Journal of Colloid and Interface Science 560 (2020) 225–236

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Journal of Colloid and Interface Science

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

Comprehensive investigation of steel corrosion inhibition at macro/

micro level by ecofriendly green corrosion inhibitor in 15% HCl medium
Ambrish Singh a,b, K.R. Ansari c,⇑, Dheeraj Singh Chauhan c, M.A. Quraishi c, H. Lgaz d, Ill-Min Chung d
a
School of Materials Science and Engineering, Southwest Petroleum University, Chengdu 610500, Sichuan, China
b
State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, Sichuan 610500, China
c
Center of Research Excellence in Corrosion, Research Institute, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
d
Department of Crop Science, College of Sanghur Life Science, Konkuk University, Seoul 05029, South Korea

g r a p h i c a l a b s t r a c t

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

Article history: Hypothesis: In the present time, there is enormous need for environmentally friendly and effective cor-
Received 11 July 2019 rosion inhibitor for the acidizing process. During acidization 15% hydrochloric acid is used, which causes
Revised 10 October 2019 corrosion of N80 steel.
Accepted 11 October 2019
Experiments: The present study aims at the synthesis of environmentally benign corrosion inhibitor,
Available online 18 October 2019
namely 2-amino-4-(5-hydroxy-3-methyl-1H-pyrazole-4-yl)-4H-chromene-3-carbonitrile (PCP), and cor-
rosion inhibition evaluation for N80 steel in 15% HCl. The inhibition potential of PCP was examined by
Keywords:
electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDP), density functional
N80 steel
Green inhibitor
theory (DFT), and molecular dynamics simulation (MSD). The surface morphology of N80 steel samples
Acidization was characterized by atomic force microscopy (AFM), contact angle measurement, UV–vis spectroscopy,
SEM/AFM and scanning electron microscopy (SEM).
DFT/MSD Findings: The EIS measurements disclosed that PCP inhibits corrosion via kinetic controlled process. PDP
results confirmed that PCP is a mixed type inhibitor and reduces the corrosion process effectively at
400 mg/L concentration with 98.4% efficiency. The adsorption of PCP followed Langmuir isotherm.
Surface analysis by SEM, AFM, contact angle measurement, and UV–vis spectroscopy supports PCP
adsorption over the N80 steel surface. The DFT study explores the adsorption and reactive regions of
the PCP molecules. The MSD reveals that the diffusion co-efficient of the corrosive species in inhibited
solution is less as compared to uninhibited.
Ó 2019 Elsevier Inc. All rights reserved.

⇑ Corresponding author.
E-mail address: kashif.ansari@kfupm.edu.sa (K.R. Ansari).

https://doi.org/10.1016/j.jcis.2019.10.040
0021-9797/Ó 2019 Elsevier Inc. All rights reserved.
226 A. Singh et al. / Journal of Colloid and Interface Science 560 (2020) 225–236
1. Introduction
Acidization is one of the most popular and effective methods
used in the petroleum industry for the enhanced recovery of oil
from the depleted wells. The process consists of forcing 15–28%
HCl solution into the wellbore to dissolve the calcareous material,
thereby facilitating oil flow. To protect steel from corrosion in
harsh acid environment, inhibitors are added to the acid solution
[1–5].
Organic compounds containing heteroatoms [6–14] are effec-
tive corrosion inhibitors. The corrosion scientists are focusing their
efforts on the development of environmentally safe corrosion inhi-
bitors. Earlier, biopolymers-nanomaterial composites have been
reported as corrosion inhibitors [15–18]. This approach, although
effective, but strongly puts the cost-effectiveness of the overall
process in question, especially considering the high cost of ZnO,
AgNp, etc. and also the high concentrations of such inhibitors. Fur-
ther, nanomaterials such as ZnO, AgNp, etc. in highly concentrated
acids are not able to retain their structural integrity for a long time,
thereby restricting the practical applicability of the approach.
Considering these issues, the present investigation aims at the syn-
thesis of eco-friendly corrosion inhibitor, namely 2-amino-4-(5-
hydroxy-3-methyl-1H-pyrazole-4-yl)-4H-chromene-3-carbonitrile
(PCP), which involves one-pot multicomponent synthesis protocol
using water as a solvent. PCP shows various biological activities
[19,20]. The choice of selection of PCP as corrosion inhibitor is
based on following facts (1) it is a nontoxic compound with the
partition coefficient (log Po/w) value of 0.45, which classified it as
a green corrosion inhibitor as per the Paris commission (PARCOM)
regulation [21] and Globally Harmonized System (GHS) of chemi-
cal classification [22]. (2) Structural considerations: It possesses
several N and O heteroatoms, and p-electrons as adsorption cen-
ters through which it can easily adsorb on the metal surface.
According to literature, pyrazole and pyran derivatives are effec-
tive corrosion inhibitors for mild steel in low acid concentration
[23–28]. Previously we have examined the pyran derivative perfor-
mance (2-amino-4-(4-methoxyphenyl)-7,7-dimethyl-5-oxo-5,6,7,
8-tetrahydro-4Hchromene-3-carbonitrile) in 15% HCl [29], which
showed good inhibition efficiency. In the present investigation,
we have synthesized a chromeno compound containing both pyra-
zole and pyran ring in a single molecule and to study its inhibition
effect on N80 steel in 15% HCl, and to explore its possible applica-
tion in the petroleum industry as an acidizing inhibitor.
The present work describes the synthesis of pyrazole chromene
derivative, namely 2-amino-4-(5-hydroxy-3-methyl-1H-pyrazole-
4-yl)-4H-chromene-3-carbonitrile (PCP) and its corrosion inhibi-
tion study on N80 steel in 15% HCl. The techniques applied for cor-
rosion inhibition analysis include electrochemical impedance
spectroscopy (EIS), potentiodynamic polarization (PDP). The metal
sample morphology was monitor by AFM and SEM. UV– vis spectra
are used to support the PCP-Fe complex formation. The hydropho-
bicity of the metal sample was analyzed by contact angle measure-
ment. Density functional theory (DFT) and molecular dynamics
simulations (MDS) were used to support the experimentally
obtained findings.
2. Materials and methods
2.1. Steel sample and corrosive medium
N80 tubular steel chemical composition (in wt%) was as fol-
lows: C (0.31), Si (0.19), Mn (0.92), P (0.01), S (0.008), Cr (0.2), Fe
(98.36). The area of N80 steel used in EIS and PDP analysis is
1.0 cm2. The mechanical polishing of the N80 steel surface was
done using SiC paper (600–1200). ASTM standard was used for
steel coupons preparation [30]. Analytical grade solvents and
chemicals have used for synthesis. Malononitrile (98%) and ethyl
acetoacetate were purchased from Avra chemicals, Hyderabad
India, 2-hydroxybenzaldehyde, and hydrazine hydrate (98%) were
purchased from Sigma Aldrich. The acidizing environment was
simulated by diluting analytical grade 37% HCl to 15%. The concen-
tration of inhibitor (PCP) used was in the range of 50–400 mg/L.
2.2. Synthesis protocol
The literature reported method was used for inhibitor synthesis
[31]. An aqueous mixture of hydrazine hydrate 98% (1 mmol) and
ethyl acetoacetate (2 mmol) was taken in a round bottom flask.
In this mixture, 2-hydroxy benzaldehyde (1 mmol) and malononi-
trile (1 mmol) were added successively at 35 °C temperature. The
reaction mixture were stirred vigorously for 10 min. The obtained
solid precipitate was washed with water, filtered, and crystallized
from ethanol. The purity of the product was tested TLC and struc-
ture was analyzed by 1H NMR spectra. The chemical route for inhi-
bitor synthesis and 1H NMR spectra are given in Fig. 1, and Fig. S1
respectively. Spectral data of inhibitor (PCP): 1H NMR (500 MHz,
DMSO d6) d (ppm): 1.9 (3H, s, ACH3), 4.57 (1H, s, 4-CH), 6.62 (2H, s,
ANH2), 6.7–6.97 (ArAH, m), 9.6 (1H, br, AOH) and 10.78 (1H, br,
ANH).
2.3. Electrochemical monitoring techniques
The experiments were conducted in the range of 50–400 mg/L
in 15% HCl at 308 K temperature using Gamry (REF3000). The
closed electrochemical cell consisting of graphite rod, saturated
calomel electrode (SCE), and N80 tubular steel coupons as a coun-
ter, reference, and working electrodes, respectively. In EIS 106 to
10-2 Hz range of frequency and peak to peak potential of 10 mV
were used. In PDP, 1.0 mV/s scan rate at the applied cathodic
potential of
250 mV and anodic potential of +250 mV vs. refer-
ence relative to OCP were used. The data analysis was done using
the Gamry E-Chem software package. All the experiments were
done under the static condition. The calculation of corrosion inhi-
bition efficiency was done using the below equations:
Rpct
Ract
gEIS% ¼  100 ð1Þ
Rpct
where Rpct Ract are the resistance of charge transfer with inhibitor and
without inhibitor respectively.
a p
icorr
icorr
gPDP% ¼ a  100 ð2Þ
icorr
a p
where icorr and icorr are corrosion current density without inhibitor
and with inhibitor respectively.
The impedance of a CPE is given by [32]:

n
Z CPE ¼ Y
1 o ðjxÞ ð3Þ
where Y0, x, j, and n correspond to constant of CPE, angular fre-
quency, imaginary number, and empirical exponent that reflects
Fig. 1. Synthetic scheme and molecular structure of inhibitor.
 A. Singh et al. / Journal of Colloid and Interface Science 560 (2020) 225–236
towards surface heterogeneity, respectively [33]. CPE values are
used for the estimation of double-layer capacitance (Cdl) and are
given as follows [34]:
C dl ¼ Y 0 ðxmax Þn
1
where xmax = 2p fmax, fmax represents the maximum impedance
value (
Zim) at the imaginary axis.
2.4. Surface studies
N80 steel coupons were immersed in 15% HCl for 24 h at 308 K
without and with optimum PCP concentration i.e., 400 mg/L. The
surface of N80 steel was analyzed by Ziess Evo 50 XVP scanning
electron microscope (SEM), at an accelerating voltage of 20 kV
and magnification of 1 KX. The AFM was done by NT-MDT multi-
mode atomic force microscope having an NOVA program. The
scanning area of steel coupons were 5 lm  5 lm.
The UV–vis spectra were recorded using a Jasco V-770 UV–vis
spectrophotometer. A dynamic sessile drop method was used for
the contact angle measurement at 308 K temperature.
2.5. Quantum chemical calculations
The atomic-level PCP analysis was achieved using Density Func-
tional Theory (DFT) with the help of the Gaussian 09W program
[35]. The calculation was done using 6-31 G (d, p) basis set and
B3LYP correlation functional [36]. The presence of most dominant
PCP forms in the corrosive environment was predicted by
Chemicalize-Instant Cheminformatics Solutions Software in the
pH range of 0–14 [37]. The pH of the acid solution in the present
investigation is 0.8. Some important parameters like (EHOMO),
(ELUMO) and (DE) that are the highest occupied molecular orbital
energy, lowest unoccupied molecular orbital energy and energy
gap was calculated. The quantitative estimation of the amount of
electrons transfer (DN) was computed and discussed. The real pic-
ture of corrosive media was achieved by applying the solvent effect
using a Polarized continuum model (PCM) during the simulation
process. In this model, the water acts continuum phase of solvent
whose dielectric constant is 78.54. The DFT results were visualized
using Gauss View 5 [38].
The mathematical equation used for the estimation of electron
transferred (DN) was analyzed as per Eq. (5): [39]
/
vinh
DN ¼
2ðgFe þ ginh Þ
where / represents the magnitude of work function with a value of
4.82 [40]. vinh corresponds to PCP electronegativity. The iron sur-
face and PCP absolute hardness are denoted by ƞFe and ƞinh,
respectively.
The UCA-FUKUI v 1.0 software was used for Fukui function esti-
mation [41]. The nucleophilic and electrophilic sites presenting on
the inhibitor molecules are given by (f–k) and (f+k), respectively. The-
oretically, Fukui function (fk) is written as follows:
! depressed semicircle is due to the heterogeneous nature of the
!
@ qð r Þ
fk ¼
@N ! without and with PCP, suggesting the same mechanism of N80
rÞ
tð
! !
where qð r Þ, N and tð r Þrepresents the electron density, a constant
and external potential, respectively.
2.6. Molecular dynamics simulation
Molecular dynamics simulations (MDS) were performed using
the Materials studio package [42]. The choice of Fe (1 1 0) plane
is based on its highly packed structure and high stabilization
energy [43]. The calculation was done taking 491 water molecules,
227
9 chlorine (Cl-), 9 hydronium (H3O+) ions along with 1 inhibitor
molecule (PCP) of neutral or protonated forms, and both forms
together. The solvent layers of each simulation were collected with
the iron layer in one simulation box (25.22  25.22  39.62 Å3)
ð4Þ
and optimized before MDS [44]. The simulation was done using
the COMPASS force field [45] and the NVT canonical ensemble at
303 K temperature [46]. The Eq. (7) was used for interaction energy
and binding energy estimation [47]:
Eintraction ¼ Etotal
ðEsurfaceþsolution þ Einhibitor Þ ð7Þ
In the above equation, Einhibitor is the inhibitor molecule total
energy alone, Esurfaceþsolution represents Fe(1 1 0) surface total energy
combined with solution energy without inhibitor molecule, and
Etotal corresponds to system total energy.
Radial distribution function (RDF) is given as follows [48]:
1 X
NA XNB
1 dðr ij
rÞ
g AB ðrÞ ¼  ð8Þ
hqB ilocal NA i2A j2B 4pr2
where qB local is the averaged particle density of B around particle A.
The amorphous cell module of Material Studio software was
used for the estimation of mean square displacement (MSD). The
calculation was done taking 1 inhibitor molecules, and 30Cl- or
H3O+. Ewald summation technique was used for electrostatic inter-
action computation [49]. MSD was calculated using the below
equation [50]:
" #
1 XN
2
MSDðtÞ ¼ jRi ðtÞ
Ri ð0Þj ð9Þ
N i¼1
The following equation was used for diffusion coefficients esti-
mation [51]:
1 dMSDðtÞ
D¼ lim ð10Þ
6 t!1 dt
Here, Ri ðtÞis the position vector of corrosive particle at time t
and Ri ð0Þis the position vector of corrosive particle at time 0. The
ensemble average of MSD is given by the term jRi ðtÞ
Ri ð0Þj2 . The
total number of target molecules is represented by N. This is the
most straightforward approach to boost the understanding of the
inhibitor-film behavior when it gets in contact with corrosive
species.
ð5Þ 3. Results and discussion
3.1. Electrochemical impedance spectroscopy (EIS)
The impedance data obtained from the EIS measurements were
used for the construction of Nyquist and Bode/phase angle plots
and are represented in Fig. 2a–b. According to Fig. 2a, Nyquist plots
have a single depressed capacitive semicircle with the center is
under the real axis, which represents a general charge transfer con-
trolled corrosion reaction process [52]. The occurrence of the
tubular N80 steel [53]. The impedance curves shape is similar both
ð6Þ
steel dissolution [54]. However, the size or diameter of semicircle
increases with the increment of PCP concentration, which signifies
that with the addition of PCP, deterioration of tubular steel
decreases [54]. This is because of the adsorption of PCP molecules,
which minimizes the active corrosion sites presenting on the metal
surface.
The extraction of impedance parameters was done by fitting the
Nyquist plots using the equivalent circuit, as shown in Fig. 2c. The
obtained impedance parameters such as solution resistance (Rs),
charge transfer resistance (Rct), phase shift (n) CPE constant (Y0),
228 A. Singh et al. / Journal of Colloid and Interface Science 560 (2020) 225–236

suggests that the metal surface becomes more corrosion-resistant

because of PCP adsorption [34].
As PCP concentration increase, the values of ‘‘n” increases
(Table 1). This increase in the ‘‘n” value is because of PCP adsorp-
tion on the steel surface, which causes the reduction of electrode
corrosion [55]. The charges at the metal solution interface under-
went fluctuation from the stationary state when a small amplitude
of the electric field was applied [56]. Thus, the system in this con-
dition characterized by the respective relaxation time constant (s).
The relaxation time‘‘s” measures the time required for returning to
the equilibrium state. The below-mentioned formula was used for
the determination of relaxation time ‘‘s” [57]:

s ¼ C dl Rct ¼ ðY o  Rct Þ1=n ð11Þ

The relaxation time can also be calculated using the below
equation:

s ¼ 1=2pf max ð12Þ

Fig. 2. (a) Nyquist plots in absence and presence of different concentration of PCP;
(b) Bode- phase angle plots in absence and presence of different concentration of
PCP; (c) Equivalent circuit used.
double layer capacitance (Cdl) are tabulated in Table 1. The simu-
lated Nyquist and Bode plots represent the accuracy of the fitting
capacity of the equivalent circuit and are shown in the Supplemen-
tary information (Fig. S2). It is interesting to note that as the PCP
concentration increases, the Rct values also increases, which
The obtained values of s in the absence of PCP is 0.00159 s in
15% HCl. However, with increasing concentration of PCP, the values
of s slowly increased and attained a value of 0.01273 s at an opti-
mum concentration (400 mg/L). Thus, the addition of PCP increases
the value of relaxation time constant (s) and decreases the value of
Cdl (Table 1), suggesting that discharging and charging rates to the
N80 steel/solution interface is significantly reduced. Thus, the
amount of charge that is stored as capacitance and the discharge
velocity as relaxation time constant (s) at the interface are in good
agreement with each other [58]. Therefore, the double layer
formed between the charged N80 steel surface, and the solution
represents an electrical capacitor. The adsorption of PCP molecules
over the N80 steel decreases electrical capacity by displacing the
pre-adsorbed water molecules and other ions. The electrical capac-
ity decrease with increasing concentration of PCP is because of the
protective layer formation of PCP onto the N80 steel [59]. Accord-
ing to Table 1, the decrease in the values of Cdl with increasing con-
centration of PCP is because of more adsorption of PCP molecules
that creates an adherent film of PCP over the N80 steel.
Fig. 2b represents the impedance magnitude of Bode and phase
angle plots. In the impedance and phase angle plots at the higher
frequency, i.e., 100 kHz the values of log |Z| and phase angle is close
to zero, which represents the resistive behavior of N80 steel and
corresponds to the resistance of solution enclosed between the ref-
erence and N80 steel electrodes [60]. Besides this, the phase angle
at the intermediate frequency is approaching
90° (Table 1), that
represents the capacitive behavior of the N80 steel surface. In gen-
eral, a pure capacitor has phase angle values of
90° [61]. The
approach of phase angle towards
90° reveals that the electrode
surface is becoming homogenous due to PCP adsorption. The
broadening of the maximum with the addition of PCP suggests
the adsorption of PCP [62].
3.2. Potentiodynamic polarization (PDP)
The potentiodynamic polarization curves for the N80 steel in
15% HCl without and with different concentrations of PCP are

Table 1
Electrochemical impedance parameters of N80 steel in 15% HCl at different concentrations of PCP at 308 K.

Cinh (mg/L) Rs (X) Rp (X cm2) Y0 (lF/cm2) n Cdl mF/cm2 s (s) ao gEIS (%)
Blank 0.82 5.404 ± 0.22 603 0.755 134.2 0.00159
39.09 –
50 2.65 39.18 ± 1.02 300 0.772 91.7 0.00414
52.53 86.2
100 0.80 53.7 ± 0.77 242 0.799 88.1 0.00509
61.40 89.9
200 0.509 78.1 ± 0.94 154 0.807 60.8 0.00637
61.74 93.0
300 2.094 108.4 ± 0.88 118 0.840 56.0 0.00796
64.54 95.0
400 0.976 346.1 ± 1.25 64 0.889 39.9 0.01273
66.99 98.4
 A. Singh et al. / Journal of Colloid and Interface Science 560 (2020) 225–236
shown in Fig. 3 at 308 K. The corrosion parameters such as corro-
sion potential (Ecorr), anodic Tafel slope (ba), cathodic Tafel slope
(bc), corrosion current density (icorr) and percentage inhibition effi-
ciency (g%) were calculated and listed in Table 2. The analysis of
Fig. 3, suggests that both anodic as well as cathodic Tafel curves
were shifted towards the lower current density with increasing
the concentration of the PCP, indicating that addition of PCP slows
down both the anodic N80 steel corrosion and cathodic hydrogen
evolution reactions simultaneously. This reveals the mixed nature
of corrosion inhibition performance of PCP.
Table 2 reveals that the value of corrosion current density (icorr)
decreases as the concentration of PCP increases suggesting that the
PCP molecules adsorbed on the N80 steel surface. The values of
anodic and cathodic Tafel slopes without and with PCP addition
are more or less the same, which reveals that PCP addition doesn’t
alter the corrosion inhibition mechanism, and its adsorbed merely
by obstructing the active sites presenting over the N80 steel sur-
face [63]. Also, the inhibition performance of PCP increases as the
concentration increased. It is important to note that the addition
of PCP causes a minor change in the values of Ecorr, thereby sug-
gesting the mixed nature of PCP inhibition action.
3.3. Adsorption isotherm
The interaction mode between the corrosion inhibitors and the
metal surface can be analyzed by understanding the adsorption
isotherms. In the present study, Langmuir, Temkin, Frumkin, Flow-
ery Huggins, and Freundlich isotherms were tested (Given in sup-
plementary file Fig. S3). The fitting accuracy of Langmuir isotherm
was best over the range of experimental data and mathematically
is given as follows [63,64]:
C=h ¼ 1=K þ C
where C is PCP concentration (mM), h is surface coverage, and Kads is
equilibrium adsorption constant.
The surface coverage data was taken from EIS and PDP for plot-
ting Langmuir isotherm. It can be observed that in each case, a plot
of C vs. C=h gives a linear graph, with a correlation coefficient (R2)
and slope values near to 1 (Fig. 4). The intercept values were used
for Kads calculation (Table S1 in the Supplementary information).
The below equation represents the relationship between the
Kads and standard free energy of adsorption (DG0ads ) [65]:
DG0ads ¼ - RTlnð55:5Kads Þ
Fig. 3. Potentidynamic polarization curves in the absence and presence of different
concentrations of PCP.
229
where R, T, and 55.5 are gas constant, the temperature of the sys-
tem, and water molecules concentration in molar. Negative values
of DG0ads indicated the spontaneity of the adsorption process. The
values DG0ads are between
40 and
20 kJ mol
1 that corresponds
to the existence of dual adsorption process i.e., physical and the
chemical.
3.4. Surface morphological analysis
3.4.1. Scanning electron microscopy
SEM micrographs without and with the addition of PCP are
depicted in Fig. 5(a,b). The morphological appearance of N80 steel
without the addition of PCP reveals a severally damaged surface
(Fig. 5a). However, the addition of PCP makes the N80 steel surface
morphology almost smooth. This is due to the adsorption of PCP
over the N80 steel surface (Fig. 5b).
3.4.2. Atomic force microscopy
The AFM micrographs of the metal surface are depicted in Fig. 5
(c, d). The N80 steel surface morphology is highly damaged with-
out adding PCP (Fig. 5c), and the surface roughness is 51.4 nm.
Although, the addition of PCP (Fig. 5d) makes the surface smooth,
and average roughness decreased to 8.3 nm.
3.4.3. UV–vis spectroscopic analysis
The spectrum of PCP solution in 15% HCl before and after
immersion of the N80 steel sample is shown in Fig. 6. It is clear that
in the presence of PCP without immersing N80 steel, three absorp-
tion bands at 217.86 nm, 256.58 nm-276.84 nm and 326.68 nm
were observed, which are due to the n ? p* transition, p ? p*
transition and intramolecular charge transfers, respectively [66].
ð13Þ The absorbance band at 217.86 nm is decreased in case of PCP
+ N80 steel solution. The band at 256.58 nm undergoes a blue shift
and appears at 252.00 nm with higher absorbance. The band at
276.84 nm has disappeared. Also, a band at 330.35 nm appeared
with higher absorbance. The significant change in the characteris-
tics of the electronic spectrum indicates the possible formation of
an inhibitor-metal complex.
3.4.4. Contact angle measurement
The difference in hydrophobicity of N80 steel without and with
PCP was analyzed via contact angle measurements, as shown in
Fig. 7. In the absence of PCP, the contact angle value is 29.31°,
ð14Þ
which corresponds to the hydrophilic nature of the tubular N80
steel surface [67]. However, as the concentration of PCP increased
from 50 mg/L to 400 mg/L, the contact angle rises from 50.25° to
112.99°. This increase in contact angle with increasing PCP concen-
tration reveals that the wettability of the N80 steel surface reduced
and surface becomes hydrophobic due to PCP adsorption and film
formation onto the metal surface [68].
3.5. Computational studies
3.5.1. Quantum chemical calculations
The results of the molecular distribution of PCP with the pKa are
represented in Fig. 8. Inspection of the figure reveals that in the pH
range of 0–2, protonation of ANH2 atom takes place, which has a
pKa value of 4.71.
In an aqueous acidic solution, there is a tendency of inhibitor
molecules to undergo protonation. The determination of protona-
tion can be done by comparing the proton affinity of heteroatoms
[69]. The Proton Affinity (PA) can be calculated using the below
equations:
PA ¼ EðproÞ
ðEðnon
proÞ þ EHþ Þ ð15Þ
230 A. Singh et al. / Journal of Colloid and Interface Science 560 (2020) 225–236
Table 2
Electrochemical polarization parameters in absence and presence of different concentrations of PCP at 308 K.
Inhibitor (mg/L) Ecorr (mV/SCE) icorr (lA/cm2)
Blank
443 1630 ± 1.63
50
412 274 ± 2.86
100
400 209 ± 2.05
200
403 183 ± 2.86
300
407 154 ± 1.63
400
420 113 ± 1.24
Fig. 4. Langmuir Isotherm plots for the adsorption of inhibitor.
where Enon-pro and Epro are the energies of the non-protonated and
protonated PCP, respectively. E+H is the energy of H+ ion and was cal-
culated as:
EHþ ¼ EðH3Oþ Þ
EðH2 OÞ ð16Þ
The higher negative is the value of PA, more would be its nucle-
ophilic character, and thus more reactive is that site. In the present
case ANH2, ACN and AOH has the most negative Mulliken charge
values (Table S2 in the Supplementary information). Therefore, the
PA of these sites was calculated and tabulated in Table S3. Accord-
ing to the table ANH2 has the most negative value of PA, which
reveals that this is the most preferred site for protonation. The
result of PA is also supporting the theoretically obtained result
by Chemaxon software [70].
The quantum chemical parameters and molecular orbitals dis-
tribution are given in Table 3 and Fig. 9(a–f).
The most stable metallic state of iron is Fe (1 1 0), which has a
BCC structure [71]. According to Huang et al., the atomic cluster of
five-iron atom, i.e., Fe5, has the values of
5.075 eV and
1.747 eV
for EHOMO and ELUMO, respectively. According to FMO, binding of
PCP (inhibitor molecules) over iron depends upon the interaction
between EHOMO and ELUMO of inhibitor molecules and iron [72]. In
general, lower the energy gap (DE) between EHOMO and ELUMO of
interacting species, stronger will be the interactions, which leads
to stronger adsorption [73].
In Table 3, the energy gap between EHOMO of the iron atom clus-
ter and ELUMO of the PCP molecule is represented by DE1. Moreover,
the DE2 corresponds to the energy gap between EHOMO of the PCP
and ELUMO of the iron atom cluster. In other words, DE1 corre-
sponds to the donation of an electron from the iron atom cluster
to inhibitor molecules, i.e., back donation. However, DE2 corre-
spond to donation of electron from PCP to iron atom cluster, i.e.,
direct contribution.
According to Table 3, in the neutral form of inhibitor, the values
of DE2 is lower than DE1, which reveals the electron-donating
Βa (mV/dec)
bc (mV/dec) gPDP (%)
86 101 –
93 133 83.1
80 125 87.1
83 144 88.7
77 134 90.5
105 161 93.1
capacity of the neutral form of PCP to iron atom cluster through
a direct donation. Moreover, the value of DE1 in the case of a pro-
tonated form of PCP is lower than the DE2, which suggests the elec-
tron acceptance tendency of the protonated form of PCP from the
iron atom cluster via back bonding. Furthermore, the lower value
DE1 of the protonated form of PCP than the neutral form suggests
that the protonated form of PCP has the electron-accepting ability.
However, lower value DE2 of the neutral form of an inhibitor than
protonated form reveals the electron-donating tendency of the
neutral form of inhibitor.
The DN values in the case of neutral PCP are more than proto-
nated, suggesting neutral inhibitor has more electron-donating
capacity to iron surface than a protonated inhibitor. From the
above discussion, it is concluded that the inhibitor (PCP) tends to
donate as well as accept electrons. So, to justify the above state-
ment, it becomes necessary to visualize the active site of the inhi-
bitor molecules that participate in donor-acceptor interactions.
Therefore, three parameters: (a) Frontier molecular orbitals distri-
bution of inhibitor molecules, (b) Molecular electrostatic potential
analysis (ESP) has to discuss.
(a) Frontier molecular orbitals distribution of inhibitor
molecules
The HOMO regions of PCP are residing onto pyrazole and pyran
rings, an amine group (ANH2), hydroxyl group (AOH), and nitrile
group (ACN) for the neutral form of PCP, while in protonated form
of PCP it is on the pyrazole ring and AOH group. However, the
LUMO regions in neutral PCP are distributed on the pyran and phe-
nyl ring, ANH2 and ACN groups, whereas in protonated PCP LUMO
regions are scattered on the pyran ring, phenyl ring and ANH2
group. The discussion related to Fukui indices is given in the Sup-
plementary information along with the data of Fukui indices as
Table S3.
(b) Molecular electrostatic potential analysis
The local reactivity center presenting in the inhibitor molecule
can be predicted using a molecular electrostatic potential (MEP)
plot, which is based on the isoelectron density surface. Computa-
tionally the calculation of molecular electrostatic potential V(r)
existing between the nucleus and electron of the inhibitor mole-
cules are given by the below equation:
X qNucleus Z qðr 0 Þdr 0
VðrÞ ¼ A

ð17Þ
A
j RA
r j jr 0
r j
where q(r) represents the electronic density function of the mole-
cule with a charge qNucleus
A . On the nucleus A located at a distance
RA. The calculation of MEP plots of neutral and protonated PCP
molecules was calculated using the B3LYP/6-31G (d, p) level of the-
ory and shown in Fig. 9(g,h). The electron-donating regions are rep-
resented by a red color that has significant negative values of the
potential, while the electron-accepting areas are presented by blue
colors that have large positive values. The other colors like orange,
yellow, and green, represent intermediate values of the potential. It
 A. Singh et al. / Journal of Colloid and Interface Science 560 (2020) 225–236 231

Fig. 5. SEM images (a) In absence of PCP (b) in the presence of PCP; and AFM images (c) in the absence of PCP; and (d) in the presence of PCP.

is evident from Fig. 9, in case of neutral PCP molecule, red regions
are located on nitrogen and oxygen atoms of pyrazole, pyran,
ACN, ANH2, and AOH. Whereas, the blue areas are on hydrogen
atoms of pyrazole and pyran rings. However, after protonation,
almost the whole PCP molecule becomes blue, and the intensity
of the blue color is more over the protonated ANH2 group. The
results obtained from MEP suggest that electron-rich centers like
nitrogen and oxygen atoms of PCP interact with the electron-
deficient center of the tubular N80 steel, whereas, the electron-
deficient center accepts electrons from the electron-rich regions
of the tubular N80 steel.
3.5.2. Molecular dynamics simulation
In the following paragraphs, we utilize molecular dynamic sim-
ulation strategy to discover hidden factors that can help us to
understand the underlying adsorption mechanisms and the inter-
active forces of the tested inhibitor, which can overcome many of
the limitations of quantum chemical-based methods. Herein, the
simulation of the interaction between the inhibitor molecule in
its neutral and protonated form with the iron surface can yield use-
ful information on how these changes influence its interactive
forces. Fig. 10 presents the optimized adsorption configurations
of the neutral (PCP-2), protonated (PCP-1), and both forms (PCP)
of the inhibitor molecule on the Fe(1 1 0) surface.
In three simulated systems, i.e., neutral (PCP-2), protonated
(PCP-1) and both neutral and protonated (PCP), we observe that
the inhibitor molecule showed a strong binding affinity towards
the iron surface and significant part of its molecular skeleton has
nearly flat or parallel adsorption over the iron surface. A close
inspection of the results showed that the protonated form exhib-
232 A. Singh et al. / Journal of Colloid and Interface Science 560 (2020) 225–236
Fig. 6. UV–visible spectra.
ited almost parallel adsorption and primarily covered the metal
surface compared to neutral form. This means that physical inter-
actions, which are the first step in the case of an organic corrosion
inhibitor in acid medium, can significantly attract protonated inhi-
bitor molecules, giving rise to the high interaction with the iron
surface. Looking now at the adsorption of both forms on the iron
surface. Both forms are close to the iron surface. However, it is
clear that the pyrazole moiety of the neutral form is oriented ver-
tically to the solvent layer.
The binding energies of PCP-2, PCP-1, and PCP are
465.47,

589.69, and
774.21 kJ/mol, respectively. The interaction ener-
gies are high that corresponds to strong adsorption among the
PCP and iron surface [74]. Inhibitors with higher values of binding
energy have a higher ability to adsorb. The trend of the increasing
interaction energy for PCP, PCP-1, and PCP-2 is as follows PCP-
2 < PCP-1 < PCP. It is predicted that PCP should provide higher
interaction energy due to accumulated multiple adsorption sites
Fig. 7. Contact angle (a) In absence of PCP (b) at 50 mg/L of PCP (c) at 100 mg/L of PCP (d) at 200 mg/L of PCP (e) at 300 mg/L of PCP (f) at 400 mg/L of PCP.
Fig. 8. Computational prediction of PCP speciation within pH 0–14 at room
temperature.
in neutral as well as protonated forms, whereas the nearly flat
adsorption of PCP-1 is the origin of its higher interaction energy.
The radial distribution functions (RDF) curves of the neutral and
protonated inhibitor, and the mean square displacement (MSD)
trajectories are given in Fig. S4 in the Supplementary information
along with the related discussion.
3.6. Inhibition efficiency comparison with environmentally friendly
inhibitors
The corrosion inhibition performance of PCP was compared
with other environmentally friendly inhibitors. For example, Solo-
 A. Singh et al. / Journal of Colloid and Interface Science 560 (2020) 225–236 233

Table 3
Energy order of the frontier molecular orbitals.

Inhibitor (mg/L) EHOMO (eV) ELUMO (eV) DE1 (eV) DE2 (eV) DN (%)
Fe5
5.075
1.747 – – –
PCP
5.452
0.441 4.634 3.705 0.373
PCP*
6.170
2.218 2.857 4.423 0.158

DE1 = ELUMO (inhibitor)
EHOMO (Fe).

DE2 = ELUMO (Fe)
EHOMO (inhibitor).
DE3 = ELUMO (inhibitor)
EHOMO (inhibitor).
*
Protonated molecule.

Fig. 9. Neutral PCP (a) Optimized geometry (b) HOMO (c) LUMO; Protonated PCP (a) Optimized geometry (b) HOMO (c) LUMO; Molecular Electrostatic Potential diagrams of
(g) Neutral PCP (h) Protonated PCP.

mon et al. [75] have investigated the corrosion inhibition of
N-(2-(2-pentadecyl-4,5-dihydro-1H-imidazol-1-YL) ethyl) palmi-
tamide in 15% HCl and obtained the corrosion inhibition efficiency
(IE%) of 97.48%. Yadav et al. [76] explored the corrosion inhibition
of carbohydrate compounds and got the corrosion protection effi-
ciency of 95% and 92%. Yadav et al. [77] synthesized 1-(2-oleylami
doethyl)-2-oleylimidazoline (OAEOI). They found IE% of 94.75%. In
the study the IE% is 98.4%.
4. Conclusions
The corrosion inhibition performance of PCP at low concentra-
tion is better than the earlier reported heterocyclic organic
inhibitors as well as nanocomposites in the acidizing environment
[17–20,78]. The ability of PCP to inhibit corrosion is 98.4% at only
400 mg/L concentration. Τhe Langmuir isotherm perfectly
describes the PCP adsorption. The spontaneity of adsorption was
justified by negative values of DG0ads and their magnitude corre-
sponds to physical and chemical adsorption phenomenon
[39,41,53,63]. The results of EIS reveals that Rct values increase as
PCP concentration increase. PDP studies suggest that PCP is a
mixed kind of inhibitor. In quantum chemical calculations, the pro-
tonation site is ANH2 group that is correlating the theoretically
obtained results. MDS study reveals that the combined forms of
neutral and protonated PCP interacted strongly with the metal sur-
face than neutral and protonated alone. Additionally, the MSD
234 A. Singh et al. / Journal of Colloid and Interface Science 560 (2020) 225–236

Fig. 10. Side and top views of the adsorption of the PCP on the Fe (1 1 0) surface in solution.

result suggests that diffusion coefficient values of corrosive parti- potential candidate during the acidizing process. In the future, the
cles, i.e., chloride and hydronium ions, in PCP films are very small performance of PCP for high-temperature wells can further
compared to that in water. The developed inhibitor (PCP) can be a enhanced by developing new formulations using PCP as a core
 A. Singh et al. / Journal of Colloid and Interface Science 560 (2020) 225–236
component. The study explains the interfacial corrosion inhibition
process at the macro as well as micro-level in detail.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgment
The authors gratefully acknowledge the funding from Deanship
of Scientific Research (project no. DF181007) King Fahd University
of Petroleum and Minerals and Youth Scientific and Innovation
Research Team for Advanced Surface Functional Materials, South-
west Petroleum University (Project no. 2018CXTD06).
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jcis.2019.10.040.
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