Heliyon 5 (2019) e02759

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Heliyon
journal homepage: www.heliyon.com

Research article

Quantum chemical and experimental evaluation of the inhibitory action of

two imidazole derivatives on mild steel corrosion in sulphuric acid medium
M. Ouakki a, M. Galai b, *, M. Rbaa c, A.S. Abousalem d, e, B. Lakhrissi b, E.H. Rifi f, M. Cherkaoui a
a
Laboratory of Materials, Electrochemistry and Environment (LMEE), Faculty of Sciences, Ibn Tofail University, PB. 133-14000, Kenitra, Morocco
b
Laboratory of Materials Engineering and Environment: Modelling and Application (LMEEMA), Faculty of Sciences, Ibn Tofail University, PB. 133-14000, Kenitra,
Morocco
c
Laboratory Agro-Resources, Polymers and Process Engineering, Faculty of Sciences, Ibn Tofail University, PB. 133-14000, Kenitra, Morocco
d
Chemistry Department, Faculty of Science, Mansoura University, El-Mansoura, 35516, Egypt
e
Quality Control Lab, Operation Department, Jotun, Egypt
f
Laboratory of Organic Synthesis and Extraction Processes (LOSEP), Faculty of Sciences, Ibn Tofail University, PB. 133-14000, Kenitra, Morocco

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

Keywords: The adsorption and corrosion inhibition properties of two imidazole derivatives namely, 2-(4-chlorophenyl)-
Materials chemistry 1,4,5-triphenyl-1H-imidazole (IM-Cl) and 1,4,5-triphenyl-2-(p-tolyl)-1H-imidazole (IM-CH3) for mild steel in 0.5
Electrochemistry M H2SO4 solution are studiedby electrochemical and computational calculations. The results obtained from the
Theoretical chemistry
electrochemical methods show that IM-Cl and IM-CH3imparted high resistance and behave as mixed type in-
H2SO4
Corrosion inhibition
hibitors. Inhibition efficiency (IE %) increases with the increase of inhibitors concentration to attain 96 % and
DFT 91% at 10
3 M of IM-Cl and IM-CH3 respectively. EISdatais analyzed to model the inhibition process through
Adsorption appropriate equivalent circuit model. Thermodynamic and kinetic parameters controlling the adsorption process
Imidazole are calculated and discussed. DFT calculations are carried out at the B3LYP levels of theory with 6-31G (d,p) basis
EIS stein gas and aqueous phase for neutral and protonated forms. Quantum chemical calculations section of the study
provides enough calculation and discussion on the relationship between corrosion inhibition and global reactivity
descriptors.

1. Introduction The nature of the metal can be modified by the use of metal coatings
(sacrificial or noble) or by the choice of a material from which a
Nowadays, the use of mild steel is widespread because of its excellent morecorrosion-resistant alloy is selected rather than a less corrosion-
structural and mechanical properties [Ouakki et al., 2018a,b]. Consid- resistant alloy. However, most frequently, the choice of materials is not
ering that acid solutions are also extensively used in the industry for acid an option because of the need to maintain other desirable properties
pickling processes, ore production, boiler cleaning, industrial cleaning, (such as mechanical strength), or is prohibited by cost. In such cases, the
acid descaling and petrochemical processes [El Faydy et al., 2018; Singh modification of the environment by the use of corrosion inhibitors be-
et al., 2016; Haque et al., 2017; Zhai et al., 2016]. Many metallic in- comes a possible means of corrosion control [Abdullah Dar, 2011].
stallations have suffered serious deterioration due to the aggressive na- However, the use of corrosion inhibitors has been found to be themos-
ture of these acid solutions. Various corrosion protection methods are teffective and thecheapest method for protection and prevention of steel
used to reduce its attack on the metallic materials. [Tebhji et al., 2005]. Generally, the inhibitors caninteractwith either
Several methods of corrosion protection have been considered so far anodic or cathodic corrosion reactions or/and form protective layers
by several authors [Gasiorek et al., 2018]. These methods can be classi- through adsorption onto the steel surface. The most efficient and effec-
fied into those that modify the potential of the electrode on the metal tive corrosion inhibitors are organic compounds containing functional
surface or those thatmodify the nature of the metal itself. Cathodic pro- electronegative groups, π-electrons, in conjugated double or triple bonds
tection and anodic protection aretwo methodsof corrosion control by or aromatic rings. There is also a specific interaction between functional
changing the electrode potential [McCafferty, 2010; Kautek, 1988]. groups containing hetero atoms like nitrogen, sulfur, oxygen, having free

* Corresponding author.
E-mail address: [email protected] (M. Galai).

https://doi.org/10.1016/j.heliyon.2019.e02759
Received 9 November 2018; Received in revised form 20 August 2019; Accepted 28 October 2019
2405-8440/© 2019 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
M. Ouakki et al. Heliyon 5 (2019) e02759

Table 1 corrosion inhibitors such aspyrazole [Hammouti et al., 1995; Aouniti

List of imidazole compounds used as corrosion inhibitors on corrosion of steel in et al., 1998; El-Ouafi et al., 2002], triazole [Salghi et al., 2000; Bentiss
acidic medium. et al., 1999], Triazepine Carboxylate [Alaoui et al., 2018], tetrazole
Structure of IUPAC name Metal Electrolyte [Kertit and Hammouti, 1996; Kertit et al., 1998], imidazopyridine
inhibitor [Ech-chihbi et al., 2016; Ech-chihbi et al., 2017] and imidazole [Galai
A 2-methyl-4-phenyl-1-tosyl-4, 5- P110 1 M HCl et al., 2016; Rbaa et al., 2017a,b]. Recently, imidazole has attracted a lot
dihydro-1H-imidazole [Zhang et al., carbon of attention in the field of metallic corrosion inhibition due to their
2015] steel interesting properties, low cost and their ease of synthesis [Verma et al.,
B N-vinylimidazolemonomer [Zhang Stainless 1N H2SO4
2018]. Imidazole derivatives have been evaluated as effective corrosion
et al., 2015] steel
C €
poly-N-vinylimidazole [Oncül et al., Stainless 1N H2SO4 inhibitors in various media by several investigators. Table 1 and Fig. 1
2011] steel displays some imidazole compounds used as corrosion inhibitorson
D 2-(1-(morpholinomethyl)-1Hbenzo[d] N80 steel 15% HCl corrosion of steel in acidic medium.
imidazol-2-yl)phenol (MBP) Most organic compounds inhibit corrosion via adsorption on the
2-(1-((piperazine-1-yl)methyl)-1H-
benzo[d]imidazol-2-yl)phenol
metal surface. This adsorption mainly depends on some physico-
(PzMBP) chemicalproperties of the molecule, related to its functional groups
2-(1-((piperidine-1-yl)methyl)-1H- (e.g. nitrogen, oxygen and sulfur atoms), aromaticity, the possible steric
benzo[d]imidazol-2-yl)phenol (PMBP) effects and electronic density. The aim of this work is to study the inhi-
[Yadav et al., 2016]
bition properties of two imidazole derivatives on mild steel corrosion in
0.5 M H2SO4 using gravimetric measurements, potentiodynamic polari-
zation curves, and electrochemical impedance spectroscopy. It also
lone pair of electrons and the metal surface, which play an important role aimsto predict the thermodynamic feasibility of these compounds on the
in inhibition. When two of these featuresare combined, increased inhi- steel surface. In addition, detailed investigation of temperature were also
bition can be observed [Moradi and Attar, 2014; Shivakumar and carried and discussed to improve a better understanding of the adsorp-
Mohana, 2012; Galai et al., 2017]. Recently many researchers have tion mechanism of the studied inhibitors.
reoriented their attention to the useof new organic compounds as

CH3
H2C CH

N
O S
O
N N
CH3
Ph N B
A HO
N

H2C CH N
n
R
N H H
N N
R= , ,
O N N
N H H
MBP PzMBP PMBP

C D
Fig. 1. Imidazole compoundsand some of its derivatives usedfor corrosion inhibition of mild steel in acid medium: (A) 2-methyl-4-phenyl-1-tosyl-4, 5- dihydro-1H-
imidazole, (B) N-vinylimidazolemonomer, (C) poly-N-vinylimidazole and (D) 2-(1-(morpholinomethyl), 1Hbenzo[d]imidazol-2-yl)phenol (MBP), 2-(1-((piperazine-1-
yl)methyl)-1H-benzo[d]imidazol-2-yl)phenol (PzMBP), 2-(1-((piperidine-1-yl)methyl)-1H-benzo[d]imidazol-2-yl)phenol (PMBP).

2
M. Ouakki et al. Heliyon 5 (2019) e02759

Table 2 previously [Gupta et al., 2016a,b]. The electrochemical impedance

Names, chemical structures and abbreviations of the studied Imidazole measurements (EIS) were performed on mild steel samplesat constant
compounds. potential (OCP) in the frequency range from 100 kHz to 100 mHz under
Inhibitor Molecular structures/chemical names Mol formulas (F.wt) potentiostatic conditions using an AC signals with amplitude of 10 mV
code peak to peak. The charge transfer resistance was calculated from Nyquist
IM-Cl 2-(4-chlorophenyl)-1,4,5-triphenyl-1H- C27H19N2Cl (406,90 g/ plot from which corrosion inhibition efficiency was calculated using the
imidazole mol) following Eq. (3) [Hermas and Morad, 2008]:
IM-CH3 1,4,5-triphenyl-2-(p-tolyl)-1H-imidazole C28H22N2 (386,48 g/

mol) Rp
Rp
ηimp% ¼  100 (3)
RP
2. Materials & methods 
Rp
Rp
θ¼  100 (4)
2.1. Materials and sample preparation RP

The aggressive medium (0.5 M H2SO4)was prepared by dilution of Where R0p and Rp are the charge transfer resistance values in the absence
analytical grade H2SO4 (98 wt.%) with distilled water. The concentra- and presence of the inhibitors, respectively and θthesurface coverage,
tions of imidazole derivatives inhibitors in the work were set as 10
6 given by Eq. (4).
to10
3M and the blank solution was also prepared for comparison. Mild The Potentiodynamic polarization studies were performed on mild
steel samples (0.17 wt.% C, 0.37 wt.% Mn, 0.20 wt.% Si, 0.03 wt.% S, steel specimens by automatically changing the electrode potential from
0.01 wt.% P and balance Fe) were cut into 2.00 cm * 1.00 cm * 0.20 cm
900 to -100 mV/Ag/AgCl versus OCP at a scan rate of 1 mVs
1. The
for weight loss tests. For electrochemical experiments, the steel samples corrosion current density (icorr) was calculated by extrapolating the linear
were used with an exposed surface of 1.0 cm2 to the acid solution. Prior Tafel slopes of anodic and cathodic curves with referenceto the corrosion
to use, the steel samples were prepared by polishing with emery paper at potential. The inhibition efficiency was determined by using the
different grit sizes (from 180 to 2000), cleaned with distilled water and following Eq. (5) [Liu et al., 2009]:
ethanol, and dried in room temperature. The chemical structures of the  
icorr
icorr
studied inhibitors are shown in Table 2 and Fig. 2. ηpp% ¼   100 (5)
icorr

2.2. Weight loss experiments where i0corrand icorr are the corrosion current densities values in the
absence and presence of theinhibitor, respectively.
The weight loss experiments were achieved using the standard
method described earlier [Gupta et al., 2016a,b]. The corrosion rate was 2.4. Surface characterization by SEM/EDX
calculated using the following Eq. (1):
The determination of the nature of the formed film on the surface of
W
CR ¼ (1) the metal, exposed to 0.5 M H2SO4 solution during 6h in theabsence and
St
presence of the studied inhibitors, was realized by Scanning Electron
Where, W is the weight loss of mild steel sample, S is the area of mild steel Microscopy (Quanta FEG 450) coupled with EDX analyses. These ana-
sampleand t is theimmersion time (6 h). lyses were performed in foundationMAScIR.
The inhibition efficiency, ηCR%, is determined according to the-
following Eq. (2) 2.5. Computational details

CR
CRinh For the theoretical study, quantum chemical calculations were per-
ηCR% ¼  100 (2)
CR formed for IM-Cl and IM- CH3 to carry out the optimized geometry using
Gaussian 09 software [Sasikumar et al., 2015; Bedair et al., 2017]. The
where CR and CRinh are the corrosion rates in the absence and presence of
molecular structures in the ground state are optimized and the structural
theinhibitors, respectively.
parameters have been computed using density functional theory (DFT).
Theoretical calculations were performed with the hybrid B3LYP func-
2.3. Electrochemical measurements tional, i.e., a combination of the Becke's three parameters potential with
the hybrid correlation functional of Lee-Yang-Parr using 6-31G (d,p)
Electrochemical measurements were carried by the method described basis set level.

Fig. 2. Chemical structures of IM-Cl (A) and IM-CH3(B).

3
M. Ouakki et al. Heliyon 5 (2019) e02759

N N
CH3
Cl
N N

A B
Fig. 3. Mesomeric effect and inductive effect of compounds IM-Cl (A) and IM-CH3 (B).

The spatial distribution of the HOMO, LUMO, and Electrostatic Po-

Table 3
tential (ESP) maps are important to understand the adsorption prefer-
Corrosion rate (CR) Values and inhibition efficiency ηCR (%)of mild steel in 0.5 M
ences of the inhibitors [Lee et al., 1988; Becke, 1993; Parr and Yang,
H2SO4obtained from gravimetric measurementsat 298 K.
1989]. The corresponding quantum chemical descriptorsof molecules
Medium Concentration (M) CR (mg/cm2.h) ηCR (%)
both in gas and aqueous phase for neutral and protonated forms were
calculated including EHOMO, ELUMO, Energy gap, chemical hardness, H2SO4 0.5 M – 10.53  0.1 -
softness, electronegativity and chemical potential. Theseare highly IM-Cl 10
6 1,469  0.03 86,0
10
5 1,422  0.02 86,5
effective and useful tools in corrosion studies of metals. Other parameters 10
4 0,851  0.03 91,9
describing the local selectivity such as the local charge populations and 10
3 0,350  0.01 96,7
the condensed Fukui functions are also considered. IM-CH3 10
6 1,969  0.02 81,3
10
5 1,722  0.04 83,6
10
4 1,451  0.01 86,2
2.6. Molecular dynamic simulation 10
3 0,848  0.08 91,9

As part of the computational chemical studies, Materials Studio

software was used to carry out the MD simulation via the application of gravimetric experiments in the presence of different concentrations of
Monte Carlo simulations [Fouda et al., 2017a,b]. This method find inhibitors in 0.5 M H2SO4are presented in Table 3. The observed weight-
practical importance in corrosion inhibition studies because it predicts loss values of triplicate measurements are highly reproducible giving
the interaction mode of inhibitor molecules on the Fe (1 1 0) surface standard deviations. The resultsshow that the mild steel corroded
[Fouda et al., 2017a,b]. In this simulation process, the pure Fe crystal was severely in the uninhibited 0.5 M H2SO4 solution, whereas the presence
used and cleaved along (1 1 0) surface plane with a vacuum slab of 30 Å. of inhibitors reduced the dissolution rate considerably. Shahin et al.
The Fe (1 1 0) surface was first allowed to relaxation and then, enlarged pointed out in their work [Shahin et al., 2002] that the relative inhibition
to a (10  10) super cell. This provides a sufficient surface area for the efficiencies of the studied compounds can be rationalized qualitatively
interaction of inhibitor on metal surface. In order to make the MD under the assumptions that:
simulation closer to the real system, a simulation box with dimension of
24.82  24.82  42.25 Å3 contains 271 H2O, 6 H3O, 3 SO2
4 and 1 in- ✓ The corrosion inhibitionis essentially based on the coverage of the
hibitor molecule was created. The simulations were undertaken in metal surface by the inhibitor molecules, thus making the contact of
through the adsorption locator tool implemented in Material Studio the corrosive mediumdifficult;
software with COMPASS force field. Insights on the adsorption of the ✓ Attachment of the molecules on the metal surface is facilitated
tested inhibitors and Fe (1 1 0) surface were determined by the calcu- through the coordination of π-electron system to the metal atom;
lation of the interaction energies. ✓ The stability of the complex formed at the metal/solution interface is
somewhat related to the molecule's being planar.
3. Results and discussion
Both IM-Cl and IM- CH3 exhibited substantial protection efficiency for
3.1. Effect of substitution mild steel in 0.5 M H2SO4. As the concentration of the inhibitor is
increased %ηCR also increases. At higher concentration, Maximum inhi-
The IM-CH3 molecule has a negative value of the constant Hammett bition efficiencies of 96.7% and 91.9% were observed for IM-Cl and IM-
constant σp (- CH3; σp ¼ - 0,17) compared to the other substituents CH3respectively at 10
3 M. The %ηCR is almost leveled off and only slight
studied {(Cl; σp ¼ 0,23, H; σp ¼ 0, 0)}. This negative value has the variation is observed. This can be explained bythe adsorption of the IM-Cl
electron donor capacity for the IM-CH3 molecule in organic solvents. and IM- CH3onto mild steel surface resulting in the blocking of the re-
But in our case we worked in an acid medium (H2SO4) that affects the action sites. The increase in concentration of the inhibitor leads to the
molecular structure by protonation. Generally in the acidic medium the gradual formation of multilayers that further reduce the rate of corrosion
mesomeric effect comes into play instead of substituting Hammett. The from the attack of the corrosion active ions in the acid medium beyond
chlorine group (Cl) is an electron donor by mesomeric effect (þM). On what can be achieved with mono layer coverage below that concentra-
the other hand, the methyl (CH3) group is an electron donor by inductive tion [Amin et al., 2009].
effect (þI) Fig. 3. The mesomeric effect of chlorine creates an electro-
static/magnetic field that produces the molecule that promotes the 3.3. Electrochemical studies
adsorption of the chlorine molecule on the surface of the steel.
3.3.1. Open circuit potential
3.2. Gravimetric measurement The variances of OCP of the mild steel as a function of time in aerated
H2SO4 0.5 M solution, in the absence and presence of different concen-
Thecorrosion rate and inhibition efficiencies obtained from the trations of IM-Cl and IM-CH3after 30 min of immersionare shown in

4
M. Ouakki et al. Heliyon 5 (2019) e02759

-0,300 -0,300

-0,325 -0,325
Blnak Blank
-3
10 M -3
10 M
-0,350 -4 -0,350
(a) 10 M (b)
-4
10 M
-5
10 M -5
10 M

E (V/Ag/AgCl)
-6
-0,375 10 M -0,375 -6
10 M
E (V/Ag/AgCl)

-0,400 -0,400

-0,425 -0,425

-0,450 -0,450

-0,475 -0,475

-0,500 -0,500
0 200 400 600 800 1000 1200 1400 1600 1800 0 200 400 600 800 1000 1200 1400 1600 1800
time (s) time (s)

Fig. 4. Evolution of open circuit potential (OCP) versus time for mild steel in H2SO4 0.5 M with different concentrations of IM-Cl (a) and IM-CH3 (b) at 298 K.

3 3
10 10
(a) (b)

2
10
2 10

1
1
10
10
icorr (mA/cm )
icorr (mA/cm )

2
2

0
10
0
10

-1
10
-1
Blank H2SO4 0.5 M Blank H2SO4 0.5 M
10
-3
-3
10 M 10 M
-4
-4
10 M 10
-2 10 M
-5
-5
10 M 10 M
-2
10 -6
-6
10 M
10 M
-3
10
-0,9 -0,8 -0,7 -0,6 -0,5 -0,4 -0,3 -0,2 -0,1 -0,9 -0,8 -0,7 -0,6 -0,5 -0,4 -0,3 -0,2 -0,1
E (V/Ag/AgCl) E (V/Ag/AgCl)

Fig. 5. Polarization curves for mild steel recorded in 0.5 M H2SO4 for selected concentrations of the inhibitors IM-Cl (a) and IM-CH3 (b).

In acidic solutions, the anodic reaction is the movement of metal ions

Table 4
from the working electrode into thecorrosive solution, and the cathodic
Polarization parameters for mild steel in 0.5 M H2SO4in the absence and presence
reaction is the discharge ofthe ions in the electrolyte such as the reduc-
of different concentrations of IM-Cl and IM-CH3.
tion of hydrogen ions to form hydrogen gas. The inhibitors may affect
Inhibitor Conc. - Ecorrvs Ag/ icorr (μA/ -βc mV/ βa mV/ IE% either the anodic, cathodic, or both reactions. Since the anodic Tafel
(M) AgCl (mV) cm2) dec dec
slope (βa) and cathodic Tafel slope (βc) of imidazole were found to
Blank – 451 1850 99 121 - change with inhibitor concentration, the inhibitors affected both these
IM-Cl 10
6 444 255 114 132 86,2
reactions and referred to as mixed-type inhibitors. The adsorption of
10
5 442 237 116 136 87,2
10
4 431 155 118 133 91,6 inhibitors can affect the corrosion rate in two ways:
10
3 414 68,5 105 131 96,3
IM-CH3 10
6 446 320 99 125 82,7 ✓ by decreasing the available reaction area, the so-called geometric
10
5 449 270 94 132 85,4 blocking effect and
10
4 433 263 95 137 85,8
10
3 422 154 106 133 91,7
✓ by modifying the activation energy of the cathodic and/or anodic
reactions occurring in the inhibitor-free metal in the course of the
inhibited corrosion process.
Fig. 4. It was noticed that the addition of the inhibitors molecules induces
shift in OCP (i.e., Ecorr). It is a difficult task to determine which aspect of the inhibiting effect
is connected to the geometric blocking action and which are connected to
3.3.2. Polarization studies the energy effect. Theoretically, no shifts in Ecorrshould be observed after
In order to know the kinetics of anodic and cathodic reactions, po- addition of the corrosion inhibitors if the geometric blocking effect is
larization experiments were carried out potentiodynamically in unagi- stronger than the energy effect [De Souza and Spinelli, 2009]. It is
tated H2SO4 0.5 M solutions in the absence and presenceof different observed from Table 3 that the corrosion current density (icorr)decreases
concentrations of inhibitors and the obtained polarization curves are with increasing inhibitor concentration and it can be seen also that the
shown in Fig. 5. The electrochemical parameters derived from Tafel corrosion potentials (Ecorr) do not shift, which suggests that the both
curves are given in Table 4. inhibitors act as very good organic inhibitors for mild steel in 0.5M

5
M. Ouakki et al. Heliyon 5 (2019) e02759

250 100
(a) (b)
-3 -3
10 M 10 M
200 -4
10 M 80 -4
10 M
-5
10 M -5
10 M
-6 -6
10 M 10 M
Fitting curves Fitting curves
60

- ZIm (Ω.cm )
150
- ZIm (Ω.cm )

2
2

40
100

20
50

0
0

0 50 100 150 200 250 300 350 0 20 40 60 80 100 120 140 160
2 2
ZRe (Ω.cm ) Z (Ω.cm )

7
Blank H2SO4 0.5 M
6 Fitting curves

5 (c)

4
-Zim(Ω cm²)

-1
0 2 4 6 8 10 12
ZRe(Ω cm²)

Fig. 6. Nyquist plots of mild steel in 0.5 M H2SO4 (c) solution in the absence and presenceof various concentrations of IM-Cl (a) and IM-CH3 (b) at 298K.

H2SO4 solution. presented as EIS Nyquist and Bode's plots in Figs. 6 and 7. In the Nyquist
The Tafel curves in solutions containing inhibitors do not shift, which plot (Fig. 6) a depressed charge-transfer semicircle was appeared which
suggests that the inhibitors could also suppress the anodic and cathodic is related to a single time constant shown in Bode's plot [El Mehdi et al.,
reactions. An inhibitor can be classified as an anodic or cathodic type 2003; Wang et al., 2003]. But in blank solution and (10
4,10
5) M of
inhibitor when the displacement in Ecorr value is >85 mV [Kowsari et al., IM-Cl and (10
3,10
4) M of IM-CH3, we note a first loop at high fre-
2014]. In the present study, it is found that the displacement exhibited by quency (HF) attributed to the relaxation of the double layer capacitance
the studied inhibitors was <85 mV, which indicates that IM-Cl and in parallel with the charge transfer resistance Rt inversely proportional to
IM-CH3 act as mixed type inhibitors. Otherwise, the anodic and cathodic the corrosion rate and an inductive loop at low frequency (LF) [Lgaz
tafel slope values of inhibited solution have changed with respect to et al., 2018a,b; Singh et al., 2009]. The LF inductive loop may be
uninhibited solution, which also states that the tested inhibitors are of attributed to the relaxation process obtained by adsorption species as
þ
mixed type. The higher values of βa compared to those of βc at each SO2
4 ads and H ads on the electrode surface [Singh and Quraishi, 2010a,
concentration of the inhibitor further confirm that these inhibitors are b]. It can be observed from Fig. 6 that the impedance response of IM-Cl
regarded as mixed type inhibitors with anodic predominance. The ob- and IM-CH3has been considerably increased with increasing concentra-
tained inhibition efficiencies values are in good agreement with those tion of inhibitors to the electrolyte. The results obtained from EIS were of
obtained bygravimetric measurements. the similar orderas those obtained from polarization and gravimetric
measurements.
3.3.3. EIS studies The capacitive behavior of mild steel in the presence of IM-Cl and IM-
Electrochemical impedance spectroscopy (EIS) technique is popularly CH3could be visualized from Bode's plot (Fig. 7). A destructive outbreak
used in corrosion inhibitionto study the electrical properties of the of sulfuric acid corroded the mild steel and made the metal surface highly
metal/solutioninterface. The mechanistic information of the system asymmetrical, which could be explained out bysmall phase angle. On the
under subject is provided by the nature and shape of the impedance contrary, adsorption of the inhibitors on mild steel surface effectively
curves [Asan et al., 2006]. This technique is extensively used in corrosion lowered surface irregularities; additionally, we address the evolution of
inhibition investigations. The electrochemical characteristics of mild phase angle by measuring their values at arbitrarily chosen frequency
steel in 0.5 M H2SO4 solution at 298 K in the absence and presenceof (100 Hz) (Fig. 7). Clearly, with increasing concentration of both in-
different concentrations of IM-Cl and IM-CH3 (corrosion inhibitors) are hibitors the phase angle values dramatically increases as well.

6
M. Ouakki et al. Heliyon 5 (2019) e02759

40 30
2,4
2,5 30 20
2,2
20 10
2,0
10 0
2,0
1,8
0

phase angle α /°
-10

phase angle α /°
log Z (Ω.cm2)

1,6

log Z (Ω.cm2)
-10
1,5 -20
1,4
-20
-30
1,2
-30
1,0 (a) 1,0 (b) -40
-40
-3
10 M 0,8
-3
10 M -50
-4
-50 -4
10 M 10 M
0,5 -5
-60 0,6 -5 -60
10 M 10 M
-6 -6
10 M 10 M
-70 0,4 -70
Fitting curves Fitting curves
0,0 -80 0,2 -80
0,1 1 10 100 1000 10000 100000 0,1 1 10 100 1000 10000 100000
log f (Hz) log f (Hz)

10

1,2 Blank H2SO4 0.5 M

Fitting curves
0
1,0 (c)

-10
log Z (Ω.cm )

phase angle α /°
2

0,8

-20
0,6

-30
0,4

0,2 -40

10 100 1000 10000 100000

log f (Hz)

Fig. 7. Bode's plots and Phase angle values at 100 Hz at 298 K for mild steel in 0.5 M H2SO4 (c) solution in the absence and presence of various concentrations of IM-Cl
(a) and IM-CH3 (b).

Fig. 8. The electrochemical equivalent circuit used to fit the impedance and bode's spectra/(a) charge-transfer semicircle, (b) charge-transfer semicircle and an
inductive loop.

Furthermore, whatever the concentration used, the phase angle values describes the non-ideal capacitor [Lgaz et al., 2018a,b]. This indicates
are higher than that of the blank but lower than - 90 which also anincreased capacitance of the interference due to the presence of

Table 5
Impedance parameters for mild steel in 0.5 M H2SO4 at 298 K in the absence and presence ofvarious concentrations of IM-Cl and IM-CH3.
Inhibitor Conc (M) Rs (Ω.cm2) Q (Ω
1cm2s
1) n Cdl (μF cm
2) Rp (Ω.cm2) RL (Ω.cm2) L (H) χ2 Ө EI%

Blank – 1.6  0.2 430  0.7 0.830  0.003 180.0 11.7  0.3 2.17  0.1 0.48  0.02 0.06 - -
IM-Cl 10
6 2.6  0.3 179  1.4 0.892  0.005 108.0 83.98  0.5 - - 0.07 0.861 86,1
10
5 2.7  0.3 149  1.2 0.881  0.01 83.77 89.62  1.4 6.17  0.18 6.96  0.37 0.05 0.869 86,9
10
4 2.5  0.2 117  0.9 0.905  0.01 75.92 130.9  1.5 15.44  0.2 11.24  0.30 0.08 0.911 91,1
10
3 2.9  0.2 124  0.2 0.887  0.005 82.14 306.0  0.4 - - 0.06 0.962 96,2
IM-CH3 10
6 2.6  0.2 265  2.3 0.887  0.05 158.9 64.68  0.5 - - 0.07 0.819 81,9
10
5 3.2  0.3 230  1.8 0.888  0.03 139.0 77.58  0.4 - - 0.08 0.849 84,9
10
4 3.3  0.3 202  1.9 0.894  0.04 124.0 80.19  1.5 6.93  0.2 7.67  0.4 0.09 0.854 85,4
10
3 3.2  0.2 154  1.5 0.901  0.05 98.92 132.1  1.4 13.17  0.3 12.53  0.33 0.1 0.911 91,1

7
M. Ouakki et al. Heliyon 5 (2019) e02759

adsorbed inhibitors molecules at the interface [Oguzie et al., 2007]. 1,2x10

-3

Solution with IM-Cl

EIS and bode's spectra were analyzed using the equivalent circuits in Solution with IM-CH3
Fig. 8. 1,0x10
-3 Fitting curves
The equivalent circuits used to model mild steel/solution interface for
these systems are presented in Fig. 8. -4
8,0x10
The Table 5 results described below can be interpreted in terms of the

Cinh/θ (mol/l)
equivalent circuitof the electrical double. The results show that the Rp
-4
values increases and Cdl decreases with increasing inhibitors concentra- 6,0x10

tion, which is attributed to the increase in surface coverage of mild steel

-4
by inhibitor molecules leadingto a decrease in the corrosion rate [El 4,0x10
Ouali et al., 2010; Singh and Quraishi, 2010a,b]The decreased value of
Cdl attributed towards decrease in local dielectric constant and/or an 2,0x10
-4

increase in the thickness of the protective layer, suggesting thatIM-Cl and

IM-CH3 act byadsorptionmechanism at mild steel/acid interface [Gerengi 0,0
et al., 2012]. The capacitance of thedouble layer (Cdl) is linkedwith the
thickness ofthe protective layer (d) by the following relation (6): 0,0 -4
2,0x10 4,0x10
-4 -4
6,0x10 8,0x10
-4 -3
1,0x10
Cinh (mol/l)
εε0 S
Capacitance Cdl ¼ (6)
e Fig. 9. Langmuir adsorption isotherm for mild steel in 0.5 M H2SO4 solution
containing different concentrations of IM-Cl and IM-CH3 at 298 K.
Where Ɛ and Ɛo are dielectric constant of the medium and vacuum
permittivity, e is the thickness of the protective layer and S is the surface
area of the electrode. Table 6
With increase in the concentration of IM-Cl and IM-CH3 the Cdl values Thermodynamic parameters for IM-Cl and IM-CH3adsorption on mild steel sur-
are decreasing (Table 5) which depicts that the thickness of theprotective face in0.5M H2SO4 at 298 K.
layer (e) is increasing. The values of n parameter are known as “phase
Inhibitor Kads (L/mol) ΔGads (Kj/mol) R2 Slope
shifts” which are often related to the degree of surface heterogeneity
4
according to the following Eq. (7) [Ouakki et al., 2018a,b]: IM-Cl 43.4 10 -42.11 0.99999 1.03755
IM-CH3 37.4 104 -41.74 0.99998 1.09548

Cdl ¼ Qðωmax Þα
1 (7)

values are listed in Table 6. The isotherm is given by the following Eq.
Where, ωmax ¼2π fmax is the angular frequency at the maximum value of (8).
the imaginary part of the impedance spectrum, Q is the admittance of the
constant phase element (CFE) in Ω
1 cm2 s
1. Cinh 1
¼ þ Cinh (8)
The values of the n parameter for inhibited systems are close to unity θ Kads
at higher concentrations implying thatthe interface behaves nearly
capacitive [Singh et al., 2009; Quartarone et al., 2008]. The inhibition where Cinh is the concentration of inhibitor, θ is the surface coverage
efficiencies of both products at 10
3 M reached 96.2% of IM-Cl and degree, and Kads is the adsorptive equilibrium constant. The linear re-
91.1% of IM-CH3, indicating that the synthesized compounds act as an lationships of Cinh/θ versus Cinhare depicted in Fig. 9.
effective corrosion inhibitors for mild steel in H2SO4 medium. The value of Kads was found to be large, namely, 43.4 104 (L/mol)of
IM-Cl and 37.4 104 (L/mol)of IM-CH3, implying efficient adsorption and
3.3.4. Adsorption isotherm and effect of temperature based on which the free energy of adsorption (ΔGads) was calculated
using the following Eq. (9):
3.3.4.1. Adsorption parameters. The interaction between the both in-
ΔGads ¼
RT lnð55:55  Kads Þ (9)
hibitor molecules and steel surface is best explained by adsorption iso-
therms. The efficiency of inhibitors is dependent mainly on their Where, R is universal gas constant and the absolute temperature is
adsorption ability on the metal surface. The adsorption process involves denoted by T. The molar concentration of water is expressed in mol/L
replacement of water molecules at a metal solution interface [Gabrielli, and in solution its value is 55.5 [Flis and Zakroczymski, 1996].
1980; Kalman et al., 1994; El-Taib Heakal et al., 2017] according to the Generally, values ofΔGads around or less than
20 kJ mol
1suggested
following process: that the adsorption process is related with the electrostatic interaction
Org(sol) þ nH2O(ads) → Org(ads) þ nH2O(sol) between charged inhibitor molecules and the charged surface of the
metal, which is termed as “physisorption” [Bellman and Stamm, 2008;
where Org(sol) and Org(ads) are the organic molecules in the solution and Bentiss et al., 2005]; while values around or higher than
40 kJ mol
1
adsorbed on the metal surface, respectively, and n is the number of water are associated with sharing of charge or transfer from the inhibitor
molecules replaced by the organic molecules. In order to acquire more molecules to the metal surface to form a coordinate type of metal bond
information regarding the interaction of these compounds and the sur- termed as “chemisorption” [Mu et al., 2006; Eteram and Aisha, 2008].
face of mild steel, it is important todetermine the mode of adsorption and In the present case of the adsorption of imidazole derivatives, ΔGads
the type of adsorption isotherm as there are ten different adsorption was determined to be -42.11 kJ/mol of IM-Cl and -41.74 kJ/mol of IM-
isotherms (Langmuir, Temkin, Freundlich, Frumkin, Modified, Langmuir, CH3, suggesting the chemical adsorption of the inhibitor molecules into
Henry, Viral, Damaskin, Volmer, and Flory–Huggins) [Oguzie et al., the corroding metal surface.
2004; Bellman and Stamm, 2008; Mu et al., 2006] which were tested for
their fit to the experimental data for the current investigation. 3.3.4.2. Temperature kinetics. The influence of the reaction temperature
The best description of the adsorption behavior of studied inhib- on the potentiodynamic polarization curves in the absence and presence
itorswas explained by Langmuir adsorption isotherm (Fig. 9) [Kalman of 10
3 M of IM-Cl and IM-CH3inhibitor's for mild steel in 0.5 M H2SO4 in
et al., 1994], as the average linear regression coefficient values (R2) the temperature range 298  2 K to 328  2 K are represented in Figs. 10
obtained for IM-Cl and IM-CH3and slope are very close to unity. All the and 11.

8
M. Ouakki et al. Heliyon 5 (2019) e02759

Blank solution Ea
lnicorr ¼ ln A
(11)
2
RT
10
The change of enthalpy {ΔHa} and entropy {ΔSa} for the formation of
activated complex in the transition state was obtained from the transition
1
state Eq. (12) [Singh and Quraishi, 2010a,b; Yadav et al., 2013].
10
      
icorr (mA/cm²)

icorr R ΔSa ΔHa

ln ¼ ln þ
(12)
T hNa R RT
0
10
where icorr is the corrosion current density, A is the pre-exponential fac-
tor, h is the Planck's constant, Na is the Avogadro's number, Ea is the
-1 298 K apparent activation energy, R is the gas constant (R ¼ 8.314 J mol
1.
10
308 K K
1) and T is the absolute temperature.
318 K A plot of ln (icorr) vs 1000/T presented in Fig. 12a show straight line
328 K with slope of the line (-Ea/R). The values of Ea were calculated from the
-2
10 slope and given in Table 8. From the Table 8 it is clear that the Ea values
-0,9 -0,8 -0,7 -0,6 -0,5 -0,4 -0,3 -0,2 -0,1
E (V/Ag/AgCl) of solution containing 10
3 M of IM-Cl and IM-CH3 is higher than that in
case of uninhibited solution which may be attributed to the formation of
Fig. 10. Potentiodynamic polarization curves for mild steel immersedin 0.5 M compact barrier film on the mild steel surface [Shaban et al., 2016]. The
H2SO4(Blank) at various temperatures between (298–328  2 K). higher energy barrier for corrosion process in case of inhibited solutions
suggest that adsorbed inhibitor's film prevents the charge/mass transfer
There is a clear acceleration of both the cathodic and anodic reactions reaction occurring on the surface [Murulana et al., 2016] and thus pro-
with an increase in temperature. As it is observed from the polarization tecting metal from dissolution. The higher value of Ea for IM-Cl than that
parameters (Table 7), for mild steel, the corrosion current densities of IM-CH3can be attributed to the fact that IM-Cl is substituted by the
increased with the increase of temperature in 0.5 M H2SO4 solution in the donor group corresponding to the mesomeric effect (Cl) whereas IM-CH3
absence and presence of 10
3 M of the studied inhibitors. These results is substituted by an inductive effect group (CH3).
could be attributed to the acceleration of chemical process as the tem- A plot of ln (icorr/T) vs 1000/T (Fig. 12b) gave a straight line with
perature is increased such as electrochemical, chemical, transport [Nesic,
2007].
It is noted from Table 7 that, the inhibition efficiency reduced with Table 7
temperature rise, indicating chemical adsorption of the imidazole mol- Polarization parameters for mild steel in 0.5 M H2SO4 with 10
3 M of IM-Cl and
IM-CH3at various temperatures.
ecules on the mild steel surface [Okafor et al., 2008].
Name of the Temperature - Ecorr icorr μA -βc mV βa mV ηPP
3.3.5. Activation energy inhibitor K mV/Ag/ cm
2 dec
1 dec
1 %
AgCl
The thermodynamic and kinetic parameters includingthe apparent
activation energy (Ea), the enthalpy of activation (ΔHa) and the entropy Blank 298 451 1850 99 121 -
308 453 2250 92 114 -
of activation (ΔSa) for mild steel dissolution in 0.5 M H2SO4 solutions in
318 449 2480 96 102 -
the absence and presenceof 10
3M of IM-Cl and IM-CH3at 298–328 K 328 442 3340 102 97 -
were calculated from the Arrhenius Eq. (10) [Chetouani et al., 2005; IM-Cl 298 414 68,5 105 131 96,3
Ekanem et al., 2010]: 308 472 124 110 123 94.5
318 477 196 107 124 92.1
Ea 328 476 348 103 127 89.6
icorr ¼ Ae
RT (10) IM-CH3 298 422 154 106 133 91,7
308 484 227 105 135 89,9
Taking the logarithm of both sides of the Arrhenius Eq. (11) could be
318 485 306 103 137 87,6
obtained 328 482 484 99 140 85,5

2 2
(b)
10 10
(a)

1
10 10
1
icorr (mA/cm )
icorr (mA/cm )

2
2

0
10 0
10

298 K
10
-1 308 K
318 K -1
328 K 10 298 K
308 K
318 K
10
-2 328 K

-2
10
-0,9 -0,8 -0,7 -0,6 -0,5 -0,4 -0,3 -0,2 -0,1 -0,9 -0,8 -0,7 -0,6 -0,5 -0,4 -0,3 -0,2 -0,1
E (V/Ag/AgCl) E (V/Ag/AgCl)

Fig. 11. Potentiodynamic polarization curves for mild steel immersed in 0.5 M H2SO4 in the present of 10
3 M of IM-Cl (a) and IM-CH3 (b) at various temperatures
between (298–328  2 K).

9
M. Ouakki et al. Heliyon 5 (2019) e02759

2,5
8,0
2,0
7,5
1,5

ln(icorr/T) (mA.cm .K )
-1
7,0

-2
(a) Blank H2SO4 0.5 M 1,0 Blank H2SO4 0.5 M
ln (icorr) (mA/cm )
2

6,5 -3
10 M of IM-Cl -3
-3
10 M of IM-CH3 0,5 (b) 10 M of IM-Cl
-3
10 M of IM-CH3
6,0 Fitting curves
Fitting curves
0,0
5,5
-0,5
5,0
-1,0
4,5
-1,5
4,0
-2,0
3,05 3,10 3,15 3,20 3,25 3,30 3,35 3,05 3,10 3,15 3,20 3,25 3,30 3,35
-1
1000/T (K ) 1000/T (K )
-1

Fig. 12. Arrhenius plots for mild steel corrosion in 0.5 M H2SO4 in the absence and in presence of 10
3 M of IM-Cl and IM-CH3/(a) of ln (icorr) vs 1000/T and (b) ln
(icorr/T) vs 1000/T.

uninhibited solution. The positive signs of the enthalpies ΔHareflected

Table 8 the endothermic nature of the steel dissolution process. The higher value
Activation parameters for mild steel dissolution in 0.5 M Sulfuric acid solution in of the entropy of activation, ΔSa in the presence of 10
3M of IM-Cl and
the absence and presence of optimum concentration of IM-Cl and IM-CH3.
IM-CH3 in solution compared to the case of the blank acid solution might
Medium Concentration Ea (KJ/ ΔHa (KJ/ ΔSa (KJ/ Ea- be due to the enhanced randomness of the molecules [Martinez and
mol) mol) mol.K) ΔH
Stern, 2002].
0.5 M Blank 15.00 12.50 -140.5 2.5
H2SO4 10
3 M of IM-Cl 43.33 40.73 -70.0 2.6
3.4. Surface analysis
10
3 M of IM- 30.29 27.69 -110.2 2.6
CH3
In order to confirm the obtained results with electrochemical mea-
surements. Qualitative microscopic analyses of MEB coupled with
slope of the line (-ΔHa/R) and an intercept (ln (R/hNa) þ (ΔSa/R) from quantitative analyses EDX have been done. Fig. 13 shows MEB micro-
which the values of ΔHa and ΔSa were calculated and summarized in graphs of the steel surface, before and after exposed in 0.5 M H2SO4
Table 7. From these data, it was found that the thermodynamic param- medium during 6 h at T ¼ 298K, in absence and presence of both in-
eters, ΔHa and ΔSaof dissolution reaction of mild steel in 0.5 M H2SO4 in hibitors. The characteristics of the parallel treatment on the polished
the presence of 10
3 M of IM-Cl and IM-CH3 were higher than surface of mild steel before immersion in the corrosive solution are

Fig. 13. SEM image (50 μm) of mild steel before (a) and after 6 h of immersion in 0.5 M H2SO4 solution Blank (b) and solution with 10
3 M of inhibitors: IM-Cl (c)
and IM-CH3 (d) at 298 K.

10
M. Ouakki et al. Heliyon 5 (2019) e02759

Fig. 14. Qualitative and quantitative EDAX analysis of the corroded surface before (a) and after 6h of immersion in the blank solution containing 0.5 M H2SO4 (b) and
solution with 10
3 M of inhibitors: IM-Cl (c) and IM-CH3 (d) at 298 K.

11
M. Ouakki et al. Heliyon 5 (2019) e02759

Table 9 1996; Shetty and Shetty, 2017; Rbaa et al., 2019a,b]. As a consequence,
%mass of the different elements resulting from the EDX analysis of the surface these results confirm those obtained with electrochemical
steel in 0.5 M H2SO4 in the absence and presenceof the inhibitors: IM-Cl and IM- measurements.
CH3 at 298 K.
Elements % mass % mass of % mass of steel in % mass of steel in
of steel steel in Blank blank solution blank solution 3.5. Quantum chemical calculations
only solution with IM-Cl with IM-CH3

C 4.6 3.95 3.26 4.56 Recently, Quantum chemical calculation using density function the-
O 4.4 19.22 2.79 2.78 ory (DFT) was employed to explain and correlate the experimental results
N – – 0.29 0.38
in order to give an overview ofthe inhibition action on the metal surface.
S – 1.70 – –
Fe 91.0 72.4 95.26 92.94 The frontier orbital includingHOMO and LUMO of a chemical species are
Total 100.0 98.27 101.6 100.67 very important in defining its reactivity [Madkour and Elroby, 2015]. So,
it becomes indispensable to investigate the electron distribution in
HOMO and LUMO. The optimized structure and HOMO/LUMO distri-
clearly visible in the image of mild steel only, which is associated with bution of neutral and protonated molecules are presented in Fig. 15. The
scratch friction. HOMO and LUMO of IM-Cl and IM-CH3 (neutral forms) are extended
The resulting of the high-resolution SEM micrograph shows that the over the imidazole ring and the phenyl rings attached to the C1, C2 and
steel surface was strongly damaged in the absence of the two inhibitors C4 atoms. However, for the protonated forms the HOMO density is
(Blank solution). However, there are less pits and cracks observed in the mostly distributed over the imidazole ring, Cl atom and the two phenyl
micrographs in the presence of IM-Cl and IM-CH3 (Fig. 13) which sug- rings areattached to C1 and C2 carbons. While, the LUMO density is
gests a formation of protective film on steel surface which was respon- delocalized with a high density on the imidazole ring and preferentially
sible for the corrosion inhibition [Ouakki et al., 2018a,b; Saxena et al., focused around the substituted phenyl rings for both inhibitors. The
2018; Tan et al., 2018]. Indeed, IM-Cl and IM-CH3 has a strong tendency quantum chemical parameter for the inhibitors in neutral and protonated
to adhere to the steel surface and can be regarded as good inhibitors for imidazole derivatives in gas phase and aqueous solution such as the en-
steel corrosion in 0.5 M H2SO4. The high inhibitive performance of these ergy of the highest occupied molecular orbital (HOMO), energy of the
imidazole derivatives suggests a strong bonding of the IM-Cl and lowest unoccupied molecular orbital (LUMO), energy gap (Egap ¼ ELUMO –
IM-CH3on the metal surface due to presence of lone pairs from hetero- EHOMO), dipole moment (μ), electronegativity (χ ), absolute hardness (η),
atom (nitrogen) and π-orbitals, blocking the active sites and therefore absolute softness (σ ) and fraction of transferred electrons (ΔN) were
decreasing the corrosion rate [Rbaa et al., 2019a,b]. calculated and given in Table 10.
EDX analyses (Fig. 14) shows a decrease in the peaks of O atoms and The value of EHOMO is often associated with the electron donating
apparition of peaks of Nitrogen N, indicating that the molecules of the ability of a molecule. High value of EHOMO indicates the tendency of a
products IM-Cl and IM-CH3 are strongly adsorbed on the metal surface molecule to donate electrons to an appropriate acceptor molecule with
and justifies the inhibitory role of this product (Table 9) [Suzuki et al., low energy and empty molecular orbital. However, the value of ELUMO

Fig. 15. Gas phase optimized structures of neutral and protonated forms of IM-Cl (a) and IM-CH3 (b) at B3LYP/6-31G (d,p) level of theory.

12
M. Ouakki et al. Heliyon 5 (2019) e02759

Table 10
Calculated quantum chemical parameters for non-protonated and protonatedmolecules fIM-Cl and IM-CH3obtained with the DFT at (B3LYP/6–31 (d,p) level in gas (G)
and aqueous phases (A).
Parameter Phase IM-Cl IM- CH3 IM-Clþ (IM- CH3)þ

EHOMO(eV) G -5.3270 -5.1547 -8.3004 -8.9274

A -5.5417 -5.4581 -6.4617 -6.3814
ELUMO(eV) G -1.0419 -0.8136 -4.1041 -4.5550
A -1.1146 -0.9159 -1.9842 -1.7842
ΔEgap (eV) G 4.2850 4.3411 4.1963 4.3724
A 4.4271 4.5422 4.4774 4.5971
η(eV) G 2.1425 2.1705 2.0981 2.1862
A 2.2135 2.2711 2.2387 2.2985
σ (eV
1) G 0.4667 0.4607 0.4766 0.4574
A 0.4517 0.4403 0.4466 0.4350
χ (eV) G 3.1844 2.9842 6.2022 6.7412
A 3.3281 3.1870 4.2230 4.0828
ΔN G 0.8904 0.9250 0.1900 0.0591
A 0.8293 0.8394 0.6202 0.6345
μ(D) G 4.83 4.1757 1.3143 2.4682
A 6.4064 5.7676 1.9257 3.3976
Total energy G -43813.1627 -32376.6645 -43603.391 -32387.8875
A -43813.4550 -32376.9625 -43825.853 -32389.4391

shows the ability of a molecule to accept electrons [Madkour and Elroby, is in good agreement with the experimental results which showed that
2015; Khadiri et al., 2016]. The HOMO– LUMO gap, i.e., the difference in IM-Cl has higher efficiency than IM-CH3. As we know that the values of
energy between the HOMO and LUMO is an important stability index. ΔEgap in the both inhibitors are lower in neutral forms than protonated
Smaller value of energy gap (ΔE) of the inhibitor molecules will render forms, which reveal that neutral species can easily adsorb on the steel
good inhibition efficiency, because the energy required to remove an surface than protonated forms.
electron from the lowest occupied orbital will be low [El Belghiti et al., The different values of the electrostatic potential at the surface are
2016]. ΔN evaluates the electronic flow in a reaction of two systems with represented by different colors. Potential increases in the order red <
different electronegativities, in particular, an inhibitor molecule anda orange < yellow < green < blue. The negative electrostatic potentials are
metallic surface. N values were calculated according to Pearson theory shown in red region, the intensity of which is proportional to the absolute
[El Belghiti et al., 2016] by the following Eq. (13): value of the potential energy, and positive electrostatic potentials are
shown in blue region [Mahalakshmi and Balachandran, 2015]. The total
χ Fe
χ inh
ΔN ¼ (13) electron density surfaceismapped with the electrostatic potential (ESP)
2ðηFe þ ηinh Þ
and the electrostatic potential contour maps. It is obviously from the
Fig. 16 that the region around imidazole ring and chlorine atoms rep-
While χ Fe ¼ 7eVand ηFe ¼ 0 eV are the theoretical values of electro-
resents the most negative potential region (red to yellow), while more
negativity and hardness for iron.
positive charge around the ring hydrogen atoms. The molecular elec-
It was pointed out that the positive number of electrons transferred
trostatic potentials (ESP) and ESP contours of thestudied imidazole de-
(ΔN) indicates that the molecule act as an electron acceptor, while a
rivatives are presented in Fig. 17.
negative number of electrons transferred (ΔN) indicates that the mole-
The adsorption of the inhibitor molecule on the metal surface takes
cule act as electron donor [Erdogan et al., 2017]. Both of the ΔN values
place by the donor-acceptor interaction, which can be analyzed by the
are positive, which demonstrates thatIM-Cl and IM-CH3can donate
local reactivity i.e. condensed Fukui functions at DFT-B3LYP/6-31G (d,p)
electrons to the iron surface to form self-assembled layers of inhibitors.
level of theory. These descriptors are measurements of the chemical
In terms of reactivity, soft molecules are more reactive than hard ones
reactivity, as well as an indicative of the nucleophilic and electrophilic
since they have small energy gap that can enable the easy transfer of
behavior of the inhibitor molecule. The condensed Fukui functions
electrons [Elemike Elias et al., 2017]. The hardness value of a molecule
calculated by natural population analysis (NPA)using the following Eqs.
can be determined by the formula (14) [Mahalakshmi and Balachandran,
(15) and (16) [Khaled, 2010]:
2015]:
For nucleophilic attack: f þ
k ¼ qk ðN þ 1Þ
qk ðNÞ (15)
ðE
EHOMO Þ
η ¼ LUMO (14)
2
For electrophilic attack: f

k ¼ qk ðNÞ
qk ðN
1Þ (16)
Where, EHOMO and ELUMO are the energies of the HOMO and LUMO
orbitals. where qk is the gross charge of atom k in the molecule and N is the
IM-Cl with the largest inhibition efficiency has the smallest hardness number of electrons.
value 2.1425 eV. Additionally, IM-Cl has the largest softness (the inverse Fukui indices from the calculations for the charged species (Nþ1 and
of hardness), σ ¼ 0.4667. The dipole moment (μ) is another important N–1) as well as the neutrals molecules in the both phases are given in
electronic parameter that results from a non-uniform distribution of Table 11, respectively. For simplicity, only the charges and Fukui func-
charges on the various atoms in the molecule. The high value of the tions over the heteroatoms and some carbons of inhibitors the most
dipole moment most likely increases the adsorption of the inhibitor on reactive are presented. The maximum value of f þ k index is related to
the metal surface [Wazzan, 2014]. It is clear that increasing values of reactivity pertaining to a nucleophilic attack whereas the maximum of f
k
EHOMO, softness and ΔN follows the trend IM-Cl > IM-CH3 and the index indicates the favored site for adsorption of electrophilic agents
decreasing values of ELUMO, hardness and the energy gap follows the [Singh et al., 2017]. The higher value of f
k suggests acceptance of
order IM-Cl < IM-CH3indicating that the inhibition efficiency of IM-Cl is electron from the metal and higher value of f þ k suggests higher electron
better than that of IM-CH3. The substitution of the methyl group in donation ability of inhibitor molecules [Masroor et al., 2017]. In the case
IM-CH3 by the Cl atom results in an increase in the density of the entire of IM-Cl, the largest values of f

k are located on Cl30, C2 and C4 atoms
molecule (IM-Cl) and facilitates their adsorption onto steel surface. This which indicates that these atoms prefer to form a chemical bond by

13
M. Ouakki et al. Heliyon 5 (2019) e02759

Fig. 16. HOMO and LUMO surfaces of the neutral and protonated forms of imidazole compounds in gas phase using DFT/6-31G (d,p) calculation level: IM-Cl (a), IM-
CH3 (b), IM-Clþ (c) and IM-CHþ
3 (d).

donation of electrons to the metal surfaceand the favorable sites for comparison to IM-Cl and would therefore likely interact strongly with the
electron acceptance (f þk ) i.e., nucleophilic attacks are Cl30, C2, C4, C1
metal surface.
and C12 atoms. In IM-CH3case, the favorable sites for electrophilic at-
tacks are C4, C2 and N5 atoms while the favorable sites for nucleophilic 3.6. Molecular dynamic simulations
attacks are C2, C4, C1 and N5 atoms. After the analysis, it can be
concluded that the C4, C2 and N5 atoms of the imidazole ring are more The interaction of compounds with metal surface at the atomic level is
responsible for donor-acceptor interactions and thus facilitate the widely investigated by Molecular dynamics simulations [Khadiri et al.,
adsorption of the both inhibitors over the metallic surface. It is also 2018]. This theoretical method holds a great promise to mimic the real
possible to observe from Table 11 that the Cl30 atom in IM-Cl is the most corrosion environment and explore themolecular processes related to the
susceptible site for electrophilic and nucleophilic attack in the gas and corrosion behavior of metal in aqueous solutions and inhibition mecha-
aqueous phases, indicating that IM-Cl has the highest reactivity in nism [Lgaz et al., 2018a,b]. In this section, we aim to obtain insightful

14
M. Ouakki et al. Heliyon 5 (2019) e02759

Fig. 17. ESP maps and contours of mentioned inhibitors at B3LYP/6–31 (d,p) level: IM-Cl (a) and IM-CH3 (b).

Table 11
Calculated Fukui functions of IM-CH3and IM-Cl calculated at B3LYP/6-31G (d,p) in gas (G) and aqueous (A) phases.
Inhibitor Atom k phase P(N) P(Nþ1) P(N-1) fþ
k
f

k

IM-Cl 30Cl G -0.0127 0.0756 -0.0924 0.0883 0.0797

A -0.0251 0.0245 -0.0946 0.0497 0.0694
2C G 0.1971 0.2798 0.1680 0.0827 0.0290
A 0.2119 0.3210 0.1603 0.1091 0.0515
4C G 0.3944 0.4542 0.3627 0.0598 0.0316
A 0.2119 0.3210 0.1603 0.1091 0.0515
N5 G -0.5556 -0.5324 -0.5801 0.0231 0.0245
A -0.5858 -0.5585 -0.6160 0.0272 0.0302
12C G -0.0824 -0.0590 -0.0908 0.0233 0.0084
A -0.0993 -0.0684 -0.1062 0.0309 0.0068
IM-CH3 C2 G 0.1895 0.2705 0.1650 0.0809 0.0245
A 0.2051 0.3091 0.1552 0.1039 0.0498
C4 G 0.3929 0.4476 0.3651 0.0547 0.0277
A 0.3971 0.4785 0.3459 0.0813 0.0512
O30 G -0.5344 -0.5008 -0.5455 0.0336 0.0110
A -0.5480 -0.5200 -0.5565 0.0280 0.0085
C1 G 0.1600 0.1910 0.1438 0.0309 0.0161
A 0.1457 0.2003 0.1260 0.0545 0.0197
N5 G -0.5633 -0.5385 -0.5858 0.0247 0.0225
A -0.5951 -0.5649 -0.6159 0.0302 0.0208

explanation of the fundamental inhibition processes that determine the that the adsorption of SO2

4 is around -600 Kcal/mol which aretwice more
action of inhibitors as corrosion inhibitors [El Bakri et al., 2018]. In than the adsorption of inhibitors; this means that SO2-
4 ions have higher
Fig. 18, the side view of molecular interaction of inhibitor on C-steel affinity to metal surface and the adsorption of compounds on metal
surface after reaching equilibrium is presented in the presence of simu- surface proceeds physically via competing adsorption and interaction
lated acid solution of 0.5 M H2SO4. It can be seen that the inhibitors in the between inhibitors and sulfate ions adsorbed on Fe surface. Moreover the
final configuration of the simulation system was close to the Fe surface. presence of Cl atom in IM-Cl stabilizes the charges on the aromatic
Interestingly, the IM-Cl inhibitor molecule is oriented more parallel to moieties and facilitates the adsorption of compounds on metal surface.
the Fe surface than IM-CH3. Meaning thatmore surface coverage is ach-
ieved by IM-Cl inhibitor than IM-CH3; hence IM-Cl is expected to give 4. Conclusion
higher inhibition than IM-CH3. The adsorption energies of inhibitor
molecules obtained under equilibrium conditions are -227.75 kcal/mol The following conclusions can be derived from the study of Corrosion
and -245.73 kcal/mol for IM-CH3 and IM-Cl, respectively. It is also clear inhibition characteristics of two organic compounds of imidazole

15
M. Ouakki et al. Heliyon 5 (2019) e02759

Fig. 18. Most stable orientation of inhibitors on Fe (110) surface in 0.5 M H2SO4/IM-CH3 (a) and IM-Cl (b).

derivatives, IM-Cl and IM-CH3on mild steel corrosion in 0.5 M H2SO4 Additional information
medium:
No additional information is available for this paper.
❖ Both IM-Cl and IM-CH3 are efficient corrosion inhibitors for mild steel
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Funding statement studies of 3,5-disubstituted-4-amino-1,2,4-triazoles as corrosion inhibitors on mild
steel in acidic medium. J. Mol. Liq. 218, 281–293.
El Faydy, Mohamed, Galai, Mouhsine, Rbaa, Mohamed, Ouakki, Moussa,
This research did not receive any specific grant from funding agencies Lakhrissi, Brahim, Touhami, Mohamed Ebn, El Kacimi, Younes, 2018. Synthesis and
in the public, commercial, or not-for-profit sectors. application of new quinoline as hydrochloric acid corrosion inhibitor of carbon steel.
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Competing interest statement comparative study of the inhibitive effect of some new triazole derivatives towards
corrosion of mild steel in hydrochloric acid solution. Mater. Chem. Phys. 77, 489.

The authors declare no conflict of interest.

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