
was polished with emery papers in different girt (10 0 0, 120 0 150 0)
to make the surface of the metal smooth, then, rinsed with ace-
tone, cleaned with distilled water and dried with hot air [17].
The open circuit potential (OCP) were carried out for 30 min
to establish the potential stable.
The polarization curves (PC) were carried using 1 mV as scan-
ning rate, this scanning rate getting as close as possible to the
steady-state conditions of the studied system. The inhibition effi-
ciency was calculated using the following relation [4].
i0 − iinh
η %= × 100
i0
i0 is the current density of the blank, iinh is the current density
in presence of the different concentrations.
Impedance diagrams (IS) were carried out after OCP using
10 mV amplitude signals in the frequency spectrum interval of
frequencies between 100 kHz to 0.10 Hz at open circuit potential
(OCP) [18].
The inhibition efficiency was calculated using the following re-
lation [3].
Rinh − R0
η %= × 100
Rinh
R0 The polarization resistance of the blank, Rinh the polarization
resistance in presence of the inhibitor.
2.5. Surface analysis
The surface analysis of the working electrode without and with
100 mg/l of Ceratonia Siliqua L extract was evaluated using a scan-
ning electron microscope model FEA450 and the surface charac-
terization was evaluated by X-ray flash (model 6130 Bruker brand)
with an acceleration voltage of 20 KV. After 24 h of immersion
time in the presence and absence of the inhibitor. The working
electrode was cleaned with distilled water and dried.
2.6. Computational procedure
The optimization of neutral geometries (Table 1) (NFs) (i.e.VN,
AT, HP, MI, DT and LA) and their protonated forms PFs (i.e. VNH+ ,
ATH+ , HPH+ , MIH+ , DTH+ and LAH+ ) were performed utilizing
DFT method [14] using Gaussian 09 software [19] in the scheme
of B3LYP [20] with the 6–31G++(d,p) [21]. The optimized ge-
ometry was confirmed by the absence of imaginary wave num-
bers in the hessian matrix. Then, we have calculated for NFs
and PFs the following global quantum descriptors (GQDs): en-
ergy of HOMO (highest occupied molecular orbital) and LUMO
(lowest unoccupied molecular orbital), the electronegativity χ
(χ = - (EHOMO + ELUMO )/2), the energy gap of frontier orbital
S. Abbout, D. Chebabe, M. Zouarhi et al.
Table 1
Neutral and protonated structures of the molecules used in the computational calculations.
Eg (Eg = ELUMO - EHOMO ) [22,23], the hardness η (η = ELUMO
– EHOMO ), [24,25], the fraction of electrons transferred N from
inhibitor to the bulk iron surface (110) (N =0.5((χFe(110) –
χ)(ηFe(110) +η)−1 ) [26]; where the values of χ Fe(110) and ηFe(110) are
7 and 0 eV/mol, respectively [10] . The back-donation parameter
Ebd (-η/4) for all structures is also calculated [28]. The atomic
charge delivery over atomic structures of NFs was calculated in
terms of natural bond orbitals (NBO) analysis [28]. Additionally, the
reactive areas of the concerned compounds with iron surface (110)
were estimated from the analysis of molecular electrostatic poten-
tial surface (MESP). The activation energies (Ea) were drawn by us-
ing the quadratic synchronous transit-guided quasi-Newton (QST3)
approach [27–30].
The most stable adsorption configurations of VN, AT, HP, MI, DT
and LA together (NFs) on the iron surface (110) were attained from
adsorption locator module using Biovia Materials studio 8.0 [31].
For this, the Fe (110) plane was firstly built from Fe crystal and op-
timized using smart minimizer. Then, the plane was expanded to
the supercell of 12×9 × 12. The simulation of the interaction be-
tween adsorbent and Fe (110) surface was implemented in a sim-
ulation box of 24.82×24.82×40 Å with periodic boundary condi-
tions. The simulation study was conducted in two environments:
first, in vacuum (NFs and Fe (110) surface) and secondly, in solu-
tion (NFs, 260 molecules of water, 20 of oxonium, 20 of chlorine
3
Journal of Molecular Structure 1240 (2021) 130611
and Fe (110) surface) using COMPASS (Condensed-phase Optimized
Molecular Potentials for Atomistic Simulation Studies) force field
[32].
3. Results and discussion
3.1. GC–MS analysis
Fig. 1 shows the GC–MS analysis of the chloroform extract from
seeds of the Ceratonia Siliqua L.
The GC–MS analysis led to identify eighteen compounds from
the Ceratonia Siliqua L seeds extract (Fig. 1). The compounds identi-
fied were five fatty acids (Meristic acid, Palmitic acid, Linoleic acid,
Oleic Acid and Stearic acid), and three terpenoides compounds,
namely Lupeol, p-Cymen-7-ol and Ar-tumerone. In addition, we
identified the Vanillin and other organic compounds. This analysis
also showed the presence of the vitamin compound called inositol
with lower quantity.
The Table 2 presents the identified compounds of Ceratonia Sili-
qua L with their retention time.
These identified compounds were characterized by some good
biological activities such as antioxidant potential [33]. Therefore,
these compounds have an excellent activity against the free rad-
S. Abbout, D. Chebabe, M. Zouarhi et al. Journal of Molecular Structure 1240 (2021) 130611

Fig. 1. GC–MS Chromatogram of the chloroform extract from seeds of the Ceratonia Siliqua L.

Table 2
Chemical composition of the chloroform extract from Ceratonia Siliqua L seeds (CFE).

Retention Time (min) Compound Percentage (%) Retention Time (min) Compound Percentage (%)

15.13 2-Heptenal 11.68 49.51 Oleic Acid 1.45

19.12 (2E,4E)−2,4-Decadiene 0.59 52.15 Stearicacid 2.60
25.51 p-Cymen-7-ol 2.30 54.92 9-Octadecenal 1.93
42.19 Vanillin 27.78 56.84 1-Dotriacontanol 4.94
45.33 α -tumerone 25.69 57.60 1-Heptatriacotanol 0.72
45.63 Mome inositol 9.49 58.88 Oxalicacid,cyclohexylmethy 0.45
46.99 Myristicacid 0.37 60.75 Lupeol 0.35
47.88 Palmiticacid 0.60 63.01 Cyclohexane, Nonadecyl- 3.55
48.99 Linoleicacid 2.92 66.13 Anacardicacid 0.97

Fig. 2. open circuit potential with and without different concentrations of the CFE.

Fig. 3. the electrochemical polarization curves of the carbon steel with and without
icals. This propriety suggests the use of the seeds extract as in- different concentrations of the CFE at 298 K.
hibitor of corrosion in acidic solution [34].

3.2.2. Electrochemical polarization

3.2. Inhibition effect study
3.2.1. Open circuit potential
The following figure presents the open circuit potential with
and without different concentrations of the inhibitor (Fig. 2).
The Fig. 2, indicate that in the absence of the inhibitor, the cor-
rosion potential is stabilized at −485 mV. Therefore, in the pres-
ence of the inhibitor, the value of the potential shifts to a value of
−435 mV for 100 mg/l of the inhibitor. This result evidences the
acts of the inhibitor compound against the corrosive elements and
the good ability of these compounds to adsorb on the surface of
carbon steel [35].
The electrochemical polarization curves of the electrode in 1 M
HCl solution without and with different concentrations of the in-
hibitor after 30 min of immersion are presented in the Fig. 3.
According to the Fig. 3, the addition of the Ceratonia Siliqua
L extract into the acidic solution is accompanied by a significant
decrease of the current densities compared to the blank, this re-
mark is more significant in the cathodic branch than in the anodic
one. In addition, in the cathodic domain, the curves are parallel
and suggest that there is no change in cathodic reaction mecha-
nism (hydrogen reduction 2H+ + 2e− → H2 ) while in the anodic
branch we noticed a significant change in the plot by adding of the
inhibitor that indicates a change in the mechanism of the anodic
reaction (metal dissolution Fe → Fe2+ + 2e− ).

4
S. Abbout, D. Chebabe, M. Zouarhi et al. Journal of Molecular Structure 1240 (2021) 130611

Table 3
Electrochemical polarization parameters of the carbon steel with and without different of the CFE concentrations at
298 K.

Concentration Ecorr (mV/ECS) icorr (μA.cm−2 ) β c (mV/dec) β a (mV/dec) Rp(.cm2 ) η (%)

1 M HCl −441.94±0.02 242.35±0.02 −141.7 ± 0.1 155.6 ± 0.1 133.1 ± 0.1 —–
25 mg/l −436.59±0.02 20.34±0.02 −141.5 ± 0.1 59.3 ± 0.1 894.2 ± 0.1 90.51±0.03
50 mg/l −429.39±0.02 16.48±0.02 −142.9 ± 0.1 81.0 ± 0.1 1482.1 ± 0.1 93.21±0.03
75 mg/l −434.75±0.02 12.28±0.02 −144.1 ± 0.1 62.5 ± 0.1 1611.0 ± 0.1 94.89±0.03
100 mg/l −442.94±0.02 11.42±0.02 −143.7 ± 0.1 60.4 ± 0.1 1658.1 ± 0.1 95.30±0.03

In the anodic branch, we observed a significant change in slop

between the potential of corrosion 0.45 mV/ECS and −300 mV/ECS,
after this region, an increase of current density was obvious, that
indicates a disruption of inhibitory molecules from the surface
of the electrode [36], this phenomena is named desorption and
it is characterized by potential of desorption, in our case equal
−300 mV/ECS.
For the corrosion potential value in the presence of the in-
hibitor, there is no significant displacement. The potential gap be-
tween the blank potential and the different concentrations of the
inhibitor are less to 85 mV, which can classify our inhibitor as a
mixed type inhibitor [13].
The electrochemical polarization curve parameters such as the
corrosion potential, Tafel slopes and current densities were calcu-
lated by the Tafel extrapolation method. These parameters are re-
grouped in Table 3.
From Table 3, we noticed a decrease of current density with
the addition of the inhibitor compared with the blank, however,
its value decreased from 242.35μA.cm−2 to 11.42μA.cm−2 in the Fig. 4. Electrochemical impedance diagrams of the carbon steel with and without
presence of a 100 mg/l of Ceratonia Siliqua L extract. The value of different concentration of the CFE at 298 K.
the inhibition efficiency increase with increasing in the inhibitor
concentration and it’s reached a maximum value of 95.30% at
100 mg/l.
The obtained result indicates a good ability to protect the elec-
trode surface from aggressive attack, thus the protective effect may
be explained by the adsorption of the inhibitor molecules [37].
This excellent inhibition is due to presence of the donors and
acceptors sites (such as N and O) in the inhibitor molecular struc-
tures.

3.2.3. Electrochemical impedance spectroscopy

The electrochemical impedance diagrams of the carbon steel in
the presence and in the absence of different inhibitor concentra-
tions are presented in the Fig. 4.
From Fig. 4, all diagrams are semi-circles, its attribute to charge
transfer process [37]. The increasing of the diameter with increas-
ing of the concentration of the inhibitor indicate the good inhibi-
tion effect of our inhibitor [38]. The high inhibition effect reached
at 100 mg/l of inhibitor.
The modeling of these diagrams by the Ec-Lab software led us
to propose the following equivalent electrical circuit (Fig. 5).
The circuit consists of the solution resistance Rs, charge trans-
fer resistance Rt, due to heterogeneity of the surface capacity, the
constant phase element, CPE was used to calculate the double layer
capacity, α is the surface roughness [39].
The Cdl was calculated by using the following equation.
Cdl = (CPE.RP 1-α )1/α
The characteristic parameters associated to this impedance dia-
gram are given in Table 4.
From Table 4, we noticed that the addition of inhibitor increase
the value of the resistance of the charge transfer and decrease of
the capacity of the double layer values. The value changed from
24.91 to 404.6.cm2 at 100 mg/l for the charge transfer resistance
and from 142.90μF.cm−2 to 47.09μF.cm−2 for the same concentra-
tion. This indicates that the presence of Ceratonia Siliqua L seeds
Fig. 5. Equivalent circuit of the carbon steel with and without different concentra-
tion in inhibitor at 298 K.
extract reduce the charge transfer by adsorption on the electrode
surface [40].
In addition, we are noticing increasing of the α coefficient with
increasing of the concentration of the inhibitor, it’s increased from
0.78 in case of the blank to 0.85 at 100 mg/l, thus increasing of α
coefficient indicate that the surface of the electrode becomes more
smooth compared to the blank [13].
The inhibition efficiency increase with the increase of the in-
hibitor concentration, it has reached an optimum value 93.84% at
100 mg/l.
3.3. Adsorption Isotherm
The Langmuir adsorption isotherm is plotted in the Fig. 6 used
the parameters, extract from polarization curves using the follow-
ing equation CInh /θ =1/b + CInh with Cinh is the inhibitor concen-
tration and θ is the recourve rate.
From Fig. 6, we noticed a linear plot with linear regression co-
efficient equal to 1 indicate that the adsorption process obeys to
Langmuir model [41]. The adsorption energy is calculated from the
Fig. 6 using the following equation:

5
S. Abbout, D. Chebabe, M. Zouarhi et al. Journal of Molecular Structure 1240 (2021) 130611

Table 4
Electrochemical impedance parameters extract from the impedance diagrams.

Concentration Rs (.cm2 ) Rt (.cm2 ) CPE(Sn/Ω.cm2) α Cdl (μF.cm−2 ) η (%)

1 M HCl 2.15±0.03 24.91±0.3 282.5 ± 0.2 0.78±0.02 142.90±0.02 —–
25 mg/l 1.28±0.03 206.6 ± 0.3 271.3 ± 0.2 0.78±0.02 136.03±0.02 87.94±0.3
50 mg/l 1.28±0.03 260.3 ± 0.3 232.1 ± 0.2 0.79±0.02 134.20±0.02 90.43±0.3
75 mg/l 1.28±0.03 360.5 ± 0.3 103.9 ± 0.2 0.82±0.02 49.66±0.02 93.09±0.3
100 mg/l 1.28±0.03 404.6 ± 0.3 86.72±0.2 0.85±0.02 47.09±0.02 93.84±0.3

From Fig. 8, we noticed a linear plot with linear regression co-

efficient superior at 0.98 that indicate a good correlation between
the ln (icorr ) and ln (icorr /T) and 10 0 0/T.
The values of thermodynamic parameters indicate (Table 6) the
increase of the Ea value with the addition of the inhibitor that sug-
gests electrostatic metal-inhibitor interactions. While, the negative
values of the Sa indicates that the surface becomes more ordered
[37]. In addition, the increase in this value indicates the replace-
ment of the water molecules by the inhibitor molecules. While, the
Ha value reveals the endothermic spontaneous adsorption pro-
cess [43].

3.5. Morphological analysis

The morphological analysis used to confirm the values of effi-

Fig. 6. Langmuir adsorption isotherm obtained for the polarization curves parame-
ters at 298 K.
Gads =-RT.ln(55.5 K)
With R is the gas parfait constant equal 8.314, T is the temper-
ature equal 298 K and K is the inverse of the intercept of the plot.
The obtained adsorption energy Gads value is −32.55 kJ/mol,
which indicate that the adsorption process of the Ceratonia Siliqua
L extract on the carbon steel surface is mixed type between ph-
ysisorption and chemisorptions [42].
3.4. Effect of the temperature and thermodynamic parameters
To determine the thermodynamic parameters an effect of the
temperature was investigated in the range of 298 K to 328 K. The
Fig. 7 presents the polarization curves without and with 100 mg/l
of inhibitor.
In case of the blank (Fig. 7), we noticed no change in the shape
of the Tafel curves that suggest no change in the anodic and
cathodic behaviors. The corrosion potential shift to the neg-
ative values when the temperature increases.
In case of the inhibitor (Fig. 7), we observed no change in ca-
thodic behavior that suggest no change in cathodic reaction,
therefore, we noticed the same change in the anodic shape
may be explained by disappearing zone of passivation with
increasing of the temperature.
The electrochemical parameters and inhibition efficiencies in
the absence and in the presence of inhibitor at various tempera-
tures (298 K, 308 K, 318 K and 328 K) are regrouped in the follow-
ing Tables 5.
From these electrochemical parameters, we determined the
Ha , Sa and Ea by using the following equations [37]:
   
RT S a H a
icorr = exp exp − and icorr = A exp
hN R RT
T is the temperature, N is the Avogadro’s constant, h is the
plank constant and icorr is the corrosion current density.
The Arrhenius plots are regrouped in the following figures
(Fig. 8).
ciencies and to have an information about the state of the elec-
trode surface in the absence and the presence of 100 mg/L of the
Ceratonia Silique L extract.
The Fig. 9 represents the micrographs of the morphological
metal surface in the case of the blank and in the presence of the
100 mg/L of inhibitor in acidic solution after 24 h of immersion.
From these micrographs, we note that in the absence of in-
hibitor, the surface was deeply attacked by the corrosive solu-
tion with a presence of damage, including pits. In the presence of
100 mg/L of inhibitor, the electrode surface becomes smooth, and
we also note the disappearance of damage and pits caused by the
corrosive solution confirming the protective effect of the inhibitor
on the electrode surface [44].
The EDS spectra indicates the presence of the oxygen peak
in the case of the blank and its absence in the presence of the
100 mg/L of the chloroform extract. This result confirms the inhi-
bition effect of the chloroform extract molecules and the inhibition
efficiency determined by different corrosion test [45].
3.6. CIA behavior study using theoretical approaches
3.6.1. DFT, NBO and MESP calculations
The optimized geometries of natural form (NFs) structures were
obtained by DFT/B3LYP/6–311G++(d,p) computations, on which
the optimization was confirmed by the presence of zero imag-
inary frequency in hessian matrix. In order to determine atoms
that have high tendency to react with H+ protons, we have cal-
culated the atomic charges over natural form (NFs) structures bas-
ing on the NBO analysis. The Data obtained for all atoms (except
hydrogen atoms) of NFs are presented in Fig. 10. From this figure,
the strong negative atomic charges of NFs structures are associ-
ated to the O2(−0.659e for VN), O5(−0.753e for AT), C5(−0.570e
for HP), O1(−0.752e for LA), O1(−0.808e for MI) and C6(−0.627e
for DT). Even though the C5 of HP and C6 of DT have strong
 −E  negative charges, their protonation has proved difficult because of
a
their high activation energies (Ea) for the protonation attack pro-
RT
cess; while the others atomic centres such as O1 of HP and O4
of DT their protonation has evidenced relatively easy because of
their lower activation energies for the protonation process (see
Fig. 10). Consequently, the corresponding protonated structures
(PFs) of NFs are obtained as result of H+ attacks on oxygen atoms

6
S. Abbout, D. Chebabe, M. Zouarhi et al. Journal of Molecular Structure 1240 (2021) 130611

Fig. 7. Polarization curves recorded at different temperature in the case of blank and the case of presence of 100 g/L of the inhibitor.

Table 5
Electrochemical parameters and inhibition efficiencies in absence and presence of the CFE (100 mg/l) at
various temperature.

Temperature -Ecorr (mV/ECS) icorr (μA.cm−2 ) -β c (mV/dec) β a (mV/dec) η (%)

without
298 K 441.71±0.02 242.35±0.02 141.7 ± 0.1 155.6 ± 0.1 —–
inhibitor
308 K 458.21±0.02 1 260.70±0.02 141.9 ± 0.1 109.9 ± 0.1 —–
318 K 456.92±0.02 1 704.67±0.02 147.7 ± 0.1 105.2 ± 0.1 —–
328 K 452.17±0.02 1 989.29±0.02 164.3 ± 0.1 114.8 ± 0.1 —–
with298 K 442.93±0.02 39,92±0.02 116.7 ± 0.1 60.4 ± 0.1 95.3 ± 0.3
inhibitor
308 K 515,41±0.02 66,79±0.02 137,7 ± 0.1 135,9 ± 0.1 94.7 ± 0.3
318 K 513,22±0.02 91,73±0.02 110,6 ± 0.1 136,7 ± 0.1 94.6 ± 0.3

Fig. 8. Variation of ln (icorr ) and ln(icorr /T) as a function of the 10 0 0/T in the absence and presence of 100 mg/l of the CFE (icorr is the corrosion current density).

Fig. 9. image of scanning electron microscopy and spectrum Energy Dispersive X-Ray Spectroscopy without (a) and with 100 mg/l of the CFE (b).

7
S. Abbout, D. Chebabe, M. Zouarhi et al. Journal of Molecular Structure 1240 (2021) 130611

Fig. 10. Optimized geometries of natural form (NFs) structures and atomic charges. Hydrogen atoms are omitted. (Ea is the activation energy of the protonation associated
to HP and DT compounds and NBO atomic charges unit is e.).

Table 6 4.789 eV for DT) and the higher values of Ebd (−1.157 eV for
Arrhenius plot parameters for carbon steel in 1 M HCl for the
NV and −1.197 eV for DT); then, for PFs structures (NVH+ , ATH+ ,
blank and in presence 100 mg/l of the CFE.
HPH+ , MIH+ , DTH+ and LAH+ ), we noticed that HPH+ and ATH+
Ha (kJ.mol−1 ) Sa (J.K − 1
.mol−1 ) Ea (kJ.mol−1 ) compounds have the lower values of Eg (2.476 eV for HPH+ and
Blank 20.78 −118.71 23.38 2.775 eV for ATH+ ) and the higher values of Ebd (−0.619 eV for
CFE 38.05 −100.26 40.66 HPH+ and −0.694 eV for ATH+ ). These results can be attributed to
the fact that there are strong interactions between NV, DT, HPH+
and ATH+ compounds and iron surface. In addition, we showed
that the protonation of NFs structures caused the increase of Ebd
such as O2 for VN, O5 for AT, O1 for HP, O1 for LA, O1 for MI
and the decrease of both N and Eg values; this suggests the
and O4 for DT (Fig. 10). The NPs structures were also optimized
prominent role of protonation to ensure the formation of adsorp-
through DFT/B3LYP/6–311G++(d,p). Additionally, DFT calculations
tive bonds between adsorbent molecules and metal surface.
were conducted to describe physico-chemical properties of both
To gain further insights about reactivity and selectivity of the
NFs and PFs structures towards the bulk iron atoms surface (110).
studied structures (NFs and PFs) towards iron surface, the MESP
The global quantum descriptors (GQDs) of NFs and PFs were calcu-
calculations are used to know the nucleophilic and electrophilic
lated such as EHOMO , ELUMO , the energy gap of frontier orbital Eg,
regions over NFs and PFs structures which responsible to the re-
the electronegativity χ , the hardness η, the fraction of electrons
action attacks with the metal. Fig. 11 exposes the MESP fitting
transferred N from the NFs or PFs to the bulk iron surface (110)
schemes of NFs and PFs structures on which: the red color signifies
and the back-donation character Ebd (Table 7).
a strong negative electrostatic potential distribution (EP); yellow
According to Table 7, we noticed that all the studied structures
(moderately negative EP); blue (strong positive EP); green (mod-
(NFs and PFs) have a positive values of N which lower to the
erately positive EP) and cyan (low positive EP) [46].
3.6e, suggesting the ability of both NFs and PFs molecules to do-
As presented in Fig. 11, it can be seen for VN and VNH+ that
nate electrons (π and/or lone pair electrons) to vacant 3d-orbital
the carbonyl group (>–C = O) is the most susceptible region for
of the iron surface to form coordinate covalent bonds. On the other
the nucleophilic attacks (red color); while the hydroxyl group (>–
hand, the negative values of Ebd of NFs and PFs indicate clearly
OH) presents both a weak nucleophilic region (yellow color) and a
that these structures have also capability to accept free electrons
strong electrophilic region (blue color). It is also noticed for NV and
(3d) from the iron surface to form retro-donating bonds.
NVH+ that both the aromatic ring and oxygen atom of (>–OCH3 )
Therefore, the comparison of Eg and Ebd descriptors for
are not reactive towards iron surface. This result could be probably
both cases of structures (NFs and PFs): first, for NFs structures
due to the presence of two conjugate systems route in molecule.
(NV, AT, HP, MI, DT and LA), we observed that the VN and DT
As for HP and HPH+ , exhibit a good nucleophilic region which lo-
compounds have the lower values of Eg (4.626 eV for NV and

8
S. Abbout, D. Chebabe, M. Zouarhi et al. Journal of Molecular Structure 1240 (2021) 130611

Table 7
Global quantum descriptors for natural form (NFs) and Protonated forms (PFs) structures.

EHOMO (eV) ELUMO (eV) Eg (eV) χ (eV) η (eV) N (e) Ebd (eV)
VN −6.504 −1.878 4.626 4.191 4.626 0.304 −1.157
AT −7.674 −0.463 7.211 4.069 7.211 0.203 −1.803
HP −7.129 −1.878 5.251 4.504 5.251 0.238 −1.313
MI −7.510 1.905 9.415 2.803 9.415 0.223 −2.354
DT −6.422 −1.633 4.789 4.028 4.789 0.310 −1.197
LA −6.340 0.218 6.558 3.061 6.558 0.300 −1.640
VNH+ −5.197 −2.095 3.102 3.646 3.102 0.541 −0.776
ATH+ −3.782 −1.007 2.775 2.395 2.775 0.830 −0.694
HPH+ −4.218 −1.742 2.476 2.980 2.476 0.812 −0.619
MIH+ −4.109 0.517 4.626 3.592 4.626 0.368 −1.157
DTH+ −5.225 −1.796 3.429 3.511 3.429 0.509 −0.857
LAH+ −3.837 −0.871 2.966 2.354 2.966 0.783 −0.742

Fig. 11. Molecular electrostatic potential surface fitting schemes for natural form (NFs) and Protonated forms (PFs) structures.

calized at the carbonyl group (–C=O) and a low electrophilicity
(cyancolor) entire the molecule (except –C=C– and –C=O regions).
Concerning AT and ATH+ , we observed the existence of both nucle-
ophilic and electrophilic regions which essentially generated from
the hydroxyl groups of molecule. For the same molecule, we have
documented that the ATH+ has a high tendency to donate and re-
ceive electrons than AT. By the same way, we observed that –C=O
group of DT and DTH+ has a high capability to interact with elec-
trophilic species. Further, it is noticed that the nucleophilic behav-
ior of DT is increased with the protonation process. For MI and
MIH+ , the hydroxyl group has been proven to be good nucleophilic
and electrophilic region; while the carbon chain is appeared as
very low reactive region with the metal surface. The same obser-
vation was noticed for LA and LAH+ , the carboxylic group presents
both nucleophilic and electrophilic characters; whereas the carbon
chain region is considered low reactive.
It is also worth noting that the protonation process has no sig-
nificant changes on the local reactivity (except for DT, the protona-
tion increases highly its nucleophilic character related to the –C=O
region).
3.6.2. Metropolis Monte Carlo simulations
In the context of the Monte Carlo calculations, adsorption en-
ergy (Eads ) is a very important parameter which represents a direct
tool to classify the efficiency of the studied inhibitor (NFs struc-
tures). This energy is defined according to the following relation-
ship [47].
Eads = ERads + EDef

9
S. Abbout, D. Chebabe, M. Zouarhi et al. Journal of Molecular Structure 1240 (2021) 130611

Table 8 4. Conclusion
Energies (Es) for the most stable ad-
sorption configurations for (natural
forms/vacuum or solution/Fe(110)) in- The Ceratonia Siliqua L seeds extract using chloroform as sol-
terfaces calculated using Mont Carlo vent, and it characterized by GC–MS analysis.
simulation. The inhibition study is carried out using polarization curves
Es (kcal.mol−1 ) Vacuum Solution method indicated that the CFE acts as a mixed type inhibitor and
EIS measurements confirmed that the inhibition process is con-
Eads −167.4 −760.9
trolled by transfer charges. In addition, the efficiency reached a
ERads −22.5 −99.1
EDef −144.9 −661.8 value of 95.30% and 93.85% at 100 mg/L of CFE for polarization
dEads /dNHP −70.4 −39.1 and EIS tests, respectively.
dEads /dNAT −115.3 −27.1 The Langmuir adsorption and the temperature effect show that
dEads /dNDT −182.1 −40.2
the adsorption process of the CFE on the carbon steel is mixed type
dEads /dNIN −433.4 −51.3
dEads /dNLA −116.8 −37.2 between physisorption and chemisorption. While, the value of the
dEads /dNVN −163.0 −40.1 Sa indicates that the surface becomes smooth and more ordered.
Finally, the surface analysis confirms the protective effect of Cera-
tonia Siliqua L. seeds extract.
The inhibition and adsorption behavior of the main constituents
of Ceratonia Siliqua L. seeds extract on iron surface was emphasized
using DFT, NBO, MESP and MC studies.

Credit author statement

All persons who meet authorship criteria are listed as authors,

and all authors certify that they have participated sufficiently in
the work to take public responsibility for the content, including
participation in the concept, design, analysis, writing, or revision
of the manuscript. Furthermore, each author certifies that this ma-
terial or similar material has not been and will not be submitted
to or published in any other publication before its appearance in
the molecular structure journal.

Authorship contributions

Please indicate the specific contributions made by each author.

The name of each author must appear at least once in each of the
three categories below.

Fig. 12. Side views of the most stable adsorption configurations (natural
form/vacuum or solution/Fe(110)) interfaces. Category 1

Conception and design of study: Said ABBOUT, Meryem

ZOUARHI, Zouhair LAKBAIBI
Where ERads and EDef are the rigid adsorption energy and defor-
Acquisition of data: Said ABBOUT, Malak REHIOUI, Driss
mation energy of NFs structures during their adsorption onto iron
CHEBABE, Najat HAJJAJI,
surface, respectively. In addition to the Eads , we have discussed an-
Analysis and/or interpretation of data: Said ABBOUT, Driss
other term of energy, noted dEads /dNNFs , which is the desorption
CHEBABE, Meryem ZOUARHI.
energy, i.e., the necessary energy to remove one molecule of NFs
structures to the iron surface (110) [47]. These energies are calcu-
lated in vacuum and in solution (260 H2 O, 20 H3 O+ and 20 Cl−− ) Category 2
and reported in Table 8. Side views of the most stable configura-
tions for (NFs/vacuum or solution/Fe(110)) interfaces are depicted Drafting the manuscript: Said ABBOUT, Meryem ZOUARHI,
in Fig. 12. Zouhair LAKBAIBI; revising the manuscript critically for important
As shown in Table 8,the negative values of Eads suggest that intellectual content: Said ABBOUT, Malak REHIOUI,
the studied adsorption is spontaneously shaped [48]. Moreover, Driss CHEBABE, Najat HAJJAJI,
it is noticed that NFs/solution/Fe(110) interface has a higher
negative value of Eads (−760.949 kcal.mol−1 ) compared to the Category 3
NFs/vacuum/Fe(110) interface (−167.380 kcal.mol−1 ), indicating
clearly the prominent role of acidic medium (presence of protona- Approval of the version of the manuscript to be published (the
tion process) to reaching high interaction for adsorption interface names of all authors must be listed):
under study. This is in good consistent with the finding obtained Said ABBOUT, Driss CHEBABE, Meryem ZOUARHI,
by the GQDs analysis of NFs (without protonation) and PFs (with Malak REHIOUI, Zouhair lAKBAIBI,
protonation) structures; which predicted that the PFs structures Najat HAJJAJI
are more preferred than PFs ones to adsorb onto iron surface.This
observation is strengthened by comparison of the desorption en- Declaration of Competing Interest
ergy (dEads /dNNFs ) values that show that the (NFs/solution/Fe(110))
system has the higher values of dEads /dNNFs comparing to that of We confirm that this work is not submitted in any journal and
(NFs/vacuum/Fe(110)) system. no conflict between authors. Thank you for your consideration.

10
S. Abbout, D. Chebabe, M. Zouarhi et al.
Acknowledgment
The authors extend their appreciation to the Moroccan Associa-
tion of theoretical chemists (AMCT) for access to the computational
facility.
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