Journal of Molecular Structure 1197 (2019) 535e546

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Journal of Molecular Structure

journal homepage: http://www.elsevier.com/locate/molstruc

Electrochemical and quantum chemical assessment of linoleic acid as

a corrosion inhibitor for carbon steel in sulfuric acid solution
I.A. Hermoso-Diaz a, A.E. Foroozan b, J.P. Flores-De los Rios c, L.L. Landeros-Martinez d,
J. Porcayo-Calderon a, J.G. Gonzalez-Rodriguez a, *
a
Universidad Autonoma del Estado de Morelos, CIICAp, Av. Universidad 1001, 62009, Cuernavaca, Mor., Mexico
b
Department of Chemical Engineering and Applied Chemistry, University of Toronto, 200 College Street, Toronto, ON, M5S 3E5, Canada
c
Universidad Autonoma de Chihuahua, Facultad de Ingenieria, Circuito No.1, Campus Universitario 2, C.P., 31125, Chihuahua, Chih., Mexico
d
Universidad Autonoma de Chihuahua, Facultad de Ciencias Quimicas, Circuito No.1, Campus Universitario 2, C.P., 31125, Chihuahua, Chih., Mexico

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

Article history: The corrosion inhibition performance of linoleic acid (LA) for 1018 carbon steel in 0.5 M H2SO4 solution
Received 14 September 2018 was evaluated by using potentiodynamic polarization curves, electrochemical impedance spectroscopy
Received in revised form and weight loss measurements. These tests were complemented by theoretical calculations using density
22 July 2019
functional theory (DFT). The inhibition efficiency increased with increasing the LA concentration but it
Accepted 22 July 2019
decreased with an increase in the temperature. LA was found to be a mixed type inhibitor which is
Available online 23 July 2019
physically adsorbed on to carbon steel by following the Langmuir adsorption isotherm. Theoretical
studies suggest that LA is a more effective inhibitor in acidic media than in neutral environments. Thus,
Keywords:
Linoleic acid
in acidic media LA had the highest EHOMO value, the best chemical reactivity, the greatest tendency to
Carbon steel transfer electrons and a greater facility of modifying its electronic configuration in presence of carbon
DFT steel specimens according to its chemical hardness value. Finally, the Tomasi Polarized Continuum Model
Electrochemical measurements to explain the LA adsorption on to the metal is provided.
Acid corrosion © 2019 Elsevier B.V. All rights reserved.

1. Introduction scientific results of studies on any types of inhibitor are highly

Metals and alloys are used in a myriad of engineering applica-
tions due to their desirable mechanical properties to weight ratios.
Carbon steel, owing to its low price, is among the most common
material used in different industries [1]. However, because of its
susceptibility to corrosion, its application needs extra consider-
ations especially when it is being used in petrochemical industries,
where acid cleaning, descaling, pickling, and oil well acidizing are
frequently performed [2e6]. To date, organic inhibitors have
proved to be one of the most efficient methods of corrosion pre-
vention; consequently, a vast number of studies have examined the
beneficial effects of the use of different organic inhibitors in
corrosion mitigation of carbon steel exposed to various corrosive
environments [7e10]. While having a high inhibition efficiency is a
chief factor, environmental concerns, such as toxicity, biodegrad-
ability, and cost apply some restrictions in the identification of an
effective inhibitor for industrial applications [11e13]. Nevertheless,
* Corresponding author.
E-mail address: ggonzalez@uaem.mx (J.G. Gonzalez-Rodriguez).
valuable from the academic point of view, since it would shed light
on the role of any distinct feature within an inhibitor molecular
structure in inhibition efficiency and mechanism.
The corrosion inhibition efficiency of organic compounds is
closely related to their adsorption ability, which depends on the
metal surface charge, type of corrosive medium, chemical and their
molecular properties. Generally, organic compounds containing
polar functional groups, which could include heteroatoms and/or
conjugated double bonds, exhibit excellent inhibition efficiency
[14e16]. In this sense, organic compounds obtained from roots,
seeds, leaves or fruits have been evaluated as green inhibitor for
carbon steel in acid solutions as a result of its antioxidant properties
[17e24]. Salvia hispanica (S. hispanica) is an ancient seed used in
both food and folk medicine in Mexico, due to the high level of
antioxidants, notably linoleic and linolenic acids [25,26]. Recently
S. Hispanica was found to be a good corrosion inhibitor for carbon
steel in sulfuric acid [27]. Nonetheless, since S. hispanica containes
several compounds, it was not evident which one of the organic
antioxidants compounds is the responsible for its inhibitive capa-
bility. Main compounds contained in S. Hispanica includes linoleic

https://doi.org/10.1016/j.molstruc.2019.07.085
0022-2860/© 2019 Elsevier B.V. All rights reserved.
536 I.A. Hermoso-Diaz et al. / Journal of Molecular Structure 1197 (2019) 535e546
acid, a-linolenic acid, myricetin, quercetin, kaemperol, and caffeic
acid with potent antioxidant activity [27]. Most abundant com-
pounds in S. Hispanica, close to 80%, are Linoleic acid (LA), a-lino-
lenic acid and myricetin, but it not so obvious which one is the
responsible for the inhibitive properties of S. hispanica. Since
S. Hispanica is very abundant in Mexico, the production of LA, a-
linolenic acid or myricetin is relatively cheap. Since recently we
reported the inhibitive properties of S. hispanica for 1018 carbon
steel [27] but it contains several compounds, from which LA is one
of the most abundant, in the present study, we are reporting the
results of using LA as a green corrosion inhibitor for 1018 carbon
steel in the same experimental conditions as those reported in
Ref. [27], i.e. in 0.5 M sulfuric acid, under the same testing tem-
peratures, by using the same techniques. Corrosion inhibition ef-
ficiency was evaluated via various electrochemical methods,
together with gravimetric measurements. Then the experimental
results are compared with the theoretical predictions obtained by
the means of density functional theory (DFT) calculations. In
addition, theoretical calculations are performed on LA in neutral
medium and the results are compared with that in acidic envi-
ronment. However, experimental evaluations of LA inhibitor in
neutral solutions and their comparison to the theoretical pre-
dictions are the subject of future studies.
2. Materials and methods
2.1. Materials and sample preparation
1018 carbon steel rods, (2.5 cm in length and 0.6 cm in diam-
eter), with chemical composition reported in Table 1, were used as
testing material. Prior to the experiments, samples were abraded
with 1200 grade emering paper, rinsed with de-ionized water,
degreased with acetone and finally blow-dried with compressed
air. Sulfuric and linoleic acid LA was purchased from Sigma Aldrich
since it was much easier to buy it than to extract it from S. hispanica.
2.2. Weight loss measurements
Weight loss experiments were performed by exposing carbon
steel rods to the solution of different concentrations of LA during
72 h at different temperatures (i.e. 25, 40 and 60
C) for triplicate.
After the exposure, the specimens were taken out, washed with de-
ionized water and prepared for weighing according to ASTM G1
standard.
2.3. Electrochemical tests
Electrochemical measurements were conducted in a three-
electrode glass cell using a Gamry PC4 300 potentiostat
controlled by Gamry Instruments Framework software. The work-
ing electrodes were encapsulated in commercial epoxy resin prior
to the preparation described in section 2.1, leaving unmasked a
circular area of 0.5 cm2. A graphite rod with an immersed area of
4 cm2 and a saturated calomel electrode (SCE) were used as auxil-
iary and reference electrode respectively. Experiments were carried
Table 1
Chemical composition of 1018 carbon steel.
Element Content (wt%)
Fe Balance
C 0.14
Mn 0.60
S <0.05
P <0.05
out at room temperature with the solution open to the air. All tests
were conducted using freshly prepared test specimens and were
repeated three times to ensure the accuracy and the reproducibility
of the data. Specimens were allowed to stabilize their open circuit
potential value (OCP) during 30 min prior to the electrochemical
tests. Subsequently, EIS measurements were carried out at 0 V vs.
OCP, by applying an AC voltage 10 mV rms, frequency range 10 kHz
to 0.04 Hz with 10 points/decade. Potentiodynamic polarization
tests were carried out by polarizing the specimen from 800 up
to þ1000 mV vs. OCP, voltage 1 mV/s.
2.4. Surface characterization
Surface morphology of testing samples after immersion in sul-
furic acid solutions in absence and presence of 1000 ppm LA in-
hibitor during 72 h were characterized by a high vacuum scanning
electron microscope (LEO VP 1450).
2.5. Theoretical calculations
2.5.1. Electronic structure calculations
Geometry optimization and frequency calculations of neutral
and protonated forms of LA were performed using the density
functional theory (DFT). The absence of imaginary frequencies
confirmed that the structures are true minima. The Becke's three-
parameter hybrid functional [28] was combined with the Lee,
Yang and Parr (LYP) correlation functional [29]. Calculations were
carried out by using 6-31G(d) basis set [30]. Chemical descriptors
were calculated firstly, for the gas form, and then for the protonated
form to simulate the acidic media. In order to have a better corre-
lation with experimental results obtained in aqueous solution and
to understand dispersive, repulsive and electrostatic forces be-
tween solute and solvent molecules, Tomasi Polarized Continuum
Model (PCM) [31] implemented in the Gaussian 09 package was
used to study the solvent effects. In PCM, solute is embedded into a
cavity which is surrounded by the solvent, described by its
dielectric constant (ε ¼ 78:56). All theoretical calculations,
including ground state geometry optimization and frequency
analysis calculations were performed in Gaussian 09 V 5.09. The
relationship between the corrosion inhibition efficiency, the
chemical structure, and electronic properties of LA [32,33] was
studied using the following descriptors: EHOMO, ELUMO, DE, dipole
moment (m), absolute electronegativity (c), global softness (s),
global hardness (h), and fraction of transferred electrons (DN).
2.5.2. Molecular dynamics
In order to simulate the interaction between the linoleic acid
molecule and the surface, we have used molecular dynamics by
means of the DFTBþ (Density Functional based Tight Binding
method) software. DFTBþ is a fast (typically around two orders of
magnitude faster than a normal DFT code) and efficient quantum
mechanical simulation software package able to carry out quantum
mechanical simulations similar to the density functional theory but
in an approximate way [34]. The parameters (Slater-Koster)
trans3d-0e1 [30] and mio-1-1 [35] were used to represent the
atomic interactions. These parameter sets have been developed for
organic molecules with first row transition metal elements,
included Fe.
The parameters used for molecular dynamics simulation were:
Velocity Verlet integration algorithm, a Nose-Hoover thermostat, a
time step of 1 fs and a temperature of 300 K. For the self-consistent
part of the calculation, we used a Monkhorst-Pack type k-point
distribution with 2  2  1 k-points for the Fe calculations and
1  1  1 for those containing only the LA molecule. A tolerance of
1e-5 was used for the electronic part and, for all the calculations
 I.A. Hermoso-Diaz et al. / Journal of Molecular Structure 1197 (2019) 535e546 537

that included the Fe surface, spin was included (colinear).
Once the calculation parameters for the molecular dynamics
were defined, a bcc Fe (100) with four cells in the X and Y direction
and four layers in Z (64 atoms) was used to represent the surface.
The bottom layer was kept fixed and a repetition vector of 40 Å was
used in the Z direction, sufficient for the molecule not to interact
with its Z-image. The cell was optimized using the Conjugate
Gradient optimization method. The optimization was stopped
when the force component with the maximal absolute value went
below 1.0e-8 (eV/Å) giving a lattice constant of 2.504 Å.
3. Results and discussion
3.1. Weight loss measurements
Corrosion rates (CR) were calculated using the weight loss of
carbon steel specimens immersed in 0.5 M H2SO4 solutions
including different LA concentrations at 25, 40, and 60
C, for 72 h,
according to Eq. (1),
Dm
CR ¼
SDt
the metal surface can be provided by the use of adsorption iso-
therms [36]. The adsorption process of an inhibitor is a displace-
ment reaction, where the molecules of the inhibitor replace the
water molecules on the metal surface, which can be expressed
according to the following equation,
InhðsolÞ þ H2 OðadsÞ 4InhðadsÞ þ H2 OðsolÞ # (3)
where Inh(sol) and Inh(ads) are the inhibitor added in the aqueous
solution and adsorbed on the metal surface respectively. As
observed in data presented in Fig. 1, the best fitting was obtained.
Cinh 1
¼ þ Cinh # (4)
q Kads
Kads in Eq. (4) is the equilibrium constant of the adsorption
process, which can be calculated from the intercept of the fitted line
in Fig. 1 (Kads ¼ 3:12  102 L/mg). Kads is related to the standard
free energy of adsorption (DG0ads ) according to the following
equation:
 
(1) DG0ads ¼  RT In 106 Kads # (5)

where R is the universal gas constant, T is the absolute temperature,

where Dm is the average weight loss (mg), S is the exposed coupon
surface area (cm2) and Dt is the immersion time (h). Eq. (2) was
used to determine the inhibition efficiency according to the weight
loss measurements (hw ),

CR  CRinh
hw ¼  100# (2)
CR

where CR and CRinh are the weight losses in the absence and
presence of inhibitor, respectively.
Table 2 summarizes the corrosion rates and inhibition effi-
ciencies data as afunction of the LA concentration at different
temperatures. Accordingly, LA addition decreases the corrosion rate
of carbon steel at the different testing temperatures. The highest
inhibition was achieved at 25
C for an LA concentration of
3566 mol L1. However, the inhibition dramatically decreases at
higher temperatures for all concentrations. This is expected as
corrosion reactions take place at higher rates as the temperature
increases. Moreover, at higher temperatures adsorption and sub-
sequently surface coverage of LA on carbon steel decreases due to a
decrease in the strength of the adsorption process.
Fig. 1. Langmuir isotherm plot for 1018 carbon steel in 0.5 M H2SO4 containing
3.1.1. The adsorption isotherm different concentrations of LA at room temperature with the Langmuir type of
adsorption isotherm. By using Eq. (4) which describes the relationship between the
Since we are assuming that the decrease in the corrosion rate of surface coverage (q ¼ hw =100) and the inhibitor concentration, Cinh, the adsorption
1018 carbon steel is due to the adsorption of LA onto its surface, process at room temperature was found to follow the Langmuir adsorption isotherm
very important information about the interaction between LA and (Fig. 1).

Table 2
Corrosion rates and inhibition efficiencies obtained from the weight loss experiments on carbon steel in 0.5 M H2SO4 containing various concentrations of LA at different
temperatures.

Concentration (mol L1) Temperature

25
C 40
C 60
C

CR (mg =cm2 h) hw (%) CR (mg =cm2 h) hw (%) CR (mg =cm2 h) hw (%)

0 1.78 e 12.87 e 16.06 e
356.6 0.47 74 11.69 9 15.73 2
713.2 0.42 76 10.01 22 14.32 11
1426.4 0.20 89 9.86 23 13.15 18
2139.6 0.18 90 8.82 31 13.00 19
2852.8 0.11 94 7.63 41 11.61 28
3566 0.06 97 6.29 51 11.00 32
538 I.A. Hermoso-Diaz et al. / Journal of Molecular Structure 1197 (2019) 535e546

and 106 is the concentration of water in the solution in mg/L. Table 3

1 Activation parameters for 1018 carbon steel in 0.5 M H2SO4 containing different
Calculated value for DG0ads at room temperature is 25.64 kJ mol . concentrations of LA at 298, 313 and 333 K.
Generally, DG0ads values of around 20 kJ mol1 or greater are
Cinh (mol L1) Ea (kJ mol1) DH (kJ mol1)
associated with an electrostatic interaction between charged in-
0 33.41 30.79
hibitor molecules and charged metal surface, i.e. physisorption;
356.6 60.18 57.55
those around 40 kJ mol1 or less involve charge sharing or 713.2 63.42 60.80
transfer from the inhibitor molecules to the metal surface to form a 1426.4 83.47 80.84
coordinate type bond, i.e., chemisorption [36]. Therefore, a mixture 2139.6 83.64 81.02
of physisorption and chemisorption, dominated by a weak, physical 2852.8 93.66 91.00
3566 104.96 102.33
type of adsorption, seems to be responsible for the adsorption
process of LA inhibitor on to carbon steel. The negative value for
DG0ads indicates that it is a spontaneous process.

3.1.2. Thermodynamics parameters

The apparent activation energy (Ea) in absence and presence of
LA was calculated by using the following relationship:

Ea
logðCRÞ ¼ þ A# (6)
2:303RT

where Ea is the apparent activation energy for the corrosion of 1018

carbon steel in 0.5 M H2SO4 solution, R the general gas constant, A
the Arrhenius pre-exponential factor and T is the absolute tem-
perature. A plot of the logarithm of the corrosion rate (mg cm2
h1) of 1018 carbon steel obtained from the weight loss measure-
ments vs. 1/2.303RT gave straight lines as shown in Fig. 2. The
values of Ea obtained from the slope of the lines are given in Table 3.
Data show that the thermodynamic activation functions (Ea and
DH) for the corrosion of1018 carbon steel in 0.5 M H2SO4 solution in
presence of the inhibitor are higher than those in its absence. Ea and Fig. 3. Effect of LA concentration in the polarization curves of 1018 carbon steel in
DH increase with increasing the inhibitor concertation, indicating 0.5 M H2SO4 solution at room temperature.
higher energy barriers for the reaction in presence of the inhibitor
[37e39].
calculated by using:

3.2. Potentiodynamic polarization curves

The effect of LA concentration on the polarization curves for
1018 carbon steel in 0.5 M H2SO4 solution at room 25
C is given in
Fig. 3. Electrochemical parameters such as Ecorr, icorr, anodic and
cathodic Tafel slopes (ba, bc), inhibitor efficiency and surface
coverage values (q) are given in Table 4. Inhibitor efficiency, hpc, was
Fig. 2. Arrhenius plots for the weight loss of carbon steel in 0.5 M H2SO4 containing
different concentrations of LA.
icorr  icorr=inh
hpc ¼  100# (7)
icorr
where icorr and icorr/inh are the corrosion current density values
obtained in absence and presence of the inhibitor. From Fig. 3 and
data given in Table 4, it can be seen that both the anodic dissolution
and cathodic hydrogen evolution reactions are inhibited with the
addition of LA.
Additionally, the icorr value decreases whereas the inhibitor ef-
ficiency increases with an increase in the LA concentration. The
surface area covered by the inhibitor, q, increases with an increase
in the LA concentration also, which is an indicative that the
corrosion inhibition is due to the adsorption of the LA onto the
metal surface. However, there is no a clear trend on the shift of the
Ecorr value with the inhibitor addition, although this shift was in the
interval of 10e50 mV more cathodic than that value obtained for
the uninhibited solution. Anodic Tafel slope was virtually unaf-
fected only the cathodic one. However, it has been established
[38,39] that if the change in Ecorr value induced by the inhibitor
addition is more than 85 mV, such a compound could be identified
as an anodic or a cathodic type inhibitor. On the contrary, if the shift
in the Ecorr value is less than 85 mV, then the compound can be
considered as mixed type of inhibitor. In our case, the largest shift
in the Ecorr value is 50 mV, the largest shift indicates that the tested
leaf extracts are performed as mixed-type inhibitor with a pre-
dominant cathodic effect as data in Table 4 indicates. This means
that this inhibitor affects both the anodic metal dissolution reaction
but more predominately the cathodic hydrogen evolution (HE) and
oxygen reduction (OR) reactions. However, since we are using an
 I.A. Hermoso-Diaz et al. / Journal of Molecular Structure 1197 (2019) 535e546 539

Table 4
Electrochemical parameters obtained from polarization curves for 1018 carbon steel in 0.5 M H2SO4 solution containing various concentrations of linoleic acid.

Cinh (mol L1) Ecorr (mVSCE) icorr (mA/cm2) ba (mV/dec) bc (mV/dec) hPC (%) q
0 425 5.49 45 90 e e
356.6 435 2.47 48 120 54 0.54
713.2 449 1.93 49 130 65 0.65
1426.4 475 1.41 53 135 74 0.74
2139.6 444 1.24 40 140 78 0.78
2852.8 445 0.4 48 150 87 0.87
3566 463 0.1 40 150 97 0.97

acidic solution, the HE reaction is the predominant cathodic reac-
tion, it indicates that this inhibitor is blocking thy sites where
protons can be adsorbed on to the surface metal for the HE reaction
to take place.
3.3. Electrochemical impedance spectroscopy (EIS)
To understand the inhibitive effect of LA on the metal-solution
interface, EIS measurements were performed at room tempera-
ture. Nyquist and Bode plots for LA at different concentrations are
shown in Fig. 4. From data given in this figure, we can see that
Nyquist diagrams display a single depressed, capacitive loop at high
and intermediate frequency values. However, at the lowest
frequency values, the imaginary impedance values remain con-
stant, which we will call “tails” or “elongations”. On the other hand,
Bode plots show only one peak, and, therefore, only one capacitive
time constant, indicating that only one phenomenon is happening
and that the corrosion process is under charge transfer control. The
loops shape did not change with the LA concentration, indicating
that the corrosion mechanism was not affected. However, the
diameter of the loops in the Nyquist diagrams as well as the
impedance modulus in the Bode plots increased with an increase in
the LA concentration, increasing from a value of 30 U cm2, obtained
for the uninhibited solution, up to a value of 1800 U cm2 obtained
for a LA concentration of 1000 ppm which is due to the adsorption
of the inhibitor on the metal surface [40e42]. In addition to this, the
phase angle also increased with the LA concentration. The charge
transfer resistance values (Rct ) were calculated from the difference
in the lowest and the highest frequency impedances, that is, sub-
tracting the electrolyte resistance from the total impedance. As a
film is formed on the metal surfaces by the inhibitor, the contri-
bution of the film resistance should be taken into the account as
well as other resistances such as double layer resistance and others
due to the accumulations of corrosion products atmetal/solution
interface. The sum of all of these resistances is the polarization
resistance, Rp. Thus, diameter of Nyquist plots should be related
tothe polarization resistance which contains charge transfer resis-
tance, double layer resistance, film resistance and other accumu-
lations at metal/solution interface. The inhibition efficiency was
calculated by using Eq. (8):

Rp=inh  Rp
hEIS ¼  100# (8)
Rp=inh

where Rp=inh and Rp represent the polarization resistance with and

Fig. 4. Effect of LA concentration in the a) Nyquist and b) Bode plots for carbon steel in
0.5 M H2SO4 solution at room temperature.
without inhibitor, respectively.
We observed that the loops displayed in the Nyquist plot are
depressed, and, in addition to this, the slope of the plot of logarithm
of the impedance against the logarithm of the frequency curves is
not 1, which indicates that they deviate from an ideal behaviour of
a double layer capacitance. This might be due to the metal surface
roughness due to its dissolution, the potential presence of scratches
and imperfections on the surface of the working electrodes, as well
as accumulation of the corrosion products; in fact, the accumula-
tion of these corrosion products is the cause of the tales observed at
the lowest frequency values in the Nyquist diagrams, which is more
evident at a concentration of 1000 ppm [41,42]. Therefore, the
constant phase element (CPE) was used to model the data, using Eq.
(9):where Y0 is the magnitude of the CPE, j is the imaginary unit, u
is the angular frequency (u ¼ 2pf, where f is the AC frequency),
and n is the CPE exponent (phase shift) [38] which provides some
surface parameters such as roughness. Electrochemical parameters
such as Rct, the charge transfer resistance and CPE, the double layer
constant phase element are given in Table 5. It can be seen that the
Rp value increases whereas the Y0 value decreases with an increase
in the LA concentration. The increase in Rp is caused by the
540 I.A. Hermoso-Diaz et al. / Journal of Molecular Structure 1197 (2019) 535e546

Table 5
Electrochemical parameters to fit the EIS results for 1018 carbon steel in 0.5 M H2SO4 solutions containing various concentrations of LA.

1
ZCPE ¼ # (9)
Y0 ðjuÞn

Cinh (ppm) Rs (ohm cm2) Rp (ohm cm2) Y0 106 ðsn U1 cm2 Þ n hEIS (%)
0 4 28 79.9 0.78 e
100 4 80 72.7 0.81 62
200 6 293 29.0 0.85 89
400 6 362 23.4 0.89 91
600 9 550 15.9 0.91 94
800 7 870 9.4 0.94 96
1000 8 2232 9.1 0.96 98

accumulation of the organic inhibitor on the metal surface, which
decreases the surface activity [43,44]. Water molecules on the
metal-solution interface are replaced by the adsorbed LA molecules
[45e47]. The addition of LA to the 0.5 M H2SO4 results in higher
charge transfer resistance and thus a decrease in the corrosion rate
for carbon steel which is also observed in the n values. In absence of
the inhibitor, a high dissolution rate is obtained and, thus, a high
surface roughness, obtaining values for parameter “n” close to 0.5.
On the other hand, with addition of the inhibitor, a low dissolution
rate is observed, with a low surface roughness, obtaining values for
“n” close to the unit. This deviation from an ideal behaviour push us
to use a constant phase element instead of a pure capacitor in the
electric circuit [48,49]. Thus, from data given in Table 5, as the LA
concentration increases, the n value increases from 0.78 to 0.96 for
0 and 1000 ppm respectively due to a decrease in the surface
roughness. By using the Helmholtz model and the standard formula
for conventional plate capacitors (Eq. (10)), assuming a constant
surface area value for the electrodes throughout the measurements,
and noting the close dipole moment values (in vacuum) for water
and LA molecules (~1.8 D), the decrease in Y0 can be related to an
increase in double-layer thickness, as a result of LA inhibitor
adsorption.
A occupied molecular orbitals (HOMO) and lowest unoccupied mo-
C ¼ ε0 ε #
d
3.4. Surface characterization
The scanning electron micrographs of specimens corroded to
0.5 M H2SO4 solutions without and with 1000 ppm of LA after 72 h
of exposure at room temperature are shown in Fig. 5. The contrast
between the highly corroded surface in absence of inhibitor,
featuring accumulation of a porous, cracked corrosion products film
layer, and the smooth surface shown by specimen corroded in
presence of LA agrees with the results from electrochemical and
gravimetric measurements [50].
3.5. Quantum chemical calculations
Since acidic aqueous solution is the medium in which corrosion
is investigated in this study, the effect of solvent in the LA pro-
tonated form has been taken into account in the calculations. In
addition to an analysis of linoleic acid in acidic medium (LAAM), an
analysis for linoleic acid in neutral medium (LANM) has been done
in order to compare the molecular properties and the behaviour of
LA in such environments. Quantum chemical calculations were
performed using the DFT methodology [51e54] in order to corre-
late the inhibition efficiency determined from the experimental
results to a number of relevant molecular properties and chemical
descriptors, such as dipole moment, electronegativity, highest
(10) lecular orbitals (LUMO) as well as the energy associated to them
(EHOMO and ELUMO), etc., of which a brief description is provided in
the following.
According to the frontier molecular orbital theory, the transition
of electrons is due to an interaction between HOMO and LUMO of
reactants [51]. EHOMO is related to the ability of a molecule to donate
electrons, consequently ionization energy (IE):

Fig. 5. SEM images of specimens after exposure to 0.5 M H2SO4 containing a) 0 ppm and b) 1000 ppm of LA at 25
C.
 I.A. Hermoso-Diaz et al. / Journal of Molecular Structure 1197 (2019) 535e546
IE ¼  EHOMO # (11)
Higher EHOMO values indicate a higher tendency of a molecule to
donate electrons, preferably to a molecule with a low energy or
empty electron orbitals. Such a feature facilitates the adsorption
and enhances the efficiency of inhibitors [47]. Similarly, ELUMO is
related to the ability of a molecule to accept electrons, consequently
electron affinity (EA), which is described by the following equation:
EA ¼  ELUMO # (12)
Lower ELUMO values suggest a higher tendency for accepting
electrons. The energy gap between EHOMO and ELUMO, (DE ¼
ELUMO  EHOMO ), also known as activation energy is used as a
reactivity index [51]. The higher the energy gap, the more stable the
molecule is, that is low reactivity, which is indicative of hard
molecules. Conversely, soft molecules have a low DE and a high
reactivity and polarizability [55]. The dipole moment (m) is a
measure used for describing the total polarity of a molecule. It has
been reported that the inhibition efficiency has a direct relationship
with the dipole moment of the inhibitor, since it is easier for a
highly polar molecule to adsorb to a conductive surface [55e59].
On the other hand, DFT has been used to understand the
selectivity of molecular systems [60]. The reactivity of a particular
site of a molecular species can be explained by local quantities such
as electron density and Fukui function have been used successfully
in studies on site selectivity in a molecule [61]. Fukui function are
mathematical expressions that define the sensitivity that a mo-
lecular system has to have to undergo changes in its electronic
density, at different sites in its structure [61]. With the quantifica-
tion of Fukui function is possible through a condensation scheme in
an atomic region of the molecule. This reaction can proceed under
the influence of an electrophilic, nucleophilic, or radical attack at a
particular reaction site. The equations are [61]:
fk ¼ ½qk ðNÞ  qk ðN  1Þfor an electrophilic attack (13)
fkþ ¼ ½qk ðN þ 1Þ  qk ðNÞfor nucleophilic attack (14)
1
fk0 ¼ ½q ðN þ 1Þ þ qk ðN  1Þfor attck by a radical (15)
2 k
According to Koopman theorem, the global hardness (h) and
softness (s) of a molecule can be calculated through ionization
energy and electron affinity:
1 IE  EA
h¼ ¼ # (16)
s 2
Moreover, the mean of IE and EA is a measure of electronega-
tivity (c) of a molecule:
IE þ EA
c¼ # (17)
2
Electron flow occurs with regards to the electronegativity of the
molecules; from a molecule with a lower c (donor) to a molecule
with a higher c (acceptor). The number of transferred electrons
(DN) is an indicative of “electron-donating ability” and can be
calculated as follows:
f  cinh
DN ¼ # (18)
2ðhFe þ hinh Þ
where the f values obtained from DFT calculations are 3.91eV,
4.82 eV and 3.88 eV for Fe (100), (110) and (111) surface, respec-
tively [59]. The hFe z 0 is accepted due to the extremely small
541
number [60].
Optimized structure, HOMO, and LUMO of LA in neutral and
protonated states are depicted in Fig. 6. As can be seen, the distri-
bution of the electronic density in HOMO in LA is located along the
structure where the double bonds are located, while in the LUMO it
is in the carboxylic acid. Also in the case of LAAM due to the pro-
tonation of the C6 the electronic density distribution is modified,
being located in HOMO in the carboxyl group and in LUMO in the
zone where the double bond is located. In addition, Fig. 7 shows
that the most susceptible site for electrophilic attack occur at the C6
which is protonated to obtain the structure LAAM. The calculated
values for the above mentioned descriptors are reported in Table 6.
All the descriptors predict a higher efficiency for protonated LA.
Lower ELUMO and DE values, and higher m and EHOMO values indicate
that LAAM is a better acceptor and donator of electrons, more
reactive, and has higher polarizability than LANM. Consequently,
LAAM is identified with higher electronegativity and global soft-
ness, which are all characteristics of an effective organic inhibitor.
DN is higher for LAAM than LANM; according to the literature, for
DN < 3:6 the inhibition efficiency increases as DN increases and
inverse is true for DN > 3:6 [59]. Table 6 shows that all values of DN
are lower that 3.6 for the three iron planes, indicating that the
molecule can donate electrons to iron surface favouring the for-
mation of adsorptive bonds [60].
Calculated molecular electrostatic potential (MEP) map of LANM
(a) and LAAM (b) are illustrated in Fig. 8. This plot reflects the
electron density distribution, which is the sum of all interactions
between the electrons and nuclei of the comprising atoms. Red
colour indicates the highly electronegative regions corresponding
to the lone pair of the carbonyl oxygen groups. On the contrary, the
so-called tail of the molecule, coloured in green, is more electro-
positive, that is the electron cloud is inclined towards the head of
the molecule (red region).
3.6. Mechanism of corrosion inhibition
Since the addition of LA to the 0.5 M H2SO4 solution mitigated
the corrosion of carbon steel, regardless of its concentration or
temperature, it can be concluded that LA adsorption has occurred.
The adsorption takes place via a strong attraction between the
partially negative charged carboxyl group of the inhibitor molecule
and the (oxidized) metal surface. As the inhibitor concentration
goes higher, the entropy of the adsorbates increases, i.e. the in-
hibitor molecules would align themselves in a more disorganized
manner on the surface (Fig. 9), which in turn results in lateral hy-
drophobic interactions among the adsorbed inhibitor molecules
and multi-layers interactions. Upon a dramatic increase in inhibi-
tion efficiency after 400 ppm solutions, the increase rate in effi-
ciency seems to slow down for higher concentrations. This is
usually the case for organic inhibitors, whose inhibition mechanism
involves formation of a protective film on the surface. After a
certain point in the concentration of inhibitor, the surface is almost
fully covered, thus the effect of adding more inhibitor becomes less
significant. Thus, in this research work we have demonstrated that
LA is an excellent corrosion inhibitor for 1018 carbon steel in
0.5 M H2SO4 in a very similar way that S. hispanica was reported to
be [27]. In this sense, although it is not possible to say that this
inhibitory ability S. hispanica is only due to the presence of LA
within its structure, it is possible to say that LA is one of the main
compounds contained in S. hispanica responsible for this ability. In
the case of S. hispanica we could not say the way it was adsorbed on
to 1018 carbon steel since it is a mixture of several compounds, in
the case of LA it is possible to say that this inhibitory ability is due
its high EHOMO value, chemical reactivity, and its great tendency to
542 I.A. Hermoso-Diaz et al. / Journal of Molecular Structure 1197 (2019) 535e546

Fig. 6. Optimized molecular structure, HOMO and LUMO orbitals of linoleic acid in neutral and acid media. Atomic colors represent: gray (C), white(H), red (O).

was left evolve 50 ps. Fig. 9 b shows its final configuration. The
configuration changes when the LA molecule is at 300 K which
provides the vertical position on the metal surface.

3.6.2. Analysis of LA deposition on the metallic surface

Fig. 7. The electrophilic and nucleophilic attack in the linoleic acid molecule using the
Fukui function. Atomic colors represent: gray (C), white(H) and red (O).
transfer electrons and a greater facility of modifying its electronic
configuration in presence on carbon steel.
3.6.1. Molecular dynamics analysis
In this part is shown trough molecular dynamics, the LA inter-
acion on the metal surface.
LA molecule obtained from quantum chemical analysis (Fig. 9 a)
Once the LA molecule was obtained, the final configuration of
the calculation was taken (Fig. 9 a) and placed on the metal surface
at a distance of 3.5 Å (without a defined position) Fig. 10 a. The
molecule is attracted to the metal surface and after 6 ps a bond has
been formed. The potential energy fluctuates around a given value
(Fig. 10 b), from which we can conclude that the system has reached
a stable configuration. Fig. 10 c shows the final configuration after
the molecular dynamics (~20 ps) and Fig. 10 d shows the final po-
sitions of the oxygen atoms belonging to the carboxylic acid. As it
can be seen, linoleic acid molecule acquires a more elongated
configuration compared to the free molecule. This is because the
biggest configurational change occurs where the double bonds are
located. Fig. 10 c also shows that once the bond between the LA
molecule and surface has been formed, one of the oxygen atoms
(OH) of the carboxylic acid is located in the so called “hollow” site
and the other oxygen is almost in the “on-top” site.
To demonstrate that there is chemisorption, we calculated the
Charge density difference defined by Ref. [61].

Table 6
The calculated quantum chemical descriptors for Linoleic acid in the neutral and acid form obtained using DFT at the B3LYP/6-31G basis set in aqueous phase.

Quantum Properties EHOMO (eV) ELUMO (eV) DE (eV) m (Debye) IE (eV) EA (eV) c (eV) h (eV) s DN(100) (110) (111)
Neutral 6.42 0.23 6.18 5.28 6.42 0.23 3.33 3.09 0.32 0.09 0.24 0.08
Acidic 7.58 3.35 4.23 13.00 7.58 3.35 5.47 2.11 0.47 0.36e0.15 -0.37
 I.A. Hermoso-Diaz et al. / Journal of Molecular Structure 1197 (2019) 535e546 543

Fig. 8. The calculated molecular electrostatic potential (MEP) map of LA in (a) neutral and (b) acidic media. Colour range (blue more positive, red more negative) oscillates for LANM
from 9.185  102 to 9.185  102 and from 0.179 to 0.179 for LAAM. Atomic colors represent: gray (C), white(H) and red (O).

Fig. 9. LA molecules (a) obtained with Gaussian in vacuum (b) obtained with molec-
ular dynamics at 300 K. Atomic colors represent: gray (C), white(H) and red (O).

Dr ¼ rAB  ðrA þ rBÞ
where rAB, rB, and rA are the total charge density difference of the
system (metallic surface and LA), the clean metallic surface, and the
isolated LA molecule, respectively. To calculate the charge density
difference, the positions of the atoms were taken as the average
positions during the last 0.5 ps of the molecular dynamics simu-
lation. Fig. 11 shows the calculated charge density difference. Blue
region denotes electronic accumulation and red region denotes the
electronic loss between the metallic surface and the LA molecule.
The charge density difference is located mostly between one of the
oxygens of the carboxylic acid (OH) and its closest Fe atom from
surface, giving a clear proof that a chemical bond has been formed.
The charge redistributions between the inhibitor molecule (LA) and
the metallic surface seem to be caused by the electron-donating
effects of the electron rich groups.
There is also some charge density difference located on some of
the LA atoms far from the interface molecule-surface. This can be
explained remembering that the biggest change in the LA molecule
(19) Fig. 10. Adsorption of a LA molecule on a Fe (100) surface. (a) Initial configuration
placed on the metal surface at a distance of 3.5 Å, (b) potential energy during simu-
lation, (c) final configuration after 6 ps and, (d) position of carboxylic acid oxygens on
the metal surface.
caused by its interaction with the Fe surface is located around these
atoms, and when we calculated the charge distribution for the LA
molecule, only a single point (no minimization of the structure) is
performed. This causes a charge redistribution around the atoms
where the double bonds are located.
Finally, the binding energy obtained from the metallic surface
with LA was 4.17 eV. This value is close to previously reported
results [62], where chemisorption was also found for this system by
using a different method. However, this value is smaller than the
one obtained by placing only one oxygen on the surface (5.60 eV).
3.6.3. Multi-layer formation
To simulate the multi-layer formation, we have taken the last
544 I.A. Hermoso-Diaz et al. / Journal of Molecular Structure 1197 (2019) 535e546
Fig. 11. Charge density difference for the system Fe suface-LA molecule. Blue regions
denote electronic accumulation and red regions denote electronic loss. A value of ±0.01
e Å3 is shown. Atomic colors represent: gray (C), white(H), red (O) and orange (Fe).
configuration from the LA-Fe (1 0 0) molecular dynamics simula-
tion and repeated the cell in the X direction, so, the system contains
two LA molecules. We let the system evolve during 10 ps and the
last configuration is used for the next part of the simulation.
Using the PACKMOL software [63] we inserted two more LA
molecules and 50 water molecules in the simulation box, with the
LA oxygen atoms pointing upwards. Fig. 12 a and b show two
different views of the initial configuration. The chosen configura-
tion would represents a density of approximately 0.036 molecules/
Fig. 12. LA molecules on metallic surface. (a) and (b) show different views of the initial configuration before molecular dynamics. (c) Potential energy versus simulation time. (d)
Final configuration after 20 ps. Atomic colors represent: gray (C), white(H), red (O) and orange (Fe).
Å2.
Finally, we let the system evolve during 20 ps, and by means of
the analysis of the potential energy (Fig. 12 c), we can conclude that
the system has reached a stable point (at this point the total energy
fluctuates around the same value). Fig. 12 d shows how the system
has formed a multi-layer. We have changed the atoms represen-
tation and repeated the cell 3 times along the X direction to show
more clearly how the multi-layer would look and that there is a
clear boundary between this layer and the water molecules.
4. Conclusions
Corrosion inhibition of different concentrations of linolenic acid
added to 0.5 M sulfuric acid solution on carbon steel specimens
were evaluated. Corrosion rate of 1018 carbon steel was efficiently
inhibited by Linolenic acid. The inhibition efficiency increases with
increasing the LA concentration, reaching its highest value in a
concentration of 1000 ppm, but decreases with rising the setting
temperature, obtaining the best efficiency value at 25
C. LA be-
haves as a mixed, type of corrosion inhibitor, however it has a
cathodic dominating effect. This inhibition is due to a physical
adsorption of LA by following a Langmuir type of adsorption
isotherm. Theoretical studies suggest that LA is a more effective
inhibitor in acidic media than in neutral environments. This was
corroborated since LA in acidic media had the highest EHOMO value,
the best chemical reactivity, the greatest tendency to transfer
electrons and a greater facility of modifying its electronic config-
uration in presence on carbon steel specimens according to its
chemical hardness value. In addition, results of molecular dynamics
indicated that there are a chemisorption and a formation of a
protective multilayer with the LA molecules in the metallic surface.
We have seen that a cheap, natural occurring compound obtained
from a seed has excellent corrosion inhibition properties, very
similar to those obtained with similar synthetic, toxic, expensive
compounds.
 I.A. Hermoso-Diaz et al. / Journal of Molecular Structure 1197 (2019) 535e546
Declarations of interest
None.
Acknowledgements
The authors would like to acknowledge the National Council of
Science and Technology (CONACyT) of Mexico for funding this
research.
References
[1] D. Dwivedi, K. Lepkova , T. Becker, Carbon steel corrosion: a review of key
surface properties and characterization methods, RSC Adv. 7 (2017)
4580e4610.
[2] Mo nica Corrales-Luna, Tu Le Manh, Mario Romero-Romo, Manuel Palomar-
Pardave , Elsa M. Arce-Estrada, 1-Ethyl 3-methylimidazolium thiocyanate ionic
liquid as corrosion inhibitor of API 5L X52 steel in H2SO4 and HCl media,
Corros. Sci. 153 (2019) 85e99.
[3] U.C. Nwaogu, C. Blawert, N. Scharnagl, W. Dietzel, K.U. Kainer, Influence of
inorganic acid pickling on the corrosion resistance of magnesium alloy AZ31
sheet, Corros. Sci. 51 (2009) 2544e2556.
[4] Priyanka Singh, D.S. Chauhan, S.S. Chauhan, G. Singh, M.A. Quraishi, Chemi-
cally modified expired Dapsone drug as environmentally benign corrosion
inhibitor for mild steel in sulphuric acid useful for industrial pickling process,
J. Mol. Liq. 286 (2019) 1e15.
[5] Moses M. Solomon, Saviour A. Umoren, Mumtaz A. Quraishi,
Mohammad Salman, Myristic acid based imidazoline derivative as effective
corrosion inhibitor for steel in 15% HCl medium, J. Colloid Interface Sci. 551
(2019) 47e60.
[6] Chunxiao Chai, Yanhua Xu, Dongyi Li, Xiaowei Zhao, Ying Xu, Lei Zhang,
Yufeng Wu, Cysteamine modified polyaspartic acid as a new class of green
corrosion inhibitor for mild steel in sulfuric acid medium: synthesis, elec-
trochemical, surface study and theoretical calculation, Prog. Org. Coat. 129
(2019) 159e170.
[7] M. Abd El-Raouf, E.A. Khamis, Maram T.H. Abou Kana, Nabel A. Negm, Elec-
trochemical and quantum chemical evaluation of new bis (coumarins) de-
rivatives as corrosion inhibitors for carbon steel corrosion in 0.5 M H2SO4,
J. Mol. Liq. 255 (2018) 341e353.
[8] G. Babaladimath, Vishalakshim Badalamoole, S.T. Nanibewoor, Electrical
conducting Xanthan gum-graft-polyaniline as corrosion inhibitor for
aluminium in hydrochloric acid environment, Mater. Chem. Phys. 205 (2018)
171e179.
[9] Sumayah Bashir, Vivek Sharma, Hassane Lgaz, Ill-Min Chung, Ambrish Singh,
Ashish Kumar, The inhibition action of analgin on the corrosion of mild steel
in acidic medium: a combined theoretical and experimental approach, J. Mol.
Liq. 263 (2018) 454e462.
[10] M. Chellouli, D. Chebabe, A. Dermaj, H. Erramli, N. Bettach, N. Hajjaji,
M.P. Casaletto, C. Cirrincione, A. Privitera, A. Srhiri, Corrosion inhibition of iron
in acidic solution by a green formulation derived from Nigella sativa L, Elec-
trochim, Acta 204 (2016) 50e59.
[11] G. Gece, Drugs: a review of promising novel corrosion inhibitors, Corros. Sci.
53 (2011) 3873e3898.
[12] P.B. Raja, M.G. Sethuraman, Natural products as corrosion inhibitor for metals
in corrosive media- A review, Mater. Lett. 62 (2008) 113e116.
[13] B. Sanyal, Organic compounds as corrosion inhibitors in different environ-
mets- A review, Prog. Org. Coat. 9 (1981) 165e236.
[14] S. Varvara, R. Bostan, O. Bobis, L. Gaina, F. Popa, V. Mena, R.M. Souto, Propolis
as a Green corrosion inhibitor for bronze in weakly acidic solution, Appl. Surf.
Sci. 426 (2017) 1100e1112.
[15] A. Saxena, D. Prasad, R. Haldhar, G. Singh, A. Kumar, Use of Sida cordifolia
extract as green corrosion inhibitor for mild steel in 0.5M H2SO4, J. Env.
Chem.Eng. 6 (2018) 694e700.
[16] J. Xiong, D.K.X. Grant Chen, Superhydrophobic honeycomb-like cobalt stearate
thin films on aluminium with excellent anti-corrosion properties, Appl. Surf.
Sci. 407 (2017) 361e370.
[17] M.K. Bagga, R. Gadi, O.S. Yadav, R. Kumar, R. Chopra, G. Singh, Investigation of
phytochemical components and corrosion inhibition property of Ficus race-
mose stem extract on mild steel in H2SO4 medium, J. Environ. Chem. Eng. 4
(2016) 4699e4707.
[18] A.S. Fouda, K. Shalabi, A.A. Idress, Ceratonia siliqua extract as a green corro-
sion inhibitor for copper and brass in nitric acid solutions, Green Chem. Lett.
Rev. 8 (2015) 17e29.
[19] Z.V.P. Murthy, K. Vijayaragavan, Mild steel corrosion inhibition by acid extract
of leaves of Hibiscus sabdariffa as a green corrosion inhibitor and sorption
behavior, Green Chem. Lett. Rev. 7 (2014) 209e219.
[20] G. Khan, K.Md, S. Newaz, W.J. Basirun, H.B.M. Ali, F.L. Faraj, G.M. Khan,
Application of natural product extracts as green corrosion inhibitors for
metals and alloys in acid pickling processes- a review, Int. J. Electrochem. Sci.
10 (2015) 6120e6134.
[21] R. Haldhar, D. Prasad, A. Saxena, Myristica fragrans extract as an eco-friendly
545
corrosion inhibitor for mild steel in 0.5M H2SO4 solution, J. Env. Chem. Eng. 6
(2018) 2290e2301.
[22] K.K. Anupama, K. Ramya, K.M. Shainy, Abraham Joseph, Adsorption and
electrochemical studies of Pimenta dioica leaf extracts as corrosion inhibitor
for mild steel in hydrochloric acid, Mater. Chem. Phys. 167 (2015) 28e41.
[23] M. Hazwan Hussin, Afidah Abdul Rahim, Mohamad Nasir Mohamad Ibrahim,
Nicolas Brosse, Improved corrosion inhibition of mild steel by chemically
modified lignin polymers from Elaeis guineensis agricultural waste, Mater.
Chem. Phys. 163 (2015) 201e212.
[24] Naoual El Hamdani, Rabiaa Fdil, Mustapha Tourabi, Charafeddine Jama, Fouad
Bentiss, Alkaloids extract of Retama monosperma (L.) Boiss. seeds used as novel
eco-friendly inhibitor for carbon steel corrosion in 1 M HCl solution:Electro-
chemical and surface studies, Appl. Surf. Sci. 357 (2015) 1294e1305.
[25] Bruria Heuer, Zohara Yaniv, Israela Ravina, Effect of late salinization of chia
(Sal_ia hispanica), stock (Matthiola tricuspidata) and evening primrose
(Oenotherabiennis) on their oil content and quality, Ind. Crops Prod. 15 (2002)
163e167.
[26] P.G. Peiretti, F. Gai, Fatty acid and nutritive quality of chia Salvia hispanica L.
seeds and plant during growth, Anim. Feed Sci. Technol. 148 (2009) 267e275.
[27] I.A. Hermoso-Diaz, J.G. Gonzalez-Rodriguez, J. Uruchurtu-Chavarin, Use of EIS
and electrochemical noise fractal analysis to study Salvia hispanica as green
corrosion inhibitor for carbon steel, Int. J. Electrochem. Sci. 11 (2016)
4253e4266.
[28] Z. Liyun, Histidine and histidine dimer as green inhibitors for carbon steel in
3wt% sodium chloride solution; Electrochemical, XPS and quantum chemical
calculation studies, Int. J. Electrochem. Sci. 13 (2018) 2136e2153.
[29] X. Zheng, S. Zhang, W. Li, M. Gong, L. Yin, Experimental and theoretical studies
of two imidazolium-based ionic liquids as inhibitors for mild steel in sulfuric
acid solution, Corros. Sci. 95 (2015) 169e179.
[30] Y. Resit, An electrochemical and theoretical evaluation of 4,6-diamino-2-
pyrimidinethiol as a corrosion inhibitor for mild steel in HCl solutions, Cor-
ros. Sci. 90 (2015) 544e553.
[31] S. Miertus, E. Scrocco, J. Tomasi, Electrostatic interaction of a solution with a
Continuum a direct utilization of Ab initio molecular potentials for the pre-
vision of solvent effects, Chem. Phys. 55 (1981) 117e129.
[32] G. Gece, The use of quantum chemical methods in corrosion inhibitor studies,
Corros. Sci. 50 (2008) 2981e2992.
[33] I.B. Obot, D. D Macdonald, Z.M. Gasem, Density functional theory (DFT) as a
powerful tool for designing new organic corrosion inhibitors. Part 1: an
overview, Corros. Sci. 99 (2015) 1e30.
[34] M.M. Elstner Elstner, D. Porezag, G. Jungnickel, J. Elsner, M. Haugk,
T. Frauenheim, S. Suhai, G. Seifert, Phys. Rev. B 58 (1998) 7260.
[35] G. Zheng, H.A. Witek, P. Bobadova-Parvanova, S. Irle, D.G. Musaev,
R. Prabhakar, K. Morokuma, M. Lundberg, M. Elstner, C. Kohler,
T.J. Frauenheim, Chem. Theory and Comput 3 (2007), 1349-136.
[36] C. Verna, L.O. Olasunkanmi, E.E. Ebenso, M.A. Quraishi, Adsorption charac-
teristics of Green 5-arylaminomethylene pyrimidine-2,4,6-triones on mild
Steel Surface in acidic medium: experimental and computational approach,
Results in Physics 8 (2018) 657e670.
[37] M.L. Free, Understanding the effect of surfactant aggregation on corrosion
inhibition of mild steel in acid medium, Corros. Sci. 44 (2002) 2865e2870.
[38] Z. Tao, S. Zhang, W. Li, B. Hou, Corrosion inhibition of mild steel in acidic
solution by some oxo-triazole derivatives Corros, Sci 51 (2009) 2588e2595.
[39] S.A. Pauline, S. Sahila, C. Gopalakrishnan, S. Nanjundan, N. Rajendran, Syn-
thesis, characterization and corrosion protection property of terpolymers
derived from poly(MAn-co-MMA) containing benzimidazole derivative as
pendant group, Prog. Org. Coat. 72 (2011) 443e452.
[40] F.B. Growcock, R.J. Jasinski, Time-resolved impedance spectroscopy of mild
steel in concentrated hydrochloric acid, J. Electrochem. Soc. 136 (1989)
2310e2314.
[41] S.J. Chiao, C.A. Mann, Nitrogen-Containing organic inhibitors of corrosion, Ind.
Eng. Chem. 39 (2017) 910e918.
[42] N. Hackerman, A.C. Makrides, Action of polar organics inhibitors in acid
dissolution of metals, Ind. Eng. Chem. 46 (1954) 523e527.
[43] C.G. Liu, K.G.H. Desai, X.G. Chen, H.J. Park, Linolenic acid-modified chitosan for
formation of self-assenbled nanoparticles, J. Agric. Food Chem. 53 (2005)
437e441.
[44] F. Bentiss, M. Traisnel, M. Lagrenee, The substituted 1,3,4-oxadiazoles: a new
class of corrosion inhibitors of mild steel in acidic media, Corros. Sci. 42 (2000)
127e146.
[45] A. Popova, Temperature effect on mild steel corrosion in acid media in
presence of azoles, Corros. Sci. 49 (2007) 2144e2158.
[46] Y.J. Tan, S. Bailey, B. Kinsella, The monitoring of the formation and destruction
of corrosion inhibitor films using electrochemical noise analysis, Corros. Sci.
38 (1996) 1681e1695.
[47] M. Hernandez, J. Genesca, J. Uruchurtu, A. Barba, Correlation between elec-
trochemical impedance and noise measurements of waterborne coatings,
Corros. Sci. 51 (2009) 499e510.
[48] Manilal Murmu, Sourav Kr Saha, Naresh Chandra Murmu, Priyabrata Banerjee,
Effect of stereochemical conformation into the corrosion inhibitive behaviour
of double azomethine based Schiff bases on mild steel surface in 1 mol L-1 HCl
medium: an experimental, density functional theory and molecular dynamics
simulation study, Corros. Sci. 146 (2019) 134e151.
[49] L.W. Vasconcelos, I.C.P. Margarit, O.R. Mattos, F.L. Fragata, A.S.B. Sombra,
Inhibitory properties of calcium exchanged silicaepoxy paintings, Corros. Sci.
546 I.A. Hermoso-Diaz et al. / Journal of Molecular Structure 1197 (2019) 535e546
43 (2001) 2291e2303.
[50] E.E. Ebenso, T. Arslan, F. Kandermirli, N. Caner, I. Love, Quantum chemical
studies of some rhodanine azosulpha drugs as corrosion inhibitors for mild
steel in acidic medium, Int. J. Quantum Chem. 110 (2010) 1003e1018.
[51] G. Gece, The use of quantum chemical methods in corrosion inhibitor studies,
Corros. Sci. 50 (2008) 2981e2992.
[52] K.F. Khaled, M.A. Amin, Computational and electrochemical investigation for
corrosion inhibition of nickel in molar nitric acid by piperidines, J. Appl.
Electrochem. 35 (2008) 1609e1621.
[53] Z. Zho, R.G. Parr, Activation Hardness: new index for describing the orienta-
tion of electrophilic aromatic substitution, Am. Chem. Soc. 112 (1990)
5720e5724.
[54] R.G. Pearson, Absolute electronegativity and hardness correlated with mo-
lecular orbital theory, in: Proc. Natl. Acad. Sci. U. S. A 83, 1986, pp. 8440e8441.
[55] M. Bouklah, N. Benchat, A. Aouniti, B. Hammouti, M. Benkddour, M. Lagrenee,
H. Vezin, F. Bentiss, Effect of the substitution of an oxygen atom by sulphur in
a pyridazinic molecule towards inhibition of corrosion of steel in 0.5 M H2SO4
medium, Prog. Org. Coat. 51 (2004) 118e124.
[56] I.B. Obot, N.O. Obi-Egbedi, Theoretical study of benzimidazole and its de-
rivatives and their potential activity as corrosion inhibitors, Corros. Sci. 52
(2010) 657e660.
[57] S. Zor, M. Saracoglu, F. Kandermirli, T. Arslan, Inhibition effects of amides on
the corrosion of copper in 1.0 M HCl: theoretical and experimental studies,
Corrosion 67 (2011) 125003.
[58] V.S. Sastri, J.R. Perumareddi, Molecular orbital theoretical studies of some
organic corrosion inhibitors, Corros. Sci. 53 (1997) 617e622.
[59] W. Yang, R.G. Parr, Hardness, softness and the fukui function in the electronic
theory of metals and catalysis, Proc. Natl. Acad. Sci. U.S.A. 82 (1985)
6723e6726.
[60] M.K. Awad, M.R. Mustafa, M.M.A. Elnga, Computational simulation of the
molecular structure of some triazoles as inhibitors for the corrosion of metal
surface, J. Mol. Struct. Theochem 959 (2010) 66e74.
[61] T.A. Baker, C.M. Friend, E. Kaxiras, Nature of Cl bonding on the Au (111)
surface: evidence of a mainly covalent interaction, J. Am. Chem. Soc. 130
(2008) 3720e3721.
, C. Matta, C. Minfray, T. Le Mogne, R. Iovine, Y. Obara, J.M. Martin,
[62] S. Loehle
Mixed lubrication of steel by C18 fatty acids revisited. Part II: influence of
some key parameters, Tribol. Int. 94 (2016) 207e216.
[63] L. Martínez, R. Andrade, E.G. Birgin, J.M. Martínez, Packmol: a package for
building initial configurations for molecular dynamics simulations, J. Comput.
Chem. 30 (2009) 2157e2164.