Vidyadharani Gopalakrishnan et al.

/ Portugaliae Electrochimica Acta 41 (2023) 223-246

Experimental and Theoretical Analysis on Mild Steel

Corrosion Inhibition by Two Novel Compounds
(FD and ACP) in Acidic Media

Vidyadharani Gopalakrishnan,1 Anand Balasubramanian,2

Loganathan Subramanian,2 Rabiu Ibraheem Muhammed,3
Rajni Garg4 and Nnabuk Okon Eddy3*
1
Department of Microbiology, Valiammal College for Women,
Chennai, Tamilnadu, India
2
Department of Chemistry, Sir Theagaraya College, Chennai, Tamilnadu, India
3
Department of Pure and Industrial Chemistry, University of Nigeria,
Nsukka, Enugu State Nigeria
4
R&D Department, Institute of Sci-Tech Affairs, Mohali, Punjab, India
*Corresponding author: [Link]@[Link]

Received 26/11/2021; accepted 10/03/2022

[Link]

Abstract
Two novel synthesized compounds (FD and ACP) have been applied as inhibitors for MS
corrosion in HCl and H2SO4 solutions. Gravimetric, PDP, EIS, SEM and theoretical
approaches were employed for the investigation of FD and ACP synthesized compounds
IE%. Their corrosion IE% and calculated quantum chemical properties were comparable
to each other, and indicated that ACP is a slightly less effective inhibitor than FD in HCl
and H2SO4 solutions. Langmuir’s, Temkin’s, Frumkin’s and Freundlich’s adsorption
isotherms were used for describing the inhibitors adsorption behavior. The adsorption
was spontaneous and followed a mixed mechanism, but with initial physisorption.
Polarization data revealed that the inhibitors were more cathodic, because they tended to
enforce MS HER retardation. The inhibitors decreased the electrolyte impedance, while
Rct increased. The adsorption mechanism was influenced by the protonation and solvation
environment, and it was concentrated within the heteroatoms and the aromatic systems.
Calculated quantum parameters agreed effectively with the obtained experimental results,
while FF indices were useful for predicting the nucleophilic and electrophilic attacks
positions.
Keywords: ACP, adsorption isotherm, corrosion, EIS, FD, IE (%), MS and PDP.

Introduction
In many industries, corrosion is a major threat to the infrastructures, and also tends
to affect the GDP of a nation, due to the economic costs associated with it. Based
on the recent GDP growth rate, the Indian government is losing about 2.4% of its
economy, due to metals and alloys corrosion [1]. In Nigeria, corrosion economic


The abbreviations and symbols definition lists are in pages 243-244.

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costs in the oil industry were estimated to be from 3 to 4% of the country’s GDP
[2], while, in South Africa, they were calculated in the range from 3 to 5%, and
closely related to the global losses of $255 billion [3]. MS is an iron and carbon
alloy, being the major metal in several industrial installations [4]. However, within
most of these industries, activities such as acid cleaning, etching, engraving and
others, can accelerate MS CR, especially in acidic or basic environments [5-10].
Approaches to protecting metals against corrosion damages are varied, but include
methods such as coating, electroplating, painting/greasing, cathodic/anodic
protection and the use of corrosion inhibitors [11-14]. Inhibitors can be added to
the corrosive substance in minute C, to protect metals against corrosion, through
the initial adsorption mechanism [15, 16]. Most compounds employed as corrosion
inhibitors are required to be biodegradable, less expensive, non-toxic and simple
to handle [17]. The above-listed properties are valuable, and have positioned the
use of corrosion inhibitors as one of the greatest alternatives for metal corrosion
prevention [18].
The choice or design of a corrosion inhibitor is based on several chemical
considerations, but the basic ones are the possession of heteroatoms, pi-electron or
conjugated systems, high molecular weight, aromatic systems, multiple bonds, etc.
[19]. Given the depth of knowledge that is available for guiding the choice of new
ecofriendly inhibitors synthesis, several compounds have been explored for their
corrosion IE (%) [18]. Some literature on the usage of carboxamide derivatives as
corrosion inhibitors is available. For example, Dadgarinezhad and Daghael [20]
explored the corrosion inhibition potential of 2-phenyl-1-hydrazine carboxamide
in H3PO4, and observed that the adsorption mechanism obeyed the Langmuir’s
isotherm. Chafig et al. [21] reported (E)-2-(4-(2-(methyl(pyridine-2-
yl)amino)ethoxy) benzylidiene)hydrazine-1-carboxamide as a cost-effective and
efficient corrosion inhibitor, with maximum IE (%) of 97%, at a C of 0.005 M.
Their experimental findings were in good agreement with data generated from
theoretical calculations. Other related works about corrosion inhibitors have also
been documented on 2-(1-(2-oxo-2H-chromen-3-yl) rthylidene) hydrazine
carboxamide, for Zn-Al alloy in HCl solutions [22], and salicylaldehyde-based
Schiff bases of semicarbazide and p-toluidine, for MS in an acidic medium [7]. On
the other hand, studies on the inhibitive properties of pyridine substituted amines
are much scanty, except some reports that include the study conducted by Farahati
et al. [23], who found that 4-(pyridic-3-yl) thiazol-2-amine was an effective and
eco-friendly inhibitor for Cu corrosion in HCl.
In continuation of this novel exercise, we have successfully synthesized and
applied two aromatic compounds (FD and ACP), as inhibitors for MS corrosion in
acidic media. Despite the other relevant works, the use of these compounds as
inhibitors for MS corrosion in HCl and H2SO4 has not been previously reported.
The current study researched the synthesis and corrosion inhibitive properties of
these compounds, at 303 K, which is the approximate temperature in which most
fluids are handled in industries. Although most industrial fluids pH values are
relatively acidic, the study was conducted under simulated acidic conditions, at 1 M.
The compounds chosen for the present study have hetero atoms, pi-electrons and
aromatic rings, and were expected to exhibit corrosion IE (%).

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Experimental
Material preparation
A commercially available MS sheet was procured and cut into coupons of the required
dimensions 5  1 and 1  1  1 cm, for gravimetric and electrochemical experiments,
respectively. MS composition was (%): C = 0.014; Si = 0.007; Mn = 0.195; S = 0.014;
P = 0.010; Ni = 0.014; Mo = 0.014; Cr = 0.041 and Fe = 99.691. Each coupon was
polished using varying grades (120-1200 grits) of emery sheets. They were further
cleaned with ethanol, for degreasing, and rinsed with acetone, before being stored in a
desiccator.

FD preparation
At a temperature from 0 to 5 ºC, 0.02 M aniline were dissolved in glacial acetic
acid and 0.5 mL HCl. The mixture was diazotized with 0.2 g sodium nitrite, under
constant stirring, while 0.01 M semi-carbazone was slowly added, and allowed to
cool overnight. The resulting solution was decanted into cold water, and the
precipitated crystals were separated and recrystallized with ethanol. The re-
crystalized crystals were used to prepare formazan of p-dimethyl amino
benzaldehyde, by dissolving 10 mg of this compound. FD C needed for the
corrosion study were prepared through serial dilution.

ACP preparation
ACP was synthesized using the method described by Zhang et al. [24]. A stock
solution of ACP was made by dissolving 10 mg of it in 100 mL of the test solution,
and carrying out serial dilution to obtain the desired C.

WL method
WL experiments were conducted by completely immersing the weighed MS
specimens into various beakers containing different FD and ACP C. Each MS
coupon was taken out from the solution, following 24 h of immersion, washed, and
returned to the solution after weighing. The experiments used a thermostated water
bath (303 K), and they were repeated and concluded in seven days. MS CR, FD
and ACP IE (%) and θ were computed by the measured values substitution into
Equations 1, 2 and 3, respectively [25]:
87.6∆𝑤
𝐶𝑜𝑟𝑟𝑜𝑠𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 (𝑚𝑚/𝑦) = (1)
𝐴𝜌𝑡
𝐶𝑅 − 𝐶𝑅 100 (2)
%𝐼𝐸 = ×
𝐶𝑅 1

𝐼𝐸 𝐶𝑅 − 𝐶𝑅
𝜃=% = (3)
100 𝐶𝑅

where Δw, A and  are the MS coupons WL, cross-sectional area and density, and
t is the contact period, respectively.

PDP study
The MS sample, SC and Pt were used as WE, RE and AE, respectively, in the PDP
cell. The electrolyte was the respective corrosive acid (HCl or H2SO4). PDP

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measurements were accomplished in the potential ranges from -1000 to 250 mV

and from 1000 to 2000 mV, at a SR of 0.5 mV/s-1. Data obtained from the PDP
cell were Ecorr, Icorr, c and a. From PDP measurements, FD and ACP IE% were
computed by the following equation [25]:
𝐼𝐸% = × (4)

where Iºcorr and Icorr are the corrosion current without and with inhibitor. LPR
experiment was also carried out in the same electrochemical cell. From Rp
calculated values, IE% was evaluated by using the following equation [26]:
𝑅 () − 𝑅 100
𝐼𝐸% =
𝑅
×
1
(5)
()

where Rp(i) and Rp are polarization resistance without and with inhibitor,
respectively.

EIS
EIS study was performed using an electrochemical analyzer, and the conventional
three electrodes that were similar to those used in the PDP experiment. A steady-
state potential wave was first obtained, and sine wave AC signal of 10 mV
amplitude was overlaid, in order to obtain OCP. This was conducted using the
frequency range from 100 kHz to 10 MHz, in order to obtain values for the real
(Z') and imaginary (Z'') parts. Cdl was calculated by the following equation [27]:
1
𝐶 = (6)
2𝜋𝑓 𝑅

where fmax is the frequency at Z” value. IE% was calculated by using the following
equation 7 [28]:
𝑅 () − 𝑅 100
𝐼𝐸% =
𝑅
×
1
(7)
()

where Rct and Rct(i) are the charge transfer resistance without and with inhibitor
respectively.

SEM
Morphological analysis of the corroded MS surface (without and with inhibitor)
was carried out at Metallurgical and Material Department, NIT Tiruchi, India,
using SEM (Model- HITACHI S3000H, Japan). The MS coupons were immersed
in the test solutions (without and with 35% inhibitors C), and allowed to stand for
seven days, before they were withdrawn for SEM analysis.

Computational calculations
Chemical structures were drawn with the aid of ChemBio 12.0 software, and the
structured produced were saved as a SDF input file, for structural optimization.
DFT calculations were performed with a /631G** basis set and B3LYP hybrid
functional. FMO graphs plotting was also performed at this level of theory.
Calculations were performed for both aqueous and gaseous phases. FF calculations

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were carried out using electrostatic E, MC and NBOC. In order to determine the
interaction between the inhibitor and the MS surface, Monte Carlo simulation was
performed using HyperChem software.

Results and discussion

WL method
The MS coupons CR was observed to decline with increasing ACP and FD C, as
shown in Table 1.

Table 1. MS CR, ACP and FD θ and IE (%) with various C.

CR CR IE
System  IE(%) 
(mm/y) mm/y %
1.0 M HCl 1.0 M H2SO4
Blank 29.5715 - - 30.9832 -
7% FD 13.9385 0.5287 52.87 18.5786 0.4004 40.04
14% FD 11.023 0.6272 62.72 14.0184 0.5475 54.75
21% FD 8.3217 0.7186 71.86 10.2385 0.6695 66.95
28% FD 6.231 0.7893 78.93 7.7921 0.7485 74.85
35% FD 4.8987 0.8343 83.43 5.6743 0.8169 81.69
Blank 29.5715 - - 30.9832 - -
7 % ACP 24.2961 0.1784 17.84 21.0269 0.3213 32.13
14% ACP 19.4666 0.3417 34.17 17.6091 0.4317 43.17
21% ACP 14.6371 0.5050 50.50 12.631 0.5923 59.23
28% ACP 9.9562 0.6633 66.33 10.2534 0.6691 66.91
35% ACP 6.9099 0.7663 76.63 5.8697 0.8106 81.06

MS coupons CR were 29.5715 and 30.9832 mmpy, in 1 M HCl and H2SO4,

respectively. As ACP C was increased from 7 to 35%, CR decreased from 13.9385
to 4.8982 mmpy, in HCl, which corresponded to an IE (%) increase from 52.87 to
83.43%. In H2SO4, CR decreased from 18.5786 to 5.6743 mmpy, while the
corresponding IE (%) rose from 40.04 to 81.69%. This reveals that MS coupons
CR in 1.0 M H2SO4 was higher than that in 1.0 M HCl, because the former is a
stronger dibasic acid than the latter. Similarly, FD IE (%) for MS coupons CR in
HCl was found to be slightly better than that in H2SO4. ACP exhibited relatively lower
corrosion IE (%) than that of FD, within the studied C range (from 7 to 35%). ACP
demonstrated the capacity to reduce MS coupons CR from 24.2961 to 6.9099 mmpy
in 1 M HCl, and from 21.0269 to 5.8697 mmpy in H2SO4. ACP seems to be a better
inhibitor for MS coupons corrosion in H2SO4 than in HCl. This may be because
H2SO4 tends to form a passivating layer on the metal surface, through
tetraoxosulphate (VI) ions adsorption.
Further, the observed trend for the changes in corrosion IE (%) concerning the
inhibitors and the acidic media was: FD in HCl > FD in H2SO4 > ACP in H2SO4 >
ACP in HCl (Fig. 1). Considering the two inhibitors chemical structures, it is
obvious that FD has more functional corrosion inhibition enhancing properties
than those of ACP, including two aromatic rings and several heteroatoms, with
multiple bonds and higher molecular mass. Therefore, the observed results are
consistent with the compounds chemical structures.

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Figure 1. Variation of (a) MS CR and (b) ACP and FD IE (%) with various C.

MS CR, and instantaneous ACP and FD IE (%), with eight 4 h intervals (from 4 to 24 h),
were also calculated, and the obtained results are presented in Table 2.

Table 2. Instantaneous ACP and FD CR and IE(%).

ACP FD
Time CR CR
(h) mmpy IE (%) mmpy IE (%)
1 M HCl 1 M H2SO4 1 M HCl 1 M H2SO4 1 M HCl 1 M H2SO4 1 M HCl 1 M H2SO4
4 4.5210 5.5241 75.64 79.71 6.8987 5.5432 77.21 81.98
8 4.2891 5.4001 76.78 81.75 6.7654 5.5098 78.37 83.84
12 4.0051 5.3198 77.92 83.79 6.4589 5.4678 79.53 85.70
16 3.7895 5.2779 79.06 85.83 6.2897 5.4318 80.69 87.56
20 3.4879 5.0988 80.20 87.87 6.1544 5.4218 81.85 89.42
24 3.4870 5.0897 80.77 88.89 6.1320 5.4119 82.43 90.35

The recorded results clearly show that the instantaneous ACP and FD IE (%) were
much better than those of other inhibitors. Similar results have been reported for
some effective corrosion inhibitors [29].
The instantaneous MS coupons CR, and ACP and FD IE (%) in the acidic media
linearly decreased with time (Fig. 2), which implies that MS corrosion in both
media was uniform.

Figure 2. Time variation with instantaneous: (a) MS CR in 1 M HCl and 1 M H2SO4; and
(b) ACP and FD IE (%).

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Time changes with MS C in the corrosive media were also monitored through WL
measurement, and the obtained data were used to test for the best suited kinetic
plots. The requirements for a first-order kinetic were satisfied:
[𝑀𝑆]
𝑙𝑜𝑔
[𝑀𝑆]
= −𝑘 𝑡 (8)

where [MS]0 and [MS]t are the alloy initial and final C in the corrosive media, t is
time and k1 is the first-order rate constant.
[ ] .
From the plots of 𝑙𝑜𝑔 [ ] against t (figure not shown), half-life 𝑡 =
was estimated (Table 3).

Table 3. Kinetic parameters for MS CR in 1 M HCl and 1 M H2SO4 without and with
ACP and FD.
ACP FD
Time Rate constant t1/2 Rate constant t1/2
(h) K*10-1 K*10-1
1 M HCl 1 M H2SO4 1 M HCl 1 M H2SO4 1 M HCl 1 M H2SO4 1 M HCl 1 M H2SO4
4 0.3674 0.4194 188.6 165.2 0.3377 0.4302 205.2 161.0
8 0.1902 0.2125 364.3 326.1 0.1712 0.2158 404.7 321.1
12 0.1325 0.1429 523.0 484.9 0.1180 0.1445 587.2 479.5
16 0.1028 0.1076 674.1 644.0 0.0902 0.1088 768.2 636.9
20 0.0864 0.0878 802.0 789.2 0.0732 0.0871 946.7 795.6
24 0.0720 0.0732 962.5 946.7 0.0611 0.0726 1134.2 954.5

The presented results reveal that the inhibitors effectively extended MS half-life
up to 963, 947, 1134 and 955 h, with ACP and FD in HCl and H2SO4, respectively.

Adsorption/thermodynamic study
ACP and FD characteristics against MS corrosion in HCl and H2SO4 solutions are
essential parameters in their interaction level, inhibition mechanisms and other
inhibitory roles features. The adsorption linear fitness results indicated that the
mechanism best fitted Langmuir’s, Temkin’s, Frumkin’s, and Freundlich’s
isotherms, which are expressed in Equations 9 to 12, respectively [30, 31].
𝐶 1
𝑙𝑛
𝜃
= 𝑙𝑛
𝑘 ( )
+ 𝑙𝑛𝐶 (9)
1 1
𝜃= 𝑙𝑛𝑘 ( ) − 𝑙𝑛𝐶 (10)
2𝑎 2𝑎
𝜃
𝑛 [𝐶] × = 𝑙𝑛𝑘 ( ) + 2𝛼 (11)
1−𝜃
1
𝑙𝑛(𝜃) = 𝑙𝑛𝑘 ( ) + 𝑙𝑛𝐶 (12)
𝑛
where a is Temkin’s interaction parameter, 𝛼 is the lateral interaction factor
describing the adsorption layer and 1/n is the Freundlich’s constant for the
adsorption intensity or surface heterogeneity. Langmuir’s, Temkin’s, Frumkin’s
and Freundlich’s isotherms are presented in Table 4.
The plots fitness was excellently supported by R2 high values. The various
adsorption constants for the isotherms are illustrated in Fig. 3.
ΔG°ads for the inhibitors adsorption was calculated from the respective kads values
using equation 13 [32]:
∆𝐺 = −𝑅𝑇𝑙𝑛(55.5𝑘 ) (13)

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where R is the gas constant, T is temperature and 55.5 is the molar heat of water
adsorption.

Table 4. Parameters for ACP and FD adsorption onto the MS surface in HCl and H2SO4
solutions.
FD in FD in ACP in ACP in
Isotherms and parameters 1 M HCl 1 M H2SO4 1 M HCl 1 M H2SO4
Langmuir’s
Slope 0.7107 0.5525 0.0787 0.4267
Intercept 1.2104 1.7815 3.5064 2.2866
Gºads kJ/mol -12.25 -18.02 -35.48 -23.14
R2 0.9993 -0.9990 0.8093 0.9732
Temkin’s
Slope 0.1930 0.2599 0.3678 0.2954
Intercept 0.1394 -0.1181 -0.5768 -0.2926
α 2.5907 1.9238 1.3594 1.6926
Gºads kJ/mol -11.94 -8.97 -6.17 -7.62
R2 0.9861 0.9935 0.9682 0.9456
Frumkin’s
Slope 9.9730 8.3148 7.1492 7.6254
Intercept -3.1720 -1.7737 -0.6659 -1.1103
α 4.9865 4.1574 3.5746 3.8127
Gºads kJ/mol -21.27 -56.50 -84.40 -73.21
R2 0.9983 0.9992 0.9912 0.9932
Freundlich’s
Slope 0.2893 0.4475 0.9213 0.5733
Intercept -1.2104 -1.7815 -3.5064 -2.2866
1/n 0.2893 0.4475 0.9213 0.5733
Gºads kJ/mol -70.69 -56.30 -12.85 -43.58
R2 0.9957 0.9985 0.9983 0.9850

Figure 3. Isotherms for ACP and FD adsorption onto the MS surface.

The ideal Langmuir’s isotherm describes a homogenous adsorption layer with no

interaction between the adsorbed species. Since the expected slope value for the ideal

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Langmuir’s isotherm is unity (Equation 9), there was an observable deviation

concerning ACP and FD adsorption onto the MS surface (slope > 1 for ACP and
FD). Hence, there was an interaction between the adsorbed species. The interaction
parameters calculated through Temkin’s and Frumkin’s isotherms reflected the
inhibitors adsorption behavior, since they were positive. In both cases, the
interaction strength was most intense for FD in HCl.
The calculated ΔG°ads (Table 4) values correspond to different adsorption
mechanisms. For example, the Langmuir’s, Temkin’s, Frumkin’s and
Freundlich’s models generated ΔG°ads values of -12.25, -11.94, -21.27 and -
70.29 kJ/mol, for FD in HCl, respectively. ΔG°ads values lower than -20 kJ/mol
and higher than -40 kJ/mol favor physical and chemical adsorption mechanisms,
respectively. Free energy values from -20 to -40 kJ/mol often indicate a mixed
adsorption mechanism. Therefore, the inhibitors adsorption onto the metal surface
first underwent physisorption, and then chemisorption. Interestingly, Freundlich’s
constant (1/n) was lower than unity, and supported chemisorption mechanism
(unlike cooperative adsorption, which requires that 1/n should be greater than
unity). Some levels of agreement between data obtained from the various
isotherms were also observed, for example, ΔG°ads values evaluated from
Frumkin’s and Freundlich’s isotherms were -56.50 and -56.30 kJ/mol,
respectively, for FD adsorption onto the MS surface (in H2SO4).

Polarization studies
PDP and LPR studies were also useful in ACP and FD IEs evaluation (Fig. 4).

Figure 4. PDP plots for MS corrosion inhibition in HCl and H2SO4 solutions, by ACP
and FD.

Table 5 contains polarization data and calculated ACP and FD IE (%). The inhibitors
addition to HCl and H2SO4 led to an increase in Ecorr absolute value, while Icorr
decreased. This indicates that ACP and FD inhibited MS corrosion in the acidic media.

Table 5. PDP data for ACP and FD in 1 M HCl and H2SO4.

System PDP LPR
βc βa ECorr ICorr x CR IE(%) Rp IE(%)
V/dec-1 V/dec-1 V 10-4 (A) mmpy
1 M HCl 5.593 18.793 -0.411 7.625 12.384 - 245.45 -
ACP in 1 M HCl 7.515 17.007 -0.436 2.315 5.679 69.63 977.58
20 74.89
FD in 1 M HCl 8.240 20.719 -0.483 1.910 7.015 74.95 1340.2
80 81.69
1 M H2SO4 4.015 15.354 -0.387 9.125 13.666 - 151.45
479 -
ACP in 1 M H2SO4 5.905 12.905 -0.532 2.493 7.241 72.67 705.62
13 78.54
FD in 1 M H2SO4 4.191 6.088 -0.554 1.870 6.985 79.50 576.37
33 73.72
60

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The observed changes in βc were more significant than those in βa, which suggests that the
inhibition process significantly retarded H reduction mechanism. It also implies that the
anodic reaction was more favored than the cathodic one. Calculated differences in E were
also greater than the threshold value (85 mV), confirming that the inhibitors are majorly
anodic [33]. Further investigation of the inhibitors anodic character was made through the
results obtained from the transfer coefficient calculations. The transfer coefficient can be
calculated by the substitution of R values, temperature and Tafel slope, and by the number
of electrons associated with the redox reaction, into equation 14:
2.303𝑅𝑇
𝛼= (14)
𝑎𝑛𝐹
where  is the Tafel slope, n is the number of electrons in the redox reaction and
F is Faraday’s constant. The Tafel slope was deduced from the following equation:
𝛽 𝛽
β= (15)
2.303(𝛽 + 𝛽 )

 calculated values are shown in Table 6. Generally, anodic reaction and cathodic
polarization are favored when 𝛼 values are from 0.25 to less than 0.5, and close to
0.75, respectively. The presented results also confirmed that the inhibitors are
majorly anodic, and suppress HER more than MS anodic dissolution.

Table 6. ACP and FD charge transfer coefficients and Tafel constant.

System Charge transf. coef. α
1 M HCl 1.8716 0.0563
ACP in 1 M 2.2631 0.0681
HCl
FD in 1 M HCl 2.5599 0.0771
1 M H2SO4 1.3820 0.0416
ACP in 1 M 1.7591 0.0529
H SO
FD in 1 M 1.0778 0.0324
H SO
LPR study on the acidic solutions (Table 5) indicated that Rp was increased by ACP
and FD, which imply that the inhibitors decreased CR in the acidic media. IE (%)
calculated from PDP and LPR studies are consistent with each other, and with the
instantaneous IE (%) presented in Table 2.

EIS
EIS measurements were also performed to study ACP and FD corrosion inhibition
properties. The Nyquist plots generated from the EIS study are shown in Fig. 5, which
reveals that the semicircle widened in FD presence, showing higher increment and better
IE (%) than those from ACP. The phase angles approached 80, implying that diffusion
was not the rate control parameter. Cdl values can also be calculated through the following
equation [34]:
𝐶 = 𝛾 (𝜔 ) = 𝛾 (2𝑓 ) (16)
Corrosion inhibition may be thought of as the inhibitor displacing adsorbed water
onto the metal surface (Equation 17):
Inh(sol) + H2Oads Inhads + H2O (17)
In most cases, organic inhibitors have a lower dielectric constant and higher
volume than water, and the relationship between Cdl and dielectric constant is
given as follows:

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𝜀 𝑎𝑛𝑑 𝜀
𝐶 = 𝐴 (17)
𝑙
where 0 and  are the dielectric constant in vacuum and in the solution,
respectively, 𝑙 is Cdl thickness and A is the MS cross-sectional area.

Figure 5. Nyquist plots for ACP and FD inhibition of MS corrosion in HCl and H2SO4.

From equation 18, it is evident that the higher the  value, the higher will be Cdl.
Therefore, the replacement of the adsorbed water molecule (with a higher
dielectric constant), on the metal surface, by an organic inhibitor (with a lower
dielectric constant) will cause a reduction in Cdl, as shown in the results obtained
for FD and ACP (Table 7). Thus, the observed decreasing trend in Cdl indicates
that the inhibitors were adsorbed at the MS-solution interface. On the other hand,
FD addition to the acidic solutions led to the highest increase in their Rct. This can
be ascribed to Cdl reduction and, hence, to MS corrosion inhibition by the
formation of a protective film on its surface, through the inhibitors electrostatic
attraction.

Table 7. AC impedance parameters of MS immersed in 1 M HCl and H2SO4 without and

with inhibitors.
Rct Cdl
System (ohm/cm2) (F x 10-5) IE (%)
1 M HCl 64.69 3.979 ---
ACP in 1 M HCl 207.1 1.738 68.76
FD in HCl 269.4 1.280 75.98
1 M H2SO4 64.34 4.831 ---
ACP in 1 M 242.7 1.447 73.48
FD in H2SO4 286.0 0.938 77.50

The radius of the semi-circle for the blank solutions is larger than those observed
for ACP or FD in the corrosive media. This is due to the depressive capacitive loop
(of which center is below the real axis) made by the impedance spectra, causing
roughness and inhomogeneities at the MS surface.

SEM
Fig. 6 shows MS SEM in 1 M HCl and H2SO4, without and with ACP and FD.
The micrographs reveal that the MS surface was intensely rough, but got smoother
with ACP and FD, which have formed a protective coverage on it through
adsorption.

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Figure 6. MS SEM in HCl and H2SO4 solutions without and with ACP and FD.

Quantum chemical study

Global reactivity
Semi-empirical parameters were calculated for ACP and FD in the gas phase. They
included EHOMO, ELUMO, E and µ (Table 8).
The reactivity of a corrosion inhibitor can be predicted from FMO theory, which states
that LUMO is located in the electrophilic site. The theory requires the molecule
reactivity to be a function of FMO energies. Consequently, reactivity (and, hence,
adsorption) increases with higher EHOMO value and with lower ELUMO and E values.
E is the measure of a compound  or σ, in terms of its tendency towards
adsorption or reactivity [7]. Higher the E, higher the reactive molecules σ (hence,
lower ). Molecular σ and  are defined as follows [35]:
1
𝑆= (18)
𝐸 −𝐸
1 (19)
 = (𝐸 −𝐸 )
2
IP and EA of an inhibitor are defined as EHOMO and ELUMO negative values,
respectively, while χ is defined as the inhibitor chemical E negative value, which
can be calculated by IP and EA substitution into the following equation:
1 1
 = (𝐼𝑃 + 𝐸𝐴) = (−𝐸 − 𝐸 ) (20)
2 2
N from the inhibitor to the metal vacant d-orbital and the initial inhibitor-MS
interaction were estimated using Equations 22 and 23, respectively:
 − 
∆𝑁 = (21)
2  + 

 − 
∆ = (22)
4  + 

Calculated values of all the variables obtained from Equations 17 to 21 are also presented in
Table 8. The results favor FD as better corrosion inhibitor than ACP, because it has EHOMO, N,

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, σ,  and µ higher values. Also, FD better IE (%) than that of ACP was supported by its
observed E lower values. This theoretical proposal is in agreement with the results obtained
for the average IE (%) of ACP and FD. Also, the relative closeness of the calculated global
parameters between the two inhibitors explains why their IE (%) are also close to each other.

Table 8. Gas phase semi-empirical and associated parameters for ACP and FD.
Semi-empirical parameters FD ACP
EHOMO
(eV) -5.76 -5.86
ELUMO
(eV) -3.17 -2.18
E
(eV) 2.59 3.68
µ
(debye) 6.02 5.86
σ 0.39 0.17
 2.56 5.88
ᵡ 4.07 4.02
µ 1.30 1.84
ΔN 1.12695 0.8098
Δφ 1.6509 1.2066

The corrosion inhibitor protonation is an essential step towards its adsorption, because higher
fractions of inhibitor molecules are adsorbed in the protonated state. Energy minimization was
first carried out on the inhibitors molecules, to identify the protonation sites, which were
carboxyl oxygen and aromatic nitrogen in FD and ACP, respectively. Consequently, we
calculated the two inhibitors protonation affinity , using the following Equation 24 [36]:
𝐸 ( ) = 𝐸 ( ) − 𝐸 ( ) −𝐸 (23)
𝐸 ( ), 𝐸 ( ) 𝑎𝑛𝑑 𝐸

where Eprot(aq), Eneut and Eprot are the protonated inhibitor, neutral inhibitor and proton total
energy, respectively. FD and ACP calculated PA values were 277.98 and 703.01 kJ/mol,
respectively, which implies that the former can be easily protonated, because it requires
lower energy than that of the latter. Therefore, FD IE (%) is expected to be better than
that of ACP, as observed in the experimental results. Fig. 7 shows HOMO and LUMO
optimized structures and gas-phase diagrams for ACP and FD.

Figure 7. Inhibitors HOMO and LUMO optimized structures and gas-phase diagrams.

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Fig. 8 shows similar diagrams for the inhibitors aqueous phase neutral and protonated
forms. The diagrams reveal that the lobes are mostly concentrated in the benzene ring
and on the heteroatoms, and that protonation seemed to enhance the inhibitors
adsorption (especially FD), by increasing available active sites.

Figure 8. HOMO and LUMO aqueous phase neutral and protonated ACP and FD
diagrams.

Recorded in Table 9 are FMO energies of neutral and protonated ACP and FD, in
an aqueous solution.

Table 9. Aqueous phase FMO of neutral and protonated ACP and FD.
FMOs FD (aqueous) ACP (aqueous)
Neutral Protonated Neutral Protonated
EHOMO
(eV) -5.03 -3.91 -5.66 -5.98
ELUMO
(eV) -2.38 -0.57 -2.38 -1.95
E
(eV) 2.65 3.34 3.28 4.03
µ
(debye) 7.97 16.51 8.75 7.04

The results show more significant and favorable changes in the FMO of the FD protonated
species than of that in the neutral species (in an aqueous medium). For example, EHOMO

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increased, while ELUMO decreased, due to protonation. The contrary was observed for
ACP inhibitors, which also explains why ACP IE (%) is lower than that of FD.

LRD
Approaches to LRD analysis involve exploring the functions that can predict the
molecules reactivity through their atoms. Some of the indices include charges on
the molecules, FF, local σ and other parameters. FMO theory proposed that an
electrophilic attack favors LUMO, while a nucleophilic attack favors HOMO. The
electrons and charges involvement in the adsorption process can be simplified by
ΔN from HOMO to LUMO, which corresponds to nucleophilic and electrophilic
attacks, respectively. The transfer process depends on E and other factors, such
as electrons density in the respective sites, metal charge, etc. DFT was used to
evaluate the condensed FF for the electrophilic and nucleophilic attacks, which can
formally be defined according to the following equations [37]:
𝑓 = 𝑞 − 𝑞 (24)

𝑓 = 𝑞 − 𝑞 (25)
where qN, qN1 and QN+1 are the ground state charges of the neutral, positive and
negative species, respectively. In this study, different FD and ACP charges were
used for evaluating FF indices, including EPC, MAC and NOBC. The results are
shown in Tables 10-15.

Table 10. ACP and FD EPC calculated FF parameters for the gas-phase.
FD ACP
Atom 𝒇𝒙 𝒇𝒙 ∆𝒇𝒙 Atom 𝒇𝒙 𝒇𝒙 ∆𝒇𝒙
N0 0.000 -0.02 0.02 C0 -0.017 -0.148 0.131
N1 -0.075 -0.066 -0.009 N1 -0.085 -0.033 -0.052
C2 -0.118 -0.002 -0.116 C2 0.096 -0.063 0.159
N3 -0.06 -0.106 0.046 C3 -0.124 -0.094 -0.03
N4 0.067 -0.065 0.132 C4 0.005 -0.05 0.055
C5 -0.028 -0.016 -0.012 C5 -0.082 0.005 -0.087
C6 0.006 -0.049 0.055 N6 0.037 -0.245 0.282
C7 -0.013 -0.01 -0.003 C7 0.119 0.116 0.003
C8 -0.024 -0.052 0.028 C8 -0.436 -0.157 -0.279
C9 -0.014 -0.036 0.022
C10 0.018 -0.012 0.030
C11 -0.006 0.031 -0.037
C12 -0.024 -0.035 0.011
C13 -0.048 -0.009 -0.039
C14 -0.05 -0.021 -0.029
C15 -0.045 -0.011 -0.034
C16 -0.03 -0.009 -0.021
N17 0.034 -0.03 0.064
C18 0.002 -0.023 0.025
C19 0.009 0.002 0.007
C20 -0.029 -0.017 -0.012
O21 -0.069 -0.043 -0.026
N22 -0.001 -0.01 0.009
N23 0.012 -0.007 0.019
C24 0.017 -0.013 0.030
C25 0.01 -0.022 0.032

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Table 11. ACP and FD MAC calculated FF parameters for the gas-phase.
FD ACP
Atom 𝒇𝒙 𝒇𝒙 ∆𝒇𝒙 Atom 𝒇𝒙 𝒇𝒙 ∆𝒇𝒙
N0 -0.003 -0.011 0.008 C0 -0.02 -0.068 0.048
N1 -0.076 -0.054 -0.022 N1 -0.052 -0.054 0.002
C2 -0.069 -0.017 -0.052 C2 -0.007 -0.048 0.041
N3 -0.020 -0.038 0.018 C3 -0.039 -0.019 -0.02
N4 0.018 -0.066 0.084 C4 -0.013 -0.039 0.026
C5 -0.004 0.007 -0.011 C5 -0.033 -0.006 -0.027
C6 0.004 -0.026 0.030 N6 0.000 -0.121 0.121
C7 -0.001 -0.015 0.014 C7 0.022 0.015 0.007
C8 -0.013 -0.031 0.018 C8 -0.360 -0.174 -0.186
C9 0.001 -0.015 0.016
C10 0.000 -0.027 0.027
C11 -0.006 0.002 -0.008
C12 -0.025 -0.013 -0.012
C13 -0.003 -0.012 0.009
C14 -0.044 -0.013 -0.031
C15 -0.005 -0.012 0.007
C16 -0.020 -0.008 -0.012
N17 0.004 -0.009 0.013
C18 0.035 -0.008 0.043
C19 0.035 -0.009 0.044
C20 -0.013 -0.021 0.008
O21 -0.066 -0.039 -0.027
N22 -0.01 -0.017 0.007
N23 -0.003 -0.004 0.001
C24 0.027 -0.004 0.031
C25 0.028 -0.005 0.033

Table 12. ACP and FD NBOC FF parameters for the gas phase.
FD ACP
Atom 𝒇𝒙 𝒇𝒙 ∆𝒇𝒙 Atom 𝒇𝒙 𝒇𝒙 ∆𝒇𝒙
N0 -0.011 -0.026 0.015 C0 -0.02 -0.105 0.085
N1 -0.091 -0.07 -0.021 N1 -0.054 -0.03 -0.024
C2 -0.118 -0.009 -0.109 C2 -0.078 -0.089 0.011
N3 -0.021 -0.066 0.045 C3 -0.046 -0.046 0.000
N4 0.007 -0.112 0.119 C4 -0.017 -0.040 0.023
C5 0.009 0.010 -0.001 C5 -0.046 -0.028 -0.018
C6 0.000 -0.043 0.043 N6 -0.017 -0.194 0.177
C7 -0.004 -0.009 0.005 C7 0.022 0.021 0.001
C8 -0.034 -0.07 0.036 C8 -0.352 -0.146 -0.206
C9 0.001 -0.012 0.013
C10 -0.003 -0.042 0.039
C11 -0.004 0.015 -0.019
C12 -0.049 -0.019 -0.03
C13 -0.002 -0.012 0.01
C14 -0.100 -0.025 -0.075
C15 -0.007 -0.011 0.004
C16 -0.042 -0.011 -0.031
N17 0.011 -0.043 0.054
C18 0.026 -0.007 0.033
C19 0.026 -0.007 0.033
C20 -0.006 -0.009 0.003
O21 -0.068 -0.040 -0.028
N22 -0.012 -0.019 0.007
N23 0.003 -0.031 0.034
C24 0.022 -0.005 0.027
C25 0.021 -0.005 0.026

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Table 13. ACP and FD EPC calculated FF parameters for the aqueous phase.
FD ACP
Atom 𝒇𝒙 𝒇𝒙 ∆𝒇𝒙 Atom 𝒇𝒙 𝒇𝒙 ∆𝒇𝒙
N0 0.007 0.009 -0.002 C0 -0.051 -0.154 0.103
N1 -0.102 -0.083 -0.019 N1 -0.104 -0.032 -0.072
C2 -0.152 0.009 -0.161 C2 0.082 -0.069 0.151
N3 -0.075 -0.125 0.05 C3 -0.137 -0.030 -0.107
N4 0.065 -0.154 0.219 C4 -0.034 -0.125 0.091
C5 -0.062 -0.029 -0.033 C5 -0.045 0.050 -0.095
C6 0.013 -0.082 0.095 N6 -0.03 -0.402 0.372
C7 -0.02 -0.015 -0.005 C7 0.092 0.043 0.049
C8 0.018 -0.061 0.079 C8 -0.487 -0.077 -0.410
C9 -0.025 -0.054 0.029
C10 0.028 -0.032 0.060
C11 -0.024 0.012 -0.036
C12 -0.040 -0.014 -0.026
C13 -0.068 -0.010 -0.058
C14 -0.017 -0.001 -0.016
C15 -0.063 -0.01 -0.053
C16 -0.044 0.004 -0.048
N17 0.021 0.003 0.018
C18 -0.032 -0.032 0.000
C19 -0.023 0.016 -0.039
C20 -0.047 -0.023 -0.024
O21 -0.042 -0.025 -0.017
N22 -0.004 -0.001 -0.003
N23 -0.002 0.030 -0.032
C24 -0.003 -0.021 0.018
C25 -0.012 -0.03 0.018

Table 14. ACP and FD MAC calculated FF parameters for the aqueous phase.
FD ACP
Atom 𝒇𝒙 𝒇𝒙 ∆𝒇𝒙 Atom 𝒇𝒙 𝒇𝒙 ∆𝒇𝒙
N0 0.007 -0.003 0.010 C0 -0.050 -0.083 0.033
N1 -0.128 -0.071 -0.057 N1 -0.072 -0.034 -0.038
C2 -0.108 -0.047 -0.061 C2 -0.078 -0.058 -0.02
N3 -0.053 -0.048 -0.005 C3 -0.099 -0.015 -0.084
N4 0.018 -0.146 0.164 C4 -0.036 -0.088 0.052
C5 -0.057 -0.033 -0.024 C5 -0.022 -0.054 0.032
C6 -0.01 -0.062 0.052 N6 -0.013 -0.216 0.203
C7 0.014 -0.006 0.02 C7 0.015 0.016 -0.001
C8 0.016 -0.012 0.028 C8 -0.387 -0.062 -0.325
C9 0.016 -0.009 0.025
C10 -0.014 -0.070 0.056
C11 -0.044 -0.026 -0.018
C12 -0.067 0.005 0.000
C13 -0.01 0.013 -0.023
C14 -0.015 0.022 -0.037
C15 -0.015 0.015 -0.030
C16 -0.055 -0.018 -0.037
N17 -0.01 -0.004 -0.006
C18 0.005 0.002 0.003
C19 0.005 0.002 0.003
C20 -0.008 0.002 -0.01
O21 -0.050 -0.029 -0.021
N22 -0.013 -0.003 -0.010
N23 -0.003 -0.011 0.008
C24 0.001 0.006 -0.005
C25 0.001 -0.255 0.256

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Table 15. ACP and FD NBOC calculated FF parameters for the aqueous phase.
FD ACP
Atom 𝒇𝒙 𝒇𝒙 ∆𝒇𝒙 Atom 𝒇𝒙 𝒇𝒙 ∆𝒇𝒙
N0 -0.012 -0.012 0.000 C0 -0.037 -0.113 0.076
N1 -0.122 -0.074 -0.048 N1 -0.066 -0.024 -0.042
C2 -0.150 0.000 -0.150 C2 -0.131 -0.091 -0.040
N3 -0.034 -0.085 0.051 C3 -0.072 -0.014 -0.058
N4 -0.006 -0.21 0.204 C4 -0.031 -0.099 0.068
C5 -0.008 0.007 -0.015 C5 -0.048 -0.001 -0.047
C6 -0.005 -0.074 0.069 N6 -0.024 -0.324 0.300
C7 -0.003 -0.005 0.002 C7 0.009 0.008 0.001
C8 -0.009 -0.093 0.084 C8 -0.383 -0.059 -0.324
C9 -0.001 -0.008 0.007
C10 -0.007 -0.076 0.069
C11 -0.018 0.003 -0.021
C12 -0.071 -0.007 -0.064
C13 -0.011 -0.004 -0.007
C14 -0.089 -0.009 -0.080
C15 -0.016 -0.004 -0.012
C16 -0.063 -0.002 -0.061
N17 0.003 0.001 0.002
C18 0.002 0.001 0.001
C19 0.002 0.001 0.001
C20 -0.023 -0.004 -0.019
O21 -0.039 -0.022 -0.017
N22 -0.015 -0.008 -0.007
N23 0 0.006 -0.006
C24 0 0.003 -0.003
C25 0 0.003 -0.003

Since FD and ACP behavior was significantly influenced by protonation in the

aqueous, gas and aqueous phases, FF were evaluated and applied for the
interpretation of the respective reaction sites. The sites of nucleophilic and
electrophilic attacks in FD and ACP, for both gas and aqueous phases, were
predicted using different FF predictors, including 𝑓 , 𝑓 𝑎𝑛𝑑 ∆𝑓 . The nucleophilic
attacks were at the N(4) and C(7) atoms, in FD and ACP molecules, respectively.
The electrophilic attacks were located at the C(20)-O(21) and N(6)-N(7) bonds
(which are also the most favorable sites for protonation), for FD and ACP,
respectively (Table 16).

Table 16. ACP and FD sites for electrophilic and nucleophilic attacks in the gas and
aqueous phases.
FF Gas phase Aqueous phase
FD ACP FD ACP
, ,
Nucleophilic (EPC) N4 (𝑓 , ∆𝑓 ) C7(𝑓 ) N4 (𝑓 ) C7(𝑓 )
, ,
Nucleophilic (MAC) N4 (𝑓 , ∆𝑓 ) C7(𝑓 , ∆𝑓 ) N4 (𝑓 , ∆𝑓 ) C7(𝑓 )
Nucleophilic (NBOC) N4 (∆𝑓 ) C7(𝑓 ) N4 (∆𝑓 ) C7(𝑓 )
Electrophilic (EPC) O21 (∆𝑓 ) N6-N7 (∆𝑓 ) O21 (∆𝑓 ) N6-N7 (∆𝑓 )
Electrophilic (MAC) O21 (∆𝑓 ) N6-N7 (𝑓 , ∆𝑓 ) O21 (∆𝑓 ) N6-N7 (𝑓 )
Electrophilic (NOBC) O21 (∆𝑓 ) N6-N7 (∆𝑓 ) O21 (∆𝑓 ) N6-N7 (∆𝑓 )

Binding energy
The interaction between the inhibitors and the MS surface was evaluated by
calculating the binding energy that existed between the formers and the latter, after

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merging their optimized structures of the metal crystal (Fig. 9). Equation 25 was
adopted to calculate the binding energy between MS and the inhibitors [38]:
𝐸 ( ) = 𝐸 ( ) − 𝐸 (𝑀𝑆) +𝐸 ( ) (26)

where 𝐸 ( ) and 𝐸 ( ) are MS and inhibitors total binding energies,

respectively. The calculated inhibitors binding energies are shown in Table 17.
The results reveal that FD binding energy (12195.39 eV) was lower than that of
ACP (63914.25 eV). Therefore, FD average IE (%) was better than that of ACP,
because the interaction between the MS surface and FD was stronger than that
between the former and ACP.

Figure 9. Optimized structures showing MS and inhibitors interaction.

Table 17. Binding and interaction energies between the MS surface and inhibitors.
Inhibitor Eint(Total) Ebind(inhib) Ebind(MS) Ebind(inhib-MS)
s (eV) (eV) (eV) (eV)
FD 72502.65 -668.61 9257.01 63914.25
ACP 21245.51 -206.89 9257.01 12195.39

Adsorption mechanism
ACP and FD went through chemical adsorption, which involves electrons transfer.
One general concept on the adsorption of a corrosion inhibitor is believed to be a
displacement of an adsorbed water molecule from the metal surface by the
inhibitor, as expressed in Equation 17. However, where other components (such
as acidic anions) tend to be adsorbed, this model may not suffice to predict the
adsorption mechanism. Therefore, to propose a suitable model, the mechanisms of
MS anodic dissolution and the corresponding cathodic HER should be considered.
The mechanism for MS anodic dissolution can be presented as follows:
𝑀𝑆 + Cl ↔ (MSCl ) → [MSCl] + e (28)
MSCl = (MSCl) + e (29)
(MSCl) → MS + Cl (30)

On the other hand, the mechanism for cathodic HER can be written as:
𝑀𝑆 + 𝐻 ↔ (𝑀𝑆𝐻 ) (27)
(𝑀𝑆𝐻 ) + 𝑒 → (𝑀𝑆𝐻) (28)
(𝑀𝑆𝐻) + 𝐻 + 𝑒 → 𝑀𝑆 + 𝐻 (29)

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From the above, it is most probably that the initial mechanism was the adsorption
of HCl- or SO42- ions released by the respective acid ionization [39], as shown in
the following equations:
𝐻𝐶𝑙 + 𝑀𝑆 = (𝑀𝑆𝐶𝑙) (30)
𝐻 𝑆𝑂 + 𝑀𝑆 = (𝑀𝑆𝑆𝑂 ) (31)

However, without inhibitors, the passivation zone will be overcome, and MS will
corrode. However, with an inhibitor, further adsorption may involve the anions
(HCl- or SO42- ) displacement (Equation 27a) or join adsorption onto MS
passivating layer (Equation 36):
(𝐹𝑒(𝐴) + 𝐼𝑛ℎ𝑖𝑏 → 𝐹𝑒[𝐼𝑛ℎ)] (32)
(33)
(𝐹𝑒(𝐴) + 𝐼𝑛ℎ → [𝐹𝑒𝐶𝑙. (𝐼𝑛ℎ) ]

where A is the conjugate base of the acid and Inh represents the charged/protonated
inhibitor. In the above-proposed mechanism, whichever reaction is favored
depends on several factors, especially temperature, protonation degree, etc.

Conclusions
The results of the present study and the findings drawn therein led to the following
conclusions:
1. ACP and FD are good inhibitors for MS corrosion in both HCl and H2SO4
solutions. Although their IE (%) are relatively comparable, FD seems to
perform slightly better than ACP.
2. ACP and FD IE (%) had a strong correlation with calculated quantum
parameters, such as FMO energies, σ,  and N.
3. The inhibitors adsorption favored Langmuir’s, Temkin’s, Freundlich’s and
Frumkin’s isotherms, and presented an energy barrier that suggested mixed
type adsorption, with an initial physisorption mechanism.
4. Polarization data confirmed that the inhibitors majorly acted as cathodic, by
retarding cathodic HER more than suppressing MS dissolution. Cdl varied
inversely with Rct, and gave a strong signal that the inhibitors were effective
against MS corrosion in the acidic media.
5. The protonated inhibitors adsorption seems to have prevailed over the neutral
molecules adsorption. FF indices were useful in predicting the inhibitors
adsorption sites, and the strong influence of the aqueous environment over the
inhibitors reactivity was upheld through calculated aqueous phase data.

Acknowledgement
The authors acknowledge tertiary education trust fund of Nigeria for providing the
computational chemistry calculations through National Research fund, with
Professor Nnabuk Okon Eddy as Principal Investigator.

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Authors’ contributions
Anand Balasubramanian: conceived and designed the analysis; collected the data;
inserted data or analysis tools; wrote the paper. Vidyadharani Gopalakrishnan:
conceived and designed the analysis; collected the data. Loganathan Subramanian:
conceived and designed the analysis; collected the data. Rabiu Ibraheem
Muhammed: conceived and designed the analysis; collected the data; inserted data or
analysis tools. Rajni Garg: inserted data or analysis tools; edited and formatted the
paper. Nnabuk Okon Eddy: inserted data or analysis tools; performed the analysis;
wrote the paper.

Abbreviations
AC: alternating current
ACP: 6-chloro-5-methylpyridin-3-amine
AE: auxiliary electrode
C: concentration
Cdl: double-layer capacitance
CR: corrosion rate
DFT: density functional theory
E: electric potential
EA: electron affinity
Ecorr: corrosion potential
EHOMO: energy of the highest occupied molecular orbital
EIS: electrochemical impedance spectroscopy
ELUMO: energy of the lowest unoccupied molecular orbital
EPC: electrostatic potential charges
FD: ((Z)-2-(4-(dimethylamino)phenyl)(2-phenylhydrazinyl)methylene) hydrazinecarboxamide
FF: Fukui function
FMO: frontier molecular orbital
GDP: gross domestic product
H2SO4: sulfuric acid
H3PO4: phosphoric acid
HCl: hydrochloric acid
HER: hydrogen evolution reaction
HOMO: energy of the highest occupied molecular orbital
Icorr: corrosion current density
IE (%): inhibition efficiency
IP: ionization potential
kads: adsorption equilibrium constant
kads(FK): adsorption-desorption constant
LPR: linear polarization resistant
LRD: local reactivity descriptors
LUMO: energy of the lowest unoccupied molecular orbital
MAC: Mulliken atomic charges
MS: mild steel
NBOC: natural bond orbital charges
OCP: open circuit potential

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PA: protonation affinity

PDP: potentiodynamic polarization
R: gas constant
R2: correlation coefficient
Rct: charge transfer resistance
RE: reference electrode
Rp: polarization resistance
SC: saturated calomel
SDF: spatial data file
SEM: scanning electron microscopy
SR: scanning rate
WE: working electrode
WL: weight loss

Symbols definition
βa: anodic Tafel constant
βc: cathodic Tafel constant
E: energy gap
ΔG°ads: Gibb’s free energy of adsorption
N: fraction of electrons transference
Δφ: inner potential difference
: global hardness
θ: degree of surface coverage
µ: dipole moment
σ: softness
χ: electronegativity

References
1. Bhonge S, Dalwi P, Kulkarni J et al. Recommendations for rehabilitation and
corrosion protection of a 100-year-old steel bridge (Durgadee) across heavily
polluted river near Mumbai, India. Rev Alconpat. 2020;10(2):259-73.
2. Fayomi OSI, Akande IG, Odigie S. Economic Impact of Corrosion in Oil
Sectors and Prevention: An Overview. J Phys Conf Ser. 2019;1378(2).
3. Bhaskaran R, Palaniswamy N, Rengaswamy NS et al. Global Cost of
Corrosion—A Historical Review. In: Corrosion: Materials [Internet]. ASM
International. 2018:621-8. [Link]
4. Eddy NO, Odoemelam SA. Sparfloxacin and norfloxacin as corrosion
inhibitors for mild steel: Kinetics, thermodynamics and adsorption
consideration. J Mater Sci. 2008;4(1):1-5.
5. Khadom AA, Yaro AS, Altaie AS et al. Electrochemical, activations and
adsorption studies for the corrosion inhibition of low carbon steel in acidic
media. Port Electrochim Acta. 2009;27(6):699-712.
6. Khaled KF. Studies of the corrosion inhibition of copper in sodium chloride
solutions using chemical and electrochemical measurements. Mater Chem Phys.
2011;125(3):427-33. [Link]
7. Olasunkanmi LO, Idris AO, Adewole AH et al. Adsorption and Corrosion
Inhibition Potentials of Salicylaldehyde-based Schiff Bases of Semicarbazide and
p-Toluidine on Mild Steel in Acidic Medium: Experimental and Computational
Studies. Surf Interf. 2020;21:100782. [Link]

244
 Vidyadharani Gopalakrishnan et al. / Portugaliae Electrochimica Acta 41 (2023) 223-246

8. Eddy NO, Odoemelam SA, Odiongenyi AO. Joint effect of halides and ethanol
extract of Lasianthera africana on inhibition of corrosion of mild steel in
H2SO4. J Appl Electrochem. 2009;39(6):849-57.
9. Negm NA, Kandile NG, Badr EA et al. Gravimetric and electrochemical evaluation
of environmentally friendly nonionic corrosion inhibitors for carbon steel in 1 M
HCl. Corros Sci. 2012;65:94-103. [Link]
10. Abdel-Gaber AM, Abd-El-Nabey BA, Khamis E et al. A natural extract as
scale and corrosion inhibitor for steel surface in brine solution. Desalination.
2011;278(1-3):337-42. [Link]
11. Salasi M, Shahrabi T, Roayaei E et al. The electrochemical behaviour of
environment-friendly inhibitors of silicate and phosphonate in corrosion control of
carbon steel in soft water media. Mater Chem Phys. 2007;104(1):183-90.
12. Ramachandran G, Balamurugan R. Comparative study on mild steel in acidic
medium using 5-amino-2-chloro-3-picoline as inhibitor. Asian J Chem.
2018;30(4):917-9.
13. ASTM Standard G-31. Standard Practice for Laboratory Immersion Corrosion
Testing of Metals, Annual Book of ASTM Standards. ASTM Int West
Conshohocken, USA. 1999;3.02(Reapproved):101.
14. Yurt A, Ulutas S, Dal H. Electrochemical and theoretical investigation on the
corrosion of aluminium in acidic solution containing some Schiff bases. Appl
Surf Sci. 2006;253(2):919-25.
15. Shainy KM, Rugmini Ammal P, Unni KN et al. Surface Interaction and
Corrosion Inhibition of Mild Steel in Hydrochloric Acid Using Pyoverdine, an
Eco-Friendly Bio-molecule. J Bio- Tribo-Corros. 2016;2(3):1-12.
16. Rosaline Vimala J, Leema Rose A, Raja S. Cassia auriculata extract as
corrosion inhibitor for mild steel in acid medium. Int J ChemTech Res.
2011;3(4):1791-801.
17. Hooshmand Zaferani S, Sharifi M, Zaarei D et al. Application of eco-friendly
products as corrosion inhibitors for metals in acid pickling processes - A review. J
Environ Chem Eng. 2013;1(4):652-7. [Link]
18. Osarolube E, Owate IO, Oforka NC. Corrosion behaviour of mild and high
carbon steels in various acidic media. Sci Res Essays. 2008;3(6):224-8.
19. Singh A, Ebenso EE, Quraishi MA. Corrosion inhibition of carbon steel in HCl
solution by some plant extracts. Int J Corros. 2012.
20. Dadgarinezhad FB. The inhibition mild steel corrosion in phosphoric acid solutions
by 2-phenyl-1-hydrazine carboxamide. J Chil Chem Soc. 2016;3:229-50.
21. Chafiq M, Chaouiki A, Lgaz H et al. Synthesis and corrosion inhibition evaluation
of a new schiff base hydrazone for mild steel corrosion in HCl medium:
electrochemical, DFT, and molecular dynamics simulations studies. J Adhes Sci
Technol. 2020;34(12):1283-314. [Link]
22. Aladesuyi O, Fatile BO, Adedapo EA et al. Corrosion Inhibitive Effect of 2-
(1-(2-Oxo-2H-Chromen-3-Yl) Ethylidene) Hydrazine Carboxamide on Zinc-
Aluminum Alloy in 1.8 M Hydrochloric Acid. Int J Adv Res Chem Sci.
2016;3(2):15-21.
23. Farahati R, Behzadi H, Mousavi-Khoshdel SM et al. Evaluation of corrosion
inhibition of 4-(pyridin-3-yl) thiazol-2-amine for copper in HCl by
experimental and theoretical studies. J Mol Struct. 2020;1205:127658.
[Link]

245
 Vidyadharani Gopalakrishnan et al. / Portugaliae Electrochimica Acta 41 (2023) 223-246

24. Zhang J, Zhang J, Zhu F et al. Improved Synthesis of 6-Chloro-5-

methylpyridin-2-amine: A Key Intermediate for Making Lumacaftor. Org
Process Res Dev. 2020;24(6):1175-9.
25. Abd El Rehim SS, Sayyah SM, El-Deeb MM et al. Adsorption and corrosion
inhibitive properties of P(2-aminobenzothiazole) on mild steel in hydrochloric
acid media. Int J Ind Chem. 2016;7(1):39-52.
26. Deyab MA, Essehli R, El Bali B. Inhibition of copper corrosion in cooling
seawater under flowing conditions by novel pyrophosphate. RSC Adv.
2015;5(79):64326-34. [Link]
27. Lai C, Xie B, Zou L et al. Adsorption and corrosion inhibition of mild steel in
hydrochloric acid solution by S-allyl-O,O′-dialkyldithiophosphates. Results
Phys. 2017;7:3434-43. [Link]
28. Saeed MT, Saleem M, Usmani S et al. Corrosion inhibition of mild steel in 1 M HCl
by sweet melon peel extract. J King Saud Univ Sci. 2019;31(4):1344-51.
[Link]
29. Ameh P, Ebenso E, Eddy NO et al. Corrosion Inhibition Potential of Daniella oliverri Gum
Exudate for Mild Steel in Acidic Medium. 2012;7(July):7425-39. [Link]
30. Ogunleye OO, Arinkoola AO, Eletta OA et al. Green corrosion inhibition and adsorption
characteristics of Luffa cylindrica leaf extract on mild steel in hydrochloric acid
environment. Heliyon. 2020;6(1):e03205. [Link]
31. Chokkalingam M, Singh P, Huo Y et al. Facile synthesis of Au and Ag nanoparticles
using fruit extract of Lycium chinense and their anticancer activity. J Drug Deliv Sci
Technol. 2019 Feb;49:308-15. [Link]
32. Pilepi V, Urši S. Nucleophilic reactivity of the nitroso group. Fukui function DFT calculations
for nitrosobenzene and 2-methyl-2-nitrosopropane. J Mol Struct. 2001;538:41-9.
33. Xu X, Singh A, Sun Z et al. Theoretical, thermodynamic and electrochemical
analysis of biotin drug as an impending corrosion inhibitor for mild steel in
15% hydrochloric acid. R Soc Open Sci. 2017;4(12).
34. Alhaffar MT, Umoren SA, Obot IB et al. Isoxazolidine derivatives as
corrosion inhibitors for low carbon steel in HCl solution: Experimental,
theoretical and effect of KI studies. RSC Adv. 2018;8(4):1764-77.
35. Perea-Ramírez LI, Guevara-García A, Galván M. Using local softness to
reveal oxygen participation in redox processes in cathode materials. J Mol
Model. 2018;24(9):0-8.
36. Gao L, Peng S, Gong Z et al. A combination of experiment and theoretical methods
to study the novel and low-cost corrosion inhibitor 1-hydroxy-7-azabenzotriazole
for mild steel in 1 M sulfuric acid. RSC Adv. 2018;8(67):38506-16.
37. Eddy NO, Ita BI. Experimental and theoretical studies on the inhibition
potentials of some derivatives of cyclopenta-1,3-diene for the corrosion of
mild steel in HCl solutions. Int J Quantum Chem. 2011;111(14):3456-74.
38. Eddy NO, Momoh-Yahaya H, Oguzie EE. Theoretical and experimental studies on
the corrosion inhibition potentials of some purines for aluminum in 0.1 M HCl. J
Adv Res. 2015;6(2):203-17. [Link]
39. Roling LT, Abild-Pedersen F. Structure-Sensitive Scaling Relations: Adsorption
Energies from Surface Site Stability. Chem Cat Chem. 2018;10(7):1643-50.

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