Desalination 470 (2019) 114100

Contents lists available at ScienceDirect

Desalination
journal homepage: www.elsevier.com/locate/desal

Highly efficient corrosion inhibitor for C1020 carbon steel during acid T
cleaning in multistage flash (MSF) desalination plant
Aeshah H. Alamria, I.B. Obotb,
⁎

a
Chemistry Department, College of Science, Imam Abdulrahman Bin Faisal University, P.O. Box 76971, Dammam, Saudi Arabia
b
Center of Research Excellence in Corrosion, Research Institute, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: A new environmentally friendly and cost effective molecule, thiabendazole (TBZ), was evaluated as a potential
Thiabendazole acid corrosion inhibitor for a typical carbon steel (C1020 grade) used as construction material in MSF desali-
Corrosion inhibitor nation plant using electrochemical and (weight loss) immersion techniques. Electrochemical measurements after
Carbon steel 1, 4 and 8 h immersion in 1.0 M HCl at 25 °C showed that TBZ is an excellent corrosion inhibitor for C1020 grade
Electrochemistry
steel and its inhibition efficiency reaches ≈90% at 4 mM concentration with no substantial increase at 10 mM.
Theoretical calculations
In the presence of iodide ions, TBZ showed improved corrosion inhibition attaining inhibition efficiency of
94.3% with 4 mM concentration after 4 h of testing with no increase in inhibition efficiency after 8 h. However,
weight loss measurements indicate that the corrosion inhibition performance of TBZ, and TBZ in combination
with KI decreased with immersion time up to 24 h and temperature up to 60 °C. SEM-EDX and ATR-IR spec-
troscopy confirm that the inhibition process was due to the formation of an adsorbed film that protects the steel
surface against corrosive medium. DFT and Monte Carlo simulation results gave further molecular and atomic
level insight on mechanism of interaction between the inhibitor and the steel surface.

1. Introduction corrosion attack on steel–based production equipment and heat ex-

changers [1–3]. The consequences of such corrosion phenomenon in-
The industrial practice of acid cleaning of multistage flash (MSF) clude the loss of material aesthetics and strength, as well as enormous
desalination plants to remove scales usually leads to significant cost of corrosion control [4,5]. In order to ameliorate such acid

⁎
Corresponding author.
E-mail address: obot@kfupm.edu.sa (I.B. Obot).

https://doi.org/10.1016/j.desal.2019.114100
Received 28 June 2019; Received in revised form 5 August 2019; Accepted 7 August 2019
0011-9164/ © 2019 Elsevier B.V. All rights reserved.
A.H. Alamri and I.B. Obot
corrosion of steel, industries adopt the economically viable approach of
adding effective corrosion inhibitors into the cleaning solution. They
derive such motivation from the reports of numerous research works
[6–15]. However, current global regulations emphasize the use of en-
vironmentally–friendly chemicals as corrosion inhibitors [16,17]. This
has encouraged research focus towards the development of acid cor-
rosion inhibitors derived from non–toxic, cheap and readily available
pharmacologically–active chemicals which form the nucleus of many
drugs.
Corrosion inhibitors derived from the active components of drugs
usually contain extended π–electron systems (in aromatic and cyclic
rings) and electronegative elements like oxygen, nitrogen and sulfur
atoms. The electrons from the π–system and/or the electronegative
elements interact with the d–states of Fe atoms on the steel surface to
facilitate the adsorption of the inhibitor molecules on the steel surface
[18]. Some of the most notable drug-like molecules which have been
reported as effective inhibitors for the acid corrosion of steel are based
on azoles [19–28]. Azoles are nitrogen–based five–membered hetero-
cyclic organic compounds which have well–established pharmacolo-
gical properties [29]. Their ability to exist as protonated species in an
acid solution enables them to retard the corrosion by blocking cathodic
sites on the steel surface and, thereby, decreasing the rate of electron
transfer from the anodic sites during the electrochemical corrosion
process. Azoles containing sulfur in their molecular structure are re-
ported to exhibit even greater inhibition compared with those con-
taining only nitrogen atoms [30–32].
Obot et al. [19] showed that, at concentration up to 10 μM, me-
tronidazole acted as an effective corrosion inhibitor for mild steel and
provided about 80% inhibition efficiency in 0.5 M HCl solution. The
inhibitive property of tinidazole on mild steel was also reported by Reza
et al. [20] whereby 400 ppm of the drug gave up to 90% efficiency in
1 M HCl solution. In 2.5 M HCl concentration, fluconazole exhibited an
inhibition efficiency of 96% by chemically adsorbing to form a highly
protective inhibitor film on mild steel surface [21]. Other azole–based
drug-like active components reported as acid corrosion inhibitors for
steel include itraconazole [22], benzimidazole [23], secnidazole [24],
albendazole [25], mebendazole [26], and even nitroimidazole [27].
The purpose of the present work is to assess thiabendazole (TBZ) as
a promising inhibitor for the acid corrosion of carbon steel at 25 and
60oC. Thiabendazole is the principal component of commercial anti-
fungal and antiparasitic drugs with trade names such as mintezol, tre-
saderm or arbotect. It exhibits a lethal dosage (LD50) value of 2080 mg/
kg in rats making it non-toxic [33,34]. As described in Fig. 1, its mo-
lecular structure consists of the fusion of benzimidazole (principal
component of many anthelmintic drugs) and thiazole (major compo-
nent of vitamin B1). This makes the investigated molecule interesting as
both benzimidazole and thiazoles are molecules containing both N and
S heteroatoms. To the best of our knowledge, no report on thiabenda-
zole as an acid corrosion inhibitor for C1020 carbon steel is available in
the literature. Such work is necessary to contribute to the growing
database of drug–related chemicals useful as environmentally–friendly
acid corrosion inhibitors.
In this work, we employ electrochemical methods (electrochemical
impedance spectroscopy (EIS), electrochemical frequency modulation
(EFM), linear polarization resistance (LPR) and potentiodynamic
Fig. 1. Structure of thiabendazole (TBZ).
2
Desalination 470 (2019) 114100
polarization (PDP)) and weight loss technique to acquire kinetic and
mechanistic information about the inhibition property of TBZ and TBZ
+ KI. Surface analytical methods such as attenuated total reflectance
infrared (ATR–IR) spectroscopy and scanning electron microscopy
(SEM) coupled with energy dispersive X–ray spectroscopy (EDX) were
used to confirm the formation of inhibition film on the steel surface.
Eventually, we harness quantum chemical calculations and Monte Carlo
simulations to provide molecular–level interpretation of the inhibitive
actions of TBZ.
2. Experimental
2.1. Materials and solution
The corrosion environment was 1 M HCl solution which was pre-
pared by diluting appropriate volume of analytical grade stock acid
(Sigma Aldrich) in distilled water, according to recommended proce-
dure [35]. The corrosion study was conducted on C1020 carbon steel
electrode with elemental composition 0.200% C, 0.470% Mn, 0.012%
P, 0.013% S, and the remainder as Fe. Stock solution of thiabendazole
(Sigma Aldrich) was prepared in formic acid because of solubility issues
with water and other organic solvents. Electrochemical measurements
were initially employed to investigate the performance of TBZ at 25 °C
using different concentrations of 1, 2, 4 and 10 mM. At the inhibitor
concentration when the increase in inhibition efficiency became insig-
nificant, the synergistic effect of 5 mM potassium iodide (KI) was stu-
died after 1, 4 and 8 h immersion of the carbon steel in the acid solu-
tion. Nevertheless, typical acid cleaning of MSF units in desalination
plants is usually conducted at relatively high temperatures (up to 60 °C)
and longer exposure times (at least 24 h). Consequently, weight loss
measurement was deployed to investigate the performance of the TBZ
alone and TBZ + KI after 8 and 24 h exposure of C1020 carbon steel at
25 and 60 °C. Prior to the electrochemical corrosion testing, the steel
samples were prepared by embedding in epoxy so as to allow an ex-
posed surface area of 1 cm2, while electrical contact was achieved with
copper wires attached to the samples. For weight loss measurements,
the total exposed surface area of the steel coupon was 20.50 cm2. The
steel electrodes were mechanically abraded using silicon carbide papers
which ended with the #800 grit size. This was followed by the sequence
of washing with distilled water, degreasing thoroughly with acetone
and drying with warm air.
2.2. Electrochemical measurement
The electrochemical measurements were performed in a standard
250 mL three–electrode cell using a Gamry 600 potentiostat/galvano-
stat. The C1020 steel electrode served as the working electrode whereas
the reference electrode was Ag/AgCl (3 M KCl) and the counter elec-
trode was a graphite rod. The establishment of a steady state condition
prior to the corrosion testing was ensured by performing an open circuit
potential (OCP) determination during 3600 s free corrosion of the steel
sample in the acid solution without and with the different TBZ working
concentrations. At the OCP, the electrochemical impedance spectro-
scopy (EIS) measurement was performed by applying a sinusoidal fre-
quency perturbation from 100 kHz to 0.1 Hz using frequency amplitude
of 10 mV. The EIS parameters were, thereafter, derived by fitting the
impedance results to an appropriate equivalent circuit with the aid of
the Gamry EChem analyst software. The electrochemical frequency
modulation (EFM) measurements were undertaken by applying a base
frequency of 1 Hz with multiplexer frequencies of 2.0 and 5.0 Hz.
Linear polarization resistance (LPR) measurement was performed by
polarizing the working electrode ± 10 mV around the OCP using a scan
rate of 0.166 mV s−1. The potentiodynamic polarization was carried
out within ± 250 mV against the OCP at a scan rate of 0.2 mV s−1.
A.H. Alamri and I.B. Obot Desalination 470 (2019) 114100

2.3. Surface analysis

(a)
After immersing for 24 h in the HCl solution without and with the
optimum TBZ concentration, the adsorption of the inhibitor on the
C1020 steel surface was ascertained by performing FTIR in attenuated
total refection (ATR) mode using a Nicolet iS5 FTIR spectrophotometer
equipped with an iD5 ATR. Additionally, the surface morphology of the
C1020 carbon steel was analysed after the 24 h immersion in the HCl
solution without and with KI, TBZ, and the TBZ + KI mixture using the
SEM/EDX Ziess Evo 50 XVP instrument.

2.4. Theoretical considerations

The DMol3 module in Materials Studio (MS) software (version 8.0,

from Dassault Systemes BIOVIA Inc. USA) was used to perform the
density functional theory (DFT) calculations [36]. The geometry of TBZ
and its protonated form TBZH were optimized by the combination of
the generalized gradient approximation (GGA) functional of Becke ex-
change plus Lee-Yang-Parr correlation (BLYP) and the double numer- (b)
ical with polarization (DNP) basis set. The effect of water molecules in
the corrosion system was accounted for in the DFT calculation by ap-
plying the conductor-like screening model (COSMO) [37]. Monte Carlo
simulation was utilized to compute the adsorption configuration and
energetics. Metropolis Monte Carlo simulation, with the adsorption
locator module in the Material Studio 8.0, was employed for this pur-
pose. The calculation was carried out using the COMPASS (Condensed-
phase Optimized Molecular Potentials for Atomistic Simulation Studies)
forcefield [38]. The adsorption parameters involved in the corrosion
inhibition were determined by simulating the interaction of TBZH on
the surface of Fe (110), which is considered as the most stable crystal
phase in steel. TBZH was adopted in the Monte Carlo simulation since
the protonated specie was found to give the least energy gap and also to
be the most dominant in 1 M HCl predicted using ACD/LABS percepta
software 14. To simulate effect of solvent, 100 water molecules were
added to the simulation box.
Fig. 2. (a) Nyquist plots and (b) Bode plots for C1020 steel in 1 M HCl con-
3. Results and discussion taining various concentrations of TBZ.

3.1. Electrochemical impedance spectroscopy (EIS)

During acid corrosion of steel, the solution species assemble at the
steel–solution interface where they constitute an electric double layer
with characteristic capacitance and resistance to transfer of charges.
The rate and mechanism of electron transfer between anodic and
cathodic sites on the steel surface are, therefore, influenced by the
property of this double layer [39]. With electrochemical impedance
spectroscopy (EIS), the dielectric properties of such interface (and the
effect of a corrosion inhibitor) can be effectively determined.
Fig. 2(a) and (b), respectively, present the Nyquist and Bode formats
of the EIS result obtained during the corrosion of C1020 carbon steel in
1 M HCl solution without and with different TBZ concentrations. The
shapes of the Nyquist plots, in the absence and presence of TBZ, are
depressed semi–circles which increase in size due to the addition of TBZ
into the acid solution. The shapes of the Nyquist plots are indicative of
corrosion processes controlled strictly by charge transfer phenomena
[40,41]. Similar shapes of the Nyquist semi–circle displayed both in the
absence and presence of TBZ implies that the corrosion inhibitor ad-
dition does not change the corrosion mechanism in the acid solution,
but strongly modifies the dielectric properties of the electric double
layer. More so, the depressed nature of the Nyquist semi–circle deviates
from the ideal shape, and is attributed to phenomena at the steel–so-
lution interface, such as frequency dispersions, surface inhomogeneity
and mass transport resistance [42,43].
The Bode plots in Fig. 2(b) show phase angles with single peaks
throughout the frequency scan. The phase angle peaks are higher and
broader in the presence of TBZ than in the blank solution, becoming
more pronounced with higher TBZ concentrations. This indicates
greater adsorption and superior inhibitive property of TBZ at higher
concentration. This can also be confirmed by the higher values of ab-
solute impedance at low frequency measured in the presence of in-
creasing TBZ concentration, as shown in the Bode plots of Fig. 2(b).
Typical interpretation of the EIS results with electrical elements was
achieved by modelling the steel–solution interface (without and with
inhibitor) using the equivalent circuit described in Fig. 3 after fitting
with the Gamry Echem Analyst software. Rs depicts the solution re-
sistance, Rct represents the charge transfer resistance and CPEdl is the
constant phase element. The CPEdl is used, in place of a capacitor, to
account for the frequency dispersion caused by inhomogeneity and
formation of porous layers on the electrode surface [44]. However, the
double layer capacitance (Cdl) provides a better validation of an
equivalent circuit model according to the Eq. (1) [45], where Yo is the
magnitude of admittance of the CPE and n is the exponential term
which is a measure of surface inhomogeneity. The values of the fitted
parameters are provided in Table 1.
1
Cdl = (YoR ct1 n) n (1)
R oct
%IE = 1 × 100
R ct (2)
The values in Table 1 clearly reveal that the Cdl decreases while the
Rct increases upon the addition of TBZ into the acid solution, and these
were more pronounced at higher TBZ concentrations. This indicates
that the adsorption of TBZ molecules on the steel surface, during the

3
A.H. Alamri and I.B. Obot Desalination 470 (2019) 114100

Fig. 3. Experimental and fitted EIS data with equivalent circuit model for C1020 steel corrosion in 1 M HCl solution without and with 1 mM TBZ.

acid corrosion, decreases the local dielectric constant and/or increases mechanism both in the absence and presence of TBZ. Therefore, the
the double layer thickness at the steel–solution interface. This ob- EFM measurements were carried out using the activation model,
servation is usually attributed to the ability of the inhibitor molecule to whereby the corrosion current density (icorr) and Tafel constants (βa)
displace water molecules and other solution species primarily adsorbed and (βc) can be derived based on the Eqs. (3)–(5). The accuracy of re-
on the steel surface [46,47]. Thus, the adsorbed TBZ molecules increase sults derived from EFM measurements is usually ratified with the use of
the hydrophobicity of the steel surface, hence, the attack on the steel causality factors (CF), CF2 and CF3, derived according to Eqs. (6) and
surface by corrosive agents in the acid solution is significantly miti- (7), where i represents the current response at the steel electrode ob-
gated. Furthermore, the value of % IE was calculated from the Eq. (2): tained at frequency ω, and U0 is the amplitude of the applied frequency.
where Rcto and Rct signify the charge transfer resistance in the absence 2
(i 1. 2 )
and presence of TBZ, respectively. The % IE also increases with increase i corr =
2
in TBZ concentration and confirms the protective ability of TBZ. 2 8i 1. 2 i2 2 ± 1 3(i 1. 2 ) (3)

3.2. Electrochemical frequency modulation (EFM) U(i 1. 2)

c =
2
( i 2± 1) + 8i 1 . 2 i2 1 ± 2 3(i 1. 2 ) (4)
As an emerging electrochemical method for corrosion analysis, the
EFM method is non–destructive and can determine corrosion current U(i 1. 2 )
density (icorr) with high speed and accuracy without prior knowledge of a =
2
(i 2 ± 1) + 8i 1 . 2 i2 2 ± 1 3(i 1. 2 ) (5)
the Tafel constants. The application of the EFM method in corrosion
analysis has been discussed extensively in a recent review by Obot and
i 1± 2
Onyeachu [48]. The EIS results showed that the corrosion of C1020 CF2 = =2
carbon steel in 1 M HCl proceeds strictly by a charge transfer
i2 1 (6)

Table 1
EIS parameters for C1020 steel in 1 M HCl containing various concentrations of TBZ.
Conc. Rs Yo n Cdl Rct Goodness of fit % IE
(mM) (Ω cm2) (μFcm−2 sn–1) (Ω cm2) (×10−3)

Blank 0.8854 ± 0.006 119.1 ± 0.14 0.8735 ± 0.000 73.23 ± 0.37 97.63 ± 3.11 0.3352 ± 0.06 –
1 1.478 ± 0.004 76.6 ± 0.08 0.8381 ± 0.000 36.90 ± 0.15 702.4 ± 7.70 0.6713 ± 0.01 86.1 ± 0.21
2 1.371 ± 0.000 68.63 ± 0.08 0.8135 ± 0.000 34.33 ± 0.07 887.9 ± 4.93 1.3745 ± 0.02 89.0 ± 0.05
4 0.8967 ± 0.003 58.96 ± 0.23 0.8278 ± 0.000 28.73 ± 0.22 952.1 ± 4.78 0.4398 ± 0.01 89.8 ± 0.24
10 0.9797 ± 0.003 51.28 ± 0.18 0.8281 ± 0.000 24.55 ± 0.29 1053.5 ± 10.50 1.977 ± 0.02 90.7 ± 0.12

4
A.H. Alamri and I.B. Obot Desalination 470 (2019) 114100

(a) (b)

(c)

(d) (e)

Fig. 4. Intermodulation frequency obtained for C1020 carbon steel in 1 M HCl (a) without and with (b) 1 mM (c) 2 mM (c) 4 mM (d) 10 mM TBZ.

5
A.H. Alamri and I.B. Obot Desalination 470 (2019) 114100

Table 2
EFM parameters for C1020 steel in 1 M HCl containing various concentrations of TBZ.
Conc. icorr βa βc CF 2 CF 3 % IEEFM
(mM) (μA/cm2) (mV/dec) (mV/dec)

Blank 223.0 ± 1.41 97 ± 0.00 102 ± 0.00 2.37 ± 0.05 3.07 ± 0.06 –
1 45.61 ± 1.70 144 ± 2.94 164 ± 2.65 1.85 ± 0.07 2.87 ± 0.03 79.3 ± 0.35
2 42.82 ± 0.49 146 ± 1.41 162 ± 1.41 1.90 ± 0.02 2.74 ± 0.06 80.9 ± 0.14
4 39.79 ± 0.18 140 ± 0.00 168 ± 1.41 1.92 ± 0.04 2.85 ± 0.01 82.3 ± 0.21
10 37.25 ± 0.42 149 ± 2.12 166 ± 2.83 1.96 ± 0.03 3.18 ± 0.07 83.4 ± 0.49

i2 1± 2
CF3 = =3
i3 1 (7)

The EFM results obtained during the corrosion of C1020 carbon

steel in 1 M HCl solution without and with different TBZ concentrations
are presented as the intermodulation frequency plots in Fig. 4. Clearly,
the current signal observed at the base frequencies of 2 and 5 Hz in the
uninhibited acid solution (Fig. 4a) are greater than 10−4 A. In the
presence of TBZ (Fig. 4b–e), the current signals are well below 10−4 A.
Increasing the TBZ concentration shifts the current signals more to-
wards 10−5 A with corresponding increase in the inhibition efficiency
(% IE). The % IE was calculated from Eq. (8) whereby iblank and iinh
represent the current signal in the absence and presence of TBZ. The
corrosion parameters derived from the EFM results are presented in
Table 2. It can be seen from Table 2 that the addition of 10 mM TBZ
shifts the current signal to 37.25 ± 0.42 A from 223.0 ± 1.41 A in
the blank solution. In the presence of the TBZ, the cathodic Tafel con-
stants (βc) are higher than the anodic Tafel constants (βa). This suggests
that TBZ would protect the steel corrosion via a more cathodic me-
chanism [49]. The reliability of the EFM results is verified by the clo-
seness of the CF2 and CF3 values to the theoretical values of 2 and 3. Fig. 5. Potentiodynamic polarization curves for C1020 steel in 1 M HCl con-
taining lowest and highest concentrations of TBZ.
iinh
%IE = 1 × 100
iblank (8)
Eq. (10), while the inhibition efficiency (% IE) was calculated from the
CR according to Eq. (11). The curves in Fig. 5 and the corresponding
3.3. Potentiodynamic Polarization measurements electrical values in Table 3 clearly show that the addition of TBZ into
the HCl solution lowers the rate of cathodic and anodic reactions (and
The corrosion of metallic materials involves simultaneous oxidation the overall corrosion current density, icorr), as evidenced from the shift
and reduction reactions during which electrons are transferred between of cathodic and anodic arms of the polarization curves towards lower
anodic and cathodic sites on the metal surface. Polarization methods current values with respect to the blank solution. The inhibition effi-
measure the quantity and rate of the transferred electrons (expressed as ciency of TBZ is also enhanced by increase in the inhibitor concentra-
corrosion current density, icorr) by applying an external potential scan tion. Consequently, TBZ acts as a mixed–type corrosion inhibitor.
to displace the corroding metal from its steady state (open circuit)
potential (Ecorr). Although current response to potential changes during CR corr
%IE = 1 × 100
an electrochemical reaction is not linear [50], linearity is commonly CR ocorr (11)
assumed when the electrode potential is displaced within ± 10 mV/
Ecorr [51,52]. Thus, the polarization (corrosion) resistance (Rp) can be Hydrogen ion reduction (2H+ + 2e → H2) is the predominant
calculated according to the Eq. (9) [51,52] whereas the corrosion rate cathodic reaction in the acid solution. The reaction serves as a sink
(CR) can be deduced from Eq. (10); where βa and βc are the anodic and which consumes the electrons released at the anode due to the oxida-
cathodic Tafel constants, k is a constant (0.1288 mpy·g/μA·cm), ρ is the tion reaction of iron (Fe → Fe2+ + 2e). According to the observation
density (g cm−3), EW is the equivalent weight for the steel and icorr is from the PDP curves, the inhibitive mechanism of TBZ definitely in-
the measured corrosion current density (μA cm−2). volves the inhibitor adsorption on the steel surface so as to block the
cathodic and anodic sites and, hence, the tendency for electron transfer
a c
Rp = from anode to cathode is also reduced. In the acid medium with
2.303( + c )i corr (9)
a
abundant H+ ions, it is plausible that TBZ exists as a cationic species
k such that it can compete strongly with the H+ ions for adsorption on
CR (mpy) = × i corr × EW the cathodic sites on the steel surface. The tendency for TBZ to proto-
(10)
nate in the acid solution is justified by considering the chemistry of its
Representative potentiodynamic polarization curves obtained for constituent moieties; namely, the benzimidazole and thiazole moieties.
the carbon steel in 1 M HCl solution without and with the lowest Both species contain nitrogen atoms with lone pair of electrons that
(1 mM) and highest (10 mM) concentrations of TBZ are presented in confer some basic characteristics on them, and make them susceptible
Fig. 5. For all inhibitor concentrations considered, the polarization to electrophilic attack by H+ ions to form the cationic benzimidazolium
parameters such as icorr, Ecorr, βa and βc are derived according to the or thiazolium species, respectively [53–55].
Tafel extrapolation method [51,52] and the values are provided in The results obtained from the linear polarization (LPR) measure-
Table 3. The corrosion rate (CR) was calculated from the icorr based on ments are also provided in Table 3. By polarizing the steel electrode

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A.H. Alamri and I.B. Obot Desalination 470 (2019) 114100

Table 3
Polarization parameters for C1020 steel in 1 M HCl containing various concentrations of TBZ.
Conc. Ecorr PDP LPR
(mM) (mV/Ag/AgCl)
icorr CR βa βc IEPDP Rp IELPR
(μA/cm2) (mpy) (mV/dec) (mV/dec) (%) (Ω cm2) (%)

Blank –439 168.00 75.78 71 93 – 112 ± 4.73 –

1 −462 34.20 15.43 112 129 79.60 748 ± 1.19 85.1 ± 0.45
2 −462 29.70 13.39 128 144 82.32 988 ± 1.98 88.7 ± 0.50
4 −458 25.46 11.48 124 140 84.85 1044 ± 6.30 89.3 ± 0.34
10 −456 20.40 9.20 121 141 87.86 1125 ± 9.45 90.1 ± 0.20

(a)

(b)

Fig. 6. (a) Langmuir and (b) Temkin isotherm plots for the adsorption of TBZ on C1020 carbon steel using different electrochemical techniques.

within ± 10 mV/Ecorr and assuming Tafel constants of 120 mV/dec, the
instantaneous polarization resistance (Rp) was derived as the slope of
the potential–current curve. The Rp values are seen to vary inversely
with the corresponding CR values deduced from PDP measurement;
confirming that TBZ enhances the resistance of the carbon steel to
corrosion in the HCl solution. The corrosion inhibition efficiency (% IE)
was calculated from the LPR result based on Eq. (12), where Rpo and Rp
represent the polarization resistance in the uninhibited and inhibited
acid solution, respectively. The % IE also increases with TBZ con-
centration and agree, in trend, with the values derived from the PDP
and EIS results.

7
A.H. Alamri and I.B. Obot Desalination 470 (2019) 114100

Table 4 obtained from the electrochemical measurements were fitted into two
The values of Kads and ΔGads0 for C1020 carbon steel in 1 M HCl solution ob- of the most adopted adsorption isotherms in corrosion inhibition stu-
tained from different electrochemical techniques. dies, i.e. Langmuir and Temkin isotherms. The Langmuir isotherm [56]
Method Kads (M−1) −ΔGads0 (kJ mol−1) can be expressed by the Eq. (13), where C represents the inhibitor
concentration (M), θ ( % IE ) represents the surface coverage and Kads
100
EIS 1.5 × 104 33.7 represents the equilibrium constant for the adsorption–desorption
EFM 1.3 × 104 33.4
process. Using the θ values derived from the different electrochemical
LPR 1.7 × 104 34.1
PDP 1.7 × 104 34.1 results, the Langmuir isotherm plot of C against C is presented in
Fig. 6a. On the other hand, the Temkin isotherm describes the ad-
sorption of uncharged molecules on the heterogeneous surface of the
R op corroding metal according to the Eq. (14) [57]. It describes a multilayer
%IE = 1 × 100 chemical interaction between the inhibitor molecules and the metal
Rp (12)
surface whereby the factor, α, accounts for the lateral interaction be-
tween inhibitor and metal surface. Fig. 6b presents the plot of θ against
log C for the Temkin isotherm.
3.4. Adsorption isotherm
C 1
= +C
During inhibition, corrosion inhibitor molecules continuously un- K ads (13)
dergo adsorption–desorption processes on the metal surface until a
2.303 log K ads 2.303 logC
quasi–equilibrium adsorption is attained. An appropriate adsorption =
2 2 (14)
isotherm is, therefore, useful to understand the nature of this quasi–e-
2
quilibrium and, hence, interpret the mode of interaction between the The plots in Fig. 6a are linear with correlation coefficient (R ) va-
corrosion inhibitor and the metal surface. Consequently, the results lues approximate equal to unity. On the other hand, most of the R2

(a)

(b)

Fig. 7. Nyquist with corresponding Bode plots for C1020 steel after 1, 4 and 8 h in 1 M HCl containing (a) 5 mM KI and (b) 4 mM TBZ + 5 mM KI.

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A.H. Alamri and I.B. Obot Desalination 470 (2019) 114100

Table 5
EIS parameters for C1020 steel after 1, 4, and 8 h in 1 M HCl containing KI and TBZ + KI.
Time (h) Conc. (mM) Rs (Ω cm2) Yo (μFcm−2 sn–1) n Cdl Rct (Ω cm2) Goodness of fit % IE

1 TBZ 0.8967 ± 0.003 58.96 ± 0.23 0.8278 ± 0.000 28.73 ± 0.22 952.1 ± 4.78 0.4398 ± 0.01 89.8 ± 0.24
1 KI 0.9615 ± 0.001 121.0 ± 1.41 0.8470 ± 0.002 41.03 ± 0.30 107 ± 0.06 0.3343 ± 0.06 10 ± 0.01
TBZ + KI 0.960 ± 0.003 73.2 ± 0.21 0.8400 ± 0.001 38.83 ± 0.06 1082 ± 0.00 0.5652 ± 0.01 91.0 ± 0.03
4 KI 0.9013 ± 0.006 110 ± 2.83 0.8455 ± 0.000 40.52 ± 2.06 168.5 ± 0.06 0.2627 ± 0.03 42.0 ± 0.01
TBZ + KI 0.9780 ± 0.002 47.0 ± 1.41 0.8291 ± 0.001 25.03 ± 1.32 1709 ± 0.11 1.209 ± 0.01 94.3 ± 0.20
8 KI 0.7803 ± 0.004 109 ± 1.41 0.8429 ± 0.001 30.36 ± 1.03 184 ± 0.24 0.4947 ± 0.02 47.0 ± 0.14
TBZ + KI 0.9638 ± 0.002 41 ± 1.41 0.8329 ± 0.001 21.31 ± 1.10 1738 ± 0.04 1.068 ± 0.02 94.4 ± 0.20

calculated values of ΔGads from each of the electrochemical methods are

presented in Table 4. The values vary between −33.4 to
−34.1 kJ mol−1 and the negative values conclude that the adsorption
of TBZ on the steel surface is spontaneous and highly feasible.
o
Gads = RTln(55.5K ads) (15)

3.5. Synergism consideration

Synergism involves the combination of two or more corrosion in-

Fig. 8. Potentiodynamic polarization curves for C1020 steel after 8 h in 1 M
HCl containing (a) 5 mM KI and (b) 4 mM TBZ + 5 mM KI.
values obtained from Temkin adsorption isotherm were far from unity
(Fig. 6b). Therefore, the adsorption of TBZ on the C1020 steel surface
definitely obeys the Langmuir isotherm. According to the Langmuir
isotherm [56], the adsorbing species forms only a mono–layer coverage
on the metal surface, without interactions between the adsorbing spe-
cies. Nevertheless, the Langmuir isotherm model fails to consider that
in the real condition, adsorbing species actually interact with one an-
other. Indeed, many studies have shown that organic molecules which
possess polar groups can interplay through common repulsion or at-
traction mechanism which causes the slope of the Langmuir linear plots
to deviate from unity [58], as observed in Fig. 6a.
More so, the values of the equilibrium constant (Kads) obtained from
Langmuir plot (using the different electrochemical methods) are high
and imply a strong interaction between the inhibitor molecules and the
metal surface. The Kads can be related to the free energy of adsorption
(ΔGads) according to the Eq. (15), where R = universal gas constant
(8.314 J K−1 mol−1) and T = absolute temperature (298 K). The
hibitors in order to achieve enhanced corrosion inhibition efficiency
greater than provided by each of the components of the mixture.
Synergism with iodide ion is greatly employed in corrosion inhibitor
development because of the high ionic radius of the iodide ion which
reduces its electronegativity and increases its hydrophobicity [59,60].
In the previous sections, the electrochemical results reveal that beyond
4 mM, the corrosion inhibition efficiency of TBZ was not significantly
changed. Thus, TBZ was synergized with potassium iodide (KI) by
combining 4 mM TBZ + 5 mM KI and investigating the corrosion in-
hibition effect after 1, 4 and 8 h period.
The Nyquist and Bode plots in Fig. 7a and b, respectively, present
the EIS results obtained for C1020 carbon steel in 1 M HCl solution
containing 5 mM KI and 4 mM TBZ + 5 mM KI. For comparison, the
plots for the blank and 4 mM TBZ are also presented in Fig. 7a and b,
respectively. The result in Fig. 7a reveals that the addition of KI alone to
the acid solution increases the acid corrosion resistance of the steel. It
can be seen that the size of the Nyquist semi-circle becomes larger,
relative to the observation in the absence of KI. It displays a sharp in-
crease between 1 and 4 h but increases only slightly thereafter which
may indicate saturation of the steel surface with the iodide ion. Similar
phenomenon could be observed in the absolute impedance and phase
angle peaks of the corresponding Bode plots. The inhibitive property of
KI alone can be seen more clearly in Table 5 whereby corrosion in-
hibition efficiency up to 47% could be obtained with 5 mM KI after 8 h
immersion in the 1 M HCl solution.
Fig. 7b shows the Nyquist and Bode plots for TBZ + KI system.
When compared with the observation with only 4 mM TBZ, it is clearly
observed that the KI addition enhances the inhibitive property of TBZ.
For instance, it can be seen the addition of KI significantly increases the
Rct value from 952.1 Ω cm2 ± 4.78 (after 1 h with only 4 mM TBZ) to

Table 6
Polarization parameters for C1020 steel after 8 h in 1 M HCl containing KI and TBZ + KI.
Time (h) Conc. (mM) Ecorr (V) LPR PDP

Rp (Ω cm2) IELPR (%) icorr (μA/cm2) CR (mpy) βa (mV/dec) βc (mV/dec) IEPDP (%)

1 TBZ −458 1044 ± 6.30 89.3 ± 0.34 25.46 11.48 124 140 84.85
1 Blank + KI −434 120.3 ± 1.91 7.8 ± 0.5 – – – – –
4 mM TBZ + KI −443 1194.0 ± 6.80 90.7 ± 0.34 – – – – –
4 Blank + KI −440 175.3 ± 0.35 33.7 ± 0.5 – – – – –
4 mM TBZ + KI −445 1843.5 ± 9.45 93.9 ± 0.28 – – – – –
8 Blank + KI −441 194.4 ± 3.23 41.8 ± 1.14 98.60 44.47 71 93 41.3
4 mM TBZ + KI −451 1871.1 ± 6.30 94.2 ± 0.5 20.20 9.11 112 129 88.0

9
A.H. Alamri and I.B. Obot Desalination 470 (2019) 114100

Table 7
Weight loss results for C1020 steel after 8 and 24 h immersion in 1 M HCl without and with 5 mM KI, 10 mM TBZ, and 4 mM TBZ + 5 mM KI at 25 °C and 60 °C.
Temp. Conc. ΔW CR IEWL ΔW CR IEWL
(°C) (mM) (g) (mpy) (%) (g) (mpy) (%)

25 8h 24 h
Blank 0.19 ± 0.01 13.64 ± 1.02 – 0.36 ± 0.01 25.84 ± 1.02 –
KI 0.13 ± 0.01 9.33 ± 1.02 31.78 ± 3.36 0.26 ± 0.00 18.98 ± 0.00 26.55 ± 4.12
TBZ 0.03 ± 0.00 2.15 ± 0.00 84.15 ± 1.68 0.07 ± 0.00 4.31 ± 0.00 83.30 ± 0.95
TBZ + KI 0.01 ± 0.00 0.72 ± 0.00 94.69 ± 3.36 0.03 ± 0.00 2.15 ± 0.00 91.67 ± 0.47
60 8h 24 h
Blank 1.14 ± 0.00 77.88 ± 0.00 – 1.33 ± 0.01 90.87 ± 0.98 –
KI 0.92 ± 0.00 62.85 ± 0.00 19.30 ± 0.00 1.04 ± 0.01 76.09 ± 0.98 16.27 ± 0.25
TBZ 0.21 ± 0.01 14.30 ± 0.98 81.64 ± 1.78 0.64 ± 0.01 43.73 ± 0.98 51.88 ± 0.79
TBZ + KI 0.09 ± 0.00 6.10 ± 0.00 92.17 ± 0.00 0.40 ± 0.00 27.33 ± 0.00 69.92 ± 0.45

1738 Ω cm2 ± 0.04 (after 8 h with KI), equivalent to a shift in corro-
sion inhibition efficiency from 89.8% ± 0.24 to 94.4% ± 0.20. This
improvement in the TBZ corrosion inhibition is definitely due to the
synergy with the iodide ions from KI. As proposed by Aramaki and
Hackerman [61], and applied by Roy et al. [62], the synergism between
TBZ and KI can be verified by the value of synergism parameter,
So = 1.45, which was deduced according to Eq. (16), whereby IE1, IE2
and IE1+2 represent the inhibition efficiency provided by TBZ, KI and
TBZ + KI, respectively. The synergism parameter determines whether
corrosion inhibitors in a mixture interact competitively or co-
operatively. A competitive interaction is characterized by So value less
than 1 while a cooperative interaction shows So greater than 1. The
TBZ–KI interaction is, therefore, cooperative. According to [59,63], this
indicates that the negatively–charged iodide ion would first adsorb on
the steel surface, via a chemisorption mechanism, and then promote the
adsorption of the protonated TBZ through some columbic attractive
force leading to the formation of large surface area coverage on the
steel surface.
1 (IE1 + IE2 )
So =
1 IE1 + 2 (16)
The potentiodynamic polarization plots obtained for the C1020
carbon steel after 8 h immersion in 1 M HCl solution with KI, TBZ and
TBZ + KI are provided in Fig. 8. The derivable electrical parameters,
alongside the parameters obtained from the LPR measurements after 1,
4 and 8 h, are provided in Table 6. Clearly, it could be seen that,
compared with only TBZ, the TBZ + KI combination further reduced
both anodic and cathodic current densities and still acted as a mix-
ed–type inhibitor, without significant shift in the Ecorr value. The trend
in increase of Rp values is consistent with the observation from EIS
measurement whereby the resistance sharply increased after 4 h and
further increase was insignificant, thereafter. When compared with the
result obtained for only TBZ, the significant decrease in icorr in the PDP
result and increase in % IE in LPR and PDP results strongly attest to the
synergistic effect of the TBZ + KI combination.
3.6. Time and temperature considerations
The results from electrochemical measurements reveal that, at 25 °C
and up to 8 h exposure, TBZ is a highly efficient corrosion inhibitor for
the acid corrosion of C1020 carbon steel in 1 M HCl solution. More so,
the TBZ + KI combination provides even greater inhibition efficiency
for the steel. In order to replicate the real acid cleaning conditions as
applied in the desalination plant, the performances of both TBZ and
TBZ + KI combination were investigated at longer time and higher
temperature conditions. For this purpose, weight loss measurement was
conducted on the steel sample in 1 M HCl solution without and with KI,
TBZ and TBZ + KI at room temperature and 60 °C after 8 and 24 h
immersion. The results obtained are presented in Table 7.
The results show clearly that the addition of a corrosion inhibitor
(either as KI, TBZ or TBZ + KI) imparts appreciable degree of
protection on the carbon steel as indicated by the lower values of
weight loss (ΔW) relative to the steel in the blank solution. While the
presence of TBZ provides more significant inhibition compared with KI,
it is the TBZ + KI combination that confers the greatest protection
against the acid corrosion of the C1020 steel at any given time con-
sidered. The Table 7 shows that the TBZ + KI mixture can reduce the
corrosion rate of the steel down to 4.10 mpy (after 8 h) and 27.33 mpy
(after 24 h) immersion, equivalent to inhibition efficiency of 94.74%
and 69.92%, respectively, under the more aggressive condition at 60 °C.
Given a total exposed surface area, A (20.50 cm2), density, ρ
(7.87 g cm−3) and working temperature, T (298 or 313 K), the corro-
sion rate (CR) in mpy was calculated from the weight loss (ΔW) value
according to Eq. (17), while the inhibition efficiency was deduced from
the CR values, based on Eq. (11). This result strongly supports the ob-
servations from the electrochemical screening and confirms that the
TBZ + KI mixture is effective in protecting the steel surface during acid
cleaning up to 24 h. However, increasing immersion time from 8 h to
24 h clearly increases the corrosion rate and lowers the efficiency of the
corrosion inhibitors. Given the observations from electrochemical
measurements wherein the inhibitors show no significant improvement
during 8 h exposure, it may be reasoned that the surface of the carbon
steel becomes saturated with inhibitor molecules at this time. This
implies that longer time may induce some inhibitor detachment due to
interaction between adsorbed and un-adsorbed inhibitor molecules
[64] or even due to weakening interfacial bonding between adsorbed
inhibitor molecules and steel surface as a result of formation of corro-
sion products.
W × 3.45 × 106
CR (mpy) =
A× ×T (17)
Increasing temperature from room temperature to 60 °C causes a
noticeable increase in the rate of corrosion of the carbon steel in the
uninhibited and inhibited acid solution at any given time. The effi-
ciencies of the inhibitor systems also decrease with the temperature
increase. For instance, the temperature increase caused a decrease in
efficiency for the TBZ + KI mixture from 94.69% ± 3.36 to
92.17% ± 0.00 (after 8 h) and 91.67 ± 0.47 to 69.92% ± 0.45
(after 24 h). This phenomenon can be attributed to an increase in the
activation energy required for dissolution of the steel surface in the acid
solution, as well as the shift in the adsorption–desorption equilibrium
towards desorption as reported elsewhere [65]. Consequently, this
observation confirms that the inhibitors adsorb via a physical adsorp-
tion mechanism. Howbeit, prolonged immersion time (24 h) in the acid
solution leads to the removal of the inhibitor species on the steel sur-
face, as evidenced by the relative changes in inhibition efficiency due to
temperature increase for the two immersion times considered.
3.7. Surface analysis
Fig. 9 presents the SEM surface morphologies and corresponding
EDX elemental analysis of C1020 carbon steel after 24 h immersion in

10
A.H. Alamri and I.B. Obot Desalination 470 (2019) 114100

(a)

(b)

(c)

(d)

Fig. 9. SEM-EDX surface analysis of C1020 carbon steel after corrosion in 1 M HCl solution (a) without and with (b) TBZ (c) KI and (d) TBZ + KI.
11
A.H. Alamri and I.B. Obot
Fig. 10. ATR–IR characterization of pure TBZ inhibitor and C1020 carbon steel
surface after corrosion in 1 M HCl solution containing 10 mM TBZ.
1 M HCl solution without and with KI, TBZ and TBZ + KI. In Fig. 9a,
the steel sample in the uninhibited acid solution displays a strongly
damaged microstructure, indicative of intense acid attack on the steel
surface. From the image, it can be concluded that the acid preferentially
attacked the steel along its grain boundaries. Such localized (cracking)
corrosion is typical of a metal surface experiencing extremely high
anodic current density due to very large area ratio between cathodic
and anodic sites [66]. The cracks become propagated as a result very
large cathodic surface adjacent to a small anodic crack tip. The corre-
sponding EDX analysis reveal appreciable amount of Fe, O and Cl on the
steel surface, which confirm the significant extent of corrosion attack by
the acid solution. The observed cracking corrosion must, therefore, be
attributed to the localized incorporation of the acid chloride ions within
the steel microstructure which initiates the high anodic current density
through rapid localized dissolution typically triggered by chloride ions
[67].
Conversely, Fig. 9b reveals a denser steel surface with highly
minimized microstructural damage. The adsorption of TBZ definitely
isolates the steel surface from attack by the HCl solution (especially the
aggressive chloride ions which cause localized corrosion). These ob-
servations corroborate the results obtained from the electrochemical
measurements which show that the addition of 10 mM TBZ could
protect the surface of the C1020 carbon steel with efficiency up to 90%.
The adsorption of TBZ on the steel surface can be ascertained by the
EDX detection of O and Cl content far lower than detected on the sur-
face of the uninhibited steel, which indicate reduced participation in
the corrosion process. More so, the detection of N and S atoms provide
Fig. 11. Optimized geometries and molecular orbitals for TBDZ and TBDZH at the GGA/BLYP/DNP level of theory.
12
Desalination 470 (2019) 114100
greater conviction of the presence of TBZ on the steel surface corroding
in the inhibited acid solution.
In the presence of KI, Fig. 9c shows that the corrosion attack on the
steel surface becomes less localized. However, several pits of different
sizes can be seen scattered over the steel surface. This indicates that the
KI addition provides some degree of inhibition for the steel during the
acid corrosion. This can also be corroborated with the decreased ele-
mental composition of Cl detected by the EDX analysis. Furthermore,
the most significant inhibition provided by the TBZ + KI system can be
seen both from the smoother surface morphology of the steel and the
increased detection of elemental N and S from the EDX analysis, as
evidenced in Fig. 9d. These show that the synergism between TBZ and
KI increases the inhibitor adsorption on the steel surface, which
translates into greater isolation of the surface from the acid solution.
These observations confirm the inferences drawn from both electro-
chemical and weight loss measurements that, although TBZ is an ef-
fective inhibitor for the acid corrosion of C1020 carbon steel in 1 M HCl
solution, the combination of TBZ with KI provides even greater pro-
tection.
The ATR–IR characterization of the C1020 steel surface after 24 h
corrosion in 1 M HCl solution containing 10 mM TBZ is compared with
the spectrum of pure TBZ in Fig. 10. The most prominent functional
groups and their respective peaks include the NeH stretching around
3200 cm−1, the CeN stretching in imidazole and thiazole, respectively,
located around 1622 and 1404 cm−1 [68]. The bands around 1012 and
985 cm−1 represent CeS bond [69]. These signals can still be found on
the surface of the steel after corrosion in the inhibited acid solution.
However, the peaks are reduced in intensity and their wavenumbers are
slightly shifted. These are, therefore, the interaction points between
TBZ and the steel surface [23]. The TBZ–steel interaction is feasible
because the CeN and CeS groups readily furnish lone pair of electrons
into the unoccupied d–orbitals of Fe atoms on the steel surface. Such
interaction leads to the formation of covalent bonds between inhibitor
molecules and the steel surface, such that the hydrophobic phenyl ends
of the inhibitor are extended towards the solution to prevent the con-
tact of the acid solution with the steel surface. This is the reason that the
elemental composition of Cl detected on the steel surface is relatively
lower after immersion in the acid solution containing KI and TBZ + KI.
Furthermore, no absorption peak in the TBZ–steel spectrum sig-
nificantly differs from the spectrum of the pure TBZ, which indicates
that no new chemical substance is formed due to the TBZ–steel inter-
action. This also supports the mechanism of physical adsorption de-
duced from the adsorption isotherm result.
3.8. Theoretical consideration
3.8.1. Quantum chemical calculations
Fig. 11 presents the optimized geometries and corresponding dis-
tributions of the frontier molecular orbitals for TBZ in the neutral (TBZ)
and protonated (TBZH) forms. The protonated form has been con-
sidered because of the capability of the TBZ constituents
A.H. Alamri and I.B. Obot Desalination 470 (2019) 114100

Table 8
Calculated quantum chemical descriptors at the GGA/BLYP/DNP level for TBZ and TBZH in aqueous phase.
Inhibitor EHOMO(eV) ELUMO(eV) I(eV) A(eV) ∆E(eV) χ (eV) η(eV) ∆N

TBDZ −5.447 −2.290 5.447 2.290 3.157 3.869 1.579 5.775

TBDZH −2.264 −1.845 2.264 1.845 0.419 2.055 0.209 2.093

(a)

(b)

Fig. 12. Snapshots of the most stable low energy configurations for the adsorption of TBZH on Fe (110)/100 H2O interface obtained through the Monte Carlo
simulation.

Table 9 effect of water molecules on the interaction, can be investigated. Such is

Outputs and descriptors calculated by the Monte Carlo simulation for the lowest necessary because the correlation of corrosion inhibitor performance
adsorption configuration of TBDZH on Fe (110)/100 H2O Interface (kcal/mol). with mere analysis of their molecular electronic structure has been
Systems Total energy Adsorption energy shown to be insufficient [74,75]. Fig. 12a presents the equilibrium
configuration of the TBZH/Fe (110)/100 H2O system from the top view
and side view perspectives. TBZH can be seen to reside on the slab
3
TBDZH −1.261 × 10 −136.425
surface in a perfectly flat orientation. Such orientation can definitely
ensure effective surface coverage and protection of the steel surface.
The energy parameters derived from the simulation are provided in
(benzimidazole and thiazole) to protonate in acid solutions [70–72].
Table 9. A large negative adsorption energy (−136.425 kcal/mol) in-
The highest occupied molecular orbital (HOMO) in the neutral (TBZ)
dicates the TBZH adsorbs on the steel surface spontaneously and
form can be seen to be localized around the C]C (benzene) and
strongly. Based on this, the Fig. 12b provides a schematic illustration of
N–C=N (imidazole) and CeS (thiazole) rings, while the lowest un-
the inhibition mechanism between TBZH and the C1020 carbon steel.
occupied molecular orbital (LUMO) are dense around CeC (linking
The electrons are donated by the TBZH from the N atoms and aromatic
benzimidazole with thiazole) and S atom on the thiazole. In the pro-
ring in the benzimidazole moiety to fill the unoccupied d–orbitals of the
tonated (TBZH) form, electron localization is somewhat modified. This
Fe2+ on the steel surface, and simultaneous back–donation of electrons
can be observed more clearly in the LUMO orbitals. The values of the
from the Fe2+ species into the N and S atoms of the thiazole moiety of
quantum chemical descriptors, such as electron affinity (A), ionization
TBZH. This cycle of electron transfer is responsible for the adsorption of
energy (I), electronegativity (χ), hardness (η) and the fraction of elec-
the inhibitor molecule on the steel surface, and the eventual corrosion
trons transferred from TBZ to Fe surface (ΔN) are presented in Table 8.
inhibition observed.
The result reveals that the TBZH exhibits more positive EHOMO and
ELUMO and lower ΔE, than TBZ. These suggest easier electron transfer
4. Conclusion
between the TBZH and the Fe atoms on the steel surface. Consequently,
the dominant form which is responsible for the corrosion inhibition
The corrosion inhibition of thiabendazole (TBZ), a drug-like–active
property displayed by TBZ is in the protonated form. In furtherance, the
azole, has been studied for carbon steel in 1 M HCl solution at 25 and
value of ΔN is less than 3.6 for the TBZH unlike the TBZ, which in-
60oC using electrochemical, weight loss, surface characterization and
dicates more favorable transfer of electrons from the protonated form of
theoretical calculation methods. The following conclusions can be
the inhibitor to the metal surface [73].
drawn from this study:
3.8.2. Monte Carlo simulations
1. Thiabendazole (TBZ) is an excellent corrosion inhibitor for C1020
With Monte Carlo simulation, the direct interaction between the
carbon steel in the 1 M HCl solution and its inhibition efficiency
adsorbed corrosion inhibitor and the metal surface, considering the

13
A.H. Alamri and I.B. Obot
increases with concentration.
2. TBZ shifts the steel corrosion potential towards cathodic potential
and its inhibition mechanism is more cathodic than anodic
3. The addition of KI improves the corrosion inhibition efficiency of
TBZ even at longer immersion time.
4. The inhibition efficiency of TBZ and TBZ + KI system decreases
with increase in time and temperature.
5. Quantum chemical calculation indicates that the active sites use for
the interaction of TBZ with the steel surface were the -N-H, –C=N
and the –C-S groups.
6. The dominant form of TBZ is in a protonated form with which it
adsorbs efficiently and effectively on the Fe (110) plane of steel via a
parallel orientation.
7. Surface characterization such as SEM-EDX, ATR-IR confirms the
inhibition of Carbon steel corrosion by TBZ.
8. The adsorption of TBZ on C1020 carbon steel significantly mitigates
localized corrosion of the steel.
Acknowledgments
The authors gratefully acknowledge the Center of Research
Excellence in Corrosion (CoRE–C), at the Research Institute of King
Fahd University of Petroleum and Minerals, Saudi Arabia for their
support. Aeshah H. Alamri acknowledges the Scientific and High-
Performance Computing Center at Imam Abdulrahman Bin Faisal
University, Dammam, Saudi Arabia for providing technical services and
resources for this project. We sincerely thank Dr. Ikenna Onyeachu for
technical support.
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