Portugaliae Electrochimica Acta 2019, 37(3), 147-165 PORTUGALIAE

ELECTROCHIMICA
DOI: 10.4152/pea.201903147 ACTA
ISSN 1647-1571

New Benzohydrazide Derivative as Corrosion Inhibitor for

Carbon Steel in a 1.0 M HCl Solution: Electrochemical, DFT
and Monte Carlo Simulation Studies

A. Chaouikia,b, H. Lgaza b, R. Salghib,*, Santosh L. Gaonkarc,

K. Subrahmanya Bhatc, S. Jodehd, K. Toumiate and H. Ouddaa
a
Laboratory Separation Processes, Faculty of Science, Ibn Tofail University,
P.O. Box 242, Kenitra, Morocco
b
Laboratory of Environmental Engineering and Biotechnology, ENSA, Ibn Zohr University,
P.O. Box 1136, 80000 Agadir, Morocco
c
Department of Chemistry, Manipal Institute of Technology,
Manipal University, Manipal-576 104, India
d
Department of Chemistry, An-Najah National University, P.O. Box 7, Nablus, Palestine
e
Department of Materials Sciences, Laghouat University, P.O. Box 37,
03000, Laghouat, Algeria

Received July 17, 2017; accepted April 1, 2018

Abstract
The present study aimed to evaluate the inhibition effect of an organic compound,
namely, (E)-N'-(2-hydroxybenzylidene)isonicotinohydrazide (BIH), for carbon steel
corrosion in a 1.0 M HCl solution, by using weight loss (WL), potentiodynamic
polarization (PDP) and electrochemical impedance spectroscopy (EIS). Results show
that BIH is a good inhibitor, and the percentage of inhibition efficiency increases on its
higher concentrations. The maximum inhibition efficiency of 94% was obtained at
5×10-3 M. Polarization studies revealed that the BIH compound acts as a mixed type
inhibitor. EIS showed that increasing the concentration of the inhibitor led to an
increase in the charge transfer resistance and a decrease in the double layer capacitance.
It was found that the adsorption of this compound obeyed the Langmuir adsorption
isotherm. The associated activation energies and thermodynamic parameters of the
adsorption process were evaluated and discussed. The temperature effect was studied in
the range from 303 to 333 K. In addition, quantum chemical calculations based on the
density function theory (DFT) and Monte Carlo simulations were done to support the
experimental results.

Keywords: benzohydrazide derivative; corrosion inhibition; carbon steel; HCl; DFT;

Monte Carlo simulations.

*
Corresponding author. E-mail address: [email protected]
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Introduction
Nowadays, metals and their alloys are widely used in various technological and
industrial applications, due to their excellent structural and mechanical strength
[1–14]. Hydrochloric acid and sulfuric acid are most commonly used at various
industrial processes, such as steel acid pickling, scale removal in metallurgy,
boilers acid cleaning and oil-well acidizing [15–18].The metal dissolution in the
corrosive media is not only a source of raw materials wastage and energy, but
also contributes to environmental pollution. In terms of corrosion protection, it is
possible to act on the material itself, on its surface, and on the environment with
which it is in contact. Therefore, the special importance of corrosion inhibitors is
more pronounced, and many scientists are conducting research on this topic. The
chemical compounds used as corrosion inhibitors are considered as some of the
most used substances for reducing the dissolution of various metals and,
consequently, to raise their cycle life. The selection of a good corrosion inhibitor
is controlled by its economical availability, its efficiency to inhibit the substrate
material and its environmental side effects. Most organic substances employed
as corrosion inhibitors can adsorb onto the metal surface through heteroatom’s
such as nitrogen, oxygen, sulfur and phosphorus, as well as multiple bonds or
aromatic rings [19-20].These organic inhibitors are usually adsorbed onto the
metal surface via the formation of a coordinate covalent bond (chemical
adsorption) or the electrostatic interaction between the metal and the inhibitor
(physical adsorption), and sometimes following both routes, thus preventing
metallic dissolution in acidic media [21]. The constituents of the metal and its
alloys, the inhibitor concentration and structure, and the metal environment
temperature, are notable factors that determine the extent of the adsorption
which, in its turn, dictates the inhibition efficiency [22].
The aim of the present work was to study the inhibition efficiencies of (E)-N'-(2
hydroxybenzylidene)isonicotinohydrazide on carbon steel corrosion in a 1.0 M
HCl solution, using electrochemical techniques such as potentiodynamic
polarization (PDP), electrochemical impedance spectroscopy (EIS) and weight
loss (WL) measurements. The temperature effect on the efficiency of this
inhibitor for carbon steel corrosion in a 1.0 M HC1 solution, in the range of 303-
333 K, has been systematically studied.
Besides that, quantum chemical calculations and Monte Carlo simulations studies
were also carried out to provide more insights into the theoretical explanations of
the studied compound’s inhibition activities. They can also be utilized to add
theoretical support to the experimental results [23-24]. The structural formula of
the examined inhibitor is shown in Fig. 1.

Experimental details
Synthesis
(E)-N'-(2-hydroxybenzylidene)isonicotinohydrazide 4 was prepared as follows:
isonicotinic acid 1 (1g, 8.1 mmol) in ethanol (3 mL) and conc. H2SO4 (1 mL)
were refluxed for 2 hours under stirring. This reaction mixture was cooled down
to 15 ºC, using an ice-water bath. With stirring, sodium carbonate (2.15 g) was

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carefully added to get a pH value between 8 and 9. The temperature during

neutralization was maintained between 5 and 10 ºC. The solid was filtered, and
the filtrate was extracted with ethyl acetate. The solvent was removed to get ethyl
isonicotinate. The obtained ethyl isonicotinate was dissolved in ethanol (3 mL)
in a round bottomed flask, and hydrazine hydrate (0.5 g) was added. The mixture
was refluxed for two hours. The reaction mixture was cooled, and the product
was isolated by suction filtration, to give hydrazine derivative 3. The crude
product was recrystallized using ethanol as a solvent. The product yield was
0.8 g, and its melting point was around 172 ºC.

Figure 1. Chemical structure of (E)-N'-(2-hydroxybenzylidene)isonicotinohydrazide

(BIH).

An equimolar mixture of hydrazine derivative 3 (0.1 g, 7.3 mmol) and

salicylaldehyde (0.1 g, 7.3 mmol) was dissolved in IPA/AcOH (0.5 mL), in a
conical flask. The mixture was stirred at 70 ºC, for 2 hours. The reaction mixture
mass was cooled, then, the formed solid was filtered and recrystallized using
methanol as a solvent, to get 0.14 g of isonicotinohydrazide derivative 4, with a
yield of around 80 % (Scheme 1).

Scheme 1. Synthesis of (E)-N'-(2-hydroxybenzylidene) isonicotinohydrazide.

White crystals yield 0.14 g, mp 262–264 ºC, IR (Ѵmax, cm-1, KBr): 3344 (–OH),
3178 (NH), 3004 (–CH), 1685 (amide C=O), 1566 (imine C=N ). 1H NMR (400
MHz, DMSO-d6): δ ppm 11 (s, OH), 8.8–8.9 (d, pyridine 2H), 8.6–8.8 (d,

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pyridine 2H), 8.7 (s, CH), 7.5–7.6 (d, aromatic1H), 8.6 (s, NH), 6.8–7.0 (d,
aromatic 2H), 7.3–7.4 (m, aromatic1H).

Materials
The steel used in this study was carbon steel (Euronorm: C35E carbon steel and
US specification: SAE 1035) with a chemical composition (in wt%) of 0.370 %
C, 0.230 % Si, 0.680 % Mn, 0.016 % S, 0.077 % Cr, 0.011 % Ti, 0.059 % Ni,
0.009 % Co, 0.160 % Cu, and the remainder iron (Fe). The carbon steel samples
were pretreated prior to the experiments: they were grinded with emery paper
SiC (320, 800 and 1200), rinsed with distilled water, degreased in acetone,
washed again with bidistilled water, and then dried at room temperature before
use.

Solutions
The aggressive solutions of 1.0 M HCl were prepared by dilution of analytical
grade 37% HCl with distilled water. The used concentration range of (E)-N'-(2-
hydroxybenzylidene) isonicotinohydrazide was from 5 x 10-3 to 1 x 10-4 M.

Weight loss measurements

The gravimetric measurements were performed by immersing the carbon steel
samples in a 1.0 M HC1 solution, without and with different concentrations of
the studied inhibitor, for 6.0 hours, at 303 K. The carbon steel specimens had a
rectangular form [2 x 2 x 0.08 (cm3)]. Gravimetric experiments were carried out
in a double walled glass cell equipped with a thermo stated cooling condenser
containing 80 mL of the non-de-aerated test solution. After completion of the
immersion time, the specimens were taken out, washed with double distilled
water, degreased with acetone, dried and, finally, accurately weighed using an
analytical balance (precision ± 0.1 mg). All weight loss experiments were triply
performed, and the mean value was reported, to insure the results reproducibility.

Electrochemical measurements
All the electrochemical studies were carried in a corrosion cell kit with a three
electrode configuration. The reference electrode was a saturated calomel
electrode (SCE). A platinum electrode was used as auxiliary electrode. The
working electrode was carbon steel. All potentials given in this study were
referred to this reference electrode (SCE). The working electrode was immersed
in the test solution for 30 min, to establish steady state open circuit potential
(Eocp). After obtaining OCP, the electrochemical measurements were performed.
All electrochemical tests have been performed in aerated solutions at 303 K. The
system impedance was measured as a function of the frequency of the
applied signal, and its value is given in the complex plane for each
frequency. The electrochemical impedance spectroscopy (EIS) tests were carried
out at open circuit potential (OCP), in the frequency range from 10 kHz to 100
mHz, with a signal amplitude of 10 mV, using a Voltalab (PGZ 100)
Potentiostat/Galvanostat coupled to a computer equipped with Voltamaster 4
software.

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The current-potential curves were obtained by potentiodynamic mode in the 1.0

M HCl solution, with different concentrations of the tested inhibitor, by
automatically changing the electrode potential from -800 mV to -200 mV vs. the
saturated calomel electrode, with a potential scan rate of 1 mV/s, and the Tafel
method allowed us to determine the corrosion current value and other
electrochemical parameters.

Quantum chemical study

The geometric optimization and quantum chemical computations of the
investigated molecule were performed using DFT (density functional theory),
with the help of the Becke three-parameter hybrid functional, together with the
Lee-Yang-Paar correlation functional (B3LYP) [25]. The 6-31G(d, p) basis set
that was chosen for all the calculations was implemented in Gaussian 09
software for Windows [26]. This basis set gives good geometry optimizations.
Theoretical chemical parameters, such as the energies of the highest occupied
(EHOMO) and the lowest unoccupied molecular orbitals (ELUMO), energy gap (∆E)
between LUMO and HOMO, and the fraction of electrons transferred (∆N) for
the BIH inhibitor were calculated from the obtained optimized structure.
The ionization potential (IP) and electron affinity (EA) of the inhibitors were
calculated using the following equations:

IP = − EHOMO (1)

EA = − ELUMO (2)
Mulliken electronegativity (χ) and absolute hardness (η) can be approximated
using the following equations [27-28]:

IP + EA
χ= (3)
2

IP − EA
η= (4)
2
The number of transferred electrons (∆N) was calculated by application of the
Pearson method, using the following equation [29]:

φ − χinh
∆N = (5)
2(η Fe + ηinh )
where and χinh denote the work function and absolute electronegativity of iron
and the inhibitor molecule, respectively. ηFe and ηinh denote the absolute hardness
of iron and of the inhibitor molecule, respectively. A theoretical value (ηFe = 0) is
frequently used (since, for bulk metallic atoms, I = A). The obtained DFT
derived values for Fe (1 0 0), Fe (1 1 0) and Fe (1 1 1) surfaces are 3.91, 4.82
and 3.88 eV, respectively [30-31]. Fe ( 1 1 0) was the only surface used in this
study, due to its higher stabilization energy, and to the packed surface [32].

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Monte Carlo simulations

The Monte Carlo (MC) search was adopted to compute the low configuration
adsorption energy of BIH interactions on a clean iron surface. The Monte Carlo
simulation was carried out using Materials Studio 6.0 software (Accelrys, Inc.)
[26]. The Fe crystal was cleaved along the (1 1 0) plane, being the most stable
surface, as reported in the literature. Then, the Fe (1 1 0) plane was enlarged to a
(12x12) supercell, to provide a large surface for the inhibitor interaction. The
simulation of the interaction between BIH and the Fe (1 1 0) surface was carried
out in a simulation box (19.85 × 19.85 × 38.11 Å), with periodic boundary
conditions, which modeled a representative part of the interface devoid of any
arbitrary boundary effects. After that, a vacuum slab with 50 Å thickness was
built above the Fe (1 1 0) plane. All simulations were implemented with the
COMPASS force field, to optimize the structures of all components of the system
of interest. More simulation details on the methodology of Monte Carlo
simulations can be found in previous publications [29–31].

Results and discussion

Concentration effect
Weight loss measurements
The effect of the BIH inhibitor concentration on carbon steel samples corrosion
in a 1.0 M HCl solution was studied using weight loss measurements at 303 K,
for 6 hours immersion time. The obtained data are listed in Table 1.The
inhibition efficiency (ηWL(%)) and the surface coverage (θ) values were
determined from the corrosion rate, using the following equations:

W ° − W 
ηWL (%) =  °  ×100 (6)
 W 

W ° − W 
θ = °  (7)
 W 
where W ° and W are carbon steel corrosion rate in 1.0 M HC1, without and with
different inhibitor concentrations, respectively.

Table 1. Effect of BIH concentrations on the corrosion data of carbon steel, in a

1.0 M HCl solution.
Inhibitor Concentration W ηWL (%) ϴ
(M) (mg/cm2×h)
Blank 1.0 1.135 - -
5×10-3 0.079 93 0.93
BIH 1×10-3 0.113 90 0.90
5×10-4 0.185 86 0.86
1×10-4 0.227 80 0.80

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From the results depicted in Table 1, it is clearly noticed that the inhibition
efficiency (ηWL(%)) increased with an increasing inhibitor concentration and, at
5×10−3 M concentration, BIH exhibited a maximum inhibition efficiency (93%),
which represents an excellent corrosion inhibition. On the other hand, it is also
clearly noticed from Fig. 2 that carbon steel corrosion rate (W) decreased with an
increasing inhibitor concentration. This behavior can be attributed to the increase
in BIH adsorption at the metal/solution interface, as its concentration
increased [37]. In the inhibitor absence, the corrosion rate was as high as
1.135 mg cm−2 h−1 and, in presence of 5×10−3 M of the inhibitor, this value was
reduced to 0.079 mg cm−2 h−1. This phenomenon may be due to the adsorption of
the tested compound onto the metal surface, through π-electrons of the aromatic
ring and a lone pair of electrons of N and O atoms [38].

Figure 2. Relationship between the inhibition efficiency, corrosion rate and inhibitor
concentration for carbon steel, after 6 hours of immersion time in a 1.0 M HC1 solution,
at 303 K.

Tafel polarization study

Fig. 3 shows the potentiodynamic polarization curves for carbon steel corrosion
in a 1.0 M HCl solution, without and with different BIH concentrations, at 303
K. Electrochemical parameters such as corrosion potential (Ecorr), corrosion
current density (icorr), anodic Tafel slope (βa), cathodic Tafel slope (βc) and
percentage inhibition efficiency were determined and summarized in Table 2.The
icorr values were used to calculate the inhibition efficiency ηPDP (%), using
equation 8:

 icorr 
ηPDP (%) = 1 − °  ×100 (8)
 icorr 
°
where icorr and icorr are the corrosion current densities in inhibited and uninhibited
media, respectively.
It is clearly noticed from Fig. 3 that the anodic and cathodic current densities
effectively decreased as the BIH concentration in the acidic solution increased
and, generally, with a slight shift in the Ecorr values, suggesting that the inhibitor
molecules retarded the corrosion process. In the acidic media, carbon steel

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oxidative dissolution in the anodic region, and hydrogen reduction in the

cathodic region are observed in the Tafel plots. In addition, the parallel cathodic
Tafel curves in Fig. 3 show that the hydrogen evolution was activation-
controlled, and that the reduction mechanism was not affected by the inhibitor
presence [39].

Figure 3. Potentiodynamic polarization curves of carbon steel in a 1.0 M HCl solution,

in the presence and absence of different BIH concentrations, at 303 K.

Table 2. Carbon steel PDP parameters at various BIH concentrations in a 1.0 M

HCl solution, and the corresponding inhibition efficiency, at 303 K.
Inhibitor Concentration -Ecorr -βc βa icorr
(M) (mV/SCE) (mV/dec) (mV/dec) (µA/cm2) (%)
Blank 1.0 496 162 132.2 564 -
-3
5×10 493 164 89 49 91
1×10-3 487 166 88 61 89
BIH 5×10-4 477 161 73 81 85
1×10-4 476 163 72 99 82

By inspecting the results in Table 2, we note that icorr considerably decreased with
an increasing BIH concentration. It is reported in literature that, if the
displacement in Ecorr, in the inhibitor presence, as compared to blank solution, is
greater than ± 85 mV, the inhibitor is classified as of the cathodic or anodic type
[40]. In the presence of this compound, carbon steel corrosion potential only
shifted 20 mV to the negative side. Therefore, it could be concluded that this
compound (BIH) is of the mixed-type inhibitor for carbon steel in a 1.0 M HCl
solution; icorr reached a value of 49 µA/cm2, at an inhibitor concentration of
5×10− 3 M. This icorr value led to a maximum η% value of about 91%.
Further, it can be observed from the results shown in Table 2 that the values of
the cathodic (βc) and anodic (βa) Tafel lines show slight changes with BIH
presence. These results suggest that the surface blocking effect of the adsorbed
BIH diminished the anodic and cathodic reactions [41].

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Electrochemical impedance spectroscopy (EIS) study

In order to have more information on the phenomenon of carbon steel corrosion
inhibition in a 1.0 M solution, impedance measurements were performed in the
Nyquist plan, in the absence and presence of different inhibitor concentrations, at
303 K, for an exposure time of 30 min. The Nyquist plots are shown in Fig. 4.

Figure 4. Nyquist diagrams for the carbon steel electrode in a 1.0 M HCl solution with
different BIH inhibitor concentrations.

It is clear from this figure that the impedance response of carbon steel
significantly changed after BIH addition, and that all impedance spectra
exhibited one single depressed capacitive loop at the higher frequency range.
This depression is often associated to the non-homogeneity and roughness of the
carbon steel surface [42]. Further, it was also observed that the impedance
modulus gradually increased with increasing inhibitor concentrations; this
suggests that the formed inhibitive film was strengthened by BIH addition.
Generally, loop-like capacitive EIS plots are mainly attributed to the charge
transfer process, while the increase in the semicircle diameter with a rise in BIH
concentration is the result of the inhibitor adsorption onto the carbon steel
surface [43]. The experimental data were fitted by a Zview software, and an
electrical equivalent-circuit diagram corresponding to the metal/solution interface
was proposed (Fig. 5). Impedance parameters such as the charge transfer
resistance (Rct) – whose value is a measure of electron transfer across the surface
–, Cdl values, and the compound’s efficiency values corresponding to various
concentrations, are presented in Table 3. Double layer capacitance values were
obtained using the following equation:

Cdl = n Q × Rct1-n (9)

where Q is the CPE constant and n is a coefficient that can be used as a measure
of surface inhomogeneity [44].
The inhibition efficiency was calculated using the charge transfer resistance as
follows:

 Rct(inh) − Rct 
η EIS (%) =   ×100 (10)
 Rct(inh) 

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where Rct(inh) and Rct are the charge transfer resistance values, with and without
BIH, respectively.

Figure 5. Equivalent circuit applied for fitting of the impedance spectra.

Table 3. EIS parameters for carbon steel corrosion in a 1.0 M HCl solution with various
BIH concentrations, at 303 K.
Inhibitor Concentration Rct n Q×10-4 Cdl
(M) (Ω×cm2) (sn /Ω×cm2) (µF/cm2) (%)
Blank 1.0 29.35 0.89 1.7610 91 -
5×10-3 511.7 0.79 0.3236 11 94
BIH 1×10-3 389 0.80 0.3641 13 92
5×10-4 250.5 0.81 0.4538 16 88
1×10-4 206.2 0.81 0.6558 24 85

By inspection of the results shown in Table 3, it can be noticed that Rct values
increased, while Cdl values decreased with higher inhibitor concentrations,
suggesting, in the present study, that BIH adsorbed onto the carbon steel surface,
and formed an insulating protective film [45]. In addition, the decrease in CPE
can result from a decrease in the local dielectric constant, and from an increase
in the thickness of the electrical double layer, due to the inhibitor molecules
adsorption at the metal/solution interface [46].The results also show that at the
concentration of 5×10-3 M, the percentage of inhibition efficiency reaches the
highest value (94%). The η% values obtained in the EIS study were in good
correlation with those obtained from the weight loss and PDP studies.

Effect of solution temperature

It is essential to study the temperature effect on carbon steel corrosion in a 1.0 M
HCl solution, in the absence and presence of 5×10-3 M concentration, at
temperatures ranging from 303 to 333 K, because many changes occur on the
metal surface, such as rapid etching, desorption of some inhibitor molecules and
of the inhibitor itself [47]. For the studied inhibitor, potentiodynamic polarization
measurements (Figs. 6 and 7) were performed, to investigate the temperature
effect on the inhibition efficiency, and to calculate activation parameters. The
results are given in Table 4. It can be seen from the results that η% decreased
with increased solution temperatures, from 303 to 333 K. This is due to an
appreciable decrease in the inhibitor adsorption molecules onto the metal surface,
with a rise in temperature, which further causes inhibitor molecules desorption
from carbon steel surface. It is also clear from Table 4 that the corrosion rate

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increased with increased temperatures, both in uninhibited and inhibited

solutions. From this table, it is also obvious that carbon steel corrosion rate
slowly increased in the inhibitor presence, as compared to without inhibitor.
These results confirm that BIH acts as an efficient inhibitor for carbon steel in a
1.0 M HCl solution, in the studied temperature range.

Figure 6. Potentiodynamic polarization curves of carbon steel in a 1.0 M HCl solution,

at different temperatures.

Figure 7. Potentiodynamic polarization curves of carbon steel in a 1.0 M HCl solution,

in the presence of 5×10-3 M of BIH, at different temperatures.

In addition, the temperature effect on the nature of carbon steel dissolution in a

1.0 M HCl solution can be best explained in terms of Arrhenius equation, where
the natural logarithm of icorr is a linear function of 1/T. The corresponding
relation (11) provides access to the activation energies [48-49].

icorr = kexp (11)

To access the thermodynamic characteristics – enthalpy of activation (∆Ha0) and
entropy of activation (∆Sa0) – we used the Arrhenius transition equation [50],

icorr = exp exp (12)

where k is the Arrhenius pre-exponential factor (what k?), T is the absolute

temperature, Ea is the activation corrosion energy for the corrosion process, h is

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the Planck’s constant, N is the Avogadro’s number, ∆Sa0 is the entropy of

activation, and ∆Ha0 is the enthalpy of activation.

Table 4. The influence of temperature on the electrochemical parameters for a carbon

steel electrode immersed in a 1.0 M HCl solution, and 1.0 M HCl + 5×10-3 M of BIH.
Inhibitor Temperature -Ecorr -βc icorr Η
(K) (mV/SCE) (mV des-1) (µA cm-2) (%)
303 496 162.5 564 -
Blank 313 498 154.5 773 -
323 492 176.0 1244 -
333 497 192.0 1650 -
303 493.1 184.2 49 91
5×10-3M 313 498.6 130.9 87 88
BIH 323 504.9 139.6 165 86
333 522.8 132.9 297 81

The curves of variation of Ln icorr versus 1/T and Ln (icorr/T) versus 1/T are
recorded in Fig. 8 and Fig. 9, respectively.

Figure 8. Plots for carbon steel in a 1.0 M HCl solution, and 1.0 M HCl + 5×10-3 M of
BIH.

Figure 9. Transition state plots for carbon steel in a 1.0 M HCl solution, and 1.0 M HCl
+ 5×10-3 M of BIH.

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The curves obtained in the form of lines obey the Arrhenius law, thus satisfying
the relations 11 and 12, and all the regression coefficients are close to 1. The
activation parameters in BIH absence and presence are summarized in Table 5.
According to the data in Table 5, Ea values determined in solutions with BIH are
higher than those in the inhibitor absence, suggesting that the energy barrier of
the corrosion reaction increased, which means that carbon steel dissolution is
difficult [51]. High Ea values are generally associated with low corrosion rates,
while low Ea values are associated with high corrosion rates. However, ∆Ha
positive sign reflects the endothermic nature of the carbon steel dissolution
process, suggesting that this is slow [52] in the inhibitor presence.
On the other hand, Table 5 shows that ∆Sa values increased in the inhibitor
presence, compared to the blank solution, which means that an increase in
disorder took place during the course of the transition from the reactant to the
activated complex, during the corrosion process [53-54].

Table 5. Corrosion kinetic parameters for carbon steel in a 1.0 M HCl solution, in the
presence and absence of 5×10-3 M of BIH.
Ea ∆Ha ∆Sa Ea
Inhibitor
(kJ/mol) (kJ/mol) (J mol-1 K-1) - ∆Ha
Blank 31.00 28.36 -98.8 2.64
5×10-3M BIH 50.25 47.61 -55.56 2.64

Adsorption isotherm
Adsorption isotherm is one of the most important topics in the field of corrosion,
because the organic molecules reduce metallic corrosion by adsorption at the
metal/solution interface, and the adsorption isotherm can give important
information about the interface mechanism between the inhibitor and the metal
surface. As it is known, the adsorption process of the inhibitor is a displacement
reaction, where the adsorbed water molecule is being removed from the metal
surface, according to the following process:

Org (sol) + xH 2O(ads) ↔ Org (ads) + xH 2O(sol) (13)

where Org(sol) and Org(ads) are the organic molecules in the aqueous solution, and
the ones adsorbed onto the metallic surface, respectively, H2O(ads) is the water
molecules on the metallic surface, and x the number of water molecules replaced
by the organic molecules [55].When the equilibrium of the process described in
this equation is reached, it is possible to obtain different expressions of the
adsorption isotherm plots, and thus, the surface coverage degree (θ) can be
plotted as a function of the inhibitor concentration under testing [56].
In order to assess what adsorption behaviors are likely to occur onto the carbon
steel surface, the adsorption isotherms were calculated. In our present study,
several adsorption isotherms, namely, Langmuir, Temkin and Frumkin isotherms
were tested to find the best fit. The results showed that Langmuir isotherm gave
the best fit, with the regression coefficient value closer to unity (R2 = 0.9999),
and the slope nearly 1. However, the surface coverage (θ) rate for different
concentrations in acidic media was evaluated by the potentiodynamic

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polarization (η (%)/100) method. According to the Langmuir isotherm, the

degree of surface coverage (θ) is related to the inhibitor concentration (C), by the
following way [57]:

Cinh 1
= + Cinh (14)
θ K ads
where θ is the surface coverage degree, Cinh is the inhibitor concentration in the
electrolyte and Kads is the equilibrium constant of the adsorption process. Using
Kads values, ∆Gºads values were evaluated using the following equation [58]:

∆Gads
°
= − RT ln( Kads × 55.5) (15)
where R is the universal gas constant, T is the thermodynamic temperature and
55.5 is the water concentration in the solution.
Plots of Cinh/θ as a function of Cinh yielded a straight line; the experimental
(points) and calculated isotherms (line) are plotted in Fig. 10. From the intercepts
of Fig. 10, Kads values were calculated. Table 6 summarized Kads and ∆Gºads
values.

Figure 10. Plots of BIH Langmuir adsorption isotherm on the carbon steel surface, at
303 K.

Table 6. The adsorption parameters for carbon steel corrosion in a 1.0 M HCl solution,
at 303 K.
Inhibitor Slope Kads (M-1) R2 ∆Gºads (kJ/mol)
BIH 1.09 37533 0.9999 -36.63

It can be seen from Table 6 that Kads value is high, indicating that the inhibitor is
easily and strongly adsorbed onto the metal surface, which leads to a better
inhibition performance. In our case, BIH strong interaction with carbon steel can
be attributed to the presence of heteroatoms, such as N and O, and π-electrons in
the inhibitor molecule [59]. ∆Gºads value is -36.63 kJ mol−1 in our measurements.
Generally, free energy standard values from -20 kJ mol−1, or less negative, are
associated with an electrostatic interaction between the charged molecules and
the charged metal surface (physical adsorption) [60]; those from -40 kJ mol−1, or
more negative, involve a load sharing or transfer of inhibitor molecules to the
metal surface, forming a coordinate covalent bond (chemisorption) [61].
Likewise, in the present study, the calculated ∆Gºads values are between 20 and

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40 kJ mol−1. Consequently, BIH adsorption onto the carbon steel surface

involves the combination of chemisorption and physisorption [62].

Quantum chemical study

The density function theory (DFT) has been used to analyze the characteristics of
the inhibitor/surface mechanism, and to describe the structural nature of the
inhibitor on the corrosion process. Recently, the quantum chemical study was
performed to establish a correlation between the molecular structure of the
inhibitor and inhibition efficiency. In the present study, various quantum
chemical parameters, such as EHOMO, ELUMO and the energy gap ∆E (ELUMO -
EHOMO), were obtained for the BIH molecule, to predict their activity towards the
metal surface. These quantum chemical parameters were determined from the
geometrically optimized molecule, and are given in Table 7. The optimized and
frontier molecular orbital structures of BIH are shown in Fig. 11.

Table 7. Quantum chemical parameters for BIH, calculated using B3LYP/ 6-31G (d,p).

EHOMO (eV) ELUMO (eV) ∆Egap (eV) χ (eV) η (eV) ∆N

-5.8937 - 4.1663 3.8105 2.0831 0.4222
1.7273

Figure 11. (a) Optimized molecular structure, (b) frontiers orbital’s distribution,
HOMO and (c) LUMO, of the inhibitor.

Based on the frontier molecular orbital theory, the reactants reaction mainly
occurred on the highest occupied molecular orbital (HOMO) and lowest
unoccupied molecular orbital (LUMO). Therefore, it's indispensable to analyze
the electron density distribution in the HOMO and LUMO orbitals of the
inhibitor molecule. This HOMO and LUMO orbitals distribution is a critical tool
to predict the reactivity and, consequently, the ability of the tested compound to
adsorb onto the carbon steel surface. Higher EHOMO values indicate that the
molecule has a higher tendency to donate electrons to appropriate acceptor
molecules with low energy empty molecular orbital, and lower ELUMO values,
suggesting that the molecule easily accepts electrons from the donor molecules
[63]. The lower ∆E value is another important molecular parameter which favors
higher inhibitor performance.

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The BIH molecule adsorption from the aqueous solution can be regarded as a
quasi-substitution process between BIH in the aqueous phase [BIH (sol)] and
water molecules at the electrode surface [H2O (ads)]. In its turn, the ∆E energy
gap between LUMO (ability to accept) and HOMO (ability to donate) had a
value of 4.1663 eV. It reflects BIH higher inhibition efficiency, because lower
∆E causes the improvement on the molecule reactivity, which facilitates
adsorption. The fraction of electrons transferred (∆N) from the inhibitor to the
carbon steel surface was also calculated. It was reported that ∆N value measures
the ability of a chemical compound to transfer its electrons to metal, if ∆N > 0
and, vice versa, if ∆N < 0 [64-65]. In this study, the positive value of ∆N
(0.4222) presented in Table 7 suggests the high capability of BIH to donate
electrons to the carbon steel surface.
Furthermore, from Fig. 11, it could be seen that BIH has similar HOMO and
LUMO distributions, which were all located on the entire molecular structure.
This is due to oxygen and nitrogen atoms presence, together with several
π-electrons on the entire molecule. In this study, the compound is the electrons
donator, and the iron surface is the acceptor. The unoccupied d orbitals of Fe
atoms can accept electrons from the inhibitor molecule, to form a coordinate
bond. Also, the inhibitor molecule can accept electrons from Fe atom, with its
anti-bonding orbitals, to form a back-donating bond.
It is also reported in literature that Mulliken charges can be used
for the determination of possible adsorption centers of the
inhibitors [66-67]. Mulliken charges, according to the numeration
of corresponding atoms, are shown in Fig. 12. It is evident from
this figure that the inhibitor had a considerable excess of negative
charge around nitrogen, oxygen and some carbon atoms,
indicating that these are the coordinating sites of the inhibitor.
Monte Carlo simulations
Monte Carlo simulations were carried out to better understand the interaction
between BIH and the Fe (1 1 0) surface, because it provides some essential
parameters, such as the adsorption energy. In our present study, the Monte Carlo
simulation calculation was used to find the lowest energy for the whole system.
Fig. 13 represents the most stable low energy configuration for BIH adsorption
on the Fe (1 1 0) surface obtained through the Monte Carlo simulations.

Figure 12. The Mulliken charge distribution of BIH inhibitor.

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Figure 13. (a) Side and (b) top views of the most stable low energy configuration for
the inhibitor adsorption onto the Fe (1 1 0) surface, obtained through the Monte Carlo
simulation for BIH.

It is by and large recognized that the essential phenomenon of carbon steel

corrosion inhibition is adsorption. So, the adsorption energy can furnish us with
immediate information about inhibitors efficiency. The results depicted in Table
8 show that the benzohydrazide derivative associated with high negative
adsorption energy values resulted in strong interactions between metal and the
BIH molecule [68].
By inspection of Fig. 13, it could be observed that BIH nearly adsorbed onto the
Fe (1 1 0) surface, where chemical interactions can possibly occur through
reactive sites in the molecule, as interpreted in the experimental and theoretical
study. In this case, the BIH molecule protects the carbon steel surface from the
aggressive medium, by adsorbing onto the Fe (1 1 0) surface in the possible
nearby planar form, reducing the carbon steel dissolution [69].

Table 8. Outputs and descriptors calculated by the Monte Carlo simulation for BIH
lowest adsorption configurations on the Fe (1 1 0) surface (in kcal/mol).

System Adsorption energy

Fe (1 1 0)/ BIH -103.931

Conclusion
In the present investigation, it can be concluded that the BIH compound shows
excellent inhibition properties for carbon steel corrosion in a 1.0 M HCl solution,
at 303 K, and the inhibition efficiency increases with higher BIH concentrations,
while it slightly decreases with rises in temperature. The inhibitor efficiencies
determined by weight loss, Tafel polarization and EIS methods are in good
agreement. Polarization measurements show that BIH inhibits both anodic and
cathodic processes, indicating that this is a mixed type corrosion inhibitor. The
EIS measurements showed that charge transfer resistance (Rct) increased, and
that the double layer capacitance (Cdl) decreased in the inhibitor presence,

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suggesting the inhibitor molecule adsorption onto the carbon steel surface. BIH
adsorption onto the carbon steel surface in a hydrochloric acid solution obeyed
the Langmuir adsorption isotherm. The density distributions of the frontier
molecular orbitals (HOMO and LUMO) indicate that the studied derivative
adsorbed through the active centers of N and O atoms and π electrons of the
hydroxybenzylidene and phenyl rings. Monte Carlo simulations study showed
that BIH adsorbed onto the Fe (1 1 0) surface in a near flat orientation, and the
adsorption energy value of the equilibrium configuration supports the
experimental inhibition efficiency of the compound.

References
1. El Makrini B, Lgaz H, Toumiat K, et al. Res J Pharm Biol Chem Sci.
2016;7(5):2277.
2. Adardour L, Lgaz H, Salghi R, et al. Pharm Lett. 2016;8(4):212.
3. Lgaz H, Saadouni M, Salghi R, et al. Pharm Lett. 2016;8(18):167.
4. Lgaz H, Anejjar A, Salghi R, et al. Int J Corros Scale Inhib. 2016;5(3):209.
5. Bousskri A, Anejjar A, Salghi R, et al. J Mater Environ Sci.
2016;7(11):4269.
6. Saadouni M, Larouj M, Salghi R, et al. Pharm Lett. 2016;8(4):65.
7. Adardour L, Lgaz H, Salghi R, et al. Pharm Lett 2016;8(4):173.
8. Adardour L, Lgaz H, Salghi R, et al. Pharm Lett. 2016;8(4):126.
9. El Makrini B, Toumiat K, Lgaz H, et al. Res J Pharm Biol Chem Sci
2016;7(5):2286.
10. Toumiat K, El Aoufir Y, Lgaz H, et al. Res J Pharm Biol Chem Sci
2016;7(5):1210.
11. Saadouni M, Larouj M, Salghi R, et al. Pharm Lett 2016;8(4):96.
12. El Makrini B, Larouj M, Lgaz H, et al. Pharma Chem 2016;8(2):227.
13. Lgaz H, Salghi R, Larouj M, et al. J Mater Environ Sci 2016;7(12):4471.
14. Lgaz H, Benali O, Salghi R, et al. Pharma Chem. 2016;8(2):172.
15. Lgaz H, Salghi R, Jodeh S, et al. Appl J Environ Eng Sci. 2015;1(2):57.
16. Bousskri A, Anejjar A, Lgaz H, et al. Appl J Environ Eng Sci. 2015;1(1):9.
17. Lgaz H, Toumiat K, Jodeh S, et al. Appl J Environ Eng Sci. 2016;2(2):72.
18. Bousskri A, Lgaz H, Jodeh S, et al. Appl J Environ Eng Sci. 2016;2(1):1.
19. Aljourani J, Golozar M, Raeissi K. Mater Chem Phys. 2010;121(1):320.
20. Abboud Y, Abourriche A, Saffaj T, et al. Mater Chem Phys. 2007;105(1):1.
21. Goulart CM, Esteves-Souza A, Martinez-Huitle CA, et al. Corros Sci.
2013;67:281.
22. Obot I, Obi-Egbedi N, Umoren S. Corros Sci. 2009;51(8):1868.
23. Döner A, Solmaz R, Özcan M, et al. Corros Sci. 2011;53(9):2902.
24. Obot I, Gasem Z. Corros Sci. 2014;83:359.
25. Becke AD. J Chem Phys. 1993;98(7):5648.
26. Frisch M, Trucks G, Schlegel H, et al. Gaussian 09. revision D. 01 2009.
27. Pearson RG. Inorg Chem. 1988;27(4):734.
28. Sastri V, Perumareddi J. Corrosion. 1997;53(8):617.
29. Martinez S. Mater Chem Phys. 2003;77(1):97.

164
 A. Chaouiki et al. / Port. Electrochim. Acta 37 (2019) 147-165

30. Cao Z, Tang Y, Cang H, et al. Corros Sci. 2014;83:292.

31. Kokalj A. Chem Phys. 2012;393(1):1.
32. Saha SK, Murmu M, Murmu NC, et al. J Mol Liq. 2016;224:629.
33. Materials Studio. Revision 6.0. Accelrys Inc. San Diego: USA; 2013.
34. Eivani AR, Zhou J, Duszczyk J. Comput Mater Sci. 2012;54:370.
35. Hmamou DB, Salghi R, Zarrouk A, et al. J Environ Chem Eng.
2015;3(3):2031.
36. Kaya S, Tüzün B, Kaya C, et al. J Taiwan Inst Chem Eng. 2016;58:528.
37. Obot I, Obi-Egbedi N. Curr Appl Phys. 2011;11(3):382.
38. Quraishi M, Ahmad S, Ansari M. Br Corros J. 1997;32(4):297.
39. Bentiss F, Jama C, Mernari B, et al. Corros Sci. 2009;51(8):1628.
40. Ferreira E, Giacomelli C, Giacomelli F, et al. Mater Chem Phys.
2004;83(1):129.
41. Parveen M, Mobin M, Zehra S. RSC Adv. 2016;6(66):61235.
42. Krishnaveni K, Ravichandran J. J Electroanal Chem. 2014;735:24.
43. Yadav M, Behera D, Kumar S. Surf Interf Anal. 2014;46(9):640.
44. Popova A, Christov M, Vasilev A. Corros Sci. 2007;49(8):3290.
45. Krishnaveni K, Ravichandran J. J Electroanal Chem. 2014;735:24.
46. Banerjee S, Srivastava V, Singh M. Corros Sci. 2012;59:35.
47. Bentiss F, Lebrini M, Lagrenée M. Corros Sci. 2005;47(12):2915.
48. Xu B, Yang W, Liu Y, et al. Corros Sci. 2014;78:260.
49. Xu B, Liu Y, Yin X, et al. Corros Sci. 2013;74:206.
50. Zhang S, Tao Z, Liao S, et al. Corros Sci. 2010;52, 3126.
51. Gomma GK, Wahdan MH. Mater Chem Phys. 1995;39(3):209.
52. Gerengi H, Darowicki K, Bereket G, et al. Corros Sci. 2009;51(11):2573.
53. Singh AK, Quraishi M. Corros Sci. 2011;53(4):1288.
54. Khamis E, Hosny A, Elhadary S. Afinidad 1995;52(456):95.
55. Solmaz R. Corros Sci. 2010;52(10):3321.
56. Labjar N, Bentiss F, Lebrini M, et al. Int J Corros. 2011;2011.
57. Langmuir I. J Am Chem Soc. 1917;3(9):1848.
58. Flis J, Zakroczymski T. J Electrochem Soc. 1996;143(8):2458.
59. Özkır D, Kayakırılmaz K, Bayol E, et al. Corros Sci. 2012;56:143.
60. Yurt A, Bereket G, Kivrak A, et al. J Appl Electrochem. 2005;35(10):1025.
61. Saliyan VR, Adhikari AV. Corros Sci. 2008;50(1):55.
62. Behpour M, Ghoreishi S, Soltani N, et al. Corros Sci. 2008;50(8):2172.
63. Xia S, Qiu M, Yu L, et al. Corros Sci. 2008;50(7):2021.
64. Kovačević N, Kokalj A. Corros Sci. 2011;53(3):909.
65. Kokalj A. Electrochim Acta 2010;56(2):745.
66. Kandemirli F, Sagdinc S. Corros Sci. 2007;49(5):2118.
67. Hasanov R, Sadıkoğlu M, Bilgiç S. Appl Surf Sci. 2007;253(8):3913.
68. Khaled K, Amin MA. Corros Sci. 2009;51(9):2098.
69. Zhang Z, Tian N, Huang X, et al. RSC Adv. 2016;6(27):22250.

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