Journal Pre-proof

Synthesis, characterization, theoretical calculations (DFT and MC),

and experimental of different substituted pyridine derivatives as
corrosion mitigation for X-65 steel corrosion in 1M HCl

N.M.El Basiony , Eman.H. Tawfik , M.Abd El-raouf ,

Ahmed.A. Fadda , M.M. Waly

PII: S0022-2860(21)00130-7
DOI: https://doi.org/10.1016/j.molstruc.2021.129999
Reference: MOLSTR 129999

To appear in: Journal of Molecular Structure

Received date: 25 October 2020

Revised date: 18 January 2021
Accepted date: 19 January 2021

Please cite this article as: N.M.El Basiony , Eman.H. Tawfik , M.Abd El-raouf , Ahmed.A. Fadda ,
M.M. Waly , Synthesis, characterization, theoretical calculations (DFT and MC), and experimental of
different substituted pyridine derivatives as corrosion mitigation for X-65 steel corrosion in 1M HCl,
Journal of Molecular Structure (2021), doi: https://doi.org/10.1016/j.molstruc.2021.129999

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Synthesis, characterization, theoretical calculations (DFT and MC), and experimental of
different substituted pyridine derivatives as corrosion mitigation for X-65 steel
corrosion in 1M HCl

N. M. El Basiony*1, Eman H. Tawfik2, M. Abd El-raouf1, Ahmed A. Fadda2, M. M. Waly1,2

1-Egyptian Petroleum Research Institute (EPRI), Nasr City 11727, Cairo, Egypt

2- Department of Chemistry, Faculty of Science, Mansoura University, ET-35516 Mansoura,

Egypt

Graphical abstracts

Highlights
1. IR, NMR and MS characterized the synthesized ρ-substituted pyridine derivatives

2. MC simulation shows the probability of ρ-substituted pyridine derivatives to adsorb

on Fe

3. PYR-OCH3 increased the Rct of X-65 steel against HCl corrosion with efficiency

94.07%

4. Hammett constant (σ) values ordered the performance of the tested

compounds

1
 5. EDX analysis confirms the formation of protective film over X-65 steel surface

Abstract

Newly synthesized ρ-substituted pyridine derivatives (PYR-Cl, PYR-H, and

1
PYR-OCH3) were characterized by FT-IR, MS, and HNMR. Quantum
calculations indicate the insight compounds have active adsorption centers that
suppress X-65 steel dissolution via DFT descriptors and MC simulation
calculations. Electrochemical (potentiodynamic polarization and impedance)
techniques were employed to investigate the inhibition performance of the
studied substituted pyridine derivatives. The tendency of the studied pyridine
derivatives to shield X-65 steel surface away from the HCl aggressiveness
action depends on electron-donating and withdrawing effect of ρ-substitution
groups (-Cl, -OCH3), according to Hammett constant (σ), and their addition
concentrations. Tafel data indicated that the inhibition efficiency touches the
peak (95.75%) at 1x10-3 M PYR-OCH3 at 25°C. The ρ-substituted pyridine
derivatives adsorbed chemically and physically over X-65 steel surface (ΔGads
≈-38 kJmol-1) and followed the Langmuir adsorption isotherm model. Surface
morphology (SEM and EDX) displayed the smooth X-65 steel surface due to
the adsorbed-protective layer’s formation. Both theoretical and experimental
studies confirm the inhibition efficacy order of the tested pyridine derivatives,
PYR-Cl < PYR-H < PYR-OCH3.

Keywords: Pyridine; Hammett constant; corrosion inhibitor; Langmuir adsorption

isotherm; EIS, DFT

1-Introduction
Carbon steel (CS) has numerous applications in our modern society, such as
construction, transportation, manufacturing plants, and the oil and gas industry.
This is due to its relatively low production cost and outstanding mechanical
properties such as strength, ductility, malleability, hardness, etc. [1-3]. One
significant disadvantage of CS is its susceptibility to corrosion. There are many
factors causing corrosion, such as environmental pollution, global warming,

2
and climate change [4], in addition to acidic solutions. Some widespread
industrial processes (acidic cleaning, acid descaling, and oil well acidifications)
are frequently being used for cleaning of the impure metals and alloys.
However, these processes result in the loss of metallic components by their
chemical and electrochemical reactions with the aggressive cleaning (acidic)
solutions [5-9]. Corrosion causes costly catastrophic failures with undesired
consequences on human life and the environment. At this point in time, there is
no way to completely stop the corrosion processes. Some new solutions can
only mitigate this process via several ways, such as metal coatings, cathodic
protection, and corrosion inhibitors [10-13]. Organic corrosion inhibitors are
widely used in industry because of their effectiveness, compatibility with
protected materials, good solubility, and relatively low toxicity [14, 15].
Generally, the most efficient organic inhibitors are heterocyclic compounds
containing heteroatoms with lone pairs of electrons (S, N, O, and P), π-
electrons, and aromatic rings. These compounds build up a protective film of
adsorbed molecules on the metal surface, which provides a barrier to the
dissolution of the metal in the electrolyte. This adsorption can occur physically
or/and chemically. The physical adsorption is based on electrostatic interaction
between the charged inhibitor molecule and the charged metal surface. While,
In chemical adsorption, the inhibitor molecules donate their electrons to the
vacant d-orbitals of metals to form a coordinate bond in addition to the ability
to accept electrons from the metallic surface via their antibonding orbitals to
form a π-backbond [16-19]. A literature survey revealed that Many N-heterocyclic
compounds such as the derivatives of pyridine [20], thiazole [21], triazole [22], and
pyrimidine [23] are eff ective corrosion inhibitors for carbon steel in acidic solution. K. R.
Ansari et al. used the pyridine derivatives as corrosion inhibitors for the N80 steel in 15%
HCl, which showed inhibition efficiency 92.3% at 200 ppm using the Tafel technique [20]. F.
Bentiss et al. studied the inhibition properties of 2,5-bis(n-pyridyl)-1,3,4-thiadiazoles (n-
PTH) on corrosion of mild steel in different acidic media (1 M HCl, 0.5 M H2SO4 and 1 M
HClO4) by electrochemical impedance spectroscopy (EIS). The n-PTH derivatives exhibited
good inhibition properties in different acidic solutions [24]. The use of quantum
chemical calculations is very significant in establishing the correlation between
molecular structure and chemical reactivity and selectivity of the corrosion
inhibition process. The effectiveness of a compound in a chemical reaction is
related to its spatial and electronic molecular structures [25]. Moreover, a

3
theoretical study permits the pre-selection of organic compounds with the
necessary structural characteristics to undergo chemical reactions. The present
work is aimed to prepare heterocyclic compound (ρ-substituted pyridine
derivative) and study its inhibition efficiency as corrosion inhibitor of steel in
1.0 M HCl based on electrochemical potentiodynamic polarization and
electrochemical impedance spectroscopy measurements. It also aimed to study
the effect of the structural parameters of inhibitor on inhibition efficiency and
study its adsorption mechanism on the metal surface and correlate the
experimental results with the quantum chemical parameters of the prepared
inhibitor.

2-Experimental

2.1-Preparation of the inhibitor

Synthesize of N'-(1-(4-aminophenyl)ethylidene)-2-cyanoacetohydrazidebutanamide

A mixture of 4-aminoacetophenone (0.270 g, 2 mmol) and 2-cyanoacetohydrazide (0.19 g, 2

mmol) in a round-bottomed flask containing ethanol and drops acetic acid was refluxed for
1h, then left to cool. The solid product was washed with ethanol to give compound (1) as
shown in scheme 1.
Yellowish white crystals; yield 92%; mp 227-229˚C.
IR (KBr): υ/cm-1 = 3456 (NH2), 3364 (NH), 2264 (C≡N), 1680 (C=O),
1
H NMR (DMSO-d6): δ 2.14 (s, 3H, CH3), 4.17 (s, 2H, CH2), 5.47 (s, 2H, NH2), 6.53-7.52
(m, 4H, ArCH), 10.77 (s, 2H, NH2). Fig. S 1.
MS m/z (%): 217 (M++1, 1.29), 216 (M+, 14.78), 176 (12.74), 148 (16.70), 118 (45.36), 107
(26.70), 91 (42.94), 80 (71.30), 65 (100.00). Fig. S 2.
Anal. for C11H12N4O (216.24):
Calcd.: C, 61.10; H, 5.59; N, 25.91 %.
Found: C, 61.21; H, 5.63; N, 25.82 %.

Preparation of pyridine derivative inhibitors, general procedure:

Equimolar amounts of compound (1) and 2-benzylidenemalononitrile, 2-(4-
chlorobenzylidene)malononitrile or 2-(4-methoxybenzylidene)malononitrile in ethanol (20
mL) containing few drops of piperidine were heated under reflux for 1h. The precipitated
solid product was filtered off, dried, and recrystallized from a mixture of EtOH-DMF to
afford compounds 2, 3, and 4, respectively and their analysis are:

4
6-amino-1-((1-(4-aminophenyl)ethylidene)amino)-2-oxo-4-phenyl-1,2-dihydropyridine-3,5-
dicarbonitrile (2) (PYR-H)
Yellow crystals; yield 86%; mp 243-245˚C.
IR (KBr): υ/cm-1 = 3455, 3420, 3367, 3297 (2NH2), 2214 (2C≡N), 1673 (C=O).
1
H NMR (DMSO-d6): δ 2.10 (s, 3H, CH3), 5.98 (s, 2H, NH2), 6.64-7.83 (m, 9H, ArCH), 8.18
(s, 2H, NH2) Fig. S 3.
MS m/z (%): 369 (M++1, 4.24), 368 (M+, 12.48), 352 (12.54), 251 (50.39), 180 (22.60), 133
(32.24), 127 (43.13), 118 (55.91), 77 (97.00), 65 (100.00), 51 (97.24) Fig. S 4.
Anal. for C21H16N6O (368.40):
Calcd.: C, 68.47; H, 4.38; N, 22.81%.
Found: C, 68.49; H, 4.32; N, 22.75%.

6-amino-1-((1-(4-aminophenyl)ethylidene)amino)-4-(4-chlorophenyl)-2-oxo-1,2-
dihydropyridine-3,5-dicarbonitrile (3) (PYR-Cl)
Yellow crystals; yield 87%; mp 274-276˚C.
IR (KBr): υ/cm-1 = 3426, 3346 (2NH2), 2218 (C≡N), 1669 (C=O).
1
H NMR (DMSO-d6): δ 2.08 (s, 3H, CH3), 5.97 (s, 2H, NH2), 6.61-7.81 (m, 8H, ArCH), 8.21
(s, 2H, NH2) Fig. S 5.
MS m/z (%): 403 (M+, 2.71), 216 (45.54), 176 (22.07), 148 (25.86), 133 (36.18), 118
(100.00), 107 (30.54), 91 (64.44), 80 (57.45), 68 (98.88) Fig. S 6.
Anal. for C21H15ClN6O (402.10):
Calcd.: C, 62.61; H, 3.75; N, 20.86 %.
Found: C, 62.65; H, 3.79; N, 20.77 %.
6-amino-1-((1-(4-aminophenyl)ethylidene)amino)-4-(4-methoxyphenyl)-2-oxo-1,2-
dihydropyridine-3,5-dicarbonitrile (4) (PYR-OCH3)
Yellow crystals; yield 88%; mp 261-263˚C.
IR (KBr): υ/cm-1 = 3444, 3354, 3312 (2NH2), 2215 (C≡N), 1675 (C=O).
1
H NMR (DMSO-d6): δ 2.06 (s, 3H, CH3), 3.83 (s, 3H, CH3), 5.94 (s, 2H, NH2), 6.59-7.79
(m, 8H, ArCH), 8.08 (s, 2H, NH2) Fig. S 7.
MS m/z (%): 398 (M+, 100.00), 331 (7.82), 281 (18.76), 118 (24.95), 65 (33.95) Fig. S 8.
Anal. for C22H18N6O2 (398.43):
Calcd.: C, 66.32; H, 4.55; N, 21.09 %.
Found: C, 66.27; H, 4.48; N, 21.00 %.
2.2. Quantum calculation method

5
Quantum chemical optimization descriptors such as energy of lowest unoccupied molecular
orbitals (EL), highest occupied molecular orbitals (EH), dipole moment (µ) and the fraction of
electrons transferred (∆N) and other descriptors are calculated in gas and solvent phases
based on density function theory (DFT) using gradient-corrected functional (GGA) method
with a Becke One Parameter (BOP) which has convergence tolerance parameters fine quality,
and basis set group functional Double Numerical plus polarization (DNP) included in DMol3
module using Materials Studio 6.0 software from Accelrys. The interaction between the as-
prepared ρ-substituted pyridine derivatives and the surface of X-65 steel could be simulated
by using an adsorption locator module included in the same software by Monte Carlo (MC)
method. The adsorption energy obtained from the interaction between the as-prepared ρ-
substituted pyridine derivatives molecules and the most stable substrate surface Fe (1 1 0)
were calculated by importing iron crystal with surface cleavage (1 1 0), which represent the
most stable form. The cleavage plane was expanded to a (15 × 15) supercell; after that, a
vacuum slab with 25 Å thicknesses was built above the Fe (110) crystal to avoid any arbitrary
boundary effect. Simulation annealing was run for optimization of the whole system
(Fe/PYR-(Cl, H, OCH3) in vacuum and solvent phase at smart algorithm with a fine level of
convergence through 5cycles with 15000 steps for each one till the total energy of the system
fluctuate about the mean values as presented in Fig. S 9. This means that the system tends to
equilibrate. COMPASS forcefield was used to obtain minimum energy for Fe (11 0) surface,
and the quality was fine, and both electrostatic and van der Waals were atom- and group-
based, respectively. The cutoff distance was 12.5 Å [26, 27].
2.3-Corrosion test solution:
Bi-distilled water was used to prepare the different doses (1 x 10-6 to 1 x 10-3 M) from ρ-
substituted pyridine derivatives (PYR-(Cl, H&OCH3) in aggressive solution 1 M HCl. All
solutions were freshly prepared in a closed vessel (150 mL).
2.4-Electrochemical measurements
X-65 steel alloy with chemical composition (wt. %): 0.06 C; 0.75 Mn; 0.06 Si; 0.005 P; 0.001
S; 0.015 Cr; 0.02 Cu and Fe balanced was cut into cylinder shape. X-65 was insulated with
epoxy resin, leaving an exposed area 0.283 cm2, which polished successively with different
grades of SiC paper to get a mirror image surface before each run. To investigate the
electrochemical behavior of X-65 in 1M HCl in the presence and absence of the as-prepared
ρ-substituted pyridine derivatives (PYR-Cl, PYR-H, and PYR-OCH3), X-65
steel electrode was connected to Potentiostat/Galvanostat, Tacussel Radiometer PGZ 402
(Volta lab 80), as working electrode in the three-electrode system with Pt-wire and Ag/AgCl
(3M KCl) as auxiliary and reference electrodes, respectively.

6
Potentiodynamic polarization:
Potentiodynamic polarization curves were recorded within the potential sweeping range from
-1000 mV to -100 mV at 1 mV/s scan rate, and the electrochemical parameters are calculated
at ±200 mV vs. EOCP.
The inhibition efficiency (
(1)
Where, and are corrosion current density of X-65 in free and treated 1M HCl,
respectively.
Electrochemical impedance spectroscopy (EIS):
EIS was conducted at OCP and within the frequency range from 100 kHz to 50 mHz with
sinusoidal 10 mV AC wave signal peak-to-peak amplitude to perturb the system.
The inhibition efficiency (
(2)
Where, and are ionization resistance of X-65 in free and treated 1M HCl,
respectively [28].
2.5-Surface analysis study
Effect of HCl in absence and presence of the optimum concentration (1x10-3 M) of the best ρ-
substituted pyridine; (PYR-OCH3) on the X-65 steel corrosion are displayed with the aid of
spectroscopic analysis techniques such as Scanning Electron Microscope (SEM), QUANTA
FEG 250 attached with EDX unit. The X-65’s surface analysis studies occurred after 3h
immersion in free HCl solution and treated one.
3- Results and Discussion.
3.1-Quantum
Quantum chemical calculations represent a powerful tool to display the chemical reactivity of
the as-prepared organic compounds to explain and predict their ability to act as corrosion
inhibitors and understand the mechanism of corrosion inhibition reaction. A deeper
understanding of corrosion mechanism allows us to fabricate organic inhibitors with new
modification functional groups with high inhibition/adsorption performance. The reaction
mechanism of organic corrosion inhibitor molecules occurs based on the donor-acceptor
interaction concept [29]. Fig. 1 display the geometrical optimization structure, highest
occupies molecular orbital (HOMO), and lowest unoccupied molecular orbital (LUMO) of
PYR-OCH3 as a representative ρ-substituted pyridine derivatives and the others are presented
as supplementary see Fig. S 10a,b,c. The outcome calculated descriptors are tabulated in
Table 1. The energy of HOMO and LUMO refer to the donation and the receiving affinity of
the ρ-substituted pyridine derivatives molecules to or from empty and fulfilled 3-d atomic
7
orbital of iron, respectively [30, 31]. The optimized structure indicates the most stable form
of the as-prepared compound structure. The electron density distribution appeared clearly
over multiple centers such as hetero atoms (N&O), aromatic rings, and π-bond. These centers
are the reactive centers where the electrons transferring or/and receiving process takes place
over the metallic surface. The presence of these centers indicates the probability of potential
application to be corrosion inhibitors. The higher EH and the lower EL are, the higher
adsorption ability and the higher inhibition efficiency are [32]. The energy gap (ΔEL-H) is an
index of reactivity of the inhibitor molecules. A small energy gap (ΔEL-H) is indicated to
higher chemical reactivity and, in turn, predicts high inhibition performance. So, the value
order of energy gap (ΔEL-H) reflects the probability of the insight ρ-substituted pyridine
derivatives efficiency order as the following: PYR-Cl (2.499 eV) < PYR-H (2.479 eV) <
PYR-OCH3 (2.452 eV). The PYR-OCH3 has the lowest energy gap (ΔEL-H) and
consequently has a high adsorption probability over the Fe surface. On the other hand, the
global softness (σ) and hardness (η) parameters are related to the energy gap (ΔE L-H),
according to the hard-soft acid-base (HSAB) concept. The softener molecule has a lower
energy gap (ΔEL-H) and vice versa for the hardener molecule. Table 1 shows, the PYR-OCH3
has the lowest hardness value (1.226 eV) and the highest softness (0.815 eV). According to
Lukovits’s postulation, as the electron transfer fraction (ΔN) is less than 3.6, the electron-
donating ability of the as-prepared ρ-substituted pyridine derivatives increase the propensity
to be able to adsorb on the metallic substrate. The PYR-OCH3 has the highest ΔN (0.815)
and, in turn, has the highest adsorption probability on the X-65 steel surface. Indeed, in the
corrosion inhibition reaction mechanism, there are two processes taking place
simultaneously: electron donation from the HOMO to empty 3-d orbital of iron, and electron
acceptance from fulfilled 3-d orbital to LUMO of inhibitor via the back-donation process.
Back-donation energy (ΔEback-d=-η/4) values recorded in Table 1 refer to the ability of PYR-
OCH3 to be adsorbed over X-65 steel is highly favorable. The most important quantum
calculation descriptor is the dipole moment that reflects the ability of organic molecules to
electrostatically interact with the metal surface or accumulate over the substrate surface. As
elsewhere reported before [26], the decreasing dipole moment value favors the accumulation
of inhibitor molecules and, in turn, increases the probability of adsorption affinity. So,
according to the above-calculated quantum descriptors, the order of probability of the as-
prepared ρ-substituted pyridine derivatives increases as follow: PYR-Cl <PYR-H <PYR-
OCH3.
Monte Carlo Simulation:

8
Simulation of the adsorption process takes place over the most stable Fe (1 1 0) surface via
adsorption locator module included in MS.6 software by Monte Carlo (MC) method indicates
the adsorption probability of the as-prepared ρ-substituted pyridine derivatives. Fig2. shows
the top and the side view images of of PYR-OCH3 on Fe (1 1 0) in both vacuum and
simulated acidic solution as a representative ρ-substituted pyridine derivatives and the others
are presented as supplementary see Fig. S 11a,b . From Fig. 2 it is clearly obvious that the
optimized ρ-substituted pyridine derivatives tend to be flat and parallel to the Fe (1 1 0)
surface. This, in turn, leads to their strong interaction probability with Fe (1 1 0) surface. The
most important parameter obtained from MC simulation is the adsorption energy (Eads,) which
refers to the energy released/required for the as-prepared ρ-substituted pyridine derivative
compound to be able to adsorb on Fe (1 1 0) surface. The values of Eads, recorded in Table 2,
show that the adsorption probability of the ρ-substituted pyridine derivatives over X-65 steel
is more favorable. Moreover, the values of Eads arrange the adsorption affinity of insight
derivative compounds as follows: PYR-Cl <PYR-H <PYR-OCH3. Finally, it can be stated
that the calculations of the DFT and MC simulation suggest highly potential applications of
the as-prepared ρ-substituted pyridine derivatives (PYR-Cl, PYR-H, and PYR-OCH3) as
corrosion inhibitors.
3.2. Potentiodynamic Polarization Measurements:
The response of X-65 steel after 30 min immersion to the potentiodynamic polarization with
scan rate 1mV/s in free 1M HCl and after addition of different concentrations from the as-
prepared PYR-OCH3 is displayed in Fig. 3a at 25 ◦C as a representative ρ-substituted
pyridine derivative and the others are presented as supplementary see Fig. S 12. Inspection of
Fig. 3a presented and discussed as follow: The addition of ρ-substituted pyridine derivatives
molecules shifts the anodic and the cathodic Tafel lines toward a noble direction (lower
values). This may be inferred that the ρ-substituted pyridine derivatives have a blocking
effect on the X65-steel corrosion reaction [33]. It can be seen that the Tafel curves shape dose
not significantly change after the addition of ρ-substituted pyridine derivatives. This indicates
that the X65-steel dissolution reaction mechanism is not affected by the presence of the tested
inhibitors [34]. Also, the parallel appearance of cathodic Tafel lines indicates that the
hydrogen reduction is activated-controlled [19], and its mechanism is not modified after ρ-
substituted pyridine derivatives addition. This means that X65-steel surface subjected to H+ is
shielded by adsorbed ρ-substituted pyridine derivatives, while the reaction mechanism itself
still unaffected [35, 36].

9
The electrochemical calculated kinetic parameters based on Tafel extrapolation method using
Voltamaster 4 software such as corrosion potential (Ecorr), corrosion current density (Icorr) and
Tafel line slopes (βa, βc) and other indices were computed and given in Table 3.
Close inspection of data recorded and calculated in Table 3 show that the values Ecorr after
the addition of ρ-substituted pyridine derivatives changed smoothly and within ±85mV range
compared to the Ecorr of the untreated one in the whole tested concentrations; this inferred that
the investigated ρ-substituted pyridine derivatives are calcified as a mixed-type inhibitor for
X65-steel corrosion in acid media. The corrosion current density (Icorr) value decreases in the
presence of tested compounds. Also, the further increase in their concentrations resulted in a
further dropping in Icorr. This indicates the rate of metal dissolution or/and metal oxide
formation decreased due to ρ-substituted pyridine derivatives molecules’ adsorption affinity
over substrate surface [37]. The calculated inhibition efficiency values increase with rising ρ-
substituted pyridine derivatives concentration and reached its maximum 93.49%, 95.43%,
95.73% for PYR-Cl, PYR-H, and PYR-OCH3, respectively at an optimum concentration
(1x10-3M). This inferred that the ρ-substituted groups (-Cl and -OCH3) affect the adsorption
performance of the as-prepared compounds according to Hammett substitution constant (σ).
The ρ-substituted methoxy (-OCH3) group has a negative value of σ (-0.262). This indicates
electron-donating ability that enhances the electron density over the active sites responsible
for the X-65 steel- PYR-OCH3 interaction and therefore increases the inhibition efficiency.
While in the case of the ρ-substituted chloro (-Cl) group that has a positive value σ (0.227).
The withdrawing effect of ρ-substituted chloro (-Cl) group decreases the electron density
over the active sites responsible for the X-65 steel- PYR-Cl interaction and therefore
decreases the inhibition efficiency relative to un-substituted PYR-H counterpart
molecule[38].
3.3.Electrochemical impedance spectroscopy (EIS)
EIS measurements are done to confirm the behavior of the corrosion process of X-65 steel in
the absence (HCl free) and the presence of ρ-substituted pyridine derivatives. EIS spectra of
X65-steel after 30 mints immersion in 1M HCl in the absence and presence of different
concentration of insight ρ-substituted pyridine derivatives are presented as Nyquist and bode
plots. Nyquist and bode plots of PYR-OCH3 as a representative ρ-substituted pyridine
derivative is shown in Fig.3b and 3c and the others are presented as supplementary see Fig.
S 13 and 14. Inspection of Fig.3b shows one capacitive loop at a high frequency (HF) region
with one time constant as it clearly appeared in bode plot in Fig.3c. This indicates that mass
transfer resistance control the corrosion and corrosion inhibition of the X-65 steel reaction
mechanism [39]. The overall shape of the Nyquist plot in the acid-free solution and over the

10
whole studied concentrations range of the ρ-substituted pyridine derivatives solutions are the
same without significant change unless the diameter values increase with the addition of the
tested compounds. This reflects the inhibitory effect of the additives on the X-65 steel
corrosion without altering the reaction mechanism of the X-65 steel in acid media [26]. The
impedance effect of the tested additives comes from their adsorption affinity on the X-65
steel surface, and this is also seen clearly from the shifting of the impedance modulus /Z/ to
higher values and phase angle toward -90° at lower and intermediate frequency regions,
respectively [40]. Nyquist plot curves appeared as depressed semicircle at the center of
abscissa. This phenomenon, frequency dispersion, is related to the solid surfaces is due to
roughness, impurities, and inhomogeneities of the electrode surface [41].
The proposed equivalent circuit to fit and simulate the experimental EIS data is shown in Fig.
3d. This circuit consists of electrolyte resistance (Rs) in series with the charge transfer
resistance (Rct), which in parallel with the constant phase element (CPE). The constant phase
element (CPE) has frequency dispersion replaced the ideal capacitor double layer (Cdl) to get
a more fitted simulated data. The electrochemical EIS parameters obtained such as Rs, Rct,
and CPE, and the inhibition efficiency calculated according to equation (2), double-
layer capacitance (Cdl) calculated according to equations (3) [42, 43] are recorded in Table 4.

(3)
Where , is the frequency at the maximum imaginary resistance.
Close inspection and discussion of the recorded obtained and calculated EIS data in Table 4
indicate that: Rct values of X-65 steel increased with the addition of ρ-substituted pyridine
derivatives molecules even in small concentration 1x10-6 M to the double value relative to
blank counterpart and further increased till touch the peak (253.8, 299.7, 305.7 Ω.cm2) at
1x10-3 M for the PYR-Cl, PYR-H, and PYR-OCH3, respectively. This is because these ρ-
substituted pyridine derivatives form adsorbed film over X-65 steel keeping the X-65 steel
surface away from the offensive action of HCl and consequently decrease the X-65 steel
corrosion rate [44]. On the other side, Cdl values deceased with increasing Rct, where
dropping Cdl value is related to more than one reason; one of them, the replacement of water
or/and aggressive ions of high dielectric constant (ε) with the adsorbed ρ-substituted pyridine
derivatives molecules of low ε. The other reason is the growing up of protective film
thickness (S) over X-65-steel surface according to the Helmholtz model [45, 46].
Cdl = (4)
Where A is the electrode surface area, ε° is the permittivity of air and ε is the local
dielectric constant.

11
It’s quite obvious; at the same concentration (1x10-3 M), the inhibition efficacy of the tested
ρ-substituted pyridine derivatives, PYR-Cl, PYR-H, PYR-OCH3 are 92.3%, 93.95%, 94.07%,
successively. This reflects that the order of inhibition efficiency of the tested derivative
compounds is PYR-Cl < PYR-H < PYR-OCH3. This indicates that the obtained results from
the electrochemical techniques are in good agreement with each other.
3.4.Adsorption Isotherm
Inhibition performance of ρ-substituted pyridine derivatives (PYR-Cl, PYR-H, PYR-OCH3)
is mainly related to their adsorption ability on X-65 steel surface in 1M HCl. Surface
coverage (θ) values assessed from both electrochemical techniques (Tafel & EIS) are used as
a function in inhibitor concentration to estimate the type of adsorption. Different adsorption
isotherm models are applied however, the synthesized ρ-substituted pyridine derivatives were
highly fitted with the Langmuir isotherm model. According to the following equation:
Langmuir (5)
where is the equilibrium constant of the adsorption process and is the molar
concentration of inhibitors [47]
The linear Langmuir plots are represented in Fig. 4 a,b. With high regression

coefficient (R2) values and near-unity suggested that the adsorption of ρ-substituted pyridine
derivatives molecules on X-65 steel surface obeyed Langmuir isotherm models.
The standard free energy change of the adsorption process ( ) value that predicts the
type of adsorption process (physical, chemical, or/and both of them) can be calculated
according to the equation (6). Adsorption equilibrium constant values determined
from the intercept of Fig. 4 a,b. indicate the strength of the adsorption process.

( ) (6)

where (55.5) is the molar, M, value water in the solution, and (R) is the gas constant at the
standard conditions [48].
Regarding the data of Langmuir adsorption isotherm tabulated in Table 5, the higher value of
refers to the higher adsorption ability of ρ-substituted pyridine derivatives molecules
over the X-65 steel surface and higher corrosion inhibition efficiency [49]. The negative sign
of indicates the spontaneity of the adsorption process and fastness of the adsorbed film
formation on the X-65 steel surface [50, 51]. The higher value of (
indicates the physical and chemical adsorption type of ρ-substituted pyridine derivatives
molecules adsorption [52]. This means that the ρ-substituted pyridine derivatives impede the
corrosion reaction physically via the electrostatic attraction forces between charged centers
(protonated) in the tested molecules and those of the steel surface and suppress the X-65 steel

12
corrosion chemically via the charge or/and an electron transfer from high electron density
centers (O, N & π-bond) to the empty 3d orbital of Fe. Obviously, from values,
according to Langmuir adsorption isotherm, the ρ-substituted pyridine derivatives molecules
are adsorbed by both types: physisorption and chemisorption with prone to chemical
adsorption. The values of the standard free energy change of adsorption process ( ) for
the as-prepared ρ-substituted pyridine derivatives PYR-Cl, PYR-H, PYR-OCH3, are -37.54, -
38.74, -39.95 kJmol-1, successively. This inferred the order of adsorption ability are PYR-Cl
< PYR-H < PYR-OCH3, and this matched with the behavior obtained from the Tafel and the
EIS techniques.

3.5.SEM, EDX, and corrosion inhibition mechanism

Surface analysis study is an important tool to image the harmful action of acidic media (HCl)
and emphasize the safeguard action of the insight ρ-substituted pyridine derivatives on the X-
56 steel surface. Fig. 5a. shows the 2-D SEM image for X-65 steel slide immersed in 1M HCl
for 3h. The images display the offensive action of HCl on the steel surface, where the surface
appears to be damaged, filled with corrosion product. These features matched with the nature
of corrosion reaction of Fe in acidic media according to the following equations:
Anodic reaction (7)
The protection effect of 1x10-3 M PYR-OCH3 appears strikingly in Fig. 5b. It represents the
X-65 steel surface nearly free from the corrosion product, and the surface becomes smoother
compared to the blank counterpart. These better modifications prove the adsorption of ρ-
substituted pyridine derivatives molecules (PYR-OCH3) on the active sits of the X-65 steel
surface and the formation of passive film over it. At anodic sites, the protonated PYR-OCH3
molecules react electrostatically with the adsorbed chloride (FeCl-)ads and retard the anodic
reaction.
(8)
(9)
The adsorption of PYR-OCH3 on the X-65 steel surface cover and shield the surface away
from the action of HCl via electrostatic attraction between charged inhibitor molecules and
charged Fe surface and also, via the electron transfer from non-bonding lone pair of electron
on N and O atoms to the vacant 3d-orbitals of Fe. It can be said that the addition of ρ-
substituted pyridine derivatives molecules only retard the hydrogen evolution reaction
(cathodic reaction) without changing the mechanism of reduction reaction as discussed in the
potentiodynamic polarization part according to the following equations:
(At cathodic site) (10)

13
 (11)
(12)
The protonated compounds ( compete for the to be adsorbed at the
same site of Fe. So the statement of hydrogen evolution reaction is activated-controlled, and
the reaction mechanism is not changed by the inhibitor molecule addition becomes clear now.
Furthermore, the EDX analysis depicted in Fig.5c confirms the SEM observations. The
reduction of O peak intensity, while the enhancement of Fe peak intensity in case of treated
X-65 steel in compared to blank confirm that the pyridine inhibitors alleviates the severity of
1 M HCl. Also, the N peak appearance confirmed the formation of the protective film via the
adsorption of inhibitor molecules on the X-65 steel surface that minimizes the metal oxide
formation, as shown in Table 6. These observations and postulated corrosion and corrosion
inhibition mechanism matched with our previously published work [53-55]. The adsorption
mode of the tested inhibitors can be simulated, as shown in Fig.5d.
4- Conclusion.
 Pyridine derivatives (PYR-Cl, PYR-H, PYR-OCH3) were laboratory prepared, and
chemically elucidated by IR, H-NMR, and MS.
 DFT and MC simulations studies show the probability of pyridines to act as corrosion
inhibitors.
 Tafel data indicate that the pyridine derivatives act as mixed-type inhibitors.
 Both of Icorr. and Cdl are decreased, while Rct and surface coverage(θ) are increased with
the presence of pyridine derivatives.
 The inhibition order of the pyridine derivatives was PYR-Cl < PYR-H < PYR-OCH3 and
this is matched with the Hammett substitution constant (σ) and adsorption free energy
change (ΔGads.) values.
 Surface analysis (SEM& EDX) show that pyridines protect X-65 steel surface from the
action of HCl via the formation barrier adsorption film.
Declaration of competing interest

The authors of the present article would like to declare that they have no
known competing financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Credit authorship contribution statement

 N. M. El Basiony: Investigation, Methodology, Data curation, Writing

- original draft. Eman H. Tawfik: Investigation, Data curation, Writing -
original draft. M. Abd El-raouf: Investigation, Methodology, Data
curation. M. M. Waly: Investigation, Methodology, Data curation,
14
 Writing - original draft. Ahmed A. Fadda: Supervision, Validation,
Writing - review & editing.


5- Acknowledgements

The authors gratefully thank the Egyptian Petroleum Research Institute for its support.

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Figure caption

Scheme 1: The synthesized material's chemical composition

18
Fig. 1. Optimized structure(a), FMOs ( HOMO(b)& LUMO(c)) and Molecular electrostatic potential
map (d) for the PYR-OCH3 in vacuum phase

19
Fig. 2. Final configurations of thePYR-OCH3 adsorbed molecules on Fe (110) surface
vacuum slab in gas and simulated acid phases; side (left) and top (right) views respectively.

20
Fig. 3. (a) Plots of Potentiodynamic polarization and EIS spectra of Nyquist (b) and Bode (c)
plots for dissolution of X-65 steel with and without presence of various concentrations of the
as-prepared ρ-substituted pyridine derivative (PYR-OCH3), at 25°C. (d)Electrical equivalent
circuit used to simulate EIS spectra.

21
Fig.4.a,b. Langmuir isotherm plots of the as-prepared ρ-substituted pyridine derivatives at
298 K using Tafel and EIS data.

22
Fig. 5. SEM of X-65steel in (a) blank (1M HCl) and in (b) inhibited (1x10-3M PYR-
OCH3),(c) EDX of X-65steel in blank (1M HCl) and in inhibited (1x10-3M PYR-OCH3) after
3h immersion at 25 ◦C, and (d) Suggested adsorption model of the as-prepared ρ-substituted
pyridine PYR-OCH3 over the X-65 steel

23