Journal of Molecular Liquids 307 (2020) 112957

Contents lists available at ScienceDirect

Journal of Molecular Liquids

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

Corrosion inhibition of mild steel by 2-(2-methoxybenzylidene)

hydrazine-1-carbothioamide in hydrochloric acid solution: Experimental
measurements and quantum chemical calculations
Hana Ferkous a,b, Souad Djellali c, Rachid Sahraoui d, Yacine Benguerba e,⁎,
Hamza Behloul b, Alaaddin Çukurovali f
a
Département de Technologie, Faculté de Technologie, Université 20 août 1955, Skikda, Algeria
b
Laboratory LMSE University Mohamed El Bachir El Ibrahimi, Bordj BouArreridj, Algeria
c
Laboratory of Physical chemistry of High polymers (LPCHP), University Ferhat Abbas Setif 1, Setif, Algeria
d
Department of Biology and Plant Ecology, University Ferhat Abbas Setif 1, Setif, Algeria
e
Laboratoire des Matériaux Polymères Multiphasiques (LMPMP), University Ferhat Abbas Setif 1, Setif, Algeria
f
Department of Chemistry, Faculty of Sciences, Firat University, Elaziğ, Turkey

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

Article history: Corrosion inhibition effect of 2-(2-methoxybenzylidene) hydrazine-1-carbothioamide (MBHCA) for mild steel in
Received 15 January 2020 acidic medium (HCl/1 M) is evaluated using polarization tests (potentiodynamic), electrochemical impedance
Received in revised form 1 March 2020 spectroscopy (EIS) and gravimetric method. The parameters of adsorption of the inhibitor on the metal surface
Accepted 20 March 2020
are determined and the external morphology of the metal is examined by SEM. The results show that the rate
Available online 21 March 2020
of steel corrosion is significantly reduced with augmentation in the Schiff base concentration where the inhibi-
Keywords:
tion efficiency of MBHCA reaches a maximum value of 97.8% at 200 ppm. Polarization measurements reveal
Schiff base that the presence of MBHCA declines considerably the current and shifts the corrosion potential to higher values
Corrosion inhibitor indicating that this Schiff base acts as a mixed type inhibitor with a cathodic dominance. From the thermody-
Impedance spectroscopy namic results, the inhibitor adsorption on the steel surface via the chemisorption mechanism is confirmed and
Polarization Langmuir model is the most suitable to describe the MBHCA adsorption. Moreover, the metal surface examina-
Adsorption tion with SEM confirms the efficiency of MBHCA to keep mild steel protected against the used aggressive me-
DFT dium. Correlation of quantum chemical calculations with experimental results of the present work is discussed
COSMO-RS
according to the Density Functional Theory method (DFT) and molecular dynamics simulation (MD).
© 2020 Elsevier B.V. All rights reserved.

1. Introduction
Mild steel is widely used in various industries such as petroleum
production and refining, power plants, petrochemical processes and
civil engineering structures. This extensive use is mainly related to its
availability, reduced price and high strength [1]. However, the main
drawback of this metal is its tendency to corrode in acidic, alkaline
and other harmful environments [2].To remove rust from metallic sur-
faces, many industries employ acid solutions in several treatments,
such as acid pickling, industrial cleaning and acid descaling [3–5];
among the most commonly used acids are hydrochloric acid, sulphuric
acid, nitric acid, formic acid, acetic acid, etc. Conversely, these acids
make the industrial pipelines and metal vessels to corrode and thereby
⁎ Corresponding author.
E-mail address: benguerbayacine@yahoo.fr (Y. Benguerba).
reduce the production and cause economic loss. As a solution to this
problem, many papers suggest the use of organic and inorganic inhibi-
tors as an effective tool to prevent metal dissolution in acidic, basic or
neutral medium, particularly in cases with elevated degradation rates
[6]. The originality of such approach is that the protective treatment is
not carried out on the metal itself but through the corrosive medium
and the inhibiting molecules may involve various mechanisms, depend-
ing on the aggressive medium, giving them high inhibition perfor-
mances [7–10].Organic inhibitors are reported in several studies on
the corrosion protection of metals [4,11,12]. The most popular ones con-
tain nitrogen, sulfur and oxygen atoms, though, all organic molecules
holding electronegative groups and pi(π) electrons in multiple bonds
(double, triple or conjugated) are good inhibitors [13]. Recently, Schiff's
base molecules, widely used in medicinal, agricultural and pharmaceu-
tical applications [1,14–17], have received great interest due to their po-
tential applicability as metal corrosion inhibitors. The general formula of

https://doi.org/10.1016/j.molliq.2020.112957
0167-7322/© 2020 Elsevier B.V. All rights reserved.
2 H. Ferkous et al. / Journal of Molecular Liquids 307 (2020) 112957
this class of organic compoundsis represented as R3R2C=NR1 (Fig. 1)
with R1, R2 and R3 are alkyl, aryl, heteroaryl or hydrogen. At the N-
imino end (C=N), the substituent may also be a metallo atom (gener-
ally Si, Al, B, Sn) [18].
Several authors have reported that Schiff's bases are good inhibitors
for the corrosion of copper, zinc and aluminum in aggressive solutions
[19–22]. It should be noted that the presence of the imine functional
group (-C = N-) in the Schiff bases generally leads to higher inhibitory
efficiencies than the amines and aldehydes [10]. In addition, Schiff
bases, eco-friendly compounds due to the presence of heterocyclic
thiadiazole, have been widely used in the manufacture of
chemosensors, intermediate of drugs, and antibacterial agents [23].
Compared to other metals, more interest has been given to the cor-
rosion of carbon steel, mainly in acid medium, using Schiff's bases as in-
hibitors. For example, in hydrochloric acid solution, Shahabi et al. [24]
have used two benzohydrazide Schiff bases and found that they exhibit
maximum inhibition efficiencies of 94.0% and 96.5%. In addition, Aouniti
et al. [25] and Tezcan et al. [10] investigated the inhibition action of
some thiophene Shiff bases on carbon steel and their results showed a
corrosion inhibition efficiencies varying from 91% to 97%. The efficiency
of corrosion inhibition of three Shiff bases obtained from the condensa-
tion of hydroxybenzaldehyde and aniline is also stated by Elemike et al.
[26] who indicated that the corrosion inhibition on mild steel reached
maximum values ranging from of 74% to 88%. Meanwhile, the com-
pound 2-aminofluorene bis-Schiff base, synthesized by Liang et al.
[27], has shown a high corrosion inhibition capacity of 98.2% on carbon
steel.
In our work, we investigate the electrochemical features of carbon
steel in hydrochloric acid solution containing 2-(2-methoxybenzylidene)
hydrazine-1-carbothioamide (Schiff base). Corrosion inhibitory efficiency
of our compound is monitored using gravimetric measurement, electro-
chemical impedance spectroscopy (EIS) and potentiodynamic polariza-
tion tests. To elucidate the behavior of the molecules and the electron
interactions with the metal, adsorption parameters and DFT computa-
tional calculations are determined in this study.
2. Material and methods
2.1. Materials
The inhibitor tested in this study is the 2-(2-methoxybenzylidene)
hydrazine-1-carbothioamide (MBHCA), a Schiff base, having the follow-
ing structure (Fig. 2).
The metal used in this work is a carbon steel obtained from Arcelor
Mittal (Algeria) and presents the following composition: carbon
(C:0.38%), silicon (Si:0.27%), manganese (Mn:0.66%), nickel
(Ni:0.02%), chromium (Cr:0.21%), molybdenum (Mo:0.02%) and iron
(Fe: balance).
2.2. Methods
2.2.1. Solution and sample preparation
The MBHCA solutions are prepared in various concentrations (25,
50, 100, 200 ppm and 300 ppm) by dissolving an appropriate amount
of the inhibitor in one molar hydrochloric acid solution (1 M HCl).
Fig. 1. Chemical structure of Schiff bases molecules [18].
H
N H
N N
S H
H3C O
Fig. 2. Chemical structure of2-(2-methoxy benzylidene)hydrazine carbothioamide
(MBHCA).
Samples used in the gravimetric study and SEM analyses are rods with
2 × 0.5 × 0.2 cm3 in dimension; however, for the electrochemical mea-
surements, cylindrical samples embedded in an inert resin are used. The
exposed surface section of 0.27 cm2 is polished using different grades of
sand paper, cleaned with bi-distilled water then degreased with acetone
before each use.
2.2.2. Weight loss measurement
Measurements of the weight loss are realized in 1 M HCl solution
having different concentrations of inhibitor. Steel rods are polished,
cleaned, degreased and dried then immersed vertically in the corro-
sive medium. Rods are weighed before and after different times of
immersion ranging from one day (24 h) to 28 days (672 h). The cor-
rosion rates W corr (mg/cm 2 .h) are evaluated according to the
Eq. (1):
mi −m f
W corr ¼ ð1Þ
St
mi and mf are the weight of the sample (g), respectively, prior and
after immersion.
S: Surface of the sample (cm2).
t: Immersion time in the corrosive medium (hours).
2.2.3. Electrochemical measurements
Potentiodynamic polarization and impedance (EIS) measurements
are performed on a potentiostat-galvanostat (SP 300), monitored by
an EC-Lab® software. A conventional three-electrode system composed
by the steel specimen (working electrode), platinum (counter elec-
trode) and saturated Ag/AgCl (reference electrode) is used. The open-
circuit potential (OCP) is obtained using a freshly polished metal ex-
posed to the corrosive solution (1 Molar HCl), in the absence or pres-
ence of MBHCA at various concentrations, until the steady-state is
established. The polarization curves are realizedat a scan rate of
0.5 mV/s in the range of −200 mV to +200 mV, however, impedance
(EIS) experimentsare performed at the open circuit potential, with
varying the frequency from 50 kHz to 10 mHz and signal amplitude of
10 mV.
2.2.4. Surface characterization
Scanning electron microscopy (SEM) of metal surface exposed toone
molar HCl solution (blank) and the same solution containing 200 ppm
of MBHCA is analyzed on a Tescan Vega 3 microscope with an accelerat-
ing voltage of 20 kvolts.
2.2.5. Adsorption isotherms
The inhibitor adsorption on the metal surface is investigated using
three isotherm models: Langmuir model, Temkin model and Frumkin
model. The following equations relate the degree of the surface cover-
age, θ, to the inhibitor concentration (Cinh) [28]:
Langmuir isotherm model:
bC inh
θ¼ ð2Þ
1 þ bC inh
 H. Ferkous et al. / Journal of Molecular Liquids 307 (2020) 112957 3

Temkin isotherm model: For a bulk iron, A theoretical value for the electronegativity is used as
χF e = 7 eV and a global hardness ηF e = 0, (assuming that metallic bulk is
expð−αθÞ ¼ KC inh ð3Þ softer than the neutral metallic atoms, I = A) [33].

Frumkin isotherm model:

  2.2.6.2. Monte Carlo simulations (MCS). In the present study, the inhibitor
θ (MBHCA)was simulated as adsorbate on the iron surface to find its
expð−2αθÞ ¼ KC inh ð4Þ
1−θ lowest adsorption energy on the clean iron surface in water at different
acid medium concentrations. The Monte Carlo simulations (MCS) [38]
where α denotes the adsorbed particles interaction constant, b the ad- using Adsorption Locator [39] in the Materials Studio 2017™ has been
sorption coefficient and K the equilibrium adsorption constant. The ad- used. The simulations are carried out in a simulation box
sorption parameters and nature are evaluated according to the (22,93 × 22,93 × 34,29 Å3) with periodic boundary conditions. To accu-
adequate model. rately calculate the interaction forces, the Condensed-phase Optimized
Molecular Potentials for Atomistic Simulation Studies (COMPASS)
2.2.6. Theoretical study force field [40–42] was used.

2.2.6.1. Quantum calculations. The Dmol3 module [29] in Materials Stu-

dio 2017™ was used to perform all the quantum chemistry calculations
with the DFT-B3LYP functional set [30] and the DNP base (base file 4.4)
[31].The objective is to study the inhibitory action of the molecule “2-
(2-methoxy benzylidene) hydrazine carbothioamide” (MBHCA) in the
gas and in the aqueous phases while calculating the following quantum
properties: Energy of the highest occupied molecular orbital (EHOMO);
Energy of the lowest unoccupied molecular orbital (ELUMO); Energy
gap (ΔE); Hardness (η); Softness (σ = 1/η); Electrophilicity index
(ω); the fraction of electrons transferred (ΔN) from the inhibitor mole-
cule to the metal surface and Fukui indices. The Comso files produced in
liquid phase are used to build sigma profiles and sigma potentials.
The EHOMO and ELUMO energies are calculated and used to determine
the electronic chemical potential μ, the electronegativity and the global
hardness ƞ, as follows [32–34].
μ ¼ ðEHOMO þ ELUMO Þ=2
χ ¼ −μ or χ ¼ ðI þ AÞ=2
3. Results and discussion
3.1. Gravimetric measurements
Variation of the mass loss of the metal after different immersion
times in HCl solutions are shown in Fig. 3. An important weight loss of
the uninhibited steel is observed with the increase of the immersion
time; however, these mass losses become less pronounced as the con-
centration of MBHCA increases. This finding is supported by the calcu-
lated values of the corrosion rates of steel (Fig. 4), where the rate
decreases with the augmentation in the inhibitor concentration and
drops from 15.9 × 10−6(g·cm−2·h−1), for the blank, to 0.3 × 10−6
(g·cm−2·h−1) for 200 ppm of MBHCA, after 28 days of immersion. At
the same time, a concomitant increase in the inhibition efficiency with
the increase of the amount of the used Schiff base is observed and a
ð5Þ maximum inhibition value of 94.1% is attained for the concentration of
200 ppm.
ð6Þ The inhibition efficiency (EWcorr%) is determined as follows:

ƞ ¼ ðELUMO −EHOMO Þ=2 or ƞ ¼ ðI−AÞ=2 ð7Þ

Wcorr −W0corr
EWcorr % ¼ ð13Þ
where the ionization potential I = −EHOMO and electron affinity A = Wcorr
−ELUMO.
The electrophilicity index ω, characterize the capacity of a molecule
to generate an electron transfer, is given as follows [35,36]: where, W'corr and Wcorr are, respectively, the corrosion rates of the metal
in HCl solutions with and without the inhibitor.
χ2
ω¼ ð8Þ
2ƞ
Blank
Fukui indices are defined in such a way as to quantify the local reac- 25ppm
tivity / selectivity in a molecule [37]. 50ppm
Nucleophilicity of atom k in the molecule: 0,08 100ppm
200ppm
þ
f k ¼ qk ðN þ 1Þ−qk ðNÞ ð9Þ 300ppm

Electrophilicityof atom k in the molecule:

Δm (g)

−
f k ¼ qk ðNÞ−qk ðN−1Þ ð10Þ 0,04

radical attack susceptibility:

0
f k ¼ ðqk ðN þ 1Þ−qk ðN−1ÞÞ=2 ð11Þ

0,00
where, qkis the natural populations for the atom k in the molecule.
ΔN is calculated according to Pearson theory [33] for a metallic sur-
face (Fe) and an inhibitor molecule: 0 5 10 15 20 25 30

χ −χ inh Immersion time(day)

ΔN ¼  F e  ð12Þ
2 η F e þ ηinh
Fig. 3. Evolution of mass loss of steel samples with immersion time.
4 H. Ferkous et al. / Journal of Molecular Liquids 307 (2020) 112957

-5
1,8x10
which may suggest that our inhibitor is able to retard the reactions oc-
95 curring on the surface of the mild steel, namely, the iron oxidation and
1,5x10
-5
the hydrogen ions reduction in hydrochloric acid solution [43,44].
90
Corrosion rate (g.cm .h )

3.3. Polarization measurements

Inhibition efficiency (%)

-1

-5
1,2x10
85
-2

Fig. 6 illustrates the polarization curves obtained after the immer-

-6
9,0x10
-6
6,0x10
-6
3,0x10
0,0
0 50 100 150 200 250
MBHCA concentration (ppm)
Fig. 4. Variation of corrosion rates (Wcor) for steel samples and inhibition efficiency with
MBHCA concentrations after 28 days of immersion.
3.2. Open circuit potential (OCP) measurements
The change of the free potential during a corrosion test is the first in-
dication of the degradation extent during the immersion in an aggres-
sive environment. Fig. 5 shows the evolution of the open circuit
potential during the immersion of mild steel in the aggressive solution
containing different amounts of inhibitor. The obtained curves are com-
pared to a reference curve realized in the free inhibitor solution (HCl
1 M).
As stated from Fig. 5, the corrosion potential (Eocp) of the metal im-
mersed in the initial acid solution (without inhibitor) exhibits a de-
crease, attributed to the dissolution of the metal, followed by a
gradual augmentation, associated with iron oxide and hydroxide forma-
tion, to attain a quasi-steady state at around 30 min of immersion time.
However, when the studied inhibitor (MBHCA) is added to the aggres-
sive medium, the open circuit potentials (Eocp) tend to be stabilized
faster and reach the steady-state, after 500 to 1000 s of immersion.
Moreover, with rising the concentration of MBHCA, a shift of the immer-
sion potential and the steady potential to more positive values is noted
80 sion of mild steel in acidic solutions (1 M HC1) in the presence and ab-
sence of 2-(2-methoxy benzylidene) hydrazine-1-carbothioamide. The
75 first examination of these curves reveals that anodic and cathodic sec-
tions are both insignificantly affected by the addition of the inhibitor.
70 Electrochemical parameters determined from Tafel curves and the inhi-
bition efficiency of MBHCA against carbon steel corrosion in 1 M HCl so-
65 lutions are regrouped in Table 1.
The reported values of the current density “Icorr” show a significant
60 reduction even when a small amount of the inhibitor is introduced
300 where the Icorr of the blank solution (203.5 μA/cm2) falls to
27,5 μA/cm2 for 25 ppm of MBHCA. A concomitant augmentation of
the polarization resistance “Rp” is observed and the values rise from
23.7 Ω·cm2 to 1082 Ω·cm2 for the blank and for 300 ppm solutions, re-
spectively. In the same manner, the inhibitory efficiency of the Schiff
base used “IE” (Eq. (14)) is considerably enhancedwhen the inhibitor
concentration augments and reaches a relatively steady value of 97%
after 100 ppm of MBHCA. In addition, a shift of the current density to-
wards lower values is observed when the inhibitor is added which im-
plies a reduction in the corrosion rates of the metal [45].These results
suggest that molecules of the inhibitor are interacting with the metal
surface, causing the obstruction of the active sites and thus leading to
the improvement of the protection of the metal against corrosion
[46,47].
The inhibition efficiency is estimated using the following formula:
Icorr −I0corr
EIcorr % ¼ ð14Þ
Icorr
with Icorr and I'corr are, respectively, the corrosion current density of mild
steel in the blank (1 M HCl) and in the presence of inhibitor.
Moreover, the presence of MBHCA, causes a shift of Ecorr to less neg-
ative values but this displacement is very limited (about 10–40 mV)
which may lead to the conclusion that our product (MBHCA) is a
2

Blank 25ppm 50ppm 1

100ppm 200ppm 300ppm
E vs Ag/AgCl/KCl (mv)

0
Log I (µA/cm²)

-1
-400

Blank
-2
25ppm
50ppm
100ppm
-3
200ppm
300ppm
-4

2 2 2 2 2 2
-500 -7x10 -6x10 -5x10 -4x10 -3x10 -2x10
400 800 1200 1600 2000
E(mv)vs Ag/AgCl/KCl
time (s)
Fig. 6. Polarization curves of mild steel in HCl (1 M) solutions with various amounts of
Fig. 5. Open-circuit potential for mild steel with and without MBHCA. MBHCA.
 H. Ferkous et al. / Journal of Molecular Liquids 307 (2020) 112957 5

Table 1 plots represent the plot of the imaginary part of impedance (Zi) versus
Polarization parameters and the corrosion inhibitor efficiency of carbon steel in 1 M HCl the real part of impedance (Zr) for each applied frequency. The electrode
with and without MBHCA.
impedance, Zr, is related to the frequency of the AC signal in Hz (f), the
C Ecorr Icorr Rp βc βa Eicorr% ERP% resistance of polarization (Rp), the double layer capacity of double-layer
(ppm) (mV) (μA/cm2) (ohm.cm2) (mV) (mV) (Cdl), and the solution resistance (RS). It is represented by the mathe-
0 −412.6 203.52 23.7 11.3 72 / matical formula:
25 −408.5 27.52 126 155.6 240.5 86.44 81,19
50 −407.4 20.911 296 222.9 83.2 90.17 91,99
Rct
100 −450 12.048 1016 399 146.8 94.08 97,66 Z r ¼ Rs þ ð15Þ
200 −423 6.032 1071 266.2 78.5 97.03 97,78 ½1 þ ð2π f Rct CdlÞ α 
300 −445,4 5,8 1082 373,9 155 97,1 97,81
The Nyquist diagrams display semicircular shapes which indicate
that the charge transfer process governed the corrosion mechanism in
the systems under investigation [50,51]. In addition, the sizes of these
mixed-type inhibitor for carbon steel in this acidic medium. As a rule, an semicircles raise as the inhibitor concentration increases reflecting an
inhibitor classification is related to the shift of the corrosion potential of enhancement of the metal corrosion resistance and therefore a decrease
the metal, considered when the inhibitor is present or not, which must in the corrosion rate [52,53].
be greater than 85 mV [48,49]. The metal-electrolyte interface is characterized by an electrical dou-
Furthermore, the unsteady displacement of the corrosion potential ble layer which is susceptible to changes in its composition and struc-
values and the alteration of the Tafel slopes of the anodic and cathodic ture if any new compound, in our case the corrosion inhibitor, is
sections (βa, βc), observed after the addition of the inhibitor, means introduced within it. Hence, measurement of the double layer capaci-
that cathodic and anodic reactions occurred on the metal surface are tance before and following the incorporation of the corrosion inhibitor
both delayed by the presence of the inhibitor but the hydrogen evolu- could be used to monitor the inhibitor adsorption [54].
tion and the metal dissolution mechanisms (Reactions 1–2) remain un- The equivalent electrical circuit corresponding to the obtained EIS
changed. data is displayed in Fig. 8. Owing to the depressed capacitive loops in
Nyquist plots, the constant phase element (CPE) replaces the double
Metal dissolution : M→Mnþ þ ne− ðR1Þ layer capacitance The use of the CPE in the equivalent circuit is now
well accepted in the corrosion field because the macroscopic measured
impedance is deeply related to several microscopic material properties
(surface defects, local charge inhomogeneities) and to various complex
Hydrogen evolution : 2Hþ þ 2e− →H2 ðR2Þ electrochemical reactions [55,56].
The elements composing the equivalent circuit describe the solution
resistance (Rs), the constant phase element of the double layer (CPE)
and the charge transfer resistance (Rct).CPE impedance is described by
the equation below:
3.4. Electrochemical impedance spectroscopy (EIS)

1
Results of EIS obtained for steel/HCl (1 M) solutions interfaces, con- ZCPE ¼ ð16Þ
taining diverse amounts of MBHCA, are illustrated in Fig. 7. Nyquist Q ðjwÞa

1600
120 Blank
Blank

1400
100
25 ppm
80
50 ppm
-ZIm(ohm.cm )
2

60

1200 40
100 ppm
20 200 ppm
1000
0
300 ppm
-ZIm(ohm.cm )
2

0 20 40 60 80 100 120
2
ZRe(ohm.cm )

800

600

400

200

0
0 200 400 600 800 1000 1200 1400 1600
2
ZRe(ohm.cm )

Fig. 7. Nyquist plots for carbon steel in the acid solutions (1 M HCl) with and without MBHCA.
6 H. Ferkous et al. / Journal of Molecular Liquids 307 (2020) 112957

Fig. 8. Electrical equivalent circuit a) Solution without inhibitor (Blank) and b) Solution containing diverse quantities of MBHCA.

“Q” represents the CPE magnitude; “w” the angular frequency; “j”
the imaginary unit and “a” corresponds to the CPE exponent. The CPE
is considered as an ideal capacitor.
These results may reflect the adsorption of the inhibitor on the metal
surface and the formation of a protecting film. Such film gives rise to the
augmentation of the electric double layer thickness and the reduction of
the dielectric constant of the solution (ε) which improves the corrosion
protection [28,45,46,53].
3.5. Adsorption isotherm
The metal corrosion inhibition effect of organic compounds is usu-
ally associated to their adsorption onto the metal surface and the
blocking of part of the metal surface susceptible to corrosion. The ratio
of the number of sites occupied by the adsorbed inhibitor molecules
to the total number of sites per unit of surface is known as the surface
coverage “θ”. Moreover, the extent of inhibition is related to the interac-
tions level of the inhibitor molecules with steel surface and this can be
elucidated by the adsorption isotherm [28,57]. This later describes the
variation of the surface coverage (θ) of an adsorbing species with its
concentration in the solution.
The values of “θ” for the different solutions of MBHCA in 1 M HCl are
determined, at the equilibrium conditions, using the gravimetric test re-
sults as follows.
EWcorr %
θ¼ ð17Þ
100
where EWcorr% is the inhibition efficiency obtained from Eq. (13).
Variations of θ as a function of MBHCA concentrations are
established using three isotherm models: Langmuir model, Temkin
model and Frumkin model. Rearranged equations of these models are
preferred to find out the most suitable model which corroborates with
results found in this study.
Plots of selected isotherm models are illustrated in Fig. 9. Straight
lines having correlation coefficients near to the unit are observed for

(a) 1,00
(b)
R² = 0,9133
0,95 R² = 0,9133
R² = 0,9997
0,90
θ

0,85

0,80

0,75

0,70
-5,0 -4,5 -4,0 -3,5 -3,0 -2,5 -2,0

ln C

(c)
R² = 0,9437

Fig. 9. Isotherm model plots for mild steel in 1 M HCl at various concentrations of MBHCA. a) Langmuir isotherm b) Temkin isotherm c) Frumkin isotherm.
 H. Ferkous et al. / Journal of Molecular Liquids 307 (2020) 112957 7

Fig. 10. (a) Optimized structure of MBHCA and COSMO-RS results, (b) Sigma surface, (c) Sigma profile, (d) Sigma-potential.

the various isotherm models, however, the best fitting is obtained with onto the metal surface [58]. Furthermore, based on the significant
Langmuir model (R2 = 0.9997) which is given by the Eq. (18): value of ΔG°ads (N−40 kJ/mol), this adsorption may be considered as
chemisorption where strong forces are involved to bind the inhibitor
C 1 molecules and the charged ions at the surface of the metal [59,60].
¼ þ C inh ð18Þ
θ K ads

Thus, according to the Langmuir model, it may be assumed that the
used Schiff base is adsorbed on steel surface as a monolayer and each
molecule of the inhibitor is capable of blocking a single site on the
metal surface with no attraction or repulsion between the adsorbed
molecules [28].
The standard free energy (ΔG°ads) of MBHCA adsorption on carbon
steel surface is related to the adsorption equilibrium constant (Kads) ac-
cording to the following equation:
°
ΔGads ¼ −RT ln ð55:5  K ads Þ
with R: the gas constant and T: the absolute temperature.
Using Langmuir model, the value of Kads is found to be equal
to3.334 × 105 M−1 and the deduced ΔG°ads is equivalent to-41.79 KJ.
mol−1. The negative value of ΔG°ads is a good indication of the sponta-
neity and the strength of the adsorption of the inhibitor molecules
Table 2
Quantum chemical descriptors of the studied inhibitor.
3.6. Theoretical study
3.6.1. Quantum calculations
The quantum chemical calculations are carried out to further explore
the inhibition mechanism of mild steel by 2-(2-methoxybenzylidene)
hydrazine-1-carbothioamide (MBHCA) in hydrochloric acid solution.
The optimized structure of MBHCA is shown in Fig. 10-1, however,
sigma surface, sigma-profile and sigma-potential of MBHCA are repre-
sented in Fig. 10b, c and d, respectively.
ð19Þ The molecule studied is supposed to be surrounded (cavity) by a sol-
vent. The σ-profile is therefore the surface distribution of the charges of
polarity σ of this cavity. When the σ profiles are negative this corre-
sponds to positive polarities, and positive for negative polarities. The
low polarities are represented by narrow peaks while wide peaks indi-
cate high polarities [61,62].
The entire σ-profile of MBHCA (Fig. 10c) covers the range of ±0.02
e/Ǻ−2, generally taken for stable organic and inorganic molecules [63].
The σ-profile of MBHCA contains four peaks arising from the strongly
negative polar regions of the electron lone-pairs of the oxygen atom
and sulfur atom (peak located at +0.014 e/Ǻ−2), from the strongly

Parameter Phase

Gas Aqueous Table 3

Total Energy TE (kcal/mol) −650,250 −650,267 Fukui functions of the studied inhibitor.
EHOMO (eV) −5.033 −5.792
Atom k Phase f+
k f−
k f0k
ELUMO (eV) −1.037 −1580
Gap ΔE (eV) 3.996 4.212 S (14) G 0.148 0.540 0.344
Dipole moment (Debye) 4.531 5.122 A 0.106 0.655 0.381
Electronegativity χ 3.035 3.686 N (10) G 0.092 −0.060 0.016
Hardness η 1.998 2.106 A 0.102 −0.018 0.042
Electrophilicity index ω 2.305 3.225 C (9) G 0.088 0.039 0.064
Fractions of electron transferred ΔN 0.992 0.513 A 0.126 0.032 0.079
8 H. Ferkous et al. / Journal of Molecular Liquids 307 (2020) 112957
Fig. 11. Fukui indices (f+
k ) for the inhibitor molecule.
positively polar hydrogen atoms (peak located at −0.016 e/Ǻ−2) and
from the regions with low polarity (peaks located at around +0.005
and − 0.005 e/Ǻ−2) arose from methyl group and aromatic cycle. The
two former peaks reflect the excellent ability of our compound to act
as an electron-donor as well as an electron-acceptor [61,64]. In addition,
the corresponding σ-potential of MBHCA (Fig. 10d), which is a measure
for the affinity of the solvent towards a molecular surface of polarity σ,
exhibits a relatively symmetric shape which indicates a favorable elec-
trostatic interaction of our investigated Schiff base with the solvent
(water) [64].
The obtained results such as EHOMO, ELUMO, electronegativity, hard-
ness, etc. are reported in Table 2. These electronic characteristics of
MBHCA are important parameters for the prediction of its reactivity
on the steel surface. In general, the HOMO and LUMO orbitals character-
ize the molecular regions that can donate or accept electrons, respec-
tively. Molecules with a high EHOMO are more likely to donate
electrons to the unoccupied orbital of a metal atom, however, molecules
with a lower ELUMO are willing to accept electrons from the metal atom
[61].
The hardness of a molecule marked “η” corresponds to its resistance
to charge transfer. Thus, molecules with a large HOMO-LUMO gap are
hard molecules, which means very stable and not very susceptible to
charge transfer [65].
The inhibitor has a tendency to donate electrons to the metal surface.
The calculated values of the f+ k for the inhibitor atoms (Table 3 and
Table 4
The HOMO and the LUMO electrons density distributions of the studied inhibitor.
Gas-phase
HOMO
LUMO
Fig. 11) showed that atoms S(14), C(9) and N(10), have the higher
values indicating that these atoms will probably be the favourite site
for nucleophilic attacks.
From Table 4, it is noted that the HOMO orbitals are localized at the
hydrazine and the carbothioamide groups. These are the regions donat-
ing electrons to unoccupied d-orbital of metal. Conversely, LUMO or-
bitals are localized at the aromatic ring. Thus, these findings indicate
that the imine group plays an important role as active sites for the inter-
action of MBHCA with a steel surface.
3.6.2. Monte Carlo simulations
The MCS calculated descriptors of the lowest energy MBHC con-
formations on iron (001) surface in water and hydrochloric acid so-
lution, are summarized in Table 5 and Fig. 12. The effect of HCl
concentration is considered. Adsorption energy is always negative
indicating that the inhibitor molecule (MBHC) is quickly and firmly
adsorbed onto the iron surface (001) in acid solution. The higher
the absolute value of adsorption energy the stronger the adsorption
behaviour [66]. It could be also concluded that the higher the HCl
concentration the higher is the strength of the adsorption of MBHC
inhibitor on the iron surface.
The descriptor dEad/dNi reports the energy of substrate–adsorbate
configuration where one of the adsorbate components has been re-
moved. It is obvious that it is easier to remove water and HCl molecules
(2.566, 2.206 kcal/mol; 0.53, 0.415 kcal/mol respectively) from the iron
Aqueous-phase
 H. Ferkous et al. / Journal of Molecular Liquids 307 (2020) 112957 9

Table 5
MCS Outputs and descriptors for the lowest adsorption configuration for the system Fe/inhibitor(1)/water(50)/HCl(x) (All values in Kcal/mol).

x HCl Total Energy Adsorption energy Rigid adsorption energy Deformation energy Inhibitor: dEad/dNi Water: dEad/dNi HCl: dEad/dNi

10 498.364 −286.630 −286.630 −2.12e-09 −89.187 2.566 0.530

20 437.570 −368.766 −368.766 −2.70e-09 −88.420 2.206 0.415

On the other side, molecules of our studied organic inhibitor, act-

ing in an acidic medium like HCl, may occur in their neutral form or
in the form of protonated cations. Furthermore, it is now well
known that the inhibitors which contain vacant orbitals have a pro-
pensity to accept electrons from d-orbital of metal to form stable
chelates [22]. Therefore, according to the results discussed above,
the adsorption of MBHCA on the metal surface may involve at least
one of the following interactions [11,70]: (a) interaction between
unshared electron pairs of heteroatoms and free d-orbital of surface
iron atoms, (b) interaction between π-electrons of the aromatic ring
and vacant d-orbital of surface iron atoms, (c) electrostatic type in-
teraction of protonated MBHCA with Cl− ions previously adsorbed
and (d) donor-acceptor type interactions involvingthe remaining
π* orbital of the aromatic ring of the inhibitor and d-electrons. Tak-
ing into account all these possibilities, we have constructed a sche-
matic representation of the adsorption process of the MBHCA
molecules on the mild steel surface (Fig. 13).

3.8. Scanning electron microscopy

Figs. 14-a, b and c represent the surface morphology of carbon

Fig. 12. Adsorption of the inhibitor molecule on ferrous surface in a water-HCl solution.
surface than removing MBHC inhibitor. This could indicate that MBHC
will probably replace water and HCl molecules on the iron surface
which could lead to the formation of a stable layer that can protect the
plate against aqueous corrosion.
steel before immersion, after immersing in the blank solution
(without inhibitor) and after immersing in 1 M HCl with 200 ppm
of inhibitor. Respectively. Fig. 14b shows clearly that the metal sur-
face is vigorously corroded in the free inhibitor solution. The tex-
ture of the steel surface immersed in HCl solution containing
200 ppm of our Schiff base is shown in Fig. 14c. The image exhibits
a less corroded surface indicating that layers of inhibitor molecules
are formed on the metal surface to protect it from the aggressive
medium.
4. Conclusion

3.7. Mechanism of inhibition The efficiency of 2-(2-methoxy benzylidene) hydrazine-1-

The electron transfer occurring during the partial processes of the
electrolytic corrosion is a result of the anodic reaction (oxidation) in
which the metal loses electrons and enters into an ionic state and the ca-
thodic reaction (reduction) as given in Table 6. The two reactions occur
at the same time and simultaneously upon the metal's surface [67]. Fur-
ther reactions may also occur involving other ions present in the aggres-
sive solution.
The adsorbed (FeCl)ads (reaction (10)) may be dissolved in the more
positive potential.
carbothioamide as corrosion inhibitor of carbon steel in one molar hy-
drochloric acid medium was monitored experimentally with gravimet-
ric and electrochemical methods and theoretically with quantum
computations. The results revealed that the Schiff base investigated is
excellent inhibitor for corrosion of carbon steel in 1 M HCl medium. Its
efficiency to inhibit the corrosion was found to be concentration-
dependent and attained a maximum value of 97% for 100 ppm. It is
also noticed that the compound MBHCA behaved as a mixed-type inhib-
itor in 1 M HCl affecting both cathodic and anodic reactions. Moreover,
the adsorption of the studied Schiff base was conformed to the

Table 6
Reactions involved in the corrosion process of mild steel [68,69].

Cathodic reactions Anodic reactions Side reactions in HCl solution

10 H. Ferkous et al. / Journal of Molecular Liquids 307 (2020) 112957

Fig. 13. Mechanism of interactions between MBHCA and mild steel surface.

Langmuir isotherm with strong interactions of the inhibitor on carbon
steel surface (chemisorption).
Similarly, quantum chemical calculations confirmed that the inhibi-
tive efficacy of MBHCA was directly related to its HOMO and LUMO en-
ergies and that it had a penchant to act as electron-donor to the metal
surface which could lead to the development of a stable organic film
which could prevent the plate corrosion in the acidic solution. Further-
more, the results of experimental tests (mass loss and electrochemical
measurements) and the theoretical calculation were found to be in
good agreement with that of SEM observations.

A) B)

c)

10µm

Fig. 14. SEM images of carbon steel surface after exposure to: a) Before immersion, b) After immersion in HCl without inhibitor, c) After immersion in HCl with 200 ppm of inhibitor.
 H. Ferkous et al. / Journal of Molecular Liquids 307 (2020) 112957
This research did not receive any specific grant from funding agen-
cies in the public, commercial, or not-for-profit sectors.
CRediT authorship contribution statement
Hana Ferkous:Investigation, Writing - original draft.Souad Djellali:
Investigation, Writing - original draft, Writing - review & editing.Rachid
Sahraoui:Investigation, Writing - original draft.Yacine Benguerba:Meth-
odology, Writing - original draft, Writing - review & editing.Hamza
Behloul:Writing - original draft.Alaaddin Çukurovali:Investigation.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
References
[1] M. Prajila, P.R. Ammal, A. Joseph, Comparative studies on the corrosion inhibi-
tion characteristics of three different triazine based Schiff’s bases, HMMT,
DHMMT and MHMMT, for mild steel exposed in sulfuric acid, Egypt. J. Pet. 27
(2018) 467–475.
[2] G.R. Thusnavis, et al., Green seed extract of Tectona grandis as corrosion inhibitor for
mild steel in acid medium, Adv. Mater. Res. 3 (1) (2014) 5–8.
[3] V.V. Torres, et al., Inhibitory action of aqueous coffee ground extracts on the corro-
sion of carbon steel in HCl solution, Corros. Sci. 53 (7) (2011) 2385–2392.
[4] G. Khan, et al., Electrochemical investigation on the corrosion inhibition of mild steel
by Quinazoline Schiff base compounds in hydrochloric acid solution, J. Colloid Inter-
face Sci. 502 (2017) 134–145.
[5] R. Menaka, S. Subhashini, Chitosan Schiff base as effective corrosion inhibitor for
mild steel in acid medium, Polym. Int. 66 (3) (2017) 349–358.
[6] E. Naderi, et al., Effect of carbon steel microstructures and molecular structure of
two new Schiff base compounds on inhibition performance in 1 M HCl solution by
EIS, Mater. Chem. Phys. 115 (2–3) (2009) 852–858.
[7] A. Zeino, et al., Mechanistic study of polyaspartic acid (PASP) as eco-friendly corro-
sion inhibitor on mild steel in 3% NaCl aerated solution, J. Mol. Liq. 250 (2018)
50–62.
[8] R. Vera, et al., Evaluation of Fuji apple peel extract as a corrosion inhibitor for carbon
steel in a saline medium, J. Electrochem. Sci 13 (2018) 4139–4159.
[9] H. Lgaz, et al., Effect of clozapine on inhibition of mild steel corrosion in 1.0 M HCl
medium, J. Mol. Liq. 225 (2017) 271–280.
[10] F. Tezcan, et al., A novel thiophene Schiff base as an efficient corrosion inhibitor for
mild steel in 1.0 M HCl: electrochemical and quantum chemical studies, J. Mol. Liq.
269 (2018) 398–406.
[11] M. Goyal, et al., Organic corrosion inhibitors for industrial cleaning of ferrous and
non-ferrous metals in acidic solutions: a review, J. Mol. Liq. 256 (2018) 565–573.
[12] L.T. Popoola, Organic green corrosion inhibitors (OGCIs): a critical review, Corros.
Rev. 37 (2) (2019) 71–102.
[13] A. Zarrouk, et al., New 1H-pyrrole-2, 5-dione derivatives as efficient organic inhibi-
tors of carbon steel corrosion in hydrochloric acid medium: electrochemical, XPS
and DFT studies, Corros. Sci. 90 (2015) 572–584.
[14] Y. Chen, et al., Synthesis and antibacterial and antiviral activities of myricetin
derivatives containing a 1, 2, 4-triazole Schiff base, RSC Adv. 9 (40) (2019)
23045–23052.
[15] N.S. Abdel-Kader, et al., Synthesis and characterization of Schiff base complexes de-
rived from cephradine: fluorescence, photostability and photobiological applica-
tions, J. Photochem. Photobiol. A Chem. 321 (2016) 223–237.
[16] Q. Zhao, et al., Synthesis, characterization, and cytotoxicity of some novel glycosyl
thiazol-2-imines as antitumoral agents, Carbohydr. Res. 345 (3) (2010) 437–441.
[17] D. Hapău, et al., Stereoselective synthesis of β-(5-Arylthiazolyl) α-amino acids and
use in Neurotensin analogues, Eur. J. Org. Chem. 2016 (5) (2016) 1017–1024.
[18] W. Qin, et al., Schiff bases: a short survey on an evergreen chemistry tool, 18 (10)
(2013) 12264–12289.
[19] M. Ehteshamzade, T. Shahrabi, M. Hosseini, Inhibition of copper corrosion by self-
assembled films of new Schiff bases and their modification with alkanethiols in
aqueous medium, Appl. Surf. Sci. 252 (8) (2006) 2949–2959.
[20] S. Şafak, et al., Schiff bases as corrosion inhibitor for aluminium in HCl solution,
Corros. Sci. 54 (2012) 251–259.
[21] Y. Agrawal, et al., Schiff bases of ethylenediamine as corrosion inhibitors of zinc in
sulphuric acid, Corros. Sci. 46 (3) (2004) 633–651.
[22] S. Li, et al., Some aspects of quantum chemical calculations for the study of Schiff
base corrosion inhibitors on copper in NaCl solutions, Corros. Sci. 41 (9) (1999)
1769–1782.
[23] Q. Zhang, et al., Effective inhibition on the corrosion of X65 carbon steel in the
oilfield produced water by two Schiff bases, J. Mol. Liq. 285 (2019) 223–236.
[24] S. Shahabi, et al., Synthesis, experimental, quantum chemical and molecular dynam-
ics study of carbon steel corrosion inhibition effect of two Schiff bases in HCl solu-
tion, J. Mol. Liq. 285 (2019) 626–639.
11
[25] A. Aouniti, et al., Schiff's base derived from 2-acetyl thiophene as corrosion inhibitor
of steel in acidic medium, Journal of Taibah University for Science 10 (5) (2016)
774–785.
[26] E.E. Elemike, H.U. Nwankwo, D.C. Onwudiwe, Synthesis and comparative study on
the anti-corrosion potentials of some Schiff base compounds bearing similar back-
bone, J. Mol. Liq. 276 (2019) 233–242.
[27] C. Liang, et al., Synthesis of 2-aminofluorene bis-Schiff base and corrosion inhibition
performance for carbon steel in HCl, J. Mol. Liq. 277 (2019) 330–340.
[28] D. Landolt, Corrosion and Surface Chemistry of Metals, CRC Press, Boca Raton,
2007.
[29] F. Evers, F. Weigend, M. Koentopp, Coherent transport through a molecular wire:
DFT calculation, Physica E: Low-Dimensional Systems Nanostructures 18 (1–3)
(2003) 255–257.
[30] L. Lu, et al., An improved B3LYP method in the calculation of organic thermochem-
istry and reactivity, Computational and Theoretical Chemistry 1015 (2013) 64–71.
[31] B. Delley, An all-electron numerical method for solving the local density functional
for polyatomic molecules, J. Chem. Phys. 92 (1) (1990) 508–517.
[32] R.G. Parr, L.v. Szentpály, S. Liu, Electrophilicity index, J. Am. Chem. Soc. 121 (9)
(1999) 1922–1924.
[33] R.G. Pearson, Absolute electronegativity and hardness: application to inorganic
chemistry, Inorg. Chem. Commun. 27 (4) (1988) 734–740.
[34] R.G. Parr, R.G. Pearson, Absolute hardness: companion parameter to absolute elec-
tronegativity, J. Am. Chem. Soc. 105 (26) (1983) 7512–7516.
[35] L.R. Domingo, et al., Density functional theory study for the cycloaddition of 1, 3-
butadienes with dimethyl acetylenedicarboxylate. Polar stepwise vs concerted
mechanisms, J. Phys. Chem. A 106 (6) (2002) 952–961.
[36] P. Pérez, L.R.D, A. Aizman, R. Contreras, The electrophilicity index in organic chem-
istry, in: A. Toro-Labbé (Ed.), Theoretical and Computational Chemistry, Elsevier,
2007.
[37] R.K. Roy, S. Pal, K. Hirao, On non-negativity of Fukui function indices, J. Chem. Phys.
110 (17) (1999) 8236–8245.
[38] N. Metropolis, et al., Equation of state calculations by fast computing machines, J.
Chem. Phys. 21 (6) (1953) 1087–1092.
[39] D. Frenkel, B. Smit, Understanding molecular simulation: From algorithms to appli-
cations, Computational Sciences Series, Elsevier (formerly published by Academic
Press) 2002, pp. 1–638.
[40] H. Sun, P. Ren, J. Fried, The COMPASS force field: parameterization and validation for
phosphazenes, Computational Theoretical Polymer Science 8 (1–2) (1998)
229–246.
[41] H. Sun, COMPASS: an ab initio force-field optimized for condensed-phase applica-
tions overview with details on alkane and benzene compounds, J. Phys. Chem. B
102 (38) (1998) 7338–7364.
[42] D. Rigby, H. Sun, B. Eichinger, Computer simulations of poly (ethylene oxide):
force field, pvt diagram and cyclization behaviour, Polym. Int. 44 (3) (1997)
311–330.
[43] A. Hermas, M. Morad, A comparative study on the corrosion behaviour of 304 aus-
tenitic stainless steel in sulfamic and sulfuric acid solutions, Corros. Sci. 50 (9)
(2008) 2710–2717.
[44] F.S. de Souza, A. Spinelli, Caffeic acid as a green corrosion inhibitor for mild steel,
Corros. Sci. 51 (3) (2009) 642–649.
[45] S.V. Lamaka, et al., High effective organic corrosion inhibitors for 2024 aluminium
alloy, Electrochim. Acta 52 (25) (2007) 7231–7247.
[46] F.E.-T. Heakal, S. Haruyama, Impedance studies of the inhibitive effect of benzotri-
azole on the corrosion of copper in sodium chloride medium, Corros. Sci. 20 (7)
(1980) 887–898.
[47] R. Solmaz, et al., Adsorption and corrosion inhibition effect of 2-((5-mercapto-1, 3,
4-thiadiazol-2-ylimino) methyl) phenol Schiff base on mild steel, Mater. Chem.
Phys. 125 (3) (2011) 796–801.
[48] M. Benabdellah, et al., Inhibition of steel corrosion in 2 M H3PO4 by artemisia oil,
Appl. Surf. Sci. 252 (18) (2006) 6212–6217.
[49] A. Abdel-Gaber, et al., Inhibitive action of some plant extracts on the corrosion of
steel in acidic media, Corros. Sci. 48 (9) (2006) 2765–2779.
[50] P.R. Roberge, R. Beaudoin, Evaluation of charge transfer resistance by geometrical
extrapolation of the centre of semicircular impedance diagrams, J. Appl.
Electrochem. 18 (1) (1988) 38–42.
[51] J. García-Jareño, et al., Graphical analysis of electrochemical impedance spec-
troscopy of two consecutive irreversible electron transfers. 1. Theoretical
study of the anodic dissolution of metals, J. Phys. Chem. B 109 (10) (2005)
4584–4592.
[52] K. Rahmouni, et al., Corrosion and protection of high leaded tin bronze covered with
patina in NaHCO3+ Na2SO4 solution simulating acid rain in urban environment,
Bulgarian Chem Com 1 (2005) 26–34.
[53] M.L. Zheludkevich, et al., Anticorrosion coatings with self-healing effect based on
nanocontainers impregnated with corrosion inhibitor, Chem. Mater. 19 (3) (2007)
402–411.
[54] V.S. Sastri, Green Corrosion Inhibitors: Theory and Practice, Wiley, 2012.
[55] H. Cesiulis, et al., The Study of Thin Films by Electrochemical Impedance Spectros-
copy, in Nanostructures and Thin Films for Multifunctional Applications, Springer,
2016 3–42.
[56] E. Barsoukov, J.R. Macdonald, Impedance Spectroscopy Theory, Experiment, and Ap-
plications, 2nd ed. John Wiley & Sons, New Jersey, 2005.
[57] K. Khaled, The inhibition of benzimidazole derivatives on corrosion of iron in 1 M
HCl solutions, Electrochim. Acta 48 (17) (2003) 2493–2503.
[58] Z. Tao, et al., Adsorption and corrosion inhibition behavior of mild steel by one de-
rivative of benzoic− triazole in acidic solution, Industrial Engineering Chemistry Re-
search 49 (6) (2010) 2593–2599.
12 H. Ferkous et al. / Journal of Molecular Liquids 307 (2020) 112957
[59] I. Ahamad, R. Prasad, M. Quraishi, Thermodynamic, electrochemical and quantum
chemical investigation of some Schiff bases as corrosion inhibitors for mild steel in
hydrochloric acid solutions, Corros. Sci. 52 (3) (2010) 933–942.
[60] N.D. Gowraraju, et al., Adsorption characteristics of iota-carrageenan and inulin bio-
polymers as potential corrosion inhibitors at mild steel/sulphuric acid interface, J.
Mol. Liq. 232 (2017) 9–19.
[61] F.L. Gaol, K. Shrivastava, J. Akhtar, Recent Trends in Physics of Material Science and
Technology, Springer, Singapore, 2014.
[62] T. Aissaoui, et al., Computational investigation of the microstructural characteristics
and physical properties of glycerol-based deep eutectic solvents, J. Mol. Model. 23
(10) (2017) 277.
[63] J. Palomar, et al., Prediction of non-ideal behavior of polarity/polarizability scales of
solvent mixtures by integration of a novel COSMO-RS molecular descriptor and neu-
ral networks, Phys. Chem. Chem. Phys. 10 (39) (2008) 5967–5975.
[64] F. Eckert, A. Klamt, Fast solvent screening via quantum chemistry: COSMO-RS ap-
proach, AICHE J. 48 (2) (2002) 369–385.
[65] R. Mathammal, N. Jayamani, N. Geetha, Molecular structure, NMR, HOMO, LUMO,
and vibrational analysis of O-Anisic acid and anisic acid based on DFT calculations,
Journal of Spectroscopy 2013 (2013).
[66] L. Guo, et al., Theoretical studies of three triazole derivatives as corrosion inhibitors
for mild steel in acidic medium, Corros. Sci. 87 (2014) 366–375.
[67] P. Marcus, Corrosion Mechanisms in Theory and Practice, Third edition Taylor &
Francis, Boca Raton, 2011.
[68] Z. Ahmad, Principles of Corrosion Engineering and Corrosion Control, Elsevier Sci-
ence, 2006.
[69] S.K. Shukla, M. Quraishi, Cefotaxime sodium: a new and efficient corrosion inhibitor
for mild steel in hydrochloric acid solution, Corros. Sci. 51 (5) (2009) 1007–1011.
[70] M. Hosseini, et al., Asymmetrical Schiff bases as inhibitors of mild steel corrosion in
sulphuric acid media, Mater. Chem. Phys. 78 (3) (2003) 800–808.